Field of the Invention
[0001] The present invention relates to a fiber-treating agent for imparting water resistance,
heat resistance and heat shape memory ability to naturally derived fibers which are
used for hair ornament products such as wigs and extensions.
Background of the Invention
[0002] Examples of applications of naturally derived fibers include hair ornament products
such as wigs and extensions. Unlike synthetic fibers, naturally derived fibers have
natural texture and appearance originating from a natural material. Among naturally
derived fibers, regenerated protein fibers, for example, regenerated collagen fibers
are obtained by solubilizing acid-soluble collagen or insoluble collagen with an alkali
or an enzyme to obtain a spinning stock solution, and discharging the spinning stock
solution into a coagulation bath through a spinning nozzle to form fibers.
[0003] However, regenerated collagen fibers generally have higher hydrophilicity and hence
higher water absorption as compared to synthetic fibers, and the fibers have extremely
low mechanical strength when they contain a large amount of water. This leads to deterioration
of suitability as a hair ornament product such that during shampooing, mechanical
strength significantly decreases because of the high water absorption, and during
subsequent blowing with a hair drier, rupture occurs.
[0004] Regenerated collagen fibers also have the problem of low heat resistance, so that
if a set using a hair iron is performed at a temperature as high as that for human
hair, shrinkage or crimping occurs, resulting in impairment of visual quality.
[0005] Further, in plastic synthetic fibers, the shape in a heat set with a hair iron or
the like is continuously memorized even after subsequent hair washing (there is heat
shape memory ability), whereas in regenerated collagen fibers, the shape in a heat
set with a hair iron or the like is lost through subsequent hair washing (there is
no heat shape memory ability). Therefore, regenerated collagen fibers may be inferior
to conventional plastic synthetic fibers in terms of degree of freedom of styling.
[0006] The three points described above are a factor in limiting popularization of regenerated
collagen fibers which are used for hair ornament products. In particular, water resistance,
that is, a decrease in mechanical strength has a significant impact when it is wet.
Therefore, for modifying regenerated collagen fibers to impart water resistance and
heat resistance, an attempt has been made to apply a reactive substance to amino groups
of a collagen molecule, and as an example thereof, a method is known in which a compound
having a methylol group is applied (Patent Literatures 1 and 2). In the field of human
hair fibers also used for hair ornament products, a method is known in which to human
hair fibers having essentially no heat shape memory ability, a compound having a methylol
group is applied for newly imparting heat shape memory ability (Patent Literature
3).
Citation List
Patent Literature
Summary of the Invention
[0008] The present invention provides a one-part type fiber-treating agent comprising a
single composition or a multiple-part type fiber-treating agent comprising a plurality
of compositions, wherein the fiber-treating agent comprises the following components
(A) to (C) in the total composition thereof, provided that, for the one-part type,
a part or all of the components (A) and (B) is optionally a condensate formed from
the components:
- (A): a compound having a structure in which a methylol group is bonded to each of
two nitrogen atoms in the molecule;
- (B): a phenolic compound having an electron donating group on at least one of meta-positions
and a hydrogen atom on at least one of ortho-positions and a para-position, wherein
the electron donating group on the meta-position optionally forms, together with adjacent
carbon atoms, a benzene ring optionally substituted with a hydroxy group; and
- (C): water.
[0009] Further, the present invention provides a method for treating fibers, comprising
the following step (i):
- (i) immersing fibers in the fiber-treating agent.
[0010] Further, the present invention provides a method for producing fibers for hair ornament
products, comprising the step of treating fibers by the method for treating fibers.
[0011] Further, the present invention provides a method for producing a hair ornament product,
comprising the step of treating fibers by the method for treating fibers.
[0012] Further, the present invention provides a fiber for hair ornament products, comprising
a condensate formed from the components (A) and (B).
[0013] Further, the present invention provides a hair ornament product having, as a constituent
element, fibers comprising a condensate formed from the components (A) and (B).
Detailed Description of the Invention
[0014] In some situations of production of hair ornament products, fibers are intensively
extended, and in the technique disclosed in Patent Literatures 1 to 3, there are cases
where the stretchability (tenacity) of treated fibers is not sufficient. For this
reason, it is required to enhance the stretchability of treated fibers for preventing
rupture during extension.
[0015] Accordingly, the present invention relates to a fiber-treating agent for producing
fibers for hair ornament products in which the water resistance and the heat resistance
of naturally derived fibers typified by regenerated collagen fibers are improved,
heat shape memory ability is imparted, and the fibers are excellent in stretchability
(tenacity).
[0016] The present inventor found that by treating naturally derived fibers with a composition
containing a specific methylol compound and a specific phenolic compound, not only
water resistance and heat resistance in the naturally derived fibers are improved
and heat shape memory ability can be imparted, but also surprisingly, the stretchability
(tenacity) of the naturally derived fibers is improved as compared to that before
the treatment, and can be enhanced to a level close to that of human hair, leading
to completion of the invention. While it is common knowledge that a compound having
a methylol group like that used in Cited Literatures 1 to 3 normally cross-link tissues,
and therefore the tissues become fragile after the treatment, it is surprising that
results have been obtained which show that by using the specific methylol compound,
stretchability (tenacity) is improved as compared to that before the treatment when
naturally derived fibers are used as an object to be treated.
[0017] According to the present invention, it is possible to provide a fiber-treating agent
for producing fibers for hair ornament products in which the water resistance and
the heat resistance of naturally derived fibers are improved, heat shape memory ability
is imparted, and stretchability (tenacity) is improved.
[One-part type and multiple-part type]
[0018] The fiber-treating agent of the present invention comprises both the forms of a one-part
type fiber-treating agent comprising a single composition and a multiple-part type
fiber-treating agent comprising a plurality of compositions, where fibers are immersed
sequentially in the plurality of compositions, such as a two-part type.
[0019] In the present invention, the term "total composition of fiber-treating agent" refers,
in the case of the one-part type fiber-treating agent, to the composition of a single
composition forming the one-part type fiber-treating agent, and refers, in the case
of the multiple-part type fiber-treating agent in which fibers are immersed sequentially,
to the composition of a mixture when all compositions forming the multiple-part type
fiber-treating agent are virtually mixed. For example, when treatment is performed
sequentially with a first part and a second part in the same amount (that is, at a
mass ratio of 1 : 1) in the case of the two-part type, the concentration of each component
based on the total composition of the fiber-treating agent is half the concentration
of the component in each part.
[Fibers to be treated in the present invention]
[0020] Fibers to be treated with the fiber-treating agent of the present invention may be
either synthetic fibers or naturally derived fibers, and are preferably naturally
derived fibers. The naturally derived fiber refers to fibers which are taken from
a natural animal or plant, or artificially produced using keratin, collagen, casein,
soybeans, peanuts, corn, silk flocks, silk fibroin or the like as a raw material and
which are used for production of a hair ornament product. Among them, fibers produced
using keratin, collagen, casein, soybeans, peanuts, corn, silk flocks, silk fibroin
or the like as a raw material are preferable, regenerated protein fibers such as regenerated
collagen fibers made from collagen as a raw material or regenerated silk fibers made
from silk fibroin as a raw material are more preferable, and regenerated collagen
fibers are further more preferable.
[0021] Regenerated collagen fibers can be produced by a known technique, are not required
to have a composition of collagen 100%, and may contain a natural or synthetic polymer
and additives for improvement of quality. The regenerated collagen fibers may be post-processed.
Regenerated collagen fibers are preferably in the form of filaments. Filaments are
generally taken from fibers wound around a bobbin or packed in a box. It is also possible
to directly use filaments coming out from a drying step in a production process of
regenerated collagen fibers.
[Condensate formed from components (A) and (B)]
[0022] When the fiber-treating agent of the present invention is a one-part type, in the
fiber-treating agent, a methylol compound as a component (A) and a phenolic compound
as a component (B) may be contained as the compounds themselves, or may be contained
with a part or all of the components (A) and (B) being a condensate formed from the
components. The condensate may include water-soluble condensates having a small molecular
weight, and water-insoluble condensates formed by linkage of the water-soluble condensates.
Herein, the condensate includes both water-soluble and water-insoluble condensates
when referred to simply as a "condensate".
[Component (A): specific methylol compound]
[0023] The component (A) is a compound having a structure in which a methylol group is bonded
to each of two nitrogen atoms in the molecule. Examples of such a compound include
compounds (A1) to (A4) shown below. Among them, the compounds (A3) and (A4) are preferable,
and the compound (A3) is more preferable.

[0024] The content of a constituent element derived from the component (A) in the fiber-treating
agent of the present invention, based on the total composition of the fiber-treating
agent, is preferably 0.1 mass% or more, more preferably 1 mass% or more, further more
preferably 2.5 mass% or more, even more preferably 5 mass% or more, even more preferably
10 mass% or more, from the viewpoint of imparting higher shape sustainability and
strength to naturally derived fibers after treatment, and preferably 80 mass% or less,
more preferably 70 mass% or less, further more preferably 60 mass% or less, even more
preferably 50 mass% or less, even more preferably 40 mass% or less, from the viewpoint
of formulation compatibility in addition to the above-described viewpoint.
[0025] That is, the content of a constituent element derived from the component (A) in the
fiber-treating agent of the present invention is preferably from 0.1 to 80 mass%,
more preferably from 1 to 70 mass%, further more preferably from 2.5 to 60 mass%,
even more preferably from 5 to 50 mass%, even more preferably from 10 to 40 mass%,
based on the total composition of the fiber-treating agent, from the viewpoint of
imparting higher shape sustainability and strength to naturally derived fibers after
treatment and the viewpoint of formulation compatibility.
[0026] Herein, the term "constituent element derived from component (A)" refers, in the
case of the one-part type, to a constituent part derived from the component (A) in
the condensate and the remaining component (A), and refers, in the case of the multiple-part
type, to the component (A) itself.
[Component (B): specific phenolic compound]
[0027] The component (B) is a phenolic compound having an electron donating group on at
least one, preferably two of meta-positions and a hydrogen atom on at least one of
ortho-positions and a para-position. The electron donating group on the meta-position
of the phenolic compound may form a benzene ring together with an adjacent carbon
atom, and the benzene ring may be further substituted with a hydroxy group. The molecular
weight of the component (B) is preferably 110 or more, and preferably 1,000 or less,
more preferably 700 or less, further more preferably 500 or less, from the viewpoint
of good infiltration into naturally derived fibers. Examples of the phenolic compound
of the component (B) include the following components (B1), (B2) and (B3).
[0028]
(B1) resorcin derivative of formula (1)
(B2) Naphthol derivative of formula (2) or (3)
(B3) Flavan-3-ol derivative of formula (4)
[0029] The component (B1) is a compound of the following formula (1):

wherein
A
1 to A
4 are the same or different, and each represent a hydrogen atom, a hydroxy group, a
halogen atom, a carboxyl group or a salt thereof, a sulfonic acid group or a salt
thereof, a linear or branched alkyl group or alkenyl group having 1 to 6 carbon atoms,
or a linear or branched alkoxy group or alkenyloxy group having 1 to 6 carbon atoms.
[0030] Examples of the component (B1) include resorcin, 2-methylresorcin, 4-chlororesorcin,
and pyrogallol.
[0031] The component (B2) is a compound of the following formula (2) or (3) :

wherein
R1 represents a hydrogen atom or a methyl group,
A5 represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having
1 to 12 carbon atoms, an optionally substituted aralkyl group or arylalkenyl group
having 7 to 12 carbon atoms, a linear or branched alkoxy group or alkenyloxy group
having 1 to 6 carbon atoms, a halogen atom or -CO-R2 (R2 is a linear or branched alkyl group or alkenyl group having 1 to 12 carbon atoms,
an optionally substituted aralkyl group or arylalkenyl group having 7 to 12 carbon
atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon
atoms),
D represents a hydrogen atom, a hydroxy group, a methyl group, or a linear or branched
alkoxy group or alkenyloxy group having 1 to 12 carbon atoms,
E represents a hydrogen atom, a hydroxy group, a linear or branched alkyl group or
alkenyl group having 1 to 6 carbon atoms, or an alkoxy group or alkenyloxy group having
1 to 6 carbon atoms, and
G represents a hydroxy group, a linear or branched alkyl group or alkenyl group having
1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and n represents
an integer of 0 to 2.
[0032] In the naphthol derivative of formula (2) or (3), R
1 in formula (2) or (3) is preferably a hydrogen atom, or an alkyl group or alkenyl
group having 1 to 4 carbon atoms, more preferably a hydrogen atom.
[0033] A
5 is preferably a hydrogen atom, a hydroxy group, a linear or branched alkyl group
having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, more preferably
a hydrogen atom or a hydroxy group.
[0034] D is preferably a hydrogen atom, a hydroxy group, a linear or branched alkyl group
having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
[0035] E is preferably a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon
atoms, or an alkoxy group having 1 to 4 carbon atoms.
[0036] Examples of the compound include 1-naphthol, 2-naphthol, 3-methylnaphthalen-1-ol,
naphthalene-1,5-diol, and naphthalene-1,8-diol.
[0037] The compound (B3) is a flavan-3-ol derivative of the following formula (4):

wherein
R3 represents a hydrogen atom or a methyl group,
X represents a hydrogen atom, a hydroxy group or a methoxy group,
R4 represents an aromatic hydrocarbon group optionally substituted with up to 3 hydroxy
groups or methoxy groups and optionally forming a fused ring with 1,3-dioxolane, and
R5 represents a hydroxy group, a methoxy group, an aromatic hydrocarbon group optionally
substituted with up to 3 hydroxy groups or methoxy groups and optionally forming a
fused ring with 1,3-dioxolane, or an arylcarbonyloxy group or aralkylcarbonyloxy group
optionally substituted with up to 3 hydroxy groups or methoxy groups.
[0038] The molecular weight of the compound of formula (4) is preferably 150 or more. From
the viewpoint of good infiltration into fibers, the molecular weight is preferably
1,000 or less, more preferably 700 or less, further more preferably 500 or less.
[0039] Examples of the component (B3) include non-gallates such as catechin, epicatechin
and epigallocatechin, and gallates such as catechin gallate, epicatechin gallate and
epigallocatechin gallate, and herein, the term "catechins" is a generic term of these
compounds. Among them, one or more selected from the group consisting of catechin,
epigallocatechin and epigallocatechin gallate are preferable. It is also possible
to use a mixture containing any of the above-described compounds, such as a tea extract.
[0040] Analysis of catechins in a mixture can be performed by an analysis method appropriate
to a measurement sample among known methods for analyzing non-polymeric catechins.
It is possible to perform the analysis by, for example, a liquid chromatography (HPLC)
method. In the measurement, treatment may be appropriately performed if necessary,
such as freeze-drying of the sample for adaptation to the detection range of an apparatus,
or removal of contaminants in the sample for adaptation to the resolution of an apparatus.
[0041] From the viewpoint of more significantly changing the shape of naturally derived
fibers after treatment with a fiber-treating agent of the present invention by a condensate
of the component (A) and the component (B) which is formed in the naturally derived
fibers, further improving the shape sustainability and durability of the naturally
derived fibers, and further improving natural appearance and feel quality, the component
(B) is preferably one or more selected from the group consisting of resorcin, 1-naphthol,
2-naphthol, 3-methylnaphthalen-1-ol, naphthalene-1-,5-diol, naphthalene-1,8-diol,
catechin, epicatechin, epigallocatechin, catechin gallate, epicatechin gallate, epigallocatechin
gallate and a tea extract, more preferably one or more selected from the group consisting
of resorcin, catechin, epicatechin, epigallocatechin, catechin gallate, epicatechin
gallate, epigallocatechin gallate and a tea extract.
[0042] One component (B) may be used alone, or two or more compounds (B) may be used in
combination, and two or more of (B1) to (B3) may be used in combination. From the
viewpoint of being able to impart higher shape sustainability and durability to naturally
derived fibers, and the viewpoint of enhancing the feel property, one or more selected
from the group consisting of (B1) and (B3) are preferable, and from the viewpoint
of being able to suppress elution of the component (A) from naturally derived fibers
after the treatment, and improve productivity in a factory by omitting a fiber washing
step and the viewpoint of making coloring of fibers minimal to enhance suitability
for use for hair ornament products, (B3) is more preferable.
[0043] The content of a constituent element derived from the component (B) in the fiber-treating
agent of the present invention, based on the total composition of the fiber-treating
agent, is preferably 0.1 mass% or more, more preferably 1 mass% or more, further more
preferably 1.5 mass% or more, even more preferably 3 mass% or more, even more preferably
5 mass% or more, from the viewpoint of imparting higher shape sustainability and strength
to naturally derived fibers after treatment, and preferably 80 mass% or less, more
preferably 60 mass% or less, further more preferably 50 mass% or less, even more preferably
40 mass% or less, even more preferably 30 mass% or less, even more preferably 25 mass%
or less, even more preferably 20 mass% or less, from the viewpoint of improving the
feel of the fiber surfaces in addition to the above-described viewpoints. That is,
the content of a constituent element derived from the component (B) in the fiber-treating
agent of the present invention is preferably from 0.1 to 80 mass%, more preferably
from 1 to 60 mass%, further more preferably from 1.5 to 50 mass%, even more preferably
from 3 to 40 mass%, even more preferably from 5 to 30 mass%, even more preferably
from 5 to 25 mass%, even more preferably from 5 to 20 mass%, based on the total composition
of the fiber-treating agent, from the viewpoint of imparting higher shape sustainability
and strength to naturally derived fibers after treatment and the viewpoint of improving
the feel of the fiber surfaces. Herein, the term "constituent element derived from
component (B)" refers, in the case of the one-part type, to a constituent part derived
from the component (B) in the condensate and the remaining component (B), and refers,
in the case of the multiple-part type, to the component (B) itself. When a mixture
containing the component (B), such as a mixture containing catechins, such as a tea
extract, is used, the term "constituent element derived from component (B)" refers
to the component (B) contained in the mixture.
[0044] The total content of a constituent element derived from the component (A) and a constituent
element derived from the component (B) in the fiber-treating agent of the present
invention is preferably 0.1 mass% or more, more preferably 1 mass% or more, further
more preferably 5 mass% or more, further more preferably 10 mass% or more, further
more preferably 15 mass% or more, further more preferably 20 mass% or more, based
on the total composition of the fiber-treating agent, from the viewpoint of imparting
higher shape sustainability and strength to naturally derived fibers after treatment,
and preferably 80 mass% or less, more preferably 70 mass% or less, further more preferably
60 mass% or less, further more preferably 50 mass% or less, further more preferably
40 mass% or less, based on the total composition of the fiber-treating agent, from
the viewpoint of improving the feel of the fiber surfaces.
[0045] The molar ratio of a constituent element derived from the component (A) to a constituent
element derived from the component (B), (A)/(B), in the fiber-treating agent of the
present invention is preferably 0.1 or more, more preferably 0.3 or more, further
more preferably 0.5 or more, from the viewpoint of further improving the shape sustainability
and strength of naturally derived fibers after treatment by a condensate of the components
which is formed in the naturally derived fibers, and preferably less than 20, more
preferably 15 or less, further more preferably 10 or less, even more preferably 7.5
or less, from the viewpoint of a good feel.
[0046] That is, the molar ratio of a constituent element derived from the component (A)
to a constituent element derived from the component (B), (A)/(B), is preferably 0.1
or more and less than 20, more preferably from 0.3 to 15, further more preferably
from 0.5 to 10, even more preferably from 0.5 to 7.5, from the viewpoint of further
improving the shape sustainability and strength of naturally derived fibers after
treatment by a condensate of the components which is formed in the naturally derived
fibers, and the viewpoint of a good feel.
[Component (C): water]
[0047] The fiber-treating agent of the present invention has (C) water as a medium. The
content of the component (C) in the fiber-treating agent of the present invention
is preferably 10 mass% or more, more preferably 20 mass% or more, further more preferably
30 mass% or more, even more preferably 40 mass% or more, and preferably 99 mass% or
less, more preferably 97 mass% or less, further more preferably 95 mass% or less,
even more preferably 90 mass% or less, based on the total composition of the fiber-treating
agent.
[0048] That is, the content of the component (C) in the fiber-treating agent of the present
invention is preferably from 10 to 99 mass%, more preferably from 20 to 97 mass%,
further more preferably from 30 to 95 mass%, even more preferably from 40 to 90 mass%,
based on the total composition of the fiber-treating agent.
[0049] The fiber-treating agent of the present invention can be not only of one-part type,
but also in the form of multiple-part type which comprises a plurality of compositions
and in which fibers are immersed sequentially. Examples of the multiple-part type
fiber-treating agent include those in which all parts have (C) water as a medium and
the component (A) and the component (B) are contained in different parts, for example,
those comprising a first part containing the components (B) and (C) and a second part
containing the components (A) and (C).
[Component (D): organic compound having a Hansen solubility parameter SP value of
from 16 to 40 Mpa1/2]
[0050] If an insoluble condensate having a large molecular weight is formed in the fiber-treating
agent of the present invention by a reaction with the components (A) and (B) when
the fiber-treating agent is a one-part type, motions, such as bending and stretching,
of naturally derived fibers may be restricted by a hard resin layer formed on the
surfaces of the naturally derived fibers, resulting in not only impairment of the
stretchability (tenacity) of the fibers but also deterioration of the feel of the
fiber surfaces. Thus, it is preferable that the one-part type fiber-treating agent
contains an organic compound having a Hansen solubility parameter SP value of 16 Mpa
1/2 or more and 40 Mpa
1/2 or less (excluding organic salts and compounds having an aldehyde group and having
a molecular weight of 150 or less) from the viewpoint of easily dissolving oligomeric
condensation products of the components (A) and (B), which are formed in the process
of reaction and cause an increase in turbidity, by preventing aggregation of the oligomeric
condensation products. Since organic salts, which have charge, rapidly increase the
turbidity when present in the system, and compounds having an aldehyde group, such
as glutaraldehyde, rapidly increase the turbidity by crosslinking phenol compounds
of the component (B) at multiple points, the organic salts and the compounds having
an aldehyde group are excluded from the component (D).
[0052] Examples of the organic compound having a Hansen solubility parameter SP value of
16 Mpa
1/2 or more and 40 Mpa
1/2 or less in the compound (D) include monohydric alcohols, dihydric alcohols, dihydric
alcohol derivatives, polyhydric alcohols with a valence number of 3 or more, lactam,
imidazolidinone, pyrimidinone, lactone, alkylene carbonate, and other general-purpose
organic solvents whose SP value is within the above-described range.
[0053] Specific examples of the compound having a Hansen solubility parameter SP value of
16 Mpa
1/2 or more and 40 Mpa
1/2 or less are listed below. The parenthesized numerical value in each example is a
SP value calculated by the above-described method.
- Examples of monohydric alcohol: ethanol (25.4), 1-propanol (22.9), isopropyl alcohol
(22.3) and 1-butanol (22.9)
- Examples of dihydric alcohol: ethylene glycol (31.6), diethylene glycol (29.2), triethylene
glycol (26.1), tetraethylene glycol (24.3), pentaethylene glycol (23.1), hexaethylene
glycol (22.2), propylene glycol (31.7), 1-dipropylene glycol (26.0) and tripropylene
glycol (23.4)
- Examples of dihydric alcohol derivative: dipropylene glycol monomethyl ether (21.1),
dipropylene glycol dimethyl ether (17.8), dipropylene glycol diacetate (19.0) and
dipropylene glycol monomethyl ether acetate (18.5)
- Examples of polyhydric alcohol with a valence number of 3 or more: glycerin (35.7)
and sorbitol (35.8)
- Examples of lactam: 2-pyrrolidone (24.8) and N-methylpyrrolidone (22.0)
- Examples of imidazolidinone: urea of ethylene (28.5), 1,3-dimethyl-2-imidazolidinone
(22.3)
- Examples of pyrimidinone: N,N'-dimethylpropyleneurea (21.3)
- Examples of lactone: γ-butyrolactone (24.6)
- Examples of alkylene carbonate: ethylene carbonate (29.2) and propylene carbonate
(27.1)
- Examples of general-purpose organic solvent: DMF (N,N-dimethylformamide) (24.2), DMAc
(N,N-dimethylacetamide) (23.0), DMSO (dimethylsulfoxide) (23.6), THF (tetrahydrofuran)
(18.2), 1,4-dioxane (20.5) and acetonitrile (23.9)
[0054] Among them, compounds having a Hansen solubility parameter SP value of 35.8 Mpa
1/2 or less are preferable, compounds having a Hansen solubility parameter SP value of
34.7 Mpa
1/2 or less are more preferable, and compounds having a Hansen solubility parameter SP
value of 29.2 Mpa
1/2 or less are further more preferable, from the viewpoint of being able to maintain
low turbidity over a longer time by adequately dissolving a condensate of the components
(A) and (B) which is formed in the process of reaction and causes an increase in turbidity.
From the same viewpoint, compounds having a Hansen solubility parameter SP value of
17.8 Mpa
1/2 or more are preferable, compounds having a Hansen solubility parameter SP value of
21.1 Mpa
1/2 or more are more preferable, and compounds having a Hansen solubility parameter SP
value of 22.0 Mpa
1/2 or more are more preferable.
[0055] Among them, dihydric alcohols, lactam and imidazolidinone are preferable, and at
least one selected from the group consisting of diethylene glycol (29.2), triethylene
glycol (26.1), N-methylpyrrolidone (22.0) and 1,3-dimethyl-2-imidazoridinone (22.3)
is more preferable.
[0056] Any one component (D) may be used alone, or two or more compounds (D) may be used
in combination. The content of the component (D) in the fiber-treating agent of the
present invention is preferably 10 mass% or more, more preferably 15 mass% or more,
further more preferably 25 mass% or more, from the viewpoint of maintaining longer
a state in which the turbidity of the fiber-treating agent is low, and preferably
80 mass% or less, more preferably 60 mass% or less, further more preferably 45 mass%
or less, from the viewpoint of efficiently carrying out a condensation reaction and
further improving the shape sustainability and strength of naturally derived fibers
after treatment by a condensate of the component (A) and the component (B) which is
formed in the naturally derived fibers.
[Component (E): Sulfur-containing reducing agent]
[0057] It is preferable that the fiber-treating agent of the present invention contain a
sulfur-containing reducing agent from the viewpoint of improving the heat resisting
temperature and suppressing coloring of naturally derived fibers after treatment,
and suppressing an increase in turbidity of the fiber-treating agent during heating
treatment.
[0058] Examples of the component (E) include sulfurous acid salts and thiol compounds.
The sulfurous acid salt is preferably sodium sulfite or sodium pyrosulfite, and the
thiol compound is preferably thioglycerol or Mesna (sodium 2-mercaptoethanesulfonate)
because compounds having a carboxy group (for example thioglycolic acid) or an amino
group (for example cysteamine) cause yellowish coloring, resulting in deterioration
of suitability as a hair ornament product. Above all, sodium sulfite is preferable.
[0059] Any one component (E) may be used alone, or two or more components (E) may be used
in combination. The content of the component (E) in the fiber-treating agent of the
present invention is preferably 0.1 mass% or more, more preferably 0.5 mass% or more,
further more preferably 2.0 mass% or more, based on the total composition of the fiber-treating
agent, from the viewpoint of improving the heat resisting temperature, suppressing
coloring and suppressing an increase in turbidity during heating treatment, and preferably
20 mass% or less, more preferably 10 mass% or less, further more preferably 5.0 mass%
or less, based on the total composition of the fiber-treating agent, from the viewpoint
of suppressing a decrease in fiber strength due to a reducing action. When the fiber-treating
agent is of multiple-part type, the component (E) may be contained in the first part,
or may be contained in the second part, or may be contained in both the first part
and the second part.
[0060] The molar ratio of the component (E) to the component (A), (E)/(A), is preferably
0.1 or more, more preferably 0.3 or more, further more preferably 0.5 or more, from
the viewpoint of sufficiently exhibiting the effect of improving the heat resistance
and the effect of suppressing coloring of fibers treated with the component (E) and
the effect of suppressing an increase in turbidity of the fiber-treating agent, and
preferably 3.0 or less, more preferably 1.5 or less, further more preferably 1.0 or
less from the viewpoint of suppressing a decrease in fiber strength by a reducing
action.
[Cationic surfactant]
[0061] The fiber-treating agent of the present invention may contain a cationic surfactant
as long as the effects of the present invention are not impaired. The cationic surfactant
is preferably a long chain monoalkyl quaternary ammonium salt having one alkyl group
having 8 to 24 carbon atoms and three alkyl groups having 1 to 4 carbon atoms.
[0062] Preferably, at least one long chain monoalkyl quaternary ammonium surfactant is selected
from the group consisting of compounds of the following formula:

wherein R
4 is a saturated or unsaturated linear or branched alkyl group having 8 to 22 carbon
atoms, R
8-CO-NH-(CH
2)
m- or R
8-CO-O-(CH
2)
m- (R
8 represents a saturated or unsaturated linear or branched alkyl chain having 7 to
21 carbon atoms, and m represents an integer of 1 to 4), R
5, R
6 and R
7 independently represent an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl
group having 1 to 4 carbon atoms, and X
-represents a hydrochloride ion, a bromide ion, a methosulfate ion or an ethosulfate
ion.
[0063] Examples of the suitable cationic surfactant include long chain quaternary ammonium
compounds such as cetyltrimethylammonium chloride, myristyltrimethylammonium chloride,
behentrimonium chloride, cetyltrimethylammonium bromide and stearamidopropyltrimonium
chloride. One of them may be used alone, or a mixture thereof may be used.
[0064] The content of the cationic surfactant in the fiber-treating agent of the present
invention is preferably 0.05 mass% or more, more preferably 0.1 mass% or more, and
preferably 10 mass% or less, more preferably 5 mass% or less, based on the total composition
of the fiber-treating agent, from the viewpoint of improving the feel of naturally
derived fibers after treatment to further improve the effects of the present invention.
When the fiber-treating agent is of multiple-part type, the cationic surfactant may
be contained in the first part, or may be contained in the second part, or may be
contained in both the first part and the second part.
[Silicone]
[0065] The fiber-treating agent of the present invention may contain silicone from the viewpoint
of improving the feel of naturally derived fibers after treatment, and improving styling
ease. The silicone is preferably one or more selected from the group consisting of
dimethylpolysiloxane and amino-modified silicone.
[0066] As the dimethylpolysiloxane, any of cyclic or acyclic dimethylsiloxane polymers can
be used, and examples thereof include SH200 Series, BY22-019, BY22-020, BY11-026,
B22-029, BY22-034, BY22-050A, BY22-055, BY22-060, BY22-083 and FZ-4188 (each manufactured
by Dow Corning Toray), and KF-9088, KM-900 Series, MK-15H and MK-88 (each manufactured
by Shin-Etsu Chemical Co., Ltd.).
[0067] As the amino-modified silicone, any silicone having an amino group or an ammonium
group can be used, and examples thereof include amino-modified silicone oil which
is terminal-blocked at all or a part of terminal hydroxyl groups with a methyl group
or the like, and amodimethicone which is not terminal-blocked. Examples of the amino-modified
silicone preferable from the viewpoint of improving the feel of naturally derived
fibers after treatment and improving styling ease include compounds of the following
formula:

wherein R' represents a hydrogen atom, a hydroxy group or R
X, where R
X represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to
20 carbon atoms, J represents R
X, R"-(NHCH
2CH
2)aNH
2, OR
X or a hydroxy group, R" represents a divalent hydrocarbon group having 1 to 8 carbon
atoms, a represents a number of 0 to 3, and b and c represent numbers whose sum is
10 or more and less than 20,000, preferably 20 or more and less than 3,000, more preferably
30 or more and less than 1,000, further more preferably 40 or more and less than 800,
in terms of number average.
[0068] Specific examples of the suitable marketed product of amino-modified silicone include
amino-modified silicone oils such as SF8452C and SS3551 (each manufactured by Dow
Corning Toray) and KF-8004, KF-867S and KF-8015 (each manufactured by Shin-Etsu Chemical
Co., Ltd.), and amodimethicone emulsions such as SM8704C, SM8904, BY22-079, FZ-4671
and FZ4672 (each manufactured by Dow Corning Toray).
[0069] The content of the silicone in the fiber-treating agent of the present invention
is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, further more preferably
0.5 mass% or more, and preferably 20 mass% or less, more preferably 10 mass% or less,
further more preferably 5 mass% or less, based on the total composition of the fiber-treating
agent, from the viewpoint of improving the feel of naturally derived fibers after
treatment to further improve the effects of the present invention. When the fiber-treating
agent is of multiple-part type, the silicone may be contained in the first part, or
may be contained in the second part, or may be contained in both the first part and
the second part.
[Cationic polymer]
[0070] The fiber-treating agent of the present invention may contain a cationic polymer
from the viewpoint of improving the feel of naturally derived fibers after treatment.
[0071] The cationic polymer refers to a polymer having a cationic group, or a group capable
of being ionized into a cationic group, and also includes a generally cationic ampholytic
polymer. That is, examples of the cationic polymer include those in the form of an
aqueous solution, which contain an amino group or an ammonium group on the side chain
of the polymer chain or contain a diallyl quaternary ammonium salt as a constituent
unit, for example, cationized cellulose derivatives, cationic starch, cationized guar
gum derivatives, polymers or copolymers of a diallyl quaternary ammonium salt, and
quaternized polyvinylpyrrolidone derivatives. Among them, one or more selected from
the group consisting of a polymer containing a diallyl quaternary ammonium salt as
a constituent unit, a quaternized polyvinylpyrrolidone derivative and a cationized
cellulose derivative are preferable, and one or more selected from the group consisting
of a polymer or copolymer of a diallyl quaternary ammonium salt and a cationized cellulose
derivative are more preferable, from the viewpoint of improving the effects of softness,
smoothness and finger-combability in the feel during rinsing and shampooing and ease
of styling and moisture retainability during blowing, and the stability of the agent.
[0072] Specific examples of the suitable polymer or copolymer of a diallyl quaternary ammonium
salt include dimethyldiallylammonium chloride polymers (polyquaternium-6, for example,
MERQUAT 100; Lubrizol Advanced Materials, Inc.), dimethyldiallylammonium chloride/acrylic
acid copolymers (polyquaternium-22, for example, MERQUATs 280 and 295; Lubrizol Advanced
Materials, Inc.), and dimethyldiallylammonium chloride/acrylamide copolymers (polyquaternium-7,
for example, MERQUAT 550; Lubrizol Advanced Materials, Inc.).
[0073] Specific examples of the suitable quaternized polyvinylpyrrolidone derivative include
polymers obtained by polymerizing a vinylpyrrolidone copolymer and dimethylaminoethyl
methacrylate (polyquaternium 11, for example, GAFQUAT 734, GAFQUAT 755 and GAFQUAT
755N (Ashland Inc.)).
[0074] Specific examples of the suitable cationized cellulose include polymers obtained
by adding glycidyltrimethylammonium chloride to hydroxycellulose (polyquaternium 10,
for example, LEOGARDs G and GP (Lion Corporation) and POLYMERs JR-125, JR-400, JR-30M,
LR-400 and LR-30M (Amerchol Corporation)), and hydroxyethylcellulose dimethyldiallylammonium
chloride (polyquaternium-4, for example, CELQUATs H-100 and L-200 (Akzo Nobel N.V.).
[0075] The content of the cationic polymer in the fiber-treating agent of the present invention
is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, further more
preferably 0.05 mass% or more, and preferably 20 mass% or less, more preferably 10
mass% or less, based on the total composition of the fiber-treating agent, from the
viewpoint of improving the feel of naturally derived fibers after treatment. When
the fiber-treating agent is of multiple-part type, the cationic polymer may be contained
in the first part, or may be contained in the second part, or may be contained in
both the first part and the second part.
[0076] Further, the fiber-treating agent of the present invention may contain an antioxidant
such as ascorbic acid, and a pH adjuster such as sodium hydroxide, potassium hydroxide,
phosphoric acid or hydrochloric acid.
[pH]
[0077] When the fiber-treating agent of the present invention is a one-part type, the pH
of the fiber-treating agent is preferably 3.0 or more, more preferably 3.5 or more,
further more preferably 4.0 or more, and preferably 11.0 or less, more preferably
9.0 or less, further more preferably 7.0 or less, from the viewpoint of suppressing
damage to naturally derived fibers. The pH in the present invention is a value at
25°C.
[0078] That is, when the pH of the fiber-treating agent of the present invention is a one-part
type, the pH of the fiber-treating agent is preferably from 3.0 to 11.0, more preferably
from 3.5 to 9.0, further more preferably from 4.0 to 7.0, from the viewpoint of suppressing
damage to naturally derived fibers.
[0079] In the case of the multiple-part type, it is preferable that the pHs of both a part
containing the component (A), that is, the second part and a part containing the component
(B), that is, the first part be in the above-described range. In the present invention,
the pH of the hair-treating agent shows a value obtained by performing measurement
directly at room temperature (25°C) by a pH meter (manufactured by HORIBA, Ltd./Model:
F-52) without diluting the hair-treating agent.
[Method for storing fiber-treating agent]
[0080] When the fiber-treating agent produced as described above is transported and stored
before being applied to fibers, the storage temperature can be set to a cool temperature
for the purpose of preventing coloring of the component (B) by oxidation, and progress
of an unintentional reaction during transportation. The storage temperature is preferably
1°C or higher, more preferably 2°C or higher, further more preferably 5°C or higher,
from the viewpoint of preventing occurrence of freezing and recrystallization, and
preferably 25°C or lower, more preferably 20°C or lower, further more preferably 15°C
or lower, from the viewpoint of preventing coloring by oxidation and progress of an
unintentional reaction.
[Method for treating fibers]
(Basic treatment)
[0081] When using the fiber-treating agent of the present invention, naturally derived fibers
are treated by a method comprising the following step (i), it is possible to impart
shape sustainability and high durability to the naturally derived fibers while maintaining
high stretchability (tenacity) of the naturally derived fibers.
- (i) Immersing naturally derived fibers in the fiber-treating agent of the present
invention.
[0082] When the fiber-treating agent is of multiple-part type, and comprises, for example,
the first part containing the components (B) and (C) and the second part containing
the components (A) and (C), the step (i) is a step of immersing fibers in one of the
first part and the second part, and then in the other, and it is preferable that the
fibers be immersed first in the first part, and then in the second part.
[0083] When the fiber-treating agent of the present invention is a one-part type, the fiber-treating
agent may be directly applied to fibers, but when the fiber-treating agent is applied
to the fibers after being heated for a certain time without causing an increase in
turbidity of the treating agent, the stretchability of the fibers can be further enhanced.
For this reason, the following step (0) may be provided before the step (i) .
(0) step of heating fiber-treating agent
[0084] The heating treatment in the step (0) is preferably 40°C or higher, more preferably
45°C or higher, further more preferably 50°C or higher, from the viewpoint of improvement
of productivity, and preferably 100°C or lower, more preferably 80°C or lower, further
more preferably 70°C or lower, from the viewpoint of being able to stop heating at
an appropriate point.
[0085] Assuming that T is a heating time until the treating agent has a turbidity of more
than 1,000 NTU after the treating agent is heated immediately after being prepared
by mixing the components, the heating time in the step (0) is preferably 0.2T or more,
more preferably 0.3T or more, further more preferably 0.4T or more, from the viewpoint
of exhibiting a stretchability improving effect on naturally derived fibers, and preferably
0.8T or less, more preferably 0.7T or less, further more preferably 0.6T or less,
from the viewpoint of exhibiting ability to treat naturally derived fibers for a long
time.
[0086] Here, NTU (nephelometric turbidity unit) is a unit of turbidity in a turbidimetric
method using formazin as a turbidity standard solution. The turbidity of the fiber-treating
agent can be measured at room temperature (25°C) with the fiber-treating agent directly
placed in a measurement cell of a digital turbidimeter (manufactured by AS ONE Corporation/model:
TB700).
[0087] In the step (i), the naturally derived fibers immersed in the fiber-treating agent
may be dry or wet. The amount of the fiber-treating agent in which the naturally derived
fibers are immersed is preferably 2 or more, more preferably 3 or more, further more
preferably 5 or more, even more preferably 10 or more, even more preferably 20 or
more, and preferably 500 or less, more preferably 250 or less, further more preferably
100 or less, in terms of bath ratio to the mass of the naturally derived fibers (mass
of fiber-treating agent/mass of naturally derived fibers).
[0088] That is, the bath ratio is preferably from 2 to 500, more preferably from 3 to 250,
further more preferably from 5 to 100, even more preferably from 10 to 100, even more
preferably from 20 to 100. When the fiber-treating agent is of multiple-part type,
the above-described bath ratio is applied for each part.
[0089] In the step (i), the naturally derived fibers may be fixed with a curler or the like,
followed by immersion in the fiber-treating agent of the present invention under heating.
This enables a desired shape to be imparted to the naturally derived fibers together
with shape sustainability and high durability.
[0090] It is preferable that the immersion of the naturally derived fibers in the fiber-treating
agent in the step (i) be performed under heating, and this heating is performed by
heating the fiber-treating agent. This heating may be performed by immersing the naturally
derived fibers in the fiber-treating agent being heated, or by immersing the naturally
derived fibers in the fiber-treating agent at a low temperature, and then performing
heating. The temperature of the fiber-treating agent is preferably 20° or higher,
more preferably 35°C or higher, further more preferably 45°C or higher for increasing
interaction of the component (A) and the component (B) with fiber constituent molecules,
for example protein molecules, in the naturally derived fibers, and accelerating a
condensation reaction between the component (A) and the component (B) in the naturally
derived fibers to obtain the effects of the present invention, and preferably lower
than 100°C, more preferably 80°C or lower, further more preferably 70°C or lower,
further more preferably 60°C or lower for preventing the naturally derived fibers
from being degenerated by heat and thus degraded. When the fiber-treating agent is
of multiple-part type, the above-described temperature is applied for each part.
[0091] The component (A) and the component (B) in the fiber-treating agent form a condensate
after infiltration into the fiber, so that the effects of the present invention are
exhibited by interaction with the fiber, and even in the one-part type fiber-treating
agent, the components (A) and (B) are fused with each other to form a water-soluble
condensate, and similarly form a condensate having a larger molecular weight after
infiltration into the fiber, so that the effects of the present invention are exhibited.
On the other hand, with the progress of fiber treatment, the water-soluble condensates
in the one-part type fiber-treating agent are bonded to each other to gradually form
water-insoluble condensates, leading to an increase in turbidity of the fiber-treating
agent. If the water-insoluble condensate comes into contact with the fibers, a hard
resin layer is formed on the surfaces of the fibers, and thus motions, such as bending
and stretching, of the fibers are restricted, so that it is difficult to maintain
the stretchability (tenacity) of the fibers. Thus, from the viewpoint of further enhancing
the stretchability (tenacity) of naturally derived fibers and improving the feel of
the fiber surfaces, it is desirable to carry out the step (i) in a state in which
the turbidity of the one-part type fiber-treating agent is as low as possible. The
turbidity of the fiber-treating agent during treatment is preferably 1,000 NTU or
less, more preferably 500 NTU or less, further more preferably 100 NTU or less, further
more preferably 20 NTU or less. The turbidity of the fiber-treating agent refers to
one from turbidness originating from a condensate of the components (A) and (B), and
when other components causing turbidness are present, only turbidness caused by the
condensate of the components (A) and (B) is taken into account. The amount of the
condensate can be determined by, for example, a derivatization-pyrolysis GC/MS method
after filtration with a membrane filter having a pore diameter of 0.1 µm.
[0092] Assuming that T is a heating time until the treating agent has a turbidity of more
than 1,000 NTU after the treating agent is heated immediately after being prepared
by mixing the components, the immersion time in the step (i) when the fiber-treating
agent is a one-part type is preferably 0.3T or more, more preferably 0.4T or more,
further more preferably 0.5T or more, from the viewpoint of exhibiting a stretchability
improving effect on naturally derived fibers, and preferably 0.95T or less, more preferably
0.90T or less, further more preferably 0.85T or less, for suppressing damage to naturally
derived fibers.
[0093] The specific immersion time is appropriately adjusted depending on a heating temperature
used, and is preferably 15 minutes or more, more preferably 30 minutes or more, further
more preferably 1 hour or more, from the viewpoint of exhibiting a stretchability
improving effect on naturally derived fibers, and preferably 48 hours or less, more
preferably 24 hours or less, further more preferably 12 hours or less for suppressing
damage to naturally derived fibers, for example. When the fiber-treating agent is
of multiple-part type, the immersion time is applied for each part.
[0094] It is preferable to carry out the step (i) in an environment where evaporation of
moisture is suppressed. Examples of the specific means for suppressing evaporation
of moisture include a method in which a container of the fiber-treating agent in which
naturally derived fibers are immersed is covered with a film-shaped material, a cap,
a lid or the like made of a material impermeable to water vapor.
[0095] After the step (i), the naturally derived fibers may be rinsed, or is not required
to be rinsed, and it is preferable to rinse the naturally derived fibers from the
viewpoint of preventing deterioration of the feel of the naturally derived fibers
by an excess polymerized product.
[0096] These treatments may allow the components (A) and (B) to infiltrate the naturally
derived fibers and interact with fiber constituent molecules, for example protein
molecules, in the naturally derived fibers. In the naturally derived fibers, a condensate
of the component (A) and the component (B) is formed. Therefore, the naturally derived
fibers treated by the method of the present invention does not lose shape even when
washed.
[0097] If the turbidity of the treating agent increases during treatment in the step (i)
when the fiber-treating agent is a one-part type, a hard resin layer is formed on
the surfaces of naturally derived fibers, so that it is difficult to maintain high
stretchability (tenacity) of the naturally derived fibers, and it is difficult to
secure a good feel of the fiber surfaces, and therefore it is preferable to take out
the naturally derived fibers from the treating agent before the turbidity of the treating
agent exceeds 1,000 NTU. The turbidity of the treating agent can be confirmed by the
above-described turbidity measurement method with a sample appropriately taken from
the treating agent. If the naturally derived fibers taken out during treatment have
not been sufficiently treated, the step (i) may be carried out again. That is, when
the fiber-treating agent is a one-part type, it is preferable to provide the following
step (ii-2) after the step (i) and repeat the step (i) and the step (ii-a) two or
more times.
[0098] (ii-a) Taking out naturally derived fibers from the treating agent before the turbidity
of the one-part type treating agent exceeds 1,000 NTU.
[0099] On the other hand, when the fiber-treating agent is of multiple-part type, naturally
derived fibers may be merely taken out from the treating agent by the following the
step (ii-b) after the step (i).
[0100] (ii-b) Taking out naturally derived fibers from the treating agent.
[0101] It is preferable to wash out insoluble condensates by rinsing the surfaces of naturally
derived fibers after the naturally derived fibers are taken out from the treating
agent in the step (ii-a) or the step (ii-b). That is, it is preferable to carry out
the following step (iii) after the step (ii).
(iii) Rinsing naturally derived fibers taken out
[0102] It is desirable that the rinsing in the step (iii) be performed using a composition
containing the component (D). The rinsing composition may be composed only of the
component (D), or may contain water in addition to the component (D). When water is
contained, the content of the component (D) in the rinsing composition is preferably
60 mass% or more, more preferably 80 mass% or more, further more preferably 95 mass%
or more.
[Optionally added treatment]
[0103] In the method for treating fibers according to the present invention, one or more
treatments selected from the group consisting of bleaching, dyeing, surface finish
for imparting hydrophobicity and reducing friction, and heating treatment for further
improving fiber stretchability (tenacity) may be performed in addition to the steps
(i) to (iii).
[0104] Here, the treatments of bleaching and dyeing may be performed before or after the
steps (i) to (iii), or between the steps (i) to (iii). A plurality of steps may be
combined and added, and when both bleaching and dyeing are added, any of the treatments
may be performed first except that it is necessary to perform bleaching before dyeing.
It is also possible to perform another treatment between bleaching and dyeing.
[0105] On the other hand, it is necessary that surface finish for imparting hydrophobicity
and reducing friction and heating treatment for further improving fiber stretchability
(tenacity) be performed after the steps (i) to (iii). As long as surface finish for
imparting hydrophobicity and reducing friction and heating treatment for further improving
fiber stretchability (tenacity) are performed after the steps (i) to (iii) as described
above, their treatment order relation with bleaching and dyeing is not particularly
limited. One of surface finish for imparting hydrophobicity and reducing friction
and heating treatment for further improving fiber stretchability (tenacity) may be
performed before or after the other.
(Bleaching)
[0106] The bleaching is performed by immersing naturally derived fibers in a bleach composition
containing an alkali agent, an oxidizing agent and water. The bleach composition is
typically of two-part type. The first part contains an alkali agent and water, and
the second part contains an oxidizing agent and water. These two parts are typically
stored separately, and mixed before immersion of naturally derived fibers.
[0107] Examples of the suitable alkali agent include, but are not limited to, ammonia and
salts thereof; alkanolamines (monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol,
2-aminobutanol and the like) and salts thereof; alkanediamines (1,3-propanediamine
and the like) and salts thereof; carbonates (guanidine carbonate, sodium carbonate,
potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the
like); and mixtures thereof.
[0108] The content of the alkali agent in the bleach composition (mixture of first part
and second part for two-agent type) is preferably 0.1 mass% or more, more preferably
0.5 mass% or more, further more preferably 1 mass% or more, and preferably 15 mass%
or less, more preferably 10 mass% or less, further more preferably 7.5 mass% or less).
[0109] Examples of the suitable oxidizing agent include, but are not limited to, hydrogen
peroxide, urea peroxide, melamine peroxide and sodium bromate. Among these oxidizing
agents, hydrogen peroxide is preferable.
[0110] The content of the oxidizing agent in the bleach composition is preferably 1 mass%
or more, more preferably 2 mass% or more, and preferably 15 mass% or less, more preferably
12 mass% or less, further more preferably 9 mass% or less.
[0111] When the first part and the second part are stored separately, the pH of the second
part at 25°C is preferably 2 or more, more preferably 2.5 or more, and preferably
6 or less, more preferably 4 or less. The pH can be adjusted by a suitable buffering
agent. The pH of the bleach composition at 25°C is preferably 6 or more, more preferably
6.5 or more, further more preferably 6.8 or more, and preferably 11 or less, more
preferably 10.5 or less, further more preferably 10 or less.
(Dyeing)
[0112] The dyeing is performed by immersing naturally derived fibers in a dyeing composition.
The dyeing composition contains a dye, and optionally contains an alkali agent or
an acid, an oxidizing agent or the like. Examples of the dye include direct dyes,
oxidizing dyes, and combinations thereof.
[0113] The type of the direct dye is not particularly limited, and any direct dye suitable
for dyeing can be used. Examples of the direct dye include anionic dyes, nitro dyes,
disperse dyes, cationic dyes, and dyes having an azo-phenol structure selected from
the group consisting of the following HC Red 18, HC Blue 18 and HC Yellow 16, salts
thereof, and mixtures thereof.

[0114] Examples of the cationic dye include, but are not limited to, Basic Blue 6, Basic
Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 99, Basic Brown 4,
Basic Brown 16, Basic Brown 17, Natural Brown 7, Basic Green 1, Basic Orange 31, Basic
Red 2, Basic Red 12, Basic Red 22, Basic Red 51, Basic Red 76, Basic Violet 1, Basic
Violet 2, Basic Violet 3, Basic Violet 10, Basic Violet 14, Basic yellow 57, Basic
Yellow 87, and mixtures thereof. Basic Red 51, Basic Orange 31, Basin Yellow 87 and
Mixtures thereof are particularly preferable.
[0115] Examples of the anionic dye include, but are not limited to, Acid Black 1, Acid Blue
1, Acid Blue 3, Food Blue 5, Acid Blue 7, Acid Blue 9, Acid Blue 74, Acid Orange 3,
Acid Orange 4, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Red 1, Acid Red
14, Acid Red 18, Acid Red 27, Acid Red 33, Acid Red 50, Acid Red 52, Acid Red 73,
Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 155, Acid Red 180, Acid Violet 2,
Acid Violet 9, Acid Violet 43, Acid Violet 49, Acid Yellow 1, Acid Yellow 10, Acid
Yellow 23, Acid Yellow 3, Food Yellow No. 8, D&C Brown No. 1, D&C Green No. 5, D&C
Green No. 8, D&C Orange No. 4, D&C Orange No. 10, D&C Orange No. 11, D&C Red No. 21,
D&C Red No. 27, D&C Red No. 33, D&C Violet 2, D&C Yellow No. 7, D&C Yellow No. 8,
D&C Yellow No. 10, FD&C Red 2, FD&C Red 40, FD&C Red No. 4, FD&C Yellow No. 6, FD&C
Blue 1, Food Black 1, Food Black 2, alkali metal salts (sodium salts, potassium salts
and the like), and mixtures thereof.
[0116] Among them, preferred anionic dyes are Acid Black 1, Acid Red 52, Acid Violet 2,
Acid Violet 43, Acid Red 33, Acid Orange 4, Acid Orange 7, Acid Red 27, Acid Yellow
3, Acid Yellow 10, and salts thereof. More preferred anionic dyes are Acid Red 52,
Acid Violet 2, Acid red 33, Acid Orange 4, Acid Yellow 10, and salts and mixtures
thereof.
[0117] Examples of the nitro dye include, but are not limited to, HC Blue No. 2, HC Blue
No. 4, HC Blue No. 5, HC Blue No. 6, HC Blue No. 7, HC Blue No. 8, HC Blue No. 9,
HC Blue No. 10, HC Blue No. 11, HC Blue No. 12, HC Blue No. 13, HC Brown No. 1, HC
Brown No. 2, HC Green No. 1, HC Orange No. 1, HC Orange No. 2, HC Orange No. 3, HC
Orange No. 5, HC Red BN, HC Red No. 1, HC Red No. 3, HC Red No. 7, HC Red No. 8, HC
Red No. 9, HC Red No. 10, HC Red No. 11, HC Red No. 13, HC Red No. 54, HC Red No.
14, HC Violet BS, HC Violet No. 1, HC Violet No. 2, HC Yellow No. 2, HC Yellow No.
4, HC Yellow No. 5, HC Yellow No. 6, HC Yellow No. 7, HC Yellow No. 8, HC Yellow No.
9, HC Yellow No. 10, HC Yellow No. 11, HC Yellow No. 12, HC Yellow No. 13, HC Yellow
No. 14, HC Yellow No. 15, 2-amino-6-chloro-4-nitrophenol, picramic acid, 1,2-diamino-4-nitrobenzol,
1,4-diamino-2-nitrobenzol, 3-nitro-4-aminophenol, 1-hydroxy-2-amino-3-nitrobenzol,
2-hydroxyethylepicramic acid, and mixtures thereof.
[0118] Examples of the disperse dye include, but are not limited to, Disperse Blue 1, Disperse
Black 9, Disperse Violet 1, and mixtures thereof.
[0119] One of these direct dyes may be used alone, or two or more thereof may be used in
combination. Direct dyes different in ionicity may be used in combination.
[0120] The content of the direct dye in the dyeing composition is preferably 0.001 mass%
or more, more preferably 0.01 mass% or more, further more preferably 0.05 the mass%
or more, from the viewpoint of obtaining sufficient dyeability, and preferably 10
mass% or less, more preferably 7.5 mass% or less, further more preferably 5.0 mass%
or less, further more preferably 3.0 mass% or less, from the viewpoint of compatibility.
[0121] When the dyeing composition contains only direct dyes, an oxidizing agent is not
necessary for dyeing naturally derived fibers. When it is desirable that naturally
derived fibers be light-colored, the composition may contain an oxidizing agent.
[0122] When the dyeing composition contains an oxidizing dye, the composition is typically
of two-part type. The first part contains an oxidizing dye intermediate (precursor
and coupler) and an alkali agent, and the second part contains an oxidizing agent
such as hydrogen peroxide. These two parts are typically stored separately, and mixed
before immersion of naturally derived fibers.
[0123] The oxidizing dye intermediate is not particularly limited, and it is possible to
suitably use any known of precursors and couplers which are commonly used for dyeing
products.
[0124] Examples of the precursor include, but are not limited to, paraphenylenediamine,
toluene-2,5-diamine, 2-chloro-paraphenylenediamine, N-methoxyethyl-para-phenylenediamine,
N-phenylparaphenylenediamine, N,N-bis(2-hydroxyethyl)-paraphenylenediamine, 2-(2-hydroxyethyl)-paraphenylenediamine,
2,6-dimethyl-paraphenylenediamine, 4,4'-diaminodiphenylamine, 1,3-bis(N-(2-hydroxyethyl)-N-(4-aminophenyl)amino)-2-propanol,
PEG-3,3,2'-paraphenylenediamine, paraaminophenol, paramethylaminophenol, 3-methyl-4-aminophenol,
2-aminomethyl-4-aminophenol, 2-(2-hydroxyethylaminoethyl)-4-aminophenol, ortho-aminophenol,
2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-acetamidophenol, 3,4-diaminobenzoic
acid, 5-aminosalicylic acid, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine,
4,5-diamino-1-(4'-chlorobenzyl)pyrazole, 4,5-diamino-1-hydroxyethylpyrazole, salts
of these substances, and mixture thereof.
[0125] Examples of the coupler include, but are not limited to, metaphenylenediamine, 2,4-diaminophenoxyethanol,
2-amino-4-(2-hydroxyethylamino)anisole, 2,4-diamino-5-methylphenetole, 2,4-diamino-5-(2-hydroxyethoxy)toluene,
2,4-dimethoxy-1,3-diaminobenzene, 2,6-bis(2-hydroxyethylamino)toluene, 2,4-diamino-5-fluorotoluene,
1,3-bis(2,4-diaminophenoxy)propane, metaaminophenol, 2-methyl-5-aminophenol, 2-methyl-5-(2-hydroxyethylamino)phenol,
2,4-dichloro-3-aminophenol, 2-chloro-3-amino-6-methylphenol, 2-methyl-4-chloro-5-aminophenol,
N-cyclopentyl-metaaminophenol, 2-methyl-4-methoxy-5-(2-hydroxyethylamino)phenol, 2-methyl-4-fluoro-5-aminophenol,
paraaminoorthocresol, resorcin, 2-methylresorcin, 4-chlororesorcin, 1-naphthol, 1,5-dihydroxynaphthalene,
1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-isopropyl-5-methylphenol, 4-hydroxyindole,
5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 6-hydroxybenzomorpholine, 3,4-methylenedioxyphenol,
2-bromo-4,5-methylenedioxyphenol, 3,4-methylenedioxyaniline, 1-(2-hydroxyethyl)amino-3,4-methylenedioxybenzene,
2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2,3-diamino-6-methoxypyridine,
2-methylamino-3-amino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 2,6-diaminopyridine,
salts of these substances, and mixtures thereof.
[0126] The content of each of the precursor and the coupler in the dyeing composition is
preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and preferably 10
mass% or less, more preferably 7.5 mass% or less, further more preferably 5 mass%
or less.
[0127] When the dyeing composition contains an oxidizing dye, the dyeing composition further
contains an alkali agent. Examples of the suitable alkali agent include, but are not
limited to, ammonia and salts thereof; alkanolamines (monoethanolamine, isopropanolamine,
2-amino-2-methylpropanol, 2-aminobutanol and the like) and salts thereof; alkanediamines
(1,3-propanediamine and the like) and salts thereof; carbonates (guanidine carbonate,
sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen
carbonate and the like); and mixtures thereof.
[0128] The content of the alkali agent in the dyeing composition is preferably 0.1 mass%
or more, more preferably 0.5 mass% or more, further more preferably 1 mass% or more,
and preferably 15 mass% or less, more preferably 10 mass% or less, further more preferably
7.5 mass% or less.
[0129] The composition containing an oxidizing agent (second part) when the dyeing composition
contains an oxidizing dye is stored separately from the composition containing an
oxidizing agent (first part), and mixed before naturally derived fibers are immersed.
Examples of the suitable oxidizing agent include, but are not limited to, hydrogen
peroxide, urea peroxide, melamine peroxide and sodium brominate. Among these oxidizing
agents, hydrogen peroxide is preferable.
[0130] The content of the oxidizing agent in the dyeing composition is preferably 1 mass%
or more, more preferably 2 mass% or more, and preferably 15 mass% or less, more preferably
12 mass% or less, further more preferably 9 mass% or less.
[0131] When the first part and the second part are stored separately, the pH of the second
part at 25°C is preferably 2 or more, more preferably 2.5 or more, and preferably
6 or less, more preferably 4 or less. The pH can be adjusted by a suitable buffering
agent. The pH of the dyeing composition obtained by mixing the first part and the
second part at 25°C is preferably 6 or more, more preferably 6.5 or more, further
more preferably 6.8 or more, and preferably 11 or less, more preferably 10.5 or less,
further more preferably 10 or less.
[0132] When the dyeing composition contains an oxidizing dye, the dyeing composition may
further contain any of the direct dyes exemplified above.
[0133] Preferably, the dyeing composition may further contain the following surfactant,
conditioning component and the like. Preferably, the dyeing composition can be in
the form of solution, emulsion, cream, paste and mousse.
[0134] The temperature of the dyeing composition is preferably 0°C or higher, more preferably
10°C or higher, further more preferably 20°C or higher, and preferably 90°C or lower,
more preferably 80°C or lower, from the viewpoint of efficiently infiltrating and
diffusing the dyeing composition into naturally derived fibers to enhance the effect
of dyeing.
(Surface finish for imparting hydrophobicity and reducing friction)
[0135] The surface finish for imparting hydrophobicity and reducing friction is performed
by immersing naturally derived fibers in the following surface finish agent after
the steps (i) to (iii), or alternatively, when step (iv) for improving the feel is
carried out, after the step (iv).
[0136] The surface finish agent comprises the following component (F) and water.
(F) epoxyaminosilane copolymer which is a reaction product of the following compounds
(a) to (d):
- (a) polysiloxane having at least two oxiranyl groups or oxetanyl groups;
- (b) polyether having at least two oxiranyl groups or oxetanyl groups;
- (c) aminopropyltrialkoxysilane; and
- (d) a compound selected from the group consisting of the following primary and secondary
amines:
- primary amine: methylamine, ethylamine, propyleneamine, ethanolamine, isopropylamine,
butylamine, isobutylamine, hexylamine, dodecylamine, oleylamine, aniline, aminopropyltrimethylsilane,
aminopropyltriethylsilane, aminomorpholine, aminopropyldiethylamine, benzylamine,
naphthylamine, 3-amino-9-ethylcarbazole, 1-aminoheptafluorohexane and 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octaneamine;
and
- secondary amine: methylethylamine, methyloctadecylamine, diethanolamine, dibenzylamine,
dihexylamine, dicyclohexylamine, piperidine, pyrrolidine phthalimide and polymer amine.
[Component (F): epoxyaminosilane copolymer]
[0137] The epoxyaminosilane copolymer as the component (F) is a reaction product of the
following compounds (a) to (d).
<Compounds (a) and (b)>
[0138] The compound (a) is polysiloxane having at least two oxiranyl groups or oxetanyl
groups, and examples thereof include compounds of the following formula (5):

wherein R represents a hydrocarbon group having 1 to 6 carbon atoms and an oxiranyl
group or an oxetanyl group at the terminal and optionally having a hetero atom, and
x represents a number of 1 to 1,000.
[0139] The compound (b) is polyether having at least two oxiranyl groups or oxetanyl groups,
and examples thereof include compounds of the following formula (6):

wherein R represents the same meaning as described above, y is 1 to 100, z is 0 to
100, and y + z represents a number of 1 to 200.
[0140] In formulae (5) and (6), the hetero atom optionally contained in R is preferably
an oxygen atom. Examples of R include an oxiranylmethyl group (glycidyl group), an
oxiranylmethoxy group (glycidyloxy group), an oxiranylmethoxypropyl group (glycidyloxypropyl
group), an oxetanylmethyl group, an oxetanylmethoxy group, an oxetanylmethoxypropyl
group and a 3-ethyloxetanylmethyl group. Among them, hydrocarbon groups having 1 to
4 carbon atoms and an oxiranyl group and optionally having a hetero oxygen atom are
preferable, and at least one selected from the group consisting of an oxiranylmethyl
group (glycidyl group), an oxiranylmethoxy group (glycidyloxy group) and an oxetanylmethyl
group, an oxiranylmethoxypropyl group (glycidyloxypropyl group) is more preferable.
<Compound (c)>
[0141] The compound (c) is aminopropyltrialkoxysilane. Examples of the alkoxy group in the
compound (c) include alkoxy groups having 1 to 6 carbon atoms, preferably 2 to 4 carbon
atoms, more preferably 3 carbon atoms, and among them, an isopropoxy group is preferable.
Examples of the compound (c) include aminopropyltrimethoxysilane, aminopropyltriethoxysilane,
aminopropyltripropoxysilane, aminopropyltriisopropoxysilane, aminopropyltributoxysilane,
and aminopropyltri-tert-butoxysilane, and among them, aminopropyltriisopropoxysilane
is preferable. Any one compound (c) may be used alone, or two or more compounds (c)
may be used in combination.
<Compound (d)>
[0142] The compound (d) is a compound selected from the group consisting of the following
primary and secondary amines:
- primary amine: methylamine, ethylamine, propyleneamine, ethanolamine, isopropylamine,
butylamine, isobutylamine, hexylamine, dodecylamine, oleylamine, aniline, aminopropyltrimethylsilane,
aminopropyltriethylsilane, aminomorpholine, aminoethyldimethylamine, aminoethyldiethylamine,
aminoethyldibutylamine, aminopropyldimethylamine, aminopropyldiethylamine, aminopropyldibutylamine,
benzylamine, naphthylamine, 3-amino-9-ethylcarbazole, 1-aminoheptafluorohexane and
2,2,3,3,4,4,5,5, 6, 6,7,7, 8, 8, 8-pentadecafluoro-1-octane amine
- secondary amine: methylethylamine, methyloctadecylamine, diethanolamine, dibenzylamine,
dihexylamine, dicyclohexylamine, piperidine, pyrrolidine phthalimide and polymer amine.
[0143] Among them, primary amines are preferable, and one selected from the group consisting
of aminopropyldiethylamine, aminopropyldimethylamine and aminopropyldibutylamine is
more preferable. One compound (d) may be used alone, or two or more compounds (d)
may be used in combination.
[0144] The reaction of compounds (a) to (d) is carried out by, for example, refluxing the
compounds in a solvent such as isopropanol for a certain time. Here, the molar ratio
of oxiranyl groups or oxetanyl groups of compounds (a) and (b) to amino groups of
the compound (c) is preferably 1 or more, more preferably 1.1 or more, further more
preferably 1.2 or more, and preferably 4 or less, more preferably 3.9 or less, further
more preferably 3.8 or less.
[0145] Examples of the component (F) include those having the INCI name of polysilicone-29,
and examples of the marketed product thereof include Silsoft CLX-E (containing an
active ingredient at 15 mass%, dipropylene glycol and water) from Momentive Performance
Materials Company.
[0146] The content of the component (F) in the surface finish agent is preferably 0.01 mass%
or more, more preferably 0.05 mass% or more, further more preferably 0.10 mass% or
more, further more preferably 0.20 mass% or more, from the viewpoint of imparting
sufficient hydrophobicity to naturally derived fibers, and preferably 15.00 mass%
or less, more preferably 10.00 mass% or less, further more preferably 8.00 mass% or
less, further more preferably 6.00 mass% or less, from the viewpoint that a sticky
feel is not given.
[0147] From the viewpoint of increasing the reaction rate of the trialkoxysilane part of
the component (F) in an acidic region or a basic region, the pH of the surface finish
agent at 25°C is preferably in the following range. When the surface finish agent
is set as an acidic region, the pH is preferably 1.0 or more, more preferably 1.5
or more, further more preferably 2.0 or more, and preferably 5.0 or less, more preferably
4.0 or less, further more preferably 3.5 or less. When the surface finish agent is
set as a basic region, the pH is preferably 7.0 or more, more preferably 7.5 or more,
further more preferably 8.0 or more, and preferably 11.0 or less, more preferably
10.5 or less, further more preferably 10.0 or less. The surface finish agent may appropriately
contain a pH adjuster for adjusting the pH of the surface finish agent to be within
the above-described range. As the pH adjuster, alkanol amines such as monoethanolamine,
isopropanolamine, 2-amino-2-methylpropanol and 2-aminobutanol, or salts thereof; alkanediamines
such as 1,3-propanediamine, or salts thereof; carbonates such as guanidine carbonate,
sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen
carbonate; hydroxides such as sodium hydroxide, potassium hydroxide; and the like
can be used as the alkali agent. As the acid agent, inorganic acids such as hydrochloric
acid and phosphoric acid, hydrochlorides such as monoethanolamine hydrochloride, phosphorates
such as monopotassium dihydrogen phosphate and disodium monohydrogen phosphate, and
organic acids such as lactic acid and malic acid, and the like can be used.
[0148] The amount of the surface finish agent in which naturally derived fibers are immersed
is preferably 2 or more, more preferably 5 or more, further more preferably 10 or
more, and preferably 100 or less, more preferably 50 or less, further more preferably
20 or less, in terms of bath ratio to the mass of the naturally derived fibers (mass
of surface finish agent/mass of naturally derived fibers).
(Post-heating: heating treatment for further improving fiber stretchability (tenacity))
[0149] Further, from the viewpoint of more effectively improving the stretchability of naturally
derived fibers, naturally derived fibers can be heated while being stretched by applying
tension to the fibers. When the naturally derived fibers are small in amount, it is
preferable to use a hair iron for the heating, and when the naturally derived fibers
are large in amount, an equivalent result can be obtained by, for example, performing
hot air heating while applying tension by a rewinder.
[0150] The fiber draw ratio during heating is preferably 0.1% or more, more preferably 0.2%
or more, further more preferably 0.5% or more, from the viewpoint of more effectively
improving the stretchability of the fibers, and preferably 10% or less, more preferably
5% or less, further more preferably 2% or less, from the viewpoint of suppressing
damage to the fibers.
[0151] The heating temperature is preferably 120°C or higher, more preferably 140°C or higher,
further more preferably 160°C or higher, from the viewpoint of more effectively improving
the stretchability of the fibers, and preferably 240°C or lower, more preferably 220°C
or lower, further more preferably 200°C or lower, from the viewpoint of suppressing
damage to the fibers.
[0152] The heating time is preferably 1 second or more, more preferably 3 seconds or more,
further more preferably 5 seconds or more, from the viewpoint of more effectively
improving the stretchability of the fibers, and preferably 60 seconds or less, more
preferably 30 seconds or less, further more preferably 20 seconds or less, from the
viewpoint of suppressing damage to the fibers.
[0153] After heating, from the viewpoint of more effectively improving the stretchability
of the fibers, naturally derived fibers can be left to stand in water while being
stretched by applying tension to the fibers.
[0154] The draw ratio here is preferably 0.1% or more, more preferably 0.2% or more, further
more preferably 0.5% or more, from the viewpoint of more effectively improving the
stretchability of the fibers, and preferably 10% or less, more preferably 5% or less,
further more preferably 2% or less, from the viewpoint of suppressing damage to the
fibers.
[0155] The water temperature is preferably 5°C or higher, more preferably 20°C or higher,
further more preferably 30°C or higher, from the viewpoint of more effectively improving
the stretchability of the fibers, and preferably 80°C or lower, more preferably 60°C
or lower, further more preferably 50°C or lower, from the viewpoint of suppressing
damage to the fibers.
[0156] The time for leaving the fibers to stand in water is preferably 1 minute or more,
more preferably 5 minutes or more, further more preferably 30 minutes or more, from
the viewpoint of more effectively improving the stretchability of the fibers, and
preferably 48 hours or less, more preferably 24 hours or less, further more preferably
3 hours or less, from the viewpoint of suppressing damage to the fibers.
[0157] Depending on conditions for polymerization in the steps (i) to (iii), stretchability
equivalent to that of human hair can be achieved during drying of the fibers.
(Suppression or elimination of coloring)
[0158] Further, for the purpose of suppressing or eliminating coloring in naturally derived
fibers treated with the fiber-treating agent of the present invention, treatment can
be performed with a composition containing the component (E). The preferred component
(E) is as described above. The composition is preferably an aqueous solution of the
component (E). The pH of the composition is preferably 2.0 or more, more preferably
3.0 or more, further more preferably 4.0 or more, and preferably 9.0 or less, more
preferably 7.0 or less, further more preferably 6.0 or less, from the viewpoint of
preventing a decrease in strength of naturally derived fibers.
[0159] The content of the component (E) in the composition is preferably 0.5 mass% or more,
more preferably 1.0 mass% or more, further more preferably 2.0 mass% or more, from
the viewpoint of exhibiting an effect of suppressing or eliminating coloring of naturally
derived fibers, and preferably 20 mass% or less, more preferably 10 mass% or less,
further more preferably 5.0 mass% or less, from the viewpoint of preventing a decrease
in strength of naturally derived fibers by a reducing action.
[0160] The temperature for the treatment with the composition containing the component (E)
is preferably 5°C or higher, more preferably 10°C or higher, further more preferably
20°C or higher, from the viewpoint of exhibiting an effect of suppressing or eliminating
coloring of naturally derived fibers, and preferably 100°C or lower, more preferably
60°C or lower, further more preferably 40°C or lower, from the viewpoint of avoiding
the onset of yellowish coloring.
[0161] The time for the treatment with a composition containing the component (E) is preferably
1 second or more, more preferably 30 seconds or more, further more preferably 1 minute
or more, from the viewpoint of exhibiting an effect of suppressing or eliminating
coloring of naturally derived fibers, and preferably 60 minutes or less, more preferably
30 minutes or less, further more preferably 15 minutes or less, from the viewpoint
of avoiding the onset of yellowish coloring.
[0162] For the purpose of suppressing or eliminating coloring in naturally derived fibers
treated with the fiber-treating agent of the present invention, the naturally derived
fibers can be treated with a composition containing the following component (G) as
in the treatment with a composition containing the component (E).
Component (G): compound having chelating action
[Component (G): compound having chelating action]
[0163] Examples of the component (G) include compounds in which the total number of hydroxy
groups, carboxy groups and phosphoric acid groups is 2 or more, and specifically,
etidronic acid, disodium ethylenediaminetetraacetate, disodium catechol-3,5-disulfonate
monohydrate and phytic acid are preferably exemplified.
[0164] The composition containing the component (G) is preferably an aqueous solution. The
pH of the composition is preferably 2.0 or more, more preferably 3.0 or more, further
more preferably 4.0 or more, and preferably 9.0 or less, more preferably 7.0 or less,
further more preferably 6.0 or less, from the viewpoint of preventing a decrease in
strength of naturally derived fibers.
[0165] Any one component (G) may be used alone, or two or more components (G) may be used
in combination. The content of the component (G) in the composition containing the
component (G) is preferably 0.1 mass% or more, more preferably 0.5 mass% or more,
furthermore preferably 2.0 mass% or more, from the viewpoint of exhibiting an effect
of suppressing or eliminating coloring of naturally derived fibers, and preferably
20 mass% or less, more preferably 10 mass% or less, further more preferably 5.0 mass%
or less, from the viewpoint of suppressing a decrease in fiber strength.
[0166] The temperature for the treatment with the composition containing the component (G)
is preferably 5°C or higher, more preferably 10°C or higher, further more preferably
20°C or higher, from the viewpoint of exhibiting an effect of suppressing or eliminating
coloring of naturally derived fibers, and preferably 100°C or lower, more preferably
60°C or lower, further more preferably 40°C or lower, from the viewpoint of suppressing
a decrease in fiber strength.
[0167] The time for the treatment with the composition containing the component (G) is preferably
1 second or more, more preferably 30 seconds or more, further more preferably 1 minute
or more, from the viewpoint of exhibiting an effect of suppressing or eliminating
coloring of naturally derived fibers, and preferably 72 hours or less, more preferably
48 hours or less, further more preferably 24 hours or less, from the viewpoint of
suppressing a decrease in fiber strength.
[0168] It is more preferable that the treatment with the composition containing the component
(E) and the treatment with the composition containing the component (G) be performed
in combination as the treatment for suppressing or eliminating coloring of naturally
derived fibers. Coloring of fibers which is caused by treatment with the fiber-treating
agent of the present invention is considered to include both brownish coloring by
oxidation (which can be countered by treatment with a sulfur-containing reducing agent
as the component (E)) and yellowish coloring by a catechin-metal complex (which can
be countered by a chelating agent as the component (G)), and it may be possible to
more adequately suppress coloring of the fibers by performing bleaching treatment
corresponding to each case.
[0169] When the treatment with the composition containing the component (E) and the treatment
with the composition containing the component (G) are performed in combination, the
treatments with the compositions may be performed in a sequential order (the treatment
order is not limited), and it is also possible to perform the treatments as one treatment
using a single composition containing the components (E) and (G). Here, the contents
of each of components in the composition, the treatment temperature and the treatment
time are the same as in the case where separate compositions are used. With regard
to the treatment time, the upper limit for the composition containing the component
(G) is greater than that for the composition containing the component (E), and in
the case of the treatment with a single composition containing both the components,
the treatment time may be in the treatment time range for the composition containing
the component (E) from the viewpoint of avoiding the onset of yellowish coloring.
[0170] When naturally derived fibers are treated by the above method for treating fibers,
the fibers contain a condensate formed from the components (A) and (B), so that it
is possible to produce fibers for hair ornament products in which the fibers are excellent
in shape sustainability and tensile elastic modulus and the stretchability (tenacity)
of the naturally derived fibers is highly improved, and it is also possible to produce
a hair ornament product using the fibers.
[0171] In the present invention, examples of the hair ornament product include hair wigs,
wigs, weavings, hair extensions, blade hairs, hair accessories, and doll hairs.
[0172] Concerning the embodiments described above, preferred aspects of the present invention
will be further disclosed below.
[0173]
<1> A one-part type fiber-treating agent comprising a single composition or a multiple-part
type fiber-treating agent comprising a plurality of compositions, wherein the fiber-treating
agent comprises the following components (A) to (C) in the total composition thereof,
provided that, a part or all of the components (A) and (B) is optionally a condensate
formed from the components:
- (A): a compound having a structure in which a methylol group is bonded to each of
two nitrogen atoms in the molecule; and
- (B): a phenolic compound having an electron donating group on at least one of meta-positions
and a hydrogen atom on at least one of ortho-positions and a para-position, wherein
the electron donating group on the meta-position optionally forms, together with adjacent
carbon atoms, a benzene ring optionally substituted with a hydroxy group; and
- (C): water.
<2> The fiber-treating agent according to <1>, wherein the component (A) is preferably
one or more selected from the group consisting of the following compounds (A1) to
(A4), more preferably one or more selected from the group consisting of the compounds
(A3) and (A4), further more preferably the compound (A3).


<3> The fiber-treating agent according to <1> or <2>, wherein a content of a constituent
element derived from the component (A) in the fiber-treating agent is preferably 0.1
mass% or more, more preferably 1 mass% or more, further more preferably 2.5 mass%
or more, even more preferably 5 mass% or more, even more preferably 10 mass% or more,
and preferably 80 mass% or less, more preferably 70 mass% or less, further more preferably
60 mass% or less, even more preferably 50 mass% or less, even more preferably 40 mass%
or less, based on the total composition of the fiber-treating agent.
<4> The fiber-treating agent according to any one of <1> to <3>, wherein the component
(B) is preferably one or more selected from the group consisting of the following
components (B1), (B2) and (B3):
(B1) a resorcin derivative of formula (1):

wherein
A1 to A4 are the same or different, and each represent a hydrogen atom, a hydroxy group, a
halogen atom, a carboxyl group or a salt thereof, a sulfonic acid group or a salt
thereof, a linear or branched alkyl group or alkenyl group having 1 to 6 carbon atoms,
or a linear or branched alkoxy group or alkenyloxy group having 1 to 6 carbon atoms;
(B2) a naphthol derivative of formula (2) or (3):


wherein
R1 represents a hydrogen atom or a methyl group,
A5 represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having
1 to 12 carbon atoms, an optionally substituted aralkyl group or arylalkenyl group
having 7 to 12 carbon atoms, a linear or branched alkoxy group or alkenyloxy group
having 1 to 6 carbon atoms, a halogen atom or -CO-R2 (R2 is a linear or branched alkyl group or alkenyl group having 1 to 12 carbon atoms,
an optionally substituted aralkyl group or arylalkenyl group having 7 to 12 carbon
atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon
atoms),
D represents a hydrogen atom, a hydroxy group, a methyl group, or a linear or branched
alkoxy group or alkenyloxy group having 1 to 12 carbon atoms,
E represents a hydrogen atom, a hydroxy group, a linear or branched alkyl group or
alkenyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group or
alkenyloxy group having 1 to 6 carbon atoms, and
G represents a hydroxy group, a linear or branched alkyl group or alkenyl group having
1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and n represents
an integer of 0 to 2; and
(B3) a flavan-3-ol derivative of formula (4):

wherein
R3 represents a hydrogen atom or a methyl group,
X represents a hydrogen atom, a hydroxy group or a methoxy group,
R4 represents an aromatic hydrocarbon group optionally substituted with up to 3 hydroxy
groups or methoxy groups and optionally forming a fused ring with 1,3-dioxolane, and
R5 represents a hydroxy group, a methoxy group, an aromatic hydrocarbon group optionally
substituted with up to 3 hydroxy groups or methoxy groups and optionally forming a
fused ring with 1,3-dioxolane, or an arylcarbonyloxy group or aralkylcarbonyloxy group
optionally substituted with up to 3 hydroxy groups or methoxy groups,
more preferably one or more selected from the group consisting of resorcin, 1-naphthol,
2-naphthol, 3-methylnaphthalen-1-ol, naphthalene-1-,5-diol, naphthalene-1,8-diol,
catechin, epicatechin, epigallocatechin, catechin gallate, epicatechin gallate, epigallocatechin
gallate and a tea extract, further more preferably one or more selected from the group
consisting of resorcin, catechin, epicatechin, epigallocatechin, catechin gallate,
epicatechin gallate, epigallocatechin gallate and a tea extract.
<5> The fiber-treating agent according to any one of <1> to <4>, wherein a content
of a constituent element derived from the component (B) in the fiber-treating agent
is preferably 0.1 mass% or more, more preferably 1 mass% or more, further more preferably
1.5 mass% or more, even more preferably 3 mass% or more, even more preferably 5 mass%
or more, and preferably 80 mass% or less, more preferably 60 mass% or less, further
more preferably 50 mass% or less, even more preferably 40 mass% or less, even more
preferably 30 mass% or less, even more preferably 25 mass% or less, even more preferably
20 mass% or less, based on the total composition of the fiber-treating agent.
<6> The fiber-treating agent according to any one of <1> to <5>, wherein a total content
of the constituent element derived from the component (A) and the constituent element
derived from the component (B) in the fiber-treating agent is preferably 0.1 mass%
or more, more preferably 1 mass% or more, further more preferably 5 mass% or more,
further more preferably 10 mass% or more, further more preferably 15 mass% or more,
further more preferably 20 mass% or more, and preferably 80 mass% or less, more preferably
70 mass% or less, further more preferably 60 mass% or less, further more preferably
50 mass% or less, further more preferably 40 mass% or less, based on the total composition
of the fiber-treating agent.
<7> The fiber-treating agent according to any one of <1> to <6>, wherein a molar ratio
of the constituent element derived from the component (A) to the constituent element
derived from the component (B), (A)/(B), is preferably 0.1 or more, more preferably
0.3 or more, further more preferably 0.5 or more, and preferably 20 or less, more
preferably 15 or less, further more preferably 10 or less, even more preferably 7.5
or less.
<8> The fiber-treating agent according to any one of <1> to <7>, wherein a content
of the component (C) in the fiber-treating agent is preferably 10 mass% or more, more
preferably 20 mass% or more, further more preferably 30 mass% or more, even more preferably
40 mass% or more, and preferably 99 mass% or less, more preferably 97 mass% or less,
further more preferably 95 mass% or less, even more preferably 90 mass% or less, based
on the total composition of the fiber-treating agent.
<9> The fiber-treating agent according to any one of <1> to <8>, which is of multiple-part
type fiber-treating agent comprising a first part containing the components (B) and
(C) and a second part containing the components (A) and (C).
<10> The fiber-treating agent according to any one of <1> to <8>, wherein the fiber-treating
agent is a one-part type, and preferably, further comprises the following component
(D):
(D): an organic compound having a Hansen solubility parameter SP value of 16 Mpa1/2 or more and 40 Mpa1/2 or less (excluding organic salts and compounds having an aldehyde group and having
a molecular weight of 150 or less).
<11> The fiber-treating agent according to <10>, wherein the component (D) is preferably
at least one selected from the group consisting of a monohydric alcohol, a dihydric
alcohol, a dihydric alcohol derivative, a polyhydric alcohol with a valence number
of 3 or more, lactam, imidazolidinone, pyrimidinone, lactone, alkylene carbonate and
a general-purpose organic solvent, more preferably at least one selected from the
group consisting of a dihydric alcohol, lactam and imidazoline, further more preferably
at least one selected from the group consisting of diethylene glycol, triethylene
glycol, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and DMDM hydantoin.
<12> The fiber-treating agent according to <10> or <11>, wherein Hansen solubility
parameter SP value of the component (D) is preferably 35.8 Mpa1/2 or less, more preferably 34.7 Mpa1/2 or less, further more preferably 29.2 Mpa1/2 or less, and preferably 17.8 Mpa1/2 or more, more preferably 21.1 Mpa1/2 or more, further more preferably 22.0 Mpa1/2 or more.
<13> The fiber-treating agent according to any one of <10> to <12>, wherein a content
of the component (D) in the fiber-treating agent is preferably 10 mass% or more, more
preferably 15 mass% or more, further more preferably 25 mass% or more, and preferably
80 mass% or less, more preferably 60 mass% or less, further more preferably 45 mass%
or less.
<14> The fiber-treating agent according to any one of <1> to <13>, preferably further
comprising the following component (E):
(E): a sulfur-containing reducing agent.
<15> The fiber-treating agent according to <14>, wherein the component (E) is one
or more selected from the group consisting of a sulfurous acid salt and a thiol compound,
more preferably one or more selected from the group consisting of sodium sulfite,
sodium pyrosulfite, thioglycerol and Mesna (sodium 2-mercaptoethanesulfonate), further
more preferably sodium sulfite.
<16> The fiber-treating agent according to <14> or <15>, wherein a content of the
component (E) in the fiber-treating agent is preferably 0.1 mass% or more, more preferably
0.5 mass% or more, further more preferably 2.0 mass% or more, and preferably 20 mass%
or less, more preferably 10 mass% or less, further more preferably 5.0 mass% or less,
based on the total composition of the fiber-treating agent.
<17> The fiber-treating agent according to any one of <14> to <16>, wherein a molar
ratio of the component (E) to the component (A), (E)/(A), is preferably 0.1 or more,
more preferably 0.3 or more, further more preferably 0.5 or more, and preferably 3.0
or less, more preferably 1.5 or less, further more preferably 1.0 or less.
<18> The fiber-treating agent according to any one of <1> to <17>, preferably further
comprising a cationic surfactant.
<19> The fiber-treating agent according to <18>, wherein the cationic surfactant is
preferably a long chain monoalkyl quaternary ammonium salt having one alkyl group
having 8 to 24 carbon atoms and three alkyl groups having 1 to 4 carbon atoms, more
preferably at least one selected from the group consisting of compounds of the following
formula:

wherein R4 is a saturated or unsaturated linear or branched alkyl group having 8 to 22 carbon
atoms, R8-CO-NH-(CH2)m- or R8-CO-O-(CH2)m- (R8 represents a saturated or unsaturated linear or branched alkyl chain having 7 to
21 carbon atoms, and m represents an integer of 1 to 4), R5, R6 and R7 independently represent an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl
group having 1 to 4 carbon atoms, and X-represents a hydrochloride ion, a bromide ion, a methosulfate ion or an ethosulfate
ion,
further more preferably at least one selected from the group consisting of cetyltrimethylammonium
chloride, myristyltrimethylammonium chloride, behentrimonium chloride, cetyltrimethylammonium
bromide and stearamidopropyltrimonium chloride.
<20> The fiber-treating agent according to <18> or <19>, wherein a content of the
cationic surfactant is preferably 0.05 mass% or more, more preferably 0.10 mass% or
more, and preferably 10 mass% or less, more preferably 5 mass% or less, based on the
total composition of the fiber-treating agent.
<21> The fiber-treating agent according to any one of <1> to <20>, preferably further
comprising silicone, more preferably one or more selected from the group consisting
of dimethylpolysiloxane and amino acid-modified silicone.
<22> The fiber-treating agent according to <21>, wherein a content of the silicone
is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, further more preferably
0.5 mass% or more, and preferably 20 mass% or less, more preferably 10 mass% or less,
further more preferably 5 mass% or less, based on the total composition of the fiber-treating
agent.
<23> The fiber-treating agent according to any one of <1> to <22>, preferably further
comprising a cationic polymer.
<24> The fiber-treating agent according to <23>, wherein a content of the cationic
polymer is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, further
more preferably 0.05 mass% or more, and preferably 20 mass% or less, more preferably
10 mass% or less, based on the total composition of the fiber-treating agent.
<25> The fiber-treating agent according to any one of <1> to <24>, wherein a pH is
preferably 3.0 or more, more preferably 3.5 or more, further more preferably 4.0 or
more, and preferably 11.0 or less, more preferably 9.0 or less, further more preferably
7.0 or less.
<26> The fiber-treating agent according to any one of <1> to <25>, wherein the fiber-treating
agent is a treating agent preferably for naturally derived fibers, more preferably
for fibers taken from a natural animal or plant, or fibers artificially produced using
keratin, collagen, casein, soybeans, peanuts, corn, silk flocks, silk fibroin or the
like as a raw material, further more preferably for regenerated protein fibers selected
from the group consisting of regenerated collagen fibers made from collagen as a raw
material and regenerated silk fibers made from silk fibroin as a raw material, even
more preferably for regenerated collagen fibers.
<27> A method for treating fibers, comprising the following step (i):
- (i) immersing fibers in the fiber-treating agent according to any one of <1> to <26>.
<28> The method for treating fibers according to <29>, wherein the fiber-treating
agent is a one-part type, and preferably, the step (i) is carried out while a state
is maintained in which a turbidity of the treating agent is 1,000 NTU or less.
<29> The method for treating fibers according to <27> or <28>, wherein the fiber-treating
agent is a one-part type, and preferably, the following step (0) is carried out before
the step (i).
(0) heating the fiber-treating agent.
<30> The method for treating fibers according to <29>, wherein, assuming that T is
a heating time until the treating agent has a turbidity of more than 1,000 NTU after
the treating agent is heated immediately after being prepared by mixing the components,
the heating time in the step (0) is preferably 0.2T or more, more preferably 0.3T
or more, further more preferably 0.4T or more, and preferably 0.8T or less, more preferably
0.7T or less, further more preferably 0.6T or less.
<31> The method for treating fibers according to any one of <27> to <30>, wherein
an amount of the fiber-treating agent in which the fibers are immersed in the step
(i) is preferably 2 or more, more preferably 3 or more, further more preferably 5
or more, even more preferably 10 or more, even more preferably 20 or more, and preferably
500 or less, more preferably 250 or less, further more preferably 100 or less, in
terms of bath ratio to a mass of the fibers (mass of fiber-treating agent/mass of
fibers).
<32> The method for treating fibers according to any one of <27> to <31>, wherein
a temperature of the fiber-treating agent in the step (i) is preferably 20°C or higher,
more preferably 35°C or higher, further more preferably 45°C or higher, and preferably
lower than 100°C, more preferably 80°C or lower, further more preferably 70°C or lower,
further more preferably 60°C or lower.
<33> The method for treating fibers according to any one of <27> to <32>, wherein
the fiber-treating agent is a one-part type, and wherein, assuming that T is a heating
time until the treating agent has a turbidity of more than 1,000 NTU after the treating
agent is heated immediately after being prepared by mixing the components, an immersion
time in the step (i) is preferably 0.3T or more, more preferably 0.4T or more, further
more preferably 0.5T or more, and preferably 0.95T or less, more preferably 0.90T
or less, further more preferably 0.85T or less.
<34> The method for treating fibers according to any one of <27> to <33>, wherein
the fiber-treating agent is a one-part type, and preferably, the following step (ii-a)
is carried out after the step (i), and the step (i) and the step (ii-a) are repeated
two or more times:
(ii-a) taking out the fibers from the treating agent before the turbidity of the treating
agent exceeds 1,000 NTU.
<35> The method for treating fibers according to <27>, <31> or <32>, wherein the fiber-treating
agent is of multiple-part type, and the step (i) is preferably a step of immersing
fibers in one of the first part and the second part set forth in <9>, and then in
the other, more preferably a step of immersing fibers first in the first part set
forth in <9>, and then in the second part set forth in <9>.
<36> The method for treating fibers according to <35>, wherein the following step
(ii-b) is carried out after the step (i):
(ii-b) taking out the fibers from the treating agent.
<37> The method for treating fibers according to <34> or <36>, wherein preferably,
the following step (iii) is carried out after the step (ii-a) or the step (ii-b):
(iii) rinsing the fibers taken out.
<38> The method for treating fibers according to <37>, wherein preferably, the rinsing
in the step (iii) is performed using a rinsing composition containing a component
(D):
(D): an organic compound having a Hansen solubility parameter SP value of 16 Mpa1/2 or more and 40 Mpa1/2 or less (excluding organic salts and compounds having an aldehyde group and having
a molecular weight of 150 or less).
<39> The method for treating fibers according to <38>, wherein the rinsing composition
contains water in addition to the component (D), and the content of the component
(D) in the rinsing composition is preferably 60 mass% or more, more preferably 80
mass% or more, further more preferably 95 mass% or more.
<40> The method for treating fibers according to any one of <27> to <39>, wherein
the step of immersing the fibers in a surface finish agent containing the following
components (F) and (C) is further carried out after the steps (i) to (iii):
(F) an epoxyaminosilane copolymer which is a reaction product of the following compounds
(a) to (d):
- (a) polysiloxane having at least two oxiranyl groups or oxetanyl groups;
- (b) polyether having at least two oxiranyl groups or oxetanyl groups;
- (c) aminopropyltrialkoxysilane; and
- (d) a compound selected from the group consisting of the following primary and secondary
amines:
- primary amine: methylamine, ethylamine, propyleneamine, ethanolamine, isopropylamine,
butylamine, isobutylamine, hexylamine, dodecylamine, oleylamine, aniline, aminopropyltrimethylsilane,
aminopropyltriethylsilane, aminomorpholine, aminopropyldiethylamine, benzylamine,
naphthylamine, 3-amino-9-ethylcarbazole, 1-aminoheptafluorohexane and 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octaneamine;
and
- secondary amine: methylethylamine, methyloctadecylamine, diethanolamine, dibenzylamine,
dihexylamine, dicyclohexylamine, piperidine, pyrrolidine phthalimide and polymer amine;
and
(C) water.
<41> The method for treating fibers according to <40>, wherein preferably, the component
(F) is polysilicone-29.
<42> The method for treating fibers according to <40> or <41>, wherein a content of
the component (F) in the surface finish agent is preferably 0.01 mass% or more, more
preferably 0.05 mass% or more, further more preferably 0.10 mass% or more, further
more preferably 0.20 mass% or more, and preferably 15.00 mass% or less, more preferably
10.00 mass% or less, further more preferably 8.00 mass% or less, further more preferably
6.00 mass% or less.
<43> The method for treating fibers according to any one of <27> to <42>, wherein
preferably, the fibers are further heated while being stretched by applying tension
to the fibers.
<44> The method for treating fibers according to <43>, wherein a fiber draw ratio
during heating is preferably 0.1% or more, more preferably 0.2% or more, further more
preferably 0.5% or more, and preferably 10% or less, more preferably 5% or less, further
more preferably 2% or less.
<45> The method for treating fibers according to <43> or <44>, wherein a heating temperature
is preferably 120°C or higher, more preferably 140°C or higher, further more preferably
160°C or higher, and preferably 240°C or lower, more preferably 220°C or lower, further
more preferably 200°C or lower.
<46> The method for treating fibers according to any one of <43> to <45>, wherein
a heating time is preferably 1 second or more, more preferably 3 seconds or more,
further more preferably 5 seconds or more, and
preferably 60 seconds or less, more preferably 30 seconds or less, further more preferably
20 seconds or less.
<47> The method for treating fibers according to any one of <43> to <46>, wherein
preferably, the fibers are left to stand while being stretched by applying tension
to the fibers after heating.
<48> The method for treating fibers according to <47>, wherein the draw ratio is preferably
0.1% or more, more preferably 0.2% or more, further more preferably 0.5% or more,
and preferably 10% or less, more preferably 5% or less, further more preferably 2%
or less.
<49> The method for treating fibers according to <47> or <48>, wherein a water temperature
is preferably 5°C or higher, more preferably 20°C or higher, further more preferably
30°C or higher, and preferably 80°C or lower, more preferably 60°C or lower, further
more preferably 50°C or lower.
<50> The method for treating fibers according to any one of <47> to <49>, wherein
a time for standing in water is preferably 1 minute or more, more preferably 5 minutes
or more, further more preferably 30 minutes or more, and preferably 48 hours or less,
more preferably 24 hours or less, further more preferably 3 hours or less.
<51> The method for treating fibers according to any one of <27> to <50>, wherein
further, the treated fibers are treated with a composition containing the following
component (E):
(E): a sulfur-containing reducing agent.
<52> The method for treating fibers according to any one of <27> to <51>, wherein
further, the treated fibers are treated with a composition containing the following
component (G):
(G): a compound having a chelating action.
<53> The method for treating fibers according to any one of <27> to <50>, wherein
further, the treated fibers are treated with a composition containing the following
components (E) and (G).
(E): a sulfur-containing reducing agent; and
(G): a compound having a chelating action.
<54> The method for treating fibers according to any one of <27> to <53>, wherein
the fibers to be treated are preferably naturally derived fibers, more preferably
fibers taken from a natural animal or plant, or fibers artificially produced using
keratin, collagen, casein, soybeans, peanuts, corn, silk flocks, silk fibroin or the
like as a raw material, further more preferably regenerated protein fibers selected
from the group consisting of regenerated collagen fibers made from collagen as a raw
material and regenerated silk fibers made from silk fibroin as a raw material, even
more preferably regenerated collagen fibers.
<55> A method for producing fibers for hair ornament products, comprising the step
of treating fibers by the method for treating fibers according to any one of <27>
to <54>.
<56> A method for producing a hair ornament product, comprising the step of treating
fibers by the method for treating fibers according to any one of <27> to <54>.
<57> A fiber for hair ornament products comprising a condensate formed from components
(A) and (B):
- (A): a compound having a structure in which a methylol group is bonded to each of
two nitrogen atoms in the molecule; and
- (B): a phenolic compound having an electron donating group on at least one of meta-positions
and a hydrogen atom on at least one of ortho-positions and a para-position, wherein
the electron donating group on the meta-position optionally forms, together with adjacent
carbon atoms, a benzene ring optionally substituted with a hydroxy group.
<58> A hair ornament product having, as a constituent element, fibers comprising
a condensate formed from components (A) and (B):
- (A): a compound having a structure in which a methylol group is bonded to each of
two nitrogen atoms in the molecule; and
- (B): a phenolic compound having an electron donating group on at least one of meta-positions
and a hydrogen atom on at least one of ortho-positions and a para-position, wherein
the electron donating group on the meta-position optionally forms, together with adjacent
carbon atoms, a benzene ring optionally substituted with a hydroxy group).
<59> A fiber-treating agent comprising the following components (A) to (C) :
- (A) DMDM hydantoin or imidazodinyl urea: 10 to 50 mass%;
- (B) resorcin or catechins: 5 to 30 mass%; and
- (C) water: balance.
<60> The fiber-treating agent according to <59>, wherein the fiber-treating agent
is a one-part type, and further comprises the following component (D).
(D) one or more selected from the group consisting of diethylene glycol, triethylene
glycol, N-methylpyrrolidone and 1,3-dimethyl-2-imidazolidinone: 15 to 45 mass%
<61> A fiber-treating agent comprising the following components (A) to (C) and (E):
(A) DMDM hydantoin or imidazodinyl urea: 10 to 50 mass%;
(B) resorcin or catechins: 5 to 30 mass%;
(C) water: balance; and
(E) one or more selected from the group consisting of sodium sulfite, thioglycerol
and Mesna (sodium 2-mercaptoethanesulfonate): 2 to 10 mass%.
<62> The fiber-treating agent according to any one of <59> to <61>, wherein the fiber-treating
agent is a treating agent preferably for naturally derived fibers, more preferably
for fibers taken from a natural animal or plant, or fibers artificially using keratin,
collagen, casein, soybeans, peanuts, corn, silk flocks, silk fibroin or the like as
a raw material, further more preferably for regenerated protein fibers selected from
the group consisting of regenerated collagen fibers made from collagen as a raw material
and regenerated silk fibers made from silk fibroin as a raw material, even more preferably
for regenerated collagen fibers.
<63> A fiber-treating agent kit comprising the fiber-treating agent according to any
one of <59> to <62>, and a surface finish agent containing components (F) and (C):
(F) polysilicone-29: 0.1 to 15 mass%; and
(C) water: balance.
Examples
Examples 1 to 9 and Comparative Examples 1 and 2
[0174] Using compositions whose formulations are shown in Table 1, regenerated collagen
fibers were treated by the following method, and various properties were evaluated.
The pH of each composition was measured with the prepared composition directly applied
to a pH meter (F-52 manufactured by HORIBA, Ltd.) at room temperature (25°C). The
turbidity of the composition was measured with a fiber-treating agent directly placed
in a measurement cell (φ25 × 60 mm borosilicate glass) of a digital turbidimeter (manufactured
by AS ONE Corporation/model: TB700/measurement method: equivalent to ISO 7027, Nephelometry
(90°)/light source: infrared emitting diode (850 nm)/detector: crystal silicon solar
cell module) at room temperature (25°C).
<Treatment method (the following cycle repeated a predetermined number of times when
the number of treatments was 2 or more)>
[0175]
- 1. A 22 cm-long tress with 0.5 g of regenerated collagen fibers (*) was immersed in
a container containing 40 g of the fiber-treating agent, the opening of the container
was closed, the container was immersed together with its contents in a water bath
(manufacturer: TOYO SEISAKUSHO, Ltd./Model: TBS221FA) at 50°C, and heating was performed
for a predetermined time. For Examples other than Example 7, the heating time was
fixed to a time equivalent to about 0.6T (T is as described above). For Example 7,
heating for a time equivalent to 0.3T was performed as the step (0), then the fibers
were immersed, and then further heating for a time equivalent to 0.3T was performed
twice.
*: Regenerated collagen fibers manufactured by Kaneka Corporation were purchased in
the form of a marketed extension product, and cut, and the cut fibers were segmented
into tresses, and used for evaluation. In this evaluation, extension products were
used which display the use of Ultima 100% as a fiber species, and are brown with a
color number of 3, and straight in shape.
- 2. The container containing the tress was taken out from the water bath, and brought
back to room temperature.
- 3. The tress was taken out from the container, immersed in 50 g of triethylene glycol
for 30 seconds, then rinsed with running tap water at 30°C for 30 seconds, lathered
with evaluating shampoo for 60 seconds, rinsed with running tap water at 30°C for
30 seconds, and lightly drained with a towel, and the tress was blown by a hot air
dryer (Nobby White NB 3000 manufactured by TESCOM Company) while being combed. At
this time, the tress remained straight.
<Increase in average breaking elongation during fiber tensioning>
[0176] As an index of stretchability (tenacity) during fiber tensioning, an average breaking
elongation, that is, an average value in evaluation on a plurality of fibers (ten
fibers) for the percentage by which the fiber was stretched by tensioning with respect
to the original fiber length when rupture occurred was used. The evaluation was performed
in the following procedure using a tress immediately after treatment performed as
described in <Treatment method> above.
- 1. Ten fibers were cut from the root of the tress. A 3 cm fiber fragment was taken
from near the center between the root and the hair tip of each fiber, so that a total
of ten 3 cm hair fragments were obtained.
- 2. The fiber fragment was set in "MTT690 Miniature Tensile Tester" manufactured by
DIA-STRON Limited, automatic measurement was started, and an average breaking elongation
was determined when the fiber was in a wet. A large numerical value indicates that
the fiber has high stretchability, and is excellent in tenacity and excellent in durability.
[0177] The degree of increase (C%) in average breaking elongation of the treated tress (B%)
with respect to an untreated state when the average breaking elongation during fiber
tensioning in an intact state (untreated) at the time of being cut from the marketed
product (A%) is used as a reference is determined from the following expression, and
shown as "ratio of increase in average breaking elongation during fiber tensioning
[%]" in the table.

<Increase in average breaking load during fiber tensioning>
[0178] Evaluation of the average breaking load during fiber tensioning was performed using
a tress immediately after treatment performed as described in <Treatment method> above.
As a numerical value, an average value in evaluation on a plurality of fibers (ten
fibers) was used. The evaluation was performed in the following procedure.
- 1. Ten fibers were cut from the root of the tress. A 3 cm fiber fragment was taken
from near the center between the root and the hair tip of each fiber, so that a total
of ten 3 cm hair fragments were obtained.
- 2. The fiber fragment was set in "MTT690 Miniature Tensile Tester" manufactured by
DIA-STRON Limited, automatic measurement was started, and a breaking load was determined
when the fiber stretched in a wet state. A large numerical value indicates that the
fiber has suppleness and resilience, and is insusceptible to stretching by an external
force, and excellent in durability.
[0179] The degree of increase (Y (gf)) in average breaking load of the treated tress with
respect to an untreated state when the average breaking load during fiber tensioning
in an intact state (untreated) at the time of being cut from the marketed product
(Wo (gf)) is used as a reference is determined from the following expression, and
shown as "amount of increase in average breaking load during fiber tensioning [gf]"
in the table.

<Suppression of shrinkage during set with iron at high temperature>
[0180] Suppression of shrinkage during a set with an iron at a high temperature was performed
using a tress immediately after treatment performed as described in <Treatment method>
above. As a numerical value, an average value in evaluation on a plurality of fibers
(ten fibers) was used. The evaluation was performed in the following procedure.
- 1. Ten fibers were cut from the root of the tress, an average value of the lengths
of the fibers was recorded (length L1), the fibers were bundled together with two untreated tresses with 0.5 g of regenerated
collagen fibers, and a flat iron (manufactured by Miki Denki Sangyo K.K./Model: AHI-938)
set at 180°C was applied ten times over the whole tress at a rate of 5 cm/sec.
- 2. After the iron operation, ten fibers were taken out, and an average value of the
lengths of the fibers were recorded again (length L2).
- 3. The shrinkage ratio during a set with an iron at a high temperature was defined
as S = {1 - (L2/L1)} × 100 [%] . When S is close to 0%, the fiber is hardly shrunk, and thus excellent
in heat resistance.
<Heatshape memory ability>
[0181] Evaluation of heat shape memory ability was performed using a tress immediately after
treatment performed as described in <Treatment method> above. When the value of the
result of "I: shaping (curl)" was 5% or less, it was determined that there was no
effect, and subsequent treatment and evaluation were not performed.
• I: Shaping (curl)
[0182]
- 1. A 22 cm-long tress with 0.5 g of regenerated collagen fibers was wetted with tap
water at 30°C for 30 seconds, and the wet tress was then wound around a plastic rod
having a diameter of 14 mm, and fixed with a clip.
- 2. The tress wound around the rod was immersed together with the rod in a water bath
(manufacturer: TOYO SEISAKUSHO, Ltd./Model: TBS221FA) at 60°C, and heated for 1 minute.
- 3. The tress was taken out from the water bath, and immersed in water at 25°C for
1 minute to be brought back to room temperature.
- 4. The tress was removed from the rod, combed three times, and then hung, and photographed
right from the side.
(Evaluation Criteria)
[0183] The curling-up ratio = ratio of decrease in tress length (I) (%) determined from
the following expression, where Lo is an untreated tress length (22 cm) and L is a
treated tress length, was defined as curling strength.

• II: Reshaping (straight)
[0184]
- 1. The tress evaluated in I was combed to eliminate entanglement, and a flat iron
(manufactured by Miki Denki Sangyo K.K./Model: AHI-938) at a measured temperature
of 140°C was then slid over the tress six times at a rate of 5 cm/sec.
- 2. The tress was rinsed with running tap water at 30°C for 30 seconds, lathered with
evaluating shampoo for 60 seconds, then rinsed with running tap water at 30°C for
30 seconds, and dried with a towel.
- 3. The tress was dried (without using a dryer) while being vibrated so as to obtain
a natural shape as hair, and was combed, then hung, and visually observed right from
the side.
(Evaluation Criteria)
[0185] The straightening ratio (ST) (%) determined from the following expression, where
Lo is an untreated tress length (22 cm) and L is a treated tress length, was defined
as a degree of attainment straightening. The tress is completely straightened when
ST is 100%.

• III: Re-reshaping (Curl)
[0186]
- 1. The tress evaluated in II was wetted with tap water at 30°C for 30 seconds, and
the wet tress was then wound around a plastic rod having a diameter of 14 mm, and
fixed with a clip.
- 2. The tress wound around the rod was immersed together with the rod in a water bath
(manufacturer: TOYO SEISAKUSHO, Ltd./Model: TBS221FA) at 60°C, and heated for 1 minute.
- 3. The tress was taken out from the water bath, and immersed in water at 25°C for
1 minute to be brought back to room temperature.
- 4. The tress was removed from the rod, combed three times, and then hung, and photographed
right from the side.
(Evaluation Criteria)
[0187] The curling-up ratio = ratio of decrease in tress length (I) (%) determined from
the following expression, where Lo is an untreated tress length (22 cm) and L is a
treated tress length, was defined as curling strength.

<Formulation of evaluating shampoo>
[0188]
Component |
(mass%) |
sodium laureth sulfate |
15.5 |
lauramide DEA |
1.5 |
sodium benzoate |
0.5 |
EDTA-2Na |
0.3 |
phosphoric acid |
amount required to adjust pH to 7 |
ion-exchange water |
balance |
total |
100 |
<Surface feel quality>
[0189] For evaluation of the feel, five skilled panelists performed evaluation on the basis
of the following criteria for feel smoothness when the tress immediately after evaluation
in <Shape sustainability> was touched by hand, and a total value for the five panelists
was taken as an evaluation result.
(Evaluation Criteria)
[0190]
5: Much smoother hand feel over untreated fibers.
4: Smoother hand feel over untreated fibers.
3: Slightly smoother hand feel over untreated fibers.
2: Comparable in hand feel to untreated fibers.
1: Rougher, more frictional and poorer in hand feel than untreated fibers.

Example 10 (surface finish treatment)
[0191] The regenerate collagen fibers treated in Example 1 were treated with a surface finish
agent shown in Table 2, and various properties were evaluated.
<Treatment method>
[0192]
- 1. The tress was immersed in a container containing 40 g of the surface finish agent,
and left to stand at room temperature for 30 minutes.
- 2. The tress was taken out from the container, and dried for 5 minutes with a household
centrifugal dryer (Ultrafast Dryer Powerful Spin Dry APD-6.0 manufactured by ALUMIS
CO., LTD.).
- 3. The tress was taken out from the dryer, and heated for 3 hours in an oven (forced
circulation dryer with a stainless window; SOFW-450 manufactured by AS ONE Corporation)
set at 60°C (spin coating method).
- 4. The tress was taken out from the oven, and brought back to room temperature.
- 5. The tress was rinses with running water at 30°C for 30 seconds, and lightly drained
with a towel, and the tress was then blown by a hot air dryer (Nobby White NB 3000
manufactured by TESCOM Company) while being combed.
[Table 2]
|
Example 10 |
Surface finish agent (mass%) |
(F) |
Polvsilicone-29 |
5.0 |
(C) |
Water |
Balance |
Total |
100 |
pH (25°C) |
4.0 |
Treatment method |
Method for surface finish treatment |
Spin coating |
Effect |
Durability improveme nt |
Ratio of increase in average breaking elongation during fiber tensioning [%] |
5.6 |
Amount of increase in average breaking load during fiber tensioning [gf] |
20.2 |
Surface feel quality |
24 |
Examples 11 to 13
[0193] Over the regenerated collagen fiber tress treated in Examples 7 and 8, a flat iron
(manufactured by Miki Denki Sangyo K.K./Model: AHI-938) at a measured temperature
of 180°C was slid six times at a rate of 5 cm/sec, and various properties were then
evaluated (Examples 11 and 13).
[0194] Further, for the tresses treated with an iron as described above (Example 11), the
tress was drawn with each of its both ends held by a hairpin for applying tension
to the extent that each fiber forming the tress was stretched at 0.1 to 0.5% on average,
and in this state, the tress was left to stand in water at 40°C for 1 hour with the
hairpins fixed to the wall of a water bath by a tape, and was then blown with a dryer.
For the thus-obtained tress, various properties were evaluated (Example 12).
[0195] Table 3 shows the results.
[Table 3]
|
Example |
11 |
12 |
13 |
Object to be treated |
Regenerated collagen fibers treated in Example 7 |
Regenerated collagen fibers treated in Example 8 |
Hair iron treatment |
Slided six times at 180°C |
Slided six times at 180°C |
Water immersion treatment |
- |
40°C 1 hr |
- |
Effect |
Durability improvement |
Ratio of increase in average breaking elongation during fiber tensioning [%] |
12.3 |
18.5 |
13.9 |
Amount of increase in average breaking load during fiber tensioning [gf] |
30.5 |
33.8 |
27.3 |
Suppression of shrinkage during setting with iron at high temperature |
- |
- |
- |
Heat shape memory ability |
I: Shaping (curl) |
- |
48 |
- |
II: Reshaping (straight) |
- |
92 |
- |
III: Re-reshaping (curl) |
- |
46 |
- |
Surface feel quality |
17 |
18 |
16 |
Examples 14 to 17
[0196] Using the first part and the second part whose formulations are shown in Table 4,
the regenerated collagen fibers were treated in accordance with the following method,
and various properties were evaluated. The pH of each composition was directly measured
with a pH meter (F-52 manufactured by HORIBA, Ltd) with the prepared composition placed
at room temperature (25°C).
[0197] The concentrations of each component described in the table are concentrations in
the first part and the second part, respectively, and the numerical value as the above-described
"total composition of fiber-treating agent" is half the numerical value in the table
because equal amounts (40 g) of the first part and the second part were used as shown
below.
<Treatment method>
[0198]
- 1. A 22 cm-long tress with 0.5 g of regenerated collagen fibers (*) was immersed in
a container containing 40 g of the first part, the opening of the container was closed,
the container was immersed together with its contents in a water bath (manufacturer:
TOYO SEISAKUSHO, Ltd./Model: TBS221FA) at 50°C, and heating was performed for a time
shown in the table.
*: Regenerated collagen fibers manufactured by Kaneka Corporation were purchased in
the form of a marketed extension product, and cut, and the cut fibers were segmented
into tresses, and used for evaluation. In this evaluation, extension products were
used which display the use of Ultima 100% as a fiber species, and are brown with a
color number of 3, and straight in shape.
- 2. The container containing the tress was taken out from the water bath, and brought
back to room temperature.
- 3. The tress was taken out from the container, rinsed with running tap water at 30°C
for 30 seconds, lathered with evaluating shampoo for 60 seconds, rinsed with running
tap water at 30°C for 30 seconds, and lightly drained with a towel, and the tress
was then blown by a hot air dryer (Nobby White NB 3000 manufactured by TESCOM Company)
while being combed.
- 4. The tress was immersed in a container containing 40 g of the second part, the opening
of the container was closed, the container was immersed together with its contents
in a water bath (manufacturer: TOYO SEISAKUSHO, Ltd./Model: TBS221FA) at 50°C, and
heating was performed for a time shown in the table.
- 5. The container containing the tress was taken out from the water bath, and brought
back to room temperature.
- 6. The tress was taken out from the container, immersed in 50 g of triethylene glycol
for 30 seconds, then rinsed with running tap water at 30°C for 30 seconds, lathered
with evaluating shampoo for 60 seconds, rinsed with running tap water at 30°C for
30 seconds, and lightly drained with a towel, and the tress was then blown by a hot
air dryer (Nobby White NB 3000 manufactured by TESCOM Company) while being combed.
At this time, the tress remained straight.
[Table 4]
|
Example |
14 |
15 |
16 |
17 |
First part (mass%) |
(B) |
Tea extract(*1) |
11.3 |
5.0 |
5.0 |
5.0 |
(C) |
Water |
Balance |
Balance |
Balance |
Balance |
pH adjuster |
Hydrochloric acid or sodium hydroxide |
*2 |
*2 |
*2 |
*2 |
Total |
100 |
100 |
100 |
100 |
pH(25°C) |
4.0 |
4.0 |
4.0 |
4.0 |
Bath ratio (mass ratio of first part to fibers) |
80 |
80 |
80 |
80 |
Heating condition |
50°C 18.0 h |
50°C 4.0 h |
50°C 4.0 h |
50°C 4.0 h |
Second part (mass%) |
(A) |
(A3): DMDM hydantoin |
20.0 |
- |
- |
- |
(A4): Imidazodinyl urea |
- |
2.5 |
5.0 |
10.0 |
(C) |
Water |
Balance |
Balance |
Balance |
Balance |
pH adjuster |
Hydrochloric acid or sodium hydroxide |
*2 |
*2 |
*2 |
*2 |
Total |
100 |
100 |
100 |
100 |
pH (25°C) |
4.0 |
4.0 |
4.0 |
4.0 |
Bath ratio (mass ratio of second part to fibers) |
80 |
80 |
80 |
80 |
Heating condition |
50°C 18.0 h |
50°C 4.0 h |
50°C 4.0 h |
50°C 4.0 h |
|
Molar ratio (A)/(B) |
3.5 |
0.5 |
1.0 |
1.9 |
Effect |
Durability improvement |
Ratio of increase in average breaking elongation during fiber tensioning [%] |
1.5 |
4.6 |
3.0 |
2.8 |
Amount of increase in average breaking load during fiber tensioning [gf] |
57.8 |
26.0 |
33.5 |
29.9 |
Heat shape memory ability |
I: Shaping (curl) |
38 |
33 |
35 |
33 |
II: Reshaping (straight) |
95 |
98 |
98 |
98 |
III: Re-reshaping (curl) |
30 |
33 |
35 |
33 |
Surface feel quality |
17 |
15 |
16 |
15 |
[0199] The tresses treated in Examples above can all be directly used as extensions by
attachment to head hair with pins or the like, and can exhibit sufficient performance
on the human head.