JP2002069137A - Unsaturated polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an unsaturated polyester resin composition which is excellent in the gloss retention of a cured product and useful for various application as a coating material such as a coating material, lining material, gel-coating material or the like and FRP molding material. SOLUTION: The composition obtained by containing (A) an unsaturated polyester and (B) a polymerizable unsaturated monomer has the hot-cold contraction stress at 70-20 deg.C of 17 MPa or less and the gloss retention rate (that after 2,000 hr weather resistance test by a sunshine weatherometer based on ISO standard) of 60% or more in the cured product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unsaturated polyester resin composition having excellent gloss retention, and a coating material, a lining material, a coating material such as a gel coating agent, a molding material, FRP using the same.
It relates to molded articles.

[0002]

2. Description of the Related Art Unsaturated polyester resins have been used in various applications because of their excellent moldability, chemical, physical, mechanical, and electrical properties in which the curing temperature conditions are wide and the curing speed is fast. ing. Its main uses are for FRP of bathtubs, unit baths, boats, fishing boats, tanks, vehicles, housings, etc., and non-FRP of casts, paints, resin concretes and the like. On the other hand, one of the performances required to be improved is weather resistance. This performance improvement is addressed by the raw material composition and other methods. That is, from the viewpoint of the raw material composition, use of an alicyclic aliphatic dibasic acid or glycol or neopentyl glycol, addition of various ultraviolet absorbers, and the like. However, although the yellowing has been improved by the improvement of the raw material composition, gloss retention still has a defect. That is, there is a problem that a decrease in gloss such as chalking (a whitening phenomenon in which powder is wiped on the surface as a result of the decrease in gloss) occurs in a relatively short time. It did not satisfy both the change and the gloss retention.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an unsaturated polyester resin composition having improved gloss retention and its application.

[0004]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies on unsaturated polyester resin compositions, and as a result, have found an unsaturated polyester resin composition having excellent gloss retention, and have achieved the present invention. It was completed.
That is, the present invention is a composition comprising A) an unsaturated polyester and (B) a polymerizable unsaturated monomer, and a cured product thereof has a hot-cold shrinkage stress at 70 ° C to 20 ° C of 17 MPa or less. And gloss retention (based on ISO standards
An unsaturated polyester resin composition having a weather resistance test by a weatherometer after 2000 hours of gloss retention of at least 60%, and a coating material, a molding material,
An object of the present invention is to provide an FRP molded product.

BEST MODE FOR CARRYING OUT THE INVENTION The unsaturated polyester resin composition of the present invention is a composition containing (A) an unsaturated polyester and (B) a polymerizable unsaturated monomer. The heat-cold shrinkage stress at 70 ° C. to 20 ° C. is 17 MPa or less, preferably 15 MPa or less, and the gloss retention after 2,000 hours of weathering test with a sunshine weatherometer is 60% or more, preferably 70% or more.

[0005] The unsaturated polyester used in the present invention may be an unsaturated dibasic acid and / or an acid anhydride and / or an aromatic dicarboxylic acid and / or an acid anhydride thereof, and / or an aliphatic dicarboxylic acid and / or an aliphatic dicarboxylic acid. The acid component containing the acid anhydride and / or the alicyclic aliphatic dicarboxylic acid and / or the acid anhydride and / or the aliphatic carboxylic acid and / or the aromatic carboxylic acid, and the polyhydric alcohol are known. Is an unsaturated polyester obtained by the reaction according to the above method. An unsaturated polyester acrylate obtained by adding, for example, an unsaturated epoxy compound or an unsaturated isocyanate compound to the terminal of the polyester may be used. Further, the terminal may be blocked with dicyclopentadiene.

Examples of the acid component and alcohol for condensation reaction of the unsaturated polyester used in the present invention are shown below, but are not limited thereto. Examples of unsaturated dibasic acids and / or acid anhydrides include α, β-unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, aconitic acid, and β such as dihydromuconic acid. , Γ-unsaturated dibasic acids are used. These may be used in combination of two or more. Among them, maleic acid, maleic anhydride and fumaric acid are preferred because they are easily available. Aromatic dicarboxylic acids and / or acid anhydrides thereof include phthalic anhydride, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid,
Examples thereof include 2,3-naphthalenedicarboxylic anhydride, 4,4′-biphenyldicarboxylic acid, trimetic acid, and pyromellitic acid. These halides; and their ester derivatives are also used. These may be used in combination of two or more. Examples thereof include tetrahydrophthalic anhydride and dimer acid. Aliphatic dicarboxylic acids and / or acid anhydrides thereof include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid, adipic acid, sebacic acid , Azelaic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3,3-diethylglutaric acid, pimelic acid, suberic acid, dodecane And diacids. These halides; and their ester derivatives are also used. These may be used in combination of two or more. The alicyclic aliphatic dicarboxylic acid and / or acid anhydride thereof is hexahydrophthalic anhydride, hexahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-
Cyclohexanedicarboxylic acid, methylhexahydrophthalic anhydride, methylhexahydrophthalic acid, hexic acid,
1,1-cyclobutanedicarboxylic acid and the like can be mentioned.
These halides; and their ester derivatives are also used. These may be used in combination of two or more. Aliphatic carboxylic acids include cyclohexane carboxylic acid, lactic acid, malic acid, tartaric acid, citric acid, and the like, and two or more of these may be used in combination. The acid component is appropriately selected from these, but when a resin composition having excellent yellowing resistance is obtained, an acid component other than an aromatic compound such as an aromatic monocarboxylic acid, an aromatic dicarboxylic acid or an anhydride thereof is used. It is preferred to use

The polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4 -Butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- Decanediol, 4,5-nonanediol, neopentyl glycol, 2-butyl-
2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanediol,
1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-butanediol,
2-ethyl-1,4-butanediol, 3-methyl-
1,5-pentanediol, hydrogenated bisphenol A,
Bisphenol A adduct with alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide, bisphenol A adduct with alkylene oxide such as ethylene oxide or propylene oxide or butylene oxide, hydrogenated bisphenol F , Hydrogenated bispheno-
Adduct of alkyl F with an alkylene oxide such as ethylene oxide or propylene oxide or butylene oxide; adduct of bisphenol F with an alkylene oxide such as ethylene oxide or propylene oxide or butylene oxide; ethylene glycol carbonate And the like. Trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric alcohols such as pentaerythritol are used. These may be used in combination of two or more, and are appropriately selected. However, when a resin composition having excellent yellowing resistance is obtained, an aromatic compound causing yellowing, that is, a chromophore is formed by a photoreaction. It is preferable not to use a compound such as an aromatic compound or an ether bond, which easily undergoes a deterioration reaction by light. Further, for blocking the terminal of the unsaturated polyester, a monohydric alcohol such as benzyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, and stearyl alcohol can be used.

[0008] The reaction between the acid component and the polyhydric alcohol is carried out mainly by proceeding with a condensation reaction by a known method, and the low molecules such as water generated when both components react are desorbed out of the system to proceed. . There is no particular limitation on the reaction ratio between the acid component and the polyhydric alcohol. It may be reacted with an unsaturated epoxy compound at a stage having a carboxyl group at the terminal, or may be reacted with an unsaturated compound having an isocyanate group at a stage having a hydroxyl group at the terminal. Further, dicyclopentadiene is first reacted with maleic anhydride, alcohol or water under ordinary esterification reaction conditions, and if necessary, aliphatic saturated mono- or dibasic acids and / or acid anhydrides and unsaturated di- or di-basic acids. A basic acid and / or an acid anhydride thereof, an aromatic dicarboxylic acid and / or an acid anhydride thereof are added, and a condensation reaction is carried out by a known method. Further, dicyclopentadiene is first reacted with maleic anhydride, alcohol or water under ordinary esterification reaction conditions, and if necessary, aliphatic saturated mono- or dibasic acids and / or acid anhydrides, unsaturated A dibasic acid and / or an acid anhydride thereof, an aromatic dicarboxylic acid and / or an acid anhydride thereof may be added, and a condensation reaction may be performed by a known method.

The reaction between the acid component and the polyhydric alcohol is carried out mainly by advancing a condensation reaction by a known method, and a low molecule such as water generated when both components react is desorbed out of the system to proceed. . There is no particular limitation on the reaction ratio between the acid component and the polyhydric alcohol. It may be reacted with an unsaturated epoxy compound at a stage having a carboxyl group at the terminal, or may be reacted with an unsaturated compound having an isocyanate group or an unsaturated carboxylic acid or an acid anhydride thereof at a stage having a hydroxyl group at a terminal. . Further, dicyclopentadiene is first reacted with maleic anhydride, alcohol or water under ordinary esterification reaction conditions, and if necessary, aliphatic saturated mono- or dibasic acids and / or acid anhydrides and unsaturated di- or di-basic acids. A basic acid and / or an acid anhydride thereof, an aromatic dicarboxylic acid and / or an acid anhydride thereof may be added, and a condensation reaction may be performed by a known method.

[0010] The method of adding an unsaturated epoxy compound such as glycidyl methacrylate to the terminal carboxyl group is not particularly limited, but may be 60 to 200 using a quaternary ammonium salt, a metal soap, various amines or the like as a catalyst.
The reaction can be carried out at 0.5 ° C. for 0.5 to 4 hours. The addition reaction includes a method of dissolving the unsaturated polyester in the polymerizable unsaturated monomer and then adding the unsaturated epoxy compound, and a method of directly adding the unsaturated epoxy compound to the unsaturated polyester. A method may be adopted.

The method of adding an unsaturated compound having an isocyanate group to the terminal hydroxyl group is not particularly limited, but if necessary, a reaction catalyst may be added and the mixture may be added at a temperature of 60 to 200 ° C. for 0.5 hour.
The reaction can be carried out for up to 8 hours. The addition reaction is a method in which a diisocyanate is added to an unsaturated polyester to react an ethylenically unsaturated monomer having a hydroxyl group, and a method in which an adduct of a diisocyanate and an ethylenically unsaturated monomer having a hydroxyl group is added to the unsaturated polyester. And a method of adding an isocyanate having an ethylenically unsaturated monomer to an unsaturated polyester, etc., and any method may be employed. The addition reaction includes a method of dissolving the unsaturated polyester in the polymerizable unsaturated monomer and then adding the unsaturated isocyanate compound, and a method of directly adding the unsaturated isocyanate compound to the unsaturated polyester. A method may be adopted.

Examples of the diisocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and tetramethyl xylylene diisocyanate.
Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate and (meth) acrylate.
2-hydroxypropyl acrylate, 3-hydroxypropyl (meth) acrylate and the like can be mentioned. As unsaturated isocyanate compounds, isopropenyldimethylbenzyl isocyanate, Karenz MOI (Showa Denko KK)
Manufactured).

The method of reacting an unsaturated carboxylic acid such as (meth) acrylic acid or di (meth) acrylic anhydride or an acid anhydride thereof with a terminal hydroxyl group is not particularly limited,
The reaction can be carried out at 60 to 200 ° C. for 0.5 to 4 hours using a known esterification and / or transesterification catalyst. The reaction may be performed under reduced pressure.
For the reaction, after dissolving the unsaturated polyester in the polymerizable unsaturated monomer, a method of reacting the unsaturated carboxylic acid or its anhydride with the unsaturated carboxylic acid or the anhydride thereof directly with the unsaturated polyester is used. There is a way to make it react,
Either method may be adopted.

As the polymerizable unsaturated monomer, one in the molecule is used.
Styrene derivatives having at least two polymerizable double bonds, such as styrene, p-methylstyrene, α-methylstyrene, vinyltoluene, divinylbenzene, chlorostyrene, and dichlorostyrene, monomethyl fumarate, dimethyl fumarate, and monomethyl maleate Dimethyl maleate, monoethyl fumarate, diethyl fumarate, monoethyl maleate, diethyl maleate, monopropyl fumarate,
Dipropyl fumarate, monopropyl maleate, dipropyl maleate, monobutyl fumarate, dibutyl fumarate, monooctyl fumarate, dioctyl fumarate, monomethyl itaconate, dimethyl itaconate, diethyl itaconate, monoethyl itaconate, monobutyl itaconate, Α, β-unsaturated polybasic acid alkyl esters such as dibutyl itaconate, monopropyl itaconate and dipropyl itaconate, and sialyl phthalate are used. These may be used in combination of two or more. The compounding amount of the polymerizable unsaturated monomer is preferably 60% by weight or less based on the unsaturated polyester.

Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, and cyanoacrylate-based compounds, and examples of the ultraviolet stabilizer include hindered amine-based compounds. Regardless of the form, they may have a polymerizable reactivity or an esterification-reactive reactivity, and are appropriately selected and used.

The unsaturated polyester resin composition of the present invention may contain, if necessary, hydroquinone, pyrocatechol,
Polymerization inhibitors such as 2,6-t-butylparacresol; metal soaps such as cobalt naphthenate and cobalt octenoate; quaternary ammonium salts such as dimethylbenzylammonium chloride; β-diketones such as acetylacetone; dimethylaniline; -Ethyl-meta toluidine,
Various additives such as curing accelerators such as amines such as triethanolamine, dyes, pigments, plasticizers, known thixotropic agents such as silica powder and asbestos powder, fillers, stabilizers, defoamers, and leveling agents. A thermoplastic polymer such as PMMA or a macromonomer AA-6 or AA-10 from Toagosei Chemical Industry Co., Ltd. can be blended within a range that does not impair the gloss retention performance.

The resin composition may contain various organic peroxides as a curing agent. Examples of the organic peroxide include methyl ethyl ketone peroxide, benzoyl peroxide, acetylacetone peroxide, bis-4-t-butylcyclohexanedicarbonate, t-
Butyl peroxy-2-ethyl hexanate and the like,
These may be used in combination of two or more.

The pigment used in the present invention is preferably used for coloring, for example, titanium white,
Vengara, condensed azo red, titanium yellow, cobalt blue, quinacridone red, carbon black,
Iron black, ultramarine green, blue, perinone, navy blue, isoindolinone, chrome green, cyanine blue, green and the like. Excellent UV stability,
A material that does not hinder the curing of the polyester resin is selected and blended according to the color tone. These coloring pigments can be directly mixed and dispersed in the polyester resin or added as a color toner which has been previously kneaded with a saturated or unsaturated polyester resin solid. The amount of the pigment added is determined by dissolving the unsaturated polyester and the polymerizable unsaturated monomer.
The pigment is preferably used in an amount of 0.1 to 50 parts by weight based on 00 parts by weight.

The filler used in the composition of the present invention includes, for example, calcium carbonate, talc, mica, clay, silica powder, colloidal silica, asbestos powder, barium sulfate, aluminum hydroxide, glass powder, alumina powder, silica powder Powder, glass beads, crushed sand, etc.,
These can be blended and used as a putty, a sealing agent or a coating material. It is also effective as a material for impregnating and reinforcing cloth, kraft paper and the like.

The composition containing the unsaturated polyester and the polymerizable unsaturated monomer of the present invention as main components has a cured product having a hot-cold shrinkage stress at 70 ° C. to 20 ° C. of 17 MPa.
Or less, preferably 15 MPa or less, and a gloss retention (a gloss retention after 2,000 hours of a weathering test with a Sunshashin Weatherometer based on ISO standards) of 6
0% or more, preferably 70% or more. The composition and the content of the unsaturated polyester and the polymerizable unsaturated monomer are appropriately adjusted so that the composition of the present invention has the above-mentioned ranges of the hot-cold shrinkage stress and gloss retention of the cured product at 70 ° C to 20 ° C. This can be achieved by choosing. In addition, as long as it is within the range of the above-mentioned hot-cold shrinkage stress, it is effective for maintaining gloss of the cured product,
In addition, it is possible to provide a property of preventing cracking caused by a change in temperature when forming a coating material or a molded article.

The conventional unsaturated polyester resin composition does not have a gloss retention of 60% or more under the conditions of the above-mentioned weather resistance test, while the unsaturated polyester resin composition of the present invention is shown in Examples described later. By adjusting the components constituting the unsaturated polyester, the content thereof, the composition ratio in the composition, and the like as described above, the polyester has the above-mentioned gloss retention and hot-cold shrinkage stress.

The heat-cold shrinkage stress in the present invention is measured as follows. First, the unsaturated polyester resin composition is applied on a glass plate so that the thickness of the cured film becomes about 0.3 mm, and left at room temperature for 24 hours to prepare a cured film. 70 mm of the obtained film
Attach × 10 mm × about 0.3 mm to Tensilon and heat it to Tg or more of the film. The cured film is stretched and loosened, but the sample length is increased and fixed by the amount of this looseness, and the generated stress is measured while lowering the temperature.
The difference between the generated stresses at a temperature of 70 ° C is defined as a hot-cold shrinkage stress of 70 ° C to 20 ° C.

A reinforcing material may be added to the composition of the present invention. Examples of the reinforcing material include glass fiber (chopped strand mat, glass roving cloth, etc.), carbon fiber, organic fiber (vinylon, polyester, phenol, etc.), Metal fibers and the like can be used, and FRP can be used in combination with 10 to 70% by weight.

The unsaturated polyester resin composition of the present invention is useful as a coating material, that is, a paint or a gel coat material, and can be used as a molding material when a reinforcing material and / or a filler is added. In the present invention, a fiber-reinforced plastic molded article having a gel coat layer made of the resin composition of the present invention on the surface of the fiber-reinforced plastic molded article can also be provided.

The resin composition of the present invention is used for applications such as FRP, putty, cast products and coatings, such as gel coating agents and lining materials. In such a case, if necessary,
An additive such as a flame retardant may be added.

[0026]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these Examples. Further, “parts” in the text indicates parts by weight. Example 1 Production of Unsaturated Polyester Composition 458 parts of neopentyl glycol, 2-methylpropane-1 in a 2 L four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. , 3-diol 99
Parts, hexahydrophthalic anhydride 308 parts, fumaric acid 34
8 parts were charged, the temperature was raised to 210 ° C., an esterification reaction was carried out, and after 14 hours of reaction, 503 parts of a styrene monomer and 0.11 parts of hydroquinone were added, and an unsaturated polyester resin composition having a nonvolatile content of 68% and an acid value of 12 was added. I got something. This composition had a gloss retention of 67% and a hot / cold shrinkage stress of 11.7 MPa according to the test described below. (Example 2) Production of unsaturated polyester composition In the same manner as in Example 1, 229 parts of neopentyl glycol, 297 parts of 2-methylbutanediol were placed in a 2 L flask,
After charging 336 parts of methylhexahydrophthalic anhydride and 294 parts of maleic anhydride, the temperature was raised to 210 ° C., and an esterification reaction was performed.
2 parts and 0.11 part of hydroquinone were added to obtain a non-volatile content of 68 parts.
%, And an unsaturated polyester resin composition having an acid value of 12 was obtained.
To 100 parts of the unsaturated polyester resin, 0.5 parts of Tinuvin 400 of Ciba Specialty Chemicals Co., Ltd. was added.
Parts, Ciba Specialty Chemicals Co., Ltd., 0.4 parts of Tinuvin 123, and Asahi Denka Kogyo Co., Ltd., LA-82, 0.1 part, to obtain an unsaturated polyester resin composition.
The composition has a gloss retention of 86% according to the following test,
The hot-cold shrinkage stress was 8.1 MPa. (Comparative Example 1) Production of unsaturated polyester composition Neopentyl glycol 208 in the same manner as in Example 1.
Parts, propylene glycol 76 parts, hexahydrophthalic anhydride 154 parts, maleic anhydride 196 parts,
The temperature was raised to 210 ° C., an esterification reaction was performed, and after 14 hours of reaction, 410 parts of a styrene monomer and 0.06 parts of hydroquinone were added to obtain an unsaturated polyester resin composition having a nonvolatile content of 60% and an acid value of 5. According to the following test, the composition had a gloss retention (a 1500-hour test) of 40% and a hot-cold shrinkage stress of 20.6 MPa. (Test Example) The following tests were performed using the above unsaturated polyester resin composition. Table 1 summarizes the results. ~ Heat-cold shrinkage stress ~ The hot-cold shrinkage stress at 70 ° C to 20 ° C is measured by the following method. 0.6% in 100 parts of the compositions of the above Examples and Comparative Examples
5 parts of cobalt naphthenate and 1.0 part of 55% methyl ethyl ketone peroxide were added and stirred, and a resin was applied on a glass plate so that the thickness of the cured film became about 0.3 mm, and left at room temperature for 24 hours. After that, it is further cured at 60 degrees for 30 minutes to produce a cured film. 70mm × 10m
A sample is cut to a size of about 0.3 mm, and the sample is mounted on Tensilon and heated to a temperature equal to or higher than the Tg of the film. The cured film causes a loosening. The sample length is increased and fixed only by the amount of this looseness, and the generated stress is measured while lowering the temperature.
The difference between the generated stress at 0 ° C. and 70 ° C. is defined as a hot-cold shrinkage stress of 70 ° C. to 20 ° C. ~ Weather Resistance Test by Sunshine Weatherometer ~ 1) Preparation of Test Plate 55% methyl ethyl ketone peroxide 1.0% was added to the unsaturated polyester resin compositions obtained in Examples and Comparative Examples.
%, 0.6% cobalt naphthenate 1% is added and stirred,
After defoaming, apply a release agent (Furicoat FRP, F-REKOTE), pour the resin onto a sealed glass plate having spacers to adjust the thickness, then leave it at room temperature for 24 hours, then at 120 ° C for 120 minutes It was further cured to obtain a casting plate having a thickness of about 3 mm. 2) Weather resistance test A test piece of 50 mm x 70 mm was cut out from the test plate obtained in method 1) to prepare a weather resistance test piece. As a weather resistance test method, an accelerated weather resistance test was performed using a sunshine weatherometer (WEL-SUN-HCH-B type manufactured by Suga Test Instruments Co., Ltd.). Test condition: Temperature 63 ± 3 ° C Cycle 18 in 120 minutes
Minute rainfall time 2000 hr. The test pieces were checked every 250 hours, and the test was stopped if the gloss was significantly reduced. 3) Evaluation of weather resistance The gloss of the test piece after the test was measured. As a measuring instrument, a gloss meter GM26D type manufactured by Murakami Color Research Laboratory was used. The measurement angle was 60 degrees. The gloss retention was determined by the equation: gloss retention = gloss after test / gloss before test × 100. The higher the retention ratio, the lower the gloss is.

[0027]

[Table 1]

In order to confirm the weather resistance in FRP,
A gel coat laminate was prepared by the method described below. First, release agent (trade name Bon Reese, KOSHIN CHEMICAL)
Co., Ltd.), and resin compositions 10 of Examples and Comparative Examples
0 parts is 1.0% of 55% methyl ethyl ketone peroxide.
% And 0.6% of cobalt naphthenate were added, stirred, spray-coated on a glass plate, left at room temperature for 1 hour, and further cured at 60 ° C. for 30 minutes. Next, 450
g / m ² glass chop strand mat (M), 57
Using a laminating resin (polylite FH-286, manufactured by Dainippon Ink and Chemicals, Inc.) on a 0 g / m ² glass roving cloth (R), the composition is (M) + (R) + (M). They were molded at once so as to overlap at the corners of the mold. At this time, 0.6% cobalt naphthenate 2 parts, 55%
1.0 part of methyl ethyl ketone peroxide was used.
Then, after standing at room temperature for 18 hours, the FR
The P molded product was peeled off to obtain a test piece. 50m from this test plate
An mx 70 mm test piece was cut out to produce a weather test piece. As the weather resistance test method, a sunshine weatherometer (WEL-SUN- manufactured by Suga Test Instruments Co., Ltd.)
HCH-B type) was used.

Test conditions: temperature 63 ± 3 ° C. cycle 1
18 minutes out of 20 minutes Rainfall time 2000 hr The test was visually checked every 250 hours, and the test was stopped if the gloss was significantly reduced. Table 2 shows the test results. (Evaluation of weather resistance) For evaluation, the degree of whitening of the surface was visually observed. Evaluation ◎: No whitening ○: Almost no whitening ×: Whitening

[0030]

[Table 2]

[0031]

Industrial Applicability The resin composition of the present invention is excellent in maintaining gloss of a cured product, and thus is useful in various applications as a coating material such as a paint, a lining material, a gel coat agent, and an FRP molding material.

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[Procedure amendment]

[Submission date] November 15, 2000 (200.11.
15)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction contents]

[0004]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies on unsaturated polyester resin compositions, and as a result, have found an unsaturated polyester resin composition having excellent gloss retention, and have achieved the present invention. It was completed.
That is, the present invention is a composition comprising A) an unsaturated polyester and (B) a polymerizable unsaturated monomer, and a cured product thereof has a hot-cold shrinkage stress at 70 ° C to 20 ° C of 17 MPa or less. and Sandhya Lee down-based gloss retention (ISO standard
An unsaturated polyester resin composition having a weather resistance test by a weatherometer after 2000 hours of gloss retention of at least 60%, and a coating material, a molding material,
An object of the present invention is to provide an FRP molded product.

BEST MODE FOR CARRYING OUT THE INVENTION The unsaturated polyester resin composition of the present invention is a composition containing (A) an unsaturated polyester and (B) a polymerizable unsaturated monomer. The heat-cold shrinkage stress at 70 ° C. to 20 ° C. is 17 MPa or less, preferably 15 MPa or less, and the gloss retention after 2,000 hours of weathering test with a sunshine weatherometer is 60% or more, preferably 70% or more.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 167/06 C09D 167/06 F term (Reference) 4F006 AA53 AB42 BA00 CA00 DA04 4J002 CF221 DE149 DE239 DG049 DJ019 DJ029 DJ039 DJ049 DJ059 DL009 EA046 EB126 EE037 EH077 EH106 EH146 EN008 EU177 FD019 FD048 FD057 GH01 GJ02 4J027 AB02 AB06 AB07 AB08 AB15 AB16 AB17 AB18 AB19 AB23 AB24 AB25 AB28 AB29 AB32 BA04 BA05 BA18 CA18 CA18 CA18 CA18 CA18 CA18 CA18 CA17 FA052 FA082 HA216 HA266 HA376 HA446 HA486 HA536 HA546 JA33 JB06 JB38 KA08 KA12 NA01 NA03 NA11 NA13 PA19 PB05 PB07 PC08

Claims (6)

[Claims] 1. A composition comprising (A) an unsaturated polyester and (B) a polymerizable unsaturated monomer, and the cured product thereof has a hot-cold shrinkage stress at 70 ° C. to 20 ° C. 17MP
a) The unsaturated polyester resin composition having a gloss retention of not more than 60% or less. Note Gloss retention: Sunshine based on ISO standards
Gloss retention after 2,000 hours weathering test with weatherometer 2. The unsaturated polyester resin composition according to claim 1, further comprising an ultraviolet absorber and / or an ultraviolet stabilizer. 3. The unsaturated polyester resin composition according to claim 1, which is used for a paint or a gel coat. 4. An unsaturated polyester resin composition comprising the unsaturated polyester resin composition according to claim 1 and a reinforcing material and / or a filler. 5. A molding material comprising the unsaturated polyester resin composition according to claim 4. 6. A fiber reinforced plastic molded article having a gel coat layer comprising the resin composition according to claim 1 on the surface of the fiber reinforced plastic molded article.