JPS6112934B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing glass fiber reinforced plastics (FRP). FRP is a composite material that uses glass fiber as a reinforcing material and resin as a matrix, and unsaturated polyester resin is usually used as the resin. The forms of glass fiber used as reinforcing materials include strand, chopped strand, chopped strand pine, surf-es pine, swirl pine,
Roving, glass cloth, etc. are available, and reinforcing materials are selected depending on the FRP molding method. In the production of FRP that uses pine, the pine itself becomes hard and soft depending on the type and amount of binder resin used in the production of pine.
It is known that in FRP production, it changes the compatibility with the matrix resin and the flow state of glass fibers, greatly affecting workability and physical properties of FRP products. Conventionally, most resins for FRP are unsaturated polyester resins that use styrene as a crosslinking agent, but the use of styrene causes a significant odor due to volatilization.
To combat this problem, unsaturated polyester resins that use allyl monomers as crosslinking agents instead of styrene are gradually attracting attention because they do not have bad odors and have good heat resistance. However, when using an unsaturated polyester resin with an allyl monomer as a crosslinking agent, the moldability is extremely poor when conventional commercially available glass fiber mat is used as a reinforcing material, and this has a large impact on the performance of FRP products. Unfavorable results occurred as an FRP product. This is considered to be due to a problem in the compatibility between the pine binder and the allyl monomer. The present inventors have conducted various studies on the bonding resin used in the production of glass fiber mat, which is a reinforcing material, when using an unsaturated polyester resin containing allyl monomers as a matrix resin for FRP. We found that polyester resin was suitable and filed a separate application, but when using this mat, we found that epoxy acrylate resin containing allyl monomers gave favorable results in terms of compatibility with mat and moldability, and that FRP The present invention was achieved by discovering that unprecedented good results can be obtained in terms of physical properties as a product. That is, the present invention provides a glass fiber-reinforced plastic characterized in that a glass fiber mat formed by adhesion using a terephthalic acid-based unsaturated polyester resin as a binder is used as a reinforcing material, and an epoxy acrylate resin containing an allyl monomer is used as a matrix. This is the manufacturing method of The reinforcing material of the present invention, the mat, is manufactured by a method usually called a dry method, in which glass fibers such as monofilament, strand, chopped strand, etc. are heated and fused with powder of terephthalic acid-based unsaturated polyester resin. used. The terephthalic acid-based unsaturated polyester resin is a dehydrated condensate of a mixed acid of terephthalic acid and an unsaturated acid such as maleic acid, maleic anhydride, fumaric acid, or itaconic acid and an equivalent amount of neopentyl glycol, and has a softening point of 80°C. Preferably, the temperature is in the range of ~120°C. The molar ratio of terephthalic acid to the unsaturated acid in the polymer is suitably in the range of 1:1 to 2. The amount of binder in the mat is usually in the range of 4 to 10% by weight. The allyl monomer of the present invention is a polybasic acid allyl ester having two or more allyl groups in the molecule, such as diallyl (ortho, iso, tere)phthalate, diallyl tetrahydrophthalate, triallyl trimellitate, isocyanuric acid, etc. Examples include triallyl acid, diallyl maleate, diallyl fumarate, and the like. The epoxy acrylate resin of the present invention is obtained by reacting an epoxy resin with (meth)acrylic acid, and as the epoxy resin, commonly used epoxy resins such as bisphenol type or novolak type epoxy resins are used. The mixing ratio of allyl monomer and epoxy acrylate resin is usually such that the allyl monomer is
A range of 10 to 50% by weight is suitable. Further, in order to adjust the viscosity of the resin, other types of vinyl monomers may be mixed in an amount of 30% by weight or less based on the total monomers. In addition, additives commonly used in the technical field, such as fillers, colorants, mold release agents,
It is free to add stabilizers, flame retardants, ultraviolet absorbers, etc. The amount of reinforcing material in the FRP of the present invention varies depending on its intended use, but typically 10 to 80% by weight of reinforcing material.
is appropriate. Methods for curing the resin of the present invention include room temperature curing using a peroxide and an accelerator, heating curing using a peroxide,
Curing methods include curing using a photosensitizer and ultraviolet irradiation, and curing using electron beam irradiation, and the method is selected as appropriate depending on the application. The present invention will be explained below with reference to Examples. In addition, in each example, parts and % are parts by weight, respectively.
Indicates weight %. Examples 1 to 3, Comparative Example 1 1 mol of terephthalic acid and 1 mol of fumaric acid as binders
polyester (binder (A)) with acid value 25, degree of unsaturation 2.4, softening point 90°C obtained from 2.1 moles of neopentyl glycol, 1 mole of terephthalic acid, 2 moles of fumaric acid and 3.2 moles of neopentyl glycol. The resulting polyester (binder (B)) with an acid value of 30, unsaturation degree of 1.6, and a softening point of 85°C, and an acid value of 20 obtained from 1 mol of terephthalic acid, 1 mol of maleic anhydride, and 2.1 mol of neopentyl glycol. Unsaturation degree 2.4,
Using polyester (binder (C)) with a softening point of 85℃,
Silane-treated glass chopped strands with a cutting length of 50 mm were stacked on a flat surface so that the weight was 450 g per 1 m ² and heated to 120°C, and each of the above binders (A) to (C) was added. Spread the powder evenly and add 5% binder.
(3 types) of pine containing the following were produced. To each of the above mats, 6% cobalt octylate was added to 100 parts of a resin solution consisting of 40% diallyl orthophthalate monomer, bisphenol A system with an epoxy equivalent of 187, and 60% epoxy acrylate resin made by reacting an epoxy resin with an equivalent amount of methacrylic acid. Part 1,
Two parts of t-butyl perbenzoate were added, and the resin solution was used to prepare a 3 mm thick laminate with a glass content of 30% by the hand drop method. For comparison, a laminate was prepared in the same manner as above using a commercially available pine (trade name: "ECM450-193" by Central Glass Co., Ltd.). The obtained laminate was subjected to physical property tests according to JISK6919, and the results are shown in Table 1.

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Claims (1)

[Claims] 1. A method for producing glass fiber-reinforced plastics, characterized in that a glass fiber mat formed by adhesion using a terephthalic acid-based unsaturated polyester resin as a binder is used as a reinforcing material, and an epoxy acrylate resin containing an allyl monomer is used as a matrix. .