JP3487260B2 - Hot-water-resistant unsaturated polyester resin composition, resin mixture for lamination using the same, and molded article - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hot water-resistant unsaturated polyester resin composition, a resin mixture for lamination using the same, and a molded article.

[0002]

2. Description of the Related Art In FRP, open-mold molding methods such as hand lay-up and spray-up have a bad working environment due to scattering of resin and glass fibers and styrene that has volatilized, as compared with molding compound methods, and production. Due to its inferiority, the molding compound method is being converted, but it is suitable for the production of small quantities of other varieties due to its relatively low capital investment. For example, Heisei 1
It accounts for about 38% in the classification by molding method in FY2000.

In this open mold forming method, facilitating the lamination and defoaming work and allowing this step to be performed in a short time not only improves the productivity but also the exposure time in the styrene vapor of the worker. Leads to shortening. For the purpose of facilitating the lamination and defoaming work, JP-A 09-235457 contains polybutadiene having a hydroxyl group or a derivative thereof and a fatty acid, and JP-A 09-235458 discloses a polyalkylene glycol and a fatty acid. Containing JP-A No. 09-2414
Japanese Patent Laid-Open No. 95-2558, which contains 2,4,7,9-tetramethyl-5-decyne-4,7-diol or its alkylene oxide adduct and fatty acid.
JP-A-60 discloses a resin composition containing polystyrene having a specific weight average molecular weight, which reduces the generation of bubbles during lamination and defoaming operations. Among them, the invention of Japanese Patent Laid-Open No. 09-202816, which contains hydroxyl group-terminated 1,4-polybutadiene such as Yokota in an unsaturated polyester resin, is excellent in defoaming property, and the residual bubbles of FRP in the open mold molding method are eliminated. It is useful as a method for facilitating the work of laminating and defoaming by reducing the amount, and by combining this with a method of controlling the dispersity of the inorganic thixotropic agent within a specific range, further laminating and defoaming can be performed. Facilitates foaming work,
Moreover, the viscosity and thixotropy change little even after a lapse of time from the time of production, and the addition amount of the inorganic thixotropic agent can be reduced. However, in the case of a hot water-resistant unsaturated polyester resin such as an isophthalic acid-based or terephthalic acid-based, bisphenol-based, hydrogenated bisphenol-based, etc. produced by this method, the workability of laminating and defoaming immediately after coating the resin is very good. When a large-sized molded product such as a bathtub is sprayed at once by the spray-up method and defoaming work is performed, the work area is large and it takes time to work.
There remains a problem that the glass fiber is entangled with the defoaming roll as the diluent in the resin evaporates.

The present inventor introduces dicyclopentadiene into an unsaturated polyester resin so that the hot water resistance and mechanical strength of the unsaturated polyester resin are the same as those of the conventional hot water unsaturated polyester resin. It has been found that the entanglement of glass fibers to the defoaming roll can be reduced even after the lapse of time. According to the present invention, changes in viscosity and thixotropicity are small even after a lapse of time from the time of production, and in addition, the amount of the inorganic thixotropic agent added can be reduced.

[0005]

SUMMARY OF THE INVENTION The present invention is directed to hot water resistance,
A hot water-resistant unsaturated polyester resin composition capable of reducing entanglement of glass fibers to a defoaming roll during lamination and defoaming work in a FRP open mold forming method while maintaining mechanical strength, The present invention provides a resin mixture for lamination and a molded product using the above.

[0006]

That is, according to the present invention,
15-45 mol% of cyclopentadiene, propylene glycol
15 to 45 mol% of the recall and maleic acid,
25 to 55 mol of one or more of maleic acid and fumaric acid
% Polyester obtained as an essential componentAnd
The equimolar amount of dicyclopentadiene, maleic anhydride and
And water or equimolar amounts of dicyclopentadiene and maleic acid
After the addition reaction at 120-150 ° C, the remaining components are
In addition, it is obtained by dehydration condensation or addition polymerization.
The weight average molecular weight measured by chromatography
Unsaturated polyester with a value divided by the amount of child is 20 or more
(A) 40 to 80 parts by weight will be 100 parts by weight in total.
Heat resistance by dissolving 60 to 20 parts by weight of crosslinkable monomer
Aqueous unsaturated polyester resin composition (first invention)
To do.

[0007]

[0008]

[0009]

Further, the present invention relates to the first invention,
The present invention relates to a hot water resistant unsaturated polyester resin composition in which the crosslinkable monomer is styrene ( second invention). The present invention also provides a hot water resistant unsaturated polyester resin composition in which 30 mol% or less of propylene glycol is replaced with dipropylene glycol in the first and second inventions ( third invention).
Regarding

The present invention further comprises dispersing 0.1 to 10 parts by weight of an inorganic thixotropic agent in 100 parts by weight of the hot-water unsaturated polyester resin composition according to the first to third aspects of the present invention to form a hydroxyl group-terminated product. 1,4-polybutadiene 0.01
To 1.2 parts by weight of the resin mixture for lamination ( fourth invention). The present invention also relates to a laminate in which the inorganic thixotropic agent according to the fourth invention is dispersed so that the dispersity measured according to paragraph 4.7 of JIS K 5400-1990 is in the range of 5 to 70 μm. Resin mixture ( fifth invention).

Further, the present invention provides the inorganic thixotropic agent according to the fourth invention, which has a specific surface area of 5 as determined by the BET method.
It relates to a resin mixture for lamination ( sixth invention) of 0 to 500 m ² / g. The present invention also relates to a resin mixture for lamination ( seventh invention), wherein the inorganic thixotropic agent in the fourth invention is fumed silica. The present invention also relates to
Inorganic thixotropic agent is in the fourth invention, the ratio was determined by the BET method surface area is 50 to 500 m ² / g and, laminating resin blend is a fumed silica (eighth invention)
Regarding The present invention also relates to a molded product ( ninth invention) obtained from the resin mixture for lamination which is the fourth invention.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION First, the hot water resistant unsaturated polyester resin composition according to the first invention will be described. The unsaturated polyester (A) used in the present invention contains 15 to 45 mol% of dicyclopentadiene, 15 to 45 mol% of propylene glycol and maleic acid as a reaction component.
25-5 maleic anhydride and fumaric acid 1 or 2 or more
It is set to 5 mol%. The reason for this is determined by the balance between the essential components, but with particular explanation, first, if dicyclopentadiene is less than 15 mol%, the required hot water resistance cannot be obtained and 45 mol% Beyond the above, other essential components cannot be introduced in the required amounts. For this reason, it is preferably 20 to 40 mol%, more preferably 2
The range is 5 to 35 mol%. Further, if propylene glycol is less than 15 mol%, the solubility in the crosslinkable monomer is deteriorated and necessary mechanical strength and hot water resistance cannot be obtained, and if it exceeds 45 mol%, other essential components are not added. We cannot introduce the required amount. For this reason, the range is preferably 20 to 40 mol%, more preferably 25 to 35 mol%. Here, in order to maintain the solubility in the crosslinkable monomer, the third
15-45 mol% propylene glycol as in the invention of
It is possible to replace not more than 30 mol% of dipropylene glycol with dipropylene glycol. Further, if one or more of maleic acid, maleic anhydride and fumaric acid is less than 25 mol%, the curability required for the resin cannot be obtained, and if it exceeds 55 mol%, other essential components are introduced in required amounts. Can not. From this meaning, preferably 30 to 50 mol%, more preferably,
The range is 35 to 45 mol%.

The unsaturated polyester (A) used in the present invention has a total amount of essential components of 55 mol% or more within a range in which necessary characteristics can be obtained in each combination.
Components other than the essential components can be used. As the α, β-unsaturated polybasic acid other than the essential components, for example,
Examples thereof include itaconic acid, citraconic acid and the like, and reactive derivatives of these acid anhydrides and the like, and one or more of these can be used. Acid components other than α, β-unsaturated polybasic acids include phthalic acid, isophthalic acid, terephthalic acid,
Tetrahydrophthalic acid, methyltetrahydrophthalic acid,
Saturated acids such as endomethylenetetrahydrophthalic acid, adipic acid, sebacic acid, het acid, tetrabromophthalic acid, trimellitic acid and the like. Derivatives of these acid anhydrides and the like can be mentioned, and it is possible to use one or more of these. it can.
If necessary, linseed oil, soybean oil, tall oil, vegetable oil fatty acid such as castor oil, glycidyl methacrylate,
A modifying component such as a methacrylate or acrylate having an epoxy group such as glycidyl acrylate may be used in a proportion of 0 to 30% by weight of this acid component.

Examples of alcohol components other than the essential components include ethylene glycol, diethylene glycol, neopentyl glycol, dibromoneopentyl glycol, 1,2-propanediol, 1,3-
Propanediol, 1,2-butanediol, 1,3-
Butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,2-
Hexanediol, 1,4-hexanediol, 1,6
-Aliphatic glycols such as hexanediol and 2,3-hexanediol, alicyclic diols such as cyclopentanediol and cyclohexanediol, hydrogenated bisphenol A, bisphenol A propylene oxide adduct, aroma such as xylene glycol and dimethylxylene glycol It is possible to use one or more ethers such as group diol, bispropylene glycol ether, bisbutylene glycol ether, allyl glycidyl ether, pentaerythrityl diallyl ether, and polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol. it can.

If desired, the unsaturated polyester (A) used in the present invention may be used in a range that does not impair the characteristics, preferably in a range of 45% by weight or less of the resin composition, such as vinyl ester. Other thermosetting resins may be used. Examples of the crosslinkable monomer used in the present invention include aromatic vinyl compounds such as styrene, vinyltoluene, p-methylstyrene, α-methylstyrene, t-butylstyrene and divinylbenzene, halogenated chlorostyrene and the like. Styrene, vinyl pivalate,
Carboxylic acid monovinyl esters such as vinyl 2-ethylhexanoate, vinyl laurate, vinyl benzoate, diallyl phthalate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Examples thereof include glycidyl (meth) acrylate, triallyl cyanurate, trimethylolpropane and tri (meth) acrylate, and one or more of these can be used. Among these, aromatic vinyl compounds are preferable because they have a good balance between viscosity and curability, and styrene is more preferable as in the fifth invention.

Here, in the unsaturated polyester resin composition, the unsaturated polyester (A) is 40 to 80 parts by weight so that the total amount of the unsaturated polyester (A) and the crosslinkable monomer is 100 parts by weight. Part, the crosslinkable monomer is 60 to
The reason why the amount is limited to 20 parts by weight is that if the amount of the crosslinkable monomer is less than 20 parts by weight, the viscosity becomes high and the workability becomes poor, and the entrapped bubbles become difficult to escape. This is because sufficient curability cannot be obtained and the cured product cannot have sufficient strength. For this reason, the proportion of the unsaturated polyester (A) and the crosslinkable monomer is preferably 45 to 70 parts by weight of the unsaturated polyester (A) and the crosslinkable monomer so that the total amount becomes 100 parts by weight. Is 55
˜30 parts by weight, more preferably 40 to 60 parts by weight of unsaturated polyester (A) and 60 to 40 parts by weight of crosslinkable monomer so that the total amount becomes 100 parts by weight.

The synthesis of the unsaturated polyester used in the first invention (A), an additional equimolar of dicyclopentadiene, dicyclopentadiene and maleic acid maleic anhydride and water or equimolar at 120 to 150 ° C. After the reaction, a method of synthesizing by adding the remaining components and conducting dehydration condensation or addition polymerization is effective. Here, the reaction of equimolar amount of dicyclopentadiene, maleic anhydride and water or equimolar amount of dicyclopentadiene and maleic acid is 120
If it is less than ℃, it will not proceed rapidly, and if it exceeds 150 ℃,
Dicyclopentadiene decomposes to cyclopentadiene,
So-called Diels added to the double bond part of maleic acid
The -Alder reaction produces endomethylenetetrahydrophthalic acid, and the desired properties cannot be obtained. It is one of the points of the present invention that the hot water resistance of the unsaturated polyester resin composition produced is improved by disposing dicyclopentadiene maleate at the molecular end.

[0019] The molecular weight of the unsaturated polyester used in the first invention (A) is that the value obtained by dividing the number-average molecular weight The weight average molecular weight measured by gel permeation chromatography is 20 or higher, heat In the open-mold molding method of FRP while maintaining the water-based property and the mechanical strength, it is preferable to reduce the entanglement of the glass fiber to the defoaming roll during the lamination and defoaming work even after a lapse of time. . There is no particular upper limit for this value,
Those over 50 are technically very difficult to synthesize without gelation. For this reason, the number average molecular weight is 50
0-8000 are preferable and 850-7000 are more preferable.

Although the acid value of the unsaturated polyester (A) is not limited, it is preferably 80 to 1 mgKOH / g, more preferably 30 to 1 in consideration of the viscosity of the resin mixture and the releasability of the molded product. The range is 5 mgKOH / g. Next, the resin mixture for lamination according to the present invention will be described.
The inorganic thixotropic agent used in the fourth invention is not limited, but fine powder silicon dioxide, mica powder, various whiskers, glass powder, fine bentonite, fine powder sepiolite,
Fine talc, asbestos powder and the like can be mentioned, and the specific surface area obtained by the BET method as in the ninth invention is 50 to 500 m ^2.
/ G is preferable in order to obtain an appropriate balance of viscosity and thixotropy. If the specific surface area is less than 50 m ² / g, the viscosity and thixotropy will be too low, and 500 m 2 / g
If it exceeds, it tends to be too high.

Further, as the inorganic thixotropic agent used in the present invention, an oxide of a metal or the like having many surface hydroxyl groups such as silicon dioxide is used for the reason of obtaining an appropriate balance of viscosity and thixotropy. Alternatively, a hydroxide is preferable, and particularly fumed silica as in the seventh invention is more preferable. In this sense, the inorganic thixotropic agent as in the eighth invention has a specific surface area of 50 to 50 determined by the BET method.
It is more preferably 500 m ² / g and fumed silica.

In addition, the amount of the inorganic thixotropic agent used in the present invention is set to the unsaturated polyester resin composition 100.
The reason why the inorganic thixotropic agent is 0.1 to 10 parts by weight with respect to parts by weight is that a proper balance of viscosity and thixotropic degree is obtained, and the inorganic thixotropic agent is 0.1. If it is less than 1 part by weight, the viscosity and the thixotropy become too low, 10
This is because if it exceeds the weight part, it tends to be too high. A thixotropic agent may be optionally used in the resin mixture for lamination of the present invention. The blending amount is preferably 3% by weight or less, and more preferably 1% by weight or less, based on the resin mixture for lamination. The type of thixotropic agent is not particularly limited, but examples thereof include compounds having a hydroxyl group such as polyhydric alcohols such as glycerin.

The 1,4-polybutadiene having less than hydroxyl groups used in the fourth invention has a number average molecular weight of 1,000 to 10,000 measured according to ASTM D2503.
The range of is preferable. In the structure of 1,4-polybutadiene, it is preferable that the butadiene component has a 1,4-bond content of 60 to 100 mol% and a 1,2-bond content of 0 to 40 mol% for achieving the effects of the present invention. Also, less than 1,
When the resin is mixed with 4-polybutadiene, the resin may be diluted with a crosslinking monomer such as styrene or a solvent such as methanol and used.

The amount of 1,4-polybutadiene to be blended is 0.01-1.100 with respect to 100 parts by weight of the unsaturated polyester resin composition, depending on the degree of entrainment and defoaming of foam during molding.
It is set to a range of 2 parts by weight, preferably 0.04 to 0.5 parts by weight, and more preferably 0.07 to 0.4 parts by weight. If the amount is less than 0.01 part by weight, a sufficient bubble-releasing effect cannot be obtained, and if the amount is more than 1.2 parts by weight, curability and thixotropy are deteriorated and sagging easily occurs during molding.

The laminating resin mixture of the present invention contains 2,6-ditertiarybutylphenol, 2,4-dimethyl-6-tertiarybutylphenol and 2,6-ditertiary phenol in order to adjust the curability. Phenols such as butyl-4-methylphenol, quinones such as parabenzoquinone, toluquinone, naphthoquinone, phenanthraquinone and 2,5-diphenylparabenzoquinone, tolhydroquinone, hydroquinone, tert-butylcatechol, monotertiarybutylhydroquinone Hydroquinones such as 2,5-ditertiarybutylhydroquinone, organic copper salts such as copper naphthenate, amidines such as acetamidine acetate, hydrazines such as phenylhydrazine hydrochloride, and quaternary ammonium such as trimethylbenzylammonium chloride. Polymerization inhibitors such as beam salts, cobalt naphthenate, cobalt octenate, metal soaps such as octene manganese, N, N-dimethylaniline, N, N
-Aromatic tertiary amines such as diethylaniline, N, N-
1 or the like of a curing accelerator such as dimethylacetoacetamide, N, N-diethylacetoacetamide, methyl acetoacetate, ethyl acetoacetate, acetylacetone, dimedone, dibenzoylmethane, acetylcyclopentane, acetylbutyrolactone, and phenyldiethanolamine. Two or more may be used as needed. The amount used is appropriately determined depending on the required curability, but is preferably 3% by weight or less, and more preferably 1% by weight or less, based on the resin mixture for lamination.

In the resin mixture for lamination of the present invention, known pigments, colorants such as dyes, patterning materials, internal release agents such as zinc stearate and calcium stearate, viscosity modifiers, wetting agents, You may use additional components, such as an ultraviolet absorber, as needed. The amount used is not particularly limited, but is preferably 20% by weight or less, and more preferably 5% by weight or less, based on the resin mixture for lamination.

In the resin mixture for lamination of the present invention, as filler, calcium carbonate powder, lime powder, zinc oxide, aluminum hydroxide, aluminum oxide, clay, kaolin, quartz powder, cold water stone powder, crushed stone, Mica powder, various whiskers, glass powder, bentonite powder, talc powder, asbestos powder, glass balloon, inorganic filler such as shirasu balloon, polyester chip, polyurethane chip, acrylic chip, polyacrylonitrile balloon, vinylidene chloride balloon, wood powder And the like, and one or more of them can be used. The average particle size of these fillers is not particularly limited as long as they can pass through the spray nozzle during spraying, but is 0.1 μm or more so that the viscosity of the resin mixture does not increase excessively, and does not reduce the surface smoothness of the molded product. It is preferably 100 μm or less, more preferably 0.3 to 20 μm.

The laminating resin mixture of the present invention further comprises, as a low-shrinking agent, thermoplastic resins such as polystyrene, polyvinyl acetate, saturated polyester, polyethylene, acrylic syrup and polymethylmethacrylate, and styrene-butadiene rubber, nitrile rubber and the like. 1 or 2 of thermoplastic rubber of
The above may be added, if necessary, in an amount of preferably 100 parts by weight or less, more preferably 50 parts by weight or less, based on 100 parts by weight of the resin mixture for lamination.

Next, a method for producing the resin mixture for lamination according to the present invention will be described. In the production of the resin mixture for lamination of the present invention, the above-mentioned essential components are used in an essential ratio.
The dispersion of the inorganic thixotropic agent, for example, a sonolator, a dispersing device such as a sand grinder, a dissolver, a planetary mixer, various stirrers such as a universal stirrer, a kneader,
It is preferable to use a device such as a ball mill, a roll mill, a screw extrusion type kneader. When dispersing, be careful not to gel the mixture due to frictional heat. Further, it is also preferable to carry out degassing under reduced pressure so as not to entrap air bubbles. At this time, the dispersity of the inorganic thixotropic agent is dispersed so that the dispersity measured according to Item 4.7 of JIS K 5400-1990 is in the range of 5 to 70 μm as in the fifth invention. It is preferable and the range of 5-60 micrometers is more preferable.

The JIS of the resin mixture for lamination of the present invention
The thixotropic degree measured with K 6901 may be in a range such that when an appropriate amount is sprayed on a vertical surface, the uncured material is still uncured, and when FRP is sprayed up for the purpose of reinforcement on the surface, sagging does not occur. However, since it is difficult to impregnate such a viscous thermosetting resin mixture with a fiber reinforcing material without performing a defoaming operation, JIS K 69
The thixotropic degree measured at 01 is preferably 2 to 9, and more preferably 2.5 to 7.

When the resin mixture for lamination according to the present invention is cured, if necessary, a curing catalyst such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide or other ketone peroxides, benzoyl peroxide, Diacyl peroxides such as isobutyl peroxide, cumene hydroperoxide, hydroperoxides such as t-butyl hydroperoxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, 1,
Peroxyketals such as 1-di-t-butylperoxy-3,3,5-trimethylcyclohexanone and 2,2-di- (t-butylperoxy) -butane, t-butylperoxybenzoate, t- Butyl peroxy-2-
Ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 2,4,4-trimethylpentylperoxy-2-ethylhexanoate, etc. Alkyl peresters, bis (4-t-butylcyclohexyl)
One or more organic peroxides such as percarbonates such as peroxydicarbonate and t-butyl peroxyisobutyl carbonate may be used in combination. The type and amount of the curing catalyst is determined by the molding temperature, and there is no limitation on this combination, but in order to obtain good reactivity, 0.1 to 0.1% of organic peroxide is added to the resin mixture for lamination. It is preferable to use 3% by weight.

The method of using the resin mixture for lamination according to the present invention is for FRP lamination using glass fiber, carbon fiber, aramid fiber, vimilon fiber, polyester fiber, nylon fiber and various metal fibers as a reinforcing material. The method is, for example, an open mold method such as a hand layup method or a spray up method. Starting with FRP molded products that are molded directly on the molding die or after applying gel coat etc., vacuum molded acrylic sheet, or compression molded sheet molding compound, bulk molding compound, cast molded thermosetting resin,
In addition to thermoplastic resin, use for any purpose such as reinforcement, hot water resistance, corrosion resistance, waterproofness, etc. on the back surface of molded products molded by any method or on the resin layer such as gel coat applied to the mold You can also

There are no particular restrictions on the molded product molded using the resin mixture for lamination, but examples include bathroom units (walls, waterproof pans, ceilings, aprons, counters, etc.), bathtubs, septic tanks, washbasins, kitchen counters. , Various kinds of housing equipment such as wall materials, various pipes, tank products, construction materials such as beams and gratings, miscellaneous goods such as cups and trays, and molded products such as boats and vehicle members.

[0034]

EXAMPLES 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) Dicyclopentadiene, 1069 g, and maleic anhydride, 793, in a 3-liter four-necked flask equipped with a reflux tube, an inert gas introduction tube, a thermometer, and a stirrer in a nitrogen stream.
g, distilled water 146 g, hydroquinone 0.6 g,
Use a mantle heater to raise the temperature while paying attention to heat generation,
Dicyclopentadiene maleate (monoester of dicyclopentadiene and maleic acid) reacted at ℃ for 2 hours
Was synthesized. Then 676 propylene glycol
g, 317 g of maleic anhydride, and 10 at 210 ℃
The reaction was carried out for a time to obtain an unsaturated polyester UP (1) having an acid value of 20 mgKOH / g, a molar ratio of dicyclopentadiene of 29 mol%, maleic acid of 40 mol% and propylene glycol of 31 mol%. The molecular weight distribution was measured by gel permeation chromatography, and the results are shown in Table 1. Also this U
Unsaturated polyester resin composition U by adding 63 parts by weight of P (1) to 37 parts by weight of styrene at 70 ° C. and completely dissolving
P-1 was obtained.

(2) With respect to 100 parts by weight of UP-1, 0.1 parts by weight of glycerin, B as an inorganic thixotropic agent
A specific surface area obtained by the ET method was added to 0.6 parts by weight of fumed silica (Aerosil 200, trade name of Nippon Aerosil Co., Ltd.) having a specific surface area of 200 m ² / g, and a dissolver equipped with an edge disk turbine type stirring blade was used. , Rotation speed 2,
Stir at 000 rpm for 60 minutes, and then JIS K 5400-
The dispersity measured according to paragraph 4.7 of 1990 is 50μ.
dispersed in m. Then, 0.2 parts by weight of hydroxyl group-terminated 1,4-polybutadiene (Poly bd R-45HT, trade name of Idemitsu Petroleum Co., Ltd.), cobalt octenoate aromatic compound solution (PT-28, product of Hitachi Chemical Co., Ltd.) Name) 0.5 part by weight, dimethylaniline 0.05 part by weight,
Toluquinone (0.005 parts by weight) and styrene (21 parts by weight) were added and thoroughly mixed to obtain a resin mixture R-1. This characteristic is shown in Table 1.

Example 2 (1) 100 parts by weight of UP-1, obtained in (1) of Example 1
In contrast, 0.1 part by weight of glycerin, an inorganic thixotropic agent
, The specific surface area obtained by the BET method is 200 m ² / G
Fumed silica (Aerosil 200, Nippon Ae)
Add 1.0 parts by weight of Rosil Co., Ltd.
Rotate using a dissolver equipped with a scuba turbine type stirring blade
Stir at 60 rpm for several minutes, JIS K 54
The degree of dispersion measured according to paragraph 4.7 of 00-1990 is
Dispersed to 90 μm. After that, 1,4-
Polybutadiene (Poly bd R-45HT, Idemitsu
Petroleum Corporation trade name) 0.2 parts by weight, cobalt octenoate
Aromatic compound solution (PT-28, Hitachi Chemical Co., Ltd.)
Product name) 0.5 parts by weight, dimethylaniline 0.05 parts by weight
Parts, toluquinone 0.005 parts by weight, styrene 26 parts by weight
Was added and mixed thoroughly to obtain a resin mixture R-2. This
The characteristics of are shown in Table 1.

Comparative Example 1 (1) 1340 g of dicyclopentadiene and 994 maleic anhydride in a nitrogen stream in the same apparatus as in (1) of Example 1.
g, distilled water 183 g, hydroquinone 0.6 g,
Use a mantle heater to raise the temperature while paying attention to heat generation,
Dicyclopentadiene maleate (monoester of dicyclopentadiene and maleic acid) reacted at ℃ for 2 hours
Was synthesized. Then 482 g of propylene glycol
Was charged and reacted at 210 ° C for 5 hours to give an acid value of 20 mg.
KOH / g, molar ratio of dicyclopentadiene 39 mol%, maleic acid 38 mol%, propylene glycol 24
A mol% of unsaturated polyester UP (II) was obtained. The molecular weight distribution was measured by gel permeation chromatography and the results are shown in Table 1.
It was shown to. Further, 75 parts by weight of this UP (II) was added to 25 parts by weight of styrene at 70 ° C. to obtain an unsaturated polyester resin composition UP-2 which was completely dissolved.

(2) With respect to 100 parts by weight of UP-2, 0.1 part by weight of glycerin, B as an inorganic thixotropic agent
A specific surface area obtained by the ET method was added to 0.7 part by weight of fumed silica (Aerosil 200, trade name of Nippon Aerosil Co., Ltd.) having a specific surface area of 200 m ² / g, and a dissolver equipped with an edge disk turbine type stirring blade was used. , Rotation speed 2,
Stir at 000 rpm for 60 minutes, and then JIS K 5400-
The dispersity measured according to paragraph 4.7 of 1990 is 50μ.
dispersed in m. Then, 0.2 parts by weight of hydroxyl group-terminated 1,4-polybutadiene (Poly bd R-45HT, trade name of Idemitsu Petroleum Co., Ltd.), cobalt octenoate aromatic compound solution (PT-28, product of Hitachi Chemical Co., Ltd.) Name) 0.5 part by weight, dimethylaniline 0.05 part by weight,
Toluquinone (0.005 parts by weight) and styrene (20 parts by weight) were added and mixed thoroughly to obtain a resin mixture R-3. This characteristic is shown in Table 1.

Comparative Example 2 (1) Isophthalic acid 9 was added to the same apparatus as in (1) of Example 1.
Charge 98 g, neopentyl glycol 835 g, propylene glycol 102 g, hydroquinone 0.6 g,
Acid number 4 after condensation reaction at 225 ° C for 8 hours in an inert gas stream.
150 mg KOH / g unsaturated polyester was synthesized and
Cooled to ° C. Then 720 g of maleic anhydride,
Charge 346 g of propylene glycol, and in a nitrogen stream 2
Condensation reaction at 20 ℃ for 12 hours, acid value 14mgKOH
/ G, the molar ratio of isophthalic acid 22 mol%, neopentyl glycol mol 29%, propylene glycol 22 mol%, maleic anhydride 27 mol% unsaturated polyester resin UP (III) was obtained. The molecular weight distribution was measured by gel permeation chromatography, and the results are shown in Table 1. Also this UP
(III), 62 parts by weight are added to 38 parts by weight of styrene at 70 ° C. and completely dissolved to give an unsaturated polyester resin composition U.
P-3 was obtained.

(2) With respect to 100 parts by weight of UP-3, 0.1 part by weight of glycerin, B as an inorganic thixotropic agent
A specific surface area obtained by the ET method was added to 0.7 part by weight of fumed silica (Aerosil 200, trade name of Nippon Aerosil Co., Ltd.) having a specific surface area of 200 m ² / g, and a dissolver equipped with an edge disk turbine type stirring blade was used. , Rotation speed 2,
Stir at 000 rpm for 60 minutes, and then JIS K 5400-
The dispersity measured according to paragraph 4.7 of 1990 is 50μ.
dispersed in m. Then, 0.2 parts by weight of hydroxyl group-terminated 1,4-polybutadiene (Poly bd R-45HT, trade name of Idemitsu Petroleum Co., Ltd.), cobalt octenoate aromatic compound solution (PT-28, product of Hitachi Chemical Co., Ltd.) Name) 0.5 part by weight, dimethylaniline 0.05 part by weight,
Toluquinone (0.005 parts by weight) and styrene (32 parts by weight) were added and thoroughly mixed to obtain a resin mixture R-4. This characteristic is shown in Table 1.

Comparative Example 3 (1) 100 parts by weight of UP-3 obtained in (1) of Comparative Example 2
In contrast, 0.1 part by weight of glycerin, an inorganic thixotropic agent
, The specific surface area obtained by the BET method is 200 m ² / G
Fumed silica (Aerosil 200, Nippon Ae)
Add 1.0 parts by weight of Rosil Co., Ltd.
Rotate using a dissolver equipped with a scuba turbine type stirring blade
Stir at 60 rpm for several minutes, JIS K 54
The degree of dispersion measured according to paragraph 4.7 of 00-1990 is
Dispersed to 90 μm. After that, 1,4-
Polybutadiene (Poly bd R-45HT, Idemitsu
Petroleum Corporation trade name) 0.2 parts by weight, cobalt octenoate
Aromatic compound solution (PT-28, Hitachi Chemical Co., Ltd.)
Product name) 0.5 parts by weight, dimethylaniline 0.05 parts by weight
Parts, toluquinone 0.005 parts by weight, styrene 36 parts by weight
Was added and mixed thoroughly to obtain a resin mixture R-5. This
The characteristics of are shown in Table 1. Next, evaluation of the properties of the resin mixture
The method will be described. The evaluation results are shown in Table 1.

(A) Preparation of cured resin 55 parts by weight of methyl ethyl ketone peroxide (Permec N, trade name of NOF CORPORATION) as a curing agent relative to 100 parts by weight of the resin mixture of R-1 to R-5. The mixture was mixed at a ratio of 1 part by weight, cast into a flat plate mold having a thickness of 3 mm, gelled, and post-cured at 50 ° C. for 16 hours to obtain a cured resin product.

(B) Mechanical strength The cured resin obtained in (A) was measured for flexural strength and flexural modulus according to JIS K7203. (C) 95 ° C. hot water immersion crack generation time The cured resin product obtained in (A) was cut into 50 mm squares and heated to 95 ° C.
The whole surface was immersed in ion-exchanged water. After that, the state was observed with time and the time until a crack was generated was measured.

(D) Laminate defoaming workability Togiken Co., Ltd. spray-up machine HLL5000 type was used and sprayed onto a bathroom unit washing area FRP type of 1100 mm × 1400 mm size under the following conditions, and immediately after that, diameter 20φ, width 100 mm The work sensation when laminating and defoaming work with a pig hair spiral roller was evaluated for the items shown in Table 1. In Table 1, fluff means a glass fiber base material sprayed on a mold and a resin mixture impregnated with a defoaming roll, and when defoamed, uncured FRP becomes a film and the film and the mold surface This is a phenomenon in which bubbles accumulate. As for the entanglement in the diameter, the time from the completion of spraying to the time when the entanglement of the glass fiber was felt and the feeling at this time were evaluated.

(Spray-up conditions) Environmental temperature: 25 ° C. Discharge of resin mixture: 5.8 kg / min Glass fiber: Asahi Fiber Glass Co., Ltd., ER346
0 PB-SP10A to 1 inch length 2.7kg
It was cut at a rate of / min (glass fiber content 32% by weight).

[0046]

EFFECT OF THE INVENTION The resin mixture for lamination using the hot water resistant unsaturated polyester resin composition of the present invention maintains the hot water resistance and the mechanical strength, and in the molding method, time elapses during lamination and defoaming work. Even so, it is possible to reduce the entanglement of the glass fibers in the defoaming roll and manufacture a molded product.

[Table 1]

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 283/01 C08F 299/00-299/08 B32B 27/36 C08G 63/553 C08J 5 /twenty four

Claims (9)

(57) [Claims] 1. A dicyclopentadiene of 15 to 45 mol%, a propylene glycol of 15 to 45 mol%, and one or more of maleic acid, maleic anhydride and fumaric acid are contained as 25 to 55 mol% as essential components. An unsaturated polyester having an equimolar amount of dicyclopentadiene,
Maleic anhydride and water or equimolar amount of dicyclopentadiene
And maleic acid were added at 120-150 ° C
After that, it is obtained by adding the remaining components and conducting dehydration condensation or addition polymerization.
And weight average measured by gel permeation chromatography
The value obtained by dividing the molecular weight by the number average molecular weight is 20 or more.
Japanese polyester (A) 40 to 80 parts by weight in total of 100
A hot water-resistant unsaturated polyester resin composition obtained by dissolving 60 to 20 parts by weight of a crosslinkable monomer so that the amount of the weight of the crosslinkable monomer becomes 60 parts by weight. Wherein the crosslinking monomer is styrene claim 1
The hot-water unsaturated polyester resin composition as described in 1. 3. A propylene hot water resistance unsaturated polyester resin composition according to any one of claims 1-2 for the 30 mol% or less was replaced by dipropylene glycol glycol. 4. Based on 100 parts by weight of the hot water resistant unsaturated polyester resin composition according to claim 1,
A resin mixture for lamination, in which 0.1 to 10 parts by weight of an inorganic thixotropic agent is dispersed and 0.01 to 1.2 parts by weight of hydroxyl-terminated 1,4-polybutadiene are mixed. 5. An inorganic thixotropic agent is defined in JIS K 540.
The degree of dispersion measured according to paragraph 4.7 of 0-1990 is 5
The resin mixture for lamination according to claim 4 , wherein the resin mixture for lamination is dispersed so as to be in the range of ˜70 μm. 6. The resin mixture for lamination according to claim 4 , wherein the inorganic thixotropic agent has a specific surface area of 50 to 500 m ² / g as determined by the BET method. 7. The resin mixture for lamination according to claim 4 , wherein the inorganic thixotropic agent is fumed silica. 8. The resin mixture for laminating according to claim 4 , wherein the inorganic thixotropic agent has a specific surface area of 50 to 500 m ² / g as determined by the BET method and is fumed silica. 9. A molded product obtained from the resin mixture for lamination according to claim 4 .