JP2007291545A - Water dispersion for fiber, method for producing fiber structure and fiber product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber structure especially exhibiting excellent hydrolysis resistance, and having stainproof properties against blood and characteristics mild to the skin, and to provide a finishing method thereof. <P>SOLUTION: The water dispersion for fiber contains (A) a copolyester resin having a sulfonate group, and (B) a (meth)acrylate copolymer resin containing a polymerizable monomer at least having a phosphorylcholine group as a constituent component. The fiber product is obtained by finishing the fiber product by using the dispersion. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an aqueous dispersion for fibers, a method for producing a fiber structure, and a textile product, which are hydrolysis resistant, exhibit excellent antifouling properties and stain removability against blood stains, and have skin-friendly properties.

  Conventionally, many fiber processing agents having antifouling properties have been proposed. In general, for example, a hydrophilic resin such as a water-soluble cellulose derivative is provided together with a crosslinking agent (Patent Document 1), a fluorine-based water repellent containing a hydrophilic group (Patent Document 2), a silicone compound, and these resins What gave both (patent document 3) etc. are known. However, it is difficult to say that these have sufficient antifouling properties.

  Those with hydrophilic resin have the effect of preventing re-contamination that makes it difficult to adsorb other dirt during washing, but sebum dirt etc. should be removed even after washing once the dirt has adhered and dried. Is becoming very difficult.

  In addition, those with a fluorinated water repellent containing a hydrophilic group are less likely to get liquid stains, both aqueous and oily, but those with a high viscosity are not fluorinated. At the same time, it adheres in the same manner, and stains from washing are difficult to remove.

  In addition, those imparted with both of these resins generally do not exhibit sufficient effects of hydrophilicity, water repellency and oil repellency, so that sufficient antifouling properties cannot be obtained.

  On the other hand, a resin containing a phosphorylcholine group is gentle to the skin and has a characteristic that blood does not coagulate, but an aqueous dispersion for antifouling fibers using this has not been put to practical use.

  Appropriate measures to improve fabric materials, especially polyester and / or cellulosic fiber-containing textile processing agents, including wash and wear properties and antifouling properties, as well as improved durability and physical properties The texture, touch, and appearance have been mainly improved. For example, a cellulose fiber-containing fiber structure using a photocatalyst (Patent Document 4) and the like have been proposed for the purpose of combining deodorization and antibacterial properties in addition to antifouling properties. Further, a method of treating with a resin composition comprising a phosphorylcholine group-containing resin and either a hydrophilic resin or a fluororesin for polyester fibers is disclosed (Patent Document 5). Is a copolymer composed of a polyalkylene glycol such as polyethylene glycol or polypropylene glycol and an aromatic dicarboxylic acid, and therefore lacks hydrolysis resistance. Therefore, it has a problem that it is not suitable for medical care such as hospital clothes and sheets to be boiled.

JP-A-6-31327 JP 2003-96673 A JP 2004-44056 A JP 2001-316773 A JP-A-2005-23465

  In view of the above-described conventional technology, the present invention provides an aqueous dispersion for fibers and a fiber product using the same, which has hydrolysis resistance, and particularly has a purpose of imparting antifouling properties against blood and skin-friendly properties. It is in.

In order to solve the above problems, the present invention provides the following configurations.
That is,
(1) A water dispersion for fibers comprising a copolymerized polyester resin (A) containing a sulfonate group and a copolymerized (meth) acrylate resin (B) containing at least a polymerizable monomer having a phosphorylcholine group.
(2) The aqueous dispersion for fibers according to (1) above, wherein the copolymerized polyester resin (A) contains 0.001 mol% to 20 mol% of a dicarboxylic acid having a sulfonate group.
(3) The acid component of the copolymer polyester resin (A) is composed of dicarboxylic acid, the glycol component is composed of 10 to 100 mol% of alkylene glycol and 90 to 0 mol% of other glycol, and the reduced viscosity is 0.10 dl / g. The aqueous dispersion for fibers according to any one of (1) and (2) above.
(4) The copolymer (meth) acrylate resin (B) is composed of 20 to 85 mol% of a polymerizable monomer having a phosphorylcholine group and 15 to 80 mol% of a hydrophilic and / or hydrophobic polymerizable monomer. The aqueous dispersion for fibers according to any one of (1) to (3) above.
(5) The copolymerized polyester resin (A), the copolymerized (meth) acrylate resin (B) obtained from the polymerizable monomer, and the fluororesin are 0.1% by weight or more and 15% by weight based on the total weight of the fiber structure. The aqueous dispersion for fibers according to any one of the above (1) to (4), wherein the aqueous dispersion is applied at a ratio of less than%.
(6) Any one of (1) to (5) above, wherein at least one selected from an epoxy resin, a blocked isocyanate compound, formaldehyde, an alkyl etherified aminoformaldehyde resin and a polyvalent oxazoline resin is used as a curing agent. An aqueous dispersion for fibers according to claim 1.
(7) A method for producing a fiber structure processed with the aqueous dispersion for fibers according to any one of (1) to (6).
(8) Sheets, aprons, lab coats, surgical gowns, surgical gloves, hats, masks, handkerchiefs, towels, curtains, pillowcases manufactured using the fiber structure obtained by the method described in (7) above A textile product characterized in that it is at least one selected from medical / nursing care, daily miscellaneous goods and clothing such as diapers, shirts, blouses and lace products.
It is.

  According to the present invention, an aqueous dispersion for fibers comprising a copolymerized polyester resin (A) containing at least a sulfonate group and a copolymerized (meth) acrylate resin (B) containing at least a polymerizable monomer having a phosphorylcholine group as constituent components. Is used to produce a fiber product that is resistant to hydrolysis, has excellent durability and anti-staining properties, and has excellent anti-staining properties and SR properties against blood stains, and has a soft texture and is gentle to the skin. It becomes possible to obtain.

  The aqueous dispersion for fibers of the present invention comprises a copolymerized polyester resin (A) containing a sulfonate group and a copolymerized (meth) acrylate resin (B) obtained from a polymerizable monomer having at least a phosphorylcholine group, a fluororesin, and a necessity. Accordingly, a heat treatment is performed after applying a curing agent or the like to the fiber structure.

  Here, the phosphorylcholine group is a group mainly possessed by phospholipid molecules that are constituents of biological membranes, and is generally known as a highly biocompatible substance. That is, when the fiber structure is used for the purpose of touching the skin, the skin does not recognize the fiber structure as a foreign substance, and allergic reaction does not occur, thereby eliminating the irritation to the skin surface of the fiber structure. And can impart skin-friendly properties at higher levels. Furthermore, it also has a feature that blood does not coagulate. By using the aqueous fiber dispersion of the present invention, it is possible to impart a blood stain-proofing effect having a washing durability to the fiber structure. Further, the copolymerized polyester resin (A) of the present invention has hydrolysis resistance, and is particularly effective for improving the adhesion to polyester fibers.

The details are described below.
Examples of the aromatic dicarboxylic acid that can be used in the copolymerized polyester resin (A) of the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid. Of these, terephthalic acid and isophthalic acid are particularly preferably used as the aromatic dicarboxylic acid from the viewpoint of processability and hardness.

  Examples of the dicarboxylic acid copolymerized with the polyester (A) of the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2, 8-Naphthalenedicarboxylic acid diphenyl-4,4′-dicarboxylic acid, aromatic dicarboxylic acid such as diphenoxyethanedicarboxylic acid and functional derivatives thereof, oxyacid such as p-oxybenzoic acid and oxycaproic acid and functional derivatives thereof , Aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid, glutaric acid, dimer acid, dodecanedicarboxylic acid, azelaic acid and functional derivatives thereof, and fats such as hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, etc. Cyclic dicarboxylic acids and their functional derivatives And so on. In addition, unsaturated double bonds such as polycarboxylic acids such as trimellitic anhydride and pyromellitic anhydride, maleic acid, fumaric acid, itaconic acid, dimer acid, dodecenyl succinic acid and the like are within the scope of the present invention. You may use together dicarboxylic acid etc. which had.

The glycol component that can be used in the copolymerized polyester resin (A) of the present invention includes ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1 , 5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propane Diols, 1,7-octanediol, 2-butyl-2-ethyl-1,3-propanediol, alkylene glycols such as 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,4 Cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, TCD glycol, alicyclic glycols such as spiro glycol, and the like dimer diols. Of these, 1,6-hexanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol are particularly preferable from the viewpoint of film properties and weather resistance. In addition, a polyhydric polyol such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol may be used in combination as long as the content of the invention is not impaired.
In the polyester of the present invention, lactones can also be subjected to ring-opening addition polymerization at molecular chain terminals. Specific examples of lactones include β-propiolactone, β-2,2-dimethylpropiolactone, δ-valerolactone, δ-3-methylvalerolactone, ε-caprolactone, and the like. Is ε-caprolactone. Moreover, the polyester resin copolymerized with said raw material etc. can also be used in combination of 2 or more type.

  Examples of the dicarboxylic acid or glycol containing a sulfonate group such as a metal salt used in the present invention include 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5 [ 4-sulfophenoxy] isophthalic acid and the like, and salts of 2-sulfo-1,4-butanediol, 2,5-dimethyl-3-sulfo-2,5-hexanediol and the like. Examples of phosphonium salts of sulfonic acid group-containing aromatic dicarboxylic acid or sulfonic acid group-containing glycol include those represented by the following general formula.

(Wherein A is an aromatic group, X1 and X2 are ester-forming functional groups, R1, R2, R3 and R4 are alkyl groups, at least one of which is an alkyl group having 6 to 20 carbon atoms)

  Specifically, sulfo-isophthalic acid tri-n-butyldecylphosphonium salt, sulfoisophthalic acid tri-n-butyloctadecylphosphonium salt, sulfoisophthalic acid tri-n-butylhexadecylphosphonium salt, sulfoisophthalic acid tri-n-butyl Tetradecylphosphonium salt, sulfoisophthalic acid tri-n-butyldodecylphosphonium salt, sulfoterephthalic acid tri-n-butyldecylphosphonium salt, sulfoterephthalic acid tri-n-butyloctadecylphosphonium salt, sulfoterephthalic acid tri-n-butylhexa Decylphosphonium salt, sulfo-terephthalic acid tri-n-butyltetradecylphosphonium salt, sulfoterephthalic acid tri-n-butyldodecylphosphonium salt, 4-sulfonaphthalene-2, 7-dicarboxylic acid tri-n-butyl Rudecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyloctadecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butylhexadecylphosphonium salt, 4-sulfonaphthalene -2,7-dicarboxylic acid tri-n-butyltetradecylphosphonium salt, 4-sulfonaphthalene-2, 7-dicarboxylic acid tri-n-butyldodecylphosphonium salt, and the like. Examples of the carboxyl group-containing glycol include dimethylolpropionic acid and dimethylolbutanoic acid. These can be used after being introduced into an organic resin and neutralized with ammonia or the like. Preferably, metal salts such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5 [4-sulfophenoxy] isophthalic acid, or 2-sulfo-1,4-butanediol , 2,5-dimethyl-3-sulfo-2,5-hexanediol, and more preferably 5-sulfoisophthalic acid and sulfoterephthalic acid tend to have good water dispersibility.

  The copolymerized polyester resin (A) used in the present invention is used in the form of an aqueous solution or a water dispersion. In order to dissolve or disperse the copolyester resin in water, the sulfonate group-containing dicarboxylic acid or polyol can be used in an amount of 0.001 to 20 mol% based on the total acid or the total polyol. Preferably it is 0.1-15 mol%, More preferably, it is 1-10 mol%. If it exceeds 20 mol%, the melt viscosity at the time of polymerization becomes excessively high, resulting in a problem that the water resistance is lowered. If the amount is less than 0.001 mol%, good water dispersibility or solubility cannot be obtained, so that a carboxyl group must be used in combination. Dicarboxylic acids or polyols containing sulfonic acid metal bases include metals such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5 [4-sulfophenoxy] isophthalic acid. Examples thereof include salts or metal salts such as 2-sulfo-1,4-butanediol and 2,5-dimethyl-3-sulfo-2,5-hexanediol. Examples of the metal salt include salts of Li, Na, K, Mg, Ca, Cu, Fe and the like. Of these, 5-sodium sulfoisophthalic acid is particularly preferable.

Later, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride, 1,8-naphthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, and the like may be added to give an acid value. By imparting an acid value, the reactivity with the curing agent can be increased and the contamination can be further improved. A preferable acid value is 20-300 equivalent / 10 < ⁶ > g. More preferably, it is 50-150 equivalent / 10 < ⁶ > g. When the acid value exceeds 300 equivalents / 10 ⁶ g, good processability cannot be obtained.

In the present invention, the (meth) acrylate resin represents at least one of an acrylate resin and a methacrylate resin.
Examples of the phosphorylcholine group-containing monomer group that is one component of the copolymer (meth) acrylate resin (B) of the present invention include, for example, 2-((meth) acryloyloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate, 3-((meth) acryloyloxy) propyl-2 '-(trimethylammonio) ethyl phosphate, 4-((meth) acryloyloxy) butyl-2'-(trimethylammonio) ethyl phosphate, 5-((meth) Acryloyloxy) pentyl-2 ′-(trimethylammonio) ethyl phosphate, 6-((meth) acryloyloxy) hexyl-2 ′-(trimethylammonio) ethyl phosphate, 2-((meth) acryloyloxy) ethyl-2 '-(Triethylammonio) ethyl phosphate, 2- ( (Meth) acryloyloxy) ethyl-2 '-(tripropylammonio) ethyl phosphate, 2-((meth) acryloyloxy) ethyl-2'-(tributylammonio) ethyl phosphate, 2-((meth) acryloyloxy) Ethyl-2 ′-(tricyclohexylammonio) ethyl phosphate, 2-((meth) acryloyloxy) ethyl-2 ′-(triphenylammonio) ethyl phosphate, 2-((meth) acryloyloxy) ethyl-2 ′ -(Trimethanolammonio) ethyl phosphate, 2-((meth) acryloyloxy) propyl-2 '-(trimethylammonio) ethyl phosphate, 2-((meth) acryloyloxy) butyl-2'-(trimethylammonio) ) Ethyl phosphate, 2-((meth) acrylic Yloxy) pentyl-2 ′-(trimethylammonio) ethyl phosphate, 2-((meth) acryloyloxy) hexyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (vinyloxy) ethyl-2 ′-(trimethylammoni) E) ethyl phosphate, 2- (allyloxy) ethyl-2 '-(trimethylammonio) ethyl phosphate, 2- (p-vinylbenzyloxy) ethyl-2'-(trimethylammonio) ethyl phosphate, 2- (p- Vinylbenzoyloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (styryloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (p-vinylbenzyl) ethyl-2 ′-( Trimethylammonio) ethyl phosphate, 2- (bi Nyloxycarbonyl) ethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (allyloxycarbonyl) ethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (acryloylamino) ethyl-2 ′-(trimethyl) Ammonio) ethyl phosphate, 2- (vinylcarbonylamino) ethyl-2 '-(trimethylammonio) ethyl phosphate, ethyl- (2'-trimethylammonioethyl phosphorylethyl) fumarate, butyl- (2'-trimethylammonio) Ethyl phosphorylethyl) fumarate, hydroxyethyl- (2′-trimethylammonioethyl phosphorylethyl) fumarate, ethyl- (2′-trimethylammonioethyl phosphorylethyl) malate, butyl- (2′-trimethylammonioethyl) Suhoriruechiru) malate, hydroxyethyl - (2'-trimethylammonio ethyl phosphoryl ethyl) maleate, and the like.

  Among these, 2-((meth) acryloyloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate is preferable, and 2- (methacryloyloxy) is more preferable from the viewpoint of availability, hygroscopicity, and good touch. Ethyl-2 ′-(trimethylammonio) ethyl phosphate (hereinafter abbreviated as MPC).

In the present invention, a hydrophilic monomer which is one constituent of the copolymerized (meth) acrylate resin (B), particularly a monomer having a hydroxyl group is particularly important.
Examples of the monomer group having a hydroxyl group as one component of the copolymer of the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4- Examples include hydroxyl group-containing (meth) acrylates such as hydroxybutyl (meth) acrylate. The alkyl group in these C1-C4 hydroxy lower alkyl (meth) acrylates may be branched. Moreover, these 1 type (s) or 2 or more types may be used together as the said hydroxyl-containing monomer.
It goes without saying that the hydrophilic monomer group having a hydroxyl group is also useful for improving the affinity with the hydrophilic fiber.

  Other hydrophilic group-containing monomers are used as copolymerization components. For example, ionic groups such as carboxyl group-containing (meth) acrylates such as acrylic acid and methacrylic acid, styrene sulfonic acid, (meth) acryloyloxyphosphonic acid, 2-hydroxy-3- (meth) acryloxypropyltrimethylammonium chloride Monomers containing monomers, nitrogen-containing monomers such as (meth) acrylamide, aminoethyl methacrylate, dimethylaminoethyl (meth) acrylate, polyethylene glycol (meth) acrylate and the like may be used. Further, one or more of these may be used in combination with the above hydroxyl group-containing monomer. Of these, those used as a copolymer component having a carboxyl group are particularly effective when a polyvalent oxazoline resin is used as a curing agent.

  When the fiber structure contains a hydrophobic synthetic fiber, a hydrophobic monomer can be used as a comonomer monomer component in order to improve the affinity with the hydrophobic fiber. For example, linear or branched alkyl (meth) acrylic such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Rate; cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate; aromatic (meth) acrylates such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, and hydrophobic poly such as polypropylene glycol (meth) acrylate Alkylene glycol (meth) acrylates, styrene monomers such as styrene, methylstyrene and chloromethylstyrene, vinyl ether monomers such as methyl vinyl ether and butyl vinyl ether, vinyl acetate Le, vinyl ester monomers such as vinyl propionate and the like are Kyora. These 1 type (s) or 2 or more types are used.

  The copolymerized polyester resin (A) and copolymerized (meth) acrylate resin (B) used as the aqueous dispersion for fibers of the present invention may be polymerized separately and then blended, or the copolymerized polyester resin (A ) Is dissolved in a solvent, and the monomer composition comprising the phosphorylcholine group-containing monomer component and the hydrophilic group and / or hydrophobic group-containing monomer component may be polymerized. It can be produced by polymerization.

  The molecular weight of the copolymerized (meth) acrylate resin (B) of the present invention is preferably in the range of 5,000 to 5,000,000, more preferably in the range of 100,000 to 2,000,000, on a weight average basis. is there. When the molecular weight is less than 5,000, it is difficult to sufficiently exhibit the good touch and moisture absorption of the copolymerized (meth) acrylate resin (B), and when it exceeds 5,000,000, the copolymerized (meth) acrylate resin Since the viscosity of the aqueous solution (B) becomes too high, it may be difficult for the treatment agent to uniformly penetrate into the fibers, which may be unfavorable because the resulting fiber may be damaged.

  The copolymer (meth) acrylate resin (B) has a phosphorylcholine group-containing monomer component of 20 to 85 mol% and a total hydrophilic group-containing monomer component of 15 to 60 mol% (however, the hydrophilic group-containing monomer containing a hydroxyl group is And a polymer obtained by polymerizing a monomer composition consisting of 2 to 40 mol% as a hydrophobic group-containing monomer component. More preferably, it is a monomer composition of 40 to 70 mol% as the phosphorylcholine group-containing monomer component, 20 to 40 mol% of the hydrophilic group-containing monomer component, and 5 to 20 mol% of the hydrophobic group-containing monomer component.

  When the phosphorylcholine group-containing monomer component is less than 20 mol% or exceeds 85 mol%, neither good tactile sensation nor moisture retention can be obtained. Moreover, if the hydrophilic monomer component containing a hydroxyl group is less than 10 mol%, it is not preferable because of lack of washing durability. If the total hydrophilic group-containing monomer component is less than 15 mol%, the affinity for the hydrophilic fiber is not preferred, and if it exceeds 60 mol%, the affinity for the fiber is insufficient when the composition ratio of the hydrophobic fiber is increased. It is an aspect. In addition, if the hydrophobic monomer component is less than 2 mol%, sufficient affinity for a fiber structure containing hydrophobic fibers such as polyester cannot be obtained, while if it exceeds 40 mol%, the affinity for hydrophilic fibers is insufficient. It is not preferable.

  As specific examples of the resin containing the phosphorylcholine group, the resins described in JP-A-8-333421 and JP-A-2001-200480 can be used.

  The fibers of the above-mentioned copolymerized polyester resin (A) and copolymerized (meth) acrylate resin (B) in order to exhibit hydrolysis resistance, a characteristic of the present invention, and exhibit antifouling properties and skin-friendly characteristics The adhesion amount to the structure is preferably 0.1% to 15% by weight, more preferably 0.5% to 10% by weight based on the total weight of the fiber structure. That is, if the amount of adhesion is less than 0.1% by weight, antifouling properties and skin-friendly characteristics cannot be sufficiently obtained, and if it exceeds 15% by weight, the texture of the fiber structure is cured, There is a tendency for skin irritation to be stronger when worn.

  The following are mentioned as a hardening | curing agent of the copolymerization polyester resin (A) and copolymerization (meth) acrylate resin (B) of this invention. That is, an isocyanate compound, an alkyl etherified amino formaldehyde resin, an epoxy compound, a phenol resin, a polyvalent oxazoline compound, and the like can be given. Of these, alkyl etherified aminoformaldehyde resins, polyvalent oxazoline compounds, and resol type phenol resins are preferred in terms of processability. Furthermore, an isocyanate compound is particularly preferable from the viewpoint of acid resistance, and the isocyanate compound is preferably used after being blocked from the viewpoint of storage stability.

  As the isocyanate compound, there are aromatic and aliphatic diisocyanates, trivalent or higher polyisocyanates, and any of low molecular compounds and high molecular compounds may be used. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, or trimers of these isocyanates, and excess of these isocyanate compounds Amount of low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine or various polyester polyols, polyether polyols, polyamides Reacts with polymer active hydrogen compounds Terminal isocyanate group-containing compounds obtained Te are exemplified.

  As the isocyanate compound, a blocked isocyanate is preferable. Examples of the isocyanate blocking agent include phenols such as phenol, thiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol, oximes such as acetoxime, methylethyl ketoxime, cyclohexanone oxime, methanol, ethanol, propanol , Alcohols such as butanol, halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol, tertiary alcohols such as t-butanol and t-pentanol, ε-caprolactam, δ- Examples include lactams such as valerolactam, γ-butyrolactam, and β-propylactam. Other examples include aromatic amines, imides, active methylene compounds such as acetylacetone, acetylacetic acid ester, and malonic acid ethyl ester, mercaptans, imines, ureas, diaryl compounds, and sodium bisulfite. The blocked isocyanate can be obtained by addition reaction using the above-mentioned isocyanate compound, an isocyanate blocking agent and a conventionally known appropriate method.

  The alkyl etherified aminoformaldehyde resin is, for example, formaldehyde or paraformaldehyde alkylated with an alcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol, urea, N, N '-Ethyleneurea, dicyandiamide, aminotriazine and the like, which are condensation products such as methoxylated methylol-N, N'-ethyleneurea, methoxylated methylol dicyandiamide, methoxylated methylol benzoguanamine, broxylated methylol benzoguanamine, methoxylated methylol melamine, Examples include butoxylated methylol melamine, mixed methoxylated / butoxylated methylol melamine, and butoxylated methylol benzoguanamine. Et Preferred are methoxy methylol melamine, butoxy methylol melamine or methoxylated / butoxylated mixed melamine, may be used alone, or in combination. In addition, as a special example, when the crosslinking reaction is performed in the form of a sewn product, a gas phase reaction using formaldehyde can also be performed.

  Examples of the epoxy compound include diglycidyl ether of bisphenol A and oligomers thereof, diglycidyl ether of hydrogenated bisphenol A and oligomers thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-oxybenzoic acid Diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and polyalkylene Glycol diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, Examples thereof include pentaerythritol tetraglycidyl ether and triglycidyl ether of glycerol alkylene oxide adduct.

  Furthermore, examples of the phenol resin include a resol type resin obtained by reacting phenol with an aldehyde in the presence of an alkali catalyst, and a novolak type obtained by reacting phenol with an aldehyde in the presence of an acidic catalyst. In particular, a resol type resin is preferable. The phenols used in these phenol resins are phenol, o-cresol, p-cresol, m-cresol, m-methoxyphenol, 2,3-xylenol, 2,5-xylenol, p-tert-butylphenol, p-ethyl. Phenol, bisphenol A, bisphenol F, etc. are mentioned, and these mono-trimethylol products and their condensates or their alkyl etherified products, or various modifications such as epoxy modification, oil modification, melamine modification, amide modification, etc. Can be used. Preferable phenols that can be used as the raw material include phenol, m-cresol, bisphenol A, and bisphenol F that are trifunctional or higher as phenol.

  Examples of the addition polymerizable monomer having an oxazoline group that can be used as a main constituent monomer component of the polyvalent oxazoline compound include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, and 2-vinyl-5-methyl. 2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2 -An oxazoline etc. can be mentioned, The 1 type, or 2 or more types of mixture chosen from these groups can be used. Among them, 2-isopropenyl-2-oxazoline is preferable because it is easily available industrially. The copolymer of these monomers having an oxazoline group and the above-described hydrophilic and / or hydrophobic (meth) acrylate can be used as a curing agent by utilizing an addition reaction of a polyvalent oxazoline group and a carboxyl group.

  These curing agents are preferably used in combination with a known curing agent or accelerator selected according to the type.

  The method for treating the copolymerized polyester resin (A) and copolymerized (meth) acrylate resin (B) of the present invention with fibers is as follows: (1) the copolymerized polyester resin (A) and copolymerized (meth) acrylate resin (B ) And a method of immersing and drying the fiber in the fiber treatment aqueous dispersion, or (2) a method of directly applying the fiber treatment to the fiber and drying the fiber treatment water dispersion.

  When it is desired to completely dry after treating the fiber, the drying temperature is preferably in the range of 40 to 180 ° C., and at a temperature lower than 40 ° C., the hygroscopic property inherent in the treating agent applied to the fiber. In this case, the phosphorylcholine group may be decomposed at a temperature higher than 180 ° C., which is not preferable.

  However, even when used for household washing, soft finishing, etc., or when used for business purposes, if there is no problem with moisture absorption after the treatment, it can be dried at room temperature.

  Still further, 0.1 to 15% by weight aqueous solution of the composition comprising the copolymerized polyester resin (A) and the copolymerized (meth) acrylate resin (B) includes, for example, ethylene glycol, 1,3-butanediol. It is more preferable to add polyhydric alcohols such as 1,4-butanediol, glycerin, and sorbitol in the range of 0.001 to 10% by weight because the familiarity between the fiber and the composition can be improved.

  Moreover, you may add other components, such as surfactant, a softening agent, a solvent, dye, a moisturizer, an antibacterial agent, and a fragrance | flavor, to the processing liquid of this invention as needed.

  The fluororesin that can be used in the present invention contains a polyfluoroalkyl group and a hydrophilic group, and a copolymer comprising a monomer having a polyfluoroalkyl group and a monomer having a hydrophilic group is preferably used.

  At this time, as a monomer having a polyfluoroalkyl group in the production of the copolymer, an acrylate ester containing a terminal perfluoroalkyl group having 3 to 20 carbon atoms, preferably 6 to 14 carbon atoms, is preferably used. It is done.

  The adhesion amount of the fluororesin used in the present invention is preferably fixed on the fiber structure at a ratio of 0.1 wt% or more and less than 15 wt% with respect to the fiber structure. If it is less than 0.1% by weight, sufficient antifouling properties cannot be obtained, and if it is 15% by weight or more, the texture of the fiber structure is cured and is not practical. More preferably, it is 0.5 wt% or more and less than 10 wt%.

  Here, the fiber surface includes, but is not limited to, the surface of one single fiber constituting the fiber structure, the surface of a yarn, or the surface of one surface of the fiber structure.

  The fiber structure referred to in the present invention includes natural celluloses such as cotton and hemp, regenerated celluloses such as rayon, woven fabrics of purified celluloses such as tencel (lyocell), fabrics such as knitted fabrics and non-woven fabrics, as well as strips, Any structure or shape may be used as long as it includes fibers such as string-like materials and thread-like materials. In addition to cellulose fibers, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6 and nylon 66, and woven fabrics, knitted fabrics and nonwoven fabrics in which synthetic fibers such as polyacrylonitrile and cellulose fibers are combined. Of course, the structure and the shape are not limited as long as the fabric includes fibers such as a strip, a string, and a thread.

  When the fiber structure of the present invention contains cellulose fibers, ordinary mercerization or liquid ammonia treatment with sodium hydroxide, and after mercerization, liquid ammonia treatment and those dyed by pre-dyeing, dip dyeing, printing, etc. Can be used. If it is necessary to mix with synthetic fibers typified by polyester, it may be heat set in advance.

  It is a preferred embodiment that a moisturizing agent and a softening agent are further added during the preparation of the treatment liquid of the present invention.

  The humectant that can be used in the present invention is not particularly limited as long as it can absorb and retain water, but polyols, squalane and the like can be used.

  Polyols that can be used in the present invention include ethylene glycol, propylene glycol compounds, copolymers of ethylene oxide and propylene oxide, glycerin, neopentyl glycol, trimethylolpropane, erythritol, pentaerythritol, sorbitol, and ethylene oxides thereof. And / or adducts of propylene oxide can be utilized.

  The softening agent that can be used in the present invention is used for the purpose of making the texture of the fiber structure preferable, or for the purpose of improving the tearing strength when the fiber structure is a woven fabric. Dimethylpolysiloxane, epoxy-modified silicone , Silicone softeners such as amino-modified silicone and water-soluble silicone, wax softener, polyethylene softener, fatty acid amide softener, polyurethane softener, polyester softener, acrylic ester softener, nonion, anion Cationic and amphoteric surfactants can be used.

  Furthermore, in the present invention, functional processing agents such as water repellents, antibacterial agents, deodorants, and antistatic agents can be used at the same time.

  The fiber structure of the present invention can be processed in any of the state of cotton, yarn, fabric, and the state of a sewn product, but it is more economical to process after making it into a sewn product. Since the shape of the sewn product is also effectively fixed, the puckering property, the shape retaining property and the like are improved, which is a preferred embodiment.

Synthesis Example of the Present Invention: Copolyester Resin (A)
Synthesis Example of Copolymerized Polyester Resin (A1) In a four-necked flask equipped with a stirrer, thermometer and Vigreux fractionating tube, 97 parts of dimethyl terephthalate, 91 parts of dimethyl isophthalate, 9 parts of dimethyl 5-sodium sulfoisophthalate, ethylene 91 parts of glycol, 76 parts of neopentyl glycol, and 0.068 part of tetrabutyl titanate as a catalyst were charged, and a transesterification reaction was carried out for 5 hours while distilling methanol generated at 180 to 230 ° C. out of the system. Subsequently, the Vigreux fractionation tube was removed, and the reaction system was depressurized to 5 mmHg over 30 minutes, and the temperature was raised to 210 ° C. during this time. Further, a polycondensation reaction was carried out at 0.3 mmHg and 230 ° C. for 60 minutes to obtain a copolymer polyester resin (A1). As a result of analysis such as NMR, the obtained polyester resin is terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // ethylene glycol / neopentyl glycol = 50/47/3 // 49/51 (molar ratio). It was a pale yellow transparent resin having a reduced viscosity of 0.55 dl / g, a number average molecular weight of 17,000, and a glass transition temperature of 67 ° C.

  Subsequently, 200 parts of a polyester resin (A1) and 700 parts of methyl ethyl ketone were charged into a four-necked flask equipped with a thermometer and a condenser and dissolved at 70 ° C. To this was charged 175 parts of isopropyl alcohol, and 800 parts of ion-exchanged hot water at 50 ° C. was gradually added with stirring. Then, the system was gently evacuated and the solvent was distilled off at 50 ° C. to obtain an aqueous dispersion (a1) of a copolyester resin. This dispersion was a translucent, stable solution having a solid content of 20%. The results are shown in Table 1.

Synthesis of polyester resin (A2) In a four-necked flask equipped with a stirrer, thermometer and Vigreux fractionation tube, 97 parts of dimethyl terephthalate, 83 parts of dimethyl isophthalate, 21 parts of dimethyl 5-sodium sulfoisophthalate, ethylene of bisphenol A 176 parts of BPE-20 (manufactured by Sanyo Chemical Industries Co., Ltd.), which is a 2.2 mol oxide product, 102 parts of ethylene glycol, and 0.068 part of tetrabutyl titanate as a catalyst were charged, and methanol produced at 180 to 230 ° C. The ester exchange reaction was carried out for 5 hours while distilling out of the system. Subsequently, the Vigreux fractionation tube was removed, and the reaction system was depressurized to 5 mmHg over 30 minutes, and the temperature was raised to 210 ° C. during this time. Furthermore, a polycondensation reaction was performed for 30 minutes at 0.3 mmHg and 230 ° C. to obtain a polyester resin (A-2). As a result of analysis such as NMR, the obtained polyester resin is terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // BPE-20 / ethylene glycol = 50/43/7 // 55/45 (molar ratio). It was a pale yellow transparent resin having a reduced viscosity of 0.40 dl / g, a number average molecular weight of 10,000, and a glass transition temperature of 73 ° C. Then, a 20% aqueous dispersion (a2) was obtained in the same manner as the polyester resin (A1). The results are shown in Table 1.

Synthesis of Copolyester Resin (A3) 97 parts of dimethyl terephthalate, 93 parts of dimethyl isophthalate, 6 parts of dimethyl 5-sodium sulfoisophthalate, neopentyl in a four-necked flask equipped with a stirrer, thermometer and Vigreux fractionation tube 176 parts of glycol, 58 parts of 3-methyl-1,5-pentanediol and 0.086 part of tetrabutyl titanate as a catalyst were charged, and the ester exchange was performed for 5 hours while distilling methanol produced at 180 to 230 ° C. out of the system. The reaction was carried out. Subsequently, the Vigreux fractionation tube was removed and the reaction system was depressurized to 5 mmHg over 30 minutes, and the temperature was raised to 210 ° C. during this time. Further, a polycondensation reaction was performed at 0.3 mmHg and 230 ° C. for 30 minutes. Next, the inside of the system was brought to normal pressure under a nitrogen atmosphere, cooled to 200 ° C., and 1.9 parts of trimellitic anhydride was charged and reacted for 30 minutes to obtain a polyester resin (A3). As a result of analysis such as NMR, the obtained polyester resin was terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid / trimellitic acid (post-addition) // neopentyl glycol / 3-methyl-1,5-pentanediol = It was a light yellow transparent resin having a 50/48/2/2 // 77/23 (molar ratio), a reduced viscosity of 0.60 dl / g, a number average molecular weight of 18,000, and a glass transition temperature of 32 ° C.

  Subsequently, 200 parts of a polyester resin (A3) and 700 parts of methyl ethyl ketone were charged in a four-necked flask equipped with a thermometer and a condenser and dissolved at 70 ° C. The mixture was charged with 175 parts of isopropyl alcohol, and a solution of 5.0 parts of 38% ammonia water in 700 parts of hot water subjected to ion exchange at 50 ° C. was gradually added with stirring. Subsequently, the system was depressurized and the solvent was distilled off at 50 ° C. to obtain an aqueous dispersion (a3) of the polyester resin (A3). This dispersion was a translucent stable solution having a solid content of 20%. The results are shown in Table 1.

Synthesis of Comparative Copolymerized Polyester Resins (A4) and (A5) Comparative polyester resins (A4) and (A5) and a 20% solid content aqueous dispersion (a4) were prepared in the same manner as in the synthesis example of the copolyester resin (A1). And (a5) were synthesized. In the same manner as the polyester resin (A1), composition analysis and measurement of resin properties were performed. The results are shown in Table 2.

Hereinafter, the synthesis examples of the present invention will be described in detail. Next, a method for analyzing the glass transition temperature and the weight average molecular weight of the copolymerized polyester resin (A) used is shown.
<Measuring method of glass transition temperature (Tg)>
Measured with a differential thermal analyzer (DSC), RDC-220, manufactured by Seiko Electronics Industry Co., Ltd. The sample was heated at a rate of temperature increase of 20 ° C./minute, and 5 mg of the sample was placed in an aluminum press-lid container and crimped.
<Measuring method of number average molecular weight (Mn)>
The average molecular weight was determined by GPC method.
(Preparation of sample) Tetrahydrofuran was used as a solvent, and 0.05 g of sample resin was dissolved in 1 g of tetrahydrofuran to prepare a sample.
(Apparatus) A high-speed GPC apparatus 150C manufactured by Waters Co., Ltd. was used.
(Standard polystyrene) TSK standard polystyrene manufactured by Tosoh Corporation was used.
(Measurement conditions) Measurement was performed at a measurement temperature of 30 ° C. and a flow rate of 1 ml / min.
(Detector) RI detector (in terms of molecular weight) calculated in terms of standard styrene

Synthesis Example 1: Copolymerized (meth) acrylate resin (B1)
44 g of MPC, 10 g of 2-hydroxyethyl methacrylate (HEMA), 3.5 g of n-butyl methacrylate (BMA) were dissolved in ethanol; 230 g, put into a four-necked flask, blown with nitrogen for 30 minutes, and then azobis at 60 ° C. 1.38 g of isobutyronitrile was added and the polymerization reaction was carried out for 8 hours. The polymerization solution was dropped into 3 liters of diethyl ether with stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 43.1 g of powder. Table 2 shows the monomer composition and number average molecular weight of the obtained copolymer (meth) acrylate resin (B1). 20 g of the above powder was dissolved in 70 g of distilled water to obtain a 20% solid content aqueous dispersion (b1) of copolymerized (meth) acrylate resin (B1).

Synthetic Example of Copolymerized (Meth) acrylate Resin (B2) of the Present Invention By changing the type and composition ratio of the monomer according to Synthetic Example 1 and operating according to Synthetic Example 1, copolymerized (meth) acrylate resin (B2) ) Table 2 shows the monomer composition and number average molecular weight of the resin (B2) obtained. Further, 20 g of the above powder was dissolved in 70 g of distilled water to obtain a 20% solid dispersion (b2) of a copolymer (meth) acrylate resin (B2).

Comparative copolymerized (meth) acrylate resin (B3)
The monomer type and composition ratio were changed in accordance with Synthesis Example 1, and a copolymerized (meth) acrylate resin (B3) was obtained by an operation in accordance with Synthesis Example 1. Table 2 shows the monomer composition and number average molecular weight of the obtained resin (B3). Subsequently, 200 parts of polyester resin (B1) and 700 parts of methyl ethyl ketone were charged into a four-necked flask equipped with a thermometer and a condenser, and dissolved at 70 ° C. To this was charged 175 parts of isopropyl alcohol, and 800 parts of ion-exchanged hot water at 50 ° C. was gradually added with stirring. Next, the system was gently evacuated and the solvent was distilled off at 50 ° C. to obtain a 20% solids dispersion (b3) of a copolymerized (meth) acrylate resin (B3).

Synthesis Example of Copolymerized Polyester Resin (A) / Copolymerized (Meth) acrylate Resin (B) Composite System of the Present Invention Copolyester Resin (A1) / Copolymerized (Meth) acrylate Resin (B1) Composite of the Present Invention In a system in which 300 parts of the copolymerized polyester resin (A1) obtained by the above method and 700 parts of methyl ethyl ketone were charged into a four-necked flask equipped with a thermometer and a condenser and dissolved at 70 ° C., a copolymer (meth) acrylate resin ( Various monomers were charged at the same composition ratio as in B1). That is, 44 parts of MPC, 10 parts of 2-hydroxyethyl methacrylate (HEMA), 3.5 parts of n-butyl methacrylate (BMA) were dissolved in 230 parts of ethanol, put into a four-necked flask, and nitrogen was blown for 30 minutes. At 60 ° C., 1.38 parts of azobisisobutyronitrile was added and allowed to undergo a polymerization reaction for 8 hours. To this was charged 175 parts of isopropyl alcohol, and 1430 parts of hot water ion-exchanged at 50 ° C. was gradually added with stirring. Next, the pressure inside the system was gradually reduced, and the solvent was distilled off at 50 ° C., and a solid type in which three (meth) acrylates were grafted onto the copolymerized polyester resin (A1) or a (meth) acrylate resin was complicatedly entangled. A 20% water dispersion (a1 / b1) was obtained.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The evaluation methods used in the examples are shown below.
1. Blood antifouling evaluation method (1) Preparation method of HL = 0 and HL = 20 test cloth A processed test cloth of 40 cm × 40 cm in an automatic inversion swirl type electric washing machine (manufactured by Mitsubishi Electric Corporation: MAW-N6UP) In addition, 1000 g of the dummy cloth and 0.1 liter of synthetic detergent (Kao Co., Ltd .: Compact Big) solution 30 liters are added, washed under strong conditions for 30 minutes, and then centrifuged for about 30 seconds, followed by tap water. Rinsing was performed for 10 minutes while overflowing. Then, it dehydrated again for about 30 seconds, and rinsed again on the said conditions. By this method, it was set as 5 times of home laundry. Therefore, a sample obtained by repeating the washing four times was used as a sample of 20 home washings (HL = 20). In the above method, the strong condition of 6 minutes is indicated as (HL = 1), and the processed finish without washing is indicated as (HL = 0).
(2) Preparation of blood-contaminated sample Fix the 40cm x 40cm test cloth face up and fix it in a glass plate. Drop 0.1ml of blood in the center and leave it for 1 minute. Filter paper and tissue paper were piled up, applied with a rubber roller, and repeated until the filter paper and tissue paper did not get blood stains, and then the test cloth was allowed to stand at room temperature for 16 hours to obtain a sample for evaluating blood stain resistance.
(3) Antifouling evaluation method The blood contamination sample with and without washing was further evaluated by a visual evaluation as follows for the degree of blood contamination after one wash (HL-1) by the above washing method. It carried out in.
5th grade: no dirt 1st grade: markedly dirty

2. Observation of skin condition at the time of wearing The skin condition after wearing for 1 week was observed.
○: No sense of discomfort when worn, Δ: Some sense of discomfort when worn, ×: Some sense of discomfort when worn The term “uncomfortable” as used herein refers to a state where the skin has some irritation.

3. Hydrolysis resistance 40cm x 40cm processed test cloth is put into a stainless steel container (capacity: about 30 liters) with a steam heater containing 20 liters of distilled water, boiled in 20 minutes, and held in that state for 1 hour Then, rinsing was performed for 10 minutes while overflowing the tap water. Thereafter, the sample was dehydrated again for about 30 seconds and naturally dried to prepare a boiled sample. This sample was prepared by the above-mentioned (2) blood contamination sample preparation method, and then subjected to hydrolysis resistance in a five-step evaluation according to the above (3) antifouling property evaluation method.
5th grade: no dirt 1st grade: markedly dirty

Example 1
Polyester fabric (made by using a 165 dtex / 48 filament twin yarn for warp and weft, scoured and dyed under normal conditions) immersed in a processing solution (P1) with the following composition and squeezing rate It was squeezed to 70%, dried at 120 ° C. for 1 minute, and then cured at 150 ° C. for 6 minutes. The evaluation results of the obtained polyester fabric are shown in Table 3. Both HL = 0, HL = 20 and boiling treatment were excellent in blood removability against blood contamination, and there was no discomfort when worn.
Processing bath composition (P1):
10 parts by weight of aqueous dispersion (a1) of the copolymerized polyester resin of the present invention, 5 parts by weight of aqueous dispersion (b1) of the copolymerized (meth) acrylate resin of the present invention, Asahi Guard AG-780 (manufactured by Meisei Chemical Co., Ltd.) Fluorine resin) 5 parts by weight, Sumimar M40W (Sumitomo Chemical Co., Ltd. melamine resin) 3 parts by weight, p-toluenesulfonic acid 0.02 part, water 80 parts by weight

(Examples 2 to 7)
In Example 1, treated fabrics of Examples 2 to 7 were obtained in the same manner as in Example 1 except that the processing bath composition and the fabric material shown in Table 3 were changed. The evaluation results of these obtained woven fabrics are shown in Table 3. Both HL = 0, HL = 20 and boiling treatment were excellent in blood removability against blood contamination, and there was no discomfort when worn.

(Examples 8 and 9)
Example 1 is the same as Example 1 except that it is changed to a processing bath composition and a woven material using a composite system of copolymerized polyester resin (A1) / copolymerized (meth) acrylate resin (B1) shown in Table 3. Thus, treated fabrics of Examples 8 and 9 were obtained. The evaluation results of these obtained woven fabrics are shown in Table 3. Both HL = 0, HL = 20 and boiling treatment were excellent in blood removability against blood contamination, and there was no discomfort when worn.

(Comparative Examples 1-3)
In Example 1, each processed fabric of Comparative Examples 1 to 4 was obtained in the same manner as in Example 1 except that the processing bath composition and the fabric material shown in Table 3 were changed. The evaluation results of these obtained woven fabrics are shown in Table 3. At HL = 0, the blood contamination was excellent in removability and no sense of incongruity when worn. However, in the case of HL = 20 and after the boiling treatment, the removability to blood contamination was lowered, and some uncomfortable feeling at the time of wearing was recognized.

(Comparative Example 4)
A treated fabric of Comparative Example 4 was obtained in the same manner as in Example 1 except that the processing bath composition and the fabric material shown in Table 3 were changed in Example 1. The evaluation results of these obtained woven fabrics are shown in Table 3. At HL = 0, there was no removability with respect to blood contamination, and a sense of incongruity at the time of wearing was recognized. Moreover, the water dispersibility was unstable, and the evaluation after HL = 20 and boiling treatment was omitted.

  Cellulosic fibers such as sheets, aprons, lab coats, surgical gowns, surgical gloves, hats, masks, handkerchiefs, towels, curtains, pillow covers, diapers, shirts, blouses, lace products, etc., daily goods and clothing To obtain durable and excellent antifouling property and SR property in a fiber product comprising a contained fiber structure, particularly excellent antifouling property and SR property against blood stains, and also has a soft texture and is gentle to the skin Is possible.

Claims (8)

  An aqueous dispersion for fibers comprising a copolymerized polyester resin (A) containing a sulfonate group and a copolymerized (meth) acrylate resin (B) containing at least a polymerizable monomer having a phosphorylcholine group as constituent components.   The aqueous dispersion for fibers according to claim 1, wherein the copolymerized polyester resin (A) contains 0.001 mol% to 20 mol% of a sulfonate group.   The acid component of the copolymer polyester resin (A) is composed of a dicarboxylic acid, the glycol component is composed of 10 to 100 mol% of alkylene glycol and 90 to 0 mol% of other glycol, and the reduced viscosity is 0.10 dl / g or more The aqueous dispersion for fibers according to claim 1.   The copolymerized (meth) acrylate resin (B) is composed of 20 to 85 mol% of a polymerizable monomer having a phosphorylcholine group and 15 to 80 mol% of a hydrophilic and / or hydrophobic polymerizable monomer. Item 4. The aqueous dispersion for fibers according to any one of Items 1 to 3.   The copolymerized polyester resin (A), the copolymerized (meth) acrylate resin (B) obtained from the polymerizable monomer, and the fluororesin are 0.1 wt% or more and less than 15 wt% with respect to the total weight of the fiber structure. The aqueous dispersion for fibers according to any one of claims 1 to 4, wherein the aqueous dispersion is applied in a proportion.   The aqueous dispersion for fibers according to any one of claims 1 to 5, wherein at least one selected from an epoxy resin, a blocked isocyanate compound, formaldehyde, an alkyl etherified aminoformaldehyde resin and an oxazoline resin is used as a curing agent. .   The manufacturing method of the fiber structure processed with the aqueous dispersion for fibers in any one of Claims 1-6.   A sheet, an apron, a lab coat, a surgical gown, a surgical glove, a hat, a mask, a handkerchief, a towel, a curtain, a pillowcase, a diaper, and a shirt manufactured using the fiber structure obtained by the method according to claim 7. A textile product characterized in that it is at least one selected from medical / nursing care, daily miscellaneous goods and clothing such as blouse and lace products.