JPS60137631A - Preparation of colored frp - Google Patents

Abstract

PURPOSE:To obtain gel coating excellent in weather resistance, boiling resistance and appearance, etc. by using specified side chain combined polymer containing color agent as the gel coating of a reinforced plastic molded item. CONSTITUTION:Color agent B (titanium white etc.) is added to side chain unsaturated combined polymer A having (meth)acryloyl group (such as a polymer in the formula) etc. and this mixture is used as gel coating that forms the surface layer of a reinforced plastic molded item to obtain the gel coating film having widely improved in physical property.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for producing a so-called gel coat for the purpose of surface coloring and protection.

Background of the Invention When molding FRP, especially at room temperature or medium temperature, by hand lay-up, spray-up, cold press, etc., a colored resin layer called gel coat, which does not contain any reinforcing material, is first formed on the mold. Lamination is carried out using reinforcing material and resin from above.

Therefore, as an FRP molded product, gel coat not only affects the finished appearance, but also plays a role in responding to changes in external conditions.
For example, in bathtubs and the like, it acts as a surface film that comes in contact with hot water, and it is no exaggeration to say that the warpage properties not only affect the appearance but also the commercial value of FRP products.

Conventionally, various polyester resins have been used for this gel coat depending on the purpose. ffp-)h Types that use phthalic anhydride as the modified acid are suitable for general use, exhibiting reasonable physical properties, and for applications that require low cost. In the field where isophthalic acid or terephthalic acid is used as a modified acid
Alternatively, a polyester resin having a bisphenol structure may be used.

However, the quality of the gel coat is still not at a satisfactory stage.

For example, there is a constant demand for a gel coat with better weather resistance for outdoor FRPK, and for bathtubs, there is a constant demand for better appearance and improved boiling resistance.

Summary of the Invention The present inventors have focused on improving the quality of FRP gel coat.
We have been conducting research for some time, and we have found that specific bonds that have an acryloyl group or methacryloyl group in the side chain via a urethane bond and are easily hydrolyzed into the main chain, such as ester bonds,
By adding a coloring agent to a side chain, unsaturated bond-type polymer that does not contain aliphatic ether bonds, and using it in the gel coat that forms the surface layer of reinforced plastic molded products, it is better than the conventional type using unsaturated polyester resin. The present invention was able to complete the present invention by discovering that physical properties can be greatly improved by using a radical-curable novel compound having an acryloyl group or a methacryloyl group in the side chain, for example, as shown in the following formula. It consists of using resin as a gel coat.

(In the formula, R0 is -CH1 or -H) Mer (hereinafter simply referred to as unsaturated polymer) is a polymer whose main chain has a hydroxyl group in the side chain obtained by polymerization of vinyl hexamer, and it cannot be hydrolyzed. It is a type that does not contain sensitive specific bonds, and is not an oligomer or propolymer like conventional radical-curable resins, but has a molecular weight of approximately 70.0.
Since it is a polymer of 00 or more, it has the advantage of less deterioration of physical properties due to deterioration.

The unsaturated polymer used in the present invention is obtained by synthesizing (a) a polymer having a Pjr desiccant group, and adding (b) 1 mole of diincyanate and an unsaturated alcohol having an acryloyl group or a methacryloyl group and a hydroxyl group. 1
It is obtained by reacting the remaining isocyanate groups with an unsaturated incyanate having an acryloyl group or a methacryloyl group.

Although there are no public funds that place particular restrictions on the vinyl nitrate that constitutes the unsaturated polymer, it is required to have water resistance and weather-resistant hardness because of its role as a gel coat that forms the surface layer of fPRP.

Examples of monomers include styrene, hyaluronic acid, methacrylic esters, acrylonitrile, acrylic esters, vinyl chloride, vinylidene chloride, vinyl versatate, and the like.

In addition, copolymerizing a heptamer that is easily saponified, such as vinyl acetate, and saponifying the acetate group of the copolymer to convert it into a hydroxyl group can also be used as a polymer having a hydroxyl group in the side chain of the present invention. It is possible.

Examples of unsaturated alcohols to be copolymerized with the above monomers to introduce a hydroxyl group into the side chain include co-hydroxyethyl acrylate, co-hydroxyethyl methacrylate, co□-hydroxyglobyl acrylate, co-hydroxypropyl methacrylate, and co-hydroxypropyl methacrylate. Examples include lyl alcohol, methylol acrylamide, etc.0
- As an unsaturated isocyanate for introducing an acryloyl group or a methacryloyl group into a polymer having a hydroxyl group in a side chain, 1 mole of diincyanate and a monoalcohol having an acryloyl group or a methacryloyl group and a hydroxyl group in the molecule are used. The type obtained by reaction with /'mol is used. , An acryloyl group or a methacryloyl group is introduced into the polymer side chain by the reaction between the incyanato group of the unsaturated incyanate and the hydroxyl group of the polymer. Examples of diisocyanates used in this reaction include tolylene diisocyanate (including mixtures of co-, di-, and co-, 6-), diphenylmethane diisocyanate,
Examples include msm chithylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethyl diisocyanate, paraphenylene diisocyanate, and the like.

As the unsaturated alcohol, -hydroxyethyl acrylate, -monohydroxypropyl acrylate, co-hydroxyethyl methacrylate, -monohydroxypropyl methacrylate, methylol acrylamide, etc. It is advantageous to use a reaction catalyst used in the reaction.

The reaction is carried out in a solvent or monomer.

Since gel coats are supposed to be colored, a coloring component is necessary.

However, initially a transparent unsaturated polymer containing no pigment was used.
It is also practical to form a layer and then incorporate a pigment into the polyester resin commonly used in gel coats to form a colored first layer.

The coloring agent uses organic peroxide to harden the resin, so
It must be able to withstand this, and currently commercially available colorants for unsaturated polyester resins are used as they are. Typical types include titanium white, grafted carbon black, cobalt blue, phthalocyanine green, strontium yellow, molybdenum orange, red iron, etc. Quinacridone type,
Isoindolinone-based and bat-based high-grade organic pigments can also be used.

The gel coat is applied by spray painting on the desired mold or by Kiryu coating, which is the same as the method used for conventional polyester resins.

Furthermore, it is not necessary to use an unsaturated polymer for laminating the backing, and commercially available resins commonly used for laminating may be used.

EXAMPLES OF THE INVENTION In order to assist in understanding the present invention, examples are shown below.

Example (1) Synthesis of unsaturated polymer (A) A stirrer, a reflux condenser, a dropping funnel, and a gas inlet pipe were placed in a separable flask equipped with a thermometer.
Styrenko! 011, co-hydroxypropyl methacrylate) ff A II, ethyl acetate/6-11 azobisisobutyronitrile 3I was charged, heated in a nitrogen stream, and finally polymerized for 72 hours under reflux of ethyl acetate. do. Lower the temperature to 600 and dibutyltin dilaurate o
, sit, hydroquinone Q, / 3! After adding 1,
Switch to a stream of air and add unsaturated isocyanate (reaction product of inphorone diisocyanate and hydroxypropyl methacrylate in a l:1 molar ratio containing 7 moles of free incyanato groups) -100 to ethyl acetate. Add the dissolved solution dropwise.

When the temperature was maintained for S hours after the completion of the dropwise addition, infrared analysis showed that the absorption of free incyanate groups disappeared, indicating that the reaction was complete.

After reducing the pressure to about 100,100 liters and distilling out about 100 CC of ethyl acetate, Styrene J! Add tOI and further collect ethyl acetate at the same pressure.

Yield: 1.3 JIl. Slightly cloudy yellow color, viscosity/
/, 9 voids unsaturated polymer (A) was obtained.

(4) Synthesis of vinyl ester resin (B) In a /1 three-turn flask equipped with a stirrer, a temperature needle, and a reflux condenser,
As the epoxy resin, Asahi Ciba's G Y & (77/5ooot, methacrylic acid/7co1, benzyldimethylamine 8-9, hydroquinone 0.Jli, /JO
When the reaction was carried out at C to 1J3C for 9 hours, the acid value became 4(,/).

Styrene uJgl was processed to obtain vinyl ester resin (B). This resin has a Gardner color number of 2 and a viscosity of 10.9.
It was Boyz.

(iii) Bisphenol type polyester resin (C)
synthesis of.

In a four-eye flask equipped with a stirrer, a gas inlet tube, a thermometer, and a fractionating condenser, add bisphenol A propylene oxide adduct [PO (7' propylene oxide) 1 mole each] J701 and fumaric acid. / A jl was prepared and esterified in a nitrogen stream to obtain an acid value. When the temperature reached 100%, the temperature was lowered to tyoU, and the hydroquinone was added to 0. /311. By adding styrene aso#, bisphenol type polyester (C) was obtained. Gardner color number, viscosity, coboise 0 (1v) Synthesis of isophthalic acid polyester resin (D) (in the same equipment as uD, neopentyl glycol coco OI, propylene glycol gcol, isophthalic acid 33
Charge 2I, proceed with esterification under an inert gas flow of /lOC~/90C5, add fumaric acid//lhl at an acid value of 9.0, and react until the acid value J'p, t at a temperature of 00C-2IOC. did. After that, the temperature/! Hydroquinone lowered to rOc 0
．． JI, styrene + bttt were added to obtain isophthalic acid polyester resin (D>.Hazen color number SO
1 viscosity, 5 voids.

100 parts of gel coat IML resin, part of Erosil, Rivolac color Rc
Three parts of si (Blue, Showa Kobunshi Co., Ltd.) was added and kneaded uniformly with three rolls to form a gel coat.

A wax-based mold release agent is thinly coated on a glass plate of JOCmXJOCm, and then a polyvinyl alcohol-based mold release agent is applied and dried.

To this, 100 parts of gel coat, 83 parts of methyl ethyl ketone peroxide, and 0.5 parts of cobalt naphthenate were added in a solution of 0.3-0. The coating was applied to a thickness of t and wa, gelled at room temperature, and then cured in a boC constant temperature bath for 2 hours.

Next Tesur face mat JOP, φHiro SO mat 3 layers, Revolac/! A test piece was prepared by impregnating and curing a resin prepared by adding 1 part of methyl ethyl ketone peroxide to 100 parts of 0HRBQT.

The test results of the above resins by continuous boiling are shown in Table 7, and it was revealed that the unsaturated polymer (A) was superior.

Table l Judgment ◎Gloss maintenance ○ Slight loss of luster Even minute swelling can be seen △ Numerous minute blisters occur Most of the gloss has disappeared ×Crack formation, loss of gloss.

Patent applicant: Showa Kobunshi Co., Ltd.

Claims (1)

[Claims] Production of colored FRP characterized in that a colorant is added to a side chain unsaturated bond type polymer having an acryloyl group or a methacryloyl group via a urethane bond in the side chain and used for a gel coat forming a surface layer of a reinforced plastic molded product. How?