JPS6031657B2 - Method for producing a corrosion-resistant multilayer molded body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention involves pressurizing and heating molding with an outer layer made of a gel-like prepreg obtained by the reaction of epoxy (meth)acrylate having a hydroxyl group and a polyisocyanate, and an inner layer made of an unsaturated polyester resin molding material. The present invention relates to a method for producing a corrosion-resistant multilayer molded article.

In recent years, in the molding of unsaturated polyester resins, heavy metal compounds such as magnesium oxide, which ionically coordinate to the carboxyl groups in the unsaturated polyesters, have been added to thicken the resin, making it non-tacky at room temperature, resulting in so-called sheet molding. Dengue compound (hereinafter abbreviated as SMC) has been developed and is used as a molding material.

SMC has little scattering of polymerizable monomers during molding processing, which has significantly improved the working environment, and it is also a high-efficiency product that has improved resin fluidity, formability, and curing properties. It is also a useful molding material. However, SMC molded products, such as chemical equipment and pollution control equipment, have inferior corrosion resistance compared to conventional hand lamp molded products, and as a result, the appearance and hardness of the molded products are not fully satisfied. ,. The present invention was completed as a result of repeated studies on bisphenol-based and polyphenol-based eboxy (meth)acrylate resins, and relates to a method for manufacturing a resin multilayer molded article that can solve the drawbacks of conventional SMC products.

The outer layer resin composition of the resin multilayer molded article in the present invention is composed of epoxy (meth)acrylate having two or more hydroxyl groups in the molecule, a polymerizable monomer, a radical polymerization initiator, and a polyester having two or more isocyanate groups. A fiber base material is impregnated with a blend containing socyanate as an essential component, and then aged at room temperature.

By aging, some of the hydroxyl groups in the epoxy (meth)acrylate react with the isocyanate groups to form a gel, forming Bripreg c. The epoxy (meth)acrylate in the prepreg c still has an unsaturated group in the molecule, and therefore the prepreg c is flexible as a whole, but the surface is in a non-adhesive state. The molded product obtained by curing this prepreg c has superior corrosion resistance compared to conventional SMC molded products containing metal oxides, and maintains its appearance and hardness for a long time even when immersed in a chemical solution. can be retained.

This is the feature of the method of the present invention.

That is, the present invention is a method for producing a corrosion-resistant multilayer molded article, which comprises laminating prepreg c, which forms an excellent corrosion-resistant layer, as an outer layer and conventional SMC or BMCd as an inner layer to a desired thickness and curing. Other features are prepreg c
When the outer layer material made of the material and the inner layer material made of SMC or BMCd are laminated and cured and molded by pressure and heating, there is no exchange of resin between the two layers, and a multilayer molded product corresponding to the laminated state can be obtained. Next, referring to the method for manufacturing the multilayer molded body, the non-adhesive sheet-like pre-reg c according to the present invention can be continuously manufactured using a normal SMC manufacturing apparatus.

Its structure is the same as when molding a corrosion-resistant molded product by the hand horizontal molding method.
Two-layer lamination is common, with the layer being a thicket layer and the reinforcing layer being conventional SMC, which uses chopped strand mat, roving cross mat, etc. as the fiber base material and reduces the amount of impregnated resin as much as possible. The fiber base material can be selected depending on the material. Typical examples of epoxy (meth)acrylates having two or more hydroxyl groups used in the present invention include reaction products of bisphenol diglycidyl ether and (meth)acrylic acid, polyphenol polyglycidyl ether and (meth) ) reaction product of acrylic acid, halogenated bisphenol diglycidyl ether and (
These include reaction products with meth)acrylic acid.

The most preferred polyisocyanate used in the present invention is polyallyl polyisocyanate (manufactured by Kasei Upjohn Co., Ltd., "PAPI ″), but there are also other active isocyanate groups such as tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, and glycerin triad or trimethylolpropane triad of these isocyanates. It has the following.

The vinyl monomer, that is, the polymerizable monomer used in the present invention is not particularly limited, and includes, for example, styrene, vinyltoluene, and vinyl.

It can be arbitrarily selected from rustyrene, t-butylsterene, methyl methacrylate, and the like. The usage ratio of epoxy (meth)acrylate having a hydroxyl group, vinyl monomer, and polyisocyanate is as follows:
If there are 2 hydroxyl groups in the meth)acrylate molecule, there are 3 or more isocyanate groups, and 3 or more hydroxyl groups.
In the case of 2 or more isocyanate groups, a polyisocyanate with 2 or more isocyanate groups is used, and hydroxyl group-containing epoxy (
meth)acrylate (molecular weight 500-4000) 75-
4 parts by weight to 25 to 6 parts by weight of vinyl monomer,
Polyisocyanate 1-1 cough protection or 2 before adduct
~8 parts by weight. When formulating resins, the presence of collected moisture and amino compounds promotes gelation of the resin. Examples of the radical polymerization initiator used in the present invention include cumene hydroperoxide, dicumyl oxide, penzoyl peroxide, t-butyl perbenzoate, cyclohexanone peroxide, and azobisisobutyronitrile. - Initiators for high temperatures are preferred.

Examples of the fiber base material include glass fibers, carbon fibers, metal fibers, natural fibers, and synthetic fibers such as vinylon, nylon, and oron, which can be selected as required.

The unsaturated polyester used in the present invention is not specified and can be obtained by an integrated reaction by adding unsaturated dihydrochloric acid, glycol, and, if necessary, a saturated polybasic acid.

For example, unsaturated dibasic acids include maleic anhydride, fumaric acid, and itaconic acid, glycol components include ethylene glycol, diethylene glycol, propylene glycol, bisphenol A, neobentyl glycol, and saturated polybasic acids. As the acid, phthalic anhydride, isophthalic acid, adipic acid, sebacic acid, tetrachrome phthalic anhydride, tetrabromo phthalic anhydride, etc. are used. The obtained unsaturated polyester is dissolved in the above-mentioned vinyl monomer, and then a radical polymerization initiator and, if necessary, a polymerization inhibitor are added and impregnated into a fiber matrix to form a sheet or bulk molding material. used. Next, examples of the present invention will be shown. Example 1 One molecule obtained by reacting polybisphenol A polyglycidyl ether and methacrylic acid in equivalent amounts has an average of 3.
Resin AI made by blending eboxy acrylate having two hydroxyl groups with 400 pp of hydroquinone equivalent as a polymerization inhibitor, 4% by weight of styrene monomer, and 0.1% HR of diethylamine hydrochloride as an esterification catalyst.
After adjusting the water content to 0.1% or less in advance, 1 part by weight of dicumyl peroxide as a radical polymerization initiator was dissolved in 0 parts by weight, and "PA" was further added as a non-tackifying agent.
6 parts by weight of PI'' (manufactured by Kasei Upjohn Co., Ltd.) was dissolved to prepare a resin compound.

Next, using general-purpose SMC manufacturing equipment, the above resin compound was applied to the lower surface of the film through a clearance of 0.17 thigh using a doctor blade through two layers of polyethylene film (upper and lower) (as a release film), and the line speed was 4. Moved to the / side of 4. 1 layer of glass surf ace mat for 30 minutes between the top and bottom polyethylene films,
Glass chopped strand mat #6 with 600 tano
The 001 layer was sandwiched between moving resins and compressed with a roller while being moved to form a sandwich to impregnate the resin.
The obtained sheet-like resin-impregnated material becomes a non-adhesive gel-like material in one minute at 25°C, and the release film can be easily peeled off.
It showed no stickiness. Glass content milk%, 3 at 25°C
It could be stored for more than several months. Hereinafter, this non-adhesive gel-like sheet-like resin-impregnated product will be referred to as B. Example 2 Hydroquinone was added as a polymerization inhibitor to epoxy methacrylate having an average of 4.4 hydroxyl groups in the molecule, which was obtained by reacting an equivalent amount of commercially available polybisphenol A polyglycidyl ether and methacrylic acid. Conversion 4
Molecule obtained by reacting equivalent amounts of novolak-type polyglycidyl ether and methacrylic acid with resin C, which is a mixture of HR, 40% by weight of styrene monomer, and 0.1% of triethylamine as an esterification catalyst. Average within 3.
Hyde as a polymerization inhibitor to epoxy methacrylate having 6 hydroxyl groups.

Quinone equivalent: 60 ■ Blood, styrene monomer 45% by weight, trisdimethylaminophenol as esterification catalyst 0
．． 2PHR is blended with resin D at a weight ratio of C:○ of 7:3, and after adjusting the moisture content to 0.1 or less in advance, dicumyl peroxa is added as a radical polymerization initiator. A resin was prepared by dissolving 1 part by weight of hydride, 3 parts by weight of "PAPI" (manufactured by Kasei Upjohn Co., Ltd.) as a non-adhesive agent, and 1 part by weight of "Isocyanate 14 Maru" (manufactured by Kasei Upjohn Co., Ltd.) based on liquid diphenylmethane diisocyanate. It was made into a compound.

Next, using a general-purpose SMC manufacturing apparatus, the above resin compound was poured between two layers of glass chopped strand mat #450 (upper and lower) via a polyethylene release film in the same manner as in Example 1 to form a sheet. This sheet-like resin soaked product became gel-like after one hour at room temperature, and the release film was easily peelable and non-adhesive. The obtained sheet with a glass content of 33% is called sheet E. Comparative Example 1 Approximately 25% of the hydroxyl groups in Resin C obtained in Example 2
was reacted with phthalic anhydride to obtain a resin with an acid value of 30.

2 parts by weight of magnesium oxide was blended with 10 parts by weight of this resin, and the mixture was left at 5 poise for 3 days to increase the viscosity to 230,000 poise. This resin liquid is abbreviated as RE-1. Resin compositions shown in Table 1 were produced using RE-1.・ However, X of filler
Depending on the type, the resin composition is indicated as RE-1 (charcoal).

The resin formulations shown in Table 1 were aged at 50°C for 2 days to produce sheet molding compounds RE-1 (charcoal), RE
-1 (silicy), RE-1 (clay), and RE-1 (mica) were manufactured.

Example 3 A two-layer molded product with a thickness of 4 layers (200 skins/layer x 200 skins/
m), and was compressed and hardened for 5 minutes under molding conditions of 13 pi○ and 200 kg/yen.

Using a running tester, this cured product was subjected to a chemical liquid test using a single-sided immersion groove method. The test results are shown in Table 2. Table 2 Example 4 Using Sheet B shown in Example 1 and Gorakmat ML-210 shown in Example 3, Sheet B with a thickness of 2 ribs was made into an outer layer on both sides, and a 1'' sheet with a thickness of 8 ribs was used. Rack mat M Yamaichi 21
Sheet B has a 3-layer laminated structure with 0 as an intermediate layer, and sheet B forms outer layers on both sides. Of the two glass fiber base layers that make up sheet B, that is, the surfacing mat layer and the chopped strand mat layer, the surfacing mat The layer faces the outside of the laminated construction of Sheet B/Rigolakmat M Yamaichi 210/Sheet B, while the chopped strand mat layer is the IJ Gorackumat M Yamaichi 21 layer of the middle layer.
It was placed facing 0.

Sandwich-like thickness 12 mm circular flange 180 mm
It was compressed for 15 minutes at k9/ground and 12chi0 to form a molded body.
When this molded product was soaked in 35% sulfuric acid at 70° C. for one month, it retained its luster with only yellowing and had a Barcoll hardness retention rate of 99%, no different from conventional hand-shaped molded products. Note that when molding was performed using only sheet B having a thickness of approximately 12 feet, bulges occurred inside and a good molded product could not be obtained. Example 5 Sheet B of Example 1 and SMC" Rigoratsu Kumat M Yamaichi 21 (manufactured by Showa Kobunshi ■) using iso-unsaturated polyester resin were used to prepare sheet B of 2 skin thickness and 3.5 ribs. A two-layer molded body was obtained from the thick SMC in the same manner as in Comparative Example 1.

The properties of the molded product are: bending strength 18-24k9/m2, bending elastic modulus 950-1000kg/image, tensile strength 11-1
2k9/fence, tensile modulus of elasticity 750-900k9/sea, Barcoal hardness 50-53. In addition, the corrosion-resistant surface of this molded article was soaked for 6 months in the same manner as in Comparative Example 1, and a corrosion resistance test was conducted.

The results are shown in Table 3. 3. Both exhibited corrosion resistance comparable to that of hand-laid glass fiber reinforcement.

Claims (1)

[Claims] 1 Regarding the number x of hydroxyl groups in one molecule of epoxy (meth)acrylate a having a hydroxyl group, and the number y of isocyanate groups in one molecule of polyisocyanate b,
A mixture obtained by adding a vinyl monomer and a radical polymerization initiator to a and b having the relationships of x≧2, y≧2, and x+y≧5 is impregnated into a fiber base material, and a mixture obtained by reversing a and b is obtained. Corrosion resistance characterized by laminating a non-adhesive prepreg c on the surface of a sheet-like or bulk-like molding material d containing a polymerizable curable unsaturated polyester resin, and then pressurizing and heating using a mold. A method for producing a multilayer molded body. 2. The method for producing a corrosion-resistant multilayer molded article according to claim 1, wherein the epoxy (meth)acrylate a is a reaction product of polybisphenol polyglycidyl ether and (meth)acrylic acid. 3. The method for producing a corrosion-resistant multilayer molded article according to claim 1, wherein the epoxy (meth)acrylate a is a reaction product of polyphenol polyglycidyl ether and (meth)acrylic acid. 4. The method for producing a corrosion-resistant multilayer molded article according to claim 1, wherein the epoxy (meth)acrylate a is a reaction product of polyhalogenated bisphenol polyglycidyl ether and (meth)acrylic acid. 5. The method for producing a corrosion-resistant multilayer molded article according to claim 1, wherein the polyisocyanate b is a polyallyl polyisocyanate having an average of 2 to 4 isocyanate groups in the molecule.