JP2006037294A - Method for producing fiber composite material and fiber composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing fiber composite material that can sufficiently prohibit the migration and can apply the resin components uniformly to the fiber substrate despite this method for producing a fiber composite material by using an aqueous resin emulsion under consideration of the environmental loading and the problems on VOC, and efficiently and surely obtains the fiber composite material having excellent uniform feeling, increased stability and abrasion resistance properties, flexible feeling, abrasion resistance, additionally can a variety of fabric hands according to the purposes, and to provide the fiber composite material produced by the production method. <P>SOLUTION: A urethane/acrylic composite resin emulsion (A) that is obtained by emulsion-polymerizing an ethylenically unsaturated monomer in the presence of a carboxyl group-bearing polyurethane resin emulsion, an ammonium carboxylate sat (B) and water (C) are mixed and fiber substrates are soaked with the solution, then dried to give the fiber composite material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a fiber composite material and a fiber composite material. More specifically, the present invention relates to a method for producing a fiber composite material obtained by impregnating a fiber substrate with a mixed solution containing a resin emulsion and drying the fiber base material, and fibers obtained by the method. It relates to composite materials.

  Conventionally, resins in the form of solvent-based polyurethane resin, polyurethane resin emulsion, acrylic resin emulsion, NBR latex, SBR latex, and the like have been used as binders for fiber composite materials. Among the binders of such fiber composite materials, polyurethane resins are characterized by being highly polar and excellent in adhesion to various fiber base materials, and being flexible and tough. Has been used for the purpose of improving the texture, tensile strength, wear resistance, and the like.

  As such a polyurethane resin binder, an organic solvent solution of polyurethane resin has been used more frequently than before, and the processing method is mainly to impregnate or apply an organic solvent solution of polyurethane resin to a fiber substrate. Is produced by a method called a wet coagulation method in which a polyurethane resin is coagulated by passing it through a coagulation liquid (usually water) which is a poor solvent for the polyurethane resin and compatible with the organic solvent, and then washed with water and dried. ing.

  However, organic solvents such as dimethylformamide, which are often used in such wet coagulation methods, are highly flammable and highly toxic. There were concerns about environmental pollution such as air and water quality. And although the manufacturing method incorporating the process of collect | recovering the organic solvent which generate | occur | produces in order to eliminate such a problem is performed, the problem that a lot of disposal cost and labor are applied remained. Moreover, since the organic solvent remains in the fiber composite material obtained using the organic solvent solution of the polyurethane resin, the influence on the human body such as skin damage has been a problem. Therefore, studies have been made to shift the polyurethane resin fixed to the fiber base material from an organic solvent type to an aqueous polyurethane resin.

  The manufacturing method of the fiber composite material using such an aqueous polyurethane resin does not use an organic solvent, so that the cost required for recovery can be eliminated, and improvement of the working environment, environmental pollution such as air pollution, water pollution, etc. However, when compared with a fiber composite obtained using an organic solvent solution of polyurethane resin, the obtained fiber composite has low texture uniformity and stability, and is inferior in wear resistance. It was. A major cause of such a problem is that when the aqueous polyurethane resin is impregnated inside the fiber base material and then dried by hot air with hot air, the aqueous polyurethane resin is caused by the movement of water evaporated from the fiber base surface. There is a so-called migration that shifts to the surface of the fiber base material. That is, when such migration occurs, the aqueous polyurethane resin moves to the surface of the fiber base material, and the polyurethane base material is hardly fixed inside the fiber base material. The fiber composite material had low uniformity and stability and poor wear resistance. Therefore, in order to solve such problems, various proposals have been made in the manufacturing method of artificial leather among the manufacturing methods of fiber composite materials using aqueous polyurethane resins.

  For example, Japanese Patent Publication No. 55-51076 (Patent Document 1) discloses a method of coagulating a synthetic resin emulsion to which a heat-sensitive gelling agent has been added to impart heat-sensitive coagulation properties in hot water.

  However, in such a method, although the migration prevention property is improved, a part of the impregnating liquid flows out into the bath and solidifies, and the solidified gel is reattached to the surface of the work piece to obtain the obtained fiber. There was a problem that the uniformity and stability of the texture of the composite material deteriorated. In such a method, as the polyurethane resin concentration decreases, the heat-sensitive coagulation property decreases, and part of the impregnating liquid easily flows out into the hot water, and the texture of the resulting fiber composite material is uniform. There is also a problem that the stability is further deteriorated.

  Japanese Patent Application Laid-Open No. 6-316877 (Patent Document 2) discloses a method of applying a water-based resin composition in which an inorganic salt is dissolved to a forcedly emulsified emulsion and drying by heating.

  However, in such a method, although the migration prevention property is improved, there is a processing problem that the stability of the treatment bath is deteriorated depending on the concentration of the inorganic salt to be blended. In addition, since the nonionic surfactant and the inorganic salt remain in the fiber base material, the obtained fiber composite material is not sufficient in texture stability and abrasion resistance.

  Furthermore, in Japanese Patent Application Laid-Open No. 2000-290879 (Patent Document 3), there is a method in which a water-based resin composition comprising a water-based urethane resin having a heat-sensitive coagulation temperature of 40 to 90 ° C. and an associative thickener is heat-coagulated with steam. It is disclosed.

  However, in such a method, although the migration prevention property is improved, since the nonionic surfactant and the associative thickener remain in the fiber base material, the obtained fiber composite material still has a stable texture. And wear resistance were not sufficient.

  Japanese Patent Application Laid-Open No. 2003-138131 (Patent Document 4) discloses a method in which a carboxylate-type polyurethane resin containing a nonionic surfactant of HLB 10-18 and an inorganic salt is applied to a fiber material substrate and heat-coagulated. It is disclosed.

  However, even in such a method, problems with surfactants and inorganic salts occur as in the methods described in Patent Documents 2 and 3, and the resulting fiber composite material still has a texture stability and wear resistance. It was not enough.

  In the methods described in Patent Documents 2 to 4, residues such as nonionic surfactants, associative thickeners and inorganic salts can be removed by a process such as water washing or hot water washing. If such a process is added, the number of processing steps increases, resulting in an economic problem. Thus, sufficient texture uniformity and stability can be obtained without adding a process of washing the residue with water or hot water, and further excellent. There is a demand for a production method that can provide a fiber composite material having abrasion resistance.

As described above, in the method of manufacturing a fiber composite material using a water-based resin, a fiber composite having sufficient texture and wear resistance by sufficiently preventing migration and fixing the resin component uniformly to the fiber base material. The present condition is that the method of manufacturing a material is not obtained.
Japanese Patent Publication No. 55-51076 JP-A-6-316877 JP 2000-290879 A JP 2003-138131 A

  The present invention has been made in view of the above-mentioned problems of the prior art, and despite the fact that it is a manufacturing method using an aqueous resin emulsion in consideration of the environmental load reduction and the VOC problem, sufficient migration is achieved. It is possible to prevent and uniformly fix the resin component to the fiber base material, and it is possible to efficiently and reliably obtain a fiber composite material having good wear resistance while improving the uniformity and stability of the texture. In addition, an object of the present invention is to provide a fiber composite material production method capable of imparting various textures according to the purpose to the obtained fiber composite material, and a fiber composite material obtained by the method. Is.

  As a result of intensive research to achieve the above object, the present inventors have impregnated a mixed liquid containing a specific urethane / acrylic composite resin emulsion, a specific organic acid salt and water into a fiber base material. According to the method for producing a fiber composite material for drying, a fiber composite material in which the urethane / acrylic resin is uniformly fixed to the inside of the fiber base material is obtained without migration of the urethane / acrylic resin during the drying. The obtained fiber composite material was found to have various textures and abrasion resistance, and the present invention was completed based on this finding.

  That is, the method for producing a fiber composite material of the present invention comprises: (A) a urethane / acrylic composite resin emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer in the presence of a carboxyl group-containing polyurethane resin emulsion; A mixed liquid containing an ammonium salt of carboxylic acid and (C) water is impregnated into a fiber base material and then dried to obtain a fiber composite material.

  As said liquid mixture concerning the said invention, the compounding ratio of (A) urethane / acryl compound resin emulsion and the ammonium salt of (B) carboxylic acid is 100: 0.5-100: in conversion of the mass of solid content. 20 is preferable.

  The mixed solution according to the present invention preferably has a pH value of 7.0 to 9.0 and a coagulation temperature of 30 to 70 ° C.

  The carboxyl group-containing polyurethane resin emulsion according to the present invention includes (a) an organic diisocyanate, (b) a polyol, and (c) a carboxyl group obtained by reacting a compound having a carboxyl group and two or more active hydrogens. It was obtained by neutralizing the containing isocyanate group-terminated prepolymer and emulsifying and dispersing it in water by self-emulsification, and then (d) chain-extending reaction using a polyamine compound having two or more amino groups and / or imino groups. A carboxyl group-containing polyurethane resin emulsion is preferred.

  As the (A) urethane / acrylic composite resin emulsion according to the present invention, the emulsion polymerization is carried out by setting the compounding ratio of the carboxyl group-containing polyurethane resin and the ethylenically unsaturated monomer to 90:10 to 10:90 in terms of solid mass. It is preferable that it is the urethane / acryl composite resin emulsion obtained.

  The ammonium salt of (B) carboxylic acid according to the present invention is preferably an ammonium salt of a carboxylic acid having 1 to 10 carbon atoms.

  The fiber composite material of the present invention is obtained by the production method of the present invention.

  According to the present invention, although it is a manufacturing method using an aqueous resin emulsion in consideration of the environmental load reduction and the VOC problem, migration is sufficiently prevented and the resin component is uniformly fixed to the fiber base material. It is possible to efficiently and reliably obtain a fiber composite material having good wear resistance while improving the uniformity and stability of the texture, and for the purpose of the obtained fiber composite material. It is possible to provide a method for producing a fiber composite material capable of imparting various textures according to the method, and a fiber composite material obtained by the method.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  The method for producing a fiber composite material of the present invention comprises: (A) a urethane / acrylic composite resin emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer in the presence of a carboxyl group-containing polyurethane resin emulsion; A mixed liquid containing an acid ammonium salt and (C) water is impregnated into a fiber base material and then dried to obtain a fiber composite material.

  In the present invention, the carboxyl group-containing polyurethane resin emulsion is an emulsion of a polyurethane resin containing a carboxyl group as a hydrophilic component in a urethane resin skeleton. As such a carboxyl group-containing polyurethane resin emulsion, (a) an organic diisocyanate, (b) a polyol, and (c) a carboxyl group-containing isocyanate terminal obtained by reacting a compound having a carboxyl group and two or more active hydrogens. A carboxyl group-containing polyurethane obtained by neutralizing a prepolymer and emulsifying and dispersing it in water by self-emulsification, and then (d) chain-extending reaction using a polyamine compound having two or more amino groups and / or imino groups. Resin emulsions are preferred.

  There is no restriction | limiting in particular as such (a) organic diisocyanate, The aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate which have two isocyanate groups can be used. Examples of such (a) organic diisocyanate include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, and 1,3-bis ( Examples thereof include alicyclic diisocyanate compounds such as isocyanatomethyl) cyclohexane, aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate. These diisocyanate compounds can be used individually by 1 type, or can also be used in combination of 2 or more type. Among these (a) organic diisocyanates, aliphatic diisocyanate compounds and alicyclic diisocyanate compounds can be suitably used because they impart non-yellowing properties to the fiber composite, and in particular, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane. Diisocyanate, norbornane diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane can be suitably used.

  The (b) polyol is not particularly limited as long as it has two or more hydroxyl groups, and is a polyether ester having an ether bond and an ester bond in addition to a polyester polyol, a polycarbonate polyol, a polyether polyol, and the like. Polyols can also be used.

  Examples of such polyester polyols include polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, polyhexamethylene isophthalate adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, poly-ε- Caprolactone diol, poly (3-methyl-1,5-pentylene) adipate, polycondensate of 1,6-hexanediol and dimer acid, copolycondensate of 1,6-hexanediol, adipic acid and dimer acid, nonane Examples thereof include polycondensates of diol and dimer acid, and copolycondensates of ethylene glycol, adipic acid and dimer acid.

  Examples of the polycarbonate polyol include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, poly-1,4-cyclohexanedimethylene carbonate diol, and 1,6-hexanediol polycarbonate polyol.

  Furthermore, as the polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol homopolymer, block copolymer, random copolymer, ethylene oxide and propylene oxide, ethylene oxide and butylene oxide random copolymer And a block copolymer.

  Such (b) polyol can be used individually by 1 type, or can also be used in combination of 2 or more type. Moreover, as an average molecular weight of such (b) polyol, it is preferable that it is 500-5000, and it is more preferable that it is 1000-3000. Furthermore, since durability can be imparted to the fiber composite material by the resulting carboxyl group-containing polyurethane resin, it is preferable to use polycarbonate polyol or polyether polyol as the above-mentioned (b) polyol.

  Examples of the compound (c) having a carboxyl group and two or more active hydrogens include 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid. Furthermore, as a compound having such a carboxyl group and two or more active hydrogens, a pendant carboxyl group obtained by reacting a diol having a carboxyl group with an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or the like is used. The polyester polyol which has can also be used. In place of the diol having a carboxyl group, a diol having no carboxyl group may be mixed and reacted as a diol component. Moreover, the compound which has such a carboxyl group and two or more active hydrogens can be used individually by 1 type, or can also be used in combination of 2 or more type.

  When an isocyanate group-terminated prepolymer is produced by reacting (a) an organic diisocyanate, (b) a polyol, and (c) a compound having a carboxyl group and two or more active hydrogens, e) Low molecular weight chain extenders having two or more active hydrogen atoms can be used.

  Such a low molecular weight chain extender having 2 or more active hydrogen atoms (e) preferably has a molecular weight of 400 or less, particularly preferably 300 or less. Such low molecular weight chain extenders include, for example, low molecular weight high molecular weights such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples thereof include low-molecular weight polyamines such as ethylene diamine, propylene diamine, hexamethylene diamine, diaminocyclohexyl methane, piperazine, 2-methyl piperazine, isophorone diamine, diethylene triamine, and triethylene tetramine. Such low molecular weight chain extenders having two or more active hydrogen atoms can be used singly or in combination of two or more.

  In the present invention, the specific method for producing the carboxyl group-containing isocyanate group-terminated prepolymer is not particularly limited. For example, by a conventionally known one-stage so-called one-shot method, multi-stage isocyanate polyaddition reaction method, etc. Can be manufactured. The reaction temperature at this time is preferably 40 to 150 ° C. In the reaction, a reaction catalyst such as dibutyltin dilaurate, stannous octoate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine, N-methylmorpholine can be added as necessary. . Furthermore, in the production of the carboxyl group-containing isocyanate group-terminated prepolymer, an organic solvent that does not react with the isocyanate group can be added during or after the reaction. As such an organic solvent, for example, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone and the like can be used.

  Moreover, neutralization of a carboxyl group-containing isocyanate group-terminated prepolymer can be performed using a known method as appropriate before or after the preparation of the carboxyl group-containing isocyanate group-terminated prepolymer. There are no particular limitations on the compound used for neutralization of such carboxyl group-containing isocyanate group-terminated prepolymers, such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine, N-methyl-diethanolamine, N, N-dimethyl. Mention may be made of amines such as monoethanolamine, N, N-diethylmonoethanolamine, triethanolamine, potassium hydroxide, sodium hydroxide, ammonia and the like. Among these, tertiary amines having no hydroxyl group such as trimethylamine, triethylamine, tri-n-propylamine and tributylamine are particularly preferable.

  In the present invention, there are no particular limitations on the emulsifying equipment used when the neutralized product of the carboxyl group-containing isocyanate group-terminated prepolymer is emulsified and dispersed in water by self-emulsification, and examples include a homomixer, a homogenizer, and a disper. Can do. In addition, when the neutralized product is emulsified and dispersed, the neutralized product of the carboxyl group-containing isocyanate group-terminated prepolymer is emulsified and dispersed in water at a temperature ranging from room temperature to 40 ° C. without using an emulsifier. It is preferable to suppress the reaction between the group and water as much as possible. Furthermore, reaction inhibitors such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, paratoluenesulfonic acid, adipic acid, and benzoyl chloride can be added as necessary.

  Furthermore, in the present invention, a neutralized product of a carboxyl group-containing isocyanate group-terminated prepolymer is emulsified and dispersed in water by self-emulsification, and then (d) a polyamine compound having two or more amino groups and / or imino groups is used. The target (A) carboxyl group-containing polyurethane resin emulsion can be obtained by chain extension reaction.

  Examples of such (d) polyamine compounds having two or more amino groups and / or imino groups include ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, hydrazine, and 2-methylpiperazine. Diamines such as isophoronediamine, norbornanediamine, diaminodiphenylmethane, tolylenediamine, xylylenediamine; polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, tris (2-aminoethyl) amine; Amidoamines derived from primary amines and monocarboxylic acids; water-soluble amine derivatives such as monoketimines of diprimary amines; oxalic acid dihydrazide, malonic acid dihydrazide Oxalic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, 1,1'-ethylenehydrazine, 1,1'-trimethylenehydrazine, 1,1 ' Examples include hydrazine derivatives such as-(1,4-butylene) dihydrazine. These polyamine compounds having two or more amino groups and / or imino groups can be used singly or in combination of two or more.

  The chain extension reaction of the neutralized product of the carboxyl group-containing isocyanate group-terminated prepolymer is carried out by adding (d) an amino group and / or an imino group to the emulsion dispersion of the neutralized product of the carboxyl group-containing isocyanate group-terminated prepolymer. It can be carried out by adding a polyamine compound having 2 or more. Further, (d) an emulsified dispersion of the neutralized product of the carboxyl group-containing isocyanate group-terminated prepolymer described above can be added to a polyamine compound having two or more amino groups and / or imino groups. Such a chain extension reaction is preferably performed at a reaction temperature of 20 to 40 ° C., and is usually completed in 30 to 120 minutes. In addition, when an organic solvent is used when producing a carboxyl group-containing isocyanate group-terminated prepolymer, it is preferable to remove the organic solvent by, for example, vacuum distillation after the chain extension reaction is completed.

  The content of the carboxyl group in the carboxyl group-containing polyurethane resin obtained as described above is preferably 0.5 to 4.0% by mass, and preferably 1.0 to 2.0% by mass. More preferred. When the carboxyl group content is less than 0.5% by mass, the storage stability of the resulting carboxyl group-containing polyurethane resin emulsion tends to deteriorate, whereas when it exceeds 4.0% by mass, (B) The heat-sensitive coagulation temperature generated when mixed with the carboxylic acid ammonia salt tends to be high, and the effect of preventing migration tends to be weakened during the production of the fiber composite material.

  In the present invention, as the ethylenically unsaturated monomer, any of (f) a monofunctional ethylenically unsaturated monomer and (g) a bifunctional or higher polyfunctional ethylenically unsaturated monomer can be used. Can be used alone, or two or more can be used in combination.

  Such (f) monofunctional ethylenically unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and (meth) acrylic. Stearyl acid, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid derivatives such as diethylaminoethyl acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene; Acrylamide, diacetone acrylamide, methacrylic Acrylamides such as maleic acid amide; heterocyclic vinyl compounds such as vinylpyrrolidone; vinyl compounds such as vinyl chloride, acrylonitrile, vinyl ether, vinyl ketone, vinylamide; α-olefins such as ethylene and propylene; maleic acid, fumaric acid, Itaconic acid and derivatives thereof may be mentioned. Here, (meth) acrylic acid represents acrylic acid or methacrylic acid. Moreover, such a monofunctional ethylenically unsaturated monomer can be used individually by 1 type, or can also be used in combination of 2 or more type.

  In addition, (g) polyfunctional ethylenically unsaturated monomers having two or more functions include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dimethylol tricyclo Di (meth) acrylates such as decane di (meth) acrylate and glycerin di (meth) acrylate; tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate; pentaerythritol tetra (meth) acrylate Tetra (meth) acrylates; polyfunctional aromatic vinyl compounds such as divinylbenzene and trivinylbenzene; two or more different ethylenically unsaturated bond-containing compounds such as allyl (meth) acrylate and vinyl (meth) acrylate; 2 2: 1 addition reaction product of hydroxy-3-phenoxypropyl acrylate and hexamethylene diisocyanate, 2: 1 addition reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate, 2: 1 addition reaction product of glycerin dimethacrylate and tolylene diisocyanate And urethane acrylate having a molecular weight of 1500 or less. Here, (meth) acrylate represents acrylate or methacrylate. Moreover, such a bifunctional or more polyfunctional ethylenically unsaturated monomer can be used individually by 1 type, or can also be used in combination of 2 or more type.

  In the present invention, the method for emulsion polymerization of the ethylenically unsaturated monomer in the presence of the carboxyl group-containing polyurethane resin emulsion is not particularly limited, and a known method can be used as appropriate. Moreover, a polymerization initiator can be used in such emulsion polymerization. Examples of the polymerization initiator include oil solubility such as benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, and the like. Peroxides; oil-soluble azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile); hydrogen peroxide, potassium persulfate, sodium persulfate And water-soluble peroxides such as ammonium persulfate; water-soluble azo compounds such as azobiscyanovaleric acid and 2,2′-azobis- (2-amidinopropane) dihydrochloride. Such a polymerization initiator can be used individually by 1 type, or can also be used in combination of 2 or more type.

  Furthermore, at the time of the emulsion polymerization, a redox initiator that is used in combination with a reducing agent and, if necessary, a chelating agent may be used together with the polymerization initiator. Examples of such a reducing agent include formaldehyde alkali metal sulfoxylates such as Rongalite (formaldehyde sodium sulfoxylate); sulfites such as sodium sulfite and sodium bisulfite; pyrosulfites such as sodium pyrosulfite; thiosulfuric acid Thiosulfates such as sodium; phosphites such as phosphorous acid and sodium phosphite; pyrophosphites such as sodium pyrophosphite; mercaptans; ascorbates such as ascorbic acid and sodium ascorbate; Examples thereof include erythorbates such as erythorbic acid and sodium erythorbate; sugars such as glucose and dextrose; metal salts such as ferrous sulfate and copper sulfate. Examples of the chelating agent include sodium pyrophosphate and ethylenediaminetetraacetate. Furthermore, the usage-amount of such a polymerization initiator, a reducing agent, and a chelating agent can be suitably determined according to the combination of each initiator.

  In the emulsion polymerization, it is preferable to add an emulsifier in order to impart polymerization stability. Examples of such emulsifiers include anionic interfaces such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium polyoxyethylene tridecyl ether acetate, sodium dodecylbenzene sulfonate, sodium alkyldiphenyl ether disulfonate, sodium di (2-ethylhexyl) sulfosuccinate. Activators: Nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene polyoxypropylene block copolymer, etc. . Among such emulsifiers, anionic surfactants such as sodium lauryl sulfate, ammonium lauryl sulfate, and sodium polyoxyethylene tridecyl ether acetate are preferable.

  Furthermore, the addition method of the ethylenically unsaturated monomer during the emulsion polymerization may be any of batch addition, divided addition and continuous addition, and multistage polymerization in which the monomer composition is changed at each stage of polymerization. You may perform superposition | polymerization by the power feed method changed continuously.

  Thus, in the presence of the carboxyl group-containing polyurethane resin emulsion, the ethylenically unsaturated monomer can be emulsion polymerized to obtain a urethane / acrylic composite resin emulsion.

  The blending ratio of the carboxyl group-containing polyurethane resin and the ethylenically unsaturated monomer in the (A) urethane / acrylic composite resin emulsion is 90:10 to 10:90 in terms of solid mass. Preferably, it is 80: 20-20: 80. When the blending ratio is less than 10:90, that is, when the ratio of the carboxyl group-containing polyurethane resin is less than 10% by mass, the adhesion between the urethane / acrylic composite resin and the fiber base material is deteriorated. The wear resistance of the material tends to deteriorate. On the other hand, when the blending ratio exceeds 90:10, that is, when the proportion of the carboxyl group-containing polyurethane exceeds 90% by mass, the weather resistance and hydrolysis resistance of the urethane / acrylic composite resin tend to be inferior. The durability of the resulting fiber composite material tends to decrease.

  The pH value of the (A) urethane / acrylic composite resin emulsion is preferably 7.0 to 9.0, and more preferably 7.5 to 8.5. When the pH value of the (A) urethane / acrylic composite resin emulsion is less than 7.0, the storage stability of the (A) urethane / acrylic composite resin emulsion tends to deteriorate, while the pH value is 9.0. When it exceeds, it exists in the tendency for the effect of migration prevention to become weak in the case of manufacture of a fiber base material.

  The ammonium salt of (B) carboxylic acid according to the present invention is not particularly limited, and a commercially available one can be used. Examples of such carboxylic acids include saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, capric acid and stearic acid; unsaturated fatty acids such as oleic acid and linoleic acid; benzoic acid, phthalic acid, Aromatic carboxylic acids such as isophthalic acid and terephthalic acid; saturated dicarboxylic acids such as malic acid, citric acid, succinic acid, malonic acid, succinic acid and adipic acid; unsaturated dicarboxylic acids such as fumaric acid and maleic acid; lactic acid and acrylic acid , Polyacrylic acid, polymaleic acid and the like. Among these carboxylic acids, it is easy to impregnate the mixed solution into the fiber base, to prevent migration of the carboxyl group-containing polyurethane resin during the drying process, and to volatilize during drying or to be washed with water after drying. From the viewpoint of being able to be removed and being less likely to remain in the fiber composite material, a carboxylic acid having 1 to 10 carbon atoms is preferable, and a carboxylic acid having 1 to 4 carbon atoms is more preferable.

  In the method for producing a fiber composite material according to the present invention, when (A) the ammonium salt of (B) carboxylic acid is mixed with (A) urethane / acrylic composite resin emulsion, (B) the ammonium salt of carboxylic acid is solid (powder). )) In the state of (A) urethane / acrylic composite resin emulsion, but (A) from the viewpoint of maintaining the stability of the urethane / acrylic composite resin emulsion, it is mixed in the state of an aqueous solution. It is preferable.

  In such an aqueous solution of an ammonium salt of a carboxylic acid, the concentration of the ammonium salt of the carboxylic acid contained in the aqueous solution is preferably 1 to 50% by mass, and more preferably 10 to 30% by mass. In the case of an aqueous solution having a carboxylic acid ammonium salt concentration of less than 1 mass, it is necessary to add a large amount of the aqueous solution to the (A) urethane / acrylic composite resin emulsion in order to exhibit the migration-preventing property during drying. Along with this, the concentration of the (A) urethane / acrylic composite resin emulsion in the mixed solution decreases. Therefore, since it is necessary to impregnate a large amount of the mixed liquid in order to fix the required amount of urethane / acrylic resin to the fiber base material, the amount of water volatilized during drying increases and the drying time becomes longer. This tends to make the economy worse. On the other hand, when the concentration of the carboxylic acid ammonium salt exceeds 50% by mass, the stability of the emulsified dispersion tends to be impaired, for example, precipitates are generated during mixing with the (A) urethane / acrylic composite resin emulsion.

  In addition, the pH value in the aqueous solution of the ammonium salt of (B) carboxylic acid is preferably 7.0 to 9.0, and more preferably 7.5 to 8.5. (B) When the pH value in the aqueous solution of ammonium salt of carboxylic acid is less than 7.0, precipitates tend to be generated during mixing with (A) urethane / acrylic composite resin emulsion, while the pH value is If it exceeds 9.0, the migration preventing effect tends to be weak in the drying process.

  In addition, (C) water according to the present invention has a role as a solvent when mixing (A) urethane / acrylic composite resin emulsion and (B) ammonium salt of carboxylic acid. Or distilled water can be used conveniently.

  In the present invention, the method for preparing the mixed solution containing (A) urethane / acrylic composite resin emulsion, (B) ammonium salt of carboxylic acid and (C) water is not particularly limited, and a known method is appropriately used. Can do.

  In the mixed solution thus prepared, the blending ratio of (A) urethane / acrylic composite resin emulsion and (B) ammonium salt of carboxylic acid is 100: 0.5 to 0.5 in terms of solid content. 100: 20 is preferable, and 100: 2 to 100: 10 is more preferable. When the blending ratio of (A) urethane / acrylic composite resin emulsion and (B) ammonium salt of carboxylic acid exceeds 100: 0.5, that is, when the ammonium salt of carboxylic acid is less than 0.5, In the drying process, the effect of preventing migration tends to be weakened. On the other hand, when it is less than 100: 20, that is, when the ammonium salt of carboxylic acid is more than 20, the mixed solution gelates in the summer temperature atmosphere. It tends to end up.

  Moreover, as a pH value of the said liquid mixture, it is preferable that it is 7.0-9.0, and it is more preferable that it is 7.5-8.5. When the pH value of the mixed solution is less than 7.0, the stability of the mixed solution tends to deteriorate. On the other hand, when the pH value exceeds 9.0, the migration preventing effect tends to be weakened in the drying process. is there.

  Furthermore, the heat-sensitive coagulation temperature of the mixed solution is preferably 30 ° C. to 70 ° C., and more preferably 40 ° C. to 60 ° C. Here, the thermal coagulation temperature means that 50 g of the mixed solution is taken into a 100 mL glass beaker, and the content is stirred and the beaker is gradually heated with hot water at 95 ° C., and the content loses fluidity and solidifies. It is the temperature when When the thermal coagulation temperature of the mixed liquid is less than 30 ° C., the mixed liquid tends to gel in the atmosphere in summer, while when it exceeds 65 ° C., the thermal coagulation is sharply expressed. Therefore, the migration prevention property tends to be weak in the drying process.

  Moreover, it is preferable that it is 15-35 mass%, and, as for content of (A) urethane / acryl composite resin in the said liquid mixture, it is more preferable that it is 20-30 mass%. (A) If the content of the urethane / acrylic composite resin is less than 15% by mass, in order to fix the required amount of resin, a large amount of the mixed solution is impregnated with respect to the fiber substrate. There is a tendency that the amount of water volatilized by drying increases, the drying time becomes longer, and the economy becomes worse. On the other hand, when the content of the (A) urethane / acrylic composite resin exceeds 35% by mass, the stability of the mixed solution tends to deteriorate.

  The fiber base material according to the present invention is not particularly limited as long as it is a fiber base material that can be impregnated with the mixed solution and can form a coating film with a resin component after drying. In addition, natural fibers, synthetic fibers, and woven fabrics, knitted fabrics, non-woven fabrics, and the like produced by blending, blending, and blending of these can be used.

  Moreover, in the manufacturing method of the fiber composite material of this invention, the objective of this invention is included in the liquid mixture containing (A) urethane / acryl composite resin emulsion, (B) ammonium salt of carboxylic acid, and (C) water. Various additives can be used in combination in order to improve the processability within the range not impaired. Examples of such additives include lower alcohols, glycol-based solvents, alcohol-based nonionic surfactants, acetylene glycol-based special surfactants, silicone-based surfactants, and fluorine-based surfactants. Various penetrants; various stabilizers such as antioxidants, light-resistant stabilizers, ultraviolet inhibitors; various antifoaming agents such as mineral oils and silicones; urethanization catalysts, plasticizers, colorants such as pigments, etc. Use time extender can be added. Moreover, such an additive can be used individually by 1 type, or can also be used in combination of 2 or more type.

  Among such additives, it is particularly preferable to use a penetrant. By using a penetrant, the nonwoven fabric can be quickly impregnated with the mixed solution, and an effect of uniformly fixing a polyurethane resin to the nonwoven fabric can be obtained. Such penetrants are not particularly limited as long as they are generally used, but lower alcohols, glycol-based solvents, alcohol-based nonionic surfactants are highly volatile at the time of drying and do not remain. Etc. are particularly preferred.

  Moreover, in the manufacturing method of the fiber composite material of this invention, the objective of this invention is included in the liquid mixture containing (A) urethane / acryl compound resin emulsion, (B) ammonium salt of carboxylic acid, and (C) water. Various polymers can be used in combination in order to improve the uniformity and stability of the texture as long as they are not impaired. Examples of such a polymer include synthetic rubbers such as acrylonitrile-butadiene copolymer, polybutadiene, polyisoprene, ethylene-propylene copolymer, polyacrylate, acrylic copolymer, silicone, and polyester-polyether block copolymer. Examples thereof include synthetic polymers such as polymers and ethylene-vinyl acetate copolymers. Such a polymer can be used individually by 1 type, or can also be used in combination of 2 or more type.

  Furthermore, in the mixed solution, a crosslinking agent that reacts with a carboxyl group can be used in combination in order to improve durability within a range that does not impair the object of the present invention. Examples of such a crosslinking agent that reacts with a carboxyl group include an oxazoline-based crosslinking agent, an epoxy-based crosslinking agent, an isocyanate-based crosslinking agent, and a carbodiimide-based crosslinking agent. Moreover, the crosslinking agent which reacts with such a carboxyl group can be used individually by 1 type, or can also be used in combination of 2 or more type.

  In the method for producing a fiber composite material of the present invention, a fiber base material is impregnated with a mixed solution containing (A) urethane / acryl compound resin emulsion, (B) ammonium salt of carboxylic acid and (C) water. After drying.

  The method for impregnating the mixed liquid into such a fiber base is not particularly limited, and conventionally known methods such as impregnation processing and spraying using a dip-nip method can be preferably employed. The concentration, processing conditions, and the like can also be selected as appropriate. In addition, before making the fiber base material impregnate the said mixed liquid, a fiber base material can be pre-processed. In such a pretreatment step, in order to adjust the adhesive force between the fiber base material and the urethane / acrylic composite resin component, an aqueous polymer solution composed of polyvinyl alcohol, carboxymethyl cellulose, etc., a silicone-based water repellent, a fluorine-based repellent agent. It is preferable to treat with a liquid agent or the like.

  Moreover, there is no restriction | limiting in particular as the said drying method, For example, the dry-drying using hot air; High-Tenpalcher steamer (HTSS) and the high pressure steamer (HPSS) were used. Wet drying; a microwave irradiation dryer or the like can be used, and dry drying using hot air can be suitably used in terms of continuous processability. Such a drying method can be used individually by 1 type, or can also be used in combination of 2 or more type. In the case of using dry drying using hot air, the treatment temperature is preferably 60 to 190 ° C. and the treatment time is preferably 1 to 20 minutes. In particular, the treatment temperature is 100 to 170 ° C. Is more preferably 2 to 5 minutes. In this way, the resin can be fixed inside the fiber base by drying after impregnating the mixed liquid into the fiber base.

  In this way, the fiber substrate is dried after impregnating the mixed liquid containing (A) urethane / acrylic composite resin emulsion, (B) ammonium salt of carboxylic acid and (C) water, and the fiber of the present invention. A composite material can be obtained.

  In such a fiber composite material of the present invention, the amount of fixed solids such as polyurethane resin in the fiber composite material is not particularly limited, but is derived from the (A) urethane / acrylic composite resin emulsion in the fiber composite material. It is preferable that a component is 5-90 mass%, and the component derived from the ammonium salt of (B) carboxylic acid is about 0.5-7.0 mass%.

  Moreover, the fiber composite material obtained by the present invention can be dyed. There is no particular limitation on the dyeing method, and the dyeing method after impregnation after the urethane / acrylic composite resin is fixed to the fiber base and the urethane / acryl composite after the fiber base is dyed. Any of the post-impregnation dyeing methods can be performed after fixing the resin.

  Furthermore, a skin layer can also be formed in the fiber composite material obtained by the present invention. As a method for forming such a skin layer, any conventionally known method may be used. For example, a skin layer is formed by applying it to a release paper and evaporating water, and then adhering to it. A release paper transfer method in which an agent is applied and directly bonded to the fiber composite material of the present invention to evaporate the moisture, or bonded after the moisture has been evaporated; A thermal transfer method in which a layer is formed and the skin layer is bonded to the fiber composite material of the present invention by heat; a spray method in which the fiber composite material of the present invention is sprayed directly; a gravure coater, knife coater, comma coater, air knife coater, etc. The direct coating method of apply | coating directly on the fiber composite material of invention is mentioned. Among such methods for forming the skin layer, the release paper transfer method is most preferable from the viewpoint of improving the physical properties of the obtained skin layer. In such a release paper transfer method, the skin layer and the adhesive used may be any as long as they can be bonded to the fiber composite material of the present invention, but a polyurethane resin is preferable from the texture and physical properties, From the viewpoint of VOC-free and environmental load reduction, an aqueous or solventless system is desirable.

  Moreover, the fiber composite material obtained by this invention is (A) adjusting the value of 100% modulus of urethane / acryl compound resin, for example, various clothing, artificial leather, synthetic leather, a filter, a heat insulating material, agriculture. It can be used in the field of industrial materials such as industrial materials and electronic equipment manufacturing. Specifically, when the fiber composite material of the present invention is used for artificial leather or synthetic leather, the (A) urethane / acrylic composite resin preferably has a 100% modulus value of 1 to 9 MPa, More preferably, it is 2-6 MPa. In addition, when the fiber composite material of the present invention is used for a use in which it is preferable to use a fiber composite material harder than artificial leather or synthetic leather, a material having a large value of 100% modulus may be appropriately selected.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

  In addition, the fiber composite material obtained by each synthesis example and comparative synthesis example, and each example and each comparative example was evaluated by the following method.

(1) Migration prevention property About the fiber composite material obtained in each Example and each comparative example, the cross section of the fiber composite material was magnified 60 times using a scanning electron microscope [Scanning Electron Microscope S-2400 (HITACHI)]. Was observed, and the fixing state of the resin existing in the center portion of the fiber base material was compared with the fixing state of the resin existing in the surface portion of the fiber base material and evaluated according to the following criteria.
Grade 5: In the cross section of the fiber composite material, there is no difference in the resin fixing amount between the central portion and the surface portion, and no migration occurs.
Fourth grade: In the cross section of the fiber composite material, there is almost no difference in the resin fixing amount between the central portion and the surface portion, and no migration occurs.
Third grade: In the cross section of the fiber composite material, a slight difference is observed in the resin fixing amount between the central portion and the surface portion, and no resin fixing is observed in 10% of the central portion in the entire thickness.
Second grade: In the cross section of the fiber composite material, a considerable difference is observed in the resin fixing amount between the central portion and the surface portion, and no resin fixing is observed in 30% of the central portion in the entire thickness.
First grade: In the cross section of the fiber composite material, there is a marked difference in the resin fixing amount between the central portion and the surface portion, and no resin fixing is observed in 50% of the central portion in the entire thickness.

(2) Abrasion test The fiber composite materials obtained in each Example and each Comparative Example were subjected to a soft wheel CS- by a Taber abrasion tester [manufactured by Yasuda Seiki Seisakusho] in accordance with the Taber method of JIS L 1096 (1999). 10 shows the amount of decrease in the weight of the fiber composite after applying a load of 500 g and wearing it 1000 times or 3000 times. The smaller the amount of wear, the better the wear resistance of the fiber composite material.

(3) Presence / absence of residue About the fiber composite material obtained by each Example and each comparative example, about content of components (residues, such as surfactant) other than the nonwoven fabric and urethane / acrylic resin in a fiber composite material Then, the extraction amount when extracted at 70 ° C. for 3 hours with a Soxhlet extractor using methanol as an extraction solvent was measured. Less than were evaluated as having no residue.

(4) 100% Modulus For the urethane / acrylic composite resin obtained in each synthesis example, the distance between marked lines is increased by 100% using a dumbbell-shaped No. 3 test piece according to JIS K 6251 (1993). The value of the predetermined elongation tensile stress (MPa) when measured (when stretched twice) was measured.

[Synthesis Examples 1 to 4 and Comparative Synthesis Example 1]
Below, the synthesis example of the urethane / acryl composite resin emulsion used for this invention and the comparative synthesis example of the polyurethane resin emulsion used for a comparative example are shown.

(Synthesis Example 1)
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube, 157.0 g of 1,6-hexanediol polycarbonate polyol (average molecular weight 2000), 7.5 g of neopentyl glycol, trimethylolpropane 1 .3 g, dimethylolpropionic acid 9.5 g, dibutyltin dilaurate 0.001 g and methyl ethyl ketone 105 g were added and mixed uniformly. Then, 69.7 g of isophorone diisocyanate was added and reacted at 80 ° C. for 300 minutes. A methyl ethyl ketone solution of a carboxyl group-containing isocyanate group-terminated prepolymer having a content of 1.9% by mass was obtained.

  After cooling the solution to 50 ° C. or lower, 6.8 g of triethylamine was added, and a neutralization reaction was performed at 40 ° C. for 30 minutes. Next, the neutralized solution is cooled to 30 ° C. or lower, and 421.9 g of water is gradually added using a disper blade to emulsify and disperse the carboxyl group-containing isocyanate group-terminated prepolymer neutralized product to obtain a dispersion. It was. Then, an aqueous polyamine solution in which 5.2 g of 60% by mass hydrazine hydrate and 1.1 g of diethylenetriamine were dissolved in 20 g of water was added to the dispersion and subjected to chain extension reaction for 60 minutes, and then the solvent was removed at 35 ° C. under reduced pressure. A stable carboxyl group-containing polyurethane resin emulsion having a carboxyl group-containing polyurethane resin content of 35.0 mass%, a viscosity of 120 mPa · s (BM viscometer, No. 2 rotor, 60 rpm), a pH value of 7.8, and an average particle size of 90 nm. Got. Moreover, content of the carboxyl group in a carboxyl group-containing polyurethane resin was 1.3 mass%.

In 640 g of the obtained carboxyl group-containing polyurethane resin emulsion, 102.0 g of water, ferrous sulfate heptahydrate (FeSO ₄ .7H ₂ O) 0.0006 g, potassium pyrophosphate 0.084 g, thiourea dioxide 0. 11 g and Clewat N [EDTA · 2Na, trade name, manufactured by Nagase Chemitex] 0.003 g were added and the temperature was raised to 40 ° C., and then the system was sufficiently purged with nitrogen.

  Next, a mixed monomer solution of 35.12 g of butyl acrylate, 18.03 g of methyl methacrylate and 2.85 g of 1,6-hexanediol diacrylate, 0.11 g of cumene hydroperoxide as a polymerization initiator, and ECT-3NEX as an emulsifier [Polyoxyethylene tridecyl ether sodium acetate, trade name, manufactured by Nikko Chemicals] A polymerization initiator solution consisting of 0.06 g and 1.68 g of water was dropped into a flask from a separate dropping funnel over 120 minutes, The polymerization is completed by holding at 40 ° C. for 120 minutes to obtain a urethane / acrylic composite resin emulsion in which the blending ratio of the carboxyl group-containing polyurethane resin and the ethylenically unsaturated monomer is 80:20 in terms of solid mass. It was.

  The obtained urethane / acrylic composite resin emulsion has a urethane / acrylic composite resin content of 35.0% by mass, a viscosity of 120 mPa · s (BM viscometer, No. 2 rotor, 60 rpm), a pH value of 7.8, an average particle size. The value of 90 nm and 100% modulus was 2 MPa. Further, this urethane / acrylic composite resin emulsion did not gel when heated at 90 ° C., and had no heat-sensitive coagulation property.

(Synthesis Example 2)
In 160 g of the carboxyl group-containing polyurethane resin emulsion obtained in Synthesis Example 1, 407.8 g of water, 0.0022 g of ferrous sulfate heptahydrate (FeSO ₄ .7H ₂ O), 0.336 g of potassium pyrophosphate, 0.45 g of thiourea and Clewat N [EDTA · 2Na, trade name, manufactured by Nagase Chemitex] 0.011 g were added and the temperature was raised to 40 ° C., and then the interior of the system was sufficiently substituted with nitrogen.

  Next, a mixed monomer liquid of 140.47 g of butyl acrylate, 72.13 g of methyl methacrylate and 11.40 g of 1,6-hexanediol diacrylate, 0.45 g of cumene hydroperoxide as a polymerization initiator, ECT-3NEX [poly A polymerization initiator solution consisting of 0.22 g of sodium oxyethylene tridecyl ether acetate, trade name, manufactured by Nikko Chemicals] and 6.72 g of water was dropped into the flask from a separate dropping funnel over 240 minutes, and then 40 ° C. For 120 minutes to complete the polymerization to obtain a urethane / acrylic composite resin emulsion in which the blending ratio of the carboxyl group-containing polyurethane resin and the ethylenically unsaturated monomer is 20:80 in terms of solid mass.

  The obtained urethane / acrylic composite resin emulsion has a urethane / acrylic composite resin content of 35.0% by mass, a viscosity of 220 mPa · s (BM viscometer, No. 2 rotor, 60 rpm), a pH value of 7.8, an average particle size. The value of 90 nm and 100% modulus was 2 MPa. Further, this urethane / acrylic composite resin emulsion did not gel when heated at 90 ° C., and had no heat-sensitive coagulation property.

(Synthesis Example 3)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, 146.8 g of 1,6-hexanediol polycarbonate polyol (average molecular weight 2000), 6.3 g of 1,4-butanediol, di After charging 10.0 g of methylol propionic acid, 0.001 g of dibutyltin dilaurate and 105 g of methyl ethyl ketone and mixing them uniformly, 81.8 g of dicyclohexylmethane diisocyanate was added and reacted at 80 ° C. for 420 minutes, so that the content of free isocyanate groups was A methyl ethyl ketone solution of carboxyl group-containing isocyanate group-terminated prepolymer of 2.25% by mass was obtained.

  After cooling the solution to 50 ° C. or lower, 7.2 g of triethylamine was added, and a neutralization reaction was performed at 40 ° C. for 30 minutes. Next, the neutralized solution is cooled to 30 ° C. or lower, and 412.1 g of water is gradually added using a disper blade to emulsify and disperse the carboxyl group-containing isocyanate group-terminated prepolymer neutralized product to obtain a dispersion. It was. Then, an aqueous polyamine solution in which 14.5 g of piperazine hexahydrate and 1.3 g of diethylenetriamine are dissolved in 20 g of water is added to the dispersion and subjected to chain extension reaction for 60 minutes, and then the solvent is removed at 35 ° C. under reduced pressure. A stable carboxyl group-containing polyurethane resin emulsion having a carboxyl group-containing polyurethane resin content of 35.0 mass%, a viscosity of 70 mPa · s (BM viscometer, No. 1 rotor, 60 rpm), a pH value of 7.8, and an average particle size of 100 nm. Obtained. Moreover, content of the carboxyl group in a carboxyl group-containing polyurethane resin was 1.3 mass%.

In 640 g of the obtained carboxyl group-containing polyurethane resin emulsion, 99.9 g of water, 0.0011 g of ferrous sulfate heptahydrate (FeSO ₄ .7H ₂ O), 0.17 g of potassium pyrophosphate, and 0.17 g of thiourea dioxide were added. 22 g and Clewat N [EDTA · 2Na, trade name, manufactured by Nagase Chemitex] 0.006 g were added and the temperature was raised to 40 ° C., and then the system was sufficiently purged with nitrogen.

  Next, 17.33 g of butyl acrylate, 35.59 g of methyl methacrylate, 3.08 g of 1,6-hexanediol diacrylate, 0.22 g of cumene hydroperoxide as a polymerization initiator, and ECT-3NEX as an emulsifier [Polyoxyethylene tridecyl ether sodium acetate, trade name, manufactured by Nikko Chemicals] 0.11 g and a polymerization initiator solution consisting of 3.08 g of water were dropped into a flask from separate dropping funnels over 120 minutes, The polymerization is completed by holding at 40 ° C. for 120 minutes to obtain a urethane / acrylic composite resin emulsion in which the blending ratio of the carboxyl group-containing polyurethane resin and the ethylenically unsaturated monomer is 80:20 in terms of solid mass. It was.

  The obtained urethane / acrylic composite resin emulsion has a urethane / acrylic composite resin content of 35.0% by mass, a viscosity of 80 mPa · s (BM viscometer, No. 1 rotor, 60 rpm), a pH value of 7.9, an average particle size. The value of 110 nm and 100% modulus was 18 MPa. Further, this urethane / acrylic composite resin emulsion did not gel when heated at 90 ° C., and had no heat-sensitive coagulation property.

(Synthesis Example 4)
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube, 141.9 g of polytetramethylene glycol (average molecular weight 2000), 30.8 g of dimethylolpropionic acid, 0.001 part of dibutyltin dilaurate And 105 g of methyl ethyl ketone were charged and mixed uniformly, and then 72.3 g of hexamethylene diisocyanate was added and reacted at 80 ° C. for 180 minutes to give a carboxyl group-containing isocyanate group having a free isocyanate group content of 3.1% by mass. A methyl ethyl ketone solution of the prepolymer was obtained.

  After cooling this solution to 50 ° C. or lower, 22.1 g of triethylamine was added, and a neutralization reaction was performed at 40 ° C. for 30 minutes. Next, the neutralized solution is cooled to 30 ° C. or less, and 402.6 g of water is gradually added using a disperse blade to emulsify and disperse the neutralized product of the carboxyl group-containing isocyanate group-terminated prepolymer. Obtained. Then, an aqueous polyamine solution prepared by dissolving 8.6 g of 60% by mass hydrated hydrazine and 1.8 g of diethylenetriamine in 20 g of water was added to the dispersion and subjected to chain extension reaction for 60 minutes, and then the solvent was removed at 35 ° C. under reduced pressure. A stable carboxyl group-containing polyurethane resin emulsion having a carboxyl group-containing polyurethane resin content of 35.0% by mass, a viscosity of 50 mPa · s (BM viscometer, No. 1 rotor, 60 rpm), a pH value of 7.9 and an average particle diameter of 150 nm is obtained. Obtained. Moreover, content of the carboxyl group in carboxyl group-containing polyurethane resin was 4.2 mass%.

In 560 g of the obtained carboxyl group-containing polyurethane resin emulsion, 252.9 g of water, 0.0008 g of ferrous sulfate heptahydrate (FeSO ₄ .7H ₂ O), 0.13 g of potassium pyrophosphate, and 0.03 g of thiourea dioxide. 17 g and Clewat N [EDTA · 2Na, trade name, manufactured by Nagase Chemitex] 0.0042 g were added and the temperature was raised to 40 ° C., and then the system was sufficiently purged with nitrogen.

  Next, a mixed monomer solution of 36.96 g of butyl acrylate, 42.84 g of methyl methacrylate and 4.20 g of 1,6-hexanediol diacrylate, 0.17 g of cumene hydroperoxide as a polymerization initiator, and ECT-3NEX as an emulsifier [Polyoxyethylene tridecyl ether sodium acetate, trade name, manufactured by Nikko Chemicals] A polymerization initiator solution consisting of 0.08 g and 2.52 g of water was dropped into a flask from a separate dropping funnel over 120 minutes, The polymerization is completed by holding at 40 ° C. for 20 minutes to obtain a urethane / acrylic composite resin emulsion in which the blending ratio of the carboxyl group-containing polyurethane resin and the ethylenically unsaturated monomer is 70:30 in terms of solid mass. It was.

  The obtained urethane / acrylic composite resin emulsion has a urethane / acrylic composite resin content of 35.0% by mass, a viscosity of 250 mPa · s (BM viscometer, No. 2 rotor, 60 rpm), a pH value of 7.8, an average particle size. The value of 60 nm and 100% modulus was 8 MPa. Further, this urethane / acrylic composite resin emulsion did not gel when heated at 90 ° C., and had no heat-sensitive coagulation property.

(Comparative Synthesis Example 1)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 76.1 g of polytetramethylene glycol (average molecular weight 1000), polyoxyethylene polypropylene glycol random copolymer glycol (average molecular weight 1000, (70% oxyethylene group content) 16.9 g, 1,4-butanediol 1.5 g, trimethylolpropane 1.9 g, dibutyltin dilaurate 0.001 g and methyl ethyl ketone 60 g were mixed and mixed uniformly, and then dicyclohexylmethane diisocyanate 40 .4 g was added and reacted at 80 ° C. for 300 minutes to obtain a methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having a free isocyanate group content of 2.1% by mass.

  After cooling the solution to 30 ° C. or lower, 0.1 g of decyl phosphate ester and 6.0 g of polyoxyethylene tristyryl phenyl ether (HLB = 15) were added and mixed uniformly, and then water 254. using a disper blade. 0 g was gradually added to perform phase inversion emulsification and dispersion to obtain a dispersion. Then, an aqueous polyamine solution in which 2.0 g of piperazine hexahydrate and 0.8 g of diethylenetriamine are dissolved in 11.3 g of water is added to the dispersion and subjected to a chain extension reaction for 90 minutes, followed by removing the solvent at 35 ° C. under reduced pressure. To obtain a stable polyurethane resin emulsion having a polyurethane resin content of 35.0 mass%, a viscosity of 50.0 mPa · s (BM viscometer, No. 1 rotor, 60 rpm), a pH value of 8.0, and an average particle diameter of 550 nm. Moreover, content of the carboxyl group in a polyurethane resin was 0.0 mass%, and the value of 100% modulus was 2 MPa. The obtained polyurethane resin emulsion was gelled at 45 ° C. and had heat-sensitive coagulation properties.

  Hereinafter, Table 1 summarizes the properties of Synthesis Examples 1 to 4 and Comparative Synthesis Example 1.

[Examples 1-6 and Comparative Examples 1-6]
Example 1
100 g of urethane / acrylic composite resin emulsion obtained in Synthesis Example 1, 17.5 g of 10% by weight aqueous solution of ammonia formate (pH 7.3), Texport BG [alcohol penetrant, trade name, manufactured by Nikka Chemical Co., Ltd. ] Was uniformly mixed with 6.0 g of a 50% by weight aqueous solution and 16.5 g of water to prepare a mixed solution. The blending ratio of the urethane / acrylic composite resin and ammonia formate in the mixed solution was 100: 5, the pH value was 7.9, the thermal coagulation temperature was 45 ° C., and the urethane / acrylic composite resin amount was 25% by mass. It was.

The mixed solution was impregnated into a non-woven fabric (0.5 dtex, density 0.3 g / cm ³ ) made of polyester fiber using a slit mangle so as to be 250% by mass of a pickup, and then a hot air dryer [TABAI SAFETYOVEN SPH -200] was dried at 100 ° C. for 3 minutes and then at 150 ° C. for 3 minutes to obtain a fiber composite material.

(Example 2)
100 g of urethane / acrylic composite resin emulsion obtained in Synthesis Example 1, 26.3 g of 20% by weight aqueous solution of ammonia formate (pH 7.3), Textport BG [alcohol penetrant, trade name, manufactured by Nikka Chemical Co., Ltd. ] Was uniformly mixed with 6.0 g of a 50 mass% aqueous solution and 7.7 g of water to prepare a mixed solution. The blend ratio of the urethane / acrylic composite resin and ammonia formate in the mixed solution was 100: 15, the pH value was 7.6, the thermal coagulation temperature was 45 ° C., and the urethane / acrylic composite resin amount was 25% by mass. It was.

  A fiber composite material was obtained in the same manner as in Example 1 except that such a mixed solution was used.

(Example 3)
100 g of urethane / acrylic composite resin emulsion obtained in Synthesis Example 2, 17.5 g of 10% by weight aqueous solution of ammonia formate (pH 7.3), Textport BG [alcohol penetrant, trade name, manufactured by Nikka Chemical Co., Ltd. ] Was uniformly mixed with 6.0 g of a 50% by weight aqueous solution and 16.5 g of water to prepare a mixed solution. The mixing ratio of the urethane / acrylic composite resin and ammonia formate in the mixed solution was 100: 5, the pH value was 7.7, the thermal coagulation temperature was 46 ° C., and the amount of the urethane / acrylic composite resin was 25% by mass. It was.

  A fiber composite material was obtained in the same manner as in Example 1 except that such a mixed solution was used.

Example 4
100 g of urethane / acryl composite resin emulsion obtained in Synthesis Example 3, 17.5 g of 10% by weight aqueous solution of ammonia formate (pH 7.3), Textport BG [alcohol penetrant, trade name, manufactured by Nikka Chemical Co., Ltd. ] Was uniformly mixed with 6.0 g of a 50% by weight aqueous solution and 16.5 g of water to prepare a mixed solution. The blend ratio of the urethane / acrylic composite resin and ammonia formate in the mixed solution was 100: 5, the pH value was 7.7, the thermal coagulation temperature was 51 ° C., and the amount of the urethane / acrylic composite resin was 25% by mass. It was.

  A fiber composite material was obtained in the same manner as in Example 1 except that such a mixed solution was used.

(Example 5)
100 g of urethane / acrylic composite resin emulsion obtained in Synthesis Example 4, 17.5 g of 10% by weight aqueous solution of ammonia formate (pH 7.3), Textport BG [alcohol penetrant, trade name, manufactured by Nikka Chemical Co., Ltd. ] Was uniformly mixed with 6.0 g of a 50% by weight aqueous solution and 16.5 g of water to prepare a mixed solution. The blending ratio of the urethane / acrylic composite resin and ammonia formate in the mixed solution was 100: 5, the pH value was 7.8, the thermal coagulation temperature was 70 ° C., and the amount of the urethane / acrylic composite resin was 25% by mass. It was.

  A fiber composite material was obtained in the same manner as in Example 1 except that such a mixed solution was used.

(Example 6)
100 g of urethane / acrylic composite resin emulsion obtained in Synthesis Example 1, 17.5 g of 10% by weight aqueous solution of ammonia stearate (pH 8.1), Carbodilite E-02 [carbodiimide-based cross-linking agent, trade name, Nisshinbo Co., Ltd. Product] 1.0 g, Textport BG [alcohol penetrant, trade name, manufactured by Nikka Chemical Co., Ltd.] 50% by weight aqueous solution 6.0 g and water 16.5 g were uniformly mixed to prepare a mixed solution. The blend ratio of the urethane / acryl composite resin and ammonia stearate in the mixed solution is 100: 5, the pH value is 7.7, the thermal coagulation temperature is 46 ° C., and the urethane / acryl composite resin amount is 25% by mass. there were.

  A fiber composite material was obtained in the same manner as in Example 1 except that such a mixed solution was used.

(Comparative Example 1)
Uniformly prepared 100 g of the urethane / acrylic composite resin emulsion obtained in Synthesis Example 1, 6.0 g of 50 mass% aqueous solution of Textport BG [alcohol penetrant, trade name, manufactured by Nikka Chemical Co., Ltd.] and 34.0 g of water. To prepare a mixed solution. The mixing ratio of the urethane / acryl composite resin and ammonia carboxylate in the mixed solution is 100: 0, the pH value is 7.8, the thermal coagulation temperature is 90 ° C. or more, and the urethane / acryl composite resin amount is 25. It was mass%.

  A fiber composite material was obtained in the same manner as in Example 1 except that such a mixed solution was used.

(Comparative Example 2)
100 g of the urethane / acrylic composite resin emulsion obtained in Synthesis Example 1, 17.5 g of a 10% by weight aqueous solution of formic acid (pH 3.0), Textport BG [alcohol penetrant, trade name, manufactured by Nikka Chemical Co., Ltd.] A 50% by weight aqueous solution of 6.0 g and 16.5 g of water were uniformly mixed to prepare a mixed solution. The mixing ratio of the urethane / acrylic composite resin and formic acid in the mixed solution was 100: 5, the pH value was 6.0, the thermal coagulation temperature was 10 ° C. or less, and the amount of the urethane / acrylic composite resin was 25% by mass. It was.

  In addition, when the 10 mass% aqueous solution of formic acid was added to the said liquid mixture, since the precipitate was immediately seen from the liquid mixture, manufacture of the fiber composite material was abandoned.

(Comparative Example 3)
100 g of the polyurethane resin emulsion obtained in Comparative Synthesis Example 1, 6.0 g of 50% by weight aqueous solution of Textport BG [alcohol penetrant, trade name, manufactured by Nikka Chemical Co., Ltd.] and 34.0 g of water were mixed uniformly. To prepare a mixed solution. The blending ratio of the polyurethane resin to the ammonia carboxylate in the mixed solution was 100: 0, the pH value was 8.2, the thermal coagulation temperature was 45 ° C., and the polyurethane resin amount was 25% by mass.

  A fiber composite material was obtained in the same manner as in Example 1 except that such a mixed solution was used.

(Comparative Example 4)
100 g of an aqueous dispersion of polyurethane resin obtained in Comparative Synthesis Example 1, 17.5 g of 10% by weight aqueous solution of ammonium formate (pH 7.0), Textport BG [alcohol penetrant, trade name, manufactured by Nikka Chemical Co., Ltd. ] Was uniformly mixed with 6.0 g of a 50% by weight aqueous solution and 16.5 g of water to prepare a mixed solution. The mixture ratio of the polyurethane resin and ammonium formate in the mixed solution was 100: 5, the pH value was 8.1, the thermal coagulation temperature was 45 ° C., and the amount of polyurethane resin was 25% by mass.

  A fiber composite material was obtained in the same manner as in Example 1 except that such a mixed solution was used.

(Comparative Example 5)
100 g of the polyurethane resin aqueous dispersion obtained in Comparative Synthesis Example 1, 17.5 g of a 10% by weight aqueous solution of calcium chloride (pH 7.0), Textport BG [alcohol penetrant, trade name, manufactured by Nikka Chemical Co., Ltd. ] Was mixed uniformly with 6.0 g of a 50 mass% aqueous solution and 16.5 g of water to prepare a mixed solution. The mixture ratio of the polyurethane resin and calcium chloride in the mixed solution was 100: 5, the pH value was 8.1, the thermal coagulation temperature was 35 ° C., and the amount of polyurethane resin was 25% by mass.

  A fiber composite material was obtained in the same manner as in Example 1 except that such a mixed solution was used.

(Comparative Example 6)
100 g of a carboxyl group-containing polyurethane resin emulsion obtained in the synthesis process of Synthesis Example 1, 17.5 g of a 10% by weight aqueous solution of ammonium formate (pH 7.0), Textport BG [alcohol penetrant, trade name, Nikka Chemical Co., Ltd. 50% by weight aqueous solution] and 16.5 g of water were uniformly mixed to prepare a mixed solution. The mixture ratio of the carboxyl group-containing polyurethane resin and ammonium formate in the mixed solution was 100: 5, the pH value was 8.1, the thermal coagulation temperature was 45 ° C., and the amount of the carboxyl group-containing polyurethane resin was 25% by mass.

  A fiber composite material was obtained in the same manner as in Example 1 except that such a mixed solution was used.

  Below, the evaluation result of the fiber composite material obtained in Examples 1-6 is collectively shown in Table 2, and the evaluation result of the fiber composite material obtained in Comparative Examples 1-6 is collectively shown in Table 3.

  In the fiber composite materials obtained in Examples 1 to 6, no migration was observed, and the resin adhered substantially uniformly to the inside of the fiber base material. By preventing migration in this way, not only a fiber composite material with improved texture uniformity and stability can be obtained, but also the wear amount at 1000 times and 3000 times in the wear resistance test is excellent. It was confirmed that a fiber composite material exhibiting wear resistance was obtained. In addition, regardless of the 100% modulus value of the urethane / acrylic composite resin emulsion, it exhibits the same wear resistance, so it is possible to produce fiber composites with various textures while maintaining the wear resistance. Was confirmed. Furthermore, it was confirmed that the residue remaining in the fiber composite material was extremely small. In the obtained fiber composite material, it was also confirmed that the residue has little influence on quality and quality.

  On the other hand, in the fiber composite material obtained in Comparative Example 1 using only the urethane / acrylic composite resin emulsion and not containing the ammonium salt of carboxylic acid, significant migration was observed during drying. Although the wear resistance was good when the wear was repeated, a significant amount of wear was seen when the wear was repeated 3000 times, and it was confirmed that the wear resistance was insufficient.

  In Comparative Example 2, a formic acid aqueous solution was used in place of the carboxylic acid ammonium salt. However, it was confirmed that the mixed solution gelled and the processability was insufficient.

  In the fiber composite material obtained in Comparative Example 3 using a polyurethane resin emulsion emulsified with a surfactant and having heat-sensitive coagulation properties and not using an ammonium salt of a carboxylic acid, the polyurethane resin emulsion is heat-sensitive. While having solidification properties, significant migration was observed during drying, and in the wear resistance test, wear resistance was good when worn 1000 times, but significant wear when 3000 times worn. It was confirmed that the wear resistance was insufficient.

  In the fiber composite material obtained in Comparative Example 4 using a polyurethane resin emulsion emulsified with a surfactant and having heat-sensitive coagulation property and using an ammonium salt of carboxylic acid, the same as in Comparative Example 3 From the results obtained, it was confirmed that ammonium salts of carboxylic acids are ineffective for polyurethane resin emulsions obtained by emulsification with a surfactant even if they have heat-sensitive coagulation properties. .

  It was obtained in Comparative Example 5 in which an inorganic salt aqueous solution made of calcium chloride was used instead of the ammonium salt of carboxylic acid, and the polyurethane resin emulsion obtained by emulsifying with a surfactant was mixed with the inorganic salt aqueous solution. The fiber composite material had a heat-sensitive coagulation temperature lowered by the inorganic salt aqueous solution and slightly improved the migration prevention property, but the migration prevention property was still insufficient when compared with Examples 1-6. Further, in the abrasion resistance test, the fiber composite material obtained in Comparative Example 5 shows good wear resistance when it is worn 1000 times, but the wear amount increases when it is worn 3000 times. It was confirmed that the wear resistance was still insufficient. In addition, it was confirmed that surfactants and inorganic salts remain in the fiber composite material, and in the obtained fiber composite material, it is expected that the influence of the residue on quality and quality will be great.

  In Comparative Example 6 in which an ethylenically unsaturated monomer was not polymerized and mixed with a carboxyl group-containing polyurethane resin emulsion and a carboxylic acid ammonium salt, no migration was observed, and the resin adhered substantially uniformly to the inside of the fiber substrate. As can be seen, it was confirmed that the wear resistance was still insufficient as compared with Examples 1-6.

  As described above, according to the method for producing a fiber composite material of the present invention, migration that occurs during impregnation and drying can be prevented, and the resin can be uniformly fixed to the inside of the fiber base material. The uniformity and stability of the fiber composite can be improved, and excellent abrasion resistance can be imparted to the fiber composite material. Moreover, in the manufacturing method of the fiber composite material of this invention, it becomes possible to obtain the fiber composite material of various textures by selecting suitably the value of 100% modulus of a urethane / acryl composite resin emulsion. Furthermore, in the manufacturing method of the fiber composite material of the present invention, it becomes possible to replace the conventional organic solvent-based polyurethane resin, so air pollution and water pollution due to the organic solvent discharged during processing, labor for collecting the solvent, It is possible to reduce problems such as workers' working environment. Furthermore, the organic solvent does not remain in the fiber composite material, and adverse effects on the human body such as skin damage are also eliminated, and the resulting fiber composite material has very few residues such as surfactants and inorganic salts. Therefore, it becomes possible to obtain a fiber composite material with improved quality and quality of the fiber composite material.

Therefore, the method for producing a fiber composite material of the present invention is particularly useful as an industrial production method for fiber composite materials, and the fiber composite material obtained by the production method of the present invention varies depending on the application. Because it has a unique texture, it can be used as it is in the field of industrial materials such as various clothing, artificial leather, synthetic leather, filters, heat insulating materials, agricultural materials, electronic equipment manufacturing, etc. It can also be used widely as a fiber composite material that is stable and excellent in quality.

Claims (7)

  (A) A urethane / acrylic composite resin emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer in the presence of a carboxyl group-containing polyurethane resin emulsion, (B) a mixture containing an ammonium salt of carboxylic acid and (C) water A method for producing a fiber composite material, wherein the fiber base material is impregnated with a liquid and then dried to obtain a fiber composite material.   In the mixed solution, the blending ratio of (A) urethane / acrylic composite resin emulsion and (B) ammonium salt of carboxylic acid is 100: 0.5 to 100: 20 in terms of solid mass. The manufacturing method of the fiber composite material of Claim 1.   The method for producing a fiber composite material according to claim 1 or 2, wherein the mixed solution has a pH value of 7.0 to 9.0 and a coagulation temperature of 30 to 70 ° C.   A carboxyl group-containing isocyanate group-terminated prepolymer obtained by reacting the carboxyl group-containing polyurethane resin emulsion with (a) an organic diisocyanate, (b) a polyol, and (c) a compound having a carboxyl group and two or more active hydrogens. After neutralizing and emulsifying and dispersing in water by self-emulsification, (d) a carboxyl group-containing polyurethane resin emulsion obtained by chain extension reaction using a polyamine compound having two or more amino groups and / or imino groups The method for producing a fiber composite material according to any one of claims 1 to 3, wherein:   (A) Urethane / acrylic composite resin emulsion obtained by emulsion polymerization with a blending ratio of the carboxyl group-containing polyurethane resin and the ethylenically unsaturated monomer of 90:10 to 10:90 in terms of solid mass The method for producing a fiber composite material according to any one of claims 1 to 4, wherein the fiber composite material is an acrylic composite resin emulsion.   (B) The ammonium salt of a carboxylic acid is an ammonium salt of a carboxylic acid having 1 to 10 carbon atoms, The method for producing a fiber composite material according to any one of claims 1 to 5.   A fiber composite material obtained by the production method according to any one of claims 1 to 6.