JP2020158908A - Sizing agent composition for fiber and fiber material - Google Patents

Abstract

To provide a sizing agent for fiber, which, when adhered to fiber, shows a good convergence property, hardly causes the fibers to fluff, and is capable of heat cleaning under a low temperature condition.SOLUTION: A sizing agent composition comprises a polyoxyalkylene alkyl ether-type surfactant (A), water (B), and a polymerization reaction product (E). The polymerization reaction product (E) is a product generated by emulsion polymerizing a monomer (D) having an ethylenic double bond in the presence of the polyoxyalkylene alkyl ether-type surfactant (A), the water (B), and a polymerization initiator (C). The polymerization initiator includes ammonium persulfate. The monomer (D) includes a (meth)acrylic monomer (D1).SELECTED DRAWING: None

Description

The present invention relates to a fiber sizing agent composition and a fiber material, and more particularly to a fiber sizing agent composition containing a polymerization reaction product and a fiber material containing the fiber sizing agent composition and an inorganic fiber.

Inorganic fiber cloths made of inorganic fiber yarns such as glass fibers and carbon fibers are made by weaving warp threads and weft threads with an air jet loom or the like. Inorganic fiber yarns are generally composed of tens to thousands of filaments having a fiber diameter of submicron to several microns, and are generally in the form of strands converged using a primary sizing agent. The main purpose of primary sizing agents such as modified starch is to protect the fibers from friction, and in the subsequent weaving process, twisting is added for the purpose of suppressing fluffing caused by filament rupture, or polyvinyl alcohol. It is necessary to improve the denaturing force of the strand by sizing the secondary sizing agent such as.

Fiber reinforced plastic (FRP) products are made by using these inorganic fiber cloths as reinforcing materials and impregnating them with a matrix resin such as nylon or polypropylene. The adhesion between the inorganic fiber cloth and the matrix resin is the physical property of FRP products. A material that can be removed from the fibers by heat cleaning or the like is used after the inorganic fiber cloth is prepared.

For example, Patent Document 1 describes (a) an acrylic acid monomer and / or a methacrylic acid monomer, (b) an acrylic acid monomer and / or a methacrylic acid monomer having a hydroxyl group, and (c) an acrylic acid having an ethylene oxide adduct. A monomer containing a monomer and / or a methacrylic acid monomer, and a monomer having a bifunctional divinyl type ethylene oxide adduct (B) having a weight ratio of (A) / (B) of 100 / 0.1 to 1 In the range of 100 / 3.0, an aqueous acrylic resin obtained by polymerizing in alcohol or in a mixed solvent of water and alcohol using an oil-based radical reaction initiator, and then neutralizing the carboxylic acid with an alkali is used to focus the glass fiber. It has been proposed to be used as an agent.

Japanese Unexamined Patent Publication No. 9-309930

However, when the water-based acrylic resin of Patent Document 1 is used as the sizing agent, it is necessary to heat it at a high temperature when removing the sizing agent from the fibers. Therefore, the fibers may be deteriorated by heat, or equipment or facilities for heat treatment at high temperature may be required. It is not easy to obtain a sizing agent that has good convergence when attached to the fiber and can be easily removed from the fiber.

An object of the present invention is a fiber sizing agent composition which has good convergence when attached to fibers, does not easily cause fluffing on the fibers, and can be heat-cleaned under low temperature conditions, and uses the same. It is to provide a fiber material.

One aspect of the fiber sizing composition according to the present invention contains a polyoxyalkylene alkyl ether type surfactant (A), water (B), and a polymerization reaction product (E). The polymerization reaction product (E) is a monomer having an ethylenic double bond in the presence of the polyoxyalkylene alkyl ether type surfactant (A), the water (B), and the polymerization initiator (C). It is a product produced by emulsion polymerization of D). The polymerization initiator (C) contains ammonium persulfate (C1). The monomer (D) contains a (meth) acrylic monomer (D1).

One aspect of the fibrous material according to the present invention includes an inorganic fiber and the fiber sizing agent composition that adheres to the inorganic fiber.

According to the present invention, it is possible to obtain a fiber sizing agent composition which has good convergence when attached to fibers, is less likely to cause fluffing of fibers, and can be heat-cleaned under low temperature conditions.

Hereinafter, the fiber sizing agent composition according to the embodiment of the present invention will be described. In the following description, "(meth) acrylic" means at least one of "acrylic" and "methacrylic". For example, (meth) acrylate means at least one of acrylate and methacrylate.

The fiber sizing composition according to the present embodiment (hereinafter referred to as composition (X)) contains a polyoxyalkylene alkyl ether type surfactant (A), water (B), and a polymerization reaction product (E). contains. The polymerization reaction product (E) contains a monomer (D) having an ethylenic double bond in the presence of a polyoxyalkylene alkyl ether type surfactant (A), water (B), and a polymerization initiator (C). It is a product produced by emulsion polymerization. The polymerization initiator (C) contains ammonium persulfate (C1). The monomer (D) contains a (meth) acrylic monomer (D1).

Since the composition (X) has such a structure, the fibers can form good strands when the composition (X) is attached to the fibers. That is, by adhering the composition (X) to the fiber, the convergence of the strand is improved, and processing such as weaving and knitting of the fiber can be facilitated.

The composition (X) is a polymerization reaction product produced by emulsion polymerization in the presence of a polymerization initiator (C) containing a polyoxyalkylene alkyl ether type surfactant (A) and ammonium persulfate (C1). Since E) is contained, the composition (X) can be easily removed from the fiber after being attached to the fiber. For example, the composition (X) can be removed by heat-treating the fiber to which the composition (X) is attached at a low temperature. Therefore, even when it is necessary to remove the composition (X) in the fiber processing step, the fiber The composition (X) can be removed without being deteriorated by the heat generated by the high temperature treatment. The low temperature is, for example, a temperature of 350 ° C. or lower or 330 ° C. or lower. In addition, the time of heat treatment when removing the composition (X) from the fiber can be shortened.

Further, for example, when the sizing agent is removed from the roll-shaped fiber cloth by a heat treatment by a method such as a batch method, oxygen may not reach the inside of the roll, but in the present embodiment, the composition (X) ) Has the above-mentioned structure, so that the composition (X) can be easily removed even in an atmosphere where oxygen is not sufficiently supplied. Further, depending on the type of fiber, if an attempt is made to remove the sizing agent by heat treatment in an oxygen atmosphere, the fiber may be oxidized. However, in the present embodiment, since the composition (X) has the above-mentioned structure, the composition (X) can be removed even by heat treatment in a nitrogen atmosphere, for example.

As described above, since the composition (X) can be easily removed from the fiber, the composition (X) is suitable when the composition (X) needs to be removed at the time of processing the fiber. Further, even when the composition (X) does not need to be removed at the time of processing the fiber, the composition (X) can be easily removed at the time of recycling the fiber, for example, and the fiber can be recycled satisfactorily. ..

Furthermore, since the composition (X) can be used as an aqueous sizing agent, it is environmentally friendly, and the fibers to which the composition (X) is attached are unlikely to have an adverse effect on the human body. Therefore, since there is a low risk of harming health, fibers processed using the composition (X) as a sizing agent can be safely used.

In the absence of the polyoxyalkylene alkyl ether type surfactant (A), the monomer (D) containing the (meth) acrylic monomer (D1) is emulsion-polymerized and polymerized in the presence of another surfactant. Even if the composition is prepared by mixing the polymerization reaction product with the polyoxyalkylene alkyl ether type surfactant (A) after obtaining the reaction product, it is easy to prepare the composition from the fiber as in the composition (X). It is not possible to obtain a removable composition. This is because the interaction between the case where the polyoxyalkylene alkyl ether type surfactant (A) is mixed after synthesizing the product and the case where the composition (X) is different is the polyoxyalkylene alkyl ether type surfactant (A). ) And the polymerization reaction product (E).

However, when the inventors analyzed both by infrared absorptiometry, high performance liquid chromatography, gel permeation chromatography, and nuclear magnetic resonance spectroscopy, no significant difference was observed between the analysis results. Therefore, the structure or characteristics of the composition (X) cannot be literally specified.

Details of the components contained in the composition (X) will be described below.

The composition (X) contains a polyoxyalkylene alkyl ether type surfactant (A) (hereinafter, also referred to as "surfactant (A)"), water (B), and a polymerization reaction product (E). ..

The surfactant (A) is an essential component contained in the composition (X) and is also an essential component used when synthesizing the polymerization reaction product (E). The polyoxyalkylene alkyl ether type surfactant (A) is at least one type mainly composed of a hydrocarbon containing one or more types of polyoxyalkylene groups as hydrophilic groups and containing 1 to 36 carbon elements as hydrophobic groups. It means a polyoxyalkylene-added nonionic surfactant containing an alkyl group or a branched alkyl group of. The alkyl group and the branched alkyl group of the hydrophobic group may contain a hetero atom.

The surfactant (A) is polyoxyethylene hexyl ether, polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene eicosyl ether, polyoxypropylene hexyl ether. , Polyoxypropylene octyl ether, polyoxypropylene nonyl ether, polyoxypropylene lauryl ether, polyoxypropylene stearyl ether, and polyoxyalkylene alkyl ethers such as polyoxypropylene eicosyl ether; and polyoxyethylene 2 ethylhexyl ether and polyoxy. It preferably contains at least one component selected from the group consisting of polyoxyalkylene branched alkyl ethers such as propylene 2-ethylhexyl ether.

In this case, since the composition (X) has good incineration property, when the composition (X) is applied to the fiber as a sizing agent, the composition (X) can be easily removed from the fiber by heat treatment at a low temperature. Can be removed. The incineration property means that it is easily removed by combustion in both the presence and absence of oxygen. The surfactant (A) may contain only one of the above-mentioned components alone, or may contain two or more of them.

It is more preferable that the surfactant (A) contains a block copolymer of polyethylene glycol and polypropylene glycol. In this case, the composition (X) has better incineration properties, which makes it easier to remove the composition (X). Examples of block copolymers of polyethylene glycol and polypropylene glycol are block copolymers of polyoxyethylene-polyoxypropylene, block copolymers of polyoxyethylene-polyoxypropylene-polyoxyethylene, and polyoxypropylene-polyoxy. Includes a block copolymer of ethylene-polyoxypropylene. In the block copolymer of polyethylene glycol and polypropylene glycol, one end or both ends of the polyoxyethylene / polyoxypropylene copolymer are bonded to an aliphatic functional group such as alkyl or branched alkyl by ether. Examples of aliphatic functional groups include alkyl groups having 6 to 20 carbon atoms such as hexyl, octyl, nonyl, lauryl, stearyl, and eicosyl. In addition to the above compounds, if there is a compound suitable for a block copolymer of polyethylene glycol and polypropylene glycol and which does not inhibit the emulsion polymerization reaction, this compound can also be included in the block copolymer of polyethylene glycol and polypropylene glycol. Of these, one or more compounds can be used as block copolymers of polyethylene glycol and polypropylene glycol.

The composition (X) may contain only the surfactant (A), or may contain both the surfactant (A) and a surfactant other than the surfactant (A). That is, when synthesizing the composition (X), only the surfactant (A) may be used, and both the surfactant (A) and the surfactant other than the surfactant (A) are used. You may use it.

Examples of surfactants other than the surfactant (A) include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and semi-polar surfactants.

Examples of anionic surfactants include higher fatty acid salt-type surfactants, sulfonate-type surfactants, sulfate ester-type surfactants, and alkyl phosphate ester-type surfactants.

Examples of higher fatty acid salt type surfactants are C12 to C18 such as potassium laurate, sodium lauryl ether carboxylate, sodium N-lauroyl sarcosin, sodium N-lauroyl glutamate, and N-lauroyl methyl-β-alanine triethanolamine. Saturated or unsaturated fatty acid salts; fatty acid salts such as palm oil fatty acid salt, hardened palm oil fatty acid salt, palm oil fatty acid salt, hardened palm oil fatty acid salt, beef fat fatty acid salt, and hardened beef fat fatty acid salt; N-acylsarcosine salt; Also contains N-acylglutamate.

Examples of sulfonate-type surfactants include N-acylaminosulfonates such as N-cocoyl methyl taurine sodium; and polyoxyethylene sulfosuccinates such as polyoxyethylene alkyl sulfosuccinate.

Examples of sulfate ester-type surfactants include higher alkyl sulfates, polyoxyethylene alkyl ether sulfates and the like.

Examples of alkyl phosphate salt-type surfactants include triethanolamine monolauryl phosphate and dipotassium monolauryl phosphate.

Of the above compounds, one or more compounds can be used as the anionic surfactant. In addition to such compounds, if there is a compound suitable for an anionic surfactant and not inhibiting the emulsion polymerization reaction, this compound can also be included in the anionic surfactant.

Examples of cationic surfactants are cetrimonium chloride, stearyltrimonium chloride, behentrimonium chloride, behentrimonium metosulfate, behenamidepropyltrimonium metosulfate, stearamidpropyltrimonium chloride, arachidtrimonium chloride, chloride. Distearyldimonium, disetyldimonium chloride, tricetylmonium chloride, oleamidepropyldimethylamine, linoleamidepropyldimethylamine, isostearamidpropyldimethylamine, oleylhydroxyethylimidazolin, stearamidpropyldimethylamine, behenamidepropyl Includes dimethylamine, behenamide propyldiethylamine, behenamide ethyldiethylamine, behenamide ethyldimethylamine, arachidamidepropyldimethylamine, arachidamidepropyldiethylamine, arachidamideethyldiethylamine, and arachidamideethyldimethylamine.

Of the above compounds, one or more compounds can be used as the cationic surfactant. In addition to such compounds, if there is a compound that is suitable for a cationic surfactant and does not inhibit the emulsion polymerization reaction, this compound can also be included in the cationic surfactant.

Examples of nonionic surfactants are polys such as polyoxyethylene sorbitan monooleate, polyoxyethylene nonylphenol ether, polyethylene glycol fatty acid ester, polyoxyethylene oleyl ether, polyoxypropylene oleyl ether, and polyoxyethylene cured castor oil. Oxyalkylene-added nonionic surfactant; monoethanolamide-type nonionic surfactant such as laurate monoethanolamide; diethanolamide-type nonionic surfactant such as coconut oil fatty acid diethanolamide; N-methyllauryl glucamido and Alkyl saccharide-based nonionic surfactants such as N-methylalkyl glucamido; sugar amide-based nonionic surfactants; sorbitan fatty acid ester-based nonionic surfactants such as sorbitan monoisostearenate and sorbitan monooleate; laurin Sucrose fatty acid ester-based nonionic surfactants such as acid sucrose ester, sucrose monostearate, and POP sucrose monolaurate; monoglycerin fatty acid ester-based such as glycerin sesquioleate and polyoxyethylene glyceryl monostearate. Nonionic surfactants; fatty acid ester-type polyglycerin-based nonionic surfactants such as polyglyceryl monoisostearate; and alkyl ether-type polyglycerin-based nonionic surfactants such as polyglyceryl / polyoxybutylene stearyl ether.

Of the above compounds, one or more compounds can be used as the nonionic surfactant. In addition to such compounds, if there is a compound suitable for a nonionic surfactant and not inhibiting the emulsion polymerization reaction, this compound can also be included in the nonionic surfactant.

Examples of amphoteric surfactants are imidazoline type (amide amine type) such as coconut oil alkyl-N-hydroxyethyl imidazolinium betaine, amide amino acid salt, lauryldimethylaminoacetic acid betaine, and carbobetaine such as coconut oil fatty acid amide propyl betaine. Carboxylic acid type amphoteric surfactants such as types (alkyl betaine type, alkylamide betaine type); sulfobetaine type (alkyl sulfobetaine type, alkyl hydroxysulfobetaine type) amphoteric surfactants such as coconut oil fatty acid dimethylsulfopropyl betaine; Includes phosphobetaine amphoteric surfactants such as lauryl hydroxyphosphobetaine; acyl tertiary amine oxides such as lauryl dimethylamine oxide; and acyl tertiary phosphon oxides such as lauryl dimethyl phosphon oxide.

Of the above compounds, one or more compounds can be used as the amphoteric surfactant. In addition to such compounds, if there is a compound that is suitable for an amphoteric surfactant and does not inhibit the emulsion polymerization reaction, this compound can also be included in the amphoteric surfactant.

Examples of semi-polar surfactants include lauryltrimethylamine oxide and amidopropylamine laurate oxide.

Among the above compounds, one or more compounds can be used as the semi-polar surfactant. In addition to such compounds, if there is a compound suitable for a semi-polar surfactant and not inhibiting the emulsion polymerization reaction, this compound can also be included in the semi-polar surfactant.

The HLB value of the surfactant (A) is preferably 7 or more. In this case, the emulsified state in the system becomes good at the time of emulsion polymerization. The HLB value of the surfactant is more preferably 9 or more. Further, the HLB value of the surfactant (A) is preferably 13 or less. In this case, the incineration property of the composition (X) is further improved. The HLB value of the surfactant (A) is more preferably 11 or less.

Water (B) is an essential component contained in the composition (X) and is an essential component used when synthesizing the polymerization reaction product (E). Water (B) is contained in the composition (X) as a solvent. That is, water (B) is used as a solvent in the synthesis of the polymerization reaction product (E). The water (B) may be normal water or purified water.

The composition (X) may contain a component other than water (B) as a solvent. That is, when synthesizing the polymerization reaction product (E), a mixed solvent of water (B) and a solvent other than water (B) may be used. As the solvent other than water (B), for example, a hydrophilic organic solvent may be used. The hydrophilic organic solvent means an organic solvent that is easily miscible with water or easily dissolved in water. Examples of hydrophilic organic solvents are alcoholic solvents such as methanol, ethanol, 1-propanol, and 2-propanol; ethylene glycol, 1,3-propanediol, propylene glycol, 1,2-butanediol, 1,4-. Glycol-based solvents such as butanediol, pentylene glycol, 1,2-hexanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, and tetraethylene glycol; methyl glycol, methyldiglycol, methyltriglycol, isopropyldi Glycol, butyl glycol, butyl diglycol, butyl triglycol, isobutyl glycol, isobutyl diglycol, hexyl glycol, hexyl diglycol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, methyl propylene glycol, methyl propylene Glycol ether-based solvents such as diglycol, methylpropylene triglycol, propylpropylene glycol, and propylpropylene diglycol; N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, ε-caprolactam, etc. Lactam-based solvents; and amide-based solvents such as formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropanamide, and 3-butoxy-N, N-dimethylpropanamide. Including. However, from the viewpoint of safety and reducing the impact on the environment, it is preferable to use only water (B) as the solvent.

The composition (X) contains a polymerization reaction product (E). The polymerization reaction product (E) is a product produced by emulsion polymerization of the monomer (D) in the presence of the surfactant (A), water (B), and the polymerization initiator (C). The surfactant (A) and water (B) used when polymerizing the polymerization reaction product (E) are as described above.

The polymerization initiator (C) is an essential component used as a polymerization initiator for emulsion polymerization of the monomer (D) during the synthesis of the polymerization reaction product (E).

The polymerization initiator (C) contains ammonium persulfate (C1). Since the polymerization initiator (C) contains ammonium persulfate (C1), the composition (X) has good incineration properties. Therefore, when the composition (X) is applied to the fiber as a sizing agent, the composition is composed. The substance (X) can be easily removed from the fiber by heat treatment at a low temperature.

The content of ammonium persulfate (C1) with respect to the polymerization initiator (C) is preferably 50% by mass or more. In this case, the incineration property of the composition (X) can be further improved. The upper limit of the content of ammonium persulfate (C1) with respect to the polymerization initiator (C) is not particularly limited, but may be, for example, 100% by mass.

The polymerization initiator (C) may contain a polymerization initiator other than ammonium persulfate (C1) in addition to ammonium persulfate (C1). Examples of polymerization initiators other than ammonium persulfate (C1) include water-soluble polymerization initiators and oil-soluble polymerization initiators. Examples of water-soluble polymerization initiators are 2,2-azobis (2-amidinopropane) dihydrochloride, 2,2-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2. -Azobis [2- (2-imidazolin-2-yl) propane] disulfate / dihydrate, 2,2-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate , 2,2-azobis [2- (2-imidazolin-2-yl) propane], 2,2-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], and 4,4-azobis ( 4-cyanovaleric acid) is included. Examples of oil-soluble polymerization initiators are 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-(2,4-dimethyl-4). −methoxyvaleronitrile), 4-dichlorobenzoyl peroxide, t-butyl peroxypivalate, benzoyl peroxide, o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide , T-Butyl Peroxy-2-ethyl Hexanoate, Cyclohexanone Peroxide, Methyl Ethyl Ketone Peroxide, Dikmyl Peroxide, Lauroyl Peroxide, Diisopropylbenzene Hydroperoxide, t-Butyl Hydroperoxide, and t-Butyl Peroxide, including.

As described above, the polymerization reaction product (E) is produced by emulsion polymerization of the monomer (D) in the presence of the surfactant (A), water (B), and the polymerization initiator (C). It is a product. That is, the monomer (D) is the main component of the polymerization reaction product (E). Monomer (D) has an ethylenic double bond.

The monomer (D) contains a (meth) acrylic monomer (D1). Since the monomer (D) contains the (meth) acrylic monomer (D1), the composition (X) has good incineration property. It is considered that this is because the monomer (D) contains the (meth) acrylic monomer (D1), so that the polymerization reaction product (E) is likely to undergo depolymerization at a relatively low temperature. The amount of the (meth) acrylic monomer (D1) with respect to the monomer (D) is preferably 45% by mass or more, more preferably 60% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the amount of the (meth) acrylic monomer (D1) with respect to the monomer (D) is not particularly limited, and may be, for example, 100% by mass.

Examples of the (meth) acrylic monomer (D1) include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid, unsaturated dicarboxylic acids such as itaconic acid, and 2- (phosphonooxy) ethyl (meth) acrylic acid. Phosphoric acid group-containing unsaturated monomer, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2-carboxyethyl (meth) acrylate, 2- (meth) acryloyloxy Anionic non-anionics such as ethyltetrahydrophthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, ω-carboxy-polycaprolactone (n = 2) monoacrylate, 2- (meth) acrylamide-2-methylpropanesulfonic acid Saturated monomer; Amino group-containing unsaturated monos such as 2- (dimethylamino) ethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 3- (dimethylamino) propyl (meth) acrylate. Quantities; cationic unsaturated monomers such as (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloylaminoethyltrimethylammonium chloride; N-methacryloylethyl-N, Amphoteric unsaturated monomers such as N-dimethylammonium-α-N-methylcarboxybetaine, 4-{[3- (methacrylicamide) propyl] (dimethyl) ammonio} butane-1-sulfonate; acrylamide, diacetoneacrylamide, (Meta) acrylamide compounds such as N, N-dimethylacrylamide, Nt-butylacrylamide, N-octylacrylamide, and Nt-octylacrylamide; methyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meta) decyl acrylate, (meth) undecyl acrylate, (meth) lauryl acrylate, (meth) tridecyl acrylate, (meth) myristyl acrylate, (meth) pentadecyl acrylate, (meth) palmityl acrylate, ( Heptadecyl acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, oleyl (meth) acrylate, (meth) a Esters of (meth) acrylic acids such as tetrahydrofurfuryl crylate, isobornyl (meth) acrylate, and glycidyl (meth) acrylate; glyceryl (meth) acrylate; -2-hydroxyethyl (meth) acrylate and ( (Meta) Acrylic Acid Hydroxyalkyl Esters such as -2-Hydroxypropyl Acrylic Acid; (Meta) Acrylic Acid Alkoxyalkyl Esters such as (Meta) Acrylic Acid ethoxyethyl and (Meta) Acrylic Acid methoxyethyl; Monoesters of polyalkylene glycol such as meta) acrylate and polypropylene glycol mono (meth) acrylate and (meth) acrylic acid; monoester of polyalkylene glycol such as methoxypolyethylene glycol mono (meth) acrylate and (meth) acrylic acid Acrylic etherified esters of hydroxyl groups; polyethylene glycol (m = 5) -polypropylene glycol (n = 2) monomethacrylate; Blemmer 70 PEP-350B (manufactured by Nichiyu Co., Ltd.), propylene glycol polybutylene glycol (n) = 6) Monomethacrylate; Blemmer 10PPB-500B (manufactured by Nichiyu Co., Ltd.), Octoxypolyethylene glycol (m = 8) Polypropylene glycol (n = 6) Monomethacrylate; Blemmer 50 POEP-800B (manufactured by Nichiyu Co., Ltd.), Octo Xyethylene glycol (m = 8) Polypropylene glycol (n = 6) monoacrylate; Oxyethylene (also referred to as ethylene oxide), oxypropylene (also referred to as propylene oxide) and oxy such as Blemmer 50AOEP-800B (manufactured by Nichiyu Co., Ltd.) A block copolymer composed of a constituent unit of butylene (also called butylene oxide) having a structure bonded to a side chain; poly (ethylene glycol (m = 3.5) -propylene glycol (n = 2.5)). Monomethacrylate; Blemmer 50PEP-300 (manufactured by Nichiyu Co., Ltd.), Poly (ethylene glycol (m = 5) -tetramethylene glycol (n = 2)) Monomethacrylate; Blemmer 55PET-400 (manufactured by Nichiyu Co., Ltd.), Poly (Ethethylene glycol (m = 6) -tetramethylene glycol (n = 10)) monomethacrylate; Blemmer 30 PET-800 (manufactured by Nichiyu Co., Ltd.), poly (ethylene glycol (m = 10) -tetramethylene glycol) Cole (n = 5)) monomethacrylate; Blemmer 55PET-800 (manufactured by Nichiyu Co., Ltd.), poly (propylene glycol (m = 4) -tetramethylene glycol (n = 8)) monomethacrylate; Blemmer 30PPT-800 (day) Oil Co., Ltd.), Poly (propylene glycol (m = 7) -tetramethylene glycol (n = 6)) monomethacrylate; Blemmer 50PPT-800 (manufactured by Nichiyu Co., Ltd.), Poly (propylene glycol (m = 10)- Tetramethylene glycol (n = 3)) monomethacrylate; and oxyethylene (also called ethylene oxide), oxypropylene (also called propylene oxide) and oxybutylene (also called butylene oxide) such as Blemmer 70PPT-800 (manufactured by Nichiyu Co., Ltd.) Includes monofunctional unsaturated monomers such as those in which a random copolymer composed of the constituent units of (referred to) has a structure bonded to a side chain. Of these, one type may be used alone as the (meth) acrylic monomer (D1), or two or more types may be used in combination.

The (meth) acrylic monomer (D1) preferably contains 2-ethylhexyl methacrylate. In this case, the composition (X) has better incineration properties, so that the composition (X) can be more easily removed by heat treatment at a low temperature. Further, when the polymerization reaction product (E) is emulsion-polymerized and synthesized, the aggregation of the monomer (D) can be prevented from occurring. Further, since the flexibility of the film of the composition (X) can be improved, the toughness against bending of the fiber when the composition (X) is attached to the fiber as a sizing agent is improved, and the fiber is processed during fiber processing. Is hard to break.

When the (meth) acrylic monomer (D1) contains 2-ethylhexyl methacrylate, the content of 2-ethylhexyl methacrylate with respect to the (meth) acrylic monomer (D1) is preferably 40% by mass or more. When the content of 2-ethylhexyl methacrylate is 40% by mass or more, the emulsified state of the monomer (D) is improved when the polymerization reaction product (E) is synthesized, and the polymerization reaction product (E) is produced. It can be synthesized well. In addition, the flexibility of the film of the composition (X) can be further improved. The content of 2-ethylhexyl methacrylate with respect to the (meth) acrylic monomer (D1) is more preferably 45% by mass or more, and particularly preferably 50% by mass or more. The upper limit of the content of 2-ethylhexyl methacrylate with respect to the (meth) acrylic monomer (D1) is not particularly limited, but is preferably 100% by mass or less, preferably 80% by mass or less, for example.

The (meth) acrylic monomer (D1) preferably further contains isobutyl methacrylate. That is, the (meth) acrylic monomer (D1) preferably contains both 2-ethylhexyl methacrylate and isobutyl methacrylate. In this case, the incineration property of the composition (X) can be further improved.

When the (meth) acrylic monomer (D1) further contains isobutyl methacrylate, the content of isobutyl methacrylate with respect to the (meth) acrylic monomer (D1) is preferably 60% by mass or less. When the content of isobutyl methacrylate with respect to the acrylic monomer (D1) is 60% by mass or less, the incineration property of the composition (X) can be further improved. The content of isobutyl methacrylate with respect to the (meth) acrylic monomer (D1) is more preferably 50% by mass or less. The lower limit of the content of isobutyl methacrylate with respect to the (meth) acrylic monomer (D1) is not particularly limited, and may be, for example, 0% by mass.

When the (meth) acrylic monomer (D1) contains both 2-ethylhexyl methacrylate and isobutyl methacrylate, the total amount of 2-ethylhexyl methacrylate and isobutyl methacrylate with respect to the (meth) acrylic monomer (D1) is , 60% by mass or more is preferable. In this case, since the incineration property of the composition (X) is further improved, the composition portion (X) can be easily removed from the fibers by heat treatment at a low temperature. The total amount of 2-ethylhexyl methacrylate and isobutyl methacrylate with respect to the (meth) acrylic monomer (D1) is more preferably 80% by mass or more. In this case, since the incineration property of the composition (X) is particularly improved, the time of heat treatment when removing the composition (X) from the fibers can be shortened. The upper limit of the total amount of 2-ethylhexyl methacrylate and isobutyl methacrylate with respect to the (meth) acrylic monomer (D1) is not particularly limited, but may be, for example, 100% by mass.

The monomer (D) may contain a monomer having an ethylenic double bond other than the (meth) acrylic monomer (D1). Examples of monomers having an ethylenic double bond other than the (meth) acrylic monomer (D1) include vinyl-based monomers. Examples of vinyl-based monomers include styrene; (meth) acrylonitrile; vinyl acetate: vinylpyrrolidone; vinylpyridine; vinyl sulfonic acid; and styrene sulfonic acid. The amount of the monomer other than the (meth) acrylic monomer (D1) with respect to the monomer (D) is preferably less than 10% by mass.

Specifically, the polymerization reaction product (E) can be synthesized as follows. First, a surfactant (A), water (B), a polymerization initiator (C), and a monomer (D) are mixed to prepare a mixed solution. Then, the polymerization reaction product (E) can be synthesized by emulsion polymerization of the monomer (D) in the mixed solution. Prior to emulsion polymerization, it is preferable to reduce the dissolved oxygen in the mixture. For that purpose, it is preferable to bubbling the mixed solution with an inert gas such as nitrogen gas. After bubbling with the mixed solution before blending the monomer (D), the mixed solution may be prepared by blending the monomer (D).

The content of the surfactant (A) in the mixture is preferably 5% by mass or more and 70% by mass or less with respect to the (meth) acrylic monomer (D1). When the content of the surfactant (A) is within this range, the fiber may have better convergence when the composition (X) is applied to the fiber as a sizing agent. The content of the surfactant (A) is more preferably 10% by mass or more and 30% by mass or less with respect to the (meth) acrylic monomer (D1). In this case, the composition (X) can form a uniform and highly continuous film. Therefore, when the composition (X) is applied to the fiber, the fiber has particularly excellent convergence, so that the filament rupture of the fiber strand can be suppressed and the fluff resistance can be improved.

The content of water (B) in the mixture is not particularly limited, and is appropriately set in consideration of the stability of the composition (X), the uniformity of the film formed from the composition (X), and the like. The content of water (B) in the mixture is preferably 100% by mass or more and 2000% by mass or less with respect to the (meth) acrylic monomer (D1), for example. In this case, the dispersibility in the mixture can be easily maintained uniformly, and the dispersibility of the polymerization reaction product (E) in the composition (X) can be improved. The content of water (B) in the mixture is more preferably 100% by mass or more and 1000% by mass or less with respect to the (meth) acrylic monomer (D). The composition (X) further contains a solvent other than water (B) contained in the mixture, that is, water (B) used for producing the polymerization reaction product (E), if necessary. You may.

The content of the polymerization initiator (C) in the mixture is preferably 0.01% by mass or more and 5% by mass or less with respect to the (meth) acrylic monomer (D1). When the content of the polymerization initiator (C) is within this range, the composition (X) can have better incineration property, so that the removal of the composition (X) can be facilitated. .. The content of the polymerization initiator (C) is more preferably 0.05% by mass or more and 1% by mass or less with respect to the (meth) acrylic monomer (D1).

The mixed solution may contain an additive or the like as long as it does not inhibit the emulsion polymerization reaction. Examples of additives include chain transfer agents, pH regulators, dispersion stabilizers, smoothing agents, plasticizers, and defoaming agents.

Examples of chain transfer agents are n-dodecyl mercaptan, octyl mercaptan, lauryl mercaptan thioglycolic acid, 2-ethylhexyl thioglycolate, glycidyl mercaptan, thioglycerol, mercaptoacetic acid, 2-mercaptoethanol, and 2,3-dimercapto-1. -Mercaptans such as propanol; aldehydes such as acetaldehyde, propionaldehyde, n-butylaldehyde, and benzaldehyde; alcohols such as methanol, ethanol, propanol, and butanol. In addition to the above compounds, any compound suitable for a chain transfer agent and capable of obtaining a repolymerizable Dormant species can also be included in the chain transfer agent. Then, among these, one kind or two or more kinds of compounds can be used as a chain transfer agent.

Examples of pH regulators include ammonium hydrogen carbonate, ammonium phosphate, ammonium acetate, and ammonium formate. In addition to the above compounds, if there is a compound that is suitable for a pH adjuster and does not inhibit the emulsion polymerization reaction, this compound can also be included in the chain transfer agent. Then, among these, one kind or two or more kinds of compounds can be used as a pH adjuster.

Examples of dispersion stabilizers are starches derived from corn, tapioca, flour, sweet potatoes, potatoes, etc., as well as etherified starch modified using them, and etherified hyamylose starch, carboxymethyl cellulose, butyl cellulose, polyvinyl alcohol, etc. Includes polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol block copolymer, polyethylene glycol-polyethylene glycol-polyethylene glycol block copolymer, polypropylene glycol-polyethylene glycol-polypropylene glycol block copolymer, and polyvinylpyrrolidone. In addition to the above compounds, if there is a compound suitable for a dispersion stabilizer and not inhibiting the emulsion polymerization reaction, this compound can also be included in the chain transfer agent. Then, among these, one kind or two or more kinds of compounds can be used as a dispersion stabilizer.

Examples of smoothing agents are ester-based smoothing agents such as oleyl oleate, stearyl oleate, lauryl oleate, oleyl stearate, oleyl laurate, and oleyl palmitate; hydrocarbons such as paraffin, isoparaffin, and cyclic paraffin; stearic acid and palmitic acid. Contains hydrocarbons with carbonyl groups such as acids. In addition to the above compounds, if there is a compound that is suitable for a smoothing agent and does not inhibit the emulsion polymerization reaction, this compound can also be included in the smoothing agent. Then, among these, one kind or two or more kinds of compounds can be used as a smoothing agent.

Examples of plasticizers are aromatic carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, and benzoic acid; aliphatic carboxylic acids such as adipic acid, sebacic acid, azelaic acid, maleic acid, and citric acid; polyvalent. Carboxylic acid: Contains an ester compound of an acid such as phosphoric acid and a higher mixed alcohol having 6 or more carbon atoms represented by octanol and nonanol. More specifically, for example, phthalates such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, and dibutyl phthalate; adipates such as dioctyl adipate and diisononyl adipate; trioctyl trimellitic acid and the like. Merit Acid Ester; Examples thereof include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized flaxseed oil. In addition to the above compounds, if there is a compound that is suitable for a plasticizer and does not inhibit the emulsion polymerization reaction, this compound can also be included in the plasticizer. Then, among these, one kind or two or more kinds of compounds can be used as a plasticizer.

As for the defoaming agent, if there is a compound that does not inhibit the emulsion polymerization reaction, this compound can also be included in the defoaming agent. Then, among these, one kind or two or more kinds of compounds can be used as an antifoaming agent.

Emulsion polymerization can proceed by heating the mixture. For example, after mixing water (B) and the polymerization initiator (C), the surfactant (A) and the monomer (D) may be added dropwise and heated to allow the emulsion polymerization to proceed. The heating temperature is, for example, in the range of 45 to 95 ° C., and the heating time is, for example, in the range of 3 to 24 hours. The conditions at the time of the reaction are appropriately set as long as the action of the polymerization reaction product (E) according to the present embodiment is not inhibited. As a result, the composition (X) containing the polymerization reaction product (E), the surfactant (A), and water (B) can be obtained.

The composition (X) may contain components other than the surfactant (A), water (B) and the polymerization reaction product (E). For example, the composition (X) may be further blended with a solvent, additives, or the like after the polymerization reaction product (E) is produced. Examples of additives include pH adjusters, dispersion stabilizers, smoothing agents, plasticizers, defoamers, as well as wetting agents, thiox-imparting agents, leveling agents, fungicides, preservatives, and thermoplastic resins. , Thermosetting resin, antistatic agent, and various other additives.

In the composition (X) synthesized as described above, the polymerization reaction product (E) is in the form of particles, and the polymerization reaction product (E) is dispersed in the composition (X).

The average particle size of the polymerization reaction product (E) is preferably 100 nm or more and 300 nm or less. In this case, the stability of the composition (X) can be further improved, and the dispersibility of the polymerization reaction product (E) in the composition (X) can be enhanced. The average particle size of the polymerization reaction product (E) is more preferably 100 nm or more and 250 nm or less, and particularly preferably 100 nm or more and 200 nm or less.

The weight average molecular weight of the polymerization reaction product (E) is preferably in the range of 100,000 or more and 1,000,000 or less. In this case, the dispersibility of the polymerization reaction product (E) in the composition (X) can be further improved, so that the composition (X) is more excellent in storage stability. Further, a film having good strength can be obtained from the composition (X). The weight average molecular weight of the polymerization reaction product (E) is more preferably in the range of 100,000 or more and 500,000 or less.

The weight average molecular weight is a value derived based on the measurement result by gel permeation chromatography (GPC). The molecular weight measurement by gel permeation chromatography can be performed under the following conditions, for example.
GPC equipment: Prominence manufactured by Shimadzu Corporation
Column: SHODEX KF-800P, KF-005, KF-003, KF-001 (4 used in series)
Mobile phase: Tetrahydrofuran Flow rate: 1 mL / min Column oven temperature: 40 ° C
Detector: RI
Molecular weight conversion: Standard polystyrene.

The glass transition temperature of the polymerization reaction product (E) is preferably in the range of −40 ° C. or higher and 50 ° C. or lower. In this case, when the composition (X) is applied to the fibers as a sizing agent, the fibers are less likely to block each other, and the convergence of the fibers can be further improved. Further, since the flexibility of the film formed from the composition (X) can be improved, the toughness against bending of the fiber when the composition (X) is attached to the fiber as a sizing agent is improved, and the fiber The fibers are less likely to break during processing. The glass transition temperature of the polymerization reaction product (E) is preferably in the range of −20 ° C. or higher and 25 ° C. or lower.

The glass transition temperature (Tg) is a value theoretically calculated from the composition ratio of the monomer (D), and is a value calculated by the following Fox formula.
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ + ... + W _n / Tg _n
In the Fox formula, n is an integer of 1 or more and indicates the type of monomer used as the monomer (D). That is, it is a calculation formula when the polymerization reaction product (E) in the composition (X) is obtained by polymerizing n kinds of monomers. W ₁ , W ₂ , ... W _n indicate each mass fraction of n kinds of monomers, and Tg ₁ , Tg ₂ , ... Tg _n indicate each glass transition temperature of n kinds of monomers. The unit of the glass transition temperature in the Fox equation is the absolute temperature “K”, and the value obtained by converting the calculated value into the Celsius temperature “° C.” is defined as the glass transition temperature of the polymerization reaction product (E).

Since the composition (X) has the above-mentioned structure, it has good convergence when attached to the fiber and can be easily removed from the fiber. The conditions of the heat treatment for removing the composition (X) are not particularly limited, but the composition (X) can be removed, for example, in an oxygen atmosphere and a nitrogen atmosphere. Further, the composition (X) can be removed by heat treatment at 350 ° C. or lower, and can also be removed by heat treatment at 330 ° C. or lower. The heating time for removing the composition (X) may be, for example, 5 hours or less, and may be 30 minutes or less depending on the heating temperature. As described above, since the composition (X) can be removed by heat treatment at a low temperature for a short time, the composition (X) can be easily removed without deteriorating the fibers.

The type of fiber to which the composition (X) is applied as a sizing agent is not particularly limited. The composition (X) can be suitably used, for example, as a sizing agent for inorganic fibers. Examples of inorganic fibers include glass fibers, carbon fibers, silicon carbide fibers, mineral fibers, basalt fibers, alumina fibers, and metal fibers. The composition (X) can be particularly usefully used as a sizing agent for glass fibers or carbon fibers.

As described above, since the composition (X) can be suitably used as a sizing agent for fibers, the composition (X) is applied to the inorganic fibers, and the inorganic fibers and the composition that adheres to the inorganic fibers ( A fiber material containing X) and can be obtained. The inorganic fiber used in producing the fiber material preferably contains at least one of glass fiber and carbon fiber. The fibrous material thus obtained can easily remove the composition (X) from the fiber as needed during processing, and even when the removal of the composition (X) is not required during processing. Since the composition (X) can be easily removed from the fiber at the time of recycling, it is useful as a fiber material and is environmentally friendly.

Hereinafter, specific examples of the present invention will be shown. However, the present invention is not limited to this embodiment, and the design can be changed to various forms.

Hereinafter, the present invention will be specifically described with reference to Examples.

(1) Synthesis of fiber sizing agent composition 260 parts by mass of water (B) in the table heated to 75 ° C. was added to a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube and a stirrer. It was. Next, after adding the components shown in the column "(C)" in the table into the flask, the components shown in columns other than (B) and (C) in the "composition" column in the table are dropped into the flask. did. After completion of the dropping, the mixture was stirred for 6 hours to carry out a polymerization reaction. As a result, the fiber sizing agent compositions of Examples and Comparative Examples 1 to 9 containing the polymerization reaction product were obtained.

The details of the components shown in the table are as follows.
<Monomer>
2-EHMA: 2-ethylhexyl methacrylate ・ iBMA: Isobutyl methacrylate ・ MMA: Methyl methacrylate ・ EMA: Ethyl methacrylate ・ PMA: Propyl methacrylate ・ iPMA: Isopropyl methacrylate ・ BMA: Butyl methacrylate ・ tBMA: Methacrylic Terriary butyl acid SLMA: Alkyl methacrylate (n = 12,13)
-HPMA: Hydroxypropyl Methacrylic Acid-PP-500: Polypropylene Glycol Monomethacrylic Acid Ester, manufactured by NOF CORPORATION, Part No. Blemmer PP-500
・ MAa: Methacrylic ・ MA: Methyl acrylate ・ BA: Butyl acrylate ・ iBA: Isobutyl acrylate ・ HA: 2 ethylhexyl acrylate ・ Aa: Acrylic acid ・ ST: Styrene <Surfactant>
-Neugen XL-160: Polyoxyalkylene branched decyl ether, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., HLB value 16.3
-Neugen XL-400: Polyoxyalkylene decyl ether, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., HLB value 18.4
-Neugen XL-40: Polyoxyalkylene decyl ether, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., HLB value 10.5
-Neugen TDS-80: Polyoxyethylene tridecyl ether, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., HLB value 13.3
Nonion HT-510: Polyoxyethylene polyoxypropylene alkyl ether, manufactured by NOF CORPORATION, HLB value 10
-Nonion HT-505: Polyoxyethylene polyoxypropylene alkyl ether, manufactured by NOF CORPORATION, HLB value 5
-NIKKOL PBC-31: Polyoxyethylene polyoxypropylene cetyl ether (1EO, 4PO), manufactured by Nikko Chemicals Co., Ltd., HLB value 9.5
-NIKKOL PBC-33: Polyoxyethylene polyoxypropylene cetyl ether (10EO, 4PO), manufactured by Nikko Chemicals Co., Ltd., HLB value 10.5
-NIKKOL PBC-34: Polyoxyethylene polyoxypropylene cetyl ether (20EO, 4PO), manufactured by Nikko Chemicals Co., Ltd., HLB value 16.5
-NIKKOL PBC-44: Polyoxyethylene polyoxypropylene cetyl ether (20EO, 8PO), manufactured by Nikko Chemicals Co., Ltd., HLB value 12.5
-Monogen Y-100: Sodium dodecyl sulfate, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.-Levon 2000: Palm oil fatty acid amide propyldimethylaminoacetate betaine, manufactured by Sanyo Kasei Kogyo Co., Ltd.-Neugen EA-87: Polyoxyethylene styrenated phenyl ether , Made by Dai-ichi Kogyo Seiyaku Co., Ltd., HLB value 10.6
<Polymerization initiator>
-APS: Ammonium persulfate-VA-057: 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropion amidine], manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.-VA-086: 2,2' -Azobis [N- (2-hydroxyethyl) -2-methylpropanamide], manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. V-50: 2,2'-azobis [2-amidine propane] dihydrochloride, Fuji Film Made by Wako Junyaku Co., Ltd.

(2) Preparation of Test Piece Water was added to the fiber sizing agent compositions of Examples and Comparative Examples 1 to 9 to adjust the concentration to 5% by mass. This 5% by mass concentration fiber sizing agent composition solution was applied to the surface of 42dTex glass fibers so that the adhesion rate of the resin component was 3% by mass. Subsequently, using a mini-sizer manufactured by Kaji Seisakusho Co., Ltd., processing was performed with a roller touch at a thread speed of 40 m / min. Then, the glass fiber was dried with hot air at 120 ° C. using a chamber having a chamber length of 4 m.

For Comparative Examples 10 and 11, polyvinyl alcohol and starch were used instead of the fiber sizing composition solution, respectively.

(3) Evaluation test (3-1) Glass transition temperature The glass transition temperature (Tg) of the polymerization reaction product in the fiber sizing agent compositions of Examples and Comparative Examples 1 to 9 synthesized in (1) above is determined. , Calculated using the Fox equation described above. The values are shown in the table below.

(3-2) Weight Average Molecular Weight The weight average molecular weight of the polymerization reaction product in the fiber sizing agent compositions of Examples and Comparative Examples 1 to 9 synthesized in (1) above was measured by a gel permeation chromatography measuring device (stock). It was calculated from the results of measurement under the above-mentioned measurement conditions using Polymer) manufactured by Shimadzu Corporation. The results are shown in the table below.

(3-3) Particle size The particle size of the polymerization reaction product in the fiber sizing agent compositions of Examples and Comparative Examples 1 to 9 synthesized in (1) above is analyzed by a laser analysis / scattering particle size distribution measuring device. It was calculated as a volume-based median diameter from the measured value of the particle size distribution measured using (Microtrack MT3000II, manufactured by Microtrack Bell Co., Ltd.). The results are shown in the table below.

(3-4) Stability The fiber sizing agent compositions of Examples and Comparative Examples 1 to 9 synthesized in (1) above were filtered immediately after the synthesis. Further, after the fiber sizing agent compositions synthesized in (1) above were left at room temperature for one week, the fiber sizing agent composition was filtered using a filter medium equivalent to 350 mesh to stabilize the composition. Was evaluated according to the following criteria. The results are shown in the table below. For Comparative Examples 10 and 11, after filtering polyvinyl alcohol and starch and leaving them at room temperature for one week, they were filtered again using a filter medium equivalent to 350 mesh, and the stability was evaluated according to the following criteria.
A: The filtration time immediately after the synthesis of the fiber sizing agent composition is equivalent to the filtration time after being left for 1 week, and no filter is generated in the filtration after being left for 1 week.
B: The filtration time after being left for 1 week was longer than the filtration time immediately after the synthesis of the fiber sizing agent composition, but no filter was generated in the filtration after being left for 1 week.
C: The filtration time after being left for 1 week is longer than the filtration time immediately after the synthesis of the fiber sizing agent composition, and a filter is generated in the filtration after being left for 1 week.

(3-5) Appearance of film On a PET film (manufactured by Toray Industries, Inc., Lumirror T60 100 μm), the fiber sizing agent compositions of Examples and Comparative Examples 1 to 9 synthesized in (1) above, and Comparative Examples 10 and 11 polyvinyl alcohol and starch were applied so as to have a film thickness of 200 μm to form a film. The appearance of this film was visually observed, and the appearance of the film was evaluated as follows. The results are shown in the table below.
A: A uniformly continuous film is formed.
B: A continuous film is formed although the part is non-uniform.
C: A non-uniform and discontinuous film is formed.
D: No film is formed.

(3-6) Incineration property The fiber sizing agent compositions of Examples and Comparative Examples 1 to 9 synthesized in the above (1) and the polyvinyl alcohols and starches of Comparative Examples 10 and 11 were subjected to TG-DTA (thermogravimetric analysis). Using a differential thermal) measuring device (Thermoplus EVO2 TG-DTA manufactured by Rigaku Co., Ltd.), the incineration rate was measured by incineration at 330 ° C. for 3 hours in an oxygen atmosphere, and the incineration property was evaluated as follows. The results are shown in the table below.
A: The incineration rate is 99.5% or more.
B: The incineration rate is 98.5% or more and less than 99.5%.
C: The incineration rate is 97% or more and less than 98.5%.
D: The incineration rate is less than 97%.
For comparison, the evaluation of polyvinyl alcohol is D.

(3-7) Incineration Time The fiber sizing agent compositions of Examples 2, 30, and 45 and Comparative Examples 1 and 9 synthesized in (1) above were subjected to a TG-DTA (thermogravimetric-differential thermal) measuring device ( Using Thermoplus EVO2 TG-DTA manufactured by Rigaku Co., Ltd., the temperature was raised from 30 ° C. to 300 ° C. at a rate of 5 ° C./min in an oxygen atmosphere and incinerated. The incineration rate at 300 ° C. is shown in the table below as an evaluation of the incineration time.

(3-8) Flexibility The fibers when the test pieces of each Example and each Comparative Example produced in (2) above were wound on a bobbin having a diameter of 3 cm were visually observed, and the flexibility was evaluated as follows. did. The results are shown in the table below.
A: The fibers can be wound evenly and evenly.
B: Only a part of the fiber does not follow the bobbin.
C: The fibers do not partially follow the bobbin, and the fibers are slightly bent.
D: The fiber does not follow the bobbin as a whole, and the fiber bends.
For comparison, the evaluation of polyvinyl alcohol is D.

(3-9) Convergence The fibers of the test piece are cut with scissors while a tension load of 2.94 N is applied to the test pieces of each Example and each Comparative Example produced in (2) above. did. The temperature at the time of cutting was 20 ° C., and the relative humidity was 70%. The defibration distance from the cut surface was measured, and the convergence was evaluated as follows. The results are shown in the table below.
A: The defibration distance is less than 1.0 cm.
B: The defibration distance is 1.0 cm or more and less than 1.5 cm.
C: The defibration distance is 1.5 cm or more and less than 2.0 cm.
D: The defibration distance is 2.0 cm or more.

(3-10) Fluff resistance A thread friction conjugation test was performed on 10 fibers of the test pieces of each Example and each Comparative Example produced in (2) above with a tension load of 4.90 N applied. Using a machine (TM type conjugation tester manufactured by INTEC Inc.), it was squeezed 100 times with a stroke length of 5 cm. The temperature at the time of the test was 20 ° C. and the relative humidity was 70%. The fibers after the test were visually observed, and the fluff resistance was evaluated as follows. The results are shown in the table below.
A: No fluff is confirmed.
B: Almost no fluff is confirmed.
C: Several fluffs are confirmed.
D: Fluff is confirmed on the whole.

Claims (11)

It contains a polyoxyalkylene alkyl ether type surfactant (A), water (B), and a polymerization reaction product (E).
The polymerization reaction product (E) is a monomer having an ethylenic double bond in the presence of the polyoxyalkylene alkyl ether type surfactant (A), the water (B), and the polymerization initiator (C). It is a product produced by emulsion polymerization of D).
The polymerization initiator (C) contains ammonium persulfate (C1) and contains.
The monomer (D) contains a (meth) acrylic monomer (D1).
Sizing agent composition for fibers. The (meth) acrylic monomer (D1) contains 2-ethylhexyl methacrylate.
The sizing agent composition for fibers according to claim 1. The content of the 2-ethylhexyl methacrylate with respect to the (meth) acrylic monomer (D1) is 40% by mass or more.
The sizing agent composition for fibers according to claim 2. The (meth) acrylic monomer (D1) further contains isobutyl methacrylate.
The fiber sizing agent composition according to claim 2 or 3. The content of the isobutyl methacrylate with respect to the (meth) acrylic monomer (D1) is 50% by mass or less.
The sizing agent composition for fibers according to claim 4. The total amount of the 2-ethylhexyl methacrylate and the isobutyl methacrylate with respect to the (meth) acrylic monomer (D1) is 60% by mass or more.
The fiber sizing agent composition according to claim 5. The content of the polyoxyalkylene alkyl ether type surfactant (A) with respect to the (meth) acrylic monomer (D1) is 5% by mass or more and 70% by mass or less.
The fiber sizing agent composition according to any one of claims 1 to 6. For inorganic fibers,
The fiber sizing agent composition according to any one of claims 1 to 7. For glass fiber or carbon fiber,
The sizing agent composition for fibers according to claim 8. Inorganic fiber and
A fiber material containing the fiber sizing agent composition according to claim 8 or 9, which adheres to the inorganic fiber. The inorganic fiber contains at least one of glass fiber and carbon fiber.
The fiber material according to claim 10.