(19) |
 |
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(11) |
EP 0 147 759 B2 |
(12) |
NEW EUROPEAN PATENT SPECIFICATION |
(45) |
Date of publication and mentionof the opposition decision: |
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06.05.1999 Bulletin 1999/18 |
(45) |
Mention of the grant of the patent: |
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24.07.1991 Bulletin 1991/30 |
(22) |
Date of filing: 15.12.1984 |
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(54) |
Latex containing odor inhibitors
Geruchsinhibitoren enthaltendes Latex
Latex contenant des désodorisants
|
(84) |
Designated Contracting States: |
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AT BE DE FR GB IT NL SE |
(30) |
Priority: |
27.12.1983 US 565689
|
(43) |
Date of publication of application: |
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10.07.1985 Bulletin 1985/28 |
(73) |
Proprietor: The B.F. GOODRICH Company |
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Akron,
Ohio 44318 (US) |
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(72) |
Inventors: |
|
- Shah, Pravinchandra Kantilal
Sheffield Lake
Ohio 44054 (US)
- Antlfinger, George John
Avon Lake
Ohio 44012 (US)
|
(74) |
Representative: von Kreisler, Alek, Dipl.-Chem. et al |
|
Patentanwälte
von Kreisler-Selting-Werner
Postfach 10 22 41 50462 Köln 50462 Köln (DE) |
(56) |
References cited: :
EP-A- 0 084 809 US-A- 3 318 722 US-A- 4 107 120
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DE-A- 2 357 068 US-A- 3 539 434 US-A- 4 268 546
|
|
|
|
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- Ullmanns Enzyklopädie der Technischen Chemie Bd 13, S.644-656,Bd 19 S.17-18.
- Vliesstoffe, Georg Thieme Verlag, Stuttgart, S.61-62
- High Polymer Latices, (1966), S. 636-671
- Brockhaus Enzyklopädie, Bd 7, S. 179-180
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BACKGROUND OF THE INVENTION
[0001] A nonwoven fabric is a textile structure consisting of a mat of fibers held together
with a bonding material. The fibers can be partially oriented or they can be completely
randomly distributed. Latex is often used as the binder for the fibers in nonwoven
fabrics.
[0002] Nonwoven fabrics are popular owing to the simplicity and economy of their production
since the traditional weaving operations are not used; hence, less equipment, less
space, and fewer personnel are required. Nonwoven fabrics can also be produced from
what would normally be considered as waste fibers, and useful characteristics are
obtained which may not be provided by woven or knitted fabrics.
[0003] Enormous quantity of fibers are consumed annually in applications of nonwoven fabrics
such as clothing, interliners, filters, automotive door panels, heat and electrical
insulation, packaging, sanitary napkins, fillers for quilted structures, wiping cloths,
towels, masks, wall coverings, shoe uppers and liners, curtains and draperies, tea
bags, simulated leather, gaskets, luggage, ribbons, and diapers.
US-A-4,107,120 discloses how the low temperature properties of resin-treated textiles
are improved by using as the resin an acrylic emulsion polymer wherein the latex particles
have a core-shell structure. The latex particles comprise 30-60 % by weight of a polymeric
core and 70-40 % by weight of a polymeric shell wherein said core is formed by emulsion
polymerization of a first monomer composition which provides a Tg of -20 °C or lower
and said shell is formed on said core by emulsion polymerization of a second monomer
which provides a Tg of 60 °C to -10 °C. The crosslinking is carried out in the presence
of a crosslinking monomer.
US-A-3,539,434 relates to non-woven materials and particularly papers treated with
acrylate polymer latices which have improved resistance to aging when protected with
an antioxidant and chelating agent in combination. It is shown that if a non-woven
material is impregnated with different α,β-monoolefinically unsaturated monocarboxylic
acids or mixtures thereof, a phenolic-type antioxidant and a polycarboxylic acid-amine-type
chelating agent help to retain the physical properties of said non-woven material.
[0004] In the medical/surgical field, nonwoven fabrics are used in surgical drapes, surgical
caps and gowns, as wraps for surgical instruments and the like. The surgical use requires
that the fabric used be sterilized. In the case of latex-impregnated fabric used for
drapes, gowns and caps, such items are wrapped and sealed in polyolefin bags and then
are sterilized with gamma ray radiation. At time of use, the bags are opened and the
doctors and nurses put on the caps and gowns and use the drapes to cover the patient
during surgery. When the bags are opened, they often emit odors. In the case of the
wraps, after being washed, surgical instruments are stacked in a tray and then wrapped
in the latex-impregnated nonwoven fabric and sterilized in steam. After steam sterilization,
the wrapped instrument trays are removed from the sterilization unit. When the door
to the sterilization unit is opened to remove the wrapped instrument tray, an odor
is emitted from the fabric that can be quite potent.
[0005] Therefore, in order to sell nonwoven fabric bonded with a latex, the post-sterilization
odor should be minimized.
[0006] In the past, antioxidants have been added to unsaturated latexes to prevent degradation
of the unsaturated polymer backbone in the presence of air, ozone, heat, and light.
Examples of unsaturated latexes include polybutadiene,
poly(butadiene-styrene),
poly(butadiene-acrylonitrile), polyisoprene, and polychloroprene. Saturated latexes
are prepared by homo-polymerizing esters of acrylic or methacrylic acids or copolymerizing
esters of acrylic or methacrylic acids with other vinyl monomers such as acrylonitrile,
styrene, vinyl chloride, and vinyl acetate. The saturated latexes do not need protection
of antioxidants and whenever antioxidants were added to saturated latexes, they were
added for colloidal stabilization, which is unrelated to the antioxidant function.
[0007] Hydrophilic acrylic latexes based on poly(ethyl acrylate) have been available in
the past for bonding nonwoven fibers. Such latexes were prepared by polymerizing in
excess of 90 weight parts ethyl acrylate; less than 5 parts of each N-methylol acrylamide,
acrylamide, or acrylonitrile; a low level of an emulsifier; and less than 1 weight
part of an antioxidant selected from hindered and partially hindered phenols, such
as a mixture of 2,2'-di-t-butyl Bisphenol A, 2-t-butyl-2'-α-methylbenzyl Bisphenol
A, 2,6-di-t-butylphenol, 2-t-butyl-isopropylphenol, etc. The antioxidant was added
as an emulsion to provide additional colloidal stability.
SUMMARY OF THE INVENTION
[0008] This invention relates to nonwoven fabrics bonded with latexes comprising 65 to 85
weight parts of a soft hydrophobic monomer, 10 to 30 weight parts of a hard hydrophobic
monomer, 0.1 to 5 weight parts of an unsaturated carboxylic acid, and 0.1 to 5 parts
of an N-alkylol acrylamide or methacrylamide, said latex having admixed thereto 0.01
to 5 weight parts of an odor inhibition agent selected from amine-type antioxidants,
and hindered or partially hindered phenols.
[0009] In detail, this invention relates to a sterilized nonwoven fabric that has a reduced
odor on sterilization comprising nonwoven fibers bonded with a saturated latex prepared
by free radical initiation comprising a preponderance of a soft hydrophobic monomer
having Tg in the range of -80° C to -20° C, a lesser amount of a hard hydrophobic
monimer having Tg in the range of +40° C to +120° C, a small amount of an unsaturated
carboxylic acid a sufficient amount of an emulsifier and a small amount of N-alkylol
acrylamide or methacrylamide, characterized in that said latex having admixed therein
0.01 to 5 weight parts per 100 weight parts of latex solids of an odor inhibition
agent selected from amine-type antioxidants and hindered phenols that have the function
of reducing the odor that is generated on sterilization of the nonwoven fabric.
DETAILED DESCRIPTION OF THE INVENTION
[0010] This invention is based on a latex that is used as a binder in making nonwoven fabrics
that are used in medical/surgical applications. This latex, when used as a binder
for making nonwoven fabrics, provides a balance of softness, physical strength, hydrophobicity,
adhesion, low skin toxicity, and minimal odor after sterilization. All of these properties
are requisites for a fabric that is used in medical/surgical applications.
[0011] The acrylic latex of this invention is prepared by free radical polymerization of
65 to 85 weight parts soft hydrophobic monomer, 10 to 30 weight parts of hard hydrophobic
monomer, 0.1 to 5 weight parts of an unsaturated carboxylic acid, and 0.1 to 5 weight
parts of an N-alkylol acrylamide or methacrylamide. Polymerization is carried out
in the presence of 0.1 to 2 weight parts of a suitable free radical initiator and
usually with less than one weight part of an emulsifier. To this latex is admixed
about 0.01 to 5 weight parts of an odor inhibition agent selected from hindered or
partially hindered phenols and amine-type antioxidants. The odor inhibition agents,
as defined herein, also include free radical terminators or shortstops. In a preferred
embodiment, free radical polymerization is carried out in the presence of 0.3 to 1
part of a free radical initiator and 0.1 to 0.5 part of an emulsifier with the monomers
to be polymerized including 70 to 80 parts of a soft hydrophobic monomer, 15 to 25
parts of a hard hydrophobic monomer, 0.5 to 4 parts of unsaturated carboxylic acid,
and 0.5 to 4 parts of N-alkylol acrylamide or methacrylamide. Amount of the odor inhibition
agent in the preferred embodiment is in the range of 0.1 to 1 part, based on the weight
of latex solids.
[0012] Typical polymerizations for the preparation of the latexes described herein are conducted
by charging the reactor with appropriate amount of water, emulsifier and a portion
of the initiator sufficient to initiate polymerization. The reactor is then evacuated,
heated to the initiation temperature of about 80° C and charged with a portion of
the monomer premix which has been previously prepared by mixing water, emulsifier,
the monomers, and polymerization modifiers, if any are employed. After the initial
monomer charge has been allowed to react for a period of time, the proportioning of
the remaining monomer premix is begun, the rate of proportioning being varied depending
on the polymerization temperature, the particular initiator employed, and the amount
of the monomer(s) being polymerized. After all the monomer premix has been charged,
the final addition of initiator is made and the reactor and the latex heated with
agitation for a length of time necessary to achieve the desired conversion. The pH
of the latex is generally in the range of about 2 to 7.
[0013] In the latex, the particle size may be in the range of about 300nm (3000 angstroms).
A generally satisfactory particle size may be, however, from 50 to 500nm (500 to 5000
angstroms). The total solids of the latexes may be varied up to about 70% and may
relate to the fluidity wanted in the composition. Generally, it is desired to use
a latex containing 45 to 55% solids.
[0014] Suitable soft hydrophobic monomers that can be used to prepare the latex of this
invention include those monomers homopolymers of which have Tg falling within the
range of -80° C to -20° C, preferably -60 to -30° C. Specific examples of such monomers
include n-butyl acrylate, 2-ethylhexyl acrylate, and isobutyl acrylate. Preferred
soft hydrophobic monomers are acrylic monomers that include n-butyl acrylate and isobutyl
acrylate. Since ethyl acrylate forms a hydrophilic polymer, it is excluded from the
class of monomers defined herein.
[0015] For purposes of this invention, suitable hard hydrophobic monomers are those that
form homopolymers having Tg in the range of + 40° C to +120° C, preferably + 80 to
+110° C. Specific examples of such hard hydrophobic monomers include styrene, α-methyl
styrene, methyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate. Preferred
monomers in this class include styrene and methyl methacrylate.
[0016] A small amount of an acid is used in conjunction with N-alkylol acrylamide to facilitate
curing at a lower temperature. Suitable acids for this purpose include monounsaturated,
diunsaturated, monocarboxylic and dicarboxylic acids generally containing at least
3 carbon atoms and up to about 12 carbon atoms, preferably 3 to 6 carbon atoms. Such
acids include acrylic, methacrylic, itaconic, fumaric, and maleic. Preferred acids
are acrylic, methacrylic, and itaconic.
[0017] A small amount of N-alkylol acrylamide is also included in the polymerization formulation
as a crosslinking agent. Such amides are derivatives of acrylic and methacrylic acids
that contain 1 to 10, preferably 1 to 4 carbon atoms in the alkyl group. This class
of amides includes N-methylol acrylamide, N-methylol methacrylamide, n and iso-butoxy
methyl acrylamide. Preferred example of such amides is N-methylol acrylamide.
[0018] The usual types of surfactants that can be used herein include anionic and nonionic
emulsifiers. Suitable anionic emulsifiers include alkali metal or ammonium salts of
the sulfates of alcohols containing 8 to 18 carbon atoms such as sodium lauryl sulfate,
alkali metal and ammonium salts of sulfonated petroleum and paraffin oils, sodium
salts of sulfonic acids, alkylaryl sulfonates, alkali metal and ammonium salts of
sulfonated dicarboxylic acid esters, and the like. Nonionic emulsifiers, such as octyl
or nonylphenyl polyethyoxyethanol, can also be used. Latices of excellent stabilty
can be prepared with emulsifiers selected from alkali metal and ammonium salts of
aromatic sulfonic acids, alkylaryl sulfonates, long chain alkyl sulfonates, and poly(oxyalkylene)
sulfonates.
[0019] Commonly used free radical initiators include the various peroxygen compounds such
as persulfates, benzoyl peroxide, t-butyl hydroperoxide,and cumene hydroperoxide;
and azo compounds such as azodiisobutyronitrile and dimethylazodiisobutyrate. Particularly
useful initiators are the water-soluble peroxygen compounds such as hydrogen peroxide
and the sodium, potassium and ammonium persulfates used by themselves or in an activated
redox system. Typical redox systems include alkali metal persulfates in combination
with a reducing substance such as polyhydroxyphenols and oxidizable sulfur compounds,
a reducing sugar, dimethylaminopropionitrile, a diazomercaptan compound, and a water-soluble
ferrous sulfate compound. Polymer latices with excellent stability can be obtained
using alkali metal and ammonium persulfate initiators. The amount of initiator used
will generally be in the range of 0.1 to 3% by weight, based on the weight of the
monomers, preferably between 0.2 to 1%. The initiator can be charged at the outset
of the polymerization, however, incremental addition of the initiator throughout polymerization
can also be employed.
[0020] The latexes described herein can be compounded with, or have mixed herein, other
known ingredients before impregnation and before curing. Such ingredients include
curing agents, fillers, water repellent materials, plasticizers, antioxidants or stabilizers,
antifoaming agents, dying adjuvants, pigments, and other compounding aids. Furthermore,
thickeners or bodying agents may be added to the polymer latices so as to control
the viscosity of the latexes and thereby achieve the proper flow properties for the
particular application desired.
[0021] The odor inhibition agent can be added during polymerization of the latex or to the
latex any time before the latex is used to form a nonwoven fabric or it can be added
with other compounding ingredients either by itself or together with the compounding
ingredients. Following addition of the odor inhibition agent, the latex is cured on
the nonwoven fabric. The odor inhibition agent is selected from fully hindered and
partially hindered phenols and amine-type antioxidants. The phenols can be partially
or fully hindered, meaning that one or both of the ortho positions to the hydroxyl
group on the benzene ring are substituted, preferably with tertiary alkyl groups of
4 to 6 carbon atoms each. As defined above, the hindered phenolic antioxidants also
include free radical terminators or shortstops, especially the oil-soluble shortstops,
such as di-t-amyl hydroquinone. However, shortstops are not considered to be hindered
phenols or antioxidants in the conventional chemical parlance. The amine-type of antioxidants
include ketone-amine condensation products, diaryldiamines, diarylamines, and ketone-diarylamine
condensation products.
[0022] Within the class of partially and fully hindered phenols is the group of hindered
phenolic antioxidants that can function as odor inhibition agents in the manner described
herein. Examples of suitable hindered phenolic antioxidants that can be admixed with
an acrylic latex in order to reduce odor upon sterilization with irradiation or steam,
include the following:
(1) phenolic compounds having the general formula
Q-(CH2)w-A
wherein Q is

A is

R is hydrogen or lower alkyl, R'is lower alkyl, R" is alkyl group having from 6-24
carbon atoms, W is an integer from 1 to 4. Illustrative examples of the compounds
shown above are

di-n-octadecyl(3,5-di-t-buty-14-hydroxy-5-methylbenzyl) malonate and di-n-octadecyl
α(3,5-di-t-butyl-4-hydroxy-5-methylbenzyl) malonate.
(2) Phenolic compounds having the general formula
Q-R
illustrative examples of which are 2,6-di-t-butylphenol, 2,4,6-tri-t-butylphenol,
2,6-dimethylphenol, and 2-methyl-4,6-di-t-butylphenol.
(3) Phenolic compounds having the formula
Q-CwH2w-Q
illustrative examples of which are 2,2'-methylene-bis(6-t-butyl-4-methylphenol), and
4,4'-butylidene-bis-(2,6-di-t-butylphenol).
(4) Phenolic compounds having the formula
R-O-Q
illustrative examples of which are 2,5-di-t-butylhydroquinone and 2,6-di-t-butyl-4-hydroxyanisole.
(5) Phenolic compounds having the formula
Q-S-Q
illustrative examples of which are 4,4'-thiobis-(2-t-butyl-5-methylphenol) and 2,2'-thiobis-(6-t-butyl-4-methylphenol).
(6) Phenolic compounds having the formula

illustrative example of which is octadecyl-(3,5-dimethyl-4-hydroxybenzylthio)-acetate.
(7) Phenolic compounds having the formula

wherein T is hydrogen, R or q as defined above, illustrative examples of which are
1,1,3-tris(3,5-dimethyl-4-hydroxyphenyl)-propane and 1,1,5,5-tetrakis-(3-t-butyl-4-hydroxy-6-methylphenyl)-n-pentane.
(8) phenolic compounds having the formula

wherein B1, B2, and B3 are hyrogen, methyl or Q, provided that when B1 and B3 are Q then B2 is hydrogen or methyl and when B3 is Q then B1 and B2 are hydrogen or methyl.
Illustrative example of such compound is 1,4-di(3,5-di-t-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethyl-benzene.
(9) Phenolic compounds having the formula

wherein Z is NHQ,-S-D or -O-Q; D is alkyl group having from 6-12 carbon atoms or
-CwH2w)-S-R". Illustrative example of such compounds is 2,4-bis-(n-octylthio)-6-(3,5-di-t-butyl-4-hydroxyaniline)-1,3,5-triazine.
(10) Phenolic compounds having the formula

wherein Z' is -O-Q, -S-D or -S(CwH2w)-SD. Illustrative example of such compounds is 2,3-bis-(3,5-di-t-butyl-4-hydroxyphenoxy)-6-(n-octylthio)-1,3,5-triazine.
(11) Phenolic compounds having the formula
[Q-CzH2z-COO-CzH2z]p-R"'-(R)4-p
wherein p is an integer from 2 to 4 and R"' is a tetravalent radical selected from
aliphatic hydrocarbons having from 1 to 30 carbon atoms, aliphatic mono and dithioethers
having from 1 to 30 carbon atoms, and aliphatic mono and diethers having from 1 to
30 carbon atoms. Illustrative example of such compounds is 1,2-propylene glycol bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].
(12) Phenolic compounds having the formula

Illustrative examples of such compounds are dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate
and di-n-octadecyl 1-(3,5-di-t-butyl-4-hydroxy-phenyl)-ethanephosphonate.
[0023] Preferred hindered phenolic antioxidants include trifunctional hindered phenols based
alkylated benzenes, isocyanuric acid, and on hydrocinnamic acid. Preferred hindered
phenolic antioxidants also include the alkylated hydroquinones and phenols having
the following general structures A, B, C and D:

where R groups are individually selected from hydrogen and alkyl groups of 1 to 12
carbon atoms with at least one R group being selected from the alkyl groups; R
1 groups are individually selected from lower alkyl groups and hydroxyl groups; X is
selected from lower alkylene groups and sulfur; and Y is selected from lower alkylene
groups and sulfur. More preferably, the R groups are individually selected from hydrogen
and alkyl groups of 3 to 12 carbon atoms, especially tertiary alkyl groups of 4 to
8 carbon atoms such as t-amyl and t-butyl, with at least one of the R groups being
selected from the alkyl groups; the R
1 groups are selected from hydroxyl and alkyl groups of 1 to 3 carbon atoms; X is either
methylene or sulfur; and Y is either methylene or sulfur.
[0024] Specific examples of the preferred hindered phenolic antioxidants include 2,2'-methylene-bis(4-ethyl-6-t-butylphenol)
sold as AO425, 2,2'-methylene-bis(4-methyl-6-nonylphenol) sold as Naugawhite, 2,2'-methylene-bis(4-t-butyl-6-t-butylphenol)
sold as Isonox 128, 2,2-methylene-bis(4-methyl-6-t-butylphenol) sold as AO 2246, 2,2'-thio-bis(4-methyl-6-t-butylphenol)
sold as CAO-6, 4,4'-thio-bis(3-methyl-6-t-butyl-phenol) sold as Santowhite Crystals,
butylated reaction product of p-cresol and dicyclopentadiene that is sold under the
trade name of Wingstay L®, 1,3,5-trimethyl-2,4,6-tris(3,5-t-butyl-4-hydroxybenzyl)
benzene sold as A0330, di-ti-amyl hydroquinone, 3,5-di-t-butyl-4-hydroxyhydrocinnamic
acid triester with 1,3,5-tris (2-hydroxyethyl)-s-triazine-2,4-6-(1H, 3H, 5H) trione
that is available as Agerite SKT and Goodrite 3125, and 2,6-di-t-butyl-4-methylphenol,
known as BHT. Also preferred in this group is the reaction product of 4,4-isopropylidene-di-phenol,
isobutylene, and styrene which includes 2,2'-di-t-butyl bisphenol A, 2-t-butyl-2'-α-methylbenzyl
bisphenol A, 2,6-di-t-butylphenol, and 2-t-butyl-4-isopropylphenol. This type of antioxidant
is available under the trade name Superlite antioxidant.
[0025] Examples of suitable amine-type antioxidants include ketone-amine condensation products
such as the polymeric dihydrotrimethylquinoline and 6-ethoxy-1,2-dihydro-2,2,4-tri-methylquinoline;
diaryldiamines such as N,N'-diphenyl-p-phenylenediamine and N,N'-di-β-naphthyl-p-phenylenediamine;
diarylamines include alkylated diphenylamines such as monooctyl diphenylamine and
dioctyl diphenylamine; and ketone-diarylamine condensation products that include complex
mixtures obtained by the reaction of diphenylamine and acetone.
[0026] The preferred amine-type of antioxidants suitable for purposes herein are the diaryldiamines,
especially N,N'-di-β-naphthyl-p-phenylenediamine.
[0027] After admixing the odor inhibiting agent to the acrylic latex, the latex is compounded
with fluorocarbons, cationic additives, and other additives to prevent static build-up
and achieve other results. The finished latex is then applied to the web or mat of
fibers in any suitable fashion such as by spraying, dipping, roll-transfer, or the
like. Application of the latex to the fibers is preferably made at room temperature
to facilitate cleaning of the associated apparatus. The solids concentration of the
latex can be in the range of 5% to 60% by weight, and preferably from 5% to 35% when
applied by dipping. When applied by roll-transfer, solids concentration of the latex
is generally about 50% whereas with the spraying technique, it an range widely.
[0028] The proportion of the latex polymer that is applied to the web or mat is such as
to provide 10 to 100%, preferably 25% to 40% by weight of the polymer, based on the
total weight of the polymer and fibers. After application of the latex to the fibrous
web, the impregnated or saturated web is dried either at room temperature or at elevated
temperature. The web is subjected, either after completion of the drying or as the
final step of the drying stage itself, to a baking or curing operation which may be
effected at a temperature of 98.9 to 260°C (210° to 500° F) for a period which may
range from about one-half hour at the lower temperatures to as low as five seconds
at the upper temperatures. The conditions of drying and curing are controlled so that
no appreciable deterioration or degradation of the fibers or polymer occurs. preferably
the curing is effected at a temperature Preferably, the curing is effected at a temperature
of 115.5 °C to 176.7° C (240° to 350° F) for a period under 3 minutes.
[0029] The fibers that are bonded with the latices described herein are formed into nonwoven
mats or webs in which they are ordered or are randomly distributed. The fibers may
comprise natural textile fibers such as jute, sisal, ramie, hemp and cotton, as well
as many of the artificial organic textile fibers including rayon, those of cellulose
esters such as cellulose acetate, vinyl resin fibers such as those of polyvinyl chloride
and copolymers thereof, polyacrylonitrile and copolymers thereof, polymers and copolymers
of olefins such as ethylene and propylene, condensation polymers such as polyimides
or nylon types, polyesters, and the like. The fibers used can be those of a single
composition or mixtures of fibers in a given web.
[0030] The preferred fibers for purposes herein are hydrophilic, especially cellulosic fibers,
and blends of hydrophobic and hydrophilic fibers. Examples of hydrophobic fibers include
polyester, polypropylene, and nylon fibers.
[0031] The acrylic latexes described herein, together with an odor inhibition agent admixed
therein, can be further compounded with fluorocarbons, cationic additives, and other
additives, in order to reduce static build-up, to obtain repellency, and achieve other
results. The finished latex is then used to bond fibers which are subsequently formed
into a nonwoven fabric, which, in turn, is used to make products that are used in
the medical/surgical applications. Examples of such products, as already disclosed,
include surgical caps, gowns, drapes, and wraps for surgical instruments. Since surgical
uses require sterilized fabric, such products are wrapped in a plastic bag and sterilized,
as by gamma ray irradiation. The plastic bag can be any suitable plastic including
polyolefins, polyesters, polyvinyl chloride, and the like. The instrument wrap is
used to wrap surgical instruments and then is sterilized, as with steam.
[0032] Sterilization by irradiation is generally accomplished using cobalt 60 at about 2.5
mega rads. Sterilization with steam is accomplished by the following schedule:
(a) 5 minutes to heat up to 135° C (275° F),
(b) 5 minutes at 135° C (275° F), and
(c) 5 minutes to cool before opening autoclave.
[0033] As was already mentioned, nonwoven fabrics bonded with acrylic latexes and subjected
to sterilization conditions noted above produced foul odors that have been described
as acidic and irritating to eyes and nose. A sample of finished acrylic latex, prepared
in absence of an odor inhibition agent and used as a bonding agent for making a nonwoven
fabric composed mostly of cellulosic fibers and a smaller amount of polyester fibers,
gave an odor panel rating of 3.2 on sterilization of the fabric. This acrylic latex
was prepared by polymerizing certain monomers in the presence of about 0.5 weight
part sodium persulfate initiator and about 0.5 weight part of sodium lauryl sulfate
emulsifier. The latex was prepared by polymerizing the following monomers, in the
indicated amounts, at about 80° C:
(a) |
n-butyl acrylate |
75 wt. parts |
(b) |
styrene |
20 wt. parts |
(c) |
glacial acrylic acid |
3 wt. parts |
(d) |
N-methylol acrylamide |
2 wt. parts |
The polymerization procedure utilized consisted of the initial preparation in a premix
pot of a premix of the monomers, some water and some emulsifier. Remainder of water
and emulsifier were added to a reactor which was then heated to the polymerization
temperature of about 80° C. While heating to the polymerization temperature, a portion
of the initiator was added to the reactor. After reaching the desired temperature,
the premix was added at a controlled rate. Once all of the premix was added to the
reactor, remainder of the initiator was also added to the reactor and the reaction
was maintained for about two hours under constant agitation. When the desired conversion
of 99% + was reached, the latex was cooled and stripped. The resulting latex had 47.5%
solids.
[0034] Different samples of the acrylic latex described above were prepared by admixing
antioxidants and then further compounding the latexes with fluorocarbons, cationic
agents, and other materials, before using the finished latexes to form nonwoven fabrics
from which surgical products were made. The surgical products were packed in a plastic
bag and sterilized by gamma ray irradiation. procedure used in preparing latex, nonwoven
fabric, and sterilization was identical in each case except for inclusion of different
odor inhibition agents in the latex samples.
[0035] The odor rating was obtained by opening a pack of nonwoven fabric that was sterilized
with gamma radiation. The pack was opened in a closed room measuring about 3.05m by
3.05m (10' by 10'). Each pack contained 16.7m
2 (20 square yards) of a nonwoven fabric, all of which was spread out in the room.
After the fabric laid spread out in the room for 5 minutes, a panel of 10 persons
entered the room and rated the odor intensity on a scale of 1 to 5, defined as follows:
- 1 =
- neutral
- 2 =
- slightly offensive
- 3 =
- mildly offensive
- 4 =
- moderately offensive
- 5 =
- extremely offensive
A number of odor inhibition agents were evaluated in this manner, results of which
are tabulated in Table I below, which indicate the level of agent on dry basis, admixed
with the acrylic latex, and the resulting averaged odor rating:
TABLE I
Additive |
Amount |
Odor Rating |
None |
0 |
3.2 |
Wingstay® 29 |
0.5 phr |
2.7 |
Wingstay L® |
0.5 phr |
2.1 |
Antioxidant SP® |
0.5 phr |
2.9 |
Naugawhite® |
0.5 phr |
2.5 |
Agerite White@ |
0.5 phr |
2.5 |
BHT® |
0.5 phr |
2.5 |
Santowhite Crystals® |
0.5 phr |
2.4 |
AO 425® |
0.5 phr |
2.4 |
Superlite® |
0.5 phr |
2.4 |
Agerite SKT® |
0.5 phr |
2.7 |
Goodrite® 3125 |
0.5 phr |
2.4 |
A0330® |
0.5 phr |
2.7 |
DTAHQ |
0.5 phr |
2.5 |
Wingstay 29 is a p-oriented styrenated diphenylamine, Wingstay L is a butylated reaction
product of p-cresol and dicyclopentadiene, Antioxidant SP stabilizer is a styrenated
phenol containing 1 to 3 styrene groups attached to the benzene ring, Naugawhite is
2,2' -methylenebis(4-methyl-6-t-butylphenol), Agerite White is N,N'-dinaphthyl-p-phenylene
diamine, BHT is 2,6-di-t-butyl-4-methyl-phenol, Santowhite Crystals is 4,4'-thio-bis(3-methyl-6-t-butylphenol),
AO 425 is 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), and Superlite is a reaction
product of bisphenol A, isobutylene, and styrene reacted at about 70° C under 0-10
psig of pressure for a period of about 4 1/2 hours in presence of a clay catalyst.
[0036] Additionally, A0330 is 1,3,5-trimethyl-2,4,6-tris (3,5-t-butyl-4-hydroxybenzyl) benzene,
DTAHQ is di-t-amyl hydroquinone, and both Agerite SKT and Goodrite 3125 are 3,5-di-t-butyl-4-hydroxyhydrocinnamic
acid triester with 1,3,5-tris (2-hydroxyethyl)-s-triazine-2,4,6-(1H,3H,5H)trione.
[0037] When styrene was replaced with the same weight of methyl methacrylate in the preparation
of the latex sample with 0.5 phr of Superlite stabilizer, otherwise prepared and tested
identically as described above, the fabric gave an odor rating of 2.0.
[0038] The data presented in Table I has a statistical deviation of ±0.5 unit for any single
determination, however, the above data represents averages of many determinations.
[0039] The latexes described herein are adapted for use as binders for fibers which are
made into nonwoven fabrics. These fabrics have applications in the medical/surgical
field which require repellancy to body fluids such as blood, urine, and perspiration.
The repellency is measured in terms of repellency to alcohol and saline solution.
Due to the particular applications wherein the nonwoven fabric comes in contact with
human body, the latexes of this invention require properties such as softness, physical
strength, hydrophobicity, low skin toxicity, adhesion during forming of the nonwoven
fabric, and of course, minimal odor after sterilization.
[0040] To obtain a hydrophobic latex that will have the repellency property, it is necessary
to select hydrophobic monomers and to have a low content of anionic emulsifier since
it is known that hydrophobicity of the latex can be increased by reducing the level
of emulsifier. Also, hydrophobicity of the latex can be enhanced by compounding the
latex with materials such as fluorocarbons. An anionic emulsifier level of 3 phr,
per 100 parts of dry latex, is normally considered high whereas less than 1.0 phr
is normally considered to be low. A high content of anionic emulsifier in a latex
recipe will not result in a repellent latex, however, the desired repellency may result
if the latex is compounded with materials such as fluorocarbons. A higher level of
nonionic emulsifier of up to about 5 phr can be used, relative to anionic emulsifier,
to maintain repellency. The use of an unsaturated acid in conjunction with a N-alkylol
acrylamide allows the curing to proceed more efficiently and at a lower temperature.
However, in the past, an acid-containing latex made on a commercial scale had to contain
in excess of 1.0 phr emulsifier to remain stable and whenever amount of emulsifer
was less than 1.0 phr, the resulting latex was unstable, meaning that it contained
floc, i.e., agglomerated particles.
[0041] Selection of specific soft and hard hydrophobic monomers, as described herein, allows
the preparation of a soft, repellent latex by the use of a low level of an emulsifier.
This is the first time that it was possible to produce a hydrophobic polymer in a
low-emulsifer recipe and this is also the first time that it was possible to successfully
combine carboxyl and N-alkylol acrylamide chemistry in a low-emulsifier recipe to
produce a stable, soft, and repellent latex. Previous work appeared to require the
functionality of acrylamide and N-alkylol acrylamide.
1. Sterilized nonwoven fabric comprising nonwoven fibers bonded with a saturated latex
prepared by free radical initiation comprising a preponderance of a soft hydrophobic
mononer having Tg in the range of -80° C to -20° C, a lesser amount of a hard hydrophobic
monomer having Tg in the range of + 40° C to +120° C, a small amount of an unsaturated
carboxylic acid a sufficient amount of an emulsifier and a small amount of N-alkylol
acrylamide or methacrylamide, characterized in that said latex having admixed therein
0.01 to 5 weight parts per 100 weight parts of latex solids of an odor inhibition
agent selected from amine-type antioxidants and hindered phenols that have the function
of reducing the odor that is generated on sterilization of the nonwoven fabric.
2. Nonwoven fabric of claim 1 that is repellent to body fluids wherein said latex is
prepared by polymerizing, in presence of 0.1 to 2 weight parts of an initiator and
less than 1.0 weight part of anionic emulsifier, 65 to 85 weight parts of a soft monomer,
10 to 30 weight parts of a hard monomer, 0.1 to 5 weight parts of an unsaturated carboxylic
acid containing 3 to 12 carbon atoms. and 0.1 to 5 weight parts of N-alkylol acrylamide
or methacrylamide containing 1 to 10 carbon atoms in the alkyl group.
3. Nonwoven fabric of claim 2 wherein said odor inhibition agent is selected from alkylated
hydroquinones and phenols, ketone-amine condensation products, diarylamines, diaryldiamines,
ketone-diarylamine condensation products, and mixtures thereof.
4. Nonwoven fabric of claim 2 made from at least a preponderance of cellulose fibers
and sterilized by irradiation or steam, wherein said odor inhibition agent is selected
from the following structures A, B, C and D:

where R groups are individually selected from hydrogen and alkyl groups of 1 to 12
carbon atoms, with at least one R group being selected from the alkyl groups; R
1 groups are individually selected from hydroxyl and lower alkyl groups; and X and
Y are selected from lower alkylene groups and sulfur.
5. Nonwoven fabric of claim 2 wherein said ordor inhibition agent is selected from 2,2'-methylene-bis(4-ethyl6-t-butylphenol);
2,2'-methylene-bis(4-methyl-6-nonylphenol); 2,2,-methylene-bis(4-t-butyl-6-1-butyl-phenol);
2,2-methylene-bis(4-methyl-6-t-butylphenol); butylated reaction product of p-cresol
and dicyclopentadiene, 2.6-di-t-butyl-4-methylphenol; reaction product of 4,4-isopropylidene-diphenol,
isobutylene, and styrene; 2.2'-thio-bis(4-methyl-6-t-butylphenol); 4,4'-thio-bis(3-methyl-6-t-butylphenol);
1,3,5-trimethyl-2,4,6-tris(3,5-t-butyl-4-hydroxybenzyl)benzene; di-t-amyl hydroquinone;
3,5-di-t-butyl-4-hydroxyhydrocinnamic acid triester with 1,3,5-tris(2-hydroxyethyl)-s-triazine-2,4,6-(1H,3H,5H)
trione; polymeric dihydrotrimethylquinoline: 6-ethoxy-1,2(dihydro-2,2,4-trimethylquinoline;
N,N'-diphenyl-p-phenylene-diamine; N,N'-di-β-naphthyl-p-phenylenediamine; alkylated
diphenylamines; reaction products of diphenylamine and acetone; and mixtures thereof.
6. Nonwoven fabric of claim 5 made from fibers selected from natural, synthetic, and
mixtures of such fibers, and sterilized by irradiation or steam wherein said soft
mononer is selected from n-butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate,
and mixtures thereof; said hard monomer is selected from styrene, α-methyl styrene,
methyl methacrylate, and mixtures thereof; said N-alkylol acrylamide or methacrylamide
is selected from N-methylol acrylamide and methacrylamide, N-butylol acrylamide and
methacrylamide, n- and iso-butoxy methyl acrylamide, and mixtures thereof; and said
unsaturated acid is selected from acrylic acid, methacrylic acid, itaconic acid, fumaric
acid, maleic acid, and mixtures thereof.
7. Method of making sterilized nonwoven fabric comprising bonding nonwoven fibers with
a saturated latex, forming a nonwoven fabric from the bonded fibers, and sterilizing
said nonwoven fabric; said nonwoven fibers are bonded with a saturated latex prepared
by free radical initiation conprising a preponderance of a soft hydrophobic monomer
having Tg in the range of -80° C to -20° C, a lesser amount of a hard hydrophobic
monomer having Tg in the range of +40° C to +120° C. a sufficient amount of an unsaturated
carboxylic acid, a small amount of an emulsifier and a small amount of N-alkylol acrylamide
or methacrylamide characterized in that said latex having admixed therein 0.01 to
5 weight parts per 100 weight parts of latex solids of an odor inhibition agent selected
from hindered phenols and amine-type antioxidants that have the function of reducing
the odor that is generated on sterilization of the nonwoven fabric.
8. Method of claim 7 wherein said odor inhibition agent is selected from alkylated hydroquinones
and phenols, ketone-amine condensation products, diarylamines, diaryldiamines, ketone-diarylamine
condensation products, and mixtures thereof.
9. Method of claim 7 wherein said agent is selected from 2.2'-methylene-bis(4-ethyl-6-tbutylphenol):
2.2'-methylene-bis(4-methyl-6-nonylphenol); 2.2'-methylene-bis(4-1-butyl-6-t-butylphenol);
2.2-methylene-bis-(4-methyl-6-t-butylphenol); butylated reaction product of p-cresol
and dicyclopentadiene, 2,6-di-t-butyl-4-methylphenol; reaction product of 4,4-isopropylidene-diphenol,
isobutylene, and styrene: 2,2'-thio-bis-(4-methyl-6-t-butylphenol); 4,4'-thio-bis(3-methyl-6-t-butylphenol);
1,3,5-trimethyl-2,4,6-tris(3,5-t-butyl-4-hydroxybenzyl)benzene; di-t-amyl hydroquinone;
3,5-di-t-butyl-4-hydroxyhydrocinnamic acid triester with 1,3,5-tris(2-hydroxyethyl)-s-triazine-2,4,6-(1H,3H,5H)trione;
polymeric dihydrotrimethylquinoline; 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline;
N,N'-diphenyl-p-phenylene-diamine N,N'-di-β-naphthyl-p-phenylenediamine; alkylated
diphenylamines; and reaction products of diphenylamine and acetone; and mixtures thereof.
10. Method of claim 9 made from at least a preponderance of cellulose fibers and sterilized
by irradiation or steam wherein said soft monomer is selected from n-butyl acrylate.
2-ethylhexyl acrylate, isobutyl acrylate, and mixtures thereof; said hard monomer
is selected from styrene, α-methyl styrene, methyl methacrylate, and mixtures thereof;
said N-alkylol acrylamide or methacrylamide is selected from N-methylol acrylamide
and methacrylamide, N-butylol acrylamide and methacrylamide, n-and iso-butoxy methyl
acrylamide, and mixtures thereof; and said unsaturated acid is selected from acrylic
acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, and mixtures thereof.
11. A saturated latex prepared by free radical initiation comprising a preponderance of
a soft hydrophobic monomer having Tg in the range of -80°C to -20°C, a lesser amount
of a hard hydrophobic monomer having Tg in the range of +40° C to +120° C, a small
amount of an unsaturated carboxylic acid, a sufficient amount of an emulsifier and
a small amount of N-alkylol acrylamide or methacrylamide characterized in that said
latex having admixed therein 0.01 to 5 weight parts per 100 weight parts of latex
solids of an odor inhibition agent selected from amine-type antioxidants and hindered
phenols that have the function of reducing the odor that is generated on sterilization
of the nonwoven fabric bonded therewith.
12. Latex of claim 11 wherein said latex is prepared by polymerizing, in presence of 0.1
to 2 weight parts of an initiator and less than 1.0 weight part of anionic emulsifier,
65 to 85 weight parts of a soft monomer, 10 to 30 weight parts of a hard monomer,
0.1 to 5 weight parts of an unsaturated carboxylic acid containing 3 to 12 carbon
atoms, and 0.1 to 5 weight parts of N-alkylol acrylamide or methacrylamide containing
1 to 10 carbon atoms in the alkyl group.
13. Latex of claim 12 wherein said odor inhibition agent is selected from alkylated hydroquinones
and phenols, ketone-amine condensation products, diarylamines, diaryldiamines, ketone-diarylamine
condensation products, and mixtures thereof.
14. Latex of claim 12 wherein said odor inhibition agent is selected from the following
structures A, B, C and D:

where R groups are individually selected from hydrogen and alkyl groups of 1 to 12
carbon atoms. with at least one R group being selected from the alkyl groups; R' groups
are individually selected from hydroxyl and lower alkyl groups; and X and Y are selected
from lower alkylene groups and sulfur.
15. Latex of claim 12 wherein said agent is selected from 2,2'-methylene-bis(4-ethyl6-t-butylphenol);
2.2'-methylene-bis(4-methyl-6-nonylphenol); 2,2'-methylene-bis(4-1-butyl-6-t-butylphenol);
2.2-methylene-bis-(4-methyl-6-t-butylphenol); butylated reaction product of p-cresol
and dicyclopentadiene, 2,6-di-t-butyl-4-methylphenol; reaction product of 4,4-isopropylidene-diphenol,
isobutylene, and styrene; 2,2-thio-bis-(4-methyl-6-t-butylphenol); 4,4'-thio-bis(3-methyl-6-t-butylphenol);
1,3,5-trimethyl-2,4,6-tris(3,5-t-butyl-4-hydroxybenzyl)benzene; di-t-amyl hydroquinone;
3,5-di-t-butyl-4-hydroxyhydrocinnamic acid triester with 1,3,5-tris(2-hydroxyethyl)-s-triazine-2,4,6-(1H,3H,5H)
trione; polymeric dihydrotrimethylquinoline; 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline;
N,N'-diphenyl-p-phenylene-diamine; N,N'-di-β-naphthyl-p-phenylenediamine; alkylated
diphenylamines; and reaction products of diphenylamine and acetone; and mixtures thereof.
16. Latex of claim 15 wherein said soft monomer is selected from n-butyl acrylate, 2-ethylhexyl
acrylate, isobutyl acrylate, and mixtures thereof; said hard monomer is selected from
styrene, α-methyl styrene, methyl methacrylate, and mixtures thereof; said N-alkylol
acrylamide or methacrylamide is selected from N-methylol acrylamide and methacrylamide,
N-butylol acrylamide and methacrylamide, n- and iso-butoxy methyl acrylamide, and
mixtures thereof; and said unsaturated acid is selected from acrylic acid, methacrylic
acid, itaconic acid, fumaric acid, maleic acid, and mixtures thereof.
1. Sterilisierter Vliesstoff, umfassend Vlies-Fasern, die mittels eines gesättigten Latex
gebunden sind, der durch radikalische Initiation hergestellt ist, umfassend eine überwiegende
Menge eines weichen hydrophoben Monomers mit einem Tg-Wert im Bereich von -80°C bis
-20°C, eine geringere Menge eines harten hydrophoben Monomers mit einem Tg-Wert im
Bereich von +40°C bis +120°C, eine kleine Menge einer ungesättigten Carbonsäure, eine
ausreichende Menge eines Emulgators und eine kleine Menge eines N-Alkylolacrylamids
oder -methacrylamids, dadurch gekennzeichnet, daß dem Latex 0,01 bis 5 Gewichtsteile,
auf 100 Gewichtsteile der Latex-Feststoffe, eines geruchshemmenden Mittels zugesetzt
sind, das ausgewählt ist aus Antioxidationsmitteln vom Amin-Typ und gehinderten Phenolen,
die die Funktion haben, den Geruch zu verringern, der bei der Sterilisation des Vliesstoffs
erzeugt wird.
2. Vliesstoff nach Anspruch 1, der Körperflüssigkeiten abweist, wobei der Latex durch
Polymerisieren von 65 bis 85 Gewichtsteilen eines weichen Monomers, 10 bis 30 Gewichtsteilen
eines harten Monomers, 0,1 bis 5 Gewichtsteilen einer ungesättigten Carbonsäure mit
3 bis 12 Kohlenstoffatomen und 0,1 bis 5 Gewichtsteilen eines N-Alkylolacrylamids
oder -methacrylamids mit 1 bis 10 Kohlenstoffatomen in der Alkylgruppe in Gegenwart
von 0,1 bis 2 Gewichtsteilen eines Initiators und weniger als 1,0 Gewichtsteilen eines
anionischen Emulgators hergestellt ist.
3. Vliesstoff nach Anspruch 2, wobei das geruchshemmende Mittel aus alkylierten Hydrochinonen
und Phenolen, Keton-Amin-Kondensationsprodukten, Diarylaminen, Diaryldiaminen, Keton-Diarylamin-Kondensationsprodukten
und deren Mischungen ausgewählt ist.
4. Vliesstoff nach Anspruch 2, der aus wenigstens einer überwiegenden Menge Cellulosefasern
hergestellt und durch Bestrahlung oder mittels Dampf sterilisiert ist, wobei das geruchshemmende
Mittel aus den folgenden Strukturen A, B, C und D ausgewählt ist:

wobei die Gruppen R unabhängig aus Wasserstoff und Alkyl-Gruppen mit 1 bis 12 Kohlenstoffatomen
ausgewählt sind, wobei wenigstens eine Gruppe R aus den Alkylgruppen ausgewählt ist,
die Gruppen R
1 unabhängig aus Hydroxy und Niederalkylgruppen ausgewählt sind und X und Y aus Niederalkylengruppen
und Schwefel ausgewählt sind.
5. Vliesstoff nach Anspruch 2, wobei das geruchshemmende Mittel aus 2,2'-Methylenbis
(4-ethyl-6-t-butylphenol), 2,2'-Methylenbis (4-methyl-6-nonylphenol), 2,2'-Methylen-bis(4-t-butyl-6-t-butylphenol),
2,2'-Methylenbis (4-methyl-6-t-butylphenol), dem butylierten Reaktionsprodukt von
p-Cresol und Dicyclopentadien, 2,6-Di-t-butyl-4-methylphenol, dem Reaktionsprodukt
von 4,4-Isopropylidendiphenol, Isobutylen und Styrol, 2,2'-Thiobis(4-methyl-6-t-butylphenol),
4,4'-Thiobis (3-methyl-6-t-butylphenol), 1,3,5-Trimethyl-2,4,6-tris(3,5-t-butyl-4-hydroxybenzyl)-benzol,
Di-t-amylhydrochinon, 3,5-Di-t-butyl-4-hydroxy-hydrozimtsäuretriester mit 1,3,5-Tris(2-hydroxyethyl)-s-triazin-2,4,6(1H,3H,5H)-trion,
polymerem Dihydrotrimethylchinolin, 6-Ethoxy-1,2-dihydro-2,2,4-trimethylchinolin,
N,N'-Diphenyl-p-phenylendiamin, N,N'-Di-β-naphthyl-p-phenylendiamin, alkylierten Diphenylaminen,
Reaktionsprodukten von Diphenylamin und Aceton und deren Mischungen ausgewählt ist.
6. Vliesstoff nach Anspruch 5, der aus Fasern, die aus natürlichen Fasern, synthetischen
Fasern und Mischungen derartiger Fasern ausgewählt sind, hergestellt und durch Bestrahlung
oder mittels Dampf sterilisiert ist, wobei das weiche Monomer aus n-Butylacrylat,
2-Ethylhexylacrylat, Isobutylacrylat und deren Mischungen ausgewählt ist, das harte
Monomer aus Styrol, α-Methylstyrol, Methylmethacrylat und deren Mischungen ausgewählt
ist, das N-Alkylolacrylamid oder -methacrylamid aus N-Methylolacrylamid und -methacrylamid,
N-Butylolacrylamid und -methacrylamid, n- und iso-Butoxymethylacrylamid und deren
Mischungen ausgewählt ist und die ungesättigte Säure aus Acrylsäure, Methacrylsäure,
Itaconsäure, Fumarsäure, Maleinsäure und deren Mischungen ausgewählt ist.
7. Verfahren zur Herstellung eines sterilisierten Vliesstoffs, umfassend das Binden von
Vlies-Fasern mittels eines gesättigten Latex, das Bilden eines Vliesstoffs aus den
gebundenen Fasern und das Sterilisieren des Vliesstoffs, wobei die Vlies-Fasern mittels
eines gesättigten Latex gebunden werden, der durch radikalische Initiation hergestellt
ist, umfassend eine überwiegende Menge eines weichen hydrophoben Monomers mit einem
Tg-Wert im Bereich von -80°C bis -20°C, eine geringere Menge eines harten hydrophoben
Monomers mit einem Tg-Wert im Bereich von +40°C bis +120°C, eine ausreichende Menge
einer ungesättigten Carbonsäure, eine kleine Menge eines Emulgators und eine kleine
Menge eines N-Alkylolacrylamids oder -methacrylamids, dadurch gekennzeichnet, daß
dem Latex 0,01 bis 5 Gewichtsteile, auf 100 Gewichtsteile der Latex-Feststoffe, eines
geruchshemmenden Mittels zugesetzt sind, das ausgewählt ist aus gehinderten Phenolen
und Antioxidationsmitteln vom Amin-Typ, die die Funktion haben, den Geruch zu verringern,
der bei der Sterilisation des Vliesstoffs erzeugt wird.
8. Verfahren nach Anspruch 7, wobei das geruchshemmende Mittel aus alkylierten Hydrochinonen
und Phenolen, Keton-Amin-Kondensationsprodukten, Diarylaminen, Diaryldiaminen, Keton-Diarylamin-Kondensationsprodukten
und deren Mischungen ausgewählt ist.
9. Verfahren nach Anspruch 7, wobei das Mittel aus 2,2'-Methylenbis (4-ethyl-6-t-butylphenol),
2,2'-Methylenbis(4-methyl-6-nonylphenol), 2,2'-Methylenbis (4-t-butyl-6-t-butylphenol),
2,2'-Methylenbis (4-methyl-6-t-butylphenol), dem butylierten Reaktionsprodukt von
p-Cresol und Dicyclopentadien, 2,6-Di-t-butyl-4-methylphenol, dem Reaktionsprodukt
von 4,4-Isopropylidendiphenol, Isobutylen und Styrol, 2,2'-Thiobis(4-methyl-6-t-butylphenol),
4,4'-Thiobis (3-methyl-6-t-butylphenol), 1,3,5-Trimethyl-2,4,6-tris(3,5-t-butyl-4-hydroxybenzyl)benzol,
Di-t-amylhydrochinon, 3,5-Di-t-butyl-4-hydroxyhydrozimtsäuretriester mit 1,3,5-Tris(2-hydroxyethyl)-s-triazin-2,4,6(1H,3H,5H)-trion,
polymerem Dihydrotrimethylchinolin, 6-Ethoxy-1,2-dihydro-2,2,4-trimethylchinolin,
N,N'-Diphenyl-p-phenylendiamin, N,N'-Di-β-naphthyl-p-phenylendiamin, alkylierten Diphenylaminen,
Reaktionsprodukten von Diphenylamin und Aceton und deren Mischungen ausgewählt ist.
10. Verfahren nach Anspruch 9, wobei der Vliesstoff aus wenigstens einer überwiegenden
Menge Cellulosefasern hergestellt und durch Bestrahlung oder mittels Dampf sterilisiert
ist, wobei das weiche Monomer aus n-Butylacrylat, 2-Ethylhexylacrylat, Isobutylacrylat
und deren Mischungen ausgewählt ist, das harte Monomer aus Styrol, α-Methylstyrol,
Methylmethacrylat und deren Mischungen ausgewählt ist, das N-Alkylolacrylamid oder
-methacrylamid aus N-Methylolacrylamid und -methacrylamid, N-Butylolacrylamid und
-methacrylamid, n- und iso-Butoxymethylacrylamid und deren Mischungen ausgewählt ist
und die ungesättigte Säure aus Acrylsäure, Methacrylsäure, Itaconsäure, Fumarsäure,
Maleinsäure und deren Mischungen ausgewählt ist.
11. Gesättigter Latex, hergestellt durch radikalische Initiation, umfassend eine überwiegende
Menge eines weichen hydrophoben Monomers mit einem Tg-Wert im Bereich von -80°C bis
-20°C, eine geringere Menge eines harten hydrophoben Monomers mit einem Tg-Wert im
Bereich von +40°C bis +120°C, eine kleine Menge einer ungesättigten Carbonsäure, eine
ausreichende Menge eines Emulgators und eine kleine Menge eines N-Alkylolacrylamids
oder -methacrylamids, dadurch gekennzeichnet, daß dem Latex 0,01 bis 5 Gewichtsteile,
auf 100 Gewichtsteile der Latex-Feststoffe, eines geruchshemmenden Mittels zugesetzt
sind, das ausgewählt ist aus Antioxidationsmitteln vom Amin-Typ und gehinderten Phenolen,
die die Funktion haben, den Geruch zu verringern, der bei der Sterilisation des damit
gebundenen Vliesstoffs erzeugt wird.
12. Latex nach Anspruch 11, wobei der Latex durch Polymerisieren von 65 bis 85 Gewichtsteilen
eines weichen Monomers, 10 bis 30 Gewichtsteilen eines harten Monomers, 0,1 bis 5
Gewichtsteilen einer ungesättigten Carbonsäure mit 3 bis 12 Kohlenstoffatomen und
0,1 bis 5 Teilen eines N-Alkylolacrylamids oder -methacrylamids mit 1 bis 10 Kohlenstoffatomen
in der Alkylgruppe in Gegenwart von 0,1 bis 2 Gewichtsteilen eines Initiators und
weniger als 1,0 Gewichtsteilen eines anionischen Emulgators hergestellt ist.
13. Latex nach Anspruch 12, wobei das geruchshemmende Mittel aus alkylierten Hydrochinonen
und Phenolen, Keton-Amin-Kondensationsprodukten, Diarylaminen, Diaryldiaminen, Keton-Diarylamin-Kondensationsprodukten
und deren Mischungen ausgewählt ist.
14. Latex nach Anspruch 12, wobei das geruchshemmende Mittel aus den folgenden Strukturen
A, B, C und D ausgewählt ist:

wobei die Gruppen R unabhängig aus Wasserstoff und Alkyl-Gruppen mit 1 bis 12 Kohlenstoffatomen
ausgewählt sind, wobei wenigstens eine Gruppe R aus den Alkylgruppen ausgewählt ist,
die Gruppen R
1 unabhängig aus Hydroxy und Niederalkylgruppen ausgewählt sind und X und Y aus Niederalkylengruppen
und Schwefel ausgewählt sind.
15. Latex nach Anspruch 12, wobei das Mittel aus 2,2'-Methylenbis (4-ethyl-6-t-butylphenol),
2,2'-Methylenbis(4-methyl-6-nonylphenol), 2,2'-Methylenbis (4-t-butyl-6-t-butylphenol),
2,2'-Methylenbis(4-methyl-6-t-butylphenol), dem butylierten Reaktionsprodukt von p-Cresol
und Dicyclopentadien, 2,6-Di-t-butyl-4-methylphenol, dem Reaktionsprodukt von 4,4-Isopropylidendiphenol,
Isobutylen und Styrol, 2,2'-Thiobis (4-methyl-6-t-butylphenol), 4,4'-Thiobis (3-methyl-6-t-butylphenol),
1,3,5-Trimethyl-2,4,6-tris(3,5-t-butyl-4-hydroxybenzyl)benzol, Di-t-amylhydrochinon,
3,5-Di-t-butyl-4-hydroxyhydrozimtsäuretriester mit 1,3,5-Tris(2-hydroxyethyl)-s-triazin-2,4,6(1H,3H,5H)-trion,
polymerem Dihydrotrimethylchinolin, 6-Ethoxy-1,2-dihydro-2,2,4-trimethylchinolin,
N,N'-Diphenyl-p-phenylendiamin, N,N'-Di-β-naphthyl-p-phenylendiamin, alkylierten Diphenylaminen,
Reaktionsprodukten von Diphenylamin und Aceton und deren Mischungen ausgewählt ist.
16. Latex nach Anspruch 15, wobei das weiche Monomer aus n-Butylacrylat, 2-Ethylhexylacrylat,
Isobutylacrylat und deren Mischungen ausgewählt ist, das harte Monomer aus Styrol,
α-Methylstyrol, Methylmethacrylat und deren Mischungen ausgewählt ist, das N-Alkylolacrylamid
oder -methacrylamid aus N-Methylolacrylamid und -methacrylamid, N-Butylolacrylamid
und -methacrylamid, n- und iso-Butoxymethylacrylamid und deren Mischungen ausgewählt
ist und die ungesättigte Säure aus Acrylsäure, Methacrylsäure, Itaconsäure, Fumarsäure,
Maleinsäure und deren Mischungen ausgewählt ist.
1. Etoffe non tissée stérilisée comprenant des fibres non tissées liées par un latex
saturé préparé par polymérisation par amorçage de radicaux libres, comprenant une
prépondérance d'un monomère hydrophobe souple ayant une Tv dans la plage de -80°C
à -20°C, une quantité moindre d'un monomère hydrophobe rigide ayant une Tv dans la
plage de +40°C à +120°C, une petit quantité d'un acide carboxylique insaturé, une
quantité suffisante d'un émulsifiant et une petite quantité d'un N-alkylolacrylamide
ou méthacrylamide, caractérisée en ce que dans ledit latex sont incorporées de 0,01
à 5 parties en poids pour 100 parties en poids de solides de latex d'un agent d'inhibition
d'odeur choisi parmi des antioxydants de type amine et des phénols à empêchement stérique
qui ont la fonction de diminuer l'odeur qui est engendrée lors de la stérilisation
de l'étoffe non tissée.
2. Etoffe non tissée selon la revendication 1, qui est répulsive à l'égard de liquides
de l'organisme, dans laquelle ledit latex est préparé par polymérisation, en présence
de 0,1 à 2 parties en poids d'un amorceur et de moins de 1,0 partie en poids d'un
émulsifiant anionique, de 65 à 85 parties en poids d'un monomère souple, de 10 à 30
parties en poids d'un monomère rigide, de 0,1 à 5 parties en poids d'un acide carboxylique
insaturé contenant de 3 à 12 atomes de carbone, et de 0,1 à 5 parties en poids d'un
N-alkylolacrylamide ou -méthacrylamide contenant de 1 à 10 atomes de carbone dans
le groupe alkyle.
3. Etoffe non tissée selon la revendication 2, dans laquelle ledit agent d'inhibition
d'odeur est choisi parmi des hydroquinones alkylées et des phénols alkylés, des produits
de condensation de cétones et d'amines, des diarylamines, des diaryldiamines, des
produits de condensation de cétones et de diarylamines, et des mélanges de ceux-ci.
4. Etoffe non tissée selon la revendication 2, produite à partir d'au moins une prépondérance
de fibres cellulosiques et stérilisée par irradiation ou à la vapeur, dans laquelle
ledit agent d'inhibition d'odeur est choisi parmi les structures A, B, C et D suivantes:

dans lesquelles les groupes R sont individuellement choisis parmi un atome d'hydrogène
et des groupes alkyle ayant de 1 à 12 atomes de carbone, au moins un groupe R étant
choisi parmi les groupes alkyle, les groupes R
1 sont individuellement choisis parmi le groupe hydroxy et des groupes alkyle inférieurs;
et X et Y sont choisis parmi un atome de soufre et des groupes alkylène inférieurs.
5. Etoffe non tissée selon la revendication 2, dans laquelle ledit agent d'inhibition
d'odeur est choisi parmi le 2,2'-méthylène-bis(4-éthyl-6-tert-butylphénol); le 2,2'-méthylène-bis(4-méthyl-6-nonylphénol);
le 2,2'-méthylène-bis-(4-tert-butyl-6-tert-butylphénol); le 2,2-méthylène-bis(4-méthyl-6-tert-butylphénol);
un produit de réaction butylé de p-crésol et dicyclopentadiène; le 2,6-di-tert-butyl-4-méthyl-phénol;
un produit de réaction de 4,4-isopropylidène-diphénol, isobutylène et styrène; le
2,2'-thio-bis(4-méthyl-6-tert-butylphénol); le 4,4'-thio-bis(3-méthyl-6-tert-butyl-phénol);
le 1,3,5-triméthyl-2,4,6-tris(3,5-tert-butyl-4-hydroxybenzyl)benzène; la di-tert-amylhydroquinone;
le triester de l'acide 3,5-di-tert-butyl-4-hydroxyhydrocinnamique avec la 1,3,5-tris(2-hydroxyéthyl)-s-triazine-2,4,6-(1H,3H,5H)trione;
une dihydrotriméthylquinoléine polymère; la 6-éthoxy-1,2-dihydro-2,2,4-triméthylquinoléine;
la N,N'-diphényl-p-phénylène-diamine; la N,N'-di-p-naphtyl-p-phénylènediamine; des
diphénylamines alkylées; des produits de réaction de diphénylamine et d'acétone; et
des mélanges de ceux-ci.
6. Etoffe non tissée selon la revendication 5, produite à partir de fibres choisies parmi
des fibres naturelles, synthétiques et des mélanges de celles-ci, et stérilisée par
irradiation ou à la vapeur, dans laquelle ledit monomère souple est choisi parmi l'acrylate
de n-butyle, l'acrylate de 2-éthylhexyle, l'acrylate d'isobutyle et des mélanges de
ceux-ci; ledit monomère rigide est choisi parmi le styrène, l'α-méthylstyrène, le
méthacrylate de méthyle et des mélanges de ceux-ci; ledit N-alkylolacrylamide ou -méthacrylamide
est choisi parmi le N-méthylolacrylamide ou -méthacrylamide, le N-butylolacrylamide
ou -méthacrylamide, le n-ou iso-butoxyméthylacrylamide et des mélanges de ceux-ci;
et ledit acide insaturé est choisi parmi l'acide acrylique, l'acide méthacrylique,
l'acide itaconique, l'acide fumarique, l'acide maléique et des mélanges de ceux-ci.
7. Procédé de fabrication d'une étoffe non tissée stérilisée comprenant la liaison de
fibres non tissées par un latex saturé, la formation d'une étoffe non tissée à partir
des fibres liées et la stérilisation de ladite étoffe non tissée; lesdites fibres
nontissées sont liées par un latex saturé préparé par polymérisation par amorçage
de radicaux libres, comprenant une prépondérance d'un monomère hydrophobe souple ayant
une Tv dans la plage de -80°C à -20°C, une quantité moindre d'un monomère hydrophobe
rigide ayant une Tv dans la plage de +40°C à +120°C, une quantité suffisante d'un
acide carboxylique insaturé, une faible quantité d'un émulsifiant et une petite quantité
d'un N-alkylolacrylamide ou méthacrylamide, caractérisé en ce que sont incorporées
audit latex de 0,01 à 5 parties en poids pour 100 parties en poids de solides de latex
d'un agent d'inhibition d'odeur choisi parmi des phénols à empêchement stérique et
des antioxydants de type amine qui ont la fonction de diminuer l'odeur qui est engendrée
lors de la stérilisation de l'étoffe non tissée.
8. Procédé selon la revendication 7, dans lequel ledit agent d'inhibition d'odeur est
choisi parmi des hydroquinones alkylées et des phénols alkylés, des produits de condensation
de cétones et d'amines, des diarylamines, des diaryldiamines, des produits de condensation
de cétones et de diarylamines, et des mélanges de ceux-ci.
9. Procédé selon la revendication 7, dans lequel ledit agent est choisi parmi le 2,2'-méthylène-bis(4-éthyl-6-tert-butylphénol);
le 2,2'- méthylène-bis(4-méthyl-6-nonylphénol); le 2,2'-méthylène-bis(4-tert-butyl-6-tert-butylphénol);
le 2,2-méthylène-bis(4-méthyl-6-tert-butylphénol); le produit de réaction butylé de
p-crésol et dicyclopentadiène; le 2,6-di-tert-butyl-4-méthylphénol; le produit de
réaction de 4,4-iso-propylidène-diphénol, isobutylène et styrène; le 2,2'-thio-bis(4-méthyl-6-tert-butylphénol);
le 4,4'-thio-bis(3-méthyl-6-tert-butylphénol); le 1,3,5-triméthyl-2,4,6-tris(3,5-tert-butyl-4-hydroxybenzyl)benzène;
la di-tert-amylhydroquinone; le triester de l'acide 3,5-di-tert-butyl-4-hydroxyhydrocinnamique
avec la 1,3,5-tris(2-hydroxyéthyl)-s-triazine-2,4,6-(1H,3H,5H)trione; une dihydrotriméthylquinoléine
polymère; la 6-éthoxy-1,2-dihydro-2,2,4-triméthylquinoléine; la N,N'-diphényl-p-phénylène-diamine;
la N,N'-di-β-naphtyl-p-phénylènediamine; des diphénylamines alkylées; et des produits
de réaction de diphénylamine et d'acétone; et des mélanges de ceux-ci.
10. Procédé selon la revendication 9, pour la fabrication d'une étoffe produite à partir
d'au moins une prépondérance de fibres cellulosiques et stérilisée par irradiation
ou à la vapeur, dans lequel ledit monomère souple est choisi parmi l'acrylate de n-butyle,
l'acrylate de 2-éthylhexyle, l'acrylate d'isobutyle et des mélanges de ceux-ci; ledit
monomère rigide est choisi parmi le styrène, l'α-méthylstyrène, le méthacrylate de
méthyle et des mélanges de ceux-ci; ledit N-alkylolacrylamide ou -méthacrylamide est
choisi parmi le N-méthylolacrylamide ou -méthacrylamide, le N-butylolacrylamide ou
-méthacrylamide, le n- ou isobutoxyméthylacrylamide et des mélanges de ceux-ci; et
ledit acide insaturé est choisi parmi l'acide acrylique, l'acide méthacrylique, l'acide
itaconique, l'acide fumarique, l'acide maléique et des mélanges de ceux-ci.
11. Latex saturé préparé par polymérisation par amorçage de radicaux libres, comprenant
une prépondérance d'un monomère hydrophobe souple ayant une Tv dans la plage de -80°C
à -20°C, une quantité moindre d'un monomère hydrophobe rigide ayant une Tv dans la
plage de +40°C à +120°C, une petite quantité d'un acide carboxylique insaturé, une
quantité suffisante d'un émulsifiant et une petite quantité d'un N-alkylolacrylamide
ou méthacrylamide, caractérisé en ce que sont incorporées audit latex de 0,01 à 5
parties en poids pour 100 parties en poids de solides de latex d'un agent d'inhibition
d'odeur choisi parmi les antioxydants de type amine et des phénols à empêchement stérique
qui ont la fonction de réduire l'odeur qui est engendrée lors de la stérilisation
de l'étoffe non tissée liée avec ce latex.
12. Latex selon la revendication 11, dans lequel ledit latex est préparé par polymérisation,
en présence de 0,1 à 2 parties en poids d'un amorceur et de moins de 1,0 partie en
poids d'un émulsifiant anionique, de 65 à 85 parties en poids d'un monomère souple,
de 10 à 30 parties en poids d'un monomère rigide, de 0,1 à 5 parties en poids d'un
acide carboxylique insaturé contenant de 3 à 12 atomes de carbone, et de 0,1 à 5 parties
en poids d'un N-alkylolacrylamide ou -méthacrylamide contenant de 1 à 10 atomes de
carbone dans le groupe alkyle.
13. Latex selon la revendication 12, dans lequel ledit agent d'inhibition d'odeur est
choisi parmi des hydroquinones alkylées et des phénols alkylés, des produits de condensation
de cétones et d'amines, des diarylamines, des diaryldiamines, des produits de condensation
de cétones et de diarylamines, et des mélanges de ceux-ci.
14. Latex selon la revendication 12, dans lequel ledit agent d'inhibition d'odeur est
choisi parmi les structures A, B, C et D suivantes:

dans lesquelles les groupes R sont individuellement choisis parmi un atome d'hydrogène
et des groupes alkyle ayant de 1 à 12 atomes de carbone, au moins un groupe R étant
choisi parmi les groupes alkyle, les groupes R
1 sont individuellement choisis parmi le groupe hydroxy et des groupes alkyle inférieurs;
et X et Y sont choisis parmi un atome de soufre et des groupes alkylène inférieurs.
15. Latex selon la revendication 12, dans lequel ledit agent est choisi parmi le 2,2'-méthylène-bis(4-éthyl-6-tert-butylphénol);
le 2,2'-méthylène-bis(4-méthyl-6-nonylphénol); le 2,2'-méthylène-bis(4-tert-butyl-6-tert-butylphénol);
le 2,2-méthylène-bis(4-méthyl-6-tert-butylphénol); un produit de réaction butylé de
p-crésol et dicyclopentadiène; le 2,6-di-tert-butyl-4-méthylphénol; un produit de
réaction de 4,4-isopropylidène-diphénol, isobutylène et styrène; le 2,2'-thiobis(4-méthyl-6-tert-butylphénol);
le 4,4'-thio-bis(3-méthyl-6-tert-butylphénol); le 1,3,5-triméthyl-2,4,6-tris(3,5-tert-butyl-4-hydroxybenzyl)benzène;
la di-tert-amylhydroquinone; le triester de l'acide 3,5-di-tert-butyl-4-hydroxyhydrocinnamique
avec la 1,3,5-tris(2-hydroxyéthyl)-s-triazine-2,4,6-(1H,3H,5H)trione; une dihydrotriméthylquinoléine
polymère; la 6-éthoxy-1,2-dihydro-2,2,4-triméthylquinoléine; la N,N'diphényl-p-phénylène-diamine;
la N,N'-di-β-naphtyl-p-phénylènediamine; des diphénylamines alkylées; des produits
de réaction de diphénylamine et d'acétone; et des mélanges de ceux-ci.
16. Latex selon la revendication 15, dans lequel ledit monomère souple est choisi parmi
l'acrylate de n-butyle, l'acrylate de 2-éthylhexyle, l'acrylate d'isobutyle et des
mélanges de ceux-ci; ledit monomère rigide est choisi parmi le styrène, l'α-méthylstyrène,
le méthacrylate de méthyle et des mélanges de ceux-ci; ledit N-alkylolacrylamide ou
-méthacrylamide est choisi parmi le N-méthylolacrylamide ou -méthacrylamide, le N-butylolacrylamide
ou -méthacrylamide, le n-ou iso-butoxyméthylacrylamide et des mélanges de ceux-ci;
et ledit acide insaturé est choisi parmi l'acide acrylique, l'acide méthacrylique,
l'acide itaconique, l'acide fumarique, l'acide maléique et des mélanges de ceux-ci.