JP2001335611A - Unsaturated polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an unsaturated polyester resin composition which can be uniformly colored without giving a color uneveness even in a thick coloring and which can produce a thermosetting molding material with a high hot water resistance. SOLUTION: The resin composition is obtained by dissolving, in a crosslinkable monomer, a mol of an unsaturated polyester resin formed by blending and reacting (a) terephthalic acid, (b) b mol of α,β-unsaturated polybasic acid or its anhydride, (c) c mol of saturated polybasic acid or its anhydride, (d) d mol of polyhydric alcohol of and (e) e mol of dicylopentadiene as raw materials in such a way that the blending molar ratios (a+b+c)/a/b/c/d/e may fall within 1/0.01 to 0.8/0.2 to 0.99/0.79/0.4 to 1.8/0.05 to 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an unsaturated polyester resin composition.

[0002]

2. Description of the Related Art Typical thermosetting molding materials for compression molding include SMC (sheet molding compound) and BMC (bulk molding compound).

[0003] SMC generally uses an unsaturated polyester resin composition, a vinyl ester resin composition, an acrylic resin composition and a mixture thereof as a matrix, a filler such as calcium carbonate and aluminum hydroxide, and a curing agent such as an organic peroxide. A low-shrinkage agent such as polystyrene and vinyl acetate, an internal mold release agent such as zinc stearate, a thickener such as magnesium oxide, and a compound appropriately mixed with a pigment, etc. It is obtained by spraying roving (glass fiber) cut into pieces, further laminating a film coated with the above-described compound, impregnating the glass fiber between rollers, defoaming, and then aging. , A sheet-like molding material, BMC is generally chopped into a compound similar to SMC By kneading adding strands (glass fiber), then, it can be obtained by aging a bulk molding material.

[0004] These thermosetting molding materials have been required to have excellent gloss and a function of being capable of deep coloring in order to obtain a molded product having a higher quality and a more flexible design. I have. In parallel with the demand for such functions, cheaper materials have been demanded in order to obtain sales competitiveness of molded products.

In response to such demands, for example, Japanese Patent Application Laid-Open
JP-120327 and JP-A-56-120722 disclose a method for producing a colored molded article without uneven color by using a styrene monomer-containing hydrogenated bisphenol-based unsaturated polyester resin composition and polystyrene powder in combination. Has been proposed. However, in this method, since the polystyrene powder swells poorly, not only the low shrinkage effect is not obtained, but also if the polystyrene powder is insufficiently dispersed, the polystyrene powder remains on the surface and decreases in surface gloss and smoothness and color. There is a problem that unevenness occurs and it is difficult to obtain a desired molded product.

Further, Japanese Patent Publication No. 60-22605 discloses an SMC using a colored filler having a specific particle size, which has a stone-grain pattern represented by a marble pattern. The purpose is to improve the aesthetics of a molded article with a stick, and it is difficult to apply the present invention to the aesthetic improvement of a fiber-reinforced plastic molded article colored in a single color, particularly a dark color.

[0007]

According to the first aspect of the present invention, it is possible to obtain a thermosetting molding material having high hot water resistance, which can be uniformly colored even if it is darkly colored and does not cause color unevenness. An unsaturated polyester resin composition is provided.

[0008]

The present invention provides (a) a mole of terephthalic acid, (b) b mole of an α, β-unsaturated polybasic acid or an anhydride thereof, and (c) a saturated polybasic acid or an anhydride thereof. C), (d) d-polyhydric alcohol, and (e) e-cyclopentadiene as e-mol components, and the compounding molar ratio is (a + b + c) / a / b / c /
d / e is 1 / 0.01 to 0.8 / 0.2 to 0.99 / 0
To 0.79 / 0.4 to 1.8 / 0.05 to 1. An unsaturated polyester resin composition obtained by dissolving an unsaturated polyester resin blended and reacted in a crosslinkable monomer. .

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The (b) α, β-unsaturated polybasic acid or anhydride thereof in the present invention includes, for example, a reaction of maleic acid, fumaric acid, itaconic acid, citraconic acid, anhydrides thereof and the like. Derivatives and the like.
Species or two or more can be used.

The (c) saturated polybasic acid or anhydride thereof in the present invention includes, for example, phthalic acid, isophthalic acid,
Terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid,
Aromatic carboxylic acids such as hexahydrophthalic acid, adipic acid, sebacic acid, glutaric acid, hetonic acid, tetrabromophthalic acid, trimellitic acid, pyromellitic acid, dimer acid, succinic acid, azelaic acid, and rosin-maleic acid adduct , A saturated acid, a derivative such as an anhydride thereof, and the like, and one or more of these can be used.

The polyhydric alcohol (d) in the present invention includes, for example, dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol and dibromo. Neopentyl glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,2- Aliphatic glycols such as hexanediol, 1,4-hexanediol, 1,6-hexanediol, and 2,3-hexanediol; cycloaliphatic diols such as cyclopentanediol, cyclohexanediol and hydrogenated bisphenol A;
Bisphenol A propylene oxide adduct, aromatic group-containing diol such as p-xylene-α, α'-diol,
Ethers such as pentaerythritol diallyl ether,
Trihydric or higher polyhydric alcohols, for example, glycerin, trimethylolpropane, pentaerythritol and the like can be mentioned, and one or more of these can be used.

In the present invention, all or a part of (e) dicyclopentadiene may be used in place of (e ') dicyclopentadiene maleate (monoester of dicyclopentadiene and maleic acid). The (e ') dicyclopentadiene maleate may be obtained by simultaneously reacting equimolar amounts of dicyclopentadiene and maleic anhydride and water, or equimolar amounts of dicyclopentadiene and maleic acid, or dicyclopentadiene and maleic anhydride. It may be obtained by reacting pentadiene and water in advance to form dihydrohydroxydicyclopentadiene, and subsequently reacting with maleic anhydride.

In the present invention, (a) terephthalic acid derived from PET (polyethylene terephthalate) can be used. As PET, for example, PE
T scraps, films, bottles, flakes generated during manufacturing
PET molded products such as chips, pellets, and bottles, objects to be discarded such as defective scraps generated in the production process, and recycled products such as collected used films and bottles can also be used.

When PET is used, it is preferable to use it after depolymerization in the presence of alcohol (it is considered that a transesterification reaction also partially proceeds). And PET is 50mm
Hereafter, it is desirable to break, pulverize, wash and dry to preferably 5 mm or less.

Since the depolymerization of PET decomposes PET rapidly, it is preferable that the softening point of PET (approximately 200
C.) or higher, but when the alcohol used has a low boiling point, it is preferably performed under pressure (preferably 0.1 to 0.5 MPa) to increase the boiling point. The decomposition temperature can be lowered by using a catalyst such as t-butyl titanate, zinc acetate, and dibutyl titanate. The compounding amount is preferably 0.01% by weight to 0.5% by weight, more preferably 0.1% by weight to 0.3% by weight, based on the compounding amount of PET. When the amount of the reaction catalyst exceeds 0.5% by weight,
The hot water resistance of the obtained cured resin decreases.

In the present invention, the molecular weight of PET was set to 192, considering that one mole of terephthalic acid and one mole of ethylene glycol except for two moles of water was regarded as one unit.

If necessary, the saturated polybasic acid ester may be replaced with PE
It can be used in the range of 0 to 20% by weight of T. Examples of the saturated polybasic acid ester include alkylene glycols such as ethylene glycol, propylene glycol and butylene glycol, and in particular, linear alkylene glycols and dialkylene such as adipic acid, sebacic acid and terephthalic acid. There are low molecular weight esters or high molecular weight esters (i.e., saturated polyesters) of basic acids, especially linear alkylene groups or dibasic acids having a paraphenyl group and a carboxyl group bonded thereto. Taret),
Di (butylene terephthalate), polyethylene-2,6
-Naphthalate, polybutylene terephthalate, di (ethylene adipate), di (butylene adipate), polyethylene adipate, polybutylene adipate, and the like. More than one species can be used.

The unsaturated polyester resin in the present invention comprises (a) a mole of terephthalic acid, (b) b mole of an α, β-unsaturated polybasic acid or an anhydride thereof, and (c) a saturated polybasic acid or an anhydride thereof. c mol and (d) polyhydric alcohol
d mol, (e) dicyclopentadiene e mol is an essential component, and the compounding ratio is (a + b + c) / a / b /
c / d / e is 1 / 0.01 to 0.8 / 0.2 to 0.99
/ 0 to 0.79 / 0.4 to 1.8 / 0.05 to 1.

(A + b + c) / a / b / c / d / e is
1 / 0.1-0.6 / 0.4-0.9 / 0-0.5 /
Preferably, it is 0.5-1.5 / 0.05-0.6, and 1 / 0.2-0.4 / 0.6-0.8 / 0-0.
It is more preferable that the ratio be 2 / 0.6 to 1.3 / 0.05 to 0.4.

When (a + b + c) / a is less than 1 / 0.01, the surface gloss of the resulting molded article is reduced. When it exceeds 1 / 0.8, (b) α, β-unsaturated polybasic acid or The amount of the anhydride decreases, and good curability cannot be obtained. vice versa,
If (a + b + c) / b is less than 1 / 0.2, good curability cannot be obtained, and if it exceeds 1 / 0.99, the surface gloss of the obtained molded article decreases. Also, (a + b + c) / c is 1
If it exceeds /0.79, (b) the amount of α, β-unsaturated polybasic acid or its anhydride is reduced, and good curability cannot be obtained. On the other hand, when (a + b + c) / d is less than 1 / 0.4 or more than 1 / 1.8, the unsaturated polyester resin does not have a high molecular weight, and a molded product cannot have sufficient strength.
When (a + b + c) / e is less than 1 / 0.05, the uniformity of coloring of the obtained molded product cannot be maintained, and when it exceeds 1/1, the molded product is difficult to be demolded, and the toughness of the molded product is high. Decrease.

(A) PET as terephthalic acid
(A + b + c) / a / b / c / (a + d) / e
Is 1 / 0.01-0.8 / 0.2-0.99 / 0-0.
What is necessary is just to mix and make it react so that it may be set to 79 / 0.4-1.8 / 0.05-1.

When dicyclopentadiene maleate is used in place of dicyclopentadiene, the maleic acid content in dicyclopentadiene maleate is taken into consideration, and in particular, (a) a mole of terephthalic acid, (b) α, β The molar ratio of each component of the unsaturated polybasic acid or its anhydride (b mol) and the (c) saturated polybasic acid or its anhydride c mol is (a +
b + c) / b is 1 / 0.15 to 0.94, preferably 1
/0.35-0.85, more preferably 1 / 0.55
In this case, (a + b + c) / b is 1 /
If it is less than 0.15, good curability cannot be obtained, and 1 / 0.0.
If it exceeds 94, the surface gloss of the obtained molded article is reduced.

The unsaturated polyester resin according to the present invention may contain, if necessary, vegetable oil fatty acids such as linseed oil, soybean oil, tall oil and castor oil; methacrylates having an epoxy group such as glycidyl methacrylate or glycidyl acrylate; A modifying component such as acrylate may be used at a ratio of 0 to 20% by weight of the acid component (a + b + c).

In order to keep the unsaturated polyester resin pale and to improve the releasability of the molded product, a compound selected from phosphoric acid triester and phosphoric acid triester, for example, trimethyl phosphite , When the total amount of the unsaturated polyester resin is 100 parts by weight, triethyl phosphite, triphenyl phosphite, triphenyl phosphate, etc. is 0.01 to 1.0 part by weight, preferably 0.05 to 1.0 part by weight.
0.5 parts by weight, more preferably 0.1 to 0.3 parts by weight may be used.

The unsaturated polyester resin of the present invention is produced by a conventional method, for example, by subjecting a polybasic acid component and a polyhydric alcohol component to a condensation reaction and removing condensed water generated when both components react outside the system. Can be PET is used to smooth the reaction and prevent problems such as gelation and side reactions.
When is used, it is preferable to initially charge a part or the whole of the polyhydric alcohol, depolymerize by the above-described method, and then react the remaining components. When dicyclopentadiene maleate is used, as described above, dicyclopentadiene and maleic anhydride, an equimolar amount of water or an equimolar amount of dicyclopentadiene and maleic acid are prepared in advance by reacting them. It is preferable to use the same as the components.

Examples of the crosslinkable monomer used in the present invention include styrene, vinyltoluene, 2-methylstyrene, 3-methylstyrene, p-methylstyrene, α
-Methylstyrene, t-butylstyrene, aromatic vinyl compounds such as divinylbenzene, halogenated styrenes such as chlorostyrene, dichlorostyrene and brominated styrene, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl laurate, benzoic acid Carboxylic acid monovinyl esters such as vinyl acrylate, neopentyl glycol dimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, pentaerythritol hexamethacrylate, polyhydric alcohol methacrylates such as pentaerythritol hexaacrylate, methyl (meth) Acrylate ((meth)
Acrylate means methacrylate or acrylate. The same applies hereinafter), ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth)
Acrylate, triallyl cyanurate, trimethylolpropane, tri (meth) acrylate, diallyl phthalate, acrylonitrile and the like.
Species or two or more can be used. Of these, styrene having a good balance between viscosity and curability is preferable.

The unsaturated polyester resin is mixed with a crosslinkable monomer and, if necessary, a polymerization inhibitor or the like is added to adjust the curability, thereby obtaining an unsaturated polyester resin composition. The mixing ratio of the unsaturated polyester resin and the crosslinkable monomer at this time, when the total amount of both is 100 parts by weight, the unsaturated polyester resin is 20 to 80 parts by weight, the crosslinkable monomer is 80 to 80 parts by weight. Preferably it is 20 parts by weight. 20
If the amount is less than part by weight, the viscosity of the unsaturated polyester resin composition is too low, and even when a thermosetting molding material using the same is molded, the curing shrinkage is large, and a molded product may be cracked or cracked. If the amount of the unsaturated polyester resin exceeds 80 parts by weight, the viscosity may be so high that it may be difficult to apply or mix with other components. From this, the unsaturated polyester resin is 45 to 70 parts by weight, and the crosslinkable monomer is 55 to 70 parts by weight.
More preferably, it is 30 parts by weight.

Examples of the polymerization inhibitor include quinones such as parabenzoquinone, tolquinone, naphthoquinone, phenanthraquinone, 2,5-diphenylparabenzoquinone and 2,5-diacetoxyparabenzoquinone, toluhydroquinone, hydroquinone, and tersha. Hydroquinones such as libutyl catechol, mono-tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl phenol, 2,4-dimethyl-6-tert-butyl phenol, 2,6- Ditertiary butyl-
Phenols such as 4-methylphenol, cresols such as di-tert-butylparacresol, organic copper salts such as copper naphthenate, amidines such as acetamidine acetate, hydrazines such as phenylhydrazine hydrochloride, trimethylbenzylammonium chloride and the like Quaternary ammonium salts, etc., of which one or two
More than one species can be used.

The amount of the polymerization inhibitor used is appropriately determined depending on the required curability, but is preferably 5% by weight or less, and more preferably 1% by weight or less, based on the unsaturated polyester resin composition. More preferred.

The unsaturated polyester resin composition of the present invention may contain, if necessary, metal soaps such as cobalt naphthenate, cobalt octenoate and manganese octoate;
Aromatic tertiary amines such as dimethylaniline and N, N-diethylaniline, N, N-dimethylacetoacetamide;
N, N-diethylacetoacetamide, methyl acetoacetate, ethyl acetoacetate, acetylacetone, dimedone,
Hardening accelerators such as dibenzoylmethane, acetylcyclopentane, acetylbutyrolactone, phenyldiethanolamine, etc., thixotropic agents such as silicon oxide fine powder, thixotropic aids such as glycerin, waxes, defoamers, calcium carbonate, water Aluminum oxide, a molding resin composition by adding a filler such as various balloons and the like, casting method, or glass fiber, impregnated with reinforcing material such as carbon fiber, for example,
It can be applied to an open molding method such as a hand lay-up method or a spray-up method, or an injection molding method such as an RTM method or a back method.

To the unsaturated polyester resin composition of the present invention, if necessary, a low shrinkage agent, a filler, a curing agent, an internal mold release agent, a polymerization inhibitor, a colorant, a thickener, a reinforcing material and the like are added. Thereby, a thermosetting molding material can be manufactured.

Examples of the low shrinkage agent include commonly used thermoplastic resins. For example, polystyrene,
Polyvinyl acetate, polymethyl methacrylate, polyethylene, poly-ε-caprolactam, saturated polyester,
Polyvinyl chloride, polybutadiene, styrene-acrylic acid copolymer, styrene-vinyl acetate copolymer, acrylonitrile-styrene copolymer and the like, also, styrene butadiene rubber, thermoplastic rubber such as nitrile rubber,
These can be used alone or in combination of two or more.

The compounding amount is determined in consideration of the shrinkage, surface smoothness and surface gloss of the molded article, and is not particularly limited.
The amount is 1 to 50 parts by weight, preferably 5 to 30 parts by weight based on 100 parts by weight of the total amount of the unsaturated polyester resin composition. If the amount is less than 1 part by weight, the molding shrinkage of the obtained molded article becomes large. If the amount exceeds 50 parts by weight, the low-shrinkage agent is easily separated, and the appearance, surface gloss and uniformity of coloring of the obtained molded product are deteriorated.

As the filler, calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, aluminum hydroxide, aluminum oxide, clay, talc, kaolin, silica (quartz powder), crushed stone,
Examples include silica sand, diatomaceous earth, mica powder, glass powder, glass balloon, shirasu balloon, carbonated balloon, organic balloon, zinc oxide, wood powder, pulverized products of various FRP molded products, and the like. Of these, calcium carbonate, particularly heavy calcium carbonate, is preferred. The average particle size of the heavy calcium carbonate is preferably 0.05 to 50 μm, more preferably 0.1 to 0.8 μm, and still more preferably 0.4 to 0.6 μm.
μm. If the average particle size is 50 μm or more, sufficient gloss cannot be obtained in the molded product. If the average particle size is 0.05 μm or less, the viscosity of the obtained compounded resin is too high, impregnation into the fiber becomes difficult, and the characteristics of the molded product deteriorate. I do.

The amount of the filler is determined in consideration of the physical properties such as the strength of the molded product, the viscosity of the unsaturated polyester resin composition, and the fluidity. The total amount of the unsaturated polyester resin composition is 100 parts by weight. Is preferably 50 to 300 parts by weight, more preferably 100 to 200 parts by weight.
If it is less than the above range, the viscosity increase of the thermosetting molding material is low, it is difficult to handle because it is sticky, and if it is more than the range, the viscosity of the resin composition for the molding material becomes high, and workability and fiber reinforced material Impregnating property is deteriorated.

As the curing agent, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide and cyclohexanone peroxide;
Diacyl peroxides such as benzoyl peroxide and isobutyl peroxide; hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide. , 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexanone, 2,2-di- (t-butylperoxy)
-Peroxyketals such as butane, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-hexylperoxy-2- Alkyl peresters such as ethylhexanoate and 2,4,4-trimethylpentylperoxy-2-ethylhexanoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisobutylcarbonate And organic peroxides such as percarbonates.

Since the type and amount of the curing agent affect not only the molding cycle but also the preservability of the material, color unevenness, and the like, the type and amount of the curing agent are determined according to the respective conditions and the molding temperature. The amount is not particularly limited, but is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the unsaturated polyester resin composition from the viewpoint of the storage stability of the material and the molding cycle. .

Examples of the internal release agent include aliphatic organic acids such as stearic acid, metal salts thereof such as zinc stearate and calcium stearate, waxes and silicones. These may be used in combination. Is also possible. In addition, as for the metal salt of the aliphatic organic acid, it is preferable to select a metal salt having a lower melting point than the molding temperature. The compounding amount is 0.5 to 20 parts by weight, preferably 1 to 7 parts by weight based on 100 parts by weight of the total amount of the unsaturated polyester resin composition. If the amount is less than 0.5 parts by weight, the molded product may stick to the mold, making it difficult to remove the molded product, and may cause cracks or the like in the molded product. If the amount is more than 20 parts by weight, the molded article strength tends to decrease if the release agent is too large.

The coloring agent is used for coloring a molded article, and includes titanium oxide, carbon black,
Examples thereof include inorganic pigments such as a red iron oxide and organic substances such as phthalocyanine blue. The compounding amount is conveniently determined depending on the design properties of the obtained molded article, but is 0.01 to 20 parts by weight, preferably 0.5 to 5 parts by weight based on 100 parts by weight of the total amount of the unsaturated polyester resin composition. It is.

Examples of the thickener include magnesium oxide, magnesium hydroxide, calcium oxide, potassium oxide, potassium hydroxide, zinc oxide and the like. The compounding amount is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the total amount of the unsaturated polyester resin composition. If the amount of the thickener is too small, the viscosity of the resin composition does not increase, and if the amount of the thickener is too large, the viscosity increases too much, and the fluidity of the thermosetting molding material during compression molding deteriorates.

Further, the thermosetting molding material of the present invention requires additional components such as colored polyesters, crushed materials such as urethane, pattern materials such as mica powder, viscosity modifiers, wetting agents, and ultraviolet absorbers. It may be used accordingly. The amount used is not particularly limited, but is preferably 20 to the thermosetting molding material.
It is preferably at most 5% by weight, more preferably at most 5% by weight.

As the reinforcing material, glass fiber, carbon fiber,
Fiber reinforcing materials such as asbestos fibers, whiskers, organic synthetic fibers, and natural fibers are exemplified. These are used by impregnating a compound obtained by mixing the above-mentioned auxiliary material with the unsaturated polyester resin composition according to the present invention in a cut to 0.5 to 60 mm. This reinforcing material is used in the thermosetting molding material of the present invention in a proportion of 0.5 to 50% by weight, and 10 to 30% by weight.
The range of weight% is more preferred.

Thermosetting molding materials such as SMC and BM
C can be manufactured using an ordinary SMC manufacturing apparatus or BMC manufacturing apparatus, respectively. In the case of SMC, a compound is prepared by mixing the above-mentioned auxiliary material with the unsaturated polyester resin composition according to the present invention by using various types of agitators such as a dissolver, a planetary mixer, and a universal agitator.

At this time, the mixing order of the components used is not particularly limited, but when a thickening agent is blended, the thickening agent is mixed later in order to avoid an increase in viscosity before the impregnation of the reinforcing material. Is preferred. This compound is applied on a release film such as a polyethylene film or a polypropylene film so as to have a uniform thickness, and a reinforcing material such as a glass fiber cut to a predetermined length is evenly sprayed thereon, Another film coated with the compounding resin is overlapped with the dispersed reinforcing material so as to be sandwiched by the compounding resin, and the film is wound into a roll to form a sheet-shaped molding material.

In the case of BMC, when a reinforcing material is mixed with a compound similar to SMC, for example, a device such as a kneader, a ball mill, a roll mill, a screw extrusion kneader, a dissolver, a planetary mixer, a universal stirrer And the like to obtain a bulk molding material.
During mixing, care is taken so that the mixture does not gel due to frictional heat. It is also preferable to perform degassing under reduced pressure so as not to involve bubbles. If necessary, aging or the like can be performed to obtain a sheet-shaped molding material. When a thickener is added, aging can be accelerated by heating to a temperature of room temperature to 60 ° C.

The aging of the thermosetting molding material is determined by the molded product and is not particularly limited, but the compound viscosity at 35 ° C. without the reinforcing material is from 1,000 to 200,000.
It is preferably adjusted to be Pa · s, and is 5,000.
The viscosity is more preferably adjusted to 150,000 Pa · s, and particularly preferably adjusted to 30,000 to 130,000 Pa · s. It can be adjusted according to conditions. If the viscosity is too low, scumming is likely to occur on the molded product surface,
On the other hand, if the viscosity is too high, the mold clamping time tends to be long and the molding cycle tends to be long.

The method for molding the thermosetting molding material according to the present invention is not particularly limited, except that it is obtained by curing the thermosetting molding material according to the present invention. It is performed by transfer molding, cold pressing or the like. The molding conditions are determined by the decomposition temperature of the used curing agent and the type and amount of the polymerization inhibitor, and are not particularly limited. Temperature 40-200
° C, more preferably 70 to 160 ° C, more preferably 120 to 150 ° C, and a surface pressure of 0.5 to 50 MPa,
More preferably 1 to 20 MPa, even more preferably 5 to 1 MPa
It is preferable to perform compression molding at 5 MPa. In addition, it is preferable to use a mold surface which has been processed to have a mirror-finished surface in order to exhibit more excellent gloss.

The plastic molded article according to the present invention is not particularly limited. Examples thereof include bathroom units (walls, waterproof pans, ceilings, aprons, counters, etc.), bathtubs, septic tanks, washstands, kitchen counters, wall materials and the like. Various types of housing equipment, various pipes, tank products, beams, construction materials such as gratings, miscellaneous goods such as cups and trays, and a wide range of molded products such as boats, vehicle members (cowl, aero parts) and the like can be considered.

[0049]

Next, the present invention will be described by way of examples.

Example 1 (1) 966.3 g of dicyclopentadiene and 696.5 g of maleic anhydride were placed in a three-liter four-necked flask equipped with a reflux tube, an inert gas introduction tube, a thermometer and a stirrer.
127.9 g of distilled water was heated with a mantle heater in an inert gas stream while suppressing heat generation, and reacted at 140 ° C. for 2 hours to obtain a monoester of dicyclopentadiene and maleic acid (dicyclopentadiene maleate) DM- 1 was obtained.

(2) Next, the same device as in (1) is PET-mounted.
682.3 g, neopentyl glycol 369.6 g
g, 540.2 g of propylene glycol, and 0.17 g of t-butyl titanate.
C. and reacted for 5 hours. Thereafter, the mixture was cooled to 160 ° C., and 895.4 g of DM-1 obtained in (1), 812.6 g of maleic anhydride, and 0.07 g of toluquinone.
Charged, heated to 210 ° C, and allowed to undergo a condensation reaction for 10 hours,
An unsaturated polyester resin UP-I having an acid value of 18 (number average molecular weight: 2800, a value determined by gel permeation chromatography and converted into standard polystyrene, and the same applies hereinafter) was obtained. 60 parts by weight of this UP-I and 0.03 parts of tolquinone
% Of styrene dissolved therein and completely dissolved to obtain an unsaturated polyester resin composition UP-1.

(3) 80-1 parts by weight of UP-1 and a number average molecular weight of 80,00 as measured by gel permeation chromatography.
20 parts by weight of a 32% by weight styrene solution of 0 polystyrene, 1 part by weight of t-butyl perbenzoate (trade name: Perbutyl Z, manufactured by NOF CORPORATION), representative particle size: 0.62 μm
130 parts by weight of calcium carbonate, zinc stearate 4
By weight, compound C-1 was obtained by sufficiently mixing parts by weight, 0.04 parts by weight of parabenzoquinone, 1 part by weight of carbon black (carbon powder having a turbostratic structure), and 1 part by weight of magnesium oxide.

Thereafter, C-1 was applied to the upper and lower polypropylene films by an SMC manufacturing apparatus, and the roving (glass fiber) cut into 1 inch was sprayed on the lower side so that the content in the SMC was 23% by weight. After the surfaces coated with C-1 were overlapped, impregnation and defoaming were performed between rollers of a dual-wire mesh system, followed by aging at 35 ° C. for 3 days to obtain SMC-1.

(4) The polypropylene film was peeled off from SMC-1, and 600 g was charged into a mold having a flat press having a size of 220 mm × 220 mm. The ratio of the area covered by the SMC on the surface) is 46.5%, and the surface pressure is 10%.
The plate was heated and compressed at a holding pressure of 7 minutes at a pressure of MPa to produce a flat molded product M-1 having a thickness of 7 mm.

Example 2 (1) PET was added to a device similar to (1) in Example 1 to 86.
1.7 g, 466.7 g of neopentyl glycol, 568.5 g of propylene glycol, and 0.22 g of t-butyl titanate were charged, heated to 200 ° C. in an inert gas stream, and reacted for 5 hours. After that, it is cooled to 160 ° C,
Further, 376.9 of DM-1 obtained in (1) of Example 1 was used.
g, 1026.2 g of maleic anhydride and 0.07 g of toluquinone, heated to 210 ° C., and allowed to undergo a condensation reaction for 10 hours to obtain an unsaturated polyester resin UP-II having an acid value of 22.
I got 60 parts by weight of the UP-II and 0.1 part of tolquinone were added.
It was added to 40% by weight of styrene dissolved in 03% and completely dissolved to obtain an unsaturated polyester resin composition UP-2.

(2) Except that UP-2 is used in place of UP-1, the SMC-
2 was obtained. (3) M-2 was obtained in exactly the same manner as in (4) of Example 1, except that SMC-2 was used instead of SMC-1.

Comparative Example 1 (1) PET was used in an apparatus similar to (1) of
2.1 g, 537.4 g of neopentyl glycol, 589.0 g of propylene glycol, and 0.25 g of t-butyl titanate were charged, heated to 200 ° C. with a mantle heater in an inert gas stream, and reacted for 5 hours. afterwards,
After cooling to 160 ° C., the maleic anhydride was further added to 1181.
5 g and 0.07 g of toluquinone were charged, heated to 210 ° C., and subjected to a condensation reaction for 10 hours to obtain an unsaturated polyester resin UP-III having an acid value of 24. 60 parts by weight of UP-III and 40 parts by weight of styrene in which 0.03% of tolquinone was dissolved were added and completely dissolved to obtain an unsaturated polyester resin composition UP-3.

(2) Except that UP-3 is used instead of UP-1, the SMC-
3 was obtained. (3) M-3 was obtained in exactly the same manner as (4) of Example 1, except that SMC-3 was used instead of SMC-1.

Comparative Example 2 (1) In a device similar to (1) of Example 1, 181.4 g of dicyclopentadiene and 134.5 of maleic anhydride were used.
g, 24.7 g of distilled water and 0.06 g of tolquinone, and heated with a mantle heater while suppressing heat generation in an inert gas stream, and reacted at 140 ° C. for 2 hours to obtain a monoester of dicyclopentadiene and maleic acid. (Dicyclopentadiene maleate) After making, cool to 100 ° C,
911.6 g of isophthalic acid, 1075.1 g of propylene glycol, and 672.6 g of maleic anhydride were charged, heated to 215 ° C. in an inert gas stream, and allowed to undergo 10 condensation reactions to obtain an unsaturated polyester resin UP having an acid value of 30. -IV was obtained. 60 parts by weight of this UP-IV and 0.03 parts of tolquinone
% Dissolved styrene and completely dissolved to obtain an unsaturated polyester resin composition UP-4.

(2) Except that UP-4 is used instead of UP-1, the SMC-
4 was obtained. (3) M-4 was obtained in exactly the same manner as in (4) of Example 1, except that SMC-4 was used instead of SMC-1.

Comparative Example 3 (1) In a device similar to (1) of Example 1, 962.9 g of neopentyl glycol and 40 propylene glycol were used.
0.4 g, 1046.0 g of maleic anhydride, 590.7 g of isophthalic acid, and 0.06 g of tolquinone,
In an inert air stream, heat to 225 ° C with a mantle heater,
The mixture was subjected to a condensation reaction for 15 hours to obtain an unsaturated polyester resin UP-V having an acid value of 22. 60 parts by weight of UP-V and 40 parts by weight of styrene in which 0.03% of tolquinone was dissolved were added and completely dissolved to obtain an unsaturated polyester resin composition U.
P-5 was obtained.

(2) Except that UP-5 is used in place of UP-1, the SMC-
5 was obtained. (3) M-5 was obtained in exactly the same manner as in (4) of Example 1, except that SMC-5 was used instead of SMC-1.

Next, a method for evaluating characteristics will be described.
The evaluation results are shown in Table 1. (A) Heat-resistant water 1 part by weight of t-butyl perbenzoate (Perbutyl Z (trade name) manufactured by NOF CORPORATION) is mixed with 100 parts by weight of the unsaturated polyester resin compositions UP-1 to UP-5. , And poured into a flat mold having a thickness of 3 mm.
Minutes, 100 ° C for 30 minutes, 120 ° C for 30 minutes, and 140
The mixture was sequentially heated at 180 ° C. for 180 minutes to be cured. The obtained cured product was cut into 50 mm × 50 mm, immersed in distilled water at 95 ° C., and visually inspected for cracks every 100 hours.

(B) Viscosity after aging (thickening) Compound C-1 of (3) of Example 1
A cylindrical metal can having a height of 88 mm was filled with 420 g and capped, and then aged at 35 ° C. for 3 days. At this time, the viscosity at 35 ° C. was measured with a Brookfield rotational viscometer HBTDV-II. Except for using UP-2 to UP-5 in place of UP-1, a compound was prepared in exactly the same manner as in (3) of Example 1, and the viscosity after aging was measured in the same manner.

(C) Uniform Coloring (Color Unevenness) The upper mold surfaces of the flat molded products M-1 to M-5 were visually observed, and according to the degree of color unevenness, the order of the color unevenness was as follows. No <Δ <×: When the color unevenness was conspicuous, it was represented by a symbol and evaluated.

[0066]

[Table 1]

[0067]

According to the unsaturated polyester resin composition of the present invention, it is possible to obtain a thermosetting molding material having high hot water resistance, which can be uniformly colored even if it is deeply colored and does not cause color unevenness. It is something.

Continued on front page F-term (reference) 4J027 AB04 AB05 AB06 AB07 AB08 AB13 AB14 AB15 AB16 AB17 AB18 AB19 AB22 AB23 AB24 AB25 BA04 BA05 BA07 BA09 BA13 BA19 BA22 BA23 BA26 BA27 BA29 4J029 AA07 AB01 AE01 AE03 BA02 BA03 BA10 BA05 BA08 BA09 BA09 BD04A BD10 BF08 BF09 BF10 BF18 BG01 CA02 CA04 CA05 CA06 CB04A CB05A CB06A CD03 FC36 FC38 GA12 GA13 GA14 GA15 GA17 GA23 GA24 GA93 HB01 HB06 KA02 KH01 KH08

Claims (1)

[Claims] 1. A mole of terephthalic acid (a), (b)
α, β-unsaturated polybasic acid or anhydride bmol,
(C) saturated polybasic acid or its anhydride c mole and (d)
Each component of d mol of polyhydric alcohol and e mol of (e) dicyclopentadiene is contained as a raw material, and the compounding molar ratio is (a + b + c) / a / b / c / d / e is 1 / 0.0.
1-0.8 / 0.2-0.99 / 0-0.79 / 0.4
An unsaturated polyester resin composition obtained by dissolving an unsaturated polyester resin blended and reacted so as to be from 1.8 to 0.05 to 1 in a crosslinkable monomer.