JP2002121372A - Vehicle member made of unsaturated polyester resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an unsaturated polyester resin composition giving an article with improved weather resistance, that is, both retention of gloss and resistance to discoloration, and having a small content of a polymerizable unsaturated monomer, and to provide a vehicle member obtained using the composition. SOLUTION: The unsaturated polyester resin composition for a vehicle member comprises an unsaturated polyester and a polymerizable unsaturated monomer and gives a cured product having a gloss retention (gloss retention after 2,000 hr of a weathering test by a sunshine weather-o-meter according to the ISO standard) of at least 60%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an unsaturated polyester resin composition for vehicle members which has excellent gloss retention and yellowing resistance and has a low content of polymerizable unsaturated monomers, and a fiber reinforced composition. The present invention relates to a cured vehicle member.

[0002]

2. Description of the Related Art Conventionally, unsaturated polyester resins have excellent molding properties such as a wide range of curing temperature conditions and a high curing speed, and have excellent chemical, physical, mechanical and electrical properties. , Aircraft, ships, etc.). In particular, FRP reinforced with unsaturated polyester resin can form molded articles of complicated shapes, so it can be used to prevent vibration from large vehicle components (toilet / washroom units, waste tanks, side windows). Utilizing the characteristics of lightness and lightness, the range of use is expanding.

On the other hand, one of the performances required to improve the unsaturated polyester resin 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 discoloration such as yellowing is improved by the improvement of the raw material composition, the 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. Both discoloration such as discoloration and gloss retention were not satisfied.

[0004] Also, recently, due to environmental problems, regulations on the release of styrene monomer into the atmosphere have been becoming stricter, so that resins having low styrene volatilization and low styrene content are required. In order to obtain an unsaturated polyester resin having a low styrene volatilization or a low styrene content, a method of reducing the styrene content by using a low molecular weight unsaturated polyester of DCPD type, a method of adding a paraffin wax, and the like are known. These methods can reduce the volatilization amount and content of the styrene monomer, but cannot satisfy the weather resistance.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an unsaturated polyester resin composition having improved weathering gloss retention and discoloration resistance, and having a low content of polymerizable unsaturated monomers. An object of the present invention is to provide a vehicle member using an object.

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on unsaturated polyester resin compositions. The inventors have found an unsaturated polyester resin composition having a low unsaturated monomer content and confirmed that it can be used to form a vehicle member, thereby completing the present invention.

That is, the present invention provides: (A) An unsaturated polyester and (B) a polymerizable unsaturated monomer, and the cured product has a gloss retention (after 2000 hours of a weathering test with a sunshine weatherometer based on ISO standards). Gloss retention) is 6
0% or more of an unsaturated polyester resin composition for a vehicle member,

[0008] 2. 2. The unsaturated polyester resin composition for a vehicle member according to the above 1, wherein the cured product has a hot-cold shrinkage stress at 70C to 20C of 17 MPa or less.

3. 3. The unsaturated polyester resin composition for a vehicle member according to the above 2, wherein the cured product has a heat / cold shrinkage stress / maximum elastic strength of 1 or less,

[0010] 4. Color difference in cured product (color difference ΔE of 3 mm thick test piece after 2000 hours of weathering test by sunshine weatherometer based on ISO standard)
Is 20 or less, the unsaturated polyester resin composition for vehicle members according to any one of the above 1 to 3,

5. A composition comprising (A) an unsaturated polyester and (B) a polymerizable unsaturated monomer,
The weight ratio of (A) the unsaturated polyester to (B) the polymerizable unsaturated monomer is (A) / (B) = 70/30 to 95/5. An unsaturated polyester resin composition for a vehicle member according to any one of the above,

6. (B) The polymerizable unsaturated monomer according to any one of (1) to (5) above, wherein the polymerizable unsaturated monomer is mainly composed of a styrene monomer and an acrylic monomer. A saturated polyester resin composition,

7. The weight ratio of (A) the unsaturated polyester to (B) the polymerizable unsaturated monomer having a styrene monomer and an acrylic monomer as main components is 5 to 95% of the unsaturated polyester, and the styrene monomer is The unsaturated polyester resin composition for a vehicle member according to the above item 6, wherein the amount of the unsaturated polyester resin composition is 1 to 30% by weight of the monomer and 4 to 65% of an acrylic monomer.

8. 8. The unsaturated polyester resin composition for a vehicle member according to any one of 1 to 7 above, further comprising an ultraviolet absorber and / or an ultraviolet stabilizer.

9. A vehicle member characterized in that the unsaturated polyester resin composition for a vehicle member according to any one of the above items 1 to 8 is fiber-reinforced and cured.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The unsaturated polyester used in the present invention may be an unsaturated dibasic acid and / or an anhydride thereof and / or an aromatic dicarboxylic acid and / or an 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.

The acid component and alcohol for the condensation reaction of the unsaturated polyester used in the present invention are illustrated below, but are not limited thereto.

Examples of the unsaturated dibasic acid and / or its acid anhydride include maleic acid, maleic anhydride, fumaric acid,
Α, β such as itaconic acid, citraconic acid, aconitic acid
Β, γ-unsaturated dibasic acids such as unsaturated dibasic acids and dihydromuconic acids are used. These may be used in combination of two or more. Among these, maleic acid, maleic anhydride,
Fumaric acid is preferred because it is readily available. Aromatic dicarboxylic acids and / or acid anhydrides thereof include phthalic anhydride, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid,
3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4′-biphenyldicarboxylic acid,
Trimet acid, pyromellitic acid and the like. These halides; and their ester derivatives are also used. These may be used in combination of two or more.

Examples 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 cycloaliphatic aliphatic dicarboxylic acid and / or anhydride thereof may be hexahydrophthalic anhydride, hexahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid,
For example, 1,3-cyclohexanedicarboxylic acid, methylhexahydrophthalic anhydride, methylhexahydrophthalic acid, hexic acid, 1,1-cyclobutanedicarboxylic acid and the like are used. These halides; and their ester derivatives are also used. These may be used in combination of two or more. Aliphatic carboxylic acids include cyclohexanecarboxylic acid, lactic acid, malic acid, tartaric acid, citric acid and the like.
More than one species may be used in combination. Examples of the aromatic carboxylic acid include benzoic acid, and these may be used in combination of two or more. The acid component is appropriately selected from these, but in order to obtain a resin composition having excellent yellowing resistance, an aromatic monocarboxylic acid,
It is preferable to use acid components other than aromatic compounds such as aromatic dicarboxylic acids and anhydrides thereof.

Examples of 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, 2-methyl-1,3-
Propanediol, 3-methyl-1,5-pentanediol, hydrogenated bisphenol A, an adduct of hydrogenated bisphenol A with an alkylene oxide such as ethylene oxide or propylene oxide or butylene oxide, and bisphenol A Adducts with alkylene oxides such as ethylene oxide or propylene oxide or butylene oxide,

Adducts of hydrogenated bisphenol F, hydrogenated bisphenol F with an alkylene oxide such as ethylene oxide or propylene oxide or butylene oxide; bisphenol F with an alkylene oxide such as ethylene oxide or propylene oxide or butylene oxide; Adducts, dihydric alcohols such as ethylene glycol carbonate, trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric alcohols such as pentaerythritol. These may be used in combination of two or more, and are appropriately selected. In order to obtain a resin composition having excellent yellowing resistance, 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.

When a polymer such as 1,3-propanediol or 2-butyl-2-ethyl-1,3-propanediol is used, glycol having a low number of carbon atoms in the main chain and a low melting point can be used. When used, there is an advantage that the content of the polymerizable unsaturated monomer can be reduced and the viscosity of the obtained composition can be lowered. That is, an alcohol having an odd-numbered carbon atom in the main chain is more preferable because the viscosity of the resin becomes lower. still,
For terminal blocking of the unsaturated polyester, monohydric alcohols such as benzyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, and stearyl alcohol can also be used.

The reaction between the acid component and the polyhydric alcohol is carried out mainly by advancing the condensation reaction by a known method, and the low molecules such as water generated when the two 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. The reaction may be carried out with an unsaturated epoxy compound at the stage having a carboxyl group at the terminal, or at the stage having a hydroxyl group at the terminal with an unsaturated compound having an isocyanate group or an unsaturated carboxylic acid or an acid anhydride thereof. 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.

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 with 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 the unsaturated compound having an isocyanate group to the terminal hydroxyl group is not particularly limited.
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 for 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. Although there is a method of reacting, 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, t-butylstyrene, vinyltoluene, divinylbenzene, chlorostyrene and dichlorostyrene, monomethyl fumarate and fumaric acid Dimethyl, 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 , Α, β such as monobutyl itaconate, dibutyl itaconate, monopropyl itaconate and dipropyl itaconate
-Unsaturated polybasic acid alkyl esters, diallyl phthalate and the like are used. These may be used in combination of two or more.

Examples of the acrylic monomer include (meth) acrylic monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, and methacrylic acid. Lauryl, propyl methacrylate, isopropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, dicyclopentenyloxyethyl methacrylate, t-butyl Methacrylic acid such as cyclohexyl methacrylate and methacrylic acid and esters thereof,

Methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, laurel acrylate, 2-hydroxyethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, dicyclohexane Acrylic acid such as pentenyloxyethyl acrylate, t-butylcyclohexyl acrylate, acrylic acid and its esters, (meth) acrylamide, methoxydiethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) ) Acrylate,

Β- (meth) acryloyloxyethyl hydrogen phthalate, β- (meth) acryloyloxypropyl hydrogen phthalate, β- (meth) acryloyloxyethyl hydrogen succinate, nonylphenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) Acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate,
Butoxydiethylene glycol (meth) acrylate,
Nonylphenoxyethyl (meth) acrylate and the like can be mentioned. These may be used in combination of two or more.

Further, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate ,
Propylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,

Trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, 2, 2-bis [4-((meth) acryloxyethoxy)
Phenyl] propane, pentaerythritol tri (meth) acrylate, cipentaerythritol hexa (meth) acrylate, oligoester (meth) acrylate, urethane (meth) acrylate oligomer, (meth) acryl-modified epoxy oligomer, epoxy-modified acrylic urethane oligomer, ( A (meth) acrylate oligomer can also be mentioned. These may be used in combination of two or more.

The compounding amount of the polymerizable unsaturated monomer is preferably such that the weight ratio of (A) unsaturated polyester to (B) polymerizable unsaturated monomer is (A) / (B) = 70/30. ~ 95 /
5, more preferably 70/30 to 85/15. Alternatively, when the polymerizable unsaturated monomer (B) is mainly composed of a styrene monomer and an acrylic monomer, (A) an unsaturated polyester and (B) a styrene monomer and The weight ratio of the polymerizable unsaturated monomer having an acrylic monomer as a main component to the unsaturated polyester 5
９５95%, styrene monomer 1-30% and acrylic monomer 4４65%. If the amount of the polymerizable unsaturated monomer is in the above range, it has a good effect on the high gloss retention of the cured product of the composition, and the polymerizable unsaturated monomer, for example, low volatility of styrene, low content. Can be brought.

The composition of the present invention has a viscosity of 10 to 10.
The one adjusted to be 0.1 Pa · s is preferable.

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, metal soaps such as cobalt naphthenate and cobalt octenoate, quaternary ammonium salts such as dimethylbenzylammonium chloride, and ゜ -diketones such as acetylacetone. , Amines such as dimethylaniline, N-ethylmethtoluidine and triethanolamine can be used in combination as a curing accelerator. The curing agent and the curing accelerator are appropriately selected from one kind or two or more kinds according to a desired molding temperature and molding time.

In molding the resin composition of the present invention, commonly used inhibitors and regulators can be used for the purpose of adjusting the curing speed, the maximum exothermic temperature or the physical properties of the molded product. As the inhibitor, for example, hydroquinone,
Examples thereof include quinones such as 1,4-benzoquinone and 1,4-naphthoquinone; pyroganols such as pyroganol and 4,6-diphenylpyroganol; catechols such as catechol and 4-t-butylcatechol. Examples of the regulator include ascorbic acid for increasing the maximum exothermic temperature and a-methylstyrene dimer for decreasing the maximum exothermic temperature. The amounts of the inhibitors and regulators that can be used in the molding method of the present invention are appropriately selected as necessary, but usually, the amounts of the unsaturated polyester resin 10
0 to 10 parts by weight relative to 0 parts by weight is preferred.

When an organic or inorganic dye or pigment is added to the unsaturated polyester resin composition, a vehicle member obtained by, for example, heat-compression molding the resin composition can be colored. Further, if necessary, an oxide or hydroxide of an alkaline earth metal such as magnesium oxide, calcium oxide, magnesium hydroxide, or calcium hydroxide can be added as a thickener in the resin composition. Stearic acid, zinc stearate, calcium stearate, etc. can be blended as an agent

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.

Known additives such as plasticizers, silica powders and asbestos powders, and various additives such as fillers, stabilizers, defoamers and leveling agents, and PMMA as long as the gloss retention performance is not impaired.
And low-shrinkage agents and / or low-shrinkage agents such as macro-monomers AA-6 and AA-10 of Toagosei Chemical Industry Co., Ltd., block polymers and graft polymers of polystyrene, and three-dimensional crosslinked powder. A compatibilizer having compatibility with the polyester resin can be blended.

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-
Butylperoxy-2-ethylhexanate, t "-butylperoxybenzoate, benzoyl peroxide, t-butylperoxyisopropyl carbonate,
t-hexylperoxyisopropyl carbonate, t
-Amyl peroxybenzoate, etc., which are 2
More than one species may be used in combination.

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, magnesium silicate,
Aluminum silicate, silicon dioxide, antimony oxide, talc, mica, clay, silica powder, colloidal silica, asbestos powder, barium sulfate, aluminum hydroxide, glass powder, glass microballoon, alumina powder,
Inorganic substances such as silica stone powder, glass beads, crushed sand, 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 of a cured product having a thickness of 3 mm (a gloss retention after 2,000 hours of a weather resistance test with a Sunshashin Weatherometer based on ISO standards) of 60% or more, preferably 70% or more. %that's all,
The color difference (ΔE) is 20 or less, preferably 16 or less, and in addition, the hot-cold shrinkage stress / maximum elastic strength is 1
It preferably has physical properties of 0.05 or more and 0.85 or less.

The above-mentioned hot-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. In addition, within the above-mentioned range of the heat-cold shrinkage stress, it is effective to maintain the gloss of the cured product, and it can also impart a property of preventing cracking caused by a temperature change when the formed boat is used.

The maximum elastic strength in the present invention is measured as follows. In the same manner as in the preparation for the measurement of the thermal shrinkage stress, the unsaturated polyester resin composition 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. For 30 minutes to produce a cured film. 7 of the obtained film
0 mm × 10 mm × about 0.3 mm is attached to Tensilon and measured at a room temperature at a test speed of 5 mm / min. In the initial stage of the strain-stress curve, the strength is determined from the maximum stress in the region according to the linear equation, which is defined as the maximum elastic strength, and the ratio of the above-mentioned hot-cold shrinkage stress / maximum elastic strength is determined. In addition, if it is in the range of the above-mentioned hot-cold shrinkage stress / maximum elastic strength, it is effective in maintaining gloss of a cured product, and has mechanical strength effective in a wide range of applications when used as a coating material or a molded product. The property of preventing the number of temperature changes, that is, cracks caused by fatigue, can also be provided.

The gloss retention and color difference in the present invention are measured as follows. A spacer for adding 1.0% of 55% methyl ethyl ketone peroxide and 0.1% of 6% cobalt naphthenate to the unsaturated polyester resin composition, stirring, defoaming, applying a release agent, and adjusting the thickness to 3 mm. The resin is poured into a sealed glass plate having the following, and then left at room temperature for 24 hours.
It is further cured to obtain a casting plate having a thickness of about 3 mm. A test piece of 75 mm × 70 mm was cut out from the test plate thus obtained to prepare a weathering test piece. As a weather resistance test method, an accelerated weather resistance test was performed using a sunshine weatherometer based on the ISO standard. The above gloss retention is
The specular glossiness is measured at an incident angle of 60 degrees by a method based on JIS Z8741-1997. The gloss retention is determined by the following equation.

Gloss retention = mirror gloss after weathering test / mirror gloss before weathering test × 100 The higher the gloss retention, the less the gloss is reduced.

The color difference is in accordance with JIS Z 8730-1995.
Use the notation specified in. JIS Z for object color
Measured according to the method specified in 8722 and L ^* a ^* b ^*
The color difference according to the color system is calculated by the following equation (1).

ΔE ^* _ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2 (1) where ΔE ^* _ab : L ^* a ^* b ^* color system Color difference. ΔL ^* ,
Δa ^* , Δb ^* : L ^* a ^* specified in JIS Z 8279
The difference between the CIE1976 lightness L ^{* and} the difference between the color coordinates a ^* and b ^* of two color bodies in the b ^* color system.

ΔE ^* _ab is abbreviated as ΔE. Since the test piece is transparent, a white plate that does not transmit light is attached to the opposite side of the measurement surface for measurement. In the case of such a measurement, since the color greatly depends on the film thickness, it is necessary to correct the film thickness according to Lambert's law when comparing test pieces other than 3 mm. The higher the ΔE value, the more severe the discoloration such as yellowing.

The composition containing the unsaturated polyester and the polymerizable unsaturated monomer of the present invention as main components has a gloss retention of a cured product having a thickness of 3 mm (a sunshashin wafer based on the ISO standard). The gloss retention after 2000 hours of the weather resistance test with a zometer is 60% or more, preferably 70% or more, and the color difference (ΔE) is 20 or less, preferably 16 or less.
These are: The composition of the present invention can be achieved by appropriately adjusting the components of the unsaturated polyester, the degree of polymerization, and the like, in order to keep the gloss retention and color difference of the cured product within the above ranges.

The conventional unsaturated polyester resin composition does not have a gloss retention of 60% or more and a color difference (ΔE) of 20 or less in a cured product having a thickness of 3 mm under the conditions of the weather resistance test. The unsaturated polyester resin composition has the above-mentioned gloss retention and hot-cold shrinkage stress // by adjusting the components constituting the unsaturated polyester, the content thereof, and the composition ratio in the composition as shown in Examples described later. Or, it has a heat-cold shrinkage stress / maximum elastic strength. At the same time, by setting the content of the polymerizable unsaturated monomer to a specific amount, the content of the monomer and the volatility can be suppressed low. It has been confirmed that a vehicle member can be formed using the resin adjusted as described above, and the present invention has been completed.

A reinforcing material may be added to the composition of the present invention. Examples of such a reinforcing material include glass fiber (chopped strand mat, glass roving cloth, etc.), carbon fiber, and organic fiber (vinylon, polyester,
Phenol, etc.), metal fibers, and the like. These can be used in combination with 10 to 70% by weight to form FRP, and thus can be used as a synthetic resin layer for a skeleton of a vehicle member.

The unsaturated polyester resin composition of the present invention is useful as a coating material for a synthetic resin vehicle member, that is, a paint or a gel coating material, and can also be used as a skeleton resin to which a reinforcing material and / or a filler is added. Also, it can be used as a synthetic resin layer for a skeleton of a vehicle member.
There is no particular limitation on these molding methods, and various methods such as hand lay-up molding, spray-up molding, RTM, compression molding, pultrusion molding, and continuous molding can be employed, but there is no limitation on the molding method.

The resin composition of the present invention may further contain additives such as a flame retardant according to the required performance.

[0061]

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 366 parts of neopentyl glycol and ethylene glycol 88 were placed in a 2 L four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. Parts, 2,2-ethylbutyl 1,3-propanediol (88 parts), hexahydrophthalic anhydride (462 parts), and fumaric acid (232 parts) were charged, the temperature was increased to 205 ° C. while blowing nitrogen gas, and after reacting for 14 hours, styrene monomer 468 was added. And hydroquinone in an amount of 0.12 parts to obtain an unsaturated polyester resin composition having a nonvolatile content of 70% and an acid value of 12. This composition had a gloss retention of 75%, a yellowing of 8.9, a hot-cold shrinkage stress of 1.6 MPa, and a hot-cold shrinkage stress / maximum elastic strength of 0.14 according to the following test.

Example 2 Production of unsaturated polyester composition In the same manner as in Example 1, 457 parts of neopentyl glycol, 51 parts of 1,3-propanediol, 2,2
-Ethylbutyl 1,3-propanediol 77 parts, hexahydrophthalic anhydride 462 parts, fumaric acid 232 parts were charged, and the temperature was raised to 210 ° C. to carry out an esterification reaction.
After reacting for 2 hours, 483 parts of a styrene monomer and 0.13 parts of hydroquinone were added to obtain an unsaturated polyester resin composition having a nonvolatile content of 70% and an acid value of 9. To 100 parts of the unsaturated polyester resin, 0.5 parts of Tinuvin 400 of Ciba Specialty Chemicals, 0.4 parts of Tinuvin 123 of Ciba Specialty Chemicals,
0.1 part of LA-82 from Asahi Denka Kogyo KK was added to obtain an unsaturated polyester resin composition. The composition had a gloss retention of 95%, a yellowing of 3.1, a hot-cold shrinkage stress of 7.3 MPa, and a hot-cold shrinkage stress / maximum elastic strength of 0.31 according to the test described below.

Comparative Example 1 Preparation of Unsaturated Polyester Composition Neopentyl glycol 416 in the same manner as in Example 1.
Parts, 1,2-propylene glycol (152 parts), isophthalic acid (332 parts) and fumaric acid (464 parts) were charged, the temperature was raised to 210 ° C., an esterification reaction was performed, and after 14 hours of reaction, 939 parts of styrene monomer and 0.12 of hydroquinone were added. Then, an unsaturated polyester resin composition having a nonvolatile content of 55% and an acid value of 9 was obtained. According to the following test, this composition had a gloss retention (1500 hours) of 60%, a yellowing of 20.4, a hot-cold shrinkage stress of 29.6 MPa, and a hot-cold shrinkage stress / maximum elasticity of 1.31. .

(Test Example) The following tests were conducted 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. In 100 parts of the resin compositions of the above Examples and Comparative Examples, 0.
Add 5 parts of 6% cobalt naphthenate and 1.0 part of 55% methyl ethyl ketone peroxide, stir, apply the resin on a glass plate so that the thickness of the cured film becomes about 0.3 mm, and allow it to stand at room temperature for 24 hours. Leave to make a cured film. A sample is cut out to a size of 70 mm × 10 mm × about 0.3 mm, and the sample is mounted on Tensilon and heated to at least Tg of the film. The cured film causes a loosening. The sample length is increased and fixed only by the amount of the looseness, and the generated stress is measured while lowering the temperature. The difference between the generated stress at 20 ° C. and 70 ° C. is defined as the 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.
%, 6% cobalt naphthenate 0.1% is added and stirred,
After defoaming, applying a release agent (Furicoat FRP, F-REKOTE), pour the resin onto a sealed glass plate having spacers for adjusting 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 75 mm × 70 mm was cut out from the test plate obtained in the 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 conditions: temperature 63 ± 3 ° C, cycle 1 in 120 minutes
8 minutes rainfall, time 2000 hours The test pieces were checked every 250 hours, and the test was stopped if the test piece had a significant decrease in gloss.

3) Evaluation of Weather Resistance The gloss and color difference of the test piece after the test were measured. The measuring equipment is
The gloss meter used was GM26D manufactured by Murakami Color Research Laboratory. The measurement angle was 60 degrees. The gloss retention was determined by gloss retention = mirror gloss after test / mirror gloss before test × 100. The higher the retention ratio, the lower the gloss is. The color difference was measured using a light emitting pipe and a sample table 30 by using Nippon Denshoku Industries Co., Ltd.
Measured in φ and the ΔE value was used for color difference. Higher values indicate more yellowing.

-Measurement of Maximum Elastic Strength- The maximum elastic strength is measured by the following method. The above embodiment,
To 100 parts of the resin composition of the comparative example, 5 parts of 0.6% cobalt naphthenate and 1.0 part of 55% methyl ethyl ketone peroxide were added and stirred, and the thickness of the cured film was reduced to about 0.3 mm on a glass plate. The resin is applied so as to be left at room temperature for 24 hours, and further cured at 60 ° C. for 30 minutes to produce a cured film. 70mm x 10mm x about 0.3m
The sample is cut out to a length of m, the sample is attached to Tensilon, and measured at a room temperature at a test speed of 5 mm / min. In the initial stage of the strain-stress curve, the strength is determined from the maximum stress in the region according to the linear equation, which is defined as the maximum elastic strength, and the ratio of the above-mentioned hot-cold shrinkage stress / maximum elastic strength is determined.

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[Table 1]

Further, in order to confirm weather resistance of a vehicle member, a panel was formed by a sheet molding compound (SMC) by the following method.

(Preparation of SMC) An SMC was prepared using the unsaturated polyester resin compositions of Examples 1, 2 and Comparative Example 1 described above. Glass fiber (RS460A-782, manufactured by Nitto Boseki Co., Ltd., trade name) was used as the fibrous reinforcing material, and chopped strands having a length of about 25 mm were used. The amount of the chopped strand was 100 parts with respect to 100 parts of the unsaturated polyester resin composition.
Parts, 75 parts of calcium carbonate, 75 parts of aluminum hydroxide, 1 part of magnesium oxide, 5 parts of zinc stearate, and Perbutyl Z (manufactured by NOF CORPORATION). The SMC was produced using an SMC coater, and both sides of the SMC were wrapped with a carrier film and aged.

(Formation of Panel) A panel was formed using the SMCs manufactured in Examples 1, 2 and Comparative Example 1 described above. Panel dimensions are 250mm long and 500m wide
m, the plate thickness is 3 mm. The molding conditions by pressurizing and heating were set at a pressure of 5.9 MPa, a mold temperature of 150 ° C., and a dwell time of 2 minutes.

(Evaluation Test) Example 1 in which pressure and heat molding were performed
50 mm x 70 m from the panels of Example 2 and Comparative Example 1
m test pieces were cut out to prepare weathering test pieces. As a weather resistance test method, a weather resistance acceleration test using a sunshine weatherometer was performed in the same manner as in the above test examples. Test time 2
Table 2 shows the gloss retention and ΔE after 000 hours.

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[Table 2]

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The resin composition of the present invention is an unsaturated polyester resin composition which is excellent in gloss retention and color difference of a cured product. By using this resin composition, it is excellent in weather resistance including gloss retention and discoloration. A vehicle member can be provided.

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Claims (9)

[Claims] 1. A cured product comprising (A) an unsaturated polyester and (B) a polymerizable unsaturated monomer and having a gloss retention (a weather resistance measured by a sunshine weatherometer based on ISO standards). An unsaturated polyester resin composition for vehicle members, which has a gloss retention (after 2000 hours of the property test) of 60% or more. 2. The unsaturated polyester resin composition for a vehicle member according to claim 1, wherein the cured product has a hot-cold shrinkage stress at 70 ° C. to 20 ° C. of 17 MPa or less. 3. The unsaturated polyester resin composition for a vehicle member according to claim 2, wherein the cured product has a heat / cold shrinkage stress / maximum elastic strength of 1 or less. 4. The cured product has a color difference (a color difference ΔE of a 3 mm-thick test piece after 2000 hours of a weather resistance test by a Sunshine Weatherometer based on the ISO standard) of 20 or less. Claims 1 to 3
The unsaturated polyester resin composition for a vehicle member according to any one of the above. 5. A composition comprising (A) an unsaturated polyester and (B) a polymerizable unsaturated monomer, wherein (A)
The weight ratio between the unsaturated polyester and the polymerizable unsaturated monomer (B) is (A) / (B) = 70/30 to 95/5, wherein the weight ratio is from 70/30 to 95/5. The unsaturated polyester resin composition for a vehicle member according to any of the above items. 6. The method according to claim 1, wherein (B) the polymerizable unsaturated monomer is mainly composed of a styrene monomer and an acrylic monomer. The unsaturated polyester resin composition for a vehicle member according to the above. 7. The unsaturated polyester having a weight ratio of (A) unsaturated polyester and (B) a polymerizable unsaturated monomer having a styrene monomer and an acrylic monomer as main components, which is 5 to 95, respectively. %, 1 to 30% of a styrene-based monomer and 4 to 65% of an acrylic-based monomer. 8. The unsaturated polyester resin composition for a vehicle member according to claim 1, further comprising an ultraviolet absorber and / or an ultraviolet stabilizer. 9. A vehicle member obtained by reinforcing and curing the unsaturated polyester resin composition for a vehicle member according to any one of claims 1 to 8.