JPS63227873A - 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 uses a glass fiber reinforced thermosetting resin molded article (hereinafter referred to as FRP) having good water resistance and boiling resistance and having an 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 a film forming agent, lubricant, antistatic agent, silanka, and bubbling agent, and are applied to the surface of the glass fibers immediately after spinning the glass fibers using a roller coater, belt-type applicator, or spraying. be done. Its functions are mainly to improve workability in the process of making glass fiber products, and to improve the workability of various FRP products.
The aim is to improve the processability of the molding method and improve the characteristics 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. A film-forming agent has been used which is a single emulsion of a polyvinyl acetate resin or an ethylene-vinyl acetate copolymer resin, or a film-forming agent prepared by adding an emulsion such as a polyester resin or/and an epoxy resin to the emulsion.

[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, we found that glass fibers were used as binders containing a mixed emulsion of ethylene-vinyl acetate coelectrolyte and polystyrene as a film-forming substance in the binder. It has been found that by using the glass fiber as a sizing agent, the water resistance and boiling resistance of FRP using the glass fiber can be improved.

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

Solid content 1 degree polystyrene emulsion 1.0-5.0 Lubricant 0.01-0.5 Antistatic agent 0. o3~i,.

Silane coupling agent 0.01 to 4.0 Although the effect of the mixed emulsion of ethylene 7-vinyl acetate copolymer and polystyrene in the binder of the present invention is not clear, the polystyrene film formed on the surface of the glass fiber is It is thought that imparting hydrophobicity to the glass fiber interface and improving compatibility with the unsaturated polyester resin of the matrix is the reason for improving the water resistance and boiling resistance of FRP. The function of ethylene-vinyl acetate copolymer is that polystyrene film has a high Tg and is hard and brittle, so it tends to become fluffy when glass fiber strands are processed by roving, cutting, etc., and the fluff inhibits impregnation with unsaturated polyester resin. However, since it promotes blistering or blistering in the molded product, it is thought that this is to be prevented, that is, to prevent blistering or blistering that occurs due to processing of glass fiber strands. Here, the ethylene component is 30% as an ethylene-vinyl acetate copolymer.
If more than % by weight is used, the glass fiber strands will become sticky, resulting in poor workability, which is not preferable.

In addition, the mixing ratio of the mixed emulsion of ethylene-vinyl acetate copolymer and polystyrene is limited to between 9:1 and 2:3, because if the ratio of polystyrene is less than 9:1, water resistance and boiling resistance This is because the improvement effect is small, and if the ratio of polystyrene exceeds 2=3, the Tg of the mixed emulsion film becomes high, hard < brittle, and fluffing tends to occur during processing of glass fiber strands. Considering the properties of the polystyrene emulsion, it is preferable to combine it with a film forming agent that has a low Tg and good compatibility with the styrene film.

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, oxycarboxylic acid and m-alcohols such as butanol and octatool, higher fatty acid esters formed by combining polyhydric alcohols such as ethylene glycol, glycerin, pentaerythritol, and 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, 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 glindoxypropyltrimethoxysilane, 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 0.05 quaternary ammonium salt 0.11N acetic acid (for pH adjustment) Small amount of ion-exchanged water
80.85M 100.0% The above binder was applied to glass fibers immediately after spinning using a roller tool, and after winding them up as a glass fiber strand, water was removed under predetermined drying conditions. The glass fiber strands were cut into 25 mm lengths, and SMC sheets were produced using a general resin compound containing unsaturated polyester, calcium carbonate, aluminum hydroxide, etc. so that the glass fiber content was 25% by weight. The S after aging
An SMC molded plate with a thickness of 3 mm was produced using a press using the MC sheet at a mold temperature of 140° C. and a press pressure of 100 kg/C♂. After cutting the SMC molded plate into a predetermined size, it was immersed in boiling ion-exchanged water and the time until blisters were measured was measured. Even after 200 hours of immersion, almost no blisters were formed.

(Example 2) Fatty acid amide 0.05 Quaternary ammonium salt 0.11-methacryloxypropyl! ,0 ion exchange water
79.35 total 100.0!
ji% Using the glass fibers spun with the above binder, a boiling test was conducted in the same manner as in Example 1. As a result, almost no blisters were formed even after immersion for 200 hours.

(Comparative Example 1) Fatty acid amide 0,05 quaternary ammonium salt o, i1N acetic acid (PH
(For adjustment) Small amount of ion-exchanged water
78.85 ro ioo, o % A boiling test was conducted in the same manner as in Example 1 using glass fibers spun with the above binder, and as a result, blisters were formed even after immersion for 150 hours.

(Comparative Example 2) Fatty acid amide 0.05 No. 4
grade ammonium salt 0.11N acetic acid (PH
(For adjustment) Small amount of ion-exchanged water
80.85 total ioo, o weight

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

Claims (1)

[Claims] In a binder for glass fibers containing a film-forming substance, a lubricant, a coupling agent, and an antistatic agent,
The film-forming material is an emulsion in which an ethylene-vinyl acetate copolymer having an ethylene component of 30% by weight or less and polystyrene are mixed at a solid content mixing ratio of 9:1 to 2:3. Binder for textiles.