JPH0123580B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a water-based glass fiber binder that is useful in producing glass fiber nonwoven fabrics, papers, or glass fiber bundles, and has excellent adhesion to glass, water resistance, acid resistance, color fastness, durability, etc. It is related to. Conventionally, as binders for glass fibers, water-soluble resins such as gelatin, starch, and CMC; copolymer emulsions such as vinyl acetate and acrylic esters; epoxy resins; and phenolic resins have been used. Among these, water-soluble resins have poor water resistance and acid resistance, so when used as a binder for glass mat or glass paper used in lead-acid battery separators, for example, the binder easily dissolves into the sulfuric acid solution and loses its adhesive strength. No, again,
It also causes contamination of the sulfuric acid solution. Vinyl acetate-based emulsions have poor color fastness, so when used as a sizing agent for chopped strands used in glass fiber reinforced thermoplastics (FRTP), for example, vinyl acetate emulsions can be used as a sizing agent for chopped strands used in glass fiber reinforced thermoplastics (FRTP). There is a drawback that the chopped strands change color due to heat during kneading, and the water resistance is also poor. Acrylic acid ester emulsions do not have sufficient adhesion to glass, and when used as a sizing agent for chopped strands, for example, they have a strong tendency to break due to their weak sizing power. As a binder for glass paper and glass mats, it also has the drawbacks of insufficient adhesive strength and low hardness and strength.
Furthermore, epoxy resins and phenolic resins have the disadvantage that the resin itself is colored and easily discolored by heat or light. The present inventors found that the adhesive strength to glass is strong;
As a result of repeated research aimed at developing a binder with excellent water resistance and acid resistance, and less coloring and discoloration,
A copolymer obtained by emulsion polymerization containing an alkyl ester of (meth)acrylic acid as a main component, and having an organosilicon group and a carboxyl group with a specific structure in the copolymer, We discovered that this material exhibits excellent properties as a binder for glass fibers, and filed a patent application earlier. Subsequently, as a result of further research, it was found that the binder has excellent adhesion to glass, water resistance, acid resistance, heat resistance, and weather resistance. It has become clear that if the product is used after the preparation, the adhesion to glass and water resistance may be inferior compared to when the product is used relatively early after production. As a result of intensive research to overcome this drawback, the inventors discovered that the above drawback could be improved by using an organic silicon compound having a specific structure in combination, and the present invention was achieved based on this finding. That is, the present invention comprises 0.1 to 40% by weight of an organosilicon monomer (A) having a polymerizable unsaturated group and a hydrolyzable group directly bonded to a silicon atom in the molecule, and 1% by weight of a polymerizable unsaturated carboxylic acid (B). ~30% by weight, 50~98.9% by weight of (meth)acrylic acid alkyl ester (C) having an alkyl group having 1 to 18 carbon atoms, and other polymerizable monomers
(D) A monomer mixture consisting of 0 to 40% by weight (however, the total of components (A), (B), (C) and (D) is 100% by weight) is emulsion polymerized in an aqueous medium. It is characterized by containing an aqueous copolymer dispersion () obtained with or without addition of a basic substance and an organosilicon compound () having a hydrolyzable group directly bonded to a silicon atom. The present invention provides a water-based binder for glass fibers. The organosilicon monomer (A) used in the present invention is a compound having a silicon atom to which at least one polymerizable unsaturated group and at least one hydrolyzable group are directly connected in the molecule, and is emulsifiable. During the polymerization process or subsequent processes, some or all of the hydrolyzable groups directly bonded to silicon atoms undergo hydrolysis to generate silanol groups, which form covalent bonds with glass. This provides strong adhesion to glass. Examples of the organic silicon monomer (A) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris(β-methoxyethoxy)silane, allyltriethoxysilane, trimethoxysilylpropylallylamine, γ-( meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane,
γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropyltris(β-methoxyethoxy)silane, N-B-(N-vinyl benzylamino)ethyl-γ-aminopropyltrimethoxysilane,
N-vinylbenzyl-γ-aminopropyltriethoxysilane, 2-styrylethyltrimethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane,
Examples include (meth)acryloxyethyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, vinyltriacetoxysilane, vinyltrichlorosilane, etc., and one type or a mixture of two or more types selected from these groups is used. be able to. In the present invention, the proportion of the organosilicon monomer (A) in the monomer mixture is 0.1 to 40% by weight,
More preferably, it is used in a proportion of 0.1 to 20% by weight.
If the organosilicon monomer (A) is less than 0.1% by weight, the adhesion to glass will be weak, and water resistance and acid resistance will be insufficient. It is not preferable because the adhesion strength is not improved as compared to the case where it is within the range of . The polymerizable unsaturated carboxylic acid (B) has one or more carboxyl groups in its molecule, and together with the organosilicon monomer (A), it improves the adhesion to glass, and also improves the adhesive strength of the aqueous copolymer dispersion. Contributes to improving the freezing stability, mechanical stability, and chemical stability of the liquid, and also makes it possible to adjust the viscosity of the aqueous copolymer dispersion to the desired range by adding an appropriate amount of a basic substance. It has the effect of Examples of the polymerizable unsaturated carboxylic acid (B) include unsaturated monobasic acids such as acrylic acid, methacrylic acid, and crotonic acid; unsaturated dibasic acids such as maleic acid, fumaric acid, and itaconic acid; Monoester compound of number 1 to 17 alkyl alcohol and unsaturated dibasic acid; monoester compound of dihydric alcohol such as ethylene glycol, diethylene glycol, propylene glycol and lower monohydric alcohol such as methyl alcohol, ethyl alcohol, butyl alcohol Examples include monoester compounds of ether and unsaturated dibasic acids, and one type or a mixture of two or more types selected from these groups can be used. In the present invention, the polymerizable unsaturated carboxylic acid (B) is used in a proportion of 1 to 30% by weight in the polymerizable monomer mixture. If the proportion of polymerizable unsaturated carboxylic acid (B) is less than 1% by weight, the adhesion improving effect and various stability improving effects of the aqueous copolymer dispersion will not be sufficient, and if the proportion exceeds 30% by weight, In this case, the water resistance and acid resistance of the binder become poor. As the (meth)acrylic acid alkyl ester (C), one or more types of acrylic acid alkyl ester and methacrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms are used; When used together with other components, it has the effect of preventing the binder from being colored by heat or light and improving long-term durability. (Meth)acrylic acid alkyl ester (C) is an ester compound of a linear or branched aliphatic alkyl alcohol or alicyclic alkyl alcohol having 1 to 18 carbon atoms and acrylic acid or methacrylic acid, such as , methyl, ethyl, propyl, isopropyl, butyl, isobutyl, octyl, 2-ethylhexyl, lauryl, stearyl or cyclohexyl ester of acrylic acid or methacrylic acid, and one or more selected from these groups. A mixture of can be used. In the present invention, the (meth)acrylic acid alkyl ester (C) is used in a proportion of 50 to 98.9% by weight in the monomer mixture. If the proportion of the (meth)acrylic acid alkyl ester (C) is less than 50% by weight, the color fastness, durability, water resistance, and acid resistance of the binder will be poor. In the present invention, the polymerizable monomer (D) may be used in a proportion of 40% by weight or less in the monomer mixture, if necessary. Examples of the polymerizable monomer (D) include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, mono- or diester of acrylic acid or methacrylic acid and polypropylene glycol, and acrylic. Mono- or diester of acid or methacrylic acid and polyethylene glycol, acrylic acid or methacrylic acid and ethylene glycol, 1,3-butylene glycol, 1,
Diesters with dihydric alcohols such as 6-hexane glycol and neopentyl glycol, triesters with acrylic acid or methacrylic acid and trimethylolpropane, styrene, vinyltoluene, vinyl chloride, vinylidene chloride, vinyl fluoride,
Vinylidene fluoride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, ethylene, propylene, butadiene, isoprene,
Examples include dicyclopentazine, divinylbenzene, diallylphthalate, (meth)acrylamide, methylolated (meth)acrylamide, alkoxymethylolated (meth)acrylamide having 1 to 4 carbon atoms, and 1 selected from these groups. Species or mixtures of two or more species can be used. When the proportion of the polymerizable monomer (D) is increased to more than 40% by weight, depending on the monomer used as the monomer (D), the discoloration resistance, durability, water resistance, Acid resistance may become poor. In the present invention, an organosilicon monomer (A), a polymerizable unsaturated carboxylic acid (B), a (meth)acrylic acid alkyl ester (C), and if necessary a polymerizable monomer (D) are mixed in an aqueous medium. emulsion polymerization. Although it is not necessarily necessary to use an aqueous medium as a binder for glass fibers, from the standpoint of preventing fires and improving the working environment,
It is preferable to use an aqueous medium rather than an organic solvent medium. Therefore, as a method for obtaining an aqueous copolymer dispersion in the present invention, there is also a method in which a polymer is obtained by carrying out a polymerization reaction in the presence or absence of an organic solvent, and then the polymer is dispersed in water. As mentioned above, emulsion polymerization in an aqueous medium is the optimal method from the viewpoint of fire prevention and improvement of the working environment, simplification of the manufacturing process, shortening of required time, and stability of the aqueous copolymer dispersion. be. For the emulsion polymerization, known methods such as a monomer dropping method, a pre-emulsion method, or a combination of these methods can be used. Furthermore, a multi-step polymerization method may be used in which the monomer mixture is divided into two or more sets, in which case the composition of the monomer mixture in each divided set may be the same or different. According to such a multi-step polymerization method, the features of the present invention may be better exhibited. That is, for example, in a two-stage polymerization method, by making the organosilicon monomer (A) and the polymerizable unsaturated carboxylic acid (B) exist only in the second stage monomer mixture, the monomer (A) ) and the unsaturated carboxylic acid (B) are distributed near the surface of the dispersed particles without being incorporated into the dispersed particles of the aqueous copolymer dispersion, thereby obtaining a binder for glass fibers with improved adhesive strength to glass. can. In emulsion polymerization, the emulsifiers used are:
Conventionally known anionic, cationic, or nonionic emulsifiers or polymeric emulsifiers may be used, such as sodium dodecyl sulfate, ammonium dodecyl sulfate, sodium dodecyl polyglycol ether sulfate, alkali metal salts of sulfonated paraffin, Ammonium salt of sulfonated paraffin, sodium dodecylbenzene sulfonate, sodium laurate, high alkylnaphthalene sulfonate, dialkyl sulfosuccinate, polyoxyethylene alkyl sulfate, polyoxyethylene alkylaryl sulfate, polyoxyethylene alkyl ether, poly Oxyethylene alkylaryl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxypropylene polymer, lauryltrimethylammonium chloride, alkylbenzyldimethylammonium chloride, polyvinyl alcohol, sodium poly(meth)acrylate, poly(meth)acrylic Examples include ammonium acid, polyhydroxyethyl (meth)acrylate, polyhydroxypropyl (meth)acrylate, and one kind or a mixture of two or more kinds selected from these groups can be used. There is no particular restriction on the amount of emulsifier used, but if too much is used, the water resistance of the binder tends to deteriorate, so it is preferable to use an amount of 10% by weight or less based on the amount of the monomer mixture. Preferably, an amount of 5% by weight or less is used. As the polymerization catalyst, those commonly used in emulsion polymerization, such as ammonium persulfate,
Potassium persulfate, sodium persulfate, ammonium perborate, hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, peracetic acid, 2,2'-azobisisobutyronitrile, 4, A radical-forming polymerization initiator such as 4'-azobis(4-cyanopentanoscinic acid) or an alkali metal salt thereof can be used, and the amount used is 0.01 to 3% by weight based on the monomer mixture.
It may be within the range of . And if it is necessary to increase the polymerization rate or lower the reaction temperature when using peroxides, peroxides and ascorbic acid, soluble sulfites, hydrosulfites, thiosulfates, sulfone oxalates, sulfuric acid It can be used as a redox system in combination with ferrous iron or the like. The polymerization temperature is preferably in the range of 30 to 90°C, and additives customary in emulsion polymerization technology, such as chelating agents, buffers, salts of mineral or organic acids, pH regulating aids, etc., may be used. is also free. After performing emulsion polymerization in this way, it can be used as is as an aqueous copolymer dispersion () as the main component of a binder for glass fibers, but by adding a basic substance to increase the pH, the aqueous copolymer dispersion can be used as is. It can improve the freezing stability, mechanical stability, and chemical stability of the polymer dispersion (), and may also improve the adhesion to glass, so it is usually made basic so that the pH is 5 or higher. Preferably, the substance is added. Examples of basic substances include ammonia, ethylamine, diethylamine, triethylamine, ethanolamine, triethanolamine, diethylethanolamine,
Caustic soda, caustic potash, etc. can be used. The aqueous copolymer dispersion () obtained in this way can exhibit excellent performance as a binder for glass fibers even when used alone when used relatively early after production; When stored for a long period of time, the performance as a binder, especially adhesiveness and water resistance, may deteriorate. By using an organosilicon compound () in combination with the aqueous copolymer dispersion () whose performance has deteriorated in this way to obtain the aqueous glass fiber binder of the present invention,
It is possible to recover the excellent performance as a binder equivalent to that exhibited immediately after production. The organosilicon compound () may be mixed with the aqueous copolymer dispersion () before use, or may be mixed in advance, but it is better to use it as soon as possible after mixing for better effects. is demonstrated. Organosilicon compound used in the present invention ()
is a compound having a hydrolyzable group directly bonded to a silicon atom in the molecule. As the organosilicon compound (), in addition to the above-mentioned organosilicon monomer (A) that can be used as is, for example, aminomethyltriethoxysilane, N-β-aminoethylaminomethyltrimethoxysilane, γ-aminopropyltrimethoxy Aminoalkylalkoxysilanes such as silane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylpropyl)ethylenediamine, etc.; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β - Epoxyalkylalkoxysilanes such as (3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxy Mercaptoalkylalkoxysilane such as silane; methyl silicate;
Tetraalkoxysilanes such as ethyl silicate, propyl silicate, butyl silicate, etc.;
Alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, ethyltrimethoxysilane; dialkyldialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane; γ-chloropropyl trimethoxysilane; Halogenated alkylalkoxysilanes such as methoxysilane, 3,3,3-trichloropropyltrimethoxysilane, etc.; Alkylacyloxysilanes such as methyltriacetoxysilane, dimethyldiacetoxysilane, etc.; Trimethoxysilane, triethoxysilane, etc. Examples include hydrosilane compounds, and one type or a mixture of two or more types selected from these groups can be used. In the present invention, it is preferable to use 0.1 to 40 parts by weight of the organosilicon compound () per 100 parts by weight of the aqueous copolymer dispersion (). If the amount added is less than 0.1 part by weight, the effect of improving adhesion and water resistance is small, and even if the amount is more than 40 parts by weight, no improvement in performance commensurate with the amount used will be observed. The organosilicon compound () may be diluted with water or other solvents if necessary prior to blending. A mixture of the aqueous copolymer dispersion () and the organosilicon compound () can be used as it is as a binder for glass fibers, but other known viscosity modifiers, coupling agents, lubricants, repellents, etc. A water agent, a crosslinking agent, an antistatic agent, etc. can be added. It can also be diluted as appropriate. The aqueous binder for glass fibers of the present invention is derived from an organosilicon monomer (A), a polymerizable unsaturated carboxylic acid (B), a (meth)acrylic acid alkyl ester (C), and a polymerizable monomer (D). Aqueous copolymer dispersion ()
and an organosilicon compound (), it has excellent adhesion to glass, water resistance, acid resistance, and discoloration resistance, and since it is an aqueous dispersion, there is no risk of fire or environmental pollution. It has excellent characteristics and can be used extremely effectively in the production of various glass fiber products. For example, a glass mat can be manufactured by attaching it to the developed glass fiber web by spray coating, shower coating, dipping, etc., and then drying it, and the obtained glass mat has good hardness, strength, and acid resistance. Because it is excellent in
For example, when used as a separator in lead-acid batteries, it exhibits excellent performance. The aqueous binder for glass fibers of the present invention can also be used in the production of glass paper by passing through a papermaking process from a glass fiber dispersion containing the binder, and the obtained glass paper has good strength, water resistance, and acid resistance. sex,
Due to its excellent color fastness and durability, it is effectively used in lead-acid battery separators, air filters, printed wiring boards, etc. Furthermore, the binder for glass fibers of the present invention can be used as a sizing agent in the production of chopped strands, rovings, yarns, and the like. For example, when used as a sizing agent for chopped strands, there is less cracking of the glass fiber bundles, no coloring of the glass fibers when kneading into molten thermoplastic resin, and the use of resin reinforced with glass fibers. It has features such as improved durability and water resistance. The binder for glass fibers of the present invention can be effectively used as a binder for various glass fiber nonwoven fabrics and woven fabrics other than those mentioned above. EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the scope of the present invention is not limited only to these Examples. In the examples, unless otherwise specified, % means % by weight and parts means parts by weight, respectively. Reference Example 1 220 parts of water was placed in a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser.
Add 1.5 parts of sodium dodecylbenzenesulfonate as an emulsifier and 0.5 parts of potassium persulfate as a polymerization catalyst, heat to 75°C while slowly blowing nitrogen gas, and stir to form a homogeneous aqueous solution, which is then added in advance through a dropping funnel. A monomer mixture consisting of 5 parts of vinyltriethoxysilane, 10 parts of methacrylic acid, 55 parts of methyl methacrylate, and 30 parts of butyl acrylate, which had been prepared, was added dropwise over a period of 2 hours. Thereafter, the temperature was maintained at 75°C and stirred for an additional hour to effect emulsion polymerization, then cooled to 30°C, and aqueous ammonia with a concentration of 2.8% was added to bring the pH to 5.5.
An aqueous copolymer dispersion () with a nonvolatile content of 30.0% was obtained. Reference Examples 2 to 5 The same operations as in Reference Example 1 were repeated except that the monomer mixture composition, emulsifier, polymerization catalyst, polymerization temperature, water and basic substance were as shown in Table 1, and aqueous copolymerization was performed. Combined dispersions (2) to (5) were obtained.

【table】

[Table] Comparative Reference Examples 1 to 5 Reference examples except that the composition of the monomer mixture is outside the scope of the present invention as shown in Table 1-2, and the water and basic compounds are as shown in Table 1-2. The same operation as in 1 was repeated to obtain comparative aqueous copolymer dispersions (1) to (5).

[Table] Example 1 The aqueous copolymer dispersion (1) obtained in Reference Example 1 was
Performance tests were conducted immediately after production, after storage at room temperature for 6 months, and after storage at room temperature for 12 months. Furthermore, a binder (1-1a) obtained by adding 3 parts of vinyltrimethoxysilane to 100 parts of the aqueous copolymer dispersion (1) after storage for 6 months and mixing well, and a water-based copolymer dispersion after storage for 12 months. The same test was also conducted on a binder (1-1b) obtained by adding 5 parts of vinyltrimethoxysilane to 100 parts of the combined dispersion (1) and mixing well.
The results of these performance tests are shown in Table 2. The performance test method is as shown below. 1 Adhesion test on glass plate Preparation of test plate: Apply binder to a clean glass plate using a No. 16 bar coater,
It was dried at ℃ for 2 minutes. Normal adhesion: Using a cutter knife, cut 10 mm x 10 mm gongs on the coating film at 1 mm intervals, press cellophane tape, and then peel it off vigorously. The degree of peeling of the goblets was scored on a 10-point scale. 10 points (good) → 1 point (poor) Water resistant adhesion: The test plate was immersed in tap water for 7 days,
After pulling up and wiping off moisture within 1 minute, an adhesion test was conducted in the same manner as above. 2 Performance test of glass pine Preparation of test piece: Glass pine mixed with glass fibers was diluted with water to a nonvolatile content of 8%, and then the pH was adjusted to about 100% with ammonia water.
Impregnated with binder adjusted to 10.5,
After adjusting to the specified adhesion amount 200
It was dried at ℃ for 2 minutes to obtain a glass mat with a binder (non-volatile content) adhesion of 15%. Hardness: A test piece cut into a strip of 1 cm x 12 cm was supported without being fixed at a position 1 cm from both ends, a 2 g weight was placed in the center of the test piece, and the number of mm in which the center part decreased was read.
The one with smaller mm number is better (harder). Acid resistance loss rate: The weight loss rate (%) was measured when the test piece was immersed in dilute sulfuric acid at 80°C with a specific gravity of 1.26 for 24 hours. 3 Performance test of chopped strands Preparation of test piece: Polyoxyethylene sorbitan fatty acid ester (manufactured by Kao Atlas Co., Ltd., A chopped strand with a length of 6 mm was obtained by a conventional method using a binder (sizing agent liquid) obtained by adding 1.5 parts of Tween 80). Convergence: The degree of cracking in the obtained chopped strand was visually determined. ◎ (No cracking) → × (Many cracking) Resistance to heat discoloration: The chopped strands were heated at 300°C for 1 minute, and the degree of coloring was judged with the naked eye. ◎ (no coloration) → × (strong coloration)

[Table] Example 2 Aqueous copolymer dispersion obtained in Reference Example 1 (1) 100
1 part of vinyltriethoxysilane was added thereto and mixed well to obtain a binder (1-2). The same performance test as in Example 1 was conducted on the binder (1-2) immediately after production, after storage at room temperature for 6 months, and after storage at room temperature for 12 months. Binder (1-2a) obtained by adding 4 parts of vinyltriethoxysilane to 100 parts and mixing well and binder (1-2) after storage for 12 months: 1.5 parts of vinyltriethoxysilane to 100 parts.
of binder (1 part) and mixed well.
-2b) was also tested in the same way. The test results are shown in Table 3.

[Table] Example 3 Aqueous copolymer dispersions obtained in Reference Examples 2 to 5 (2)
Regarding (5), the same performance tests as in Example 1 were conducted immediately after production and after 6 months of storage at room temperature, and in addition, each aqueous copolymer dispersion after 6 months of storage was
Various organic silicon compounds shown in the table were added and mixed well to obtain binders (2) to (5), which were also subjected to the same test immediately after production. The test results are shown in Table 5.

【table】

【table】

【table】

[Table] Comparative Example 1 Regarding the comparative aqueous copolymer dispersions (1), (3), (4) and (5) obtained in Comparative Reference Examples 1 to 5, immediately after production and after 6 months of storage at room temperature A performance test was conducted in the same manner as in Example 1. Furthermore, 5.0 parts of γ-glycidoxypropyltrimethoxysilane was added to 100 parts of each comparative aqueous copolymer dispersion after storage for 6 months, and mixed well. 1), (3), (4), and (5) were obtained, and the same tests were conducted on these as well. The test results are shown in Table 5. Comparative aqueous copolymer dispersion (2) generated a large amount of aggregates during emulsion polymerization and was not practical, so performance tests were not conducted.

【table】

Claims (1)

[Scope of Claims] 1. Organosilicon monomer (A) having a polymerizable unsaturated group and a hydrolyzable group directly bonded to a silicon atom in the molecule: 0.1
-40% by weight, polymerizable unsaturated carboxylic acid (B) 1-30% by weight, and (meth)acrylic acid alkyl ester (C) having an alkyl group having 1-18 carbon atoms 50-98.9
Weight% (however, the total of components (A), (B) and (C) is 100
Weight%. ) containing an aqueous copolymer dispersion () obtained by emulsion polymerization of a monomer mixture consisting of A water-based glass fiber binder with special features. 2 Organosilicon monomer (A) having a polymerizable unsaturated group and a hydrolyzable group directly bonded to a silicon atom in the molecule 0.1
-40% by weight, 1-30% by weight of polymerizable unsaturated carboxylic acid (B), 50-98.9% by weight of (meth)acrylic acid alkyl ester (C) having an alkyl group having 1-18 carbon atoms, and other polymerizations A monomer mixture consisting of more than 0 and 40% by weight or less of sexual monomer (D) (however, the total of components (A), (B), (C) and (D) is 100% by weight) Aqueous copolymer dispersion obtained by emulsion polymerization in an aqueous medium () and an organosilicon compound () having a hydrolyzable group directly bonded to a silicon atom. binder. 3 Organosilicon monomer (A) having a polymerizable unsaturated group and a hydrolyzable group directly bonded to a silicon atom in the molecule 0.1
-40% by weight, polymerizable unsaturated carboxylic acid (B) 1-30% by weight, and (meth)acrylic acid alkyl ester (C) having an alkyl group having 1-18 carbon atoms 50-98.9
Weight% (however, the total of components (A), (B) and (C) is 100
Weight%. ) Aqueous copolymer dispersion () obtained by emulsion polymerizing a monomer mixture consisting of ) in an aqueous medium and then adding a basic substance and an organosilicon compound having a hydrolyzable group directly bonded to a silicon atom ()
A water-based binder for glass fiber characterized by containing the following. 4 Organosilicon monomer (A) having a polymerizable unsaturated group and a hydrolyzable group directly bonded to a silicon atom in the molecule 0.1
-40% by weight, 1-30% by weight of polymerizable unsaturated carboxylic acid (B), 50-98.9% by weight of (meth)acrylic acid alkyl ester (C) having an alkyl group having 1-18 carbon atoms, and other polymerizations A monomer mixture consisting of more than 0 and 40% by weight or less of sexual monomer (D) (however, the total of components (A), (B), (C) and (D) is 100% by weight) It is characterized by containing an aqueous copolymer dispersion () obtained by emulsion polymerizing in an aqueous medium and then adding a basic substance, and an organosilicon compound () having a hydrolyzable group directly bonded to a silicon atom. Water-based binder for glass fiber.