JPS63227865A - Binder for glass fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention is directed to a glass fiber reinforced thermosetting resin molded article (hereinafter referred to as FRP) having good water resistance and boiling resistance and having unsaturated polyester resin as a matrix resin. ) In particular, it relates to glass fiber inders used in SMC.

[Prior Art] Various surface treatments have been carried out on inorganic substances in order to promote the bonding between inorganic substances and organic substances.
In the glass fiber industry, binders, which are surface treatments for glass fibers, have played an important role in the field of FRP, which is a combination of glass fibers and thermosetting resins.

Glass fiber binders for FRP generally consist of film-forming agents, lubricants, antistatic agents, and silane coupling agents, and are applied to the glass fiber surface with a roller coater or belt-type applicator or by spraying immediately after the glass fibers are spun. be done. Its functions are mainly to improve workability in the steps leading up to making glass fiber products, to improve processability in various FRP molding methods, and to improve properties of FRP molded products.

Conventionally, film forming agents used for glass fibers include resin emulsions such as polyvinyl acetate resin, ethylene-vinyl acetate copolymer resin, polyester resin, epoxy resin, polyacrylate resin, and polyurethane resin. These are selectively used depending on the purpose, and for FRP that requires water resistance and boiling resistance, metal ion cross-linked polyester resin as described in JP-A-51-82095, etc. Film-forming agents have been used that are formed by emulsions of polyvinyl acetate resins or ethylene-vinyl acetate copolymer resins, or by adding emulsions such as polyester resins and/or epoxy resins to these emulsions.

[Problems to be Solved by the Invention] However, in the above-mentioned conventional binder for glass fibers, if FRP made of glass fibers and unsaturated polyester resin is used in water or boiling water for a long time, water will be released into the reinforcing glass. There was a problem that it invaded the interface of fibers and caused blisters and blisters.

[Means for Solving the Problems] As a result of repeated studies to solve the above problems, the present inventors have developed a styrene-vinyl acetate copolymer having a styrene content of 10 to 50% as a film forming agent for the binder. It has been found that by using a binder containing an emulsion as a film forming agent as a sizing agent for glass fibers, the water resistance and boiling resistance of FRP using the glass fibers can be improved.

A suitable composition of the binder of the present invention is as follows.

Solid content styrene-vinyl acetate copolymer emulsion 5.0-15.0% by weight Lubricant 0.01-0.5 Antistatic agent 0.03-1.0 Silane coupling agent 0.01-4. 0 Here, the styrene content of the styrene-vinyl acetate copolymer is 10 to 50% by weight. If the styrene content is less than 10%, desirable water resistance and boiling resistance cannot be obtained, and if the styrene content is more than 50%, the Tg of the styrene-vinyl acetate copolymer film is high, making the glass fiber coated with it easy to become fluffy. .

Although the effect of the styrene-vinyl acetate copolymer emulsion in the binder of the present invention is not clear, the styrene component of the styrene-vinyl acetate copolymer film formed on the glass fiber surface is hydrophobic at the glass fiber interface in FRP. It is thought that the reason for improving the water resistance and boiling resistance of FRP is to improve the compatibility with the unsaturated polyester resin. The styrene component alone has a high Tg and is hard and brittle, so it tends to cause fuzz when processing glass fiber strands such as roving or cutting, and the fuzz inhibits the impregnation of unsaturated polyester resin, causing blistering in FRP molded products. Promotes blistering and blistering when FRP molded products are boiled. By copolymerizing styrene with vinyl acetate, which has a low Tg and good adhesive properties, it is possible to reduce fuzz during processing, and to create a film that is more uniform in composition than simply using a mixed emulsion of polystyrene and polyvinyl acetate. This is thought to have made it possible to prevent blisters and blisters. In the present invention, lubricants include aliphatic hydrocarbons such as paraffin fuchs, aliphatic alcohols such as lauryl alcohol and stearyl alcohol, fatty acid amides such as palmitic acid amide and stearic acid amide, and saturated and unsaturated higher monocarboxylic acids. ,
Higher fatty acid esters made by combining dicarboxylic acids and oxycarboxylic acids with monohydric alcohols such as butanol and octatool, and polyhydric alcohols such as ethylene glycol, glycerin, pentaerythritol, and sorbitol can be used.

In addition, as antistatic agents, inorganic substances such as lithium chloride,
Organic chlorides of metals such as aluminum chloride, triethanolamine carboxylates, sulfonates, sulfate ester salts, phosphate ester salts, ethylene oxide adducts of alkylamines, imidacillin, amine amides from higher fatty acids and lower polyamines. and its salts, quaternary ammonium salts such as alkyltrimethylammonium salts, etc. can be used.

Furthermore, as the silane coupling agent, vinyl silanes such as vinyltrichlorosilane, vinyltris-β-methoxyethoxysilane, vinyltriethoxysilane,
Amino silanes such as γ-aminopropyltriethoxysilane, methacryloxy silanes such as γ-methacryloxypropyltrimethoxysilane, β-3,4-epoxycyclohexylethyltrimethoxysilane, γ-
Epoxy silanes such as glycidoxypropyltrimethoxysilane, mercapto silanes such as γ-mercaptopropyltrimethoxysilane, and the like can be used.

The binder for glass fibers of the present invention is mainly used for FRP, especially S
Used in MC to improve its water resistance and boiling resistance.

[Example 1] Fatty acid amide O, OS quaternary ammonium salt 0.11-methacryloxypropyl 1.0 trimethoxysilane IN acetic acid (for pH adjustment) Small amount of ion-exchanged water 7B, 85° 1
00.0-x The above-mentioned binder was applied to glass fibers immediately after spinning using a roller coater, the fibers were wound up as a glass fiber strand, and then water was removed under predetermined drying conditions. The glass fiber strands were cut to 25+u+, and an SMC sheet was produced using a general resin compound containing an unsaturated polyester resin and fillers such as calcium carbonate and aluminum hydroxide so that the glass fiber content was 25% by weight.

The SMC sheet after aging at 40°C was pressed to a thickness of 3 at a mold temperature of 140°C and a press pressure of 100 kg/CI.
■An SMC molded plate of the intestine was prepared. After cutting out the SMC molded plate into a predetermined size, it was immersed in boiling ion-exchanged water and the time until blistering was measured. No blistering occurred even after 220 hours of boiling.

(Example 2) Fatty acid amide 0.05 Quaternary ammonium salt 0.17-methacryloxypropyl 1. Otrimethoxysilane IN acetic acid (for pH adjustment) Small amount of ion-exchanged water 78.85 total 10
0.0% by weight Glass fibers spun with the above binder were subjected to a boiling test in the same manner as in Example 1. As a result, almost no blistering occurred even after 220 hours of immersion.

(Example 3) Styrene-acetic acid 20.0 weight x vinyl copolymer emulsion (styrene content 130%, solid content 50%) fatty acid amide
0.05 Quaternary ammonium salt 0.17-methacryloxypropyl
1.0 trimethoxysilane IN acetic acid (for pH adjustment) Small amount of ion exchange water 78.85 total to
o, o% by weight A boiling test was conducted in the same manner as in Example 1 using the glass fibers spun with the above binder, and as a result, almost no blisters were formed even after immersion for 220 hours.

(Example 4) Fatty acid amide θ,05 Quaternary ammonium salt 0.15 γ-methacryloxypropyl 1.0 Trimethoxysilane IN acetic acid (for PH adjustment) Small amount of ion-exchanged water 78.80! 1
00.0% A boiling test was conducted in the same manner as in Example 1 using the glass fibers spun with the above binder. As a result, almost no blisters were formed even after immersion for 200 hours.

Here, in order to suppress the generation of static electricity, the amount of quaternary ammonium salt as an antistatic agent was increased.

(Comparative Example 1) Polyvinyl acetate emulsion 20.0% by weight (
Solid content 50%) Fatty acid amide 0.05 4th
grade ammonium salt 0.11N acetic acid (PH
(For adjustment) Small amount of ion-exchanged water
78.85 total, o weight

The results of Examples and Comparative Examples are summarized in Table 1.

(Comparative Example 2) Polyvinyl acetate emulsion IQ, 5mfi%
(Solid content 50%) Polystyrene emulsion 4.7 (Solid content 43%) Fatty acid amide 0.04 Quaternary ammonium salt 0.08 γ-methacryloxypropyl 0.75 Trimethoxysilane IN acetic acid (for pH adjustment) Small amount ion exchange Water 83.93 A boiling test was conducted in the same manner as in Example 1 using glass fibers spun with the above binder. As a result, blisters were generated after 80 hours of immersion.

(Comparative Example 3) Polystyrene emulsion 17.4% by weight (
Solid content 43%) Fatty acid amide 0.04 Quaternary ammonium salt 0. I2γ-methacryloxypropyl 0.75 trimethoxysilane IN acetic acid (for pH adjustment) Small amount of ion-exchanged water 81.69 total to
o, o% by weight A boiling test was conducted in the same manner as in Example 1 using the glass fibers spun with the above binder, and as a result, blisters were generated after immersion for 150 hours.

(Comparative Example 4) Styrene-acetic acid 20.0 weight x vinyl coelectronic emulsion (styrene content 70%, solid content 50x) fatty acid amide
0.05 Quaternary ammonium salt 0.15 γ-methacryloxypropyl
1.0 trimethoxysilane IN acetic acid (for pH adjustment) Small amount of ion exchange water 78.80 total 1
00.0 weight

The results of Examples and Comparative Examples are summarized in Table 1.

Claims (1)

[Claims] In a binder for glass fibers comprising a film forming agent, a lubricant, a coupling agent, and an antistatic agent, the film forming agent is an emulsion of a styrene-vinyl acetate copolymer having a styrene content of 10 to 50% by weight. Characteristic binder for glass fiber.