[0001] The present invention relates to a grained artificial leather having good colour
fastness and to a process for dyeing ultrafine polyamide fibers into deep, bright
colours, keeping good colour fastness to dry cleaning in charged system.
[0002] The grain layer of conventional artificial leathers are made by providing a porous
or/and non-porous layer of a resin such as polyurethane on porous sheets made of elastomeric
polymers and a fiber base such as woven, nonwoven or knitted fabrics. However, such
resins do not show good dyeability and colour fastness, especially when subjected
to dry cleaning processes.
[0003] Therefore, dope dyeing has been applied to the resins of grained surface. However,
dope dyeing is not suitable for manufacturing small quantities of artificial leathers
of many colours. Further, the appearance of artificial leathers which are dope dyed
is monotonous and opaque due to lack of transparancy and lusters.
[0004] On the other hand, Japanese Patent Publication No. 28041/1973, teaches that some
kinds of polyurethane whose soft segment is polyethyleneglycol (PEG-type PU) can be
dyed with a metal complex dye. However, artificial leathers comprising PEG-type PU
and a fiber base of ultra-fine fibers have no great practical value because they do
not have good colour fastness as a whole, owing to an insufficient colour fastness
of the ultra-fine fibers. Further, when the fiber base is impregnated or coated with
porous resins, the porous resins, exhibit poor colour fastness when exposed to dry
cleaning and spoil the appearance, not only of the back surface but also, of the grain
surface of the artificial leather. The faded porous polyurethane affect even appears
through the dyed grained surface.
[0005] On the other hand, a number of proposals have been made as to leather-like fabrics
made of ultrafine fibers, such as suede-like, nubuk-like, woven or knitted fabrics,
as well as grained artificial leathers. And, now, extra ultrafine fiber around or
less than 0.01 denier is attracting our interests to obtain a softer hand or a more
dense appearance.
[0006] However, as fibers become more fine, dyeing deeply and brightly become more difficult
because of increased surface reflection of the extra fine fibers.
[0007] For example, though polyamide fibers such as nylon-6 and nylon-66 have such advantages
over polyester fibers as softness, high wear resistance and brightness of colour,
the use of polyamide ultrafine fibers for clothing has been delayed so far because
dyes are very liable to come off in washing and dry cleaning.
[0008] Japanese Patent Publication No. 8128/1981 mentions the attempts to improve colour
fastness by increasing molecular orientation of the ultrafine nylon fibers. However
their colour fastness is insufficient when exposed to dry cleaning in which charge
soap is used. Extra-ultrafine fibers around or less than 0.01 denier always show
complete fading of colour even if they are dyed with the dyes said to give highest
colour fastness to fibers of ordinary thickness.
[0009] Though thren-type vat dyes (vat dyes derivatived from anthraquinone), whose colour
fastness is best amongst other dyes, can be also applied to the composite sheet of
ultrafine polyamide fiber and polyurethane (Laid-Open Japanese Patent Application
Publication No. 1365/1980), they can neither give any heavy shade nor show good resistance
to the synthetic solvents used in dry cleaning. Further, not only do they cause photo-tendering
for some hues, but also the strong base used in the dyeing process leads to deterioration
of the polyurethane.
[0010] The object of this invention is to provide a dyeable artificial leather, particularly
a dyeable grained artificial leather, having good colour fastness, bright, deep colours,
excellent lusters, soft hand and high durabilities. The object can be achieved, most
preferably by dyeing an artificial leather comprising a super-entangled ultrafine
fiber base and PEG-type PU applied thereon with a metal dye complex.
[0011] This invention provides also a method for dyeing extra ultrafine polyamide fibers
comprising dyeing with, preferably, a metal dye complex and fixing with tannin and
a metal salt. The dyeing method makes it possible to provide deep and bright colours
whilst maintaining sufficient colour fastness to enable dry cleaning of the extra-ultrafine
polyamide fibers.
[0012] The grained surface preferably comprises, a super-entangled surface made mainly
of ultrafine fibers and/or their bundles and polyurethane having at least 5% by weight
of polyoxyethylene chain of molecular weights of 500 - 5,000 based on total weight
of the soft segment.
[0013] The leathers of the invention are obtainable with at least the following four steps
(1) to (4) combined.
(1) A step for making a fiber sheet being mainly comprising ultrafine fibers or ultrafine
fiber formable fibers.
(2) A step for entangling said fiber sheets by applying high-velocity fluid streams
to at least one surface thereof.
(3) A step for applying a polyurethane, to said surface to which said high-velocity
fluid streams are applied, wherein at least 5 weight % of the soft-segment constituents
of the polyurethane is polyoxyethylene chain having molecular weight of 500 to 5,000.
(4) A step for dyeing said polyurethanes with at least one dye selected from the group
consisting of metal dye complexes, acid dyes and reactive dyes.
[0014] It is preferable for the facility of processing and handling to convert ultrafine
fiber formable fibers into ultrafine fibers or bundles thereof at an appropriate stage.
They can however be manufactured directly by methods such as wet spinning, super-drawing
or melt-blow spinning.
[0015] Ultrafine fiber formable fibers include the chrysanthemum-like cross-section fibers
in which one component is radially sandwiched between other components, multi-layered
bicomponent fibers, radially multi-layered bicomponent hollow fibers, and islands-in-sea
type composite fibers having fixed or unfixed cross section along the fiber axis.
They may be used by mixing more than two of the fibers.
[0016] For obtaining leathers having soft hand and smooth surface, the thickness of the
ultrafine fibers which can be obtained from the ultrafine fiber formable fibers should
be less than 0.2 deniers, preferably less than 0.05 denier, more preferably less than
0.01 denier.
[0017] As materials for the ultrafine fibers, polyamides such as nylon-6 and nylon-66, polyesters
such as polyethylene and polybuthylene terephthalate, polyacrylonitrile, and their
copolymers are preferable among others. Polyamides are particularly preferable because
even less than 0.01 denier they can be deeply coloured with good colour fastness by
the dyeing method stated later.
[0018] As binding components (sea components) for ultrafine fiber formable fibers, those
readily-separable type ultrafine fiber components or those different in the solubility
are selected. For the facility of spinning and removal, polystyrene, polyethylene,
their copolymers, and copolymerized polyesters are preferably used. Particularly
the copolymers of styrene with acrylic acid and/or methacrylic acid are preferable
amongst them for obtain ing strong fibers due to easiness of applying a high drawing
ratio.
[0019] In this invention, to improve colour fastness, it is preferable to increase drawing
ratio to achieve high molecular orientation or high degree of crystallinity. Drawing
ratio more than 2.0 times, preferably more than 2.5 times, are usually preferable,
provided the spinning speeds of 600 to 1,500 m/min. are used.
[0020] The ultrafine fibers of the grained surface should preferably have a size less than
0.2 denier. If not, a smooth grained surface is difficult to form because the excessive
fiber stiffness affects their smoothness, the surface can produce unsightly creases
and cracks, and crumpling readily causes cracks and surface unevenness. The ultrafine
fibers of less than 0.2 denier, preferably of less than 0.05 denier, more preferably
of less than 0.01 denier can be densely entangled so that a surface which is highly
smooth, flexible, and not liable to cause cracks, and has a soft touch feeling is
obtainable.
[0021] The fiber structure of or just beneath the grained surface should preferably have
ultrafine fibers and/or their bundles, mutually super-entangled. They should preferably
be such that the distance between the fiber entanglement points (defined later) is
less than 200 microns. The fiber structures with less entanglement such as entangled
only by needle punching are not preferable because they are apt to fluff or crack
when subjected to friction, crumpling, or repeated shearing or bending. Such fiber
bases require reinforcement with a great quantity of porous resins to maintain their
strength and dimensional stability and, consequently, such sheets are poor in dyeing
fastness. For the purpose of reducing the amount of porous resins for eliminating
such defects, the distance between the fiber entanglement points should preferably
be less than 200 microns or more preferably less than 100 microns.
[0022] The term "the distance between the fiber entanglement points" is defined in Laid-Open
Japanese Patent application Publication No. 191280/1983 (Tokkai-sho 58-191280).
[0023] A short average distance between points of entanglement produces a high density
of entanglement.
[0024] The average distance between the fiber entanglement points is measured in the following
manner. When observed from the surface with a scanning electron microscope, the fibers
are considered to form an entanglement point when an upper fiber which has passed
over and across a lower fiber then passes under and across another fiber. It will
be assumed that the constituent fibers are f₁, f₂, f₃, ....., the point at which two
fibers f₁ and f₂ are entangled with each other is a₁ and another point at which the
upper fiber f₂ is entangled with another fiber with the fiber f₂ being the lower fiber
is a₂ (the entanglement point between f₂ and f₃). Similarly, the entanglement points
a₃, a₄, a₅, .... are determined. The linear distances a₁a₂, a₂a₃, a₃a₄, a₄a₅, a₅a₆,
a₆a₇, a₇a₃, a₃a₈, a₈a₇, a₇a₉, a₉a₆, .... measured along the surface are the distance
between the fiber entangling points and their average is taken.
[0025] In the present invention, the fibers of the surface portion preferably have an average
distance between the fiber entangling points of less than about 200 microns as measured
by this method. In fiber structures where the average distance between the entangling
points is greater than about 200 microns, such as in those fiber structures in which
the entanglement of the fibers is effected only by needle punching, only little entanglement
of the fibers occurs.
[0026] If fiber entanglement is so dense that the distance between its points is less than
200 microns, the amount of polyurethanes applied thereto can be decreased. Namely
it is possible to decrease porous polyurethane to be impregnated in the fiber base
or to decrease the thickness of polyurethane layer applied to the surface. The former
spoils colour fastness and the latter spoils soft hand and delicate appearance. The
fiber base may be nonwoven, laminated nonwoven or woven or knitted fabrics laminated
and entangled with a nonwoven. Amongst them, nonwoven a fiber base comprising a surface
portion of super-entangled ultrafine fibers and/or their bundles, said ultrafine fibers
and/or their bundles being branched from the ultrafine bundles of the inner portion,
is most preferable. It is preferable that the degree of branching and entanglement
vary at the boundary between the surface and inner portions. By applying water jet
streams to the ultrafine formable fiber sheet, entanglement and branching often occur
throughout its thickness. The dense entanglement and branching around the surface
portion brings about the sheet a smooth surface and excellent stability such as against
fluff and deformation. Looser entanglement than the surface of the inner portion brings
about softness to the sheet.
[0027] The amount of resin depends on the intended purposes for the leather. For clothing,
however, it should preferably be 0 to 50% and more preferably less than 20% based
on the fiber weight.
[0028] The resins used for the grain layer in accordance with the invention are required
to be the urethane polymers having at least 5% by weight of polyoxyethylene chains
with molecular weights of 500 to 5,000 based on total weight of the soft segment.
If the amount of polyoxyethylene chains is less than 5% by weight, bright colours
are difficult to obtain by dyeing. The molecular weight of polyoxyethylene chains
is required to be 500 to 5,000 for keeping the softening temperature, resistance to
flexing and solvent within their practicable range.
[0029] Polyurethanes whose soft segment contains polyoxyethylene chains should preferably
be dyed with anionic dyes such as metal dye complexes, acid dyes and reactive dyes
because they are highly affinitive thereto and particularly dyeable with metal dye
complexes and have good colour fastness.
[0030] They may of course be blended or copolymerized with a proper quantity of another
polyether, polyester and copolymerized polyesters for improving mechanical strength.
[0031] Polyurethane polymers in accordance with the invention are not limited to linear
type and may be the cross-linked type such as cross-linked with hexamethylene diisocyanate
trimer. Cross-linked polyurethanes generally improve resistances to scratch, scuff,
organic solvent and hot water, but is defective in flex resistance. However, in the
present invention, flex resistance is much improved by virtue of super-entangled surface
structure.
[0032] The soft segment of the polyurethane may be polyoxyethylene glycol alone, but may
also be its mixtures with polyether diols such as polyoxypropyleneglycol, polyoxytetramethyleneglycol
and polyester diols such as polyethyleneadipate, polybuthyleneadipate, polyhexamethyleneadipate
and polycaprolactone, and copolymers thereof.
[0033] PEG-type PU may be mixed with other polyurethanes so that the amount of polyoxyethylene
segment is more than 5% by weight based on the total weight of the soft-segment.
[0034] Organic diisocyanates used to make the polyurethane include aromatic ones such as
diphenylmethane-4 4ʹ-diisocyanate, aromatic-aliphatic ones such as xylylenediisocyanate,
aliphatic diisocyanates such as hexamethylenediisocyanate, and alicyclic ones such
as isophoronediisocyanate and hydrogenated diphenylmethane-4,4ʹ-diisocyanate. Amongst
them, aromatic diisocyanates, particularly diphenylmethane-4 4ʹ-diisocyanate, is preferable
for obtaining good physical characteristics such as thermal stability, solution stability
and fracture strength.
[0035] Alicyclic diisocyanates such as isophorone ones are preferable for obtaining anti-yellowed
(not easily coloured even when exposed to sun) type polyurethanes.
[0036] Chain extenders for the polyurethane include water, low-molecular diols such as ethyleneglycol
and propyleneglycol, aromatic diamines such as ethylenediamine, aliphatic diamines
such as 4,4ʹ-daminodiphenylmethane, alicyclic diamines such as 4,4ʹ-diaminodicyclohexylmethane
and isopholonediamine, alkanolamines such as ethanolamine, hydrazines, and dihydrazide
such as succinic one. Amongst them diamine compounds are preferable and 4,4ʹ-diaminodiphenylmethane
is particularly preferable for practical use because of its heat resistance and 4,4ʹ-diaminodicyclohexylmethane
is more preferable for light resistance. They may of course be used alone or in combination.
[0037] The polyurethanes are generally manufactured in the presence of solvents. Suitable
solvents are dimethylformamide, (referred to DMF hereinunder), dimethylacetamide,
ethylacetate and toluene. Amongst them DMF should be preferably used. Elastomers other
than polyurethane such as polyamide, polyester, polyvinyl chloride, polyacrylic
ester copolymers, neoprene, styrene-butadiene copolymers, acrylonitrile-butadiene
copolymers, polyamino acid, polyamino acid-polyurethane copolymers, and silicone resins
may be mixed with the polyurethanes, and if necessary may be applied in less than
10 microns thickness to the grained surface of the present invention. As a matter
of course, plasticizers, fillers, stabilizers, crosslinking agent and so forth may
be added thereto.
[0038] When flexibility and soft feeling are particularly demanded, the resin should be
applied in great quantities to the uppermost very-thin portion of the grained surface
and not at all or in small quantities to the other parts.
[0039] The deep luster and bright colour are obtainable by dyeing the leathers, with one
or more dyes selected from anionic dyes which have a negative charge in aqueous solution
such as metal dye complexes, acid dyes and reactive dyes. Further, when polyamide
ultrafine fibers are used, the dyeing method described later is particularly preferable
for obtaining heavy shade, and high colour fastness.
[0040] For ultrafine fibers other than polyamide, on the other hand, the polyurethanes and
ultrafine fibers can be coloured independently.
[0041] The colour of the urethane polymers may be improved by preliminarily adding dyes
and/or pigments thereto.
[0042] For making ultrafine fibers, islands-in-sea type fiber are representative. It is
produced, for example, by using a spinning system mentioned in Japanese Patent Application
Publication No. 18369/1969 (Tokko-sho 44-18369) or dope mixed spinning. Usually ultrafine
fiber formable fibers are cut into short fibers, crimped with stuffing box, formed
into web and subjected to needle punching. Or, continuous filaments are spread into
sheet without cutting and subjected to needle punching. Further the ultrafine fiber
formable fibers may be placed on and entangled with other nonwoven, woven knitted
fabrics. After that or occasionally without needle-punching, high-velocity fluid
streams are applied to the sheet. Water is most preferably used amongst other fluids.
The branching and entanglement of the fibers are achieved through the treatment.
The ultrafine fiber formable fibers may be converted into bundles of ultrafine fibers
before treatment with high pressure fluid streams. In such a case, the pressure of
the fluids may be 5 - 100 kg/cm². Even before conversion, a similar pressure may be
applied for easy separable fibers. However, 100 - 300 kg/cm³ is preferable for the
fibers not liable to separation. The degree of branching and entanglement can also
be changed by contact times. Pressure may be changed each time of contact. The degree
of ultrafining can be controlled by treating the fiber sheets with solvents for at
least a part of components. The dissolution of part of the fibers can be carried out
even after impregnating or coating with resins. In this case, products become softer
because many spaces where the part of components were formed along the fiber axis
in the products.
[0043] The resin solution or dispersion for the grained surface may be applied by reverse
roll coater, gravure coater, knife coater, slit coater, spraying and other methods.
The coated surface is pressed and if necessary heated for smoothing or embossing the
surface. Sometimes pressing the fiber sheets before coating the resin is also effective
for improving smoothness.
[0044] In this invention, heavy shade, high colour fastness of polyamide ultrafine fibers
is attainable through the colour fixing after dyeing with metal dye complexes.
[0045] Generally speaking, polyamide fibers such as nylon-6, can be dyed beautifully with
acid dyes, disperse dyes or metal dye complexes. However, ultrafine polyamide fibers
less than 0.2 denier is inferior to ordinary fibers in colour fastness. This trend
is remarkable for as extra-ultrafine fibers with less than 0.01 denier.
[0046] We found that the ultrafine polyamide fibers can be deeply dyed using metal dye complexes
such as mordant dyes, acid mordant dyes, 1:1 metal-complex dyes, 2:1 premetallized
dyes and metal complex direct dyes of molecular weights more than 700, more preferably
of more than 900. The methods for this dyeing include dip drying, pad steam drying
and pad drying and are not limited. Amongst the dyes, 2:1 premetallized dyes of larger
molecular weights are easy to be produced. We also found that the ultrafine fibers
of less than 0.01 denier, particularly with 0.001 denier, can unexpectedly be dyed
with so-called Irgaran-type metal complex dyes having low hydrophilicity groups such
as sulfonamide and sulfonmethyl groups.
[0047] The metal dye complexes enhance dye bonding with the fibers by forming complex salts
between the dye molecules and chrome or other metal atoms and can provide ordinary
fibers with good colour fastness but in ultrafine fibers almost all colour fade by
dry cleaning with charge-soap containing synthetic solvents.
[0048] We, however, discovered that remarkable effects are obtained by fixing synthetic
tannins and tannic acid derivatives (synthetic and natural) or tannins and metal
salts in combination after dyeing with metal dye complex dyeing. The fixing after
dyeing with metal dye complexes has been said to be neither effective nor necessary
for ordinary fibers at all. However, the fixing with tannins and metal salts ensures
good colour fastness even to the extra ultrafine fibers in dry cleaning with synthetic
solvents (such as perchlene which is said to have the strongest cleaning power).
[0049] Term "tannins" in accordance with the invention is generically given to hydrolysable
tannins, condensed tannins and the complex tannins which has both properties. They
are contained in the barks, leaves, roots and fruits of plants. Preferable tannins
amongst them are gallotannins (tannic acid) classified in the category of hydrolytic
tannins that are represented by Chiness gallotannin and gallic acid.
[0050] The metal salts in accordance with the invention include antimonty complex salts,
iron salts, chrome salts, copper salts, bismuth salts and their complex compounds.
Preferable amongst them is potassium antimonyl tartrate in the category of antimonide
complex compounds.
[0051] Such fixing methods may be conducted by continuous 2-bath process or may be carried
out by separate 2-bath process, namely, impregnation with tannins solution, drying
the impregnated sheet, impregnation with metal salts solution and drying, in this
order. In the former, temperature can be set at 25 to 100°C. Too low temperatures
lower the solubility and adsorbability of the fixing agent. On the contrary, too high
temperature causes dissolving out of the absorbed dye into the treating solutions.
Temperatures of 40 to 85°C, particularly 50 to 80°C, are therefore preferable and
result in satisfactory fixing effects.
[0052] The mechanism of fixing is not known in detail, but it can be assumed that a layer
of the fixing agent is formed on the surface of the ultrafine fibers and the layer
multiplicatively enhances the affinity between the dyes and fibers so that dyes become
difficult to move. Though such fixing treatment tends to harden the sheets, it is
however also amazing that the above effects are kept even after finishing through
mechanical crumpling.
[0053] Such crumpling methods are not limited and include dry heat mechanical crumpling
and wet heat and hot water tumbler crumpling. Further it can be carried out simultaneously
with the fixing by using liquid flow dyeing machines.
[0054] The fiber sheets thus obtained may be further subjected to washing and finishing
agent treatment, if necessary, after the dyeing and fixing. Further the addition
of polyurethanes or raising such as buffing can be applied either before or after
the dyeing and fixing. Surface active agent treatment is preferable for dyeing the
fiber sheets impregnated with high-molecular elast omer other than PEG-type PU. That
is, because other type polyurethanes suitable for impregnation are extremely inferior
in colour fastness, it is rather preferable to preliminarily remove the dyes absorbed
to the impregnated elastomers with surface active agents.
[0055] Amongst such surface active agents, anionic, nonionic and amphoteric surfactants
are effective. Particularly the latter two are preferable. Particularly preferable
amongst them are polyoxyalkylene nonionic and betaine amphoteric surface active agents.
The former include plyoxyalkylenealkylamine, polyoxyethylenealkylether, polyoxyethylenealkylarylether,
polyoxyethylenealkylether, polyoxyethylenealkylester, polyoxyethylenealkylamide,
polyoxyethylenepolyoxypropylene, polyoxyethylenealkylpheonol and polyoxyethylenephenylether
for example.
[0056] When the fiber sheets are prepared with the multilayered ultrafine fiber formable
fibers made of polyamide and polyester and the products are subjected to multi-colour
dyeing, a melange coloured product having good colour fastness can be obtained.
[0057] Heretofore, description has been mainly made as to fiber dyeing and fixing after
sheet formation. However, it is needless to say that the order of the sheet formation
and the dyeing may be changed arbitrarily.
Example 1
[0058] A staple of islands-in sea type fiber (4 denier, 51mm length) having 7 islands, each
islands consist of many islands-in-island (I-I-I) and a sea-in-island (S-I-I), was
obtained by spinning at a speed of 1,200 m/min, drawing at 2.6 times, being subjected
to crimping and cutting. The islands-in-sea type fiber is composed of 65 parts of
acrylic acid-styrene copolymer (referred as AS resin hereinunder) as the sea and the
S-I-I component and 35 parts of nylon-6 as I-I-I component. The average thickness
of the I-I-I was 0.002 denier.
[0059] A web was formed through card, cross-lapper and needle-punched with single barbed
needles for entanglement. The sheet has a weight 430 gr./m², an apparent density
of 0.17 gr./cm³ and an average distance between the entanglement points of 378. Both
surfaces of the sheet were treated one time respectively with high-velocity fluid
streams of 100 kg/cm² pressure from a nozzle having 0.25 mm diameter holes arranged
in one row at 2.5 mm intervals, while oscillating the nozzle. The nonwoven sheet thus
obtained showed the super-entangled structure in which the islands-in-sea type fibers
were branched into extra ultrafine fibers and/or their bundles, and the average distance
between the fiber entanglement points was 56 microns at the surface.
[0060] Next the nonwoven sheet was shrunk in 85°C hot water, dried and smoothed between
rubber roll and hot iron roll having smooth surface.
[0061] A prepolymer obtained from polyoxyethyleneglycol of molecular weight of 600 and isophronediisocyanate
was chain extended with 4,4ʹ-diaminodicyclohexylmethane, terminated at the end with
ethanolamine and cross-linked with 15 parts of a hexamethylenediisocyanate trimer.
Then the cross-linked polyurethane was coated with gravure coater, on the smoothed
surface. The amount of coating was 5 gr./m². The coated surface was pressed with a
hot emboss roll, for embossing and integrating the coated resin with the super-entangled
surface.
[0062] Thereafter AS resin was almost completely removed with tricloroethylene and the islands-in-sea
type fibers were ultrafined.
[0063] A sheet thus obtained was subjected to dyeing and fixing using a wince dyeing machine
under the following condition.
Dyeing:
[0064] Dye stuff: Iregalan Black GBL 200%, 10% owf
[0065] Dyeing temperature × time: 98°C × 60 min.
Fixing:
[0066] Fixing agents: tannic acid and tartar emetic
[0067] Treating method: treatment with weakly acidic bath containing 10% owf tannic acid
at 50°C, for 50 min. and,
treatment with weakly acidic bath containing 5% owf tartar emetic at 50°C, for
50 min.
[0068] Next, after adding a finishing agent, the sheet was softened with a tumbler crumpling
machine and dried.
[0069] Both the grained surface and the reverse surface of thus-obtained sheet were coloured
dark black. It showed a softness free from undesirable rubber-like feeling and the
grained surface has deep luster, resistances against scuff and repeated bending. Its
washing and dry cleaning fastness according to JIS-L0844 LO860 (2% charge soap content)
was good.
Comparative Example 1
[0070] A grained artificial leather was obtained according to the same manner except using
anti-yellowed (not easily coloured even when exposed to sun light) type polyester
polyurethane instead of the PEG-type PU.
[0071] It showed a natural leather-like appearance as that of Example 1. However the grained
surface was dyed into dark-blue not into dark black. Further, the colour of the grained
surface was seriously faded by dry cleaning containing 2% charge soap.
Comparative Example 2
[0072] The sane needle-punched sheet as Example 1 was immersed in a 15% aqueous solution
of polyvinyl alcohol (referred to PVA hereinafter) at 85°C, shrunk simultaneously,
dried, impregnated with a 10% DMF solution of polyester polyurethane, coagulated with
30% DMF aqueous solution and sufficiently washed in 80°C hot water for removing PVA
and DMF.
[0073] Next, the sheet was subjected to the surface smoothing with a hot roll and the same
treatment as Example 1. The sheet showed unevenly coloured lines or portions like
stood veins along ultrafine fiber bundles, and cracks arised during the dyeing, and
ultrafine fibers were exposed therefrom. Further it had hard touch, unbright colour
and feeling not natural leather-like as compared with Example 1.
[0074] Further when picked up by fingers, so bent as to have an acute angle, and rubbed
against a thigh part of trousers with a large pressure applied, the Comparitive Example
2 leathers showed peeled grained surface and exposed raising while the leather of
Example 1 did not change in appearance at all.
Example 2 - 5, Comparative Example 3 and 4
[0075] The needle-punched sheet obtained in Example 1 was super-entangled with the high-velocity
fluid streams on one side thereof in the same manner as Example 1, immersed in an
8% aqueous PVA solution at 85°C for PVA impregnation and for the sheet shrinkage
at a time and dried.
[0076] Next a 7% DMF solution of polyester polyurethane to which a small quantity of carbon
black was added was impregnated and coagulated with water and sufficiently washed
in hot water at 80°C for removing PVA and DMF.
[0077] Thereafter the super-entangled surface of the impregnated sheet was coated with
a DMF solution containing 10% polyurethanes obtained by chain extending the prepolymers
between diphenylmethane-4,4ʹ-diisocyanate and high molecular weight diol mixtures
composed of polyoxyethyleneglycol (molecular weight, 2,000) and polyethylenebutyleneadipate
(molecular weight, 2,000) of the mixing ratios of:
(A) 100/0 (Example 2)
(B) 50/50 (Example 3)
(C) 10/90 (Example 4)
(D) 5/95 (Example 5)
(E) 3/97 (Comparative Example 3)
(F) 0/100 (Comparative Example 4)
in which the chain extending reaction was carried out adding small amount of 1,2,2,6,6-pentamethyl-4-hydroxy-peperidine.
The coating of the DMF solution was carried out with gravure coater so that the amount
of applied polyurethanes were 6 gr./m² (base on solid weight). Then the coated sheets
were dried, and pressed with a hot emboss roll so that the base sheet and the coated
layer were integrated.
[0078] Next, the embossed sheet was immersed in tricloroethylene and repeatedly subjected
to immersion and squeezing for removal of AS resin.
[0079] Further the other side not embossed was raised through buffing.
[0080] The sheets (A), (B), (C), (D), (E) and (F) thus obtained were dyed with vinylsuphone
reactive dye, Dlamira Brill Red F3B, at a bath ratio of 1:50, a dye concentration
of 20 gr/lit. and a temperature of 50°C using a liquid flow dyeing machine for 60
minutes and finished by an ordinary method.
[0081] The leathers thus obtained looks like natural grain leathers, have softness free
from rubbery elasticity and show comparatively-long ultrafine fiber nap on one side,
and a grained surface with a high quality appearance. Further, as shown in Table 1,
the leathers (A), (B), (C) and (D) showed a grained surface with a deep luster and
a bright colour, while that (E) showed an uneven-dyeing spot pattern though it was
improved in colour depth and that (F) was short of commodity value because of considerable
uneven colouring, the resin part of the grained surface being little coloured.
[0082] The dyeing fastness properties of the leathers (A), (B), (C), and (D) were not problematic
as shown in Table 1.
[0083] The distances between the entanglement points of the component fibers at the grained
surface were measured after removing the polyurethane and finishing agents with solvent
extraction. The measured value of all were about 60 microns.
1) The measurements by MS-2000 Colour Difference Meter manufactured by Macbeth
2) The dry cleaning fastness properties measured under JIS L-0860. The numeral values
of discoloration and fading, contamination and colour-off are listed in the order
of mention.
Example 7
[0084] A similar type of staple (3.5 denier, 51 mm length, 7 islands) fiber consisting of
60 parts of an AS resin as sea and S-I-I component and 40 parts of nylon-6 as I-I-I
component was obained by spinning at 1,200 m.min., drawing 3.0 times, crimping and
cutting. The I-I-I has a mean thickness of 0.003 denier.
[0085] The staple fibers were subjected to a card, cross lapper to form webs. The web was
needle-punched with single barbed needles. The needle punched sheet had 380 gr./m²
in weight and an apparent density of 0.12 gr./cm³. High-velocity fluid streams were
applied to the both surfaces of the needle-punched sheet two times respectively at
a pressure of 100 kg/cm² with a nozzle with the 0.25 mm diameter holes arranged in
one row at 2.5 mm intervals while the nozzle was oscillated. The sheet thus obtained
showed the ultrafine fibers and/or their bundles super-entangled at the surface and
branched from the islands-in-sea type fiber of the inner portion.
[0086] Next, the super-entangled sheet was shrunk in 85°C hot water, dried, and repeatedly
subjected to immersion in tricloroethylene and squeezing for the almost-complete extraction
removal of AS resin. Thereafter a raised sheet was obtained by lightly buffing one
side of the nonwoven sheet using a roll sander type buffing machine.
[0087] Next, the raised sheet was subjected to dyeing and fixing with a wince dyeing machine
under the following conditions.
[0088] Dye stuff: Irgalan Red Brown RL-200%, 10% owf
[0089] Drying temperature × time: 98°C × 60 min.
[0090] Fixing agent: tannic acid, tartar emetic
[0091] Treating method: treatment with weakly acidic bath of 10% owf of tannic acid at 50°C
for 50 min. and,
treatment with a weakly acidic bath of 5% owf tartar emetic at 50°C for 50 min.
[0092] The sheet was washed with hot water, and dried. A wine-coloured nubuk type artificial
leather was obtained. Though no polyurethane binder was added, the sheet showed excellent
dimensional stability and had an extra ultrafine fiber nap at the surface (raised),
a soft touch free from undesirable elasticity, a high drapability, a heavy shade dyeing
and as elegant an appearance as natural nubuks. Further it showed little discoloration
and fading (colour-off) even through the dry cleaning with a synthe tic solvent with
2% content of charge soap.
Comparative Example 5
[0093] A nubuk type artificial leather was obtained according to Example 6 except without
the fixing with the tannic acid and tartar emetic in Example 6. The nubuk type artificial
leather showed the same high-grade appearance as Example 6 but when subjected to the
dry cleaning with a charge-soap containing synthetic solvent almost all colour came
off and considerable fading occurred.
Example 7
[0094] A 76 denier/20 filament yarn similar to that of Example 1 (the mean size of I-I-I:
0.008 denier) was obtained through spinning and drawing at a ratio of 3. The filament
consists of 60 parts of AS resin as sea and S-I-I component and 40 parts of nylon-6
as I-I-I component and had 12 island components per filament. A double weave was
obtained by weaving the filament yarn as the first weft and 75-denier/100 nylon-6
textured yarn as the warp and second weft. The weave has 5-leaves satin construction
mainly composed of the islands-in-sea fiber at the surface and a 2/3 twill construction
mainly composed of the textured filaments at the reverse surface. The density of this
weaving was 110 warps/inch and 165 wefts/inch.
[0095] The textile was immersed in 85°C hot water, for removing sizing agent of the warp
and for shrinkage at a time, and dried.
[0096] Next, the textile was subjected to tricloroethylene immersion and squeezing repeatedly
for almost complete extraction removal of the As resin and to the ultrafining of the
weft yarn. Next, after a raising oil agent was added, it was raised using a raising
machine. Thereafter it was subjected to dyeing and fixing using a liquid flow dyeing
machine under the following conditions.
Dyeing conditions:
[0097] Dye stuff: Irgalan Navy Blue B 10% owf
[0098] Dyeing temperature × time: 98°C × 60 min.
Fixing conditions:
[0099] Fixing agents: tannic acid, tartar emetic
[0100] Treating method: treatment with weakly acidic bath containing 10% owf tannic acid
at 60°C for 30 min. and,
treatment with weakly acidic bath containing 5% owf tartar emetic at 60°C and
30 min.
[0101] Thereafter the textile was washed in a hot water, dried and treated with a finishing
agent.
[0102] The textile showed a very dense naps a soft surface touch, a lustrous navy-blue colour
and a high-grade nubuk type appearance.
[0103] The textile showed good colour fastness, causing little colour-off and surface (raised
part) fading, even on the dry cleaning with the perchloroethylene with 2% content
of charge soap.
Comparative Example 6
[0104] A nubuk type textile was manufactured by the same manner as Example 7 except that
Nylosan Blue F-GBL (high fasteness type acidic dye) and Nylon Fix-TH (multivalent
phenol derivative) as fixing agent were used. The textile was dyed into greyish blue.
[0105] When washed with the perchloroethylene with 2% content of charge soap, it was quite
short of commodity value because the colour of the raised ultrafine fibers of its
surface bad-lookingly faded.
Example 8
[0106] Islands-in-sea fibers (3.5 denier, 51 mm length, 36 islands, thickness of each island
is 0.05 denier) composed of 50 parts of AS resin as sea component and 50 parts of
nylon-6 as islands component was subjected to a card, cross lapper to form webs, needle
punched with single barbed needles.
[0107] Next the needle punched sheet was immersed in a 12% PVA aqueous solution at 85°C,
for shrinking and impreg nating with PVA at a time, and dried. Thereafter the AS
resin was almost completely removed by extracting with tricloroethylene. Next it was
impregnated with a 12% DMF solution of polyetherpolyurethane, solidified in water,
and subjected to removing of PVA and DMF in hot water.
[0108] Thereafter the both surfaces of the nonwoven sheet were buffed and a sheet with a
30% content of polyurethane was obtained.
[0109] The sheet was subjected to dyeing and fixing using a liquid flow dyeing machine under
the following conditions.
Dyeing conditions:
[0110] Dye: Irgalan Red Brown RL 200% 10% owf
[0111] Kayakalan Red BL 2% owf
[0112] Dyeing temperature × time: 98°C × 50 min.
Fixing conditions:
[0113] The same as Example 7
[0114] Thereafter the sheet was washed with water and treated with a 20 gr./lit. aqueous
solution of Bisnol A-30 (alkylamine type nonionic surface active agent manufactured
by Ipposha Yushi Co.) at 60°C for 20 minutes. It was further washed with hot and cold
waters.
[0115] The artificial suede thus obtained had soft hand, heavy shaded and high colour fastness,
and showed no colour fading even after dry cleaning with a synthetic solvent (perchlene)
with 2% content of charge soap.
[0116] Reference is directed to our copending application No. 84304074.2-2108 (Publication
No. 0165345) from which the present application is divided.