JP2001098059A - Method for manufacture of unsaturated polyester resin, unsaturated polyester resin composition, molding material, sheet molding material, and fiber reinforced plastic molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an unsaturated polyester resin composition having excellent processability toughness, crock resistance allowing weight reduction and suitable as a molding material. SOLUTION: This unsaturated polyester resin composition contains an unsaturated polyester resin having a number averaged mol.wt. of 5,000-30,000 and obtd. by reacting a polybasic acid component contg. as essential component an α, β-unsaturated polybasic acid or its anhydride with a polyvalent alcohol, a polymerizable monomer, and an isocyanate compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an unsaturated polyester resin, an unsaturated polyester resin composition, a molding material, a sheet-like molding material, and a method for producing a fiber-reinforced plastic molded product.

[0002]

2. Description of the Related Art A sheet molding compound (SMC) method widely used as one of FRP molding methods is a molding method using a sheet-like molding material, that is, SMC. The SMC is usually applied with a blended resin on a lower release film, sprinkled with glass fibers on top of it, and after laminating the release film coated with the blended resin thereon,
It is obtained by impregnating and defoaming through a roller of a book, winding and then aging at room temperature to 60 ° C. After aging, the film is peeled off, cut out arbitrarily, loaded into a mold, and subjected to thermal compression molding to obtain a molded product. Further, as a molding material, a bulk molding compound (BMC) obtained by mixing a compounded resin with glass fibers cut short, thickening and aging is also used.

[0003] The compounded resin is usually an unsaturated polyester resin, a polymerizable monomer, a filler such as calcium carbonate, a curing agent such as an organic peroxide, a low shrinkage material such as polystyrene, an internal release material, a pigment. And an unsaturated polyester resin composition in which a thickener and the like are appropriately mixed.

[0004] For deep-drawing molded products such as bathtubs and septic tanks, molding materials having good fluidity in the mold are usually used, and the molding materials are filled into the molds by high-temperature compression molding to produce molded products. .

Conventionally, a molded article molded by this method is:
It is installed at each place of use as housing equipment, but when the molded product is installed, cracks and cracks occur in the molded product due to dropping of the molded product or concentration of load on a part of the molded product, Problems such as the inability to achieve the original performance have occurred. In order to solve this, conventionally, a countermeasure has been taken with a molding material having an increased content of glass fiber as a reinforcing material.
However, in this method, the set value of the glass content is determined by a coating machine that manufactures the molding material, and if the glass fiber content is large, the impregnation into the glass fiber is poor, and the appearance of the molded product is deteriorated Troubles occurred. When a large amount of glass fiber is contained, it is difficult to uniformly disperse the glass fiber by the compression molding method.

[0006] The above-mentioned SMC molded products have disadvantages in recyclability and industrial waste treatment as compared with dicyclopentadiene or thermoplastic resin molded products which are one of thermosetting resin molded products. That is, the SMC molded product generally contains 10 to 50% by weight of glass fiber as a reinforcing material, and further contains an inorganic substance such as calcium carbonate or aluminum hydroxide as a filler. For this reason, when heat recovery and recycling is performed using raw materials such as cement fuel, compared to other thermoplastic resin molded products, the amount of heat generated is low and the heat recovery efficiency is low, or glass fibers and inorganic fillers remain, so that they are discarded after combustion. There are problems such as a large amount of processing. In addition, since material recycling contains glass fibers, it is difficult to separate the glass fibers at present and it is impossible at present. In addition, since SMC molded products contain high specific gravity glass fiber and inorganic fillers, they have higher specific gravity than dicyclopentadiene resin and thermoplastic resin, making it difficult to reduce the weight of the product and deteriorating workability. is there.

For these reasons, SMC molded products have been replaced by glass fiber-free dicyclopentadiene resins and thermoplastic resins in septic tanks, panel-assembled water tanks, exterior members for automobiles, and the like. It is getting.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an unsaturated polyester resin which is suitable for a molding material resin which can be reduced in weight and light in view of toughness.

It is another object of the present invention to provide an unsaturated polyester resin composition which is excellent in workability, is excellent in toughness, is hard to crack, and is suitable for molding materials which can be reduced in weight.

Another object of the present invention is to provide an unsaturated polyester resin composition which is excellent in workability, has a good aging property, is excellent in toughness, is hard to crack, and is suitable for molding materials which can be reduced in weight. is there.

Another object of the present invention is to provide an unsaturated polyester resin composition which is excellent in workability, good in aging, good in toughness, and suitable for producing a fiber-reinforced plastic molded product which is hard to crack. .

Another object of the present invention is to provide a molding material which is excellent in workability, good in aging, good in toughness, and suitable for producing a fiber-reinforced plastic molded product which is hard to crack.

Another object of the present invention is to provide a sheet-like molding material having good handleability, excellent workability, good maturation, good toughness, and suitable for producing a fiber-reinforced plastic molded product which is difficult to crack. Is to do.

Another object of the present invention is to provide a method for producing a fiber-reinforced plastic molded product which can produce a fiber-reinforced plastic molded product which is hard to be broken in view of toughness with good workability and yield.

Another object of the present invention is to provide a method for producing a fiber-reinforced plastic molded product which has inflammability and can be incinerated, and an unsaturated polyester resin composition used in this production method. An object, a molding material and a sheet-like molding material are provided.

[0016]

According to the present invention, there is provided a polyhydric alcohol obtained by reacting a polybasic acid component containing an α, β-unsaturated polybasic acid or its anhydride as an essential component with a polyhydric alcohol. 5,000 to 30,000 unsaturated polyester resins.

The present invention also relates to an unsaturated polyester resin composition containing the above-mentioned unsaturated polyester resin and a polymerizable monomer.

Further, the present invention relates to the above unsaturated polyester resin composition further containing an isocyanate compound.

The present invention also relates to the above unsaturated polyester resin composition further comprising a low shrinkage material, a curing agent and a filler.

[0020] The present invention also relates to the above molding material, which further comprises fibers in the above unsaturated polyester resin composition.

The present invention also relates to the molding material, wherein the fibers are a woven fabric in which fibers are entangled with each other.

[0022] The present invention also relates to the molding material, wherein the fibers are organic fibers.

Further, the present invention relates to the molding material, wherein the organic fiber is vinylon fiber.

Further, the present invention provides the above-mentioned vinylon fiber,
The molding material has a fiber length of 1 to 200 mm and a fiber diameter of 5 to 50 μm.

The present invention also relates to the molding material, wherein the content of the vinylon fiber is 1 to 60% by weight.

[0026] The present invention also relates to the molding material, wherein the filler is a crushed powder of a fiber-reinforced plastic molded product, and the content in the unsaturated polyester resin composition is 3 to 50% by weight.

Further, the present invention provides the above molding material, wherein the ground powder of the fiber-reinforced plastic molded product has an average particle diameter of 1 to 500 μm and a water content of 10.0% by weight or less. About.

The present invention also relates to a sheet-shaped molding material in which the above-mentioned molding material is present between two films.

The present invention also relates to a method for producing a fiber-reinforced plastic molded product, comprising thickening a molding material between the above-mentioned sheet-like molding materials, and then performing a heat compression molding.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the α, β-unsaturated polybasic acid or anhydride thereof, which is a polybasic acid component as a raw material for synthesizing an unsaturated polyester resin, includes, for example, α, β-
Unsaturated dibasic acids or anhydrides, such as maleic acid,
Examples thereof include fumaric acid, itaconic acid, citraconic acid, maleic anhydride and the like, and anhydrides thereof. These are 2
More than one species may be used in combination.

As the polybasic acid component, in addition to α, β-unsaturated polybasic acids or their anhydrides, from the viewpoint of controlling the concentration of unsaturated groups, and properties such as flexibility, strength and heat resistance. It is preferable to use a saturated polybasic acid or an anhydride thereof in combination. When a saturated polybasic acid or its anhydride is used in combination, α, β-
The ratio (molar ratio) of unsaturated polybasic acid or anhydride a and saturated polybasic acid b is a / (a + b) = 0.1
/0.1 to 0.95 / 1, preferably 0.4 / 1 to 0.95
/ 1 is more preferable, 0.45 / 1 to 0.95 / 1 is particularly preferable, 0.5 / 1 to 0.95 / 1 is further preferable, and 0.5 / 1 to 0.75 / 1 is extremely preferable. .

Examples of the saturated polybasic acids or anhydrides to be used in combination include, for example, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride Acid, hexahydrophthalic acid, hexahydrophthalic anhydride, glutaric acid, adipic acid, sebacic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid,
Dimer acid, succinic acid, azelaic acid, rosin-maleic acid adduct and the like. These may be used in combination of two or more. If necessary, a saturated polybasic acid ester can be used.

Examples of the saturated polybasic acid ester which can be used if necessary include alkylene glycols such as ethylene glycol, propylene glycol and butylene glycol, particularly, linear alkylene glycol and adipic acid, sebacic acid and terephthalic acid. There are low molecular weight esters or high molecular weight esters (i.e., saturated polyesters) of dibasic acids, especially linear alkylene groups or dibasic acids having a carboxyl group bonded to a paraphenylene group. Terephthalate), di (butylene terephthalate), polyethylene terephthalate, polybutylene terephthalate, di (ethylene adipate), di (butylene adipate), polyethylene adipate, polybutylene adipate and the like. These may be used in combination of two or more.

Polyhydric alcohols which are another raw material for the synthesis of unsaturated polyester resins include ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 1,
6-hexanediol, neopentyl glycol, 1,
Examples thereof include dihydric alcohols such as 4-cyclohexanediol and hydrogenated bisphenol A, trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric alcohols such as pentaerythritol. These may be used in combination of two or more.

The polybasic acid component and the polyhydric alcohol are preferably used in an equivalent ratio of 1 to 2.5 when the polybasic acid component is set to 1;
It is more preferable to use in the range of 5.
More preferably, it is used in a range of 3.0, and 1.0 is used.
It is particularly preferable to use in the range of from 0.05 to 2.0. When the polyhydric alcohol is reduced, the molecular weight of the obtained unsaturated polyester resin is reduced, or the polyester resin tends to be gelled at the time of producing the polyester resin. Progress tends to be slow.

The unsaturated polyester resin of the present invention can be produced, 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. 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.

During the reaction, it is preferable to carry out the reaction while passing an inert gas such as nitrogen or carbon dioxide in order to prevent side reactions such as coloring and gelling of the unsaturated polyester due to oxidation.

For this reason, the reaction apparatus is selected from those made of glass, stainless steel, etc., and includes a stirring apparatus, a fractionating apparatus for preventing distillation of the alcohol component due to azeotropic distillation of water and the alcohol component, and a reaction system. It is preferable to use a heating device for raising the temperature, a temperature control device for the heating device, a reaction device provided with a blowing device for an inert gas such as nitrogen, and the like.

At the time of the reaction, the reaction temperature can be lowered by using a catalyst such as t-butyl titanate. The amount of the catalyst to be used is preferably 0.01% by weight to 1% by weight, more preferably 0.1% by weight to 0.5% by weight, based on the total amount of the acid components. If the amount of the reaction catalyst exceeds 1% by weight, the weather resistance and hot water resistance of the obtained cured resin and molded product are reduced.

The reaction temperature is preferably in the range of 150 ° C. to 300 ° C., more preferably in the range of 160 ° C. to 280 ° C., and particularly preferably in the range of 190 ° C. to 280 ° C. When this temperature exceeds 300 ° C,
Boiling and evaporation of polyhydric alcohol become severe. The reaction temperature can be appropriately set depending on the boiling point of the polyhydric alcohol used.

The pressure in the reactor for conducting the synthesis reaction is as follows:
The reaction can proceed without problems even at normal pressure (760 Torr), but the reaction can be further promoted by increasing the boiling point of the polyhydric alcohol by applying pressure. in this case,
It is preferable to carry out in the range of 760 to 765 Torr.

Further, the reaction can be further promoted by reducing the pressure in the reactor in order to increase the molecular weight of the unsaturated polyester resin. In this case, 1
It is preferable to carry out in the range of 10 to 10 Torr.

The unsaturated polyester resin of the present invention has a number average molecular weight (measured by gel permeation chromatography and converted using a standard polystyrene calibration curve, the same applies hereinafter) of 5,000 to 30,000. You. Preferably it is 5,000-10,000. 5,
If it is less than 000, the toughness and impact resistance are poor. If it exceeds 30,000, the viscosity is too high, and the compatibility and workability are poor.

Examples of the polymerizable monomer used in the present invention include aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, dichlorostyrene, divinylbenzene and tert-butylstyrene. , Methyl methacrylate, ethyl methacrylate, alkyl methacrylate such as butyl methacrylate,
Alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, neopentyl glycol dimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, pentaerythritol hexamethacrylate, and polyhydric alcohols such as pentaerythritol hexaacrylate Examples include methacrylic acid ester, diallyl phthalate, triallyl cyanurate, acrylonitrile and the like. These may be used in combination of two or more. Among them, styrene is preferred from the viewpoint of compatibility with the unsaturated polyester and cost.

The unsaturated polyester resin composition of the present invention is produced by blending an unsaturated polyester resin and a polymerizable monomer, and adding a polymerization inhibitor if necessary. The mixing ratio of the unsaturated polyester resin and the polymerizable monomer at this time, when the total amount of both is 100 parts by weight, the unsaturated polyester resin is 10 to 80 parts by weight, the polymerizable monomer is 90 to 90 parts by weight. The amount is preferably 20 parts by weight, the unsaturated polyester resin is 30 to 65 parts by weight, and the polymerizable monomer is 70 parts by weight.
More preferably, it is up to 35 parts by weight. If the unsaturated polyester resin is less than 10 parts by weight, the viscosity of the unsaturated polyester resin composition is too low to be easily applied to a sheet,
In addition, it becomes difficult to mix uniformly with other components due to sedimentation and the like, and furthermore, even if the obtained fiber-reinforced molding material 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 cannot be applied in a sheet form and may be difficult to mix with other components.

The polymerization inhibitor optionally used includes p
-Benzoquinone, hydroquinone, naphthoquinone, p-
Tolquinone, 2,5-diphenyl-p-benzoquinone,
2,5-diacetoxy-p-benzoquinone, p-ter
t-butylcatechol, 2,5-di-tert-butylhydroquinone, di-tert-butyl-p-cresol, hydroquinone monomethyl ether, 2,6-di-
tert-butyl-4-methylphenol and the like. The compounding amount is appropriately determined depending on the curability of the obtained unsaturated polyester resin composition.
Total amount of unsaturated polyester resin and polymerizable monomer 100
The amount is preferably 0.01 to 5.0 parts by weight, more preferably 0.5 to 3 parts by weight based on parts by weight.

The isocyanate compound used in the present invention has a function of increasing the viscosity of the composition and gives good ripening properties. As such an isocyanate compound, a polyfunctional isocyanate compound is preferable. For example, hexamethylene diisocyanate, 2,2,4-
Aliphatic diisocyanates such as aliphatic diisocyanates such as trimethylhexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, cyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, and isopropylidene bis (4-cyclohexyl isocyanate); Aromatic diisocyanate such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, buret of hexamethylene diisocyanate, trimer of isophorone diisocyanate containing isocyanurate ring, and polymethylene polyphenyl polyisocyanate. Having compounds, lysine diisocyanate, tri Ji trimethylolpropane, glycerin, polyhydric alcohols such as pentaerythritol (n number)
Compounds obtained by reacting the above diisocyanate compound with n moles per mole, such as Millionate MR-100 (polymethylene polyphenyl polyisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like can be mentioned.

The mixing amount of these isocyanate compounds is
In the unsaturated polyester resin composition used, the amount is such that the hydroxyl group (OH group) of the unsaturated polyester resin / isocyanate group (NCO group) (molar ratio) of the isocyanate compound is 0.2 / 1 to 2/1. From the viewpoint of thickening, aging, toughness and impact resistance.
/ 1 to 1.3 / 1 is more preferable.

The unsaturated polyester resin composition of the present invention may further contain a low-shrinkage agent, a curing agent and a filler.

Examples of the low shrinkage material include polystyrene, polyvinyl acetate, polymethyl methacrylate, polyethylene, poly-ε-caprolactam, saturated polyester, polyvinyl chloride, polybutadiene, styrene-acrylic acid copolymer, and styrene-vinyl acetate. Examples thereof include copolymers, acrylonitrile-styrene copolymers, and thermoplastic rubbers such as styrene butadiene rubber and nitrile rubber, and these can be used alone or in combination of two or more. The compounding amount is 1 to 100 parts by weight of the unsaturated polyester resin from the viewpoint of the appearance, surface gloss, coloring, shrinkage and surface smoothness of the molded article obtained from the molded article.
It is preferably 10 parts by weight. If less than 1 part by weight,
The molding shrinkage of the obtained molded article increases. Also, 10
If the amount is more than 10 parts by weight, the low-shrinkage material is easily separated, and the appearance, surface gloss and uniformity of coloring of the obtained molded product are deteriorated.

Examples of the curing agent include 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 carbonates. The amount of the curing agent is preferably from 0.1 to 10 parts by weight based on 100 parts by weight of the unsaturated polyester resin from the viewpoints of storage stability and molding cycle.

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, and wood powder. Of these, calcium carbonate is preferred. The average particle size (representative particle size) of calcium carbonate is 0.05 to 50 from the viewpoint of gloss, impregnation and the like.
μm is preferred, and 0.1 to 0.8 μm is preferred.

The amount of the filler is preferably 100 to 300 parts by weight with respect to 100 parts by weight of the unsaturated polyester resin from the viewpoints of viscosity, fluidity, physical properties such as the strength of the molded article, and the like.

As a filler, a fiber-reinforced plastic molded product pulverized powder (FRP pulverized powder) can be used, and the incineration residue of the molded product can be reduced. The content of the FRP crushed powder is 3 to 50% by weight in the unsaturated polyester resin composition.
It is preferable that the average particle size of the pulverized powder is 1
It is preferable that the thickness is from 500 to 500 µm and the water content is 10.0% by weight or less. If the content of the crushed FRP powder in the unsaturated polyester resin composition is less than 3% by weight, the viscosity of the unsaturated polyester resin composition is low, and alkaline earth metal oxides such as magnesium oxide are separated and settled. The viscous reaction is difficult to proceed, the tack-free property after thickening is insufficient, the workability is reduced due to stickiness during handling, and defects such as pinholes are liable to occur during press molding. On the other hand, when the content exceeds 50% by weight, the viscosity of the unsaturated polyester resin composition increases remarkably, and when organic fibers such as vinylon fibers are blended, impregnation into the organic fibers deteriorates, and blisters and nests occur during molding. And defects such as pinholes tend to occur. Further, when the water content of the pulverized FRP powder exceeds 10.0% by weight, the water content of the unsaturated polyester resin composition increases, the rate of thickening during the production of SMC increases, and the impregnation of the vinylon fiber base material is performed. This is because there is a tendency that the properties are reduced, and as a result, defects such as blisters and pinholes may occur in the molded product.

The unsaturated polyester resin composition of the present invention can contain an internal release agent, a thickener, a coloring agent, etc. in addition to a low shrinkage agent, a curing agent and a filler.

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 preferably 1.0 to 10 parts by weight based on 100 parts by weight of the unsaturated polyester resin. If the amount is less than 1 part by weight, the molded product may stick to the mold, making it difficult to release, and may cause cracks or the like in the molded product. If it exceeds 10 parts by weight, the strength of the molded article tends to decrease.

The coloring agent is used for coloring a molded article, and examples thereof include inorganic pigments such as titanium oxide, carbon black and red iron oxide, and organic pigments such as phthalocyanine blue. The amount of the unsaturated polyester resin may be appropriately determined depending on the design properties of the obtained molded article.
It is about 0.02 to 40 parts by weight based on parts by weight.

Examples of the thickener include magnesium oxide, magnesium hydroxide, calcium oxide, potassium oxide, potassium hydroxide, zinc oxide and the like. Magnesium oxide is preferred in view of workability and viscosity. The compounding amount of the thickener is 0.1 to 100 parts by weight of the unsaturated polyester resin.
2 to 10 parts by weight are preferred. If it is less than 0.2 parts by weight, the viscosity tends to be insufficiently increased, and if it exceeds 10 parts by weight, the viscosity tends to be too high and the flowability of the molding material during compression molding tends to be poor.

The molding material of the present invention comprises the unsaturated polyester resin composition further containing fibers.

Examples of the material of the fibers include inorganic materials such as glass, and organic materials such as polyester, vinylon, nylon, aramid, and phenol resin.

From the viewpoints of handleability, workability, toughness, and resistance to cracking, the fibers are preferably woven fabrics in which fibers are entangled with each other. Examples of such a woven fabric include mats such as polyester fiber mat, vinylon fiber mat, nylon fiber mat, aramid resin fiber mat, and phenol resin fiber mat. In addition, the mats employ a mechanical method such as a needle punch method to entangle the fibers, but felts obtained by melting and bonding these mats have toughness, crack resistance and the like. Preferred from the point. These fibers can be used in combination of two or more kinds. In addition, natural fibers and the like can be added as needed.

When organic fibers such as polyester fibers and vinylon fibers are used as the fibers, the incineration residue of the molded article can be reduced. The content of organic fibers such as vinylon fibers is preferably 1 to 60% by weight, more preferably 3 to 40% by weight.
%, More preferably 5 to 30% by weight. If it is less than 1% by weight, the reinforcing effect is not sufficient and the obtained S
This is because the strength of the MC molded product is insufficient. On the other hand, if it exceeds 60% by weight, the impregnating property of the unsaturated polyester resin composition is reduced, and defects such as fibrous eyes, blisters, cracks and pinholes are generated in the molded product, resulting in impaired product appearance and reduced strength. This is because

As the form of organic fibers such as vinylon fibers to be used, non-woven fabric, cloth or chopped short fibers can be used, but the cloth has poor fluidity due to continuous fibers during molding. Although it is possible to mold a plate-like molded product such as a panel, in a deep drawing shape such as a bathtub or a septic tank, it is difficult to obtain a good molded product because the fibers do not flow. In addition, chopped short fibers are difficult to uniformly disperse and impregnate into unsaturated polyester resin compositions, and the conventional SMC
It is difficult to manufacture by a manufacturing method. Therefore, it is preferable to use a nonwoven fabric, and in particular, a vinylon fiber nonwoven fabric (mat) is preferably used. Furthermore, the fiber length is 1-2
00 mm is desirable. If the fiber length is less than 1 mm, the reinforcing effect tends to be insufficient and the strength of the molded article tends to be insufficient.
If it exceeds mm, the fluidity during molding tends to be poor, the appearance of the molded article tends to be impaired, the filling of ribs and bosses is poor, and the use and shape of the molded article tend to be limited. The fiber diameter is preferably 5 to 50 μm.

Examples of sheet-like organic synthetic fibers that can be used in combination with vinylon fiber nonwoven fabric (mat) include polyester fiber mat, nylon fiber mat, aramid resin fiber mat, and phenol resin fiber mat. Further, a combination of two or more of these can also be used. In addition, natural fibers and the like can be added as needed.

In the present invention, for example, the fibers are sandwiched with an unsaturated polyester resin composition applied to two films at a uniform thickness, and the fibers are mixed with the unsaturated polyester resin composition using a general impregnating apparatus. To obtain a sheet-shaped molding material (SMC), which can be obtained in the form of a layer between two films in the sheet-shaped molding material.

These fibers are preferably used in a molding material in view of toughness, resistance to cracking, low pressure and low temperature moldability.
It is used in a proportion of 60% by weight, more preferably 2 to 40% by weight. A particularly preferred range is from 5 to 25% by weight.
As the film, a polyethylene film, a polypropylene film, or the like can be used.

The sheet-shaped molding material of the present invention can be wound into a roll as required, and can be aged as required. Preferably, the mixture is heated to a temperature of room temperature to 60 ° C. and aged for 1 to 10 days.

The molding material of the present invention is used as a bulk molding material (B
In the case of MC), fibers are mixed with the above-mentioned unsaturated polyester resin composition, but there is no particular limitation on the mixing order of the components used in these.

A fiber-reinforced plastic molded article using the molding material of the present invention can be obtained, for example, by curing the molding material by heat compression molding, transfer molding, cold pressing or the like.

The hot compression molding conditions include a mold temperature of 40 to 200 ° C., and more preferably 70 to 200 ° C., in view of productivity, gloss and the like.
To 160 ° C, more preferably 100 to 130 ° C, and a surface pressure of 0.5 to 50 MPa, more preferably 1 to 2
It is preferably 0 MPa, more preferably 5 to 15 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.

A material using organic fibers as the fibers of the present invention and using FRP pulverized powder as the filler has a molding temperature of 100.
It can be molded at a molding pressure of 0.1 to 1 MPa at a temperature of up to 130 ° C.

The fiber-reinforced plastic molded products obtained by the present invention include, for example, various household appliances such as bathroom units (walls, waterproof pans, ceilings, aprons, counters, etc.), bathtubs, septic tanks, washstands, kitchen counters, building materials, and the like. It is suitable for a wide range of uses such as construction materials such as various pipes, tank products, beams, and gratings, miscellaneous goods such as cups and trays, boats and boats, and vehicle members (cowls, aero parts).

[0073]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Hereinafter, parts means parts by weight.

Example 1 [Synthesis of Unsaturated Polyester Resin (A)] 996 parts of terephthalic acid, 506 parts of propylene glycol, 312 parts of neopentyl glycol and 372 parts of ethylene glycol were mixed with a thermometer, a nitrogen blowing tube, and a rectification tower. And a 3 liter flask equipped with a stirrer, and heated using a mantle heater to raise the temperature to 230 ° C. in 5 hours. Thereafter, the mixture was cooled to 220 ° C., kept warm and cooled when the acid value reached 12, 882 parts of maleic anhydride was added, and the temperature was raised again to 215 ° C. in 5 hours. Thereafter, when the solution was cooled to 210 ° C. and the acid value became 3, it was cooled again to 250 ° C. in 4 hours. When the temperature reached 250 ° C., the temperature was kept under reduced pressure at 2 Torr until the torque of the stirrer became 3 kg · cm ² , and the reaction was terminated by cooling. At this time, the number average molecular weight of the unsaturated polyester resin was 5,000.

Comparative Example 1 [Synthesis of Unsaturated Polyester Resin (B)] 996 parts of terephthalic acid, 506 parts of propylene glycol, 312 parts of neopentyl glycol and 372 parts of ethylene glycol were mixed with a thermometer, a nitrogen blowing tube, and a rectification tower. And a 3 liter flask equipped with a stirrer, and heated using a mantle heater to raise the temperature to 230 ° C. in 5 hours. Thereafter, the mixture was cooled to 220 ° C., kept warm and cooled when the acid value reached 12, 882 parts of maleic anhydride was added, and the temperature was raised again to 215 ° C. in 5 hours. Thereafter, the temperature was cooled to 210 ° C., and when the acid value reached 3, the synthesis was terminated. At this time, the number average molecular weight of the unsaturated polyester resin was 3,000.

Example 2 Synthesis of unsaturated polyester resin (C) 996 parts of terephthalic acid, 506 parts of propylene glycol, 312 parts of neopentyl glycol and 372 parts of ethylene glycol were mixed with a thermometer, a nitrogen blowing tube, and a rectification tower. And a 3 liter flask equipped with a stirrer, and heated using a mantle heater to raise the temperature to 230 ° C. in 5 hours. Thereafter, the mixture was cooled to 220 ° C., kept warm and cooled when the acid value reached 12, 882 parts of maleic anhydride was added, and the temperature was raised again to 215 ° C. in 5 hours. Thereafter, when the solution was cooled to 210 ° C. and the acid value became 3, it was cooled again to 250 ° C. in 4 hours. When the temperature reached 250 ° C., the temperature was kept under reduced pressure at 2 Torr until the torque of the stirrer reached 5 kg · cm ² , and the reaction was terminated by cooling. At this time, the number average molecular weight of the unsaturated polyester resin was 7,000.

Example 3 [Synthesis of unsaturated polyester resin (D)] 996 parts of terephthalic acid, 506 parts of propylene glycol, 312 parts of neopentyl glycol and 372 parts of ethylene glycol were mixed with a thermometer, a nitrogen blowing tube, and a rectification tower. And a 3 liter flask equipped with a stirrer, and heated using a mantle heater to raise the temperature to 230 ° C. in 5 hours. Thereafter, the mixture was cooled to 220 ° C., kept warm and cooled when the acid value reached 12, 882 parts of maleic anhydride was added, and the temperature was raised again to 215 ° C. in 5 hours. Thereafter, when the solution was cooled to 210 ° C. and the acid value became 3, it was cooled again to 250 ° C. in 4 hours. When the temperature reached 250 ° C., the temperature was kept under reduced pressure at 2 Torr until the torque of the stirrer reached 6 kg · cm ² , and the reaction was terminated by cooling. At this time, the number average molecular weight of the unsaturated polyester resin was 9,000.

Example 4 An unsaturated polyester resin composition was prepared by dissolving 500 parts of the unsaturated polyester resin (A) in 500 parts of styrene, which is a polymerizable monomer, and then dissolving 0.02 part of hydroquinone as a polymerization inhibitor. I got

100 parts of the unsaturated polyester resin composition,
1.5 parts of t-butyl peroxybenzoate (perbutyl Z (trade name) manufactured by NOF CORPORATION), 100 parts of calcium carbonate having a typical particle size of 0.62 μm, and 4 parts of zinc stearate were added, and a Cowles type was added. Mix well with wings. 0.8 parts of magnesium oxide was added to this mixture, and further, Millionate MR-100 (polymethylene polyphenyl polyisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to the unsaturated polyester resin composition by the OH group / NCO
An amount such that the group (molar ratio) became 1/1 was added, and the mixture was stirred well and aged at 40 ° C. for 48 hours to prepare a prepared resin.

Using this compounded resin, the content of glass fiber was set to 32% by weight and the thickness of the protective release film was reduced to 50 μm by a dual wire mesh type SMC manufacturing apparatus.
m using a polypropylene film of m
It was aged on the third day in an aging furnace at 0 ° C. to produce a sheet-shaped molding material.

Measurement of Impact Strength The impact strength of the sheet-shaped molding material was measured as follows.

The release film was peeled from the sheet-shaped molding material, and the surface pressure was set to 7.0 MPa, the mold temperature was set to 140 ° C. at the upper side and 130 ° C. at the lower side using a 50-ton press, and the heating time was 5 minutes. It pressed and produced the flat molded article. The dimensions of the flat plate molded product were a plane of 220 × 220 mm and a thickness of 6 mm. A 1 kg conical weight was dropped vertically on the molded product, and the height at which cracks were formed in the molded product was determined.

Examples 5 to 6 In Example 4, the unsaturated polyester resin (A) was
Except for changing to (C) and (D), the same procedure was followed to prepare an unsaturated polyester resin composition, prepare a compounded resin, prepare a sheet-like molding material, and measure impact strength.

Example 7 The same procedure as in Example 4 was carried out except that the amount of the isocyanate compound was changed, to prepare an unsaturated polyester resin composition, prepare a compounded resin, prepare a sheet-like molding material, The impact strength was measured.

Comparative Example 2 In Example 4, the unsaturated polyester resin (A) was
Except for changing to (B), the same procedure was followed to prepare an unsaturated polyester resin composition, a prepared resin,
Production of a sheet-shaped molding material and measurement of impact strength were performed.

The above results are summarized in Table 1.

[0087]

[Table 1] Example 8 [Synthesis of Unsaturated Polyester Resin (E)] 996 parts of terephthalic acid, 506 parts of propylene glycol, 312 parts of neopentyl glycol and 372 parts of ethylene glycol were mixed with a thermometer, a nitrogen blowing tube, a rectifying tower, and a stirring device. Was charged into a 3 liter flask equipped with a, heated using a mantle heater, and heated to 230 ° C. in 5 hours. Thereafter, the mixture was cooled to 220 ° C., kept warm and cooled when the acid value became 3, 882 parts of maleic anhydride was added, and the temperature was raised again to 215 ° C. in 5 hours. Thereafter, when the solution was cooled to 210 ° C. and the acid value became 3, it was cooled again to 200 ° C. in 4 hours. When the temperature reached 200 ° C., the temperature was kept under reduced pressure at 5 Torr until the torque of the stirrer became 1 kg · cm ² , and the reaction was terminated by cooling. At this time, the number average molecular weight of the unsaturated polyester resin was 8,000.

Example 9 500 parts of this unsaturated polyester resin resin (E) was dissolved in 500 parts of styrene as a polymerizable monomer, and 20 parts of a 30% by weight styrene solution of polystyrene (number average molecular weight: 8,000) was dissolved. 0.02 parts of hydroquinone was dissolved as a polymerization inhibitor to obtain an unsaturated polyester resin composition.

This unsaturated polyester resin composition 100
Parts, t-butyl peroxybenzoate (using Perbutyl Z (trade name) manufactured by NOF Corporation) 1.5
Parts, 100 parts of calcium carbonate having a representative particle size of 0.62 μm, and 4 parts of zinc stearate were added, and the mixture was thoroughly mixed with a Cowles blade. 0.5 parts of magnesium oxide was added to this mixture, and further, Millionate MR-100 (polymethylene polyphenyl polyisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to the OH group of the unsaturated polyester resin composition.
An amount such that the NCO group (molar ratio) became 1/1 was added, and the mixture was stirred well and aged at 40 ° C. for 48 hours to prepare a prepared resin.

Using this compounded resin, a polyester fiber mat was used as a reinforcing material, a 50 μm thick polypropylene film was used as a protective release film, and a polyester fiber mat was used in a dual-wire mesh SMC manufacturing apparatus. While adjusting so as to obtain a sheet-shaped molding material, the sheet was sandwiched in the compounded resin while being adjusted so as to be in a weight%, and aged on a third day in an aging furnace at 40 ° C.

The impact strength of this sheet-shaped molding material was measured in the same manner as in Example 4, and the results are shown in Table 2.

Further, the combustion products remaining when the obtained molded article was incinerated using a gas burner were visually confirmed. The results are shown in Table 2.

Examples 10 to 11 In Example 9, except that the content of the polyester fiber mat as the reinforcing material was changed to 5% by weight and 20% by weight,
The same operation was performed to prepare a sheet-shaped molding material, measure the impact strength, and confirm the combustion products. The results are shown in Table 2.

Examples 12 to 13 In Example 9, the same operation as in Example 9 was carried out except that the polyester fiber mat was changed to felt (a polyester fiber mat overheat-fused) or vinylon fiber mat as a reinforcing material. Preparation of a molding material, measurement of impact strength, and confirmation of combustion products were performed, and the results are shown in Table 2.

Example 14 A sheet-like molding material was prepared in the same manner as in Example 9, except that the polyester fiber mat was changed to glass fiber as the reinforcing material, and the content of the reinforcing material was adjusted to 25%. The impact strength was measured and the products of combustion were confirmed. The results are shown in Table 2.

[0096]

[Table 2] Example 15 500 parts of an unsaturated polyester resin (E) was dissolved in 500 parts of styrene as a polymerizable monomer, and 0.02 part of hydroquinone was dissolved as a polymerization inhibitor to obtain an unsaturated polyester resin composition. .

Unsaturated polyester resin composition (a) 10
0 parts, t-butyl peroxybenzoate (perbutyl Z (trade name) manufactured by NOF Corporation) was used 1.5
Parts, 30 parts of FRP pulverized powder having a typical particle size of 1.3 μm, and 4 parts of zinc stearate were added and thoroughly mixed with a Cowles blade. Further, Millionate MR-100 (polymethylene polyphenyl polyisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.) was added in such an amount that the OH group / NCO group (molar ratio) of the unsaturated polyester resin composition became 1/1.
A prepared resin was prepared.

Preparation of sheet-shaped molding material Using the above-prepared resin, a dual-wire mesh type SMC manufacturing apparatus uses vinylon fiber non-woven fabric (mat) as a reinforcing material, and a 50 μm thick polypropylene as a protective release film. Using a film, while adjusting to be 15% by weight of polyester fiber mat,
The sheet was sandwiched in the prepared resin to form a sheet, which was then aged on a third day in an aging furnace at 40 ° C. to prepare a sheet-shaped molding material.

Measurement of Reinforcing Material Impregnating Property In order to examine the impregnating property of the sheet-like molding material, it was measured as follows.

The release film was peeled from the sheet-shaped molding material, and the impregnating property of the reinforcing material was examined by visual observation.

Measurement of Specific Gravity of Molded Article In order to examine the specific gravity of molded article of sheet-like molding material, JISK
The measurement was performed using the method of 6911.

Incineration Residue In order to check the incineration residue of the sheet-like molding material, the measurement was performed as follows.

The release film was peeled off from the sheet-like molding material, and the surface pressure was set to 7.0 MPa, the mold temperature was set to 140 ° C. at the upper side and 130 ° C. at the lower side using a 50-ton press, and the heating time was 5 minutes. The plate was pressed to produce a flat molded product. The dimensions of the flat plate molded product were a flat surface of 220 × 220 mm and a thickness of 6 mm. From this molded product, a 50 mm × 50 mm flat plate was cut out and determined from the weight change rate after being left in an electric furnace at 600 ° C. for 3 hours.

Examples 16 and 17 In Example 15, the content of the reinforcing material was 3% by weight (Example 1).
6) and 65% by weight (Example 17), except that the same operation was performed to produce and measure a sheet-shaped molding material.

[0105]

[Table 3]

[0106]

The unsaturated polyester resin of the present invention has excellent toughness and is suitable as an unsaturated polyester resin for molding materials.

The unsaturated polyester resin composition of the present invention has excellent workability and toughness, and is suitable as an unsaturated polyester resin composition for molding materials.

The unsaturated polyester resin composition of the present invention is excellent in workability, good in aging, good in toughness, and suitable for producing a fiber-reinforced plastic molded product which is hard to crack.

The molding material of the present invention is excellent in workability, good in aging, good in toughness, and suitable for producing a fiber-reinforced plastic molded product which is hard to crack.

The sheet-shaped molding material of the present invention has good handleability, excellent workability, good maturation, good toughness, and is suitable for producing a fiber-reinforced plastic molded product which is hard to crack.

According to the method for producing a fiber-reinforced plastic molded product of the present invention, it is possible to produce a fiber-reinforced plastic molded product which is hard to be cracked and has good workability and yield.

The unsaturated polyester resin composition of the present invention,
The molding material and sheet-like molding material use FRP crushed powder as a filler, and furthermore, by using organic fibers as a reinforcing material, there is almost no incineration residue because they do not contain inorganic fillers and glass fibers that cannot be incinerated. It is also easy to dispose of, has a lower specific gravity than conventional SMC molded products, and is useful for reducing the weight of products.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/00 C08K 3/00 5/14 5/14 7/02 7/02 C08L 67/06 C08L 67 / 06 101/00 101/00 F term (reference) 4F072 AA04 AA07 AB04 AB09 AB28 AD38 AD53 AD54 AE01 AF03 AF04 AF06 AF24 AG03 AG18 AJ04 AJ23 AK02 AK05 AK14 AL06 AL07 4J002 AC032 AC072 AC082 AH003 BB032 BC022 BC03 BC06 BC03 BC03 BC03 BC06 BC03 BC032 CF002 CF003 CF211 CL003 CL012 CL063 DE100 DE149 DE239 DG049 DG059 DJ000 DJ019 DJ039 DJ049 DJ059 DL000 DM009 EA046 EB126 EH076 EH146 EK018 EK028 EK038 EK048 EK068 ABEK EB088 ER007 ET006 EU186 FA040 FA043 FA0901901 AB19 AB23 AB24 AB25 AB26 BA05 BA07 BA13 BA18 BA19 BA22 BA25 BA28 BA29 CB03 CC02 CD02 4J029 AA07 AB01 AD01 BA02 BA03 BA 08 BA09 BA10 BD04A BD10 BF09 BF10 CA02 CA04 CA05 CA06 CB04A CB05A CB06A CD03 FC03 FC05 FC08 FC36 GA11 GA13 GA14 GA15 GA17 GA23 HA01 HB01 HB06 JB131 JF321 KD02 KD07 KE02 4J034 DA01 DB03 GA55 HC62 HC12 HC55 HC62 HC12 HC55 HD02 HD08 MA01 MA03 MA21 MA26 QC03 RA05

Claims (14)

[Claims] A number average molecular weight obtained by reacting a polybasic acid component containing an α, β-unsaturated polybasic acid or an anhydride thereof as an essential component with a polyhydric alcohol has a number average molecular weight of 5,000 to 3
000 unsaturated polyester resin. 2. An unsaturated polyester resin composition comprising the unsaturated polyester resin according to claim 1 and a polymerizable monomer. 3. The unsaturated polyester resin composition according to claim 2, further comprising an isocyanate compound. 4. The unsaturated polyester resin composition according to claim 3, further comprising a low shrinkage material, a curing agent and a filler. 5. A molding material comprising the unsaturated polyester resin composition according to claim 4, further comprising fibers. 6. The molding material according to claim 5, wherein the fibers are a woven fabric in which fibers are entangled with each other. 7. The molding material according to claim 5, wherein the fibers are organic fibers. 8. The molding material according to claim 7, wherein the organic fibers are vinylon fibers. 9. The vinylon fiber has a fiber length of 1 to 200 m.
The molding material according to claim 8, wherein the fiber diameter is 5 to 50 m in m. 10. The molding material according to claim 8, wherein the content of vinylon fiber is 1 to 60% by weight. 11. The filler according to claim 4, wherein the filler is a crushed powder of a fiber-reinforced plastic molded product, and its content in the unsaturated polyester resin composition is 3 to 50% by weight.
The molding material according to 7, 8, 9 or 10. 12. The molding material according to claim 11, wherein the ground powder of the fiber-reinforced plastic molded product has an average particle size of 1 to 500 μm and a water content of 10.0% by weight or less. 13. A sheet-like molding material comprising the molding material according to claim 5 present between two films. 14. A method for producing a fiber-reinforced plastic molded product, comprising thickening the molding material between the sheet-shaped molding materials according to claim 13, and then performing heat compression molding.