US3034957A - Synthetic fibers and fabrics having microbicidal activity - Google Patents
Synthetic fibers and fabrics having microbicidal activity Download PDFInfo
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- US3034957A US3034957A US746076A US74607658A US3034957A US 3034957 A US3034957 A US 3034957A US 746076 A US746076 A US 746076A US 74607658 A US74607658 A US 74607658A US 3034957 A US3034957 A US 3034957A
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- US
- United States
- Prior art keywords
- weight
- fabrics
- fibers
- trichlorocarbanilide
- microbicidal activity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 229920002994 synthetic fiber Polymers 0.000 title claims description 47
- 239000004758 synthetic textile Substances 0.000 title claims description 29
- 230000003641 microbiacidal effect Effects 0.000 title description 48
- 239000012209 synthetic fiber Substances 0.000 title description 18
- 239000000835 fiber Substances 0.000 claims description 54
- ICUTUKXCWQYESQ-UHFFFAOYSA-N triclocarban Chemical compound C1=CC(Cl)=CC=C1NC(=O)NC1=CC=C(Cl)C(Cl)=C1 ICUTUKXCWQYESQ-UHFFFAOYSA-N 0.000 claims description 27
- 229920002301 cellulose acetate Polymers 0.000 claims description 16
- 229920000728 polyester Polymers 0.000 claims description 9
- 229960001325 triclocarban Drugs 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 1
- 239000004744 fabric Substances 0.000 description 49
- 229920001577 copolymer Polymers 0.000 description 33
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 239000002855 microbicide agent Substances 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 229940124561 microbicide Drugs 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical class CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 6
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 244000005700 microbiome Species 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000002906 microbiologic effect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000004900 laundering Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 3
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- SDYWXFYBZPNOFX-UHFFFAOYSA-N 3,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C(Cl)=C1 SDYWXFYBZPNOFX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 241000193998 Streptococcus pneumoniae Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000005108 dry cleaning Methods 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000009036 growth inhibition Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ADAKRBAJFHTIEW-UHFFFAOYSA-N 1-chloro-4-isocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1 ADAKRBAJFHTIEW-UHFFFAOYSA-N 0.000 description 1
- 241000499489 Castor canadensis Species 0.000 description 1
- 241000186216 Corynebacterium Species 0.000 description 1
- 241000186227 Corynebacterium diphtheriae Species 0.000 description 1
- 244000199866 Lactobacillus casei Species 0.000 description 1
- 235000013958 Lactobacillus casei Nutrition 0.000 description 1
- 235000011779 Menyanthes trifoliata Nutrition 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 241000194017 Streptococcus Species 0.000 description 1
- 241001312524 Streptococcus viridans Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229940017800 lactobacillus casei Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000011169 microbiological contamination Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000006916 nutrient agar Substances 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
Definitions
- This invention relates to improved fibers and fabrics, and more particularly, to synthetic fibers and fabrics of cellulose acetate, resins comprising copolymers of vinylidene chloride with acrylonitrile, and polyesters of 1,4- cyclohexanedimethanol and terephthalic acid having microbicidal activity.
- any microbicidal additive to a fiber or fabric for clothing use while it must be sufiicient to kill or inhibit the growth of microorganisms, it must not be toxic or poisonous to the wearer of the clothing.
- any additive to a synthetic textile fiber must be compatible with the particular synthetic resin, have no adverse effects on dyeing characteristics and create no difficulty in the spinning thereof, many eifective microbicides for a wide variety of substrates failing to meet these and the other above-described requirements in synthetic fibers and fabrics.
- 3,4,4-trichlo rocarbanilide can be incorporated into a solution or melt of cellulose acetate, resins comprising copolymers of vinylidene chloride and acrylonitrile or polyesters of l,4-cyclohexanedimethanol and terephthalic acid, and spun, extruded or drawn into fibers by conventionalmethods to produce improved fibers having microbicidal activity.
- 3,4,4-trichlorocarbanilide By incorporating 3,4,4-trichlorocarbanilide into the liquid resin prior to spinning, a fiber results which has the 3,4,4'-.trichlorocarbanilide substantially uniformly distributed therein.
- fabrics prepared from such fibers have the 3,4,4- trichlorocarbanilide microbicide built in or locked in.
- the synthetic fibers and fabrics of the invention are quite unlike natural and synthetic fibers and fabrics which have been superficially surface'treated with various agents.
- the microbicide in the synthetic fibers and fabrics of the invention is available to render its microbicidal effect and yet can not be completely removed by repeated washings, dry cleanings and abrasions, such properties not being possessed by conventional surface treated fibers and fabrics.
- the resins or plastic compositions comprising the fibers or fabrics of the invention are cellulose acetate, resins comprising copolymers of vinylidene chloride and acrylonitrile, and polyesters of 1,4-cyclohexanedimethanol and .terephthalic acid. Polyesters of 1,4-cyclohexanedimeth anol and terephthalic acid, and their method of preparation, are described in the copending application, Ki'bler et al., US. Serial No. 554,639, filed December 22, 1955, now US. Patent No. 2,901,466. Cellulose acetate is a wellknown resin and can be prepared and spun into fibers by such methods as are disclosed in Stone US. Patent No. 2,000,047 and Stone US.
- Patent No. 2,000,- 048 Cellulose acetates having acetyl contents of about 38% to 45% by weight are suitable, with acetyl contents of about 38% to 41% being preferred.
- Fiber-forming resins comprising copolymers of vinylidene chloride and acrylonitrile are also known in the art, such being disclosed in Coover et al. US. Patent No. 2,831,826.
- Preferred fiber-forming resins of this latter type are mixtures comprising (A) 70% to by weight of a copolymer of from 30% to 65% by weight of vinylidene chloride and 70% to 35% by weight of acrylonitrile, and (B) 30% to 5% by weight of a second polymer consisting of (1) a hom-opolymer of an N-alkyl acrylamide where the alkyl group contains 1 to 6 carbon atoms, or (2) a copolymer of an N-alkyl acrylamide and an N-alkyl methacrylamide wherein the alkyl group contains 1 to 6 carbon atoms, or (3) a copolymer consisting of at least 50% by Weight of an N-alkyl acrylamide wherein the alkyl group contains 1 to 6 carbon atoms and not more than 50% by weight of a polymerizable monovinyl pyridine monomer.
- the second polymeric material added to the copolymer of vinylidene chloride and acrylonitrile is added mainly to improve the dyeing characteristics of the composition and typically includes such materials as poly- N-isopropyl acrylamides, a copolymer of N-isopropyl acrylamide and 2-methyl-5-vinyl pyridine, a copolymer of N-tert. butyl acrylamide and 2-methyl-5-vinyl pyridine, a copolymer of N-isopropyl acrylamide and N-methyl methacrylamide, or related polymeric materials.
- poly- N-isopropyl acrylamides a copolymer of N-isopropyl acrylamide and 2-methyl-5-vinyl pyridine
- a copolymer of N-tert. butyl acrylamide and 2-methyl-5-vinyl pyridine a copolymer of N-isopropyl acrylamide and N-methyl methacrylamide, or related polymeric materials
- microbicide employed in the synthetic fibers and fabrics of the invention 3,4,4-trichlorocarbanilide
- This microbicide is incorporated into a solution or dope or melt of the resin and thereafter spun by conventional methods into textile fibers to contain about .05 to 5%, and preferably .2% to 2%, by weight of the microbicide based on the weight of the synthetic fiber.
- the microbicide is substantially uniformly distributed in the fiber.
- Such fibers can thereafter be woven into fabrics, or they can be combined with other fibers, natural or synthetic, and woven into fabrics.
- These fibers and fabrics have substantial microbicidal activity against such microorganisms as Micrococcus pyogenes var. aureus, M icrococcus epidermidis, M icrococcus pyogenes, Diplococcus pneumoniae, Corynebacterium, diphtherialc, Streptococcus viridans, Lactobacillus casei, and related microorganisms.
- the synthetic fibers and fabrics of the invention show particular microbicidal activity toward gram positive microorganisms.
- the fibers and fabrics of the invention have microbicidal activity, they are substantially non-toxic and non-irritating to humans and thus can be used in clothing, blankets, carpeting, and for numerous other uses.
- a particularly desirable property of the present fibers and fabrics is the permanence of the 3,4,4-trichlorocarbanilide distributed therein. Even in view of the substantial surface area of fabrics prepared from the present synthetic fibers, these fabrics can be subjected to more than washings in household washing machines in the usual manner and still exhibit microbicidal activity. Likewise, this microbicidal activity can not be lost by mechanical abrasion of the fibers or the fabrics of the invention such as normally results in the processing and use thereof. This permanence of microbicidal activity is attributed to the incorporation of the 3,4,4-trichlorocarbanilide in the dope or melt of the resin before spinning into fibers as distinguished from coating the finished fabric with a microbicidal material.
- 3,4,4-trichlorocarbanilide in the abovedefined amounts does not adversely alfect the physical properties of the fibers and fabrics of the invention such as strength, elongation, hand and luster.
- this microbicide is compatible in the fibers and fabrics of the invention as it does not oil out and does not cause discolorating thereof under usual processing and usage. Also, this microbicide creates no difficulty in the sp nning of the fiber or in the dyeing of the fiber or fabric.
- Example 1 A cellulose acetate dope in acetone containing 28.5% by weight of cellulose acetate having an acetyl content of about 39% was prepared. To the dope was added 1% by weight of 3,4,4'-trichlorocarbanilide based on the weight of the cellulose acetate. The resulting mixture was blended and thereafter spun from the acetone into 55 denier, l3 filament fibers. The resulting fibers containing about 1% by weight of 3,4,4'-trichlorocarban1l1de substantially uniformly distributed therein were then woven into a fabric in the usual manner. The prepared fabric showed inhibition against Micrococcus pyogenes var. aureus after 25 launderings in the usual manner n a conventional household washing machine.
- This inhlbition was determined by placing samples of the fabric in a petri dish containing nutrient agar surface inoculated with the microorganism, a clear zone being formed around the test samples.
- the prepared fabric has similar permanence of microbicidal resistance to M icrococcus epidermidis, Micrococcus pyogenes, Diplococcus pneumoniae, Corynebacterium diphtheriae and Streptococcus viria'ans. Similar results were obtained with fabrics prepared from cellulose acetate fibers containing 0.3% and 1.5% by weight of 3,4,4-trichlorocarbanilide.
- the described cellulose acetate fabrics containing the 3,4,4-trichlorocarbanilide did not differ noticeably in dyeability, hand and physical appearance from comparable cellulose acetate fabrics containing no 3,4,4'-trichlorocarbanilide.
- Example 2 A copolymer prepared from about 50% by weight of vinylidene chloride and 50% by weight of acrylonitrile was prepared in accordance with the method described in Example 1 of Coover et al. U.S. Patent No. 2,831,826 and thereafter dissolved in about four times its weight of dimethyl :formamide. Then sufiicient 3,4,4'-trichlorocarbanilide wa added to the resulting dope which was spun into fibers as described in Example 1 above to produce fibers having about 1% by weight of the 3,4,4-trichlorocarbanilide substantially uniformly distributed therein. Fabrics prepared from the resulting fibers have permanence of microbicidal activity after more than 25 washings as described in Example 1 above. The described microbicidal fabric does not differ noticeably in dyeability, hand and physical appearance from comparable fabrics containing no 3,4,4'-trichlorocarbanilide.
- Example 3 Several fiber-forming mixtures of polymers prepared in accordance with the method of Coover et a1.
- U.S. Patent No. 2,831,826, were spun from acetone and woven into fabrics as described in Example 1 above.
- the fabrics prepared therefrom have substantial microbicidal activity.
- the prepared fibers had the following compositions: (a) a mixture of by weight of a copolymer of 52% by weight of acrylonitrile and 48% vinylidene chloride, and 15% by weight of poly-N-isopropyl acrylamide; (b) a mixture of 70% by weight of a copolymer of 50% by weight of acrylonitrile and 50% by weight of vinylidene chloride, and 30% by weight of a copolymer of by weight of N-tert.
- Example 4 A polyester of 1,4-cyclohexanedimethanol and terephthalic acid was prepared by reacting 1,4-cyclohexanedimethanol (70% trans, 30% cis) and dimethyl terephthalate in accordance with the method described in Example 1 of copending Kibler et al. application, U. S. Serial No. 554,639, filed December 22, 1955.
- a fabric results that has substantial microbicidal activity.
- Such a fabric has permanence of microbicidal activity after more than 25 washings as described ni Example 1 above.
- the described microbicidal fabric does not differ noticeably in dyeability, hand and physical appearance from comparable fabrics containing no 3,4,4'-trichlorocarbanilide.
- microbicide of the invention can be prepared by the method described in Example 5 below.
- Example 5 To a suitable reaction vessel equipped with a thermometer, agitator and reflux condenser and containing 8.1 parts by Weight of 3,4-dichloroaniline in 57 parts by Weight of diethyl ether is added dropwise a solution of 7.7 parts by weight of 4-chlorophenyl isocyanate in 15 parts by weight of diethyl ether at such a rate as to maintain gentle reflux. Upon completion of the isocyanate addition the reaction mass is agitated for about one hour. The mass is filtered and the residue washed with diethyl ether. The resulting 3;,4,4'-trichlorocarbanilide product can be further purified by recrystallization from ethanol.
- the present invention thus provides novel synthetic textile fibers and fabrics which have considerable utility because of their built in or locked in microbicidal activity, this microbicidal activity having a permanence in the present fibers and fabrics not possessed by conventional surface treated fibers and fabrics.
- the 3,4,4- trichlorocarbanilide additive of the invention does not adversely affect the processing, physical appearance and physical properties of the subject fibers and fabrics.
- a copolymer consisting of at least 50% by weight of an N-alkyl acrylamide wherein the alkyl group contains 1 to 6 carbon atoms and not more than 50% by weight of a polymerizable monovinyl pyridine monomer.
- a synthetic textile fiber having microbicidal activity comprising cellulose acetate having an acetyl content of about 38% to 45% with .2% to 2% by weight of 3,4,4- trichlorocarbanilide substantially uniformly distributed therein.
- a synthetic textile fiber having microbicidal activity comprising cellulose acetate having an acetyl content of about 38% to 41% with .2% to 2% by weight of 3,4,4- trichlorocarbanilide substantially uniformly dispersed therein.
- a synthetic textile fiber having microbicidal activity comprising a mixture of (A) 70% to 95% by Weight of a copolymer of from 30% to 65 by weight of vinylidene chloride and 70% to 35% by weight of acrylonitrile, and (B) 30% to 5% by weight of a second polymer from the group consisting of (l) a homopolymer of an N- alkyl acrylamide wherein the alkyl group contains 1 to 6 carbon atoms, (2) a copolymer of an N-alkyl acrylamide and N-alkyl methacrylamide wherein in the alkyl group contains 1 to 6 carbon atoms, and (3) a copolymer consisting of at least 50% by weight of an N-alkyl acrylamide wherein the alkyl group contains 1 to 6 carbon atoms and not more than 50% by weight of a polymerizable monovinyl pyridine monomer, with .2% to 2% by weight of 3,4,4--trichlorocarbani1ide substantially uniformly
- a synthetic textile fiber having microbicidal activity comprising a mixture of (A) 70% to by weight of a copolymer of from 30% to 65% by weight of vinylidene chloride and 70% to 35% by weight of acrylonitrile, and (B) 30% to 5% by Weight of poly-N-isopropylacrylamide, with .2% to 2% by Weight of 3,4,4'-trichlorocarbanilide substantially uniformly distributed therein.
- a synthetic textile fiber having microbicidal activity comprising a mixture of (A) 70% to 95 by weight of a copolymer of from 30% to 65% by weight of vinylidene chloride and 70% to 35 by weight of acrylonitrile, and (B) 30% to 5% by weight of a copolymer of N-isopropyl acrylamide and 2-methyl-5-viny1 pyridine, with .2% to 2% by weight of 3,4,4-trichlorocarbanilide substantially uniformly distributed therein.
- a synthetic textile fiber having microbicidal activity comprising a mixture of (A) 70% to 95 by weight of a copolymer of from 30% to 65 by weight of vinylidene chloride and 70% to 35% by weight of acrylonitrile, and (B) 30% to 5% by weight of a copolymer consisting of at least 50% by weight of N-isopropyl acrylamide and not more than 50% by weight of N-methyl methacrylamide, with .2% to 2% by weight of 3,4,4-trichlorocarbanilide substantially uniformly distributed therein.
- a synthetic textile fiber having microbicidal activity comprising a mixture of (A) 70% to 95 by weight of a copolymer of from 30% to 65 by weight of vinylidene chloride and 70% to 35 by Weight of acrylonitrile, and (B) 30% to 5% by weight of a copolymer of N-tert. butyl acrylamide and 2-methyl-5-vinyl pyridine, with .2% to 2% by weight of 3,4,4'-trichlorocarbanilide substan tially uniformly distributed therein.
- a synthetic textile fiber having microbicidal activity comprising a polyester of 1,4-cyclohexanedimethanol and terephthalic acid having the recurring structural unit with .2% to 2% by weight of 3,4,4'-trichlorocarbanilide substantially uniformly dispersed therein.
- a fabric having microbiological activity comprising fibers as defined in claim 1.
- CH2CH2 /CH CH 0 -0CH2 CH' cH-c1l1 -0 -c -c ⁇ c-c- ⁇ CH2CH2 ⁇ CH-CH/ Signed and sealed this 16th day of October- 1962.
Description
nited States Patent 3,034,957 SYNTHETIC FIBERS AND FABRICS HAVING MICROBICIDAL ACTIVITY James L. Smith and Robert C. Harrington, Jr., Kingsport,
Tenn, assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed July 2, 1958, Ser. No. 746,076 Claims. ((31. 167-385) This invention relates to improved fibers and fabrics, and more particularly, to synthetic fibers and fabrics of cellulose acetate, resins comprising copolymers of vinylidene chloride with acrylonitrile, and polyesters of 1,4- cyclohexanedimethanol and terephthalic acid having microbicidal activity.
For many years, attempts have been made to produce fibers and fabrics which would effectively retard the growth of various microorganisms. Generally, this purpose has been accomplished by a separate treatment in which the fabric is coated with a resinous material containing a microbicide. Such a treatment has proved to be relatively ineffective because the resin coating would tend to flake off in normal use, and the usual washing or laundering operation would very quickly destroy whatever microbicidal properties that might be present. In addition, resinous coatings tend to change the hand of fabrics in an undesirable manner. Other treatments have consisted of treating the fabric in a solution of a microbicide. Fabrics containing some of these microbicidal agents are claimed to be substantive, but the microbicidal agents are actually held so loosely that they can be easily laundered out. Hence, it is desirable to have synthetic fibers and fabrics that have permanence of microbicidal activity, this result being obtained without affecting the appearance and physical properties thereof.
Also, any microbicidal additive to a fiber or fabric for clothing use, while it must be sufiicient to kill or inhibit the growth of microorganisms, it must not be toxic or poisonous to the wearer of the clothing. In addition, any additive to a synthetic textile fiber must be compatible with the particular synthetic resin, have no adverse effects on dyeing characteristics and create no difficulty in the spinning thereof, many eifective microbicides for a wide variety of substrates failing to meet these and the other above-described requirements in synthetic fibers and fabrics.
It is an object of this invention to provide novel synthetic fibers and fabrics having improved microbiological growth inhibition.
It is another object of this invention to provide novel synthetic fibers and fabrics capable of retaining microbiological growth inhibition properties after repeated washings or launderings, dry cleanings and wearings.
it is another object of this invention to provide novel synthetic fibers and fabrics having microbicidal activity which are not significantly different from corresponding fibers and fabrics without such activity with respect to hand, dyeability, appearance, and the like.
It is another object of this invention to provide novel synthetic fibers and fabrics capable of inhibiting microbiological growth and which are amenable to the various phases of fiber and fabric processing without loss of this inhibitory power.
it is still another object of this invention to provide novel synthetic fibers or fabrics prepared therefrom which will resist the formation of obnoxious odors after having become contaminated by perspiration or like soiling agents.
it is likewise an object of this invention to provide novel sanitary synthetic fibers or fabrics prepared therefrom such that microbiological contamination spread from one wearer to another or from one place on a wearers body to another would be significantly reduced or eliminated.
It is also an object of this invention to provide novel fibers and fabrics of cellulose acetate, resins comprising copolymers of vinylidene chloride and acrylonitrile, and polyesters of l,4-cyclohexanedimethanol and terephthalic acid having microbicidal activity.
These and other objects are attained by means of this invention as described hereinafter with reference to preferred embodiments thereof.
We have found that relatively low concentrations of 3,4,4-trichlo rocarbanilide can be incorporated into a solution or melt of cellulose acetate, resins comprising copolymers of vinylidene chloride and acrylonitrile or polyesters of l,4-cyclohexanedimethanol and terephthalic acid, and spun, extruded or drawn into fibers by conventionalmethods to produce improved fibers having microbicidal activity. By incorporating 3,4,4-trichlorocarbanilide into the liquid resin prior to spinning, a fiber results which has the 3,4,4'-.trichlorocarbanilide substantially uniformly distributed therein. Thus, fabrics prepared from such fibers have the 3,4,4- trichlorocarbanilide microbicide built in or locked in. Thus, the synthetic fibers and fabrics of the invention are quite unlike natural and synthetic fibers and fabrics which have been superficially surface'treated with various agents. The microbicide in the synthetic fibers and fabrics of the invention is available to render its microbicidal effect and yet can not be completely removed by repeated washings, dry cleanings and abrasions, such properties not being possessed by conventional surface treated fibers and fabrics.
The resins or plastic compositions comprising the fibers or fabrics of the invention are cellulose acetate, resins comprising copolymers of vinylidene chloride and acrylonitrile, and polyesters of 1,4-cyclohexanedimethanol and .terephthalic acid. Polyesters of 1,4-cyclohexanedimeth anol and terephthalic acid, and their method of preparation, are described in the copending application, Ki'bler et al., US. Serial No. 554,639, filed December 22, 1955, now US. Patent No. 2,901,466. Cellulose acetate is a wellknown resin and can be prepared and spun into fibers by such methods as are disclosed in Stone US. Patent No. 2,000,047 and Stone US. Patent No. 2,000,- 048. Cellulose acetates having acetyl contents of about 38% to 45% by weight are suitable, with acetyl contents of about 38% to 41% being preferred. Fiber-forming resins comprising copolymers of vinylidene chloride and acrylonitrile are also known in the art, such being disclosed in Coover et al. US. Patent No. 2,831,826. Preferred fiber-forming resins of this latter type are mixtures comprising (A) 70% to by weight of a copolymer of from 30% to 65% by weight of vinylidene chloride and 70% to 35% by weight of acrylonitrile, and (B) 30% to 5% by weight of a second polymer consisting of (1) a hom-opolymer of an N-alkyl acrylamide where the alkyl group contains 1 to 6 carbon atoms, or (2) a copolymer of an N-alkyl acrylamide and an N-alkyl methacrylamide wherein the alkyl group contains 1 to 6 carbon atoms, or (3) a copolymer consisting of at least 50% by Weight of an N-alkyl acrylamide wherein the alkyl group contains 1 to 6 carbon atoms and not more than 50% by weight of a polymerizable monovinyl pyridine monomer. The second polymeric material added to the copolymer of vinylidene chloride and acrylonitrile is added mainly to improve the dyeing characteristics of the composition and typically includes such materials as poly- N-isopropyl acrylamides, a copolymer of N-isopropyl acrylamide and 2-methyl-5-vinyl pyridine, a copolymer of N-tert. butyl acrylamide and 2-methyl-5-vinyl pyridine, a copolymer of N-isopropyl acrylamide and N-methyl methacrylamide, or related polymeric materials. The
preparation of such mixtures is described in detail in the aforementioned Coover et al. patent.
The microbicide employed in the synthetic fibers and fabrics of the invention, 3,4,4-trichlorocarbanilide, can be readily prepared by refluxing equal molar proportions of 3,4-dichloroaniline and 4-chloropheny1 isocyanate in an inert solvent such as diethyl ether. This microbicide is incorporated into a solution or dope or melt of the resin and thereafter spun by conventional methods into textile fibers to contain about .05 to 5%, and preferably .2% to 2%, by weight of the microbicide based on the weight of the synthetic fiber. The microbicide is substantially uniformly distributed in the fiber. Such fibers can thereafter be woven into fabrics, or they can be combined with other fibers, natural or synthetic, and woven into fabrics. These fibers and fabrics have substantial microbicidal activity against such microorganisms as Micrococcus pyogenes var. aureus, M icrococcus epidermidis, M icrococcus pyogenes, Diplococcus pneumoniae, Corynebacterium, diphtherialc, Streptococcus viridans, Lactobacillus casei, and related microorganisms. The synthetic fibers and fabrics of the invention show particular microbicidal activity toward gram positive microorganisms. However, while the fibers and fabrics of the invention have microbicidal activity, they are substantially non-toxic and non-irritating to humans and thus can be used in clothing, blankets, carpeting, and for numerous other uses.
A particularly desirable property of the present fibers and fabrics is the permanence of the 3,4,4-trichlorocarbanilide distributed therein. Even in view of the substantial surface area of fabrics prepared from the present synthetic fibers, these fabrics can be subjected to more than washings in household washing machines in the usual manner and still exhibit microbicidal activity. Likewise, this microbicidal activity can not be lost by mechanical abrasion of the fibers or the fabrics of the invention such as normally results in the processing and use thereof. This permanence of microbicidal activity is attributed to the incorporation of the 3,4,4-trichlorocarbanilide in the dope or melt of the resin before spinning into fibers as distinguished from coating the finished fabric with a microbicidal material.
The addition of 3,4,4-trichlorocarbanilide in the abovedefined amounts does not adversely alfect the physical properties of the fibers and fabrics of the invention such as strength, elongation, hand and luster. In addition, this microbicide is compatible in the fibers and fabrics of the invention as it does not oil out and does not cause discolorating thereof under usual processing and usage. Also, this microbicide creates no difficulty in the sp nning of the fiber or in the dyeing of the fiber or fabric.
The invention is further illustrated by the following examples of preferred embodiments thereof.
Example 1 A cellulose acetate dope in acetone containing 28.5% by weight of cellulose acetate having an acetyl content of about 39% was prepared. To the dope was added 1% by weight of 3,4,4'-trichlorocarbanilide based on the weight of the cellulose acetate. The resulting mixture was blended and thereafter spun from the acetone into 55 denier, l3 filament fibers. The resulting fibers containing about 1% by weight of 3,4,4'-trichlorocarban1l1de substantially uniformly distributed therein were then woven into a fabric in the usual manner. The prepared fabric showed inhibition against Micrococcus pyogenes var. aureus after 25 launderings in the usual manner n a conventional household washing machine. This inhlbition was determined by placing samples of the fabric in a petri dish containing nutrient agar surface inoculated with the microorganism, a clear zone being formed around the test samples. The prepared fabric has similar permanence of microbicidal resistance to M icrococcus epidermidis, Micrococcus pyogenes, Diplococcus pneumoniae, Corynebacterium diphtheriae and Streptococcus viria'ans. Similar results were obtained with fabrics prepared from cellulose acetate fibers containing 0.3% and 1.5% by weight of 3,4,4-trichlorocarbanilide. The described cellulose acetate fabrics containing the 3,4,4-trichlorocarbanilide did not differ noticeably in dyeability, hand and physical appearance from comparable cellulose acetate fabrics containing no 3,4,4'-trichlorocarbanilide.
Example 2 A copolymer prepared from about 50% by weight of vinylidene chloride and 50% by weight of acrylonitrile was prepared in accordance with the method described in Example 1 of Coover et al. U.S. Patent No. 2,831,826 and thereafter dissolved in about four times its weight of dimethyl :formamide. Then sufiicient 3,4,4'-trichlorocarbanilide wa added to the resulting dope which was spun into fibers as described in Example 1 above to produce fibers having about 1% by weight of the 3,4,4-trichlorocarbanilide substantially uniformly distributed therein. Fabrics prepared from the resulting fibers have permanence of microbicidal activity after more than 25 washings as described in Example 1 above. The described microbicidal fabric does not differ noticeably in dyeability, hand and physical appearance from comparable fabrics containing no 3,4,4'-trichlorocarbanilide.
Example 3 Several fiber-forming mixtures of polymers prepared in accordance with the method of Coover et a1. U.S. Patent No. 2,831,826, were spun from acetone and woven into fabrics as described in Example 1 above. With 1% by weight of 3,4,4'-trichl0rocarbanilide substantially uniformly dispersed in the prepared fiber-forming polymers, the fabrics prepared therefrom have substantial microbicidal activity. The prepared fibers had the following compositions: (a) a mixture of by weight of a copolymer of 52% by weight of acrylonitrile and 48% vinylidene chloride, and 15% by weight of poly-N-isopropyl acrylamide; (b) a mixture of 70% by weight of a copolymer of 50% by weight of acrylonitrile and 50% by weight of vinylidene chloride, and 30% by weight of a copolymer of by weight of N-tert. butyl acrylamide and 10% by weight of 2-methyl-5-vinyl pyridine; (c) a mixture of 90% by weight of a copolymer of 50% by weight of acrylonitrile and 50% by weight of vinylidene chloride, and 10% by weight of a copolymer of N-isopropyl acrylamide and 2-methyl-5-vinyl pyridine; and, (d) a mixture of 70% by weight of a copolymer of 50% by weight of acrylonitrile and 50% by weight of vinylidene chloride, and 30% by weight of a copolymer of 90% by weight of N-isopropyl acrylamide and 10% by weight of N-methyl methacrylamide. Fabrics prepared from these fibers show permanence of microbicidal activity when tested as described in Example 1 above. The described synthetic fabrics do not differ noticeably in dyeability, hand and physical appearance from comparable fabrics containing no 3,4,4-trichlorocarbanilide.
Example 4 A polyester of 1,4-cyclohexanedimethanol and terephthalic acid was prepared by reacting 1,4-cyclohexanedimethanol (70% trans, 30% cis) and dimethyl terephthalate in accordance with the method described in Example 1 of copending Kibler et al. application, U. S. Serial No. 554,639, filed December 22, 1955. By drawing a melt of the resulting polymer containing 1% by weight of 3,4,4-trichlorocarbanilide into fibers, and spinning the fibers into a fabric, a fabric results that has substantial microbicidal activity. Such a fabric has permanence of microbicidal activity after more than 25 washings as described ni Example 1 above. The described microbicidal fabric does not differ noticeably in dyeability, hand and physical appearance from comparable fabrics containing no 3,4,4'-trichlorocarbanilide.
The microbicide of the invention can be prepared by the method described in Example 5 below.
Example 5 To a suitable reaction vessel equipped with a thermometer, agitator and reflux condenser and containing 8.1 parts by Weight of 3,4-dichloroaniline in 57 parts by Weight of diethyl ether is added dropwise a solution of 7.7 parts by weight of 4-chlorophenyl isocyanate in 15 parts by weight of diethyl ether at such a rate as to maintain gentle reflux. Upon completion of the isocyanate addition the reaction mass is agitated for about one hour. The mass is filtered and the residue washed with diethyl ether. The resulting 3;,4,4'-trichlorocarbanilide product can be further purified by recrystallization from ethanol.
The present invention thus provides novel synthetic textile fibers and fabrics which have considerable utility because of their built in or locked in microbicidal activity, this microbicidal activity having a permanence in the present fibers and fabrics not possessed by conventional surface treated fibers and fabrics. in addition the 3,4,4- trichlorocarbanilide additive of the invention does not adversely affect the processing, physical appearance and physical properties of the subject fibers and fabrics.
Although the invention has been described in detail with reference to certain preferred embodiments thereof, it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
We claim:
1. A synthetic textile fiber having microbicidal activity having substantially uniformly dispersed therein .05 to 5% by Weight of 3,4,4'-trichlorocarbaniiide, said fiber comprising a resin from the group consisting of:
(I) cellulose acetate having an acetyl content of about (II) a polyester comprised principally of the recurring structural unit (III) a mixture of (A) 70% to 95% by weight of a copolymer of 30% to 65 by weight of vinylidene chloride and 70% to 35% by weight of acrylonitrile, and
(B) 30% to 5% by weight of a second polymer from the group consisting of (1) a homopolymer of N-alkyl acrylamide wherein the alkyl group contains 1 to 6 carbon atoms,
(2) a copolymer of N-alkyl acrylamide and N-alkyl methacrylamide wherein the alkyl group contains 1 to 6 carbon atoms, and
(3) a copolymer consisting of at least 50% by weight of an N-alkyl acrylamide wherein the alkyl group contains 1 to 6 carbon atoms and not more than 50% by weight of a polymerizable monovinyl pyridine monomer.
2. A synthetic textile fiber having microbicidal activity comprising cellulose acetate having an acetyl content of about 38% to 45% with .2% to 2% by weight of 3,4,4- trichlorocarbanilide substantially uniformly distributed therein.
3. A synthetic textile fiber having microbicidal activity comprising cellulose acetate having an acetyl content of about 38% to 41% with .2% to 2% by weight of 3,4,4- trichlorocarbanilide substantially uniformly dispersed therein.
4. A synthetic textile fiber having microbicidal activity comprising a mixture of (A) 70% to 95% by Weight of a copolymer of from 30% to 65 by weight of vinylidene chloride and 70% to 35% by weight of acrylonitrile, and (B) 30% to 5% by weight of a second polymer from the group consisting of (l) a homopolymer of an N- alkyl acrylamide wherein the alkyl group contains 1 to 6 carbon atoms, (2) a copolymer of an N-alkyl acrylamide and N-alkyl methacrylamide wherein in the alkyl group contains 1 to 6 carbon atoms, and (3) a copolymer consisting of at least 50% by weight of an N-alkyl acrylamide wherein the alkyl group contains 1 to 6 carbon atoms and not more than 50% by weight of a polymerizable monovinyl pyridine monomer, with .2% to 2% by weight of 3,4,4--trichlorocarbani1ide substantially uniformly distributed therein.
5. A synthetic textile fiber having microbicidal activity comprising a mixture of (A) 70% to by weight of a copolymer of from 30% to 65% by weight of vinylidene chloride and 70% to 35% by weight of acrylonitrile, and (B) 30% to 5% by Weight of poly-N-isopropylacrylamide, with .2% to 2% by Weight of 3,4,4'-trichlorocarbanilide substantially uniformly distributed therein.
6. A synthetic textile fiber having microbicidal activity comprising a mixture of (A) 70% to 95 by weight of a copolymer of from 30% to 65% by weight of vinylidene chloride and 70% to 35 by weight of acrylonitrile, and (B) 30% to 5% by weight of a copolymer of N-isopropyl acrylamide and 2-methyl-5-viny1 pyridine, with .2% to 2% by weight of 3,4,4-trichlorocarbanilide substantially uniformly distributed therein.
7. A synthetic textile fiber having microbicidal activity comprising a mixture of (A) 70% to 95 by weight of a copolymer of from 30% to 65 by weight of vinylidene chloride and 70% to 35% by weight of acrylonitrile, and (B) 30% to 5% by weight of a copolymer consisting of at least 50% by weight of N-isopropyl acrylamide and not more than 50% by weight of N-methyl methacrylamide, with .2% to 2% by weight of 3,4,4-trichlorocarbanilide substantially uniformly distributed therein.
8. A synthetic textile fiber having microbicidal activity comprising a mixture of (A) 70% to 95 by weight of a copolymer of from 30% to 65 by weight of vinylidene chloride and 70% to 35 by Weight of acrylonitrile, and (B) 30% to 5% by weight of a copolymer of N-tert. butyl acrylamide and 2-methyl-5-vinyl pyridine, with .2% to 2% by weight of 3,4,4'-trichlorocarbanilide substan tially uniformly distributed therein.
9. A synthetic textile fiber having microbicidal activity comprising a polyester of 1,4-cyclohexanedimethanol and terephthalic acid having the recurring structural unit with .2% to 2% by weight of 3,4,4'-trichlorocarbanilide substantially uniformly dispersed therein.
10. A fabric having microbiological activity comprising fibers as defined in claim 1.
References Cited in the file of this patent UNITED STATES PATENTS 2,695,858 Lisle Nov. 30, 1954 2,758,955 Johnson Aug. 14, 1956 2,774,708 Cohen Dec. 18, 1956 2,812,332 Pennino Nov. 5, 1957 2,846,398 Beaver et a] Aug, 5, 1958 2,913,369 Haslam Nov. 17, 1959- FOREIGN PATENTS 627,710 Great Britain Aug. 15, 1949 684,404 Great Britain Dec. 17, 1952 709,982 Great Britain June 2, 1954 UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No- 3,034,957 May 15, 1962 James L. Smith et a1.
id Letters Patent should read as corrected below.
Column 4, line 70 for "ni" read in column 5 lines 39 to 42, the fa rmula should appear as shown below instead of as in the patent:
CH2CH2 /CH=CH 0 -0CH2 CH' cH-c1l1 -0 -c -c\ c-c- \CH2CH2 \CH-CH/ Signed and sealed this 16th day of October- 1962.
(SEAL) Attest:
ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents
Claims (1)
1. A SYNTHETIC TEXTILE FIBER HAVING MICROBICDAL ACTIVITY HAVING SUBSTANTIALLY UNIFORMLY DISPERSED THEREIN .05% TO 5% BY WEIGHT OF 3,4,4''TRICHLOROCARBANILIDE, SAID FIBER COMPRISING A RESIN FROM THE GROUP CONSISTING OF: (I) CELLULOSE ACETATE HAVING AN ACETYL CONTENT OF ABOUT 38% TO 45% (II) A POLYESTER COMPRISED PRINCIPALLY OF THE RECURRING STRUCTURAL UNIT
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US746076A US3034957A (en) | 1958-07-02 | 1958-07-02 | Synthetic fibers and fabrics having microbicidal activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US746076A US3034957A (en) | 1958-07-02 | 1958-07-02 | Synthetic fibers and fabrics having microbicidal activity |
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| Publication Number | Publication Date |
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| US3034957A true US3034957A (en) | 1962-05-15 |
Family
ID=24999384
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| Application Number | Title | Priority Date | Filing Date |
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| US746076A Expired - Lifetime US3034957A (en) | 1958-07-02 | 1958-07-02 | Synthetic fibers and fabrics having microbicidal activity |
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| US (1) | US3034957A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3161622A (en) * | 1961-10-09 | 1964-12-15 | Eastman Kodak Co | Polyamide fibers having microbiocidal activity |
| US3200035A (en) * | 1962-06-01 | 1965-08-10 | Ciba Ltd | Treatment of synthetic products, especially synthetic fibers |
| US3247058A (en) * | 1962-06-08 | 1966-04-19 | Sam M Hyman | Base fabric coated with resin having mixture of quaternary ammonium germicides |
| US3296000A (en) * | 1966-04-06 | 1967-01-03 | Fmc Corp | Shaped regenerated cellulose products having bacteriostatic properties |
| US3393196A (en) * | 1963-09-09 | 1968-07-16 | Merck & Co Inc | Process for the manufacture of aryl mercury ammonium compounds |
| US4430381A (en) | 1982-06-25 | 1984-02-07 | The Buckeye Cellulose Corporation | Monocarboxylic acid antimicrobials in fabrics |
| US5567372A (en) * | 1993-06-11 | 1996-10-22 | Kimberly-Clark Corporation | Method for preparing a nonwoven web containing antimicrobial siloxane quaternary ammonium salts |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB627710A (en) * | 1945-10-02 | 1949-08-15 | British Celanese | Improvements in plastic materials and articles |
| GB684404A (en) * | 1949-09-06 | 1952-12-17 | Walter Engel | Improvements relating to antiseptic sheeting |
| GB709982A (en) * | 1950-08-18 | 1954-06-02 | Wallington Weston & Company Lt | Improvements in sterilized plastics |
| US2695858A (en) * | 1952-05-16 | 1954-11-30 | Dow Chemical Co | Copper 3-phenylsalicylate-ammonia addition product and its employment as a cellulosic preservative |
| US2758955A (en) * | 1950-09-07 | 1956-08-14 | Fmc Corp | Process of protecting organic matter against fungus growth by applying a chlorine substituted thia-or dihydro-thianaphthene dioxide |
| US2774708A (en) * | 1954-12-27 | 1956-12-18 | Gallowhur Chemical Corp | Alkyl dimethyl dichlorobenzyl ammonium mercaptobenzothiazolates and pesticidal concentrates containing the same |
| US2812332A (en) * | 1955-04-01 | 1957-11-05 | Goodrich Co B F | Quaternary ammonium xanthates |
| US2846398A (en) * | 1955-12-27 | 1958-08-05 | Monsanto Chemicals | Antiseptic detergent composition |
| US2913369A (en) * | 1955-07-05 | 1959-11-17 | Du Pont | Fungicide |
-
1958
- 1958-07-02 US US746076A patent/US3034957A/en not_active Expired - Lifetime
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB627710A (en) * | 1945-10-02 | 1949-08-15 | British Celanese | Improvements in plastic materials and articles |
| GB684404A (en) * | 1949-09-06 | 1952-12-17 | Walter Engel | Improvements relating to antiseptic sheeting |
| GB709982A (en) * | 1950-08-18 | 1954-06-02 | Wallington Weston & Company Lt | Improvements in sterilized plastics |
| US2758955A (en) * | 1950-09-07 | 1956-08-14 | Fmc Corp | Process of protecting organic matter against fungus growth by applying a chlorine substituted thia-or dihydro-thianaphthene dioxide |
| US2695858A (en) * | 1952-05-16 | 1954-11-30 | Dow Chemical Co | Copper 3-phenylsalicylate-ammonia addition product and its employment as a cellulosic preservative |
| US2774708A (en) * | 1954-12-27 | 1956-12-18 | Gallowhur Chemical Corp | Alkyl dimethyl dichlorobenzyl ammonium mercaptobenzothiazolates and pesticidal concentrates containing the same |
| US2812332A (en) * | 1955-04-01 | 1957-11-05 | Goodrich Co B F | Quaternary ammonium xanthates |
| US2913369A (en) * | 1955-07-05 | 1959-11-17 | Du Pont | Fungicide |
| US2846398A (en) * | 1955-12-27 | 1958-08-05 | Monsanto Chemicals | Antiseptic detergent composition |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3161622A (en) * | 1961-10-09 | 1964-12-15 | Eastman Kodak Co | Polyamide fibers having microbiocidal activity |
| US3200035A (en) * | 1962-06-01 | 1965-08-10 | Ciba Ltd | Treatment of synthetic products, especially synthetic fibers |
| US3247058A (en) * | 1962-06-08 | 1966-04-19 | Sam M Hyman | Base fabric coated with resin having mixture of quaternary ammonium germicides |
| US3393196A (en) * | 1963-09-09 | 1968-07-16 | Merck & Co Inc | Process for the manufacture of aryl mercury ammonium compounds |
| US3296000A (en) * | 1966-04-06 | 1967-01-03 | Fmc Corp | Shaped regenerated cellulose products having bacteriostatic properties |
| US4430381A (en) | 1982-06-25 | 1984-02-07 | The Buckeye Cellulose Corporation | Monocarboxylic acid antimicrobials in fabrics |
| US5567372A (en) * | 1993-06-11 | 1996-10-22 | Kimberly-Clark Corporation | Method for preparing a nonwoven web containing antimicrobial siloxane quaternary ammonium salts |
| US5569732A (en) * | 1993-06-11 | 1996-10-29 | Kimberly-Clark Corporation | Antimicrobial siloxane quaternary ammonium salts |
| US5777010A (en) * | 1993-06-11 | 1998-07-07 | Kimberly-Clark Worldwide, Inc. | Melt-extrudable compositions containing antimicrobial siloxane quaternary ammonium salts |
| US5854147A (en) * | 1993-06-11 | 1998-12-29 | Kimberly-Clark Worldwide, Inc. | Non-woven web containing antimicrobial siloxane quaternary ammonium salts |
| US5853641A (en) * | 1993-06-11 | 1998-12-29 | Kimberly-Clark Worldwide, Inc. | Method for preparing polyolefin fibers containing antimicrobial siloxane quarternary ammonium salts |
| US5853883A (en) * | 1993-06-11 | 1998-12-29 | Kimberly-Clark Worldwide, Inc. | Polyolefin fibers containing antimicrobial siloxane quaternary ammonium salts |
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