JPS63227864A - 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. ) It particularly relates to binders for glass fibers 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.

Film forming agents conventionally used for glass fibers include resin emulsifiers 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 which 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 thereto.

[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 dissolve 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 conventional problems,
The styrene content as a film-forming substance in the binder is 1
0-50% by weight, acrylic acid ester content 10-50
By using a binder containing styrene-vinyl acetate-acrylic acid ester terpolymer emulsion as a film-forming substance in a weight percent range as a sizing agent for glass fibers, the water resistance and boiling resistance of FRP using the glass fibers can be improved. I found that it can be improved.

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

Solid content lubricant 0. O1~0
．． 5 Antistatic agent 0.03-1.0 Silane coupling agent 0. O1-4.0 Here, the styrene content of the styrene-vinyl acetate-acrylic ester copolymer is 10-50% by weight, and the acrylic ester content is 1! ! It is 10 to 50% by weight.

If the styrene content is less than 10% by weight, preferred water resistance and boiling resistance cannot be obtained, and if the styrene content is more than 50% by weight, the glass transition temperature Tg of the styrene-vinyl acetate-acrylic acid ester terpolymer film is high. The glass fibers coated with this coating tend to become fluffy. If the acrylic ester content is less than 10% by weight, preferred water resistance and boiling resistance cannot be obtained, and if the acrylic ester content is 50% by weight or more, the Tg of the styrene-vinyl acetate-acrylic ester terpolymer film is low. The glass fibers coated with it become sticky, which impairs workability and causes undesirable properties in the impregnating properties of the matrix resin.

Styrene-vinyl acetate in the binder of the present invention
Although the effect of the acrylic acid ester terpolymer emulsion is not clear, the styrene component of the styrene-vinyl acetate-acrylic ester terpolymer film formed on the glass fiber surface interacts with the glass fiber and matrix in FRP. F provides hydrophobicity to the resin interface and improves compatibility with unsaturated polyester resin.
This is thought to be the cause of improving the water resistance and boiling resistance of RP. 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 and cutting.The fuzz inhibits the impregnation of unsaturated polyester resin, causing blisters and other problems when boiling FRP molded products. The vinyl acetate component maintains a suitable Tg in the terpolymer film and is rubber-like, giving a film with good bending resistance and reducing fuzz during processing. The acrylic ester component improves compatibility and adhesion with unsaturated polyester resin,
It is thought to improve the water resistance and boiling resistance of FRP.

In the present invention, lubricants include aliphatic hydrocarbons such as paraffin wax, 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. , dicarboxylic acid, or oxycarboxylic acid in combination with a monohydric alcohol such as butanol or octatool, or a polyhydric alcohol such as ethylene gelicol, glycerin, pentaerythritol, or sorbitol, etc. 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 can be alkyltrimethylammonium.

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-glycidoxypropyltrimethoxysilane, Epoxy silanes such as methoxysilane, mercapto silanes such as γ-mercaptopropyltrimethoxysilane, etc. 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 (Example 1) Fatty acid amide O, OS No. 4
grade ammonium salt 0.11N acetic acid (P
(For H adjustment) Small amount of ion-exchanged water
75, 55 total too. o Weight % The above binder was applied to glass fibers immediately after spinning using a roller coater, and after winding them up as a glass fiber strand, moisture was removed under predetermined drying conditions. The glass fiber strands were cut into 25mm pieces, and an SMC sheet was made with a general resin compound containing unsaturated polyester resin and fillers such as calcium carbonate and aluminum hydroxide so that the glass fiber content was 25% by weight. Created.

The SMC sheet aged at 40°C for 24 hours was then pressed at a mold temperature of 140°C and a press pressure of 100kg/C♂.
An SMC molded plate with a thickness of 3 m was produced. 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 240 hours of boiling.

(Example 2) (Styrene: Vinyl acetate acrylate: 1:8:I
.

Solid content 39%) Fatty acid amide 0.05 quaternary ammonium salt 0.11N acetic acid (PH
(im maintenance) a small amount of ion-exchanged water
73.25 total 100, 0 weight

(Example 3) Styrene-vinyl acetate-acrylic 23.8 weight x acid ester terpolymer emulsion (styrene: vinegar and acrylic acid ester = 2:5:3
.

Solid content 42%) Fatty acid amide 0.05 4th
grade ammonium salt 0.1γ-methacryloxypropyl 1.0 trimethoxysilane IN acetic acid (for pH adjustment) Small amount of ion-exchanged water 75.05 total to
o, o weight

(Example 4) (Styrene: Vinyl acetate acrylate = 2:3:5
゜Solid content 42%) Fatty acid amide 0.05 Quaternary ammonium salt 0.1 γ-methacryloxypropyl 1.0 Trimethoxysilane 1N acetic acid (for pH adjustment) Small amount of ion exchange water 75.05 gtoo, o
% 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 blistering occurred even after 240 hours of immersion.

(Comparative Example 1) Fatty acid amide 0.05 quaternary ammonium salt 0.11N acetic acid (for pH adjustment) Small amount of ion-exchanged water
75.55 total 100.0% 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, blisters were formed after immersion for 120 hours.

(Comparative Example 2) Fatty acid amide 0.05 Quaternary ammonium salt 0.17-methacryloxypropyl 1.0 Trimethoxysilane IN acetic acid (for pH adjustment) Small amount of ion-exchanged water 78.85 Glass spun with the above binder A boiling test was conducted using the fibers in the same manner as in Example 1, and as a result, blisters were generated after 240 hours of immersion.

(Comparative Example 3) Fatty acid amide 0.05 quaternary ammonium salt 0.11N acetic acid (for pH adjustment) Small amount of ion-exchanged water
78.85 total 100.0% by weight Glass fibers spun with the above binder were subjected to a boiling test in the same manner as in Example 1, and as a result, blisters were generated after 240 hours of immersion.

(Comparative Example 4) Polyvinyl acetate emulsion 20.0 weight ff1
X (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-exchanged 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, blisters were generated after immersion for 100 hours.

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

Claims (1)

[Claims] A binder for glass fibers comprising a film-forming substance, a lubricant, an antistatic agent, and a coupling agent, wherein the film-forming substance has a styrene content of 10 to 50% by weight, an acrylic ester content of 10 to 50% by weight, and a styrene content. A binder for glass fibers, comprising a styrene-vinyl acetate-acrylic ester terpolymer emulsion in which the total content of and acrylic ester does not exceed 70% by weight.