JP2007191827A - Cellulose-based fiber-containing fiber structure and textile product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a cellulose fiber-containing fiber structure having stain resistance to blood and properties of softness to the skin and a textile product comprising the same. <P>SOLUTION: The cellulose-based fiber-containing fiber structure comprises a copolymer obtained from a polymerizable monomer containing at least a hydroxy group in the molecule and a polymerizable monomer containing at least a phosphorylcholine group in the molecule and a crosslinking agent. The textile product comprises such a cellulose-based fiber-containing fiber structure at least in a part. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a cellulosic fiber-containing fiber structure that exhibits excellent antifouling properties and stain-removing properties against blood stains and, in addition, has skin-friendly properties.

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 provided with a crosslinking agent (see, for example, Patent Document 1), or a fluorine-based water repellent containing a hydrophilic group (for example, see Patent Document 2). ), Those provided with both of a silicone compound and these resins are known (see, for example, Patent Document 3). 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 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. 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 have been made mainly. For example, a cellulose fiber-containing fiber structure using a photocatalyst (see, for example, Patent Document 4) and the like has been proposed for the purpose of combining deodorization and antibacterial properties in addition to antifouling properties.
JP 2001-316773 A

  In view of the above-described prior art, the present invention is to provide a cellulose fiber-containing fiber structure imparted with antifouling properties against blood and skin-friendly characteristics, and a fiber product including the same.

In order to solve the above problems, the present invention employs the following configuration.
1. A cellulose-based fiber-containing fiber structure comprising a polymerizable monomer having at least a hydroxyl group in the molecule, a copolymer obtained from a polymerizable monomer having at least a phosphorylcholine group in the molecule, and a crosslinking agent.
2. The cellulosic fiber-containing composition according to the first aspect, wherein the copolymer is applied to the fiber surface at a ratio of 0.1 wt% to 15 wt% with respect to the total weight of the fiber structure. Fiber structure.
3. The cellulose-based fiber-containing fiber according to the first or second aspect, wherein the fluorine-based resin is provided at a ratio of 0.1% by weight to 15% by weight with respect to the total weight of the fiber structure. Structure.
4). The cellulose-based fiber-containing fiber structure according to any one of the first to third aspects, wherein the crosslinking agent is an N-methylol resin.
5). The cellulosic fiber-containing fiber structure according to any one of the first to third aspects, wherein the crosslinking agent is formaldehyde.
6). The cellulose fiber-containing fiber structure according to any one of the first to fifth aspects, wherein the cellulosic fiber-containing fiber structure is previously treated with liquid ammonia.
7). A fiber product comprising the cellulosic fiber-containing fiber structure according to any one of the first to sixth aspects at least partially.
8). The fiber product according to the seventh aspect, wherein the fiber product is formed or formed by vapor-formation after forming or shaping a cellulosic fiber-containing fiber structure.

  According to the present invention, by using a copolymer obtained from a polymerizable monomer having at least a hydroxyl group and a phosphorylcholine group in the molecule (hereinafter simply abbreviated as a copolymer) and a crosslinking agent, a durable and excellent protective agent is obtained. It is possible to obtain a cellulosic fiber-containing fiber structure that exhibits soiling and SR properties, is particularly excellent in antifouling properties and SR properties against blood stains, and has a soft texture and is gentle to the skin.

  By introducing a hydroxyl group into the phosphorylcholine compound in order to covalently bond the phosphorylcholine compound to the cellulose fiber, it suppresses the texture hardening, and at the same time makes it hydrophilic and simultaneously undergoes a crosslinking reaction with a crosslinking agent to provide a durable antifouling property and SR property. It is characterized by giving. In addition, the cellulose fiber-containing fiber structure of the present invention is subjected to a heat treatment after a fiber surface containing a copolymer containing a phosphorylcholine group and a hydroxyl group, a crosslinking agent, and optionally a fluororesin and a crosslinking catalyst. It is characterized by.

  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 easily coagulate. By using such a copolymer, it is possible to impart a blood antifouling effect to the fiber structure.

  Examples of the phosphorylcholine group-containing monomer group that is one component of the copolymer of the present invention include 2-((meth) acryloyloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate, 3-((meth) acryloyl). Oxy) 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) Tyl-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 ′-(trimethanolammoni E) ethyl phosphate, 2-((meth) acryloyloxy) propyl-2 ′-(trimethylammonio) ethyl phosphate, 2-((meth) acryloyloxy) butyl-2 ′-(trimethylammonio) ethyl phosphate, 2 -((Meth) acryloyloxy) pentyl-2'- (Trimethylammonio) ethyl phosphate, 2-((meth) acryloyloxy) hexyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (vinyloxy) ethyl-2 ′-(trimethylammonio) 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- (Vinyloxycarbonyl) ethyl -2 '-(trimethylammonio) ethyl phosphate, 2- (allyloxycarbonyl) ethyl-2'-(trimethylammonio) ethyl phosphate, 2- (acryloylamino) ethyl-2 '-(trimethylammonio) ethyl phosphate 2- (vinylcarbonylamino) ethyl-2 ′-(trimethylammonio) ethyl phosphate, ethyl- (2′-trimethylammonioethylphosphorylethyl) fumarate, butyl- (2′-trimethylammonioethylphosphorylethyl) fumarate Hydroxyethyl- (2′-trimethylammonioethylphosphorylethyl) fumarate, ethyl- (2′-trimethylammonioethylphosphorylethyl) malate, butyl- (2′-trimethylammonioethylphosphorylethyl) malate, Dorokishiechiru - (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).

  A hydrophilic monomer capable of undergoing a crosslinking reaction via a crosslinking agent such as a resin processing agent or formaldehyde as well as a hydroxyl group of cellulose fiber, 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.

  In addition, in order to improve the affinity of the copolymer of the present invention for hydrophilic fibers, a hydrophilic group-containing monomer is used as a copolymerization component. 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.

  When the cellulosic fiber-containing 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 phosphorylcholine group-containing copolymer may be produced by polymerizing a monomer composition comprising the phosphorylcholine group-containing monomer component, the hydrophilic group-containing monomer component, and the hydrophobic group-containing monomer component, and may be produced by ordinary radical copolymerization. Can do.

  The weight average molecular weight of the copolymer of the present invention is preferably in the range of 5,000 to 5,000,000, and more preferably in the range of 100,000 to 2,000,000. If the molecular weight is less than 5,000, it is difficult to make the phosphorylcholine-like group-containing polymer 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 becomes so high that it is difficult for the treatment agent to penetrate the fibers uniformly, and the feel of the resulting fibers may be impaired. Absent.

  The copolymer 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 hydroxyl group contains at least 10 mol% of them). And a polymer formed 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, 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 80 mol%, it is difficult to obtain good tactile sensation and moisture retention, which is not preferable. Moreover, if the hydrophilic monomer component containing a hydroxyl group is less than 10 mol%, washing durability may be insufficient, which is not preferable. 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. Further, if the amount of the hydrophobic monomer component is less than 2 mol%, it is difficult to have sufficient affinity for the hydrophobic fiber in the cellulosic fiber-containing fiber structure. It is not preferable because it tends to be insufficient.

  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.

  In order to exhibit antifouling properties and skin-friendly properties that are the characteristics of the present invention, the amount of the phosphorylcholine group-containing copolymer attached to the fiber structure is based on the total weight of the fiber structure. It is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight. That is, if the amount of adhesion is less than 0.1% by weight, it is difficult to sufficiently obtain antifouling properties and skin-friendly characteristics, which is not preferable. On the other hand, if it exceeds 15% by weight, the texture of the fiber structure is cured, and there is a tendency that irritation to the skin becomes stronger at the time of wearing, which is not preferable.

  Furthermore, 0.1 to 15% by weight aqueous solution of the copolymer contains, for example, 0.1% polyhydric alcohol such as ethylene glycol, 1,3-butanediol, 1,4-butanediol, glycerin, sorbitol. Addition in the range of 001 to 10% by weight is more preferable because the compatibility between the fiber and the copolymer can be improved.

  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, which is not preferable. On the other hand, if it exceeds 15% by weight, the texture of the fiber structure may 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 cellulose fiber-containing fiber structure as used in the present invention is not only a natural cellulose such as cotton and linen, a regenerated cellulose such as rayon, a woven fabric of purified cellulose such as tencel (lyocell), a fabric such as a knitted fabric or a non-woven fabric, as well as a belt-like structure. Any structure or shape may be used as long as it includes fibers such as objects, strings, and threads. In addition to cellulose fibers, animal fibers such as wool and cashmere, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6 and nylon 66, and synthetic fibers such as polyacrylonitrile and cellulose fibers are combined. Of course, the structure and shape are not limited as long as they include fibers such as strips, strings, and yarns, as well as fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics.

  The cellulose fiber-containing fiber structure referred to in the present invention is a fiber structure containing 1% or more of cellulosic fibers, preferably a structure containing 50% or more, more preferably a fiber structure of 100% cellulose. is there.

  The surface of the cellulose fiber-containing fiber structure referred to in the present invention has a copolymer containing at least a hydroxyl group and a phosphorylcholine group and a crosslinking agent, and a fluororesin, if necessary, simultaneously.

  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.

  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 immersed 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 containing a phosphorylcholine group and a hydroxyl group, and if necessary, a fluororesin and a surfactant are used in combination to form a dispersion aqueous solution, and further, a treatment liquid is prepared by 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 gas-phase formaldehyde processing, a fiber structure to which chemicals other than the crosslinking agent and crosslinking catalyst that are not necessary are removed from the above-mentioned treatment solution (parts may be shaped by sewing or adhesion) may be reacted. After throwing into the chamber, formaldehyde methanol mixed aqueous solution is injected in a mist form 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.

  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 cellulosic fiber-containing fiber structure of the present invention can be used in the usual mercerized or liquid ammonia treatment with sodium hydroxide, and after the mercerization, the one treated with liquid ammonia and the one dyed by dyeing, dip dyeing or printing. If it is necessary to mix with synthetic fibers typified by polyester, it may be heat set in advance.

  Vapor-phase processing with formaldehyde can be processed in any state of cotton, yarn, fabric, and sewing product, but it is more economical to process after making it into a sewing product, and the shape of the sewing product is also effectively fixed. Therefore, the puckering property, the shape retention property, and the like are improved, which is a preferred embodiment.

  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 polymer is shown.

<Measurement of weight average molecular weight>
Detection was performed 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.

(Synthesis Example of the Present Invention: Copolymer Solution (A))
44.2 g of MPC, 9.7 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, and blown with nitrogen for 30 minutes. A copolymer solution (A) was obtained by adding 1.38 g of azobisisobutyronitrile at 80 ° C. and carrying out a polymerization reaction 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 156,000. Table 1 shows the monomer composition, solvent species, and weight average molecular weight of the resulting polymer (A).

(Comparative synthesis example: copolymer solution (B), (C))
According to the synthesis examples of the present invention, the types and composition ratios of the monomers were changed, and copolymer solutions (B) and (C) having a nonvolatile content of 20% by weight were obtained by operations according to the synthesis examples of the present invention. Table 1 shows the monomer composition, solvent species, and weight average molecular weight of the obtained polymers (B) and (C).

  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.

(Examples 1-4)
A cotton fabric (50/1 × 50/1/144 × 81 / inch) subjected to refining bleaching by a conventional method and then mercerized is immersed in processing liquids (a) to (d) having the following composition to obtain a drawing ratio of 70 % With a mangle, 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 lab coats of Examples 1 to 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 (I):
5 parts by weight of the present copolymer (A), 10 parts by weight of Sumtex Resin (registered trademark) NS-19 (manufactured by Sumitomo Chemical Co., Ltd., dimethylol dihydroxyethylene urea), 4 parts by weight of magnesium chloride.6H ₂ O (43% aqueous solution) Parts, polyethylene glycol (average molecular weight 200) 6 parts by weight, PEN (manufactured by Dainippon Ink & Chemicals, polyethylene softener) 3 parts by weight, water 72 parts by weight

Processing fluid composition (b):
5 parts by weight of the copolymer (A) of the present invention, 15 parts by weight of Sumtex Resin (registered trademark) NS-19 (manufactured by Sumitomo Chemical Co., Ltd., dimethylol dihydroxyethylene urea), 6 parts by weight of magnesium chloride.6H ₂ O (43% aqueous solution) Parts 6 parts by weight of polyethylene glycol (average molecular weight 200) 3 parts by weight of PEN (manufactured by Dainippon Ink & Chemicals, polyethylene softener), 65 parts by weight of water

Processing fluid composition (C):
5 parts by weight of the present copolymer (A), 10 parts by weight of Sumtex Resin (registered trademark) NS-19 (manufactured by Sumitomo Chemical Co., Ltd., dimethylol dihydroxyethylene urea), 4 parts by weight of magnesium chloride.6H ₂ O (43% aqueous solution) Parts 6 parts by weight of polyethylene glycol (average molecular weight 200), 5 parts by weight of Asahi Guard (registered trademark) AG-780 (manufactured by Meisei Chemical Co., Ltd., fluorine resin), PEN (manufactured by Dainippon Ink & Chemicals, Inc., polyethylene softener) 3 parts by weight, 67 parts by weight of water

Processing fluid composition (d):
5 parts by weight of the present copolymer (A), 10 parts by weight of Sumtex Resin (registered trademark) NS-19 (manufactured by Sumitomo Chemical Co., Ltd., dimethylol dihydroxyethylene urea), 4 parts by weight of magnesium chloride.6H ₂ O (43% aqueous solution) Parts, polyethylene glycol (average molecular weight 200) 6 parts by weight, Meikanate MF (manufactured by Meisei Chemical Co., Ltd., isocyanate cross-linking agent) 1 part by weight, PEN (manufactured by Dainippon Ink & Chemicals, polyethylene-based softener) 3 parts by weight, water 71 weights Part

(Example 5)
A cotton fabric (50/1 × 50/1/144 × 81 / inch) subjected to refining bleaching by a conventional method, then mercerized, and further processed with liquid ammonia is used as the same processing liquid (b) as in Example 2. The film was dipped and mangled to a squeezing ratio of 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 lab coat was sewn by a conventional method 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 removability against blood contamination, the tearing strength was even better than that of Example 2, and no sense of incongruity when worn.

(Examples 6 and 7)
The same liquid ammonia processed cotton fabric (50/1 × 50/1/144 × 81 / inch) as in Example 5 is immersed in processing liquids (e) and (f) having the following composition so that the drawing rate becomes 70%. It was squeezed with a mangle, dried at 120 ° C. for 1 minute, and then sanforized. 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 gas phase (VP) processing with conventional formaldehyde using a 37% formaldehyde aqueous solution and a sulfurous acid gas catalyst to obtain lab coats of Examples 6 and 7 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 fluid composition (e):
5 parts by weight of the copolymer (A) of the present invention, 6 parts by weight of polyethylene glycol (average molecular weight 200), 3 parts by weight of PEN (manufactured by Dainippon Ink & Chemicals, Inc., polyethylene softener), 86 parts by weight of water

Processing fluid composition (f):
5 parts by weight of the copolymer (A) of the present invention, 6 parts by weight of polyethylene glycol (average molecular weight 200), 5 parts by weight of Asahi Guard (registered trademark) AG-780 (manufactured by Meisei Chemical Industries, Ltd., fluorine-based resin), PEN (Dainippon) Ink Chemical Industries, polyethylene softener) 3 parts by weight, 81 parts by weight of water

(Example 8)
In Example 7, it carried out like Example 1 except having replaced with the cotton fabric and using a polyester / cotton blended fabric (50/50, 50 / 1x50 / 1 / 144x81). 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 excellent in wearing feeling.

(Comparative Example 1)
The lab coat prepared in Example 6 was designated as Comparative Example 1 in which no formaldehyde vapor phase processing was performed. The evaluation results of the white coat obtained are shown in Table 2. The removability to blood contamination with HL = 0 was relatively good, but the removability to blood contamination with HL = 20 was low. The wearing feeling was also good at HL = 0, but there was some uncomfortable feeling at HL = 20.

(Comparative Example 2)
A lab coat using a processed fabric prepared in the same process except that the processing liquid of Example 1 was changed to (g) was used as Comparative Example 2. The evaluation results of the white coat obtained are shown in Table 2. The removability to blood contamination with HL = 0 was relatively good, but the removability to blood contamination with HL = 20 was low. The wearing feeling was good at HL = 0, but there was a sense of incongruity at HL = 20.

Processing fluid composition (g):
5 parts by weight of the copolymer (B) of the present invention, 10 parts by weight of Sumtex Resin (registered trademark) NS-19 (manufactured by Sumitomo Chemical Co., Ltd., dimethylol dihydroxyethylene urea), 4 parts by weight of magnesium chloride.6H ₂ O (43% aqueous solution) Parts, polyethylene glycol (average molecular weight 200) 6 parts by weight, PEN (manufactured by Dainippon Ink & Chemicals, polyethylene softener) 3 parts by weight, water 72 parts by weight

(Comparative Example 3)
A lab coat using a processed fabric prepared in the same process except that the working fluid of Example 1 was changed to (h) was designated as Comparative Example 3. The evaluation results of the white coat obtained are shown in Table 2. Both HL = 0 and HL = 20 showed low removability against blood contamination. The feeling of wearing was also uncomfortable.

Processing fluid composition (h):
5 parts by weight of the present copolymer (C), 10 parts by weight of Sumtex Resin (registered trademark) NS-19 (manufactured by Sumitomo Chemical Co., Ltd., dimethylol dihydroxyethylene urea), 4 parts by weight of magnesium chloride.6H ₂ O (43% aqueous solution) Parts, polyethylene glycol (average molecular weight 200) 6 parts by weight, PEN (manufactured by Dainippon Ink & Chemicals, polyethylene softener) 3 parts by weight, water 72 parts by weight

(Comparative Example 4)
A lab coat using a processed fabric prepared in the same process except that the processing liquid of Example 3 was changed to (Li) was used as Comparative Example 4. The evaluation results of the white coat obtained are shown in Table 2. The removability to blood contamination with HL = 0 was relatively good, but the removability to blood contamination with HL = 20 was low. The wearing feeling was good at HL = 0, but there was a sense of incongruity at HL = 20.

Processing fluid composition (C):
5 parts by weight of the copolymer (B) of the present invention, 10 parts by weight of Sumtex Resin (registered trademark) NS-19 (manufactured by Sumitomo Chemical Co., Ltd., dimethylol dihydroxyethylene urea), 4 parts by weight of magnesium chloride.6H ₂ O (43% aqueous solution) Parts 6 parts by weight of polyethylene glycol (average molecular weight 200), 5 parts by weight of Asahi Guard (registered trademark) AG-780 (manufactured by Meisei Chemical Co., Ltd., fluorine-based resin), PEN (manufactured by Dainippon Ink & Chemicals, Inc., polyethylene-based softener) 3 parts by weight, 67 parts by weight of water

  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)

  A cellulose-based fiber-containing fiber structure comprising a polymerizable monomer having at least a hydroxyl group in the molecule, a copolymer obtained from a polymerizable monomer having at least a phosphorylcholine group in the molecule, and a crosslinking agent.   The cellulosic fiber-containing composition according to claim 1, wherein the copolymer is applied to the fiber surface at a ratio of 0.1 wt% to 15 wt% with respect to the total weight of the fiber structure. Fiber structure.   The cellulosic fiber-containing fiber structure according to claim 1 or 2, wherein the fluororesin is provided at a ratio of 0.1 wt% to 15 wt% with respect to the total weight of the fiber structure. object.   The cellulosic fiber-containing fiber structure according to any one of claims 1 to 3, wherein the crosslinking agent is an N-methylol resin.   The cellulosic fiber-containing fiber structure according to any one of claims 1 to 3, wherein the crosslinking agent is formaldehyde.   The cellulosic fiber-containing fiber structure according to any one of claims 1 to 5, wherein the cellulosic fiber-containing fiber structure is previously treated with liquid ammonia.   A fiber product comprising the cellulosic fiber-containing fiber structure according to any one of claims 1 to 6 at least partially.   The fiber product according to claim 7, wherein the fiber product is formed by vapor-formation of formaldehyde after sewing or shaping a cellulosic fiber-containing fiber structure.