JP2002121238A - Artificial marble having excellent weather resistance and composition therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an artificial marble comprising an unsaturated polyester resin composition having both improved gloss retention and discoloration resistance of weather resistance, a low content of a polymerizable unsaturated monomer and excellent weather resistance. SOLUTION: The resin composition for the artificial marble is characterized by comprising the unsaturated polyester resin composition comprising an unsaturated polyester resin and the polymerizable unsaturated monomer and providing a cured product thereof having >=60% gloss retention (gloss retention after weathering tests for 2,000 h with a sunshine weather-o-meter based on the ISO standards).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an artificial marble comprising an unsaturated polyester resin composition having excellent gloss retention and yellowing resistance and having a low content of polymerizable unsaturated monomers, and also having excellent weather resistance. It relates to a composition.

[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. And artificial marble is one of its main uses. Artificial marble is acrylic and its texture,
Since it has excellent performance in terms of strength, workability, and the like, it is widely used in many applications, such as countertops, kitchen tops, furniture, sanitary applications, interior materials, and small stationery items.

[0003] However, artificial marble includes acrylic and unsaturated polyesters from its raw materials. The unsaturated polyesters are superior to acrylics in terms of moldability, productivity and strength, but are particularly resistant to weathering. There was a problem that it was inferior. This performance improvement is addressed by the composition of the raw material resin 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, the discoloration such as yellowing is improved by the improvement of the raw material composition, but there is still a defect in gloss retention, and the gloss of the appearance of the molded product is reduced in a relatively short time. It did not satisfy both discoloration such as yellowing, which is a factor of weather resistance, and gloss retention.

[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 DCPD type low molecular weight unsaturated polyester is 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 An object of the present invention is to provide a weatherable polyester resin composition comprising an unsaturated polyester resin composition having improved gloss retention and discoloration resistance of weatherability, and having a low content of polymerizable unsaturated monomers. An object of the present invention is to provide a composition for artificial marble having excellent properties.

[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 artificial marble, 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
An unsaturated polyester resin composition for artificial marble, which is 0% or more.

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

3. 3. The unsaturated polyester resin composition for artificial marble 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 artificial marble according to any one of the above 1 to 3,

5. A composition comprising (A) an unsaturated polyester and (B) a polymerizable unsaturated monomer,
(A) / (B) = 70 / 30-95 / 5 by weight ratio of (A) unsaturated polyester to (B) polymerizable unsaturated monomer. An artificial marble unsaturated polyester resin composition according to

6. (B) The unsaturated material for artificial marble according to any one of (1) to (5) above, wherein the polymerizable unsaturated monomer contains a styrene monomer and an acrylic monomer as main components. 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 artificial marble according to the above item 6, wherein the composition is 1 to 30% of a monomer and 4 to 65% of an acrylic monomer.

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

9. 9. The unsaturated polyester resin composition according to any one of 1 to 8 above, (a) 100 parts by weight, an inorganic filler (b) 50 to 400 parts by weight, and a curing agent (c) 0.5 to
An unsaturated polyester resin composition for artificial marble, comprising 3 parts by weight as a main component,

10. [9] A method for producing an artificial marble molded article, which comprises subjecting the artificial marble resin composition according to [9] to heat molding.

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.

The aromatic dicarboxylic acid and / or anhydride thereof may be phthalic anhydride, isophthalic acid, terephthalic acid,
2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,
Examples thereof include 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 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 acids and / or acid anhydrides thereof include 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.

The aliphatic carboxylic acid includes cyclohexanecarboxylic acid, lactic acid, malic acid, tartaric acid, citric acid and the like, and these may be used in combination of two or more. 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 acid 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 components.

Examples of the polyhydric alcohol 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, hydrogenated bisphenol A ethylene oxide, propylene oxide or butylene oxide; Adduct with alkylene oxide,
Adduct of bisphenol A with an alkylene oxide such as ethylene oxide, 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.

Further, when a polymer such as 1,3-propanediol or 2-butyl-2-ethyl-1,3-propanediol is used, glycol having a low melting point and an odd number of carbon atoms in the main chain is 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 to the outside 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 methacrylic acid glycidyl ether 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 its anhydride 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, 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, tri Methylol propane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol ethane tri (meth) acrylate, tetramethylol methane tetra (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, (meth) acrylate oligomer, and the like.
These may be used in combination of two or more.

As the inorganic filler (b), any of general inorganic fillers can be used. However, in consideration of the approximation to the refractive index of the cured resin, the price, the appearance of the molded product, and the boiling resistance, silane can be used. Most preferred is borosilicate glass powder or aluminum hydroxide treated with a coupling agent. Examples of the glass powder include “Fellow Filler M-50S” or “Fellow Filler M-60” manufactured by Nippon Fellow Co., Ltd.
S "and the like. Examples of the aluminum hydroxide include" Heidilite H-100 "manufactured by Showa Denko KK
Or "Heidilite H-320" can be mentioned, and these are selected from one kind or two or more kinds.

The amount of the inorganic filler (b) is 50 parts per 100 parts by weight of the unsaturated polyester resin composition (a).
The range is from 400 to 400 parts by weight, preferably from 100 to 300 parts by weight. If the amount is less than 50 parts by weight, cracks are likely to occur during molding, and if it exceeds 400 parts by weight, the viscosity of the unsaturated polyester resin composition becomes high, the workability deteriorates, and the mechanical strength of the molded product becomes worse. Becomes weaker.

Examples of the curing agent (c) include azobis compounds such as azobisisobutyronitrile, methyl ethyl ketone peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, lauroyl peroxide, and t-butyl peroxy-2-. Ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-bis- (t-butylperoxy) 3,5,5-trimethylcyclohexane, 1,1-bis- (t- Hexyl peroxy) 3
Organic peroxides such as 5,5-trimethylcyclohexane, t-butylperoxyisopropyl carbonate, t-butylperoxybenzoate, dicumyl peroxide, cumene hydroperoxide, and the like, which are generally used as a curing agent for unsaturated polyester resins. Can be mentioned.

The compounding amount of the curing agent is in the range of 0.5 to 3 parts by weight based on 100 parts by weight of the unsaturated polyester resin composition (A). If the amount is less than 0.5 parts by weight,
If the unsaturated polyester resin composition is not completely cured and exceeds 3 parts by weight, the curing rate is too high, and cracks tend to occur in the molded product.

The compounding amount of the polymerizable unsaturated monomer is preferably such that the weight ratio of (A) the unsaturated polyester to (B) the 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.
It is preferable to adjust the pressure to 0.2 Pa · s.

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 heat generation temperature, the physical properties of the molded product, and the like. 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 required, but are usually 0 to 10 parts by weight based on 100 parts by weight of the unsaturated polyester resin composition (a). Parts by weight are preferred.

When an organic or inorganic dye or pigment is added to the unsaturated polyester resin composition, the artificial marble obtained by heating and molding the resin composition is colored and causes a pattern on the surface. Can be. Further, an oxide or hydroxide of an alkaline earth metal such as magnesium oxide, calcium oxide, magnesium hydroxide, or calcium hydroxide can be blended in the resin composition as a thickener, and stearic acid as an internal mold release agent. , Zinc stearate, calcium stearate, and the like. Further, various additives such as a plasticizer, a stabilizer, and an antifoaming agent, a thermoplastic polymer such as PMMA, and a macromonomer AA-6 of Toagosei Chemical Industry Co., Ltd. as long as the gloss retention and transparency performance are not impaired. A low-shrinking agent such as a block polymer or a graft polymer of AA-10 or polystyrene, a three-dimensionally crosslinked powder, and / or a compatibilizer having compatibility with the unsaturated polyester resin and the unsaturated polyester resin can be blended.

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 composition containing the unsaturated polyester and the polymerizable unsaturated monomer of the present invention as main components has a cured product having a thermal 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 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. 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. As in the preparation for the measurement of the thermal cooling 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. Let cure for 30 minutes to make a cured film. 70 mm × 10 mm × about 0.3 mm of the obtained film 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, and the strength is determined as the maximum elastic strength, and the ratio of the 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 the 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 more difficult the gloss is to decrease.

The color difference is 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. In this report, 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 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 the main components has a gloss retention of a cured product having a thickness of 3 mm (Sunshashin wafer based on ISO standards). 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 under the conditions of the above-mentioned 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.

Further, the unsaturated polyester resin has a disadvantage that it undergoes a large shrinkage upon curing, so that it lacks dimensional stability and is liable to crack or warp in the molded product. However, since the content of the polymerizable unsaturated monomer was small, the shrinkage ratio could be reduced, and cracks and warpage during molding could be prevented. It has been confirmed that artificial marble 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, organic fiber (vinylon, polyester,
Phenol, etc.) and metal fibers.

[0061] The unsaturated polyester resin composition of the present invention is heated and molded to produce an artificial marble molded product. These can be used in any of ordinary casting methods, compression molding methods, injection molding methods, transfer molding methods, injection molding methods, extrusion molding methods and the like, and are not particularly limited. Molding temperature is 60 ~
A range of 150 ° C. is preferred. When the molding temperature is lower than 60 ° C., productivity is deteriorated because molding takes a long time, and when the molding temperature is higher than 150 ° C., appearance defects such as burning and blistering tend to occur in the molded product. .

The resin composition of the present invention may further contain additives such as a flame retardant and an antibacterial agent, if necessary.

[0063]

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 89 were placed in a 2 L four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. Part, 2-butyl-2
-88 parts of ethyl-1,3-propanediol, 462 parts of hexahydrophthalic anhydride and 232 parts of fumaric acid were charged, and the temperature was raised to 205 ° C while blowing nitrogen gas.
After reacting for 4 hours, 468 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 12. To 100 parts of the unsaturated polyester resin, 0.5 part of Tinuvin 400 of Ciba Specialty Chemicals Co., Ltd. and 0.4 part of Tinuvin 123 of Ciba Specialty Chemicals Co., Ltd.
Parts, LA-82 of Asahi Denka Kogyo Co., Ltd. and 0.1 part of triethylene glycol dimethacrylate were added to obtain an unsaturated polyester resin composition. This composition had a gloss retention of 95%, a ΔE of 6.5, a hot-cold shrinkage stress of 15.2 MPa, and a hot-cold shrinkage stress / maximum elastic strength of 0.97 according to the following test.

Example 2 Production of unsaturated polyester composition In the same manner as in Example 1, 229 parts of neopentyl glycol, 297 parts of 2-methyl-1,3-propanediol, and 308 parts of hexahydrophthalic anhydride were placed in a 2 L flask. And 294 parts of maleic acid were charged, and the temperature was raised to 210 ° C. to carry out an esterification reaction.
85 parts and 0.11 parts of hydroquinone were added,
An unsaturated polyester resin composition having 0% and an acid value of 9 was obtained.
Such a composition has a gloss retention of 78% by the following test,
ΔE was 11.4, hot-cold shrinkage stress was 7.4 MPa, and hot-cold shrinkage stress / maximum elastic strength was 0.31.

Comparative Example 1 Production of Unsaturated Polyester Neopentyl glycol 416 in the same manner as in Example 1.
Parts, propylene glycol (152 parts), hexahydrophthalic anhydride (308 parts), and maleic anhydride (392 parts), and the mixture was heated to 210 ° C. to carry out an esterification reaction.
After the reaction for 7 hours, 749 parts of a styrene monomer and 0.14 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 (1500 hours) of 40% and a ΔE
Since the surface was whitened and did not accurately represent the color difference even when measured, the unmeasured hot-cold shrinkage stress was 20.6 MPa and the hot-cold shrinkage stress / maximum elastic strength was 0.72.

(Test Example) The following tests were conducted using the above unsaturated polyester resin composition. Table 1 summarizes the results.

Thermal Shrinkage Stress Thermal 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. A resin is applied so that it is left at room temperature for 24 hours and cured at 60 ° C. for 30 minutes to produce a cured film. 70mm x 10mm x about 0.3m
A sample is cut out to a length of m, and the sample is mounted on Tensilon and measured at a room temperature at a test speed of 5 mm / min. At the beginning of the strain-stress curve, the strength is determined from the maximum stress in the region according to the linear equation, and the strength is defined as the maximum elastic strength.

[0073]

[Table 1]

In order to confirm the weather resistance of the artificial marble, an artificial marble was prepared by the following method.

Molding of Artificial Marble 100 parts of the unsaturated polyester resin synthesized in Examples 1 and 2 and Comparative Example 1, borosilicate glass powder (manufactured by Nippon Fellow Co., Ltd., trade name: FelloW Filler M) -50S) 250 parts, t-butyl peroxybenzoate (manufactured by NOF Corporation, trade name: Perbutyl Z) 1 part as a curing agent, magnesium oxide (Kyowa Chemical Industry Co., Ltd., trade name: Kyowa Mag) as a thickener 40) 1 part, zinc stearate (manufactured by NOF CORPORATION,
Product name: Zinc stearate) 3 parts, 3m as reinforcement
10 parts of m-length glass fiber (manufactured by Nippon Sheet Glass Co., Ltd., trade name: chopped strand) was sufficiently kneaded with a mixer.

This was wrapped in a polyethylene film and
The mixture was allowed to stand in an atmosphere at a temperature of 24 ° C. for 24 hours to obtain an unsaturated polyester resin composition of the present invention shown in Table 2. Next, each of the compositions was charged into a preheated mold, and heated and pressed at a molding temperature of 140 ° C. and a molding pressure of 100 kg / cm ² for 5 minutes.
A flat plate of 00 mm × 200 mm × 8 mm, a flat plate of 200 mm × 200 mm × 4 mm, and a bathtub-shaped artificial marble having a size of 150 mm × 80 mm × 200 mm and a thickness of 10 mm were obtained. Next, 5cm x 7.
A 5 cm test piece was cut out and sunshine
A weather resistance acceleration test was performed using a weatherometer, and the results are shown in Table 3. As the weather resistance test method, a sunshine weatherometer (WEA manufactured by Suga Test Instruments Co., Ltd.)
L-SUN-HCH-B type) was used.

Test conditions: temperature 63 ± 3 ° C, cycle
The rainfall was 18 minutes out of 120 minutes, and the time was 2000 hours. The test was visually confirmed every 250 hours, and the test was stopped when the gloss was significantly reduced. Table 2 shows the test results.

(Evaluation of weather resistance) For evaluation, the gloss and color difference of the surface were measured in the same manner as described above.

[0079]

[Table 2]

[0080]

The resin composition of the present invention is an artificial marble formed by using an unsaturated polyester resin having excellent gloss retention and color difference of a cured product. The artificial marble is excellent in weather resistance including gloss retention and discoloration. Can be provided.

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Claims (10)

[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 artificial marble, which has a gloss retention (after 2000 hours of the property test) of 60% or more. 2. The unsaturated polyester resin composition for artificial marble 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 artificial marble according to claim 2, wherein the cured product has a hot-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 artificial marble 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. An unsaturated polyester resin composition for artificial marble as described in Crab. 6. The method according to claim 1, wherein (B) the polymerizable unsaturated monomer is mainly composed of a styrene monomer and an acrylic monomer. 3. The unsaturated polyester resin composition for artificial marble 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. The unsaturated polyester resin composition for artificial marble according to claim 6, wherein the content is 1% to 30% of a styrene monomer and 4 to 65% of an acrylic monomer. 8. The unsaturated polyester resin composition for artificial marble according to claim 1, further comprising an ultraviolet absorber and / or an ultraviolet stabilizer. 9. The unsaturated polyester resin composition according to any one of claims 1 to 8 (a), 100 parts by weight, an inorganic filler (b) 50 to 400 parts by weight, a curing agent (c) 0.5 to
An unsaturated polyester resin composition for artificial marble, comprising 3 parts by weight as a main component. 10. A method for producing an artificial marble molded article, comprising heating and molding the resin composition for artificial marble according to claim 9.