JP2001131269A - Preparation method for unsaturated polyester resin and its composition, and thermoset molding material and plastic molding using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a preparation method for an unsaturated polyester resin by using, as a raw material, low-cost polyethylene terephthalate of an object of discard of ends chips, a defective, etc., brought through a PET molding and its production process, and recovered used films, bottles, etc. SOLUTION: The preparation method for the unsaturated polyester resin comprises depolymerizing polyethylene terephthalate in which an each molar concentration of a terephthalic acid unit and an ethylene glycol unit which are constituting units is (a) mol in the presence of an alcohol, removing the ethylene glycol of (0.1-1.0) (a) mol outside of the system, then charging α,β-unsaturated polybasic acid or its anhydride, saturated polybasic acid or its anhydride, and a polyhydric alcohol, and dehydrating condensation reacting the resulting reactants.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an unsaturated polyester resin, an unsaturated polyester resin composition,
And a thermosetting molding material and a plastic molded product using the same.

[0002]

2. Description of the Related Art Typical thermosetting molding materials for compression molding include SMC (sheet molding compound) and BMC (bulk molding compound). SMC is generally composed of 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, a curing agent such as an organic peroxide, a polystyrene. A low-shrinkage agent such as 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 and the like were applied on a lower film, and cut on the lower film. Roving (glass fiber) is sprinkled, and the film coated with the above-mentioned compound is further superimposed thereon, then impregnated and defoamed into the glass fiber through between rollers, and then aged to obtain a sheet-like form. Molding material, BMC is generally chopped strand in the same compound as SMC Glass fibers) were kneaded added followed be obtained by aging a bulk molding material.

[0003] Since these thermosetting molding materials can be designed relatively freely and can provide high-quality molded products, they are required to be smooth and glossy in bathtubs, kitchen counters, washbasins, wall panels and the like. Also used for applications. These molded articles are required to have properties such as hot water resistance and chemical resistance, and conventionally, unsaturated polyester resins of isophthalic acid type, neopentyl glycol type, or a combination thereof have been used in many cases. However, since these unsaturated polyester resins are relatively expensive, inexpensive unsaturated polyester resins having performance equal to or higher than these unsaturated polyester resins are desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide polyethylene terephthalate (PET), for example, scraps generated during the production of PET, PET molded articles such as films and bottles, and scraps generated during the production process. Unsaturated polyester resin capable of obtaining a thermosetting molding material with excellent hot water resistance and chemical resistance using inexpensive polyethylene terephthalate such as waste products such as defective products, collected used films, bottles, etc. It is intended to provide a method of manufacturing.

Another object of the present invention is to provide an unsaturated polyester resin composition, a thermosetting molding material, and a plastic molded article using the above unsaturated polyester resin which are excellent in hot water resistance and chemical resistance. .

[0006]

That is, the present invention provides a method for depolymerizing an amount of polyethylene terephthalate in which the number of moles of terephthalic acid units and ethylene glycol units, which are constituent units, is each a mole, in the presence of an alcohol, 0.1
~ 1.0) a mole of ethylene glycol is removed out of the system, then an α, β-unsaturated polybasic acid or anhydride thereof,
A saturated polybasic acid or its anhydride and a polyhydric alcohol, a, the number of moles of terephthalic acid units in the system, b, the number of moles of α, β-unsaturated polybasic acid or its anhydride, a saturated polybasic acid or When the number of moles of the anhydride is c and the number of moles of the polyhydric alcohol is c, the molar ratio (a + b + c) / a / b / c /
((0-0.9) a + d) is 1 / 0.05-0.5 /
The present invention relates to a method for producing an unsaturated polyester resin, which is prepared so as to be 0.5 to 0.95 / 0 to 0.45 / 0.7 to 1.3, and is subjected to a dehydration condensation reaction.

[0007] The present invention also relates to an unsaturated polyester resin obtained by the above production method.

[0008] The present invention also relates to an unsaturated polyester resin composition comprising the above unsaturated polyester resin mixed with a crosslinkable monomer.

[0009] The present invention also relates to a thermosetting molding material comprising the unsaturated polyester resin composition.

[0010] The present invention also relates to a plastic molded product obtained by curing the thermosetting molding material.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION PET used in the method for producing an unsaturated polyester resin of the present invention does not have to be a high-purity material. For example, PET molded products such as scraps, films, bottles, etc. generated during PET manufacturing, wastes such as defective scraps generated in the production process, collected used films, recycled products such as bottles But it can be used. PET is preliminarily depolymerized in the presence of an alcohol (it is considered that a transesterification reaction also partially proceeds) to remove 10 to 100 mol%, preferably 50 to 100 mol%, of ethylene glycol in the PET to the outside of the system. Then use it. In order that this depolymerization and ethylene glycol removal proceed promptly, it is desirable that PET is broken, crushed, washed and dried to 50 mm or less, preferably 5 mm or less. As the alcohol, dipropylene glycol or the like is preferably used. As the alcohol, it is preferable to use a part of the polyhydric alcohol used as a raw material of the unsaturated polyester resin. The amount of alcohol used is preferably 1 to 20 mol per 1 mol of PET.

In order to quickly depolymerize PET and remove ethylene glycol, the reaction is preferably carried out at a high temperature equal to or higher than the softening point of PET (about 200 ° C.). To increase the pressure, preferably under pressure (preferably 0.1 to 0.5MP
a) is performed. Further, the pressure can be reduced to quickly remove ethylene glycol from the system. Further, for example, by using a catalyst such as t-butyl titanate, zinc acetate, dibutyl titanate, the decomposition temperature can be lowered. The amount of the reaction catalyst is preferably from 0.01% by weight to 0.5% by weight, more preferably from 0.1% by weight to 0.3% by weight, based on the amount of PET.
It is. When the amount of the reaction catalyst is more than 0.5% by weight, the hot water resistance of the resulting cured product of the unsaturated polyester resin decreases. In the present invention, the molecular weight of PET was set to 192, considering that 1 mol of terephthalic acid and 1 mol of ethylene glycol except for 2 mol of water were regarded as one unit. In the depolymerization, the number average molecular weight of the depolymerized PET is 400 to 1,
It is preferable to perform the process up to about 200.

[0013] In addition to PET, a saturated polybasic acid ester may be used, if necessary, in the range of 0 to 50% by weight of PET. As the saturated polybasic acid ester,
Ethylene glycol, propylene glycol, alkylene glycols such as butylene glycol, in particular, linear alkylene glycol and adipic acid, sebacic acid, dibasic acids such as terephthalic acid, in particular, a linear alkylene group or
There are low molecular weight esters or high molecular weight esters (ie, saturated polyesters) of a dibasic acid having a paraphenyl group and a carboxyl group bonded thereto, for example, di (ethylene terephthalate), di (butylene terephthalate), polybutylene terephthalate, Examples thereof include di (ethylene adipate), di (butylene adipate), polyethylene adipate, polybutylene adipate, and polyethylene naphthalate, and one or more of these can be used.

The α, β-unsaturated polybasic acids or anhydrides used in the present invention include, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like and reactive derivatives such as anhydrides thereof. And the like, and one or more of these can be used.

The saturated polybasic acid or anhydride used in the present invention includes phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid, Adipic acid, sebacic acid, glutaric acid, tetrabromophthalic acid, trimellitic acid, pyromellitic acid, dimer acid, succinic acid, azelaic acid, rosin-
Derivatives such as aromatic carboxylic acids such as maleic acid adducts, saturated acids and anhydrides thereof, etc.
Species or two or more can be used.

The polyhydric alcohol used 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, Bromoneopentyl 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 Propylene oxide adducts, p-
Aromatic group-containing diols such as xylene-α, α'-diol; ethers such as pentaerythritol diallyl ether; trihydric or higher polyhydric alcohols such as glycerin;
Examples thereof include trimethylolpropane and pentaerythritol, and one or more of these can be used.

[0017] The unsaturated polyester resin of the present invention is preferably made of PE
After the depolymerization reaction of T, α, β-unsaturated polybasic acid or anhydride, saturated polybasic acid or anhydride and polyhydric alcohol are converted into a, α, β -When the number of moles of the unsaturated polybasic acid or its anhydride is b, the number of moles of the saturated polybasic acid or its anhydride is c and the number of moles of the polyhydric alcohol is d, the molar ratio (a + b + c) / a / b /
c / ((0-0.9) a + d) is 1 / 0.05-0.5
/0.5 to 0.95 / 0 to 0.45 / 0.7 to 1.3, and obtained by performing a dehydration condensation reaction. If (a + b + c) / a is less than 1 / 0.05, the surface gloss of the resulting molded article is reduced, and if it exceeds 1 / 0.5, (b) α, β-unsaturated polybasic acid or anhydride thereof , And good curability cannot be obtained. Conversely, (a +
When b + c) / b is less than 1 / 0.5, good curability cannot be obtained, and when it exceeds 1 / 0.95, the surface gloss of the obtained molded article decreases. Also, (a + b + c) / c is 1/0.
If it exceeds 45, (b) the amount of α, β-unsaturated polybasic acid or its anhydride is reduced, and good curability cannot be obtained.
(A + b + c) / ((0 to 0.9) a + d) is 1
If it is less than /0.7 or more than 1 / 1.3, the unsaturated polyester resin does not have a high molecular weight, and a molded product cannot have sufficient strength.

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 article, a compound selected from phosphoric acid triesters and phosphoric acid triesters, 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.
It may be used in an amount of 0.5 parts by weight, more preferably 0.1 to 0.3 parts by weight.

The dehydration-condensation reaction of the unsaturated polyester resin in the present invention can be performed by a conventionally known method. For example, the reaction proceeds while a polybasic acid component and a polyhydric alcohol component are subjected to a condensation reaction, and condensed water generated when both components react is removed from the system. The removal of the condensed water out of the system is preferably carried out by natural distillation or vacuum distillation by passing an inert gas. In order to promote the distillation of condensed water, a solvent such as toluene or xylene can be added to the system as an azeotropic component. The progress of the reaction can be generally known by measuring the amount of distillate generated by the reaction, quantifying the functional group at the end, measuring the viscosity of the reaction system, and the like.

The reaction temperature can be conveniently selected according to the boiling point of the material used, and is not particularly limited. However, it is preferably 150 ° C. or higher. In order to prevent a side reaction due to oxidation, nitrogen, carbon dioxide or the like is used. The reaction is preferably performed while passing an inert gas. For this reason, as the reaction apparatus, those made of glass, stainless steel, etc. are selected, and a stirrer, a fractionating apparatus for preventing distillation of the alcohol component by azeotropic distillation of water and the alcohol component, and increasing the temperature of the reaction system It is preferable to use a heating device, a temperature control device for the heating device, and a reaction device provided with a device for blowing an inert gas such as nitrogen.

The order of charging each material is as follows: a one-step synthesis method in which a polybasic acid component and a polyhydric alcohol are simultaneously charged and a condensation reaction is carried out; a polybasic acid component and a polyhydric alcohol component are subjected to a condensation reaction; The reaction can be carried out by a two-stage synthesis method in which the remaining polybasic acid component and polyhydric alcohol component are charged and reacted, and other production conditions are not particularly limited. However, in order to smooth the reaction and prevent problems such as gelation and side reactions, PET or polyhydric alcohol is initially or partially charged and depolymerized by the above-described method.
A method is employed in which 10 to 100% of ethylene glycol therein is removed out of the system and the remaining components are reacted thereafter.

The unsaturated polyester resin composition of the present invention can be obtained by blending the unsaturated polyester resin obtained above with a crosslinkable monomer and, if necessary, adding a polymerization inhibitor or the like to adjust curability. .

The crosslinking monomer used in the present invention is not particularly limited.
Aromatic vinyl compounds such as methylstyrene, 3-methylstyrene, p-methylstyrene, α-methylstyrene, t-butylstyrene, divinylbenzene, halogenated styrenes such as chlorostyrene, dichlorostyrene, brominated styrene, and pivalic acid Carboxylic acid monovinyl esters such as vinyl, vinyl 2-ethylhexanoate, vinyl laurate, and vinyl benzoate, neopentyl glycol dimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, pentaerythritol hexamethacrylate, and pentaerythritol hexaacrylate Methacrylic acid esters of polyhydric alcohols such as 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.

When the total amount of the unsaturated polyester resin and the crosslinking monomer is 100 parts by weight, the unsaturated polyester resin is 20 to 80 parts by weight and the crosslinking monomer is 80 to 80 parts by weight. Preferably it is 20 parts by weight. 2
If the amount is less than 0 parts 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 the molded product tends to crack, crack, or the like. . If the amount of the unsaturated polyester resin exceeds 80 parts by weight, the viscosity tends to be too high and it tends to be difficult to apply or mix with other components. From this, 45 to 70 parts by weight of the unsaturated polyester resin and 55
More preferably, it is set to 30 parts by weight.

The method of preparing the unsaturated polyester resin composition by mixing the unsaturated polyester resin with the crosslinkable monomer is not particularly limited, but the crosslinkable monomer is heated to 40 to 100 ° C. in advance. Easy to dissolve. At this time, when dissolving the unsaturated polyester resin having a temperature of 70 ° C. or higher, the temperature of the unsaturated polyester resin composition during the dissolution should be 70 ° C. or lower so that the dissolved unsaturated polyester resin composition does not gel. preferable.

As a polymerization inhibitor, parabenzoquinone,
Tolquinone, naphthoquinone, phenanthraquinone, 2,
Quinones such as 5-diphenylparabenzoquinone and 2,5-diacetoxyparabenzoquinone; hydroquinones such as toluhydroquinone, hydroquinone, tertiarybutylcatechol, monotertiarybutylhydroquinone, 2,5-ditertiarybutylhydroquinone, and hydroquinone monomethyl ether , 2,6-ditert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-ditert-butyl-4-
Phenols such as methylphenol, cresols such as di-tert-butylparacresol, organic copper salts such as copper naphthenate, amidines such as acetamidine acetate,
Examples thereof include hydrazines such as phenylhydrazine hydrochloride, and quaternary ammonium salts such as trimethylbenzylammonium chloride, and one or more of these 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.

When the unsaturated polyester resin composition is used as a thermosetting molding material, the polymerization inhibitor may be added at the time of producing the same.

Next, the method of using the unsaturated polyester resin composition according to the present invention will be described.

The unsaturated polyester resin composition of the present invention is effective for use as a thermosetting molding material in order to exhibit high gloss and high smoothness excellent in design, uniform coloring, and high hot water resistance. However, if necessary, the unsaturated polyester resin composition of the present invention may contain metal soaps such as cobalt naphthenate, cobalt octenoate, and manganese octoate, and N, N-dimethylaniline and N, N-diethylaniline. Aromatic tertiary amines, N, N-dimethylacetoacetamide, N, N-diethylacetoacetamide, methyl acetoacetate, ethyl acetoacetate, acetylacetone;
Curing accelerators such as dimedone, dibenzoylmethane, acetylcyclopentane, acetylbutyrolactone, and phenyldiethanolamine, thixotropic agents such as silicon oxide fine powder, thixotropic aids such as glycerin, waxes, defoamers,
Fillers such as calcium carbonate, aluminum hydroxide, various balloons and the like are added to form a molding resin composition, and the casting method, or impregnating a reinforcing material such as glass fiber or carbon fiber, for example, a hand lay-up method, spraying The same effect can be obtained even when applied to an injection molding method such as an open mold method such as an up method, an RTM method, and a back method.

Next, the thermosetting molding material of the present invention will be described. The thermosetting molding material of the present invention is characterized by containing the unsaturated polyester resin composition of the present invention, and there is no particular limitation other than this, if necessary, a low shrinkage agent, a filler, It contains a curing agent, an internal release agent, a polymerization inhibitor, a colorant, a thickener, a reinforcing material, and the like.

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 depends on the shrinkage and surface smoothness of the molded product,
It is determined in consideration of the surface gloss and is not particularly limited, but is 1 to 50 parts by weight, preferably 5 to 30 parts by weight based on 100 parts by weight of the total amount with the unsaturated polyester resin composition.
If the amount is less than 1 part by weight, the resulting molded article tends to have a large molding shrinkage. On the other hand, if it 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 article tend to deteriorate.

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, and pulverized products of various FRP molded products. 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 50 μm.
It is 1 to 10 μm, more preferably 0.5 to 5 μm. If the average particle size exceeds 50 μm, sufficient gloss tends not to be obtained in the molded product. If the average particle size is less than 0.05 μm, the viscosity of the obtained compounded resin is too high, impregnation into fibers becomes difficult, and the characteristics of the molded product become poor. Tends to worsen. 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, and is determined based on 100 parts by weight of the total amount of the unsaturated polyester resin composition. The amount is preferably 50 to 300 parts by weight, more preferably 100 to 200 parts by weight. When the amount is less than the above range, the viscosity increase of the thermosetting molding material is low, there is a tendency to be sticky and it is difficult to handle, and when the amount is more than the range, the viscosity of the resin composition for the molding material becomes high, and the workability is increased. And the impregnating property to the fiber reinforcement tends to be poor.

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, etc., it is determined according to each of them and by the molding temperature. However, the 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 unsaturated polyester resin composition from the viewpoints 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 exceeds 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 by the design properties of the obtained molded product, but is preferably 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. Department.

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

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, which is cut into 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 3% by weight.
A range of 0% by weight is more preferred.

The thermosetting molding material according to the present invention, for example, S
MC and BMC can be manufactured using a normal SMC manufacturing apparatus or BMC manufacturing apparatus, respectively.

In the case of SMC, a compound is prepared by mixing the above-mentioned auxiliary materials 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 thickener is blended, it is preferable to mix the thickener afterwards in order to avoid a viscosity increase before the reinforcement is impregnated. . 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 on which the compounding resin is applied is overlapped so that the dispersed reinforcing material is 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 the reinforcing material is mixed with a compound similar to SMC, for example, devices 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.
It is more preferably adjusted to be from 00 Pa · s to 160,000 Pa · s, and from 30,000 to 160,0
It is particularly preferable to adjust the pressure to be 00 Pa · s, and these can be adjusted by the amount of the thickener and the aging conditions. If the viscosity is too low, scumming is likely to occur on the surface of the molded article, and if the viscosity is too high, the mold clamping time will be long and the molding cycle will tend to be long.

Next, a plastic molded product obtained by curing the thermosetting molding material according to the present invention will be described.

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 70-160 ° C., further preferably 120-150 ° C., and a surface pressure of 0.5-50 MPa
a, more preferably 1 to 20 MPa, even more preferably 5 to 15 MPa. Also,
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.

[0048]

Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 (1) 719.3 g (5.37 mol) of dipropylene glycol and PET (5 to 3 liter four-necked flask equipped with a reflux pipe, an inert gas introduction pipe, a thermometer and a stirrer) 1
157.1 g (0.82
Mol) and 0.04 g of t-butyl titanate, heated in an inert gas stream with a mantle heater, heated from 200 ° C. to 230 ° C. over 3 hours, kept at 230 ° C. for 1 hour, and kept at 180 ° C. ℃. At this time, 31.7 g of glycol was distilled off. Gas chromatography analysis of this glycol distillate revealed that ethylene glycol was 25.4 g.
(0.41 mol), 6.3 g of dipropylene glycol
(0.05 mol). The number average molecular weight of the depolymer (determined in terms of polystyrene using gel permeation chromatography, the same applies hereinafter) was 660. Next, at a temperature of 180 ° C., 340.3 g (3.27 mol) of neopentyl glycol, 621.7 g (8.18 mol) of propylene glycol, 1523.2 g (15.54 mol) of maleic anhydride, 0.07 g of tolquinone was charged, heated to 225 ° C., dehydrated and condensed by a conventional method, and cooled to 180 ° C. when the acid value reached 22 KOH mg / g, and dissolved in 1850 g of styrene to which 0.55 g of tolquinone was added. Thus, an unsaturated polyester resin composition UP-1 was obtained. The number average molecular weight of the unsaturated polyester resin was 3,300.

(2) 80 parts by weight of UP-1, 20 parts by weight of a 32% by weight styrene solution of polystyrene having a number average molecular weight of 80,000, 1 part by weight of t-butyl perbenzoate, and an average particle diameter of 1.7 μm. 130 parts by weight of calcium carbonate, 4 parts by weight of zinc stearate, 0.04 parts by weight of parabenzoquinone, 4 parts by weight of OP Gray SS-6675 (trade name of Mikuni Pigment Co., Ltd.), and 1 part by weight of magnesium oxide To obtain Compound C-1. afterwards,
C-1 is applied to the upper and lower polypropylene films by the SMC manufacturing equipment, and the roving (glass fiber) cut into 1 inch is sprayed on the lower side so that the content in the SMC is 23% by weight, and C-1 is applied. After overlapping the surfaces
Impregnated and defoamed through a dual wire mesh type roller, then aged at 35 ° C. for 3 days, SMC
-1 was obtained.

(3) The polypropylene film was peeled off from the SMC-1, and the temperature of a pressing device having a flat mold having dimensions of 220 mm × 220 mm was 145 ° C. on the upper side and 130 ° on the lower side.
600 g was charged into a mold set at 4 ° C. so as to have a charge rate of 46.5% (the ratio of the area covered by the SMC on the mold surface).
m flat molded article M-1 was produced.

Example 2 (1) 1307.8 g (9.76 mol) of dipropylene glycol and 14 parts of PET were placed in a three-liter four-necked flask equipped with a reflux tube, an inert gas introduction tube, a thermometer and a stirrer.
89.4 g (7.76 mol) and 0.37 g of t-butyl titanate were charged and heated with a mantle heater in an inert gas stream, and the temperature was raised from 200 ° C. to 230 ° C. over 3 hours.
The temperature was kept at 230 ° C for 3 hours, and the temperature was lowered to 180 ° C. At this time, 300.7 g of glycol was distilled off. Gas chromatography analysis of this glycol distillate revealed that ethylene glycol was 240.6 g (3.88 mol) and dipropylene glycol was 60.1 g (0.45 mol). Also, the number average molecular weight of this depolymerized product (determined in terms of polystyrene using gel permeation chromatography,
The same applies hereinafter) was 840. Next, at a temperature of 180 ° C., 322.7 g of neopentyl glycol (3.10
Mol), 760.2 g (7.76 mol) of maleic anhydride and 0.07 g of toluquinone, and the mixture was heated to 225 ° C., subjected to a dehydration condensation reaction by a conventional method, and obtained an acid value of 23 KOHm.
When g / g was reached, the mixture was cooled to 180 ° C. and dissolved in 1850 g of styrene to which 0.55 g of tolquinone was added, to obtain an unsaturated polyester resin composition UP-2. When the number average molecular weight of the unsaturated polyester resin was determined, it was 300
It was 0.

(2) Except that UP-2 is used instead of UP-1, the SMC-
2 was obtained.

(3) Except that SMC-2 is used in place of SMC-1, M-
2 was obtained.

Example 3 (1) 834.1 g (6.22 mol) of dipropylene glycol and 46 parts of PET were placed in a 3-liter four-necked flask equipped with a reflux tube, an inert gas introduction tube, a thermometer, and a stirrer.
7.0 g (2.43 mol) and 0.12 g of t-butyl titanate were charged and heated with a mantle heater in an inert gas stream, and the temperature was raised from 200 ° C. to 230 ° C. over 3 hours.
The temperature was kept at 230 ° C for 1 hour, and the temperature was lowered to 180 ° C. At this time, 94.3 g of glycol was distilled off. Gas chromatography analysis of this glycol distillate revealed that ethylene glycol was 75.4 g (1.22 mol) and dipropylene glycol was 18.9 g (0.14 mol). Also,
The number average molecular weight of this depolymer (determined in terms of polystyrene using gel permeation chromatography, the same applies hereinafter) was 710. Next, at a temperature of 180 ° C,
337.3 g (3.24 mol) of neopentyl glycol and 493.0 g (6.49 mol) of propylene glycol
Mol), 1350.8 g (13.78) of maleic anhydride.
Mol) and tolquinone (0.07 g), and the mixture was heated to 225 ° C., and subjected to a dehydration-condensation reaction by a conventional method to give an acid value of 22 KOH.
mg / g, cooled to 180 ° C. and dissolved in 1850 g of styrene to which 0.55 g of tolquinone was added,
An unsaturated polyester resin composition UP-3 was obtained. The number average molecular weight of the unsaturated polyester resin was determined to be 32.
00.

(2) Except that UP-3 is used in place of UP-1, the SMC-
3 was obtained.

(3) Except that SMC-3 is used in place of SMC-1, M-
3 was obtained.

Example 4 (1) 112.2 g (8.30 mol) of dipropylene glycol and 12 parts of PET were placed in a 3-liter four-necked flask equipped with a reflux tube, an inert gas introduction tube, a thermometer, and a stirrer.
18.5 g (6.35 mol) and 0.30 g of t-butyl titanate were charged and heated with a mantle heater in an inert gas stream, and the temperature was raised from 200 ° C. to 230 ° C. over 3 hours.
The temperature was kept at 230 ° C for 2 hours, and the temperature was lowered to 180 ° C. At this time, 245.9 g of glycol was distilled off. Gas chromatography analysis of this glycol distillate revealed that ethylene glycol was 196.7 g (3.17 mol) and dipropylene glycol was 49.2 g (0.37 mol). Also, the number average molecular weight of this depolymerized product (determined in terms of polystyrene using gel permeation chromatography,
The same applies hereinafter) was 920. Next, at a temperature of 180 ° C., 330.0 g of neopentyl glycol (3.17 g) was added.
Mol), 180.9 g (2.3
82.9 mol), 932.9 g (9.52 mol) of maleic anhydride and 0.07 g of toluquinone were charged, and the mixture was heated to 225 ° C., subjected to a dehydration-condensation reaction according to a conventional method, to obtain an acid value of 23 KOHm.
When g / g was reached, the mixture was cooled to 180 ° C. and dissolved in 1850 g of styrene to which 0.55 g of tolquinone was added to obtain an unsaturated polyester resin composition UP-4. The number average molecular weight of the unsaturated polyester resin was determined to be 340.
It was 0.

(2) Except that UP-4 is used instead of UP-1, the SMC-
4 was obtained.

(3) Except that SMC-4 is used in place of SMC-1, M-
4 was obtained.

Example 5 (1) 715.8 g (5.34 mol) of dipropylene glycol and 92 parts of PET were placed in a 3-liter four-necked flask equipped with a reflux tube, an inert gas introduction tube, a thermometer, and a stirrer.
1.8 g (4.80 mol) and 0.23 g of t-butyl titanate were charged and heated with a mantle heater in an inert gas stream, and the temperature was raised from 200 ° C. to 230 ° C. over 3 hours.
The temperature was kept at 230 ° C for 1 hour, and the temperature was lowered to 180 ° C. At this time, 37.3 g of glycol was distilled off. Gas chromatography analysis of this glycol distillate revealed that ethylene glycol was 29.8 g (0.48 mol) and dipropylene glycol was 7.5 g (0.06 mol). The number average molecular weight of the depolymer (determined in terms of polystyrene using gel permeation chromatography, the same applies hereinafter) was 680. Next, at a temperature of 180 ° C., 332.9 g (3.20 mol) of neopentyl glycol, 304.1 g (4.0 mol) of propylene glycol, 1097.9 g (11.2 mol) of maleic anhydride, 0.07 g of tolquinone was charged, the temperature was raised to 225 ° C., and a dehydration-condensation reaction was carried out by an ordinary method to obtain an acid value of 20 KOHm.
When g / g was reached, the mixture was cooled to 180 ° C. and dissolved in 1850 g of styrene to which 0.55 g of toluquinone was added, to obtain an unsaturated polyester resin composition UP-5. When the number average molecular weight of the unsaturated polyester resin was determined, it was 330
It was 0.

(2) Except that UP-5 is used instead of UP-1, the SMC-
5 was obtained.

(3) Except that SMC-5 is used in place of SMC-1, M-
5 was obtained.

Example 6 (1) In a 3-liter four-necked flask equipped with a reflux tube, an inert gas introduction tube, a thermometer, and a stirrer, 1216.9 g (9.08 mol) of dipropylene glycol and 92 PET were added.
1.8 g (4.80 mol) and 0.23 g of t-butyl titanate were charged and heated with a mantle heater in an inert gas stream, and the temperature was raised from 200 ° C. to 230 ° C. over 3 hours.
The temperature was kept at 230 ° C for 3 hours, and the temperature was lowered to 180 ° C. At this time, 297.6 g of glycol was distilled off. Gas chromatography analysis of this glycol distillate revealed that the amount of ethylene glycol was 238.1 g (3.84 mol) and that of dipropylene glycol was 59.5 g (0.44 mol). Also, the number average molecular weight of this depolymerized product (determined in terms of polystyrene using gel permeation chromatography,
The same applies hereinafter) was 640. Next, at a temperature of 180 ° C., 332.9 g of neopentyl glycol (3.20 g) was added.
Mol) and 304.1 g (4.0) of propylene glycol.
Mol), 1097.9 g (11.2 mol) of maleic anhydride and 0.07 g of toluquinone, and the mixture was heated to 225 ° C. and subjected to a dehydration-condensation reaction by a conventional method to give an acid value of 22 KOHm.
When g / g was reached, the mixture was cooled to 180 ° C. and dissolved in 1850 g of styrene to which 0.55 g of toluquinone was added, to obtain an unsaturated polyester resin composition UP-6. The number average molecular weight of the unsaturated polyester resin was determined to be 340.
It was 0.

(2) Except that UP-6 is used instead of UP-1, SMC-
6 was obtained.

(3) Except that SMC-6 is used in place of SMC-1, M-
6 was obtained.

Comparative Example 1 (1) In a device similar to (1) of Example 1, 803.3 g (5.99 mol) of dipropylene glycol, 311.7 g (3.0 mol) of neopentyl glycol, and propylene 512.5 g (6.74 mol) of glycol, 1174.9 g (11.99 mol) of maleic anhydride, 497.5 g (3.0 mol) of isophthalic acid, and 0.07 g of tolquinone were charged into an inert gas stream. The mixture was heated to 225 ° C. with a mantle heater, and allowed to undergo a condensation reaction for 15 hours.
When KOH mg / g was reached, the mixture was cooled to 180 ° C. and dissolved in 1850 g of styrene to which 0.55 g of toluquinone was added, to obtain an unsaturated polyester resin composition UP-7.
The number average molecular weight of the unsaturated polyester resin was 3,300.

(2) Except that UP-7 is used instead of UP-1, the SMC-
7 was obtained.

(3) Except that SMC-7 is used in place of SMC-1, M-
7 was obtained.

Comparative Example 2 (1) 1615.6 g (12.06 mol) of dipropylene glycol and 1 PET were placed in a 3-liter four-necked flask equipped with a reflux tube, an inert gas introduction tube, a thermometer, and a stirrer.
770.7 g (9.22 mol) and 0.44 g of t-butyl titanate were charged, and heated with a mantle heater in an inert gas stream. The temperature was raised from 200 ° C. to 230 ° C. over 3 hours. The temperature was maintained for 180 hours. At this time, 357.4 g of glycol was distilled off. Gas chromatography analysis of this glycol distillate revealed that ethylene glycol was 285.9 g (4.61 mol) and dipropylene glycol was 71.5 g (0.53 mol). The number average molecular weight of the depolymer (determined in terms of polystyrene using gel permeation chromatography, the same applies hereinafter) was 940. Next, 180 ° C
, 602.5 g (6.15 mol) of maleic anhydride and 0.07 g of tolquinone were charged, the temperature was raised to 225 ° C, and a dehydration-condensation reaction was carried out by a conventional method to obtain an acid value of 22 KOHm.
When g / g was reached, the mixture was cooled to 180 ° C. and dissolved in 1850 g of styrene to which 0.55 g of toluquinone was added, to obtain an unsaturated polyester resin composition UP-8. The number average molecular weight of the unsaturated polyester resin was determined to be 290
It was 0.

(2) Except that UP-8 is used instead of UP-1, the SMC-
8 was obtained.

(3) Except that SMC-8 is used instead of SMC-1, M-
8 was obtained.

Comparative Example 3 (1) 834.3 g (6.23 mol) of dipropylene glycol and 89 of PET were placed in a 3-liter four-necked flask equipped with a reflux tube, an inert gas introduction tube, a thermometer, and a stirrer.
6.6 g (4.67 mol) and 0.22 g of t-butyl titanate were charged, heated with a mantle heater in an inert gas stream, heated to 210 ° C., and kept at 210 ° C. for 5 hours.
The temperature was reduced to 180C. At this time, there was no distillation of glycol. The number average molecular weight of this depolymer (determined in terms of polystyrene using gel permeation chromatography, the same applies hereinafter) was 720. Next, 180
323.8 g of neopentyl glycol at a temperature of 400 ° C.
(3.11 mol), 177.5 propylene glycol
g (2.34 mol), 1067.8 g of maleic anhydride
(10.90 mol), 0.07 g of tolquinone was charged,
The temperature was raised to 225 ° C., and a dehydration-condensation reaction was performed by a conventional method. When the acid value reached 22 KOH mg / g, the solution was cooled to 180 ° C., and styrene 1850 containing 0.55 g of toluquinone was added.
g) to obtain an unsaturated polyester resin composition UP-9. The number average molecular weight of the unsaturated polyester resin was 3,200.

(2) Except that UP-9 is used instead of UP-1, SMC-
9 was obtained.

(3) Except that SMC-9 is used in place of SMC-1, M-
9 was obtained.

(A + b + c) /
Table 1 shows the values of a / b / c ((0 to 0.9) a + d).

Next, a method for evaluating characteristics will be described.
The evaluation results are shown in Table 2. (A) Hot water resistance 1 part by weight of t-butyl perbenzoate was mixed with 100 parts by weight of each of the unsaturated polyester resin compositions UP-1 to UP-9, and the mixture was poured into a flat plate having a thickness of 3 mm. 30 minutes at 80 ° C, 30 minutes at 100 ° C, 3 at 120 ° C
The mixture was heated for 0 minutes and then sequentially at 140 ° C. for 180 minutes to be cured. The obtained cured product is cut into 5 cm × 5 cm,
The entire surface was immersed in distilled water at ℃ and visually observed for cracks every 100 hours. (B) Chemical resistance Chemicals were adhered to the molded articles M-1 to M-9, left for 24 hours, washed with water, and the degree of contamination was visually determined.

Judgment ；: Can be removed, △: A little remains, X: Almost remains

[0079]

[Table 1] MAC: maleic anhydride, IPAC: isophthalic acid, NPAL: neopentyl glycol, PGAL: propylene glycol, DPAL: dipropylene glycol, EGAL: ethylene glycol

[0080]

[Table 2]

[0081]

According to the unsaturated polyester resin composition of the present invention and a thermosetting molding material using the same, a molded article having excellent hot water resistance and chemical resistance can be obtained. Inexpensive PET
By using, it is also possible to make the resin composition, thermosetting molding material, and molded product cheaper than conventional ones.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (reference) // C08L 67:02 C08L 67:02 67:06 67:06 F term (reference) 4F071 AA49 AC05 AC09 AH03 BC02 4F301 AA25 CA09 CA13 CA22 CA72 4J027 AB06 AB07 AB08 AB15 AB16 AB17 AB18 AB19 AB23 AB24 AB25 AB26 BA04 BA05 BA07 BA09 BA19 BA22 BA23 BA26 BA28 BA29 CA02 CA03 CA04 CA05 CA06 CA08 CA14 CA18 CA19 CA32 CA34 CA36 CA38 CB03 CC02 CD02 AB02 BA03 BA04 BA05 BA08 BA09 BA10 BB04A BD03A BD09A BD10 BF09 BF10 BF17 BF18 BF23 BG01 CA02 CA04 CA05 CA06 CB04A CB06A CG08X EC10 FC03 FC05 FC08 FC35 FC36 GA03 GA12 GA13 GA14 GA15 GA17 GA22 JB03 JE02 KB 182KB

Claims (5)

[Claims] 1. An amount of polyethylene terephthalate, in which the number of moles of terephthalic acid units and ethylene glycol units as constituent units are each a mole, is depolymerized in the presence of an alcohol to give (0.1 to 1.0) a mole Is removed from the system, and then the α, β-unsaturated polybasic acid or its anhydride, the saturated polybasic acid or its anhydride and the polyhydric alcohol are converted to the number of moles of terephthalic acid units in the system. a,
b, the number of moles of the α, β-unsaturated polybasic acid or anhydride
When the number of moles of the saturated polybasic acid or anhydride is c and the number of moles of the polyhydric alcohol is d, the molar ratio (a + b + c)
/A/b/c/((0-0.9)a+d) is 1 / 0.0
5-0.5 / 0.5-0.95 / 0-0.45 / 0.7
A method for producing an unsaturated polyester resin, which comprises charging the mixture so as to be 1.3 to 1.3 and performing a dehydration condensation reaction. 2. An unsaturated polyester resin obtained by the production method according to claim 1. 3. An unsaturated polyester resin composition comprising the unsaturated polyester resin according to claim 2 and a crosslinking monomer. 4. A thermosetting molding material comprising the unsaturated polyester resin composition according to claim 3. 5. A plastic molded product obtained by curing the thermosetting molding material according to claim 4.