JP2007191826A - Stain-resistant fiber structure and textile product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a fiber structure having durable stain resistance to blood and properties of softness to the skin and a textile product using the same. <P>SOLUTION: The fiber structure comprises a copolymer (A) obtained from a polymerizable monomer containing at least a carboxy group and a phosphorylcholine group in the molecule and a polyfunctional oxazoline copolymer (B) obtained from a polymerizable monomer containing at least an oxazoline group in the molecule. The textile product comprises such a fiber structure at least in a part. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fiber structure that exhibits excellent antifouling properties and stain removability against blood stains, and additionally has a skin-friendly property, and a fiber product including the same.

Conventionally, many cellulose fiber-containing fiber structures 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 (see, for example, Patent Document 1), a hydrophilic group-containing fluorine-based water repellent (for example, Patent Document 1). 2), a silicone compound or a resin to which both of these resins are added (for example, see Patent Document 3) is known. However, it is difficult to say that these have sufficient antifouling properties.
JP-A-6-31327 JP 2003-96673 A JP 2004-44056 A

  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 are those in which the effects of hydrophilicity, water repellency and oil repellency are not sufficiently exhibited, and 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. However, an antifouling cellulose fiber-containing fiber structure using this resin has not been put into practical use.

Various functionalities such as wash and wear and antifouling properties are given as measures to improve clothing materials, especially cellulose fiber-containing fiber structures, as well as improved durability, improved physical properties, texture, touch and appearance. Improvements were mainly made. For example, a cellulose fiber-containing fiber structure using a photocatalyst has been proposed for the purpose of having deodorizing properties and antibacterial properties in addition to antifouling properties (see, for example, Patent Document 4).
JP 2001-316773 A

  In view of the above-described prior art, the present invention is to provide a fiber structure to which an antifouling property against blood and skin-friendly characteristics are imparted and a fiber product including the same.

In order to solve the above problems, the present invention employs the following configuration.
1. A copolymer (A) obtained from a polymerizable monomer having at least a carboxyl group in the molecule and a polymerizable monomer having at least a phosphorylcholine group in the molecule, and a polymer obtained from a polymerizable monomer having at least an oxazoline group in the molecule A fiber structure characterized by being provided with a monovalent oxazoline copolymer (B).
2. The fiber structure according to the first aspect, wherein the copolymer (A) is a copolymer obtained using a polymerizable monomer having at least a hydroxyl group in the molecule as a raw material.
3. The copolymers (A) and (B) are applied to the fiber surface at a ratio of 0.1% by weight to 15% by weight, respectively, with respect to the total weight of the fiber structure. The fiber structure according to 1 or 2.
4). The copolymers (A), (B), and the fluororesin are provided at a ratio of 0.1 wt% to 15 wt% with respect to the total weight of the fiber structure, respectively. The fiber structure according to any one of the first to third aspects.
5). The fiber structure according to any one of the first to fourth aspects, wherein the fiber structure includes cellulosic fibers.
6). The fiber structure according to any one of the first to fifth aspects, wherein the fiber structure includes a cellulosic fiber, and the cellulosic fiber is treated with a crosslinking agent.
7). The fiber structure according to any one of the first to sixth aspects, wherein the fiber structure includes cellulosic fibers, and the cellulosic fiber-containing fiber structure is subjected to formaldehyde vapor phase processing.
8). The fiber structure according to any one of the first to sixth aspects, wherein the fiber structure includes a cellulosic fiber, and the cellulosic fiber-containing fiber structure is treated with an N-methylol resin. Structure.
9. The fiber structure according to any one of the first to eighth aspects, wherein the fiber structure includes cellulosic fibers, and the cellulosic fiber-containing fiber structure is previously treated with liquid ammonia.
10. A fiber product comprising the fiber structure according to any one of the first to ninth aspects at least in part.

  According to the present invention, a copolymer (A) obtained from a polymerizable monomer having at least a carboxyl group and a phosphorylcholine group in the molecule [hereinafter sometimes abbreviated as copolymer (A)], at least an intramolecular By using a polyvalent oxazoline copolymer (B) obtained from a polymerizable monomer having an oxazoline group (hereinafter sometimes abbreviated as copolymer (B)), it has excellent durability and antifouling properties. It is possible to obtain a fiber structure exhibiting SR properties, particularly excellent in antifouling properties against blood stains and SR properties, and having a soft texture and being gentle to the skin.

  Using the copolymer (A) in which a carboxyl group-containing monomer is introduced into a phosphorylcholine group-containing monomer and the polyvalent oxazoline copolymer (B) in combination, three-dimensionally cross-linking polymers having a carboxyl group and an oxazoline group. It is possible to form a crosslinked film on the fiber surface and to impart durable antifouling properties and SR properties. Specifically, the fiber structure of the present invention, after imparting the copolymers (A) and (B), or, if necessary, a fluororesin, a resin processing agent, and a latent acidic catalyst to the fiber surface, It is characterized by heat treatment or vapor phase processing with formaldehyde.

  Such a phosphorylcholine group is a group mainly possessed by a phospholipid molecule that is a constituent component of a biological membrane, and is generally known as a substance having high biocompatibility. That is, when the cellulose fiber-containing fiber structure is used for touching the skin, the skin does not recognize the fiber structure as a foreign substance, and no allergic reaction occurs. And a higher level of skin care can be obtained. Furthermore, it also has a feature that blood does not coagulate, and by using the copolymer (A) and the copolymer (B), it is possible to impart a blood stain resistance effect with washing durability by the fiber structure. To do.

Details of the monomer group constituting the copolymer (A) will be described below.
Examples of the phosphorylcholine group-containing monomer group that is one of the constituent monomers of the copolymer (A) of the present invention include 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) acryloylo Cis) 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- (vinyloxy) Cicarbonyl) ethyl-2 '-(trimethylammonio) ethyl phosphate, 2- (allyloxycarbonyl) ethyl-2'-(trimethylammonio) ethyl phosphate, 2- (acryloylamino) ethyl-2 '-(trimethylammoni E) ethyl phosphate, 2- (vinylcarbonylamino) ethyl-2 '-(trimethylammonio) ethyl phosphate, ethyl- (2'-trimethylammonioethylphosphorylethyl) fumarate, butyl- (2'-trimethylammonioethyl) Phosphorylethyl) fumarate, hydroxyethyl- (2′-trimethylammonioethylphosphorylethyl) fumarate, ethyl- (2′-trimethylammonioethylphosphorylethyl) malate, butyl- (2′-trimethylammonioethylphosphorylate) Ethyl) maleate, 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).

  Examples of the carboxyl group-containing monomer that is one of the constituent monomers of the copolymer (A) of the present invention include acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, and 2-methacryloyloxyethyl succinic acid. Carboxyl group-containing (meth) acrylates such as 2-acryloyloxy-ethylphthalic acid, 2-methacryloyloxy-ethylhexahydroxyphthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, and the like.

  Next, a monomer having a hydroxyl group can also be used in the copolymer (A) of the present invention. This is particularly effective in this case because when the fiber structure contains cellulose fibers, a crosslinking reaction can be carried out via a hydroxyl group of the cellulose fibers and a crosslinking agent. Examples of the monomer having a hydroxyl group include hydroxyl group-containing (meta) such as 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylates and the like. 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 monomers include styrene sulfonic acid, (meth) acryloyloxyphosphonic acid, ionic group-containing monomers such as 2-hydroxy-3- (meth) acryloxypropyltrimethylammonium chloride, (meth) acrylamide, aminoethyl methacrylate Nitrogen-containing monomers such as 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. Since the carboxyl group-containing monomer component is excellent in reactivity with the oxazoline group in the copolymer (B) described below, as a result, the adhesion between the copolymers (A) and (B) and the fiber structure is as a result. Improvement can be expected.

  Moreover, in order to improve the affinity with hydrophobic fibers such as synthetic fibers, a hydrophobic monomer can be used as a constituent monomer component of the copolymer (A). 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 copolymer (A) may be polymerized with a monomer composition comprising the phosphorylcholine group-containing monomer component, the hydrophilic group-containing monomer component, and the hydrophobic group-containing monomer component, and is produced by ordinary radical copolymerization. be able to.

  The molecular weight of the copolymer (A) 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 in terms of weight average. If the molecular weight is less than 5,000, it is difficult to make the copolymer (A) have sufficient feel and hygroscopicity, which is not preferable. On the other hand, if it exceeds 5,000,000, the viscosity of the aqueous solution of the copolymer (A) becomes so high that it becomes difficult for the treatment agent to penetrate the fibers uniformly, and the feel of the resulting fibers may be impaired. For this reason, it is not preferable.

  The copolymer (A) has a phosphorylcholine group-containing monomer component of 20 to 80 mol% and a total hydrophilic group-containing monomer component of 15 to 60 mol% (however, the hydrophilic group-containing monomer containing a carboxyl group includes at least And a polymer obtained by polymerizing a monomer composition comprising 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 containing the carboxyl group, and 5 to 20 mol% of the hydrophobic group-containing monomer component.

  As specific examples of the copolymer (A), resins described in JP-A-8-333421 and JP-A-2001-200480 can be used.

  In order to exhibit antifouling properties and skin-friendly characteristics, which are the characteristics of the present invention, the amount of the copolymer (A) attached to the fiber structure is 0. 0% relative to the total weight of the fiber structure. The amount is preferably 1 to 15% by weight, more preferably 0.5 to 10% by weight. That is, when the adhesion amount is less than 0.1% by weight, it is difficult to sufficiently obtain antifouling properties and skin-friendly characteristics, and when it exceeds 15% by weight, the texture of the fiber structure is not preferable. Is not preferred because it tends to harden and irritate the skin when worn.

One of the copolymers (B) will be described in detail.
Examples of the addition polymerizable monomer having an oxazoline group that can be used as a monomer component constituting the copolymer (B) in the present invention include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 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-oxazoline and the like can be mentioned, and one or a mixture of two or more selected from these groups can be used. Among them, 2-isopropenyl-2-oxazoline is preferable because it is easily available industrially.

  The amount of addition polymerizable oxazoline to be used is not particularly limited, but is preferably 5 to 80% by weight, more preferably 30 to 60% by weight in the monomer component. If it is less than 5% by weight, the degree of curing tends to be insufficient, which is not preferable. However, in view of the undesirable effect on water resistance, it is preferable not to exceed 60% by weight.

  In the present invention, a hydrophilic monomer capable of undergoing a crosslinking reaction via a crosslinking agent such as a resin processing agent or formaldehyde can be used for the copolymer (B) in the same manner as the hydroxyl group of the cellulose fiber, particularly a monomer having a hydroxyl group. . Examples of the monomer group having a hydroxyl group that can be used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. And hydroxyl group-containing (meth) acrylates. 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.

  In addition, examples of the monomer copolymerizable with the addition polymerizable oxazoline include methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, Monoesterified product of (meth) acrylic acid and polyethylene glycol, (meth) acrylic acid esters such as 2-aminoethyl (meth) acrylate and salts thereof; unsaturated nitriles such as (meth) acrylonitrile; (meth) Unsaturated amides such as acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether Α- such as ethylene and propylene Refins: Halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride; α, β-unsaturated aromatic monomers such as styrene, α-methylstyrene and sodium styrenesulfonate The body etc. are mentioned, These 1 type (s) or 2 or more types can be used.

  The copolymer (B) of the present invention is desirably aqueous from the viewpoint of the environment. That is, the water-soluble, water-dilutable or water-dispersible copolymer (B) is preferably used, and water-soluble is more preferable. A water-soluble oxazoline group-containing polymer can be obtained by setting the ratio of the hydrophilic monomer in the monomer component to be polymerized to preferably 50% by weight or more, from the viewpoint of water solubility and curability. 60 to 90% by weight is particularly preferred. Examples of the hydrophilic monomer include addition-polymerizable oxazoline, 2-hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, monoesterified product of (meth) acrylic acid and polyethylene glycol, (meth) acrylic acid 2-aminoethyl and its salt, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, sodium styrenesulfonate, etc. are mentioned. Among these, monomers having a polyethylene glycol chain having high solubility in water, such as methoxypolyethylene glycol (meth) acrylate and monoesterified product of (meth) acrylic acid and polyethylene glycol, are preferable.

  The copolymer (B) can be produced by subjecting the monomer component to solution polymerization in an aqueous medium by a conventionally known polymerization method. The aqueous medium is not particularly limited as long as it is a solvent that can be easily mixed with water, water alone; a mixture of water and an organic solvent; an organic solvent alone, and particularly water alone; a mixture of water and an organic solvent. Is preferred. Usable organic solvents include methanol, ethanol, propanol, isopropanol, butanol, tertiary butanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol, acetone, methyl ethyl ketone, and the like. One or more of these are used.

  In the present invention, as the copolymer (B), those having an oxazoline group introduced by post-modification of the polymer can also be used. Specifically, a reaction between a nitrile group and an aminoethanol group, and a dehydration reaction of a hydroxylalkylamide group. Etc. are available. As the usage-amount of the said copolymer (B), 0.1 to 100 weight% is preferable with respect to the said copolymer (A), and 5 to 20 weight% is more preferable. When the amount used is less than 0.1% by weight, the degree of curing tends to be insufficient, which is not preferable. When the amount used is more than 100% by weight, a large amount of the copolymer (B) that does not contribute to the reaction remains, which is not preferable because it may adversely affect water resistance.

  The copolymer (B) can be prepared according to the methods described in JP 2000-160038 A and JP 2003-238638 A.

  Furthermore, 0.1 to 15% by weight aqueous solution of the copolymer (A) obtained from a polymerizable monomer having a carboxyl group, a hydroxyl group and a phosphorylcholine group in the molecule includes, for example, ethylene glycol, 1,3- Addition of polyhydric alcohol such as butanediol, 1,4-butanediol, glycerin, sorbitol and the like in the range of 0.001 to 10% by weight can improve the familiarity between the fiber and the copolymer (A). More preferred.

  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 15 wt% or less with respect to the fiber structure. If it is less than 0.1% by weight, it is difficult to obtain sufficient antifouling property, and it is not so preferable. If it exceeds 15% by weight, the texture of the fiber structure tends to be felt hard, which is not preferable. More preferably, it is 0.5 to 10% by weight.

  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 polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6 and nylon 66, synthetic fibers such as polyacrylonitrile, natural celluloses such as cotton and hemp, and rayon. Recycled celluloses, refined celluloses such as Tencel (Lyocell), and fabrics of animal hair fibers such as wool and cashmere, fabrics such as knitted fabrics and non-woven fabrics, as well as fibers such as strips, strings and threads If there is, the structure and shape are not limited. Of course, the structure and the shape are not limited as long as they include fibers such as a woven fabric, a knitted fabric, and a non-woven fabric in which two or more kinds of various fibers are combined.

  The surface of the fiber structure referred to in the present invention is one in which the copolymer (A), the copolymer (B) and, if necessary, a fluororesin, a crosslinking agent, a catalyst and the like are simultaneously present.

  When the fiber structure used in the present invention contains cellulose fibers, a method of crosslinking the hydroxyl groups of the cellulose fibers and the copolymers (A) and (B) using a crosslinking agent can be used.

  Examples of the crosslinking agent that can be used in the present invention include aldehyde compounds, N-methylol compounds, ketone resins, acetal resins, isocyanate compounds, epoxy resins, polycarboxylic acid compounds, and the like.

  As the aldehyde compound, formaldehyde, acetaldehyde, propionaldehyde, glutaraldehyde and the like can be used.

  Examples of N-methylol compounds include formaldehyde resins such as dimethylol urea and urea formalin condensate, melamine formaldehyde resins such as trimethylol melamine and hexamethylol melamine, dimethylol ethylene urea, dimethylol propylene urea, dimethylol dihydroxyethylene urea, and dimethylol. Cyclic urea compounds such as uron, dimethylol alkyltriazine, tetramethylol acetylene diurea, 4-methoxy-5-dimethylpropylene urea, dimethylol hydroxyethyl carbamate resins, polymers of N-methylol acrylamide and other acrylic and methacrylic compounds Copolymers can be used. Also, methyl ether compounds of the above methylol compounds can be used. Furthermore, so-called non-formalin resins such as dimethyldihydroxyethylene urea can also be used.

  As the ketone resin, acetone formaldehyde resin or the like can be used.

  As the acetal resin, glycol acetal, pentaerythritol bisacetal and the like can be used.

  As the isocyanate compound, compounds having two or more isocyanate groups in the molecule such as tolylene diisocyanator, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate can be used. A compound in which a plurality of isocyanate groups are added to the polyol compound and the isocyanate groups are blocked with sodium sulfite or methyl ethyl ketoxime can also be used.

  As epoxy resins, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, polyglycerin polyglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether A glycidyl ether compound such as sorbitan polyglycidyl ether can be used.

  Examples of polycarboxylic acid compounds include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid and other linear aliphatic dicarboxylic acids, maleic acid, fumaric acid and other unsaturated dicarboxylic acids, hexahydrophthalate Acids, alicyclic dicarboxylic acids such as hexahydroisophthalic acid and hexahydroterephthalic acid, tricarboxylic acids such as tricarballylic acid, acotinic acid, and methylcyclohextricarboxylic acid, and tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid Carboxyl groups such as hydroxydicarboxylic acids such as malic acid, tartaric acid and citric acid, aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, trimellitic acid and pyromellitic acid, and acrylic polymers including acrylic acid and methacrylic acid Compounds with multiple Available.

For these crosslinking agents, a catalyst suitable for each crosslinking agent may be used for the purpose of accelerating the reaction as necessary. For example, when the crosslinking agent is an aldehyde compound or an N-methylol compound, an acidic or latent acidic catalyst can be used. As the acidic catalyst, an acidic gas such as hydrogen chloride gas or S02 gas and an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid, or an organic acid such as glycolic acid, maleic acid, lactic acid, citric acid, tartaric acid or oxalic acid can be used. As the latent acidic catalyst, AlCl ₃ , Al ₂ (SO ₄ ) ₃ , MgCl ₂ , Mg (H ₂ PO ₄ ) ₂ , Zn (BF ₄ ) ₂ , Zn (NO ₃ ) ₂ , ZnCl ₂ , Mg (BF ₄₎ ) ₂ , Mg (ClO ₄ ) ₂ , various metal salts such as Al ₂ (OH) ₄ Cl ₂ (including crystal water-containing materials), various alkanols such as 2-amino-2-methyl-1-propanol hydrochloride Acidic salts of amines, ammonium salts of strong acids such as nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid and mixtures thereof can be used. When the crosslinking agent is a ketone resin, an acetal resin, an isocyanate compound, an epoxy resin, or a polycarboxylic acid compound, a catalyst suitable for each crosslinking agent can be used.

  Among these crosslinking agents, in particular, formaldehyde and N-methylol compounds can impart a high form-stabilizing effect to the cellulosic fiber structure at the same time, and can be preferably used. These crosslinking agents may be used alone, but two or more kinds may be used in combination for the purpose of increasing the crosslinking effect.

  When the fiber structure used in the present invention mainly contains cellulose fibers, and when form-stabilization with formaldehyde or N-methylol resin is performed at the same time, the strength of the cellulose fibers is greatly reduced by these reactions, and the texture is coarse. It may become. For this reason, when mainly containing a cellulose fiber, in order to suppress the improvement of a feel and the fall of a mechanical characteristic, it is a preferable aspect to carry out a liquid ammonia process in any process as a pretreatment. In the cellulose-containing fiber structure used in the present invention, the strength of the cellulose fiber may be lowered because the inside of the cellulose fiber is also cross-linked by the cross-linking agent. For this reason, in the case of a cellulose fiber alone, it is a preferable aspect that liquid ammonia treatment is carried out in any step as pretreatment in order to suppress the improvement of texture and the deterioration of mechanical properties.

  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 method of treating the fiber according to the present invention includes (1) a method in which the fiber is dipped in an aqueous solution and dried and then cured, or (2) a method in which the fiber is applied directly to the fiber and dried and then cured. Can be mentioned.

  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 the temperature lower than 40 ° C. is sufficient for the inherent hygroscopicity of the copolymer. It cannot be dried, and a temperature higher than 180 ° C. is not preferable because the phosphorylcholine group may be decomposed. 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. Curing is performed under conditions suitable for the crosslinking agent, and a method of heat treatment at a temperature of 100 to 180 ° C. for 30 seconds to 10 minutes can be preferably used.

  For formaldehyde used in the present invention, paraformaldehyde, a mixed aqueous solution of formaldehyde methanol, an ester compound of dihydroxymethylene and formic acid, etc. can be used as the generating agent.

  The method for producing the fiber structure of the present invention is not particularly limited, but will be described with examples.

  First, a copolymer (A) containing a phosphorylcholine group and a carboxyl group, a polyvalent oxazoline copolymer (B) obtained from a polymerizable monomer having an oxazoline group, and, if necessary, fluorine-based resin properties and A treatment liquid is prepared by using a surfactant in combination to form a dispersed aqueous solution, and further mixing a crosslinking agent and, if necessary, a crosslinking catalyst. The fiber structure is immersed in the treatment liquid, and excess liquid is removed by means of a mangle or a centrifugal dehydrator, followed by drying at 50 to 120 ° C. Subsequently, it heat-processes at 140-160 degreeC for 2 to 10 minutes, and completes crosslinking reaction.

  On the other hand, in the vapor phase formaldehyde processing, after the fiber structure (which may be sewn) to which the chemicals excluding unnecessary crosslinking agents and crosslinking catalysts are added from the above treatment solution is put into the reaction chamber, formaldehyde methanol The mixed aqueous solution is injected as a mist with steam. A method of injecting an acid gas catalyst after formaldehyde injection and allowing it to stand for a while, then raising the temperature and causing a crosslinking reaction, and then injecting ammonia gas to neutralize can be used. In this case, when an acid gas catalyst is not used, a method of previously applying a latent acid catalyst to the dough can be used. Further, a method in which a crosslinking agent other than formaldehyde or a crosslinking catalyst thereof is previously applied to the dough can be used.

  Adding a moisturizing agent and a softening agent at the time of preparation of the treatment liquid of the present invention is a preferred embodiment, particularly in gas phase formaldehyde processing.

  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.

  Examples of polyols that can be used in the present invention include ethylene glycol-based, propylene glycol-based 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.

  Hereinafter, the synthesis examples of the present invention will be described in detail. Next, the analysis method of the weight average molecular weight of the used copolymer (A) and the water solubility evaluation method of the copolymer (B) are shown, respectively.

1. Measurement of weight average molecular weight Detection was carried out by gel permeation chromatography (GPC) using a phosphate buffer (pH 7.4, 20 mM) as an eluent, polyethylene glycol standard, UV (210 nm) and refractive index.

2. Water solubility 10 g of copolymer (B) was put into 90 g of ion-exchanged water, and the solubility after stirring for 10 minutes was visually judged.
○: Transparent aqueous solution, Δ: Cloudy aqueous dispersion, ×: Undissolved

Synthesis Example 1 of the Copolymer (A) of the Present Invention 1: Copolymer (A1)
45.7 g of MPC, 4.4 g of (meth) acrylic acid (MAc), 7.3 g of n-butyl methacrylate (BMA) were dissolved in ethanol; 230 g, put into a four-necked flask, blown with nitrogen for 30 minutes, then 60 A copolymer solution (A) was prepared by adding 1.4 g of azobisisobutyronitrile at 1.4 ° C. and allowing the polymerization reaction to proceed for 8 hours. The non-volatile content of the copolymer solution (A) was 20% by weight. The molecular weight evaluated by GPC was a weight average molecular weight of 137,000. Table 1 shows the monomer composition and weight average molecular weight of the obtained copolymer (A1).

Synthesis Example 2 of the Copolymer (A) of the Present Invention: Copolymer (A2)
The kind of monomer and composition ratio were changed according to Synthesis Example 1 of the copolymer (A) of the present invention, and a copolymer (A2) was obtained by the operation according to Synthesis Example 1. Table 1 shows the monomer composition and weight average molecular weight of the obtained copolymer.

Synthetic Examples 1 and 2 of Comparative Copolymer (A): Copolymers (A3) and (A4)
Comparative copolymers (A3) and (A4) were obtained by the operation according to Synthesis Example 1 by changing the type and composition ratio of the monomers according to Synthesis Example 1 of the present invention. The composition and weight average molecular weight of the obtained comparative copolymer are shown in Table 1.

Synthesis Example 1 of the Copolymer (B) of the Present Invention 1: Copolymer (B1) of the Present Invention
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 100 g of polyethylene glycol monomethyl ether having an average molecular weight of 500, and the temperature was raised to 140 ° C. under a nitrogen stream. Next, while maintaining the temperature in the glass reactor at 140 to 142 ° C., 25 g of 2-hydroxyethyl methacrylate (HEMA), 25 g of butyl (meth) acrylate (BMA), 2-isopropenyl-2-oxazoline ( IPO) 50 g and di-tert-butyl peroxide 10 g were separately added dropwise continuously over 2 hours. By stirring while maintaining at 140 to 142 ° C. for 2 hours after the completion of dropping, 0.5 g of di-tert-butyl peroxide was added, and then stirring while maintaining at 140 to 142 ° C. for 1.5 hours. Copolymer (B1) was obtained. Further, when 10 g of the obtained copolymer was dissolved in 90 g of ion-exchanged water, a transparent solution was obtained.

Comparative Synthesis Example 1: Comparative copolymer (B2)
By changing the type and composition ratio of the monomer according to Synthesis Example 1 of the copolymer (B) of the present invention, and performing the operation according to Synthesis Example 1 of the copolymer (B) of the present invention, the copolymer (B2) Got. Table 1 shows the monomer composition and water solubility of the obtained copolymer (B1).

  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, 1000g and a dummy cloth (Kao Co., Ltd .: Compact Big) are added together with the dummy cloth, and automatic washing is performed by setting the standard course for 5 minutes, rinsing twice, dehydration for 1 minute, and water volume of 30 liters. This was taken as one home washing. This laundry was repeated 20 times, and then naturally dried was used as a sample for home washing 20 times (HL = 20). In addition, the finished product which is not washed is displayed 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. Tear strength The tear strength in the horizontal direction of a processed fabric or fiber product was measured by JIS L1096 8.15.5 D method (Pendulum method). At the time of measurement, the average value of five samples was represented by cN.

Example 1
After refining the skin-wearing knitted fabric made of 55 decitex, 36 filament nylon filament yarn, it was dipped in the processing liquid (I) of the following composition and squeezed with mangle so that the squeezing rate became 70%, and then at 120 ° C. for 1 minute. Dried and then cured at 150 ° C. for 2 minutes. Using this knitted fabric, a T-shirt was sewn by a normal method to obtain a T-shirt of Example 1 of the present invention. The evaluation results of the obtained T-shirt are shown in Table 2. Both HL = 0 and 20 were excellent in removability against blood contamination, and no sense of incongruity when worn.

Processing fluid composition (I):
5 parts by weight of the copolymer (A1) of the present invention, 3 parts by weight of the copolymer (B1) of the present invention, 89 parts by weight of water

(Examples 2 and 3)
Polyester / cotton blended fabric (mixed ratio E / C = 65/35% 50/1 × 50/1/144 × 81 / inch) subjected to refining bleaching in the usual way and then mercerized, is used as a processing solution having the following composition It was dipped in (b) and (c), squeezed with a mangle so that the squeezing rate was 70%, dried at 120 ° C. for 1 minute, then cured at 150 ° C. for 3 minutes, and then subjected to sanforization. Using this cotton fabric, a white coat was sewn by a normal method to obtain the white coats of Examples 1 to 3 of the present invention. The evaluation results of the white coat obtained are shown in Table 2. Both HL = 0 and 20 were excellent in removability against blood contamination, and no sense of incongruity when worn.

Processing fluid composition (b):
5 parts by weight of the copolymer (A2) of the present invention, 3 parts by weight of the copolymer (B1) of the present invention, 3 parts by weight of PEN (manufactured by Dainippon Ink & Chemicals, Inc., polyethylene softener), 89 parts by weight of water

Processing fluid composition (C):
5 parts by weight of the copolymer (A2) of the present invention, 3 parts by weight of the copolymer (B1) of the present invention, 3 parts by weight of Asahi Guard (registered trademark) AG-780 (manufactured by Meisei Chemical Industries, Ltd., fluorine-based resin), PEN (large Nippon Ink Chemical Co., Ltd., polyethylene softener) 3 parts by weight, water 86 parts by weight

Example 4
A cotton fabric (50/1 × 50/1/144 × 81 / inch), which has been subjected to refining bleaching by a conventional method and then subjected to mercerization, is immersed in a processing solution (d) having the following composition so that the drawing rate becomes 70%. And then dried at 120 ° C. for 1 minute, then cured at 150 ° C. for 3 minutes, and sanforized. Using this cotton fabric, a lab coat was sewn by a conventional method to obtain a lab coat of Example 4 of the present invention. The evaluation results of the white coat obtained are shown in Table 2. Both HL = 0 and 20 were excellent in removability against blood contamination, and no sense of incongruity when worn.

Processing fluid composition (d):
5 parts by weight of the copolymer (A2) of the present invention, 3 parts by weight of the copolymer (B1) of the present invention, 3 parts by weight of PEN (manufactured by Dainippon Ink and Chemicals, polyethylene softener), Meikanate MF (manufactured by Meisei Chemical Co., Ltd., Isocyanate crosslinking agent) 1 part by weight, water 88 parts by weight

(Example 5)
Using the same mercerized cotton fabric as in Example 4, it was dipped in a processing solution (e) having the following composition, drawn with mangles to a drawing rate of 70%, dried at 120 ° C. for 1 minute, and then subjected to sanforization. Using this cotton fabric, a lab coat was sewn by a conventional method. Next, this lab coat was placed in an airtight container and subjected to vapor phase (VP) processing with conventional formaldehyde using a 37% formaldehyde aqueous solution and a sulfurous acid gas catalyst to obtain a lab coat of Example 5 of the present invention. The evaluation results of the white coat obtained are shown in Table 2. Both HL = 0 and 20 were excellent in removing blood contamination, and particularly excellent in wearing feeling.

Processing bath composition (e):
5 parts by weight of the copolymer (A2) of the present invention, 3 parts by weight of the copolymer (B1) of the present invention, 6 parts by weight of polyethylene glycol (average molecular weight 200), PEN (manufactured by Dainippon Ink and Chemicals, polyethylene softener) 3 Parts by weight, water 83 wt.

(Example 6)
Using the same mercerized cotton fabric as in Example 4, dipped in a processing solution (f) having the following composition, squeezed with mangle to a squeeze rate of 70%, dried at 120 ° C. for 1 minute, and then at 150 ° C. for 3 minutes. Cure and sanforize. Using this cotton fabric, a lab coat was sewn by a conventional method to obtain a lab coat of Example 4 of the present invention. The evaluation results of the white coat obtained are shown in Table 2. Both HL = 0 and 20 have excellent removability against blood contamination, and no discomfort when worn

Processing fluid composition (f):
5 parts by weight of the copolymer (A2) of the present invention, 3 parts by weight of the copolymer (B1) of the present invention, 10 parts by weight of Sumtex Resin (registered trademark) NS-19 (manufactured by Sumitomo Chemical Co., Ltd., dimethylol dihydroxyethylene urea), chloride Magnesium 6H ₂ O (43% aqueous solution) 4 parts by weight, polyethylene glycol (average molecular weight 200) 6 parts by weight, PEN (manufactured by Dainippon Ink and Chemicals, polyethylene softener) 3 parts by weight, water 69 parts by weight

(Example 7)
After the same mercerized cotton fabric as in Example 4 was further processed with liquid ammonia, it was treated with the same processing fluid as in Example 5 and subjected to the same gas phase (VP) processing with formaldehyde, and Example 7 of the present invention. I got a white coat. The evaluation results of the white coat obtained are shown in Table 2. Both HL = 0 and 20 were excellent in removing blood contamination, and particularly excellent in wearing feeling.

(Comparative Examples 1-3)
The same polyester / cotton mixed fabric as in Example 1 was dipped in the processing liquids (g) to (ri) having the following composition, drawn with a mangle so that the drawing rate was 70%, dried at 120 ° C. for 1 minute, and then at 150 ° C. It was cured for 3 minutes and then subjected to sanforization. Using this cotton fabric, a white coat was sewn by a normal method to obtain white coats of Comparative Examples 1 to 3 of the present invention. The evaluation results of the white coat obtained are shown in Table 2. Compared to the Examples, the removability with respect to blood contamination at HL = 0 and the feeling of wearing were relatively good, but the removability with respect to blood contamination at HL = 20 was inferior, and a sense of incongruity at the time of wearing was recognized.

Processing fluid composition (g):
5 parts by weight of the present copolymer (A1), 3 parts by weight of PEN (manufactured by Dainippon Ink & Chemicals, Inc., polyethylene softener), 92 parts by weight of water

Processing fluid composition (h):
5 parts by weight of the copolymer (A2) of the present invention, 3 parts by weight of the copolymer of the present invention (B2), 3 parts by weight of PEN (manufactured by Dainippon Ink & Chemicals, Inc., polyethylene softener), 92 parts by weight of water

Processing fluid composition (Li):
5 parts by weight of the copolymer (A3) of the present invention, 3 parts by weight of the copolymer (B1) of the present invention, 10 parts by weight of Sumtex Resin (registered trademark) NS-19 (manufactured by Sumitomo Chemical Co., Ltd., dimethylol dihydroxyethylene urea), chloride Magnesium 6H ₂ O (43% aqueous solution) 4 parts by weight, polyethylene glycol (average molecular weight 200) 6 parts by weight, PEN (manufactured by Dainippon Ink and Chemicals, polyethylene softener) 3 parts by weight, water 69 parts by weight

(Comparative Example 4)
The same polyester / cotton mixed fabric as in Example 1 was dipped in a processing liquid (nu) having the following composition, drawn with mangles so that the drawing ratio was 70%, dried at 120 ° C. for 1 minute, and then cured at 150 ° C. for 3 minutes. And sanforized. Using this cotton fabric, a white coat was sewn by a normal method to obtain white coats of Comparative Examples 1 to 3 of the present invention. The evaluation results of the white coat obtained are shown in Table 2. Compared to the examples, both HL = 0 and HL = 20 were poor in removability against blood contamination, and a sense of incongruity at the time of wearing was recognized.

Processing fluid composition (g):
5 parts by weight of the copolymer (A4) of the present invention, 3 parts by weight of the copolymer (B1) of the present invention, 10 parts by weight of Sumtex Resin (registered trademark) NS-19 (manufactured by Sumitomo Chemical Co., Ltd., dimethylol dihydroxyethylene urea), chloride Magnesium 6H ₂ O (43% aqueous solution) 4 parts by weight, polyethylene glycol (average molecular weight 200) 6 parts by weight, PEN (manufactured by Dainippon Ink and Chemicals, polyethylene softener) 3 parts by weight, water 69 parts by weight

  Sheets, aprons, lab coats, surgical gowns, surgical gloves, hats, masks, handkerchiefs, towels, curtains, pillow covers, diapers, shirts, blouses, lace products, etc., textile products such as daily necessities and clothing In this case, it is possible to obtain a textile product which exhibits excellent antifouling property and SR property with durability, particularly excellent antifouling property and SR property against blood stains, and has a soft texture and is gentle to the skin.

Claims (10)

  A copolymer (A) obtained from a polymerizable monomer having at least a carboxyl group in the molecule and a polymerizable monomer having at least a phosphorylcholine group in the molecule, and a polymer obtained from a polymerizable monomer having at least an oxazoline group in the molecule A fiber structure characterized by being provided with a monovalent oxazoline copolymer (B).   2. The fiber structure according to claim 1, wherein the copolymer (A) is a copolymer obtained using a polymerizable monomer having at least a hydroxyl group in the molecule as a raw material.   The copolymers (A) and (B) are applied to the fiber surface at a ratio of 0.1% by weight or more and 15% by weight or less, respectively, with respect to the total weight of the fiber structure. 3. The fiber structure according to 1 or 2.   The copolymers (A), (B), and the fluororesin are provided at a ratio of 0.1 wt% to 15 wt% with respect to the total weight of the fiber structure, respectively. The fiber structure in any one of Claims 1-3.   The fiber structure according to any one of claims 1 to 4, wherein the fiber structure contains cellulosic fibers.   The fiber structure according to any one of claims 1 to 5, wherein the fiber structure includes cellulosic fibers, and the cellulosic fibers are treated with a crosslinking agent.   The fiber structure according to any one of claims 1 to 6, wherein the fiber structure contains cellulosic fibers, and the cellulosic fiber-containing fiber structure is subjected to formaldehyde vapor phase processing.   The fiber structure according to any one of claims 1 to 6, wherein the fiber structure includes cellulosic fibers, and the cellulosic fiber-containing fiber structure is treated with an N-methylol resin. object.   The fiber structure according to any one of claims 1 to 8, wherein the fiber structure includes a cellulosic fiber, and the cellulosic fiber-containing fiber structure is previously treated with liquid ammonia.   A fiber product comprising the fiber structure according to any one of claims 1 to 9 at least partially.