JPH0216112A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To improve the weathering resistance, water resistance, corrosion resistance and stain resistance by incorporating a specific (meth)acrylate into a composition which comprises an unsaturated polyester resin and/or an unsaturated vinyl ester resin as main components. CONSTITUTION:An unsaturated polyester resin and/or an unsaturated vinyl ester resin (A) is obtained by blending an unsaturated polyester and/or an unsaturated vinyl ester with 20-70wt.% mixture of a vinyl monomer (e.g. styrene monomer) and 0.1-50wt.% (meth)acrylate having a fluorinated alkyl group and/or an alkylene group and a urethane group in the molecule (e.g. a compound of the given formula), and a polymerization catalyst. The component (A) is blended with a thixotropic agent, a colorant, and if desired, a filler, a curing promotor and a diluent.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a thermosetting resin composition that is highly resistant to chewing, water, corrosion, and staining, and is particularly useful as a gel coat composition. The present invention relates to a thermosetting resin composition.

(Prior art) Gel coat is generally the outermost layer of FRP, so it is free from air,
It is constantly in contact with the environment such as light, water, seawater, gas, and solvents, so the resins and their compounds used in these products have not only mechanical performance but also weather resistance, corrosion resistance, and stain resistance. There is a demand for something that is excellent.

The resin used for this purpose is also particularly selected, and depending on the purpose, unsaturated vinyl ester resin (epoxy acrylate), bisphenol polyester resin, isophthalic acid polyester resin, etc. are used.

However, the expectations for gel coats have become more severe year by year, and since these resins do not fully satisfy the above properties, products with particularly excellent properties have been desired.

In order to meet this demand, it has been found that it is effective to introduce fluorine into the molecule, and acrylic esters and/or methacrylic esters of alcohols having fluorinated alkyl groups and/or alkylene groups have been found to be effective. Thermosetting resin compositions containing acid esters have been developed. (Japanese Patent Application No. 57-68771) (Problem to be solved by the invention) However, the two fluorinated alkylenes (and/
Alternatively, acrylic esters and/or methacrylic esters of alcohols having alkylene ^ are not compatible with unsaturated polyester resins and/or unsaturated vinyl ester resins, so the blending amount must be lowered. WJ of weather resistance, corrosion resistance, stain resistance, etc. of cured products
'It is difficult to be completely satisfied with A reform.

In addition, since the acrylic esters and methacrylic esters described in ■- are anaerobic during curing, in order to completely cure the surface in contact with the air, the surface is coated with paraffin and the air is blocked. curing is required.

[F stage for solving problems]

As a result of extensive studies in view of the actual situation mentioned above, the authors found that, in thermosetting resins whose main components are unsaturated polyester resins and/or unsaturated vinyl ester resins, vinyl in the resin A thermosetting resin composition characterized by containing an acrylic ester and/or a methacrylic ester having both a fluorinated alkyl group and/or alkylene group and a urethane group in the molecule as a monomer. The present invention has been completed based on the results of the present invention.

That is, the terminal IJ+ is (+) an unsaturated polyester resin or an unsaturated vinyl ester resin (2) a vinyl monomer (3) an acrylic ester having both a fluorinated alkyl group and/or an alkylene group and a urethane group; Alternatively, the present invention relates to a thermosetting resin composition comprising a methacrylic acid ester (4) and a combined catalyst.

[Function] The acrylic ester and/or methacrylic ester having both a fluorinated alkyl group and/or alkylene group and a urethane group used in the present invention can be mixed with the unsaturated polyester resin or vinyl ester resin in any proportion. It is particularly useful as a gel coat resin because it can be mixed easily, has very good copolymerizability, and has little anaerobic properties.

Below, the configuration of the present invention will be explained in detail.

The composition according to the invention is characterized in that 0.1 to 50% of the vinyl monomer (generally styrene monomer) among the components of the unsaturated polyester resin and unsaturated vinyl ester resin, preferably 0.5 to 40% of the vinyl monomer (generally styrene monomer) An acrylic ester or a methacrylic ester having both a fluorinated alkyl group and/or alkylene group and a urethane group is used. The use of acrylic esters or methacrylic esters having both fluorinated alkyl and/or alkylene groups and urethane groups provides weather resistance, water resistance, corrosion resistance, and stain resistance of less than 0.11%. On the other hand, when it is used in excess of 50%, mechanical properties such as tensile strength, hardness, and bending strength are decreased.

A gel coat composition is prepared by adding a thixotropy, a coloring agent, and in some cases a filler, a curing accelerator, and a diluting agent to the thus obtained resin in accordance with the usual blending of gel coat resins.

The unsaturated polyester resin used in the present invention is
It is obtained by dissolving unsaturated polyester in vinyl monomer. The unsaturated polyester may be a conventional unsaturated polyester, and may be a polyester having a molecular weight of about 500 or more, which is obtained by dehydrating and condensing a mixture of an unsaturated polybasic acid and/or its anhydride, a saturated polybasic acid or its anhydride, glycol, and a polyhydric alcohol. 5000 oligomer, and examples of its raw materials are as follows.

Unsaturated 1'! ! Base acids or anhydrides such as maleic dianhydride, maleic acid, fumaric acid, itaconic acid, hic acid, carboxylic anhydride, etc. Base acids or their anhydrides: phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, detrahydrophthalic acid, succinic acid, adipic acid, azelaic acid, cehatic acid, het acid, het acid anhydride Polyhydric alcohol: ( 1) Glycol Ethylene glycol, diethylene glycol, propylene glycol 1, dipropylene glycol, triethylene glycol, butanediol, neopentyl glycol, powdered bisphenol A, hisphenol A with ethylene oxide added Th, etc.

(2) Trihydric or higher alcohol - pentaerythrin,
Glycerin, trimethylolpropane, etc.

Moreover, the unsaturated vinyl ester resin used in the present invention is obtained by dissolving an unsaturated vinyl ester in a vinyl monomer. Unsaturated vinyl esters are produced by reacting a polyvalent epoxy compound with an unsaturated acid, with the ratio of eboxyno 6 (/carboxyl group) approximately equal to 1.
Raw materials such as those exemplified below are used.

Polyvalent epoxy compounds: bisphenol A and epichlorohydrin condensate, phthalic acid and epichlorohydrin condensate, tutadiene oligomer oxide, imprene oligomer oxide, UNOX 201 (trade name, manufactured by Union Carbide Co., Ltd., 3.4- Epoxy-6-methylcyclohexylmethyl-3,1-epoxy-6methylcyclohexanecarboxylene 1-), Yunox 289 (trade name,
Union Kerhighton F, epoxycyclohexyl acylate), novolak epoxy, etc. Unsaturated acids: methacrylic acid, acrylic acid, crotonic acid,
Examples of vinyl monomers that can be added to the unsaturated polyesters and unsaturated vinyl esters described in "Itaconic acid, etc." are as follows: styrene, methyl methacrylate, ethyl methacrylate, methyl acrylate, 2-ethylhexyl acrylate. ,
Ethylene glycol diacrylate, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylol propane diacrylate acrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacturate, pentaerythrittetraacrylate, pentaerythritol 1-remethacrylate, pentaerythritol tetramethacrylate, etc.

The blending of these vinyl monomers includes unsaturated polyester resin or 20% of the total weight of the unsaturated vinyl ester resin.
~70%.

Acrylic esters and/or methacrylic esters that have both a fluorinated alkyl group and/or alkylene group and a urethane group in the molecule used in the uninvention are partially or completely substituted with hydrogen. and an acrylic ester or methacrylic ester of an alcohol having both an alkyl group and/or an alkylene group and a urethane group with a total carbon number of 1 to 3 (], as exemplified below) It is (
stomach! l, m=0~+8,
n=0~18, p=l~bR
= 11 or CIl Go, × = 11 or CIl,
R=l+ or C1l (C1+)).

These compounds can be easily synthesized, for example, by reacting incyanatoalkyl acrylate or incyanatoalkyl methacrylate with a fluorinated alcohol using cyphthyltin dilaurate or the like as a catalyst.

Fluorinated alkyl,! , (and/or the amount of the acrylic ester or methacrylic ester of an alcohol containing both an alkylene group and a urethane group in the molecule is determined by the amount of the vinyl monomer blended into the unsaturated polyester or unsaturated vinyl ester), 1 to 50% by weight,
Preferably, it is 0.5 to 40 ton v%.

In order to produce an unsaturated polyester resin or an unsaturated vinyl ester resin using these raw materials, a conventional method is used. That is, the unsaturated polyester resin contains an unsaturated polybasic acid lO~50 mol% and a saturated polybasic acid lO~50 mol%. ! Base acid 0-40 mol%
, 411 to 60 mol% of polyhydric alcohol was mixed, and the temperature was 1 to 180°C at 180 to 230°C in a nitrogen stream while stirring.
Heat for 12 hours. Separate the produced water, stop the reaction when the acid value, wood acid value, and viscosity reach the predetermined values, cool it,
1E drugs (e.g. hydroquinone 0.01-0.1.
'117d%/total amount) was added, and vinyl monomer (20~
7flii%/total amount).

The unsaturated vinyl ester resin contains 1 h of unsaturated acid and 0.0 of hydroquinone per 1 of the polyvalent epoxy compound.
01 to 0.1 iljψ%/total, add 0.1 to 1 insect star%/total, such as amine as a catalyst, and add vinyl monomer (2
In the presence of 0 to 70 tons (7 d%/total), the temperature was gradually raised with stirring in an air atmosphere to 110 to 1:1O'C.
It can be made by keeping it for 1 to 5 hours and cooling it when the acid value, epoxy value, and viscosity reach predetermined values.

A vinyl monomer may be further added if necessary.

A gel coat composition is prepared by adding a thixotropic agent, a coloring agent, and in some cases a filler, a curing accelerator, and a diluent to the unsaturated polyester resin or unsaturated vinyl ester resin thus produced. to make.

As the thixotropic agent, fine powder, polymer-stitched urethane resin, acrylic resin, polyester resin, etc. are used.

As the blue agent, white or colored pigments are used, such as titanium white, iron oxide, chromium oxide, etc.

Examples of fillers include calcium carbonate, silica powder, clay, glass powder, glass flakes, and mica flakes.

Cobalt naphdate, cobalt octoate, etc. are used as hardening accelerators.

As the diluent, suitable solvents such as quidylol, phthyl carbitol, lauryl acetate, dimethyl phthalate, etc. are used. Other antifoaming agents, leveling agents, etc. may also be added as appropriate.

A homo mixer, router, or kneader is used to mix the gel coat composition.

To perform gel coating using the composition of the present invention, one composition includes a polymerization catalyst (benzoyl peroxide, lauryl peroxide, methyl ethyl ketone peroxide).

cumene hydroperoxide, etc.) in an amount of 0.1 to 2 parts by volume based on MIaS is applied to the mold. Application methods include brushing, roller coating, and spraying. Paint 1+j
L/Tanochi uses a normal FRP molding and casting method to layer unsaturated polyester resin and/or unsaturated hinyl Esder resin and fibers.

The present invention will now be described in more detail with reference to Examples.

Example 1 55 moles of propylene glycol and 20 moles of isophthalic acid were mixed and mixed in a nitrogen atmosphere at 180 mols.
The reaction was carried out at ~190°C for about 2 hours, and when the acid value reached 80, the temperature of the reactant was lowered to 150°C, and then 30 mol of maleic anhydride was added and heated at 210-220°C for about 6 hours. When the acid number reaches 30, the reaction is stopped.

Next, 1 reactant was cooled, and when the temperature reached I[i0'C, 0.03% by weight of pytroquinone was added, and when the temperature reached 130°C, 32% by weight of styrene was added.

and 517ii-% of the monomer represented by formula (I) are added, mixed uniformly, and cooled. This unsaturated polyester resin has 10 t11 parts, J and f irregularities, such as Koronol (trade name, Dexa Co., Ltd., oxidized f1 elementary powder), 2 parts 1 part
Titanium white 3 tons as a coloring agent, iron chain pink pigment Q
, 5 Ij+Aibe, 5 tons of quartz powder as a filler, and 5 tons of cobalt naphthenate and sB as hardening accelerators were added and mixed in a homomixer to prepare a composition for Kelcoat.

Add 1 part of 50% benzoyl peroxide paste in dimethyl phthalate to 100 parts of this composition, gel coat the septic tank mold, and coat the FRP part with ordinary polyester resin using orthophthalic acid. Manufactured by the conventional Hunt lay-up method.

The adhesion between the gel coat and the 11 (P layer) was good, and there was no change in surface gloss even after exposing this septic tank outdoors for one year.On the other hand, when a gel coat manufactured by omitting the fluorinated alkyl urethane methacrylate was applied. For, 1
After years of outdoor exposure, the luster has disappeared and the glass grains in the FRP layer have become visible.

In addition, the septic tanks treated with the composition of the present invention had almost no dirt on the surface, and the appearance returned to its original beauty after washing with water, or the septic tanks manufactured by omitting the fluorinated alkyl methacrylates had less dirt on the surface. It was so large that even washing it with water did not improve its appearance.

Examples 2-12. and Comparative Examples 1 to 3 The same tests as in Example 1 were conducted except that the type of fluorinated alkyl urethane (meth)acrylate and the additive were changed.

Table 1 shows formulation examples and test results.

(below F margin) Types of fluorinated urethane acrylate 4￥ permit applicant Showa Ropeia Chemical Co., Ltd. teenager Reason Man

Claims (1)

[Claims] In a thermosetting resin composition containing an unsaturated polyester resin and/or an unsaturated vinyl ester resin as a main component,
A thermosetting resin characterized in that the vinyl monomer in the resin contains an acrylic ester and/or a methacrylic ester having both a fluorinated alkyl group and/or alkylene group and a urethane group in the molecule. Composition.