JPH0429620B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to glass fiber sizing agents. In particular, it relates to glass fiber sizing agents used for reinforcing unsaturated polyester resins, epoxy resins, etc. Among glass fibers, long fibers are made by pulling out molten glass through a porous plate of heat-resistant metal such as platinum, forming single fibers, cooling them while stretching, and then bundling several hundred fibers into strands. Thereafter, it is processed into roving, chopped strand, chopped strand mat, or woven into roving cloth, glass tape, glass cloth, etc., and used for reinforcing unsaturated polyester resins. The glass fiber sizing agent of the present invention has excellent weaving properties especially when used in woven roving cloth, glass tape, glass cloth, etc., and can be used without removing the sizing agent after weaving. It is used for reinforcement. The glass fiber sizing agent of the present invention is difficult to cause oxidative polymerization and difficult to become insoluble and infusible even during hot air drying at 110 to 160°C for about 10 hours in the glass fiber manufacturing process. The glass fibers bundled using this method have good compatibility with unsaturated polyester resins, etc., so they are well impregnated into the bundled glass fibers, and are strongly bonded to the unsaturated polyester resins by curing, which improves the strength of molded products. The flexibility of the polyurethane sizing agent made from unsaturated polyester polyol absorbs the strain caused by the expansion and contraction of the polyester resin during heat-curing molding of the molded product. It is considered that no bleaching phenomenon occurs. Glass fiber sizing agents are usually cationic, nonionic, or emulsified with these activators. This is because it is used in combination with antistatic agents and smoothing agents, which are cationic activators, and normal anionic activators cannot be used. However, sizing agents emulsified with cationic or nonionic activators have problems such as yellowing and inhibition of adhesion to unsaturated polyester resins by the emulsifier. As a result of intensive research in order to solve these problems, the present inventors solved these problems by adding an extremely limited amount of anion groups, and the compatibility with unsaturated polyester resin etc. The inventors discovered an aqueous polyurethane dispersion made from an unsaturated polyester polyol with excellent properties, and completed the present invention. That is, when reacting an unsaturated polyester polyol with a molecular weight of 300 to 5,000, a polyethylene glycol with a molecular weight of 300 to 6,000, and a polyol optionally combined with a reactive hydrogen atom-containing chain extender and a crosslinking agent, and a polyisocyanate. ,
A mainly cross-linked structure produced from a polyol and polyisocyanate in which the weight proportion of the unsaturated polyester polyol is 10 to 95% and the weight proportion of the polyethylene glycol is 5 to 50%, based on the total amount of polyol group-containing compounds in the polyol. When producing an aqueous polyurethane dispersion, at least one hydrogen atom reactive with an isocyanate group is added.
and an anionic salt-like group or an anionic salt-forming group in an amount capable of reacting with 0.01 to 0.5% by weight of the remaining isocyanate groups based on the prepolymer. The present invention provides a glass fiber sizing agent characterized in that the main film-forming component is an aqueous polyurethane dispersion added to isocyanate groups. The aqueous polyurethane dispersion in the present invention can be obtained by a known manufacturing method, for example, the method described in Japanese Patent Publication No. 42-24192. When the polyether of the present invention is (a) made of a polyol group-containing compound of unsaturated polyester polyol and polyethylene glycol, (b) a chain extender or crosslinking agent made of a polyol group-containing compound is used in combination with (a). (c) When (i) is combined with a chain extender or crosslinking agent that is not a polyol group-containing compound, (d) (b) is combined with a chain extender or crosslinker that is a polyol group-containing compound and a polyol group. If it consists of a chain extender or crosslinking agent that is not a containing compound, there is. In either case, the weight ratio of unsaturated polyester polyol with a molecular weight of 300 to 5000 is based on the total amount of polyol group-containing compounds in the polyol.
It is necessary that the weight proportion of polyethylene glycol having a molecular weight of 300 to 6000 be 10 to 95%, and 15 to 50% based on the total amount of polyol group-containing compounds in the polyol. Examples of unsaturated dicarboxylic acids constituting the unsaturated polyester polyol of the present invention include maleic acid,
These include fumaric acid, itaconic acid, citraconic acid, methaconic acid, anhydrides thereof, and halogenated unsaturated dicarboxylic acids such as chlormaleic acid. Examples of polyhydric alcohols include divalent alcohols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, butylene glycol, butane-1,3 diol, butane-1,-4 diol, and hexane. Examples include -1,-6 diols and higher homologs thereof, neopentyl glycol, and ethylene oxide adducts and propylene oxide adducts of bisphenol A. Further, there are trihydric and polyhydric alcohols such as glycerin, trimethylolethane, and trimethylolpropane. Polyethylene glycol is an important component for the physical properties of the aqueous polyurethane dispersion of the present invention, and is important for smoothness, fluffing effect, impregnability, etc. in the weaving properties of glass fibers. Further, although the aqueous polyurethane dispersion of the present invention is anionic, it is necessary to be compatible with antistatic agents and smoothing agents that are cation activators. If the weight proportion of polyethylene glycol exceeding the above range of usage is less than 5% by weight, it is not possible to synthesize a polyurethane aqueous dispersion that is compatible with the cationic activator, and if it exceeds 50% by weight,
It is not possible to synthesize a polyurethane aqueous dispersion with excellent focusing power. As the reactive hydrogen atom-containing chain extender, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, butylene glycol, butane 1-,3 diol, butane-4,-4 diol,
Hexane-1,-6 diol, neopentyl glycol, polycaprolactone polyol, polybutylene glycol, polybutadiene glycol, and ethylene oxide adducts of bisphenol A and bisphenol S, and
Examples include propylene oxide adducts of bisphenol A and bisphenol S. Examples of crosslinking agents include glycerin, trimethylolpropane, polycaprolactone polyol (trifunctional), and pentaerythritol. Examples of the polyisocyanate include triphenylmethane triisocyanate, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, 4,4 dicyclohexylmethane diisocyanate, and the like. Compounds containing at least one hydrogen atom reactive with an isocyanate group and at least one anionic salt-like group or anionic salt-forming group include aminocarboxylic acids such as glycine and alanine, taurine, N-methyltaurine, N-butyltaurine, aminosulfonic acids such as sulfamic acid, 2-hydroxyethanolsulfonic acid,
Hydroxysulfonic acids such as phenol 2,4-disulfonic acid, glycolic acid, salicylic acid, P-
Hydroxycarboxylic acids such as oxybenzoic acid. In the present invention, the compound added to the residual isocyanate group of the prepolymer obtained by reacting a polyol and a polyisocyanate has at least one hydrogen atom reactive with the isocyanate group,
and a compound containing at least one anionic salt-like group or an anionic salt-forming group.
The amount of the compound to be added is preferably such that it can react with 0.01 to 0.5% by weight of the remaining isocyanate groups based on the prepolymer. If it exceeds 0.5%, the anionic property will prevail and it will not be compatible with the antistatic agents and cationic activators such as smoothing agents that are usually used in combination with glass fiber sizing agents, forming complexes and causing aggregation. It cannot be used because it settles. Furthermore, if it is less than 0.01%, the excellent effects of the present invention cannot be exhibited. In the sizing agent of the present invention, if the sizing agent is compatible with the cationic activator, the larger the amount added, the more the amount of polyethylene glycol used can be reduced, and a polyurethane aqueous dispersion with excellent sizing power can be obtained. . Glass fibers surface-treated, including coating them with a sizing agent according to the invention, are particularly transparent, have excellent abrasion resistance, flexibility, tensile strength and color stability, and can exhibit excellent adhesion to glass. In addition, lubricants used in combination include, for example, condensates of stearic acid, caprylic acid, or pelargonic acid with tetraethylenepentamine, ethylene oxide adducts of fatty acids, and emulsions of paraffin.As antistatic agents, , quaternary ammonium salts such as lauryltriethylammonium chloride, sulfonates or sulfates of octyltrimethylamine, inorganic salts such as lithium chloride and sodium chloride, nonionic salts such as polyoxyethylene oleate, polyoxyethylene alkyl ether, etc. An activator or the like can be used. Next, as a coupling agent, vinyl-tris(2-methoxyethoxy)silane, β-(3,
4-Epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- It may contain a single compound or a mixture of two or more selected from the group consisting of (aminoethyl)-γ-aminopropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane. The amount of the sizing agent, lubricant, antistatic agent, and silane coupling agent of the present invention is 2 to 20% by weight in terms of solid content, respectively.
0.05-1.5% by weight, 0.01-2% by weight, and 0.1-1.5% by weight are preferred. Next, the present invention will be explained by manufacturing examples and examples. Production Example 1 (Production A ₁ of unsaturated polyester polyol) 1.3 mol of butane-1,-3 diol and 1.0 mol of phthalic anhydride were reacted at 150 to 210°C for 10 hours in a nitrogen stream using P-toluenesulfonic acid as a catalyst. An unsaturated polyester polyol (A ₁ ) having an acid value of 4.03, a water content of 0.05%, and a hydroxyl value of 55.3 was produced. Production example 2 (Production A ₂ of unsaturated polyester polyol) Butane-1,-3 diol, pentane-1,-5
A 10:6:2:10:3 mole mixture of diol, hexane-1,-6 diol, phthalic anhydride, and adipic acid was heated at 150 to 210°C for 10 hours in a nitrogen stream using P-toluenesulfonic acid as a catalyst. Reacts, acid value 3.5,
An unsaturated polyester polyol (A ₂ ) having a water content of 0.08% and a hydroxyl value of 79.4 was produced. Production example 3 (Production of polyurethane aqueous dispersion B ₁ ) 100 parts of unsaturated polyester polyol A ₁ , PEG
No. 1000 (manufactured by Daiichi Kogyo Seiyaku K/K, polyethylene glycol molecular weight 1000) 20 parts, neopentyl glycol 5 parts, trimethylolpropane 5 parts,
4,4 dicyclohexylmethane diisocyanate
54 parts were reacted in 46 parts of toluene for 1 hour, and the remaining
A prepolymer with NCO: 1.67% was made. Next, 5.32 parts of a 40% aqueous solution of glycine soda was added,
After reacting at 35℃ for 30 minutes, add 270 parts of 40℃ warm water,
An aqueous polyurethane dispersion _B1 with a solids content of 40.5% was produced. Production example 4 (Production of polyurethane aqueous dispersion B ₂ ) 100 parts of unsaturated polyester polyol (A ₂ ),
50 parts of PEG No. 1540 (manufactured by Daiichi Kogyo Seiyaku K/K, polyethylene glycol molecular weight 1500), Uniol
DB-900 (Nippon Oil & Fats K/K Bisphenol A
propylene glycol adduct, molecular weight 916) 10
Part, Plaxel 303 (Daicel Chemical Industries K/K Polycaprolactone Polyol Molecular Weight 313) 2.7
Part, 1,6 hexamethylene diisocyanate 25.6
1 part was reacted in 47 parts of acetone at 55°C for 1 hour to produce a prepolymer with residual NCO: 0.97%. Next, add 0.34 parts of glycine and incubate at 35℃ for 30 minutes.
After reacting for a minute, 0.56 parts of 28% aqueous ammonia was added, followed by 284 parts of 40°C warm water to produce polyurethane aqueous dispersion _B2 with a solid content of 39.8%. Comparative Production Example 1 (Production C of polyurethane aqueous dispersion) The unsaturated polyester polyol A ₂ in Production Example 4 was replaced with Polylite ODX-688 (Dainippon Ink Chemical K/K Co., Ltd. saturated polyester polyol molecular weight
Polyurethane aqueous dispersion C with a solid content of 40.3% was produced in the same manner instead of (2000). Example 1 Polyurethane water dispersion B ₁ obtained in Production Example 3
50 parts by weight pelargonic acid and tetraethylenepentamine condensate
0.2 parts by weight lauryltrimethylammonium chloride
0.1 parts by weight γ-methacryloxypropyltrimethoxysilane 0.3 parts by weight Acetic acid Trace amount of water Remaining part 100 parts by weight A treatment solution having the above composition was prepared and applied to the glass fibers being spun using a coating device. Glass fibers are bundled into strands and wound into a cake. A certain amount of the glass fiber strand cake was wound up and dried with hot air at 110-120°C, and then the strands were pulled out and twisted into glass yarn, which was then woven into glass cloth. Impregnated with an unsaturated polyester resin consisting of 100 parts by weight of unsaturated polyester resin dissolved in styrene monomer, 55% by weight, 2 parts by weight of methyl ethyl ketone peroxide, 6% by weight, and 0.5 parts by weight of cobalt naphthenate, 12 sheets of this were laminated and heated at 40°C for 2 hours. A molded product _F1 was produced by curing and molding at 100°C for 2 hours. Example 2 Aqueous polyurethane dispersion prepared from the aqueous polyurethane dispersion B ₁ in Example 1 in Production Example 4
A molded product F ₂ was produced in the same manner by replacing B ₂ . Comparative Example 1 The aqueous polyurethane dispersion B ₁ in Example 1 was replaced with the aqueous polyurethane dispersion C produced in Comparative Production Example 1, and a molded product F ₃ was produced in the same manner. Example 3 Various cases using FRP F ₁ , F 2 , F 3 manufactured according to Examples 1, ₂ , and Comparative Example ₁ and glass cloth F ₄ (Comparative Example 2) that was deoiled after weaving. Performance tests were conducted. Table 1 shows the physical properties of FRP molded with unsaturated polyester resin without removing the sizing agent after weaving using the glass fiber sizing agent according to the present invention, and that of FRP molded after deoiling the sizing agent. As a comparative example, we demonstrated the physical properties of FRP using a sizing agent made from saturated polyester polyol. In addition, the weavability of each sizing agent and the physical properties of the cloth were shown. Table 1 shows that the glass fiber sizing agent of the present invention not only has excellent weaving properties, but surprisingly also has better adhesion to unsaturated polyester resin than the deoiled one, and also has boiling whitening resistance. I can confirm that it is good. Furthermore, since there is no need to remove oil, the time and energy required for oil removal are not required, and it was confirmed that the physical properties of FRP are improved because the glass fibers themselves do not deteriorate. 【table】

Claims (1)

[Claims] 1. When reacting a polyisocyanate with an unsaturated polyester polyol having a molecular weight of 300 to 5000, a polyethylene glycol having a molecular weight of 300 to 6000, and optionally a polyol containing a reactive hydrogen atom-containing chain extender and a crosslinking agent, A mainly cross-linked structure produced from a polyol and polyisocyanate in which the weight proportion of the unsaturated polyester polyol is 10 to 95% and the weight proportion of the polyethylene glycol is 5 to 50%, based on the total amount of polyol group-containing compounds in the polyol. When producing an aqueous polyurethane dispersion, a compound containing at least one hydrogen atom reactive with an isocyanate group and at least one anionic salt-like group or anionic salt-forming group is added to the prepolymer. A glass fiber sizing agent characterized in that the main film-forming component is an aqueous polyurethane dispersion which is added to the remaining isocyanate groups using an amount capable of reacting with the remaining isocyanate groups of 0.01 to 0.5% by weight.