JP2002226525A - Resin composition and method for thermosetting using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having excellent surface curability during curing and capable of forming a molded product having excellent chemical resistance even without surface sealing of a Mylar (R) film during thermosetting and to provide a method for thermosetting using the resin composition. SOLUTION: This resin composition comprises (a) an unsaturated polyester with a weight ratio of 20-45 wt.% of dicyclopentenyl group, (b) a compound having an acryloyl or a methacryloyl group and (c) an aromatic monomer without the acryloyl or methacryloyl group and the contents thereof are 30-80 wt.% of (a), 3-30 wt.% of (b) and 5-60 wt.% of (c).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition, and more particularly to a radical-curable resin composition containing an unsaturated polyester and a heat-curing method using the same.

[0002]

2. Description of the Related Art Since a radical-curable resin represented by an unsaturated polyester resin or a vinyl ester resin is in a liquid state, it has a high handleability and is a lightweight and high-strength molded product as a matrix resin of fiber reinforced plastic (FRP). From the advantage of giving civil engineering materials such as concrete formwork, tanks,
It is widely used as a resin composition for molding in a wide range of fields such as housing equipment such as pipes and bathtubs (bathtubs), construction materials, ships, automobiles, industrial equipment, containers, high-strength tubes, and miscellaneous goods.

It is well known that such a resin composition causes curing inhibition in the presence of oxygen during curing. As a result, there is a possibility that the chemical resistance is reduced due to insufficient surface curability.
For this purpose, the surface is covered with a Mylar film or the like which is a polyester film, or an air-blocking layer is provided by adding paraffin wax or the like. It is also known that the use of an unsaturated polyester having a dicyclopentenyl group and an unsaturated polyester resin containing a crosslinkable monomer such as styrene improves the drying property.

However, when these materials are cured by heating, the addition of paraffin wax causes no formation of an air-barrier layer, so that the effect is lost. In addition, when an unsaturated polyester having a dicyclopentenyl group is used, Also, if not covered with a surface seal such as a mylar film, the crosslinkable monomer is volatilized and the surface curability becomes insufficient. In this case, for example, in filament winding molding, when the outer surface is provided with chemical resistance, a mylar film or the like is also required on the outer surface, and a large amount of industrial waste is generated. Further, in the case of pultrusion molding or the like, the surface hardening at the time of pulverization is often not completely completed, and there is a problem that it is difficult to use in corrosion-resistant applications. Furthermore,
Even in a hand lay-up application such as a septic tank, when heating without waiting for gelation, there is a problem that the effect of adding paraffin wax is lost and the surface chemical resistance is impaired.

As described above, when an unsaturated polyester resin or a vinyl ester resin is cured by heating, a molded product having excellent surface chemical resistance can be formed without using a surface seal by improving the surface curability. The technology for it had not been found. When curing at room temperature, it is effective to add a paraffin wax or use an unsaturated polyester having a dicyclopentenyl group. When the resin composition has excellent properties, it can be applied as a resin composition for molding in a wide range of fields, and such a resin composition has been eagerly desired.

US Pat. No. 4,753,982 (19)
88) discloses a blend of an unsaturated polyester resin having a norbornene skeleton and a vinyl ester resin as a means for improving the chemical resistance of the curable resin composition. However, there is no mention of a technique for obtaining a molded article having excellent chemical resistance when cured without a surface seal, particularly when cured by heating, by using a specific proportion of the resin composition.

[0007]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention provides a molded article having excellent surface curability at the time of curing, and having excellent chemical resistance even during heat curing without a surface seal such as a mylar film. It is an object of the present invention to provide a resin composition capable of being cured and a heat curing method using the same.

The present inventors have conducted intensive studies in view of the above-mentioned problems of the conventional radical-curable resin composition, and as a result,
In an unsaturated polyester resin having a dicyclopentenyl group and an unsaturated polyester resin containing a crosslinkable monomer such as styrene, the crosslinkable monomer is volatilized when cured by heating, and in a vinyl ester resin, the vinyl ester is Since the (meth) acryloyl group possesses anaerobic properties, there is room for contriving to improve the surface curability when heat-curing when using any of them. We found that we could solve it. As described above, when both are cured by heating, the surface curability is not sufficient, but by using both together, the surface curability is improved and the chemical resistance is excellent without a surface seal such as a mylar film. The reason why a molded article can be formed is presumed to be, for example, that a crosslinked structure is formed on the surface by the reaction between an unsaturated polyester having a dicyclopentenyl group and a (meth) acryloyl group of a vinyl ester. You.
Further, since such a resin composition exhibits excellent surface curability even when cured at room temperature or when cured by heating, it has also been found that the resin composition can be applied as a resin composition for molding in a wide range of fields. Was completed.

That is, the present invention relates to an unsaturated polyester (a) having a dicyclopentenyl group weight ratio of 20 to 45% by weight, a compound (b) having a (meth) acryloyl group, and a (meth) acryloyl group. It is a resin composition containing an aromatic monomer (c) having no (a) 30 to 80% by weight and (b) 3 to 30% by weight.
It is a resin composition in which (c) is 5 to 60% by weight. The present invention is also a heat curing method for curing the above resin composition at 40 ° C. or higher. Hereinafter, the present invention will be described in detail.

[0010] The resin composition of the present invention is mainly used for corrosion resistance. The molding method is not particularly limited. For example, filament winding in which a roving or a single strand is immersed in a resin tank from a thread winding and wound around a mandrel, or a reinforcing material such as a continuous strand is used as a liquid molding resin composition. A molded article can be obtained by dipping and impregnating in a resin bath filled with the resin, guiding the resultant to a die, shaping the rod into a rod-shaped material, and then heating and curing the same to obtain a molded product.

The resin composition contains an unsaturated polyester (a), a compound (b) having a (meth) acryloyl group, and an aromatic monomer (c) having no (meth) acryloyl group. . The above (a), (b) and (c) are collectively referred to as a radical-curable resin. The weight ratio of the radical-curable resin in the resin composition may be appropriately set in accordance with the required performance, application, and the like, in consideration of the weight ratio of the additives described below contained in the resin composition as needed. It suffices if there is no particular limitation.

The unsaturated polyester in the resin composition has a weight ratio of dicyclopentenyl groups of 20 to 45% by weight, for example, an acid component essentially including an unsaturated polybasic acid, a polyhydric alcohol and / or a polyhydric alcohol. Examples of the polymer include a polymer prepared by condensation polymerization of a polyhydric alcohol component containing an epoxy compound as an essential component. Such unsaturated polyesters may be used alone or in combination of two or more.

The unsaturated polybasic acid is a compound having a polymerizable unsaturated bond in one molecule and two or more substituents capable of reacting with a hydroxyl group or an epoxy group to form an ester bond. Is not particularly limited, for example, α, such as maleic acid, fumaric acid, aconitic acid, and itaconic acid;
β-unsaturated polybasic acids; β, γ-unsaturated polybasic acids such as dihydromuconic acid; anhydrides, halides and alkyl esters of these acids. These may be used alone or in combination of two or more.

The polyhydric alcohol is not particularly restricted but includes, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 2-methyl-1,3-
Propanediol, 1,4-butanediol, 1,3-
Butanediol, 2,3-butanediol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,7- Heptanediol, 1,8-octanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane, 2,2-diethyl-1,3-propanediol,
3-methyl-1,4-pentanediol, 2,2-diethyl-1,3-butanediol, triethylene glycol, hydrogenated bisphenol A, hydrogenated bisphenol A
And trihydric or higher alcohols such as glycol, glycerin, trimethylolpropane, and pentaerythritol, such as alkylene oxide adducts of bisphenol A. These may be used alone or in combination of two or more.

The epoxy compound is not particularly restricted but includes, for example, ethylene oxide, propylene oxide,
Examples include butylene oxide, styrene oxide, glycidyl (meth) acrylate, and diglycidyl ether of bisphenol A. These may be used alone,
Two or more kinds may be used in combination.

If necessary, the acid component may contain a saturated polybasic acid such as an aromatic saturated polybasic acid or an aliphatic saturated polybasic acid, or an unsaturated polybasic acid having an unsaturated bond such as an allyl group. A monovalent acid may be used instead of a part of the polybasic acid. Further, the polyhydric alcohol component may include a polyhydric alcohol having an unsaturated bond such as an allyl group and / or an epoxy compound, and a monohydric alcohol may be used instead of a part of the polyhydric alcohol. Good.

The unsaturated polyester includes those having a dicyclopentenyl group. The dicyclopentenyl group is represented by the following formula (1) or (2). Such unsaturated polyester having a dicyclopentenyl group,
It may have only one of the dicyclopentenyl groups, or may have both of the dicyclopentenyl groups.

[0018]

Embedded image

The unsaturated polyester preferably contains, as a main component, one having a dicyclopentenyl group, and may or may not additionally contain one having no dicyclopentenyl group. . The method for introducing the dicyclopentenyl group into the unsaturated polyester may be introduced during the preparation of the polymer using a compound having a dicyclopentenyl group or may be introduced after the polymer is prepared, and is particularly limited. It is not something to be done. For example, to introduce at the stage of preparing a polymer, an unsaturated polybasic acid adduct of dicyclopentadiene may be used instead of a part of the unsaturated polybasic acid, or dicyclopentadiene may be used instead of a part of the polyhydric alcohol. It can be carried out by using glycol adducts of pentadiene or hydroxydicyclopentadiene. Further, it can be carried out by allowing dicyclopentadiene to be present at the time of polycondensation between the acid component and the polyhydric alcohol component. For example, polycondensation may be performed by mixing an acid component and a polyhydric alcohol component with dicyclopentadiene, and dicyclopentadiene is added after mixing the acid component and the polyhydric alcohol component to start polycondensation. May be.

In the present invention, among the unsaturated polyesters obtained as described above, the reaction product (d) obtained by reacting dicyclopentadiene, maleic anhydride and water is used.
And a polyhydric alcohol (e). More preferably, it is obtained by reacting a mixture containing a polyhydric alcohol (e) with a reaction product (d ') obtained by converting maleic anhydride into maleic acid with water and then reacting with dicyclopentadiene. Things. Thereby, by-products such as endmethylenetetrahydrophthalic anhydride generated by decomposition of dicyclopentadiene are suppressed, and the surface curability of the resin composition and the chemical resistance of the molded product surface obtained from the resin composition are improved. Will do.

In the present invention, the weight ratio of dicyclopentenyl groups in the unsaturated polyester (a) is from 20 to
45% by weight. Thereby, the surface curability of the resin composition of the present invention is improved. If the amount is less than 20% by weight, the function and effect of the present invention will not be sufficiently exhibited, and if it exceeds 45% by weight, the storage stability of the resin composition will decrease.

The weight ratio of dicyclopentenyl groups in the unsaturated polyester can be calculated, for example, as described below. (1) As a component for forming an ester chain of an unsaturated polyester, it is eliminated from the total weight of an acid component including a compound having a dicyclopentenyl group and a polyhydric alcohol component by condensation of the acid component and the polyhydric alcohol component. Subtract the weight of the components and use the resulting value as the total weight of the unsaturated polyester. (2) The number of moles of the compound having a dicyclopentenyl group is multiplied by the molecular weight (133) of the dicyclopentenyl group, and the obtained value is defined as the weight of the dicyclopentenyl group. (3) The value obtained by dividing the weight of dicyclopentenyl groups by the total weight of unsaturated polyester is defined as the weight ratio of dicyclopentenyl groups in the unsaturated polyester.

In the above calculation method, when a compound having a dicyclopentenyl group is produced at the time of polycondensation for obtaining an unsaturated polyester, the weight of the compound having a dicyclopentenyl group is the weight of the compound having a dicyclopentenyl group. The amount may be a theoretical amount calculated from the weight of the raw material used for the production. A calculation example is shown below. That is, for example, a maleic acid adduct of dicyclopentadiene produced using 1 mol (132 g) of dicyclopentadiene, 1 mol (98 g) of maleic anhydride, and 1 mol (18 g) of water is
Dehydration condensation with 0.6 mol (37.2 g) of ethylene glycol is as follows. First, since the theoretical amount of the maleic acid adduct of dicyclopentadiene formed is 1 mol, the weight is 132 g + 98 g + 18 g = 248.
g. The water desorbed by the condensation is 1 mol because the hydroxyl group is 1.2 mol and the carboxyl group is 1 mol. Therefore, the weight is 18 × 1 = 18 g.
Therefore, the content of dicyclopentenyl group was 133 g /
(248 g + 37.2 g-18 g)｝ × 100 = 49.
It becomes 8% by weight.

The present invention provides a resin containing the unsaturated polyester (a), the compound (b) having a (meth) acryloyl group, and the aromatic monomer (c) having no (meth) acryloyl group. (A) is 3% based on 100% by weight of the resin composition.
0 to 80% by weight, (b) 3 to 30% by weight, and
(C) is a resin composition having 5 to 60% by weight.

In the above resin composition, (a), (b)
When the weight ratio of (c) and (c) exceeds the above ratio, the molded product formed by curing the resin composition may have tack-free properties at first glance, but little improvement in chemical resistance, or The anaerobic property of the (meth) acryloyl group is superior and the surface drying property is deteriorated. Preferably,
(A) is 40 to 70% by weight, (b) is 5 to 25% by weight,
And (c) is 10 to 50% by weight.

In the present invention, the molar ratio of the dicyclopentenyl group to the (meth) acryloyl group in the resin composition is as follows:
It is preferably from 97/3 to 55/45. By doing so, the anaerobic properties of the (meth) acryloyl group are further suppressed, and even if the aromatic monomer (c) having no (meth) acryloyl group volatilizes at the time of heat curing, the surface of the monomer (c) volatilizes. Curability can be ensured. More preferably, 95
/ 5 to 60/40, more preferably 94/6 to
70/30.

The compound (b) having a (meth) acryloyl group is not particularly restricted but includes, for example, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate and the like. Acrylic acid-based monomers; monomers containing two or more (meth) acrylates in one molecule such as ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate Urethane (meth) acrylate; compounds such as vinyl esters, high molecular compounds (oligomers or polymers), and the like. Further, a crosslinkable acryloyl polymer which is a (meth) acrylic polymer having a polymerizable double bond may be used. These may be used alone or in combination of two or more.

In the present invention, the compound (b) having a (meth) acryloyl group as described above preferably has a number average molecular weight of 300 to 100,000. By doing so, the volatilization of the compound (b) having a (meth) acryloyl group during heat curing is suppressed, and the crosslink density is secured, so that the surface curability is improved. More preferably, it is 400 to 70000,
More preferably, it is 500 to 50,000. In the present invention, more preferably, the compound (b) having a (meth) acryloyl group is a vinyl ester. The use of vinyl ester also improves chemical resistance.

The vinyl ester used in the present invention is
It may or may not contain an α, β-unsaturated monomer, and can be produced by a known method. For example, an epoxy resin and (meth) acrylic acid can be obtained as components. Epoxy (meth) acrylate, polyester (meth) acrylate obtained by using polyester polyol and (meth) acrylic acid as components, or both dicarboxylic acid and / or unsaturated dicarboxylic acid and / or polyhydric alcohol as components. Is a polyester (meth) acrylate obtained by using a polyester obtained as a component and an epoxy compound having an α, β-unsaturated carboxylic ester group as components. As an epoxy compound having an α, β-unsaturated carboxylic acid ester group, glycidyl (meth) acrylate is a typical example.

The aromatic monomer (c) having no (meth) acryloyl group in the present invention is not particularly limited.
For example, styrene, vinyl toluene, α-methylstyrene, p-methylstyrene, p-chloromethylstyrene,
Styrene monomers such as divinylbenzene; and allyl ester aromatic monomers such as diallyl phthalate and diallyl isophthalate. These may be used alone or in combination of two or more. Among them, in the present invention, an aromatic monomer containing styrene as a main component can be preferably used.

It is preferable to add a polymerization inhibitor to the above resin composition. Examples of the polymerization inhibitor include toluhydroquinone, hydroquinone, 1,4-naphthoquinone, parabenzoquinone, trihydroquinone, p-tert-butylcatechol, , 6-tert-butyl-4-methylphenol and the like. The polymerization inhibitor is 20 to
Used in the range of 500 ppm. Further, at least one compound selected from the group consisting of phenothiazines, onium salts and ionic inorganic metal compounds, and a phosphite may be added in an amount of 10 to 500 ppm, whereby the storage stability of the resin composition and the like may be added. Can be improved. Further, additives such as an ultraviolet absorber, a flame retardant, a coupling agent, and a pigment may be further added to the resin composition as needed.

[0032] The resin composition may contain a curing accelerator. As the curing accelerator, any metal compound having a redox effect may be used, and a metal salt of an aliphatic carboxylic acid,
Carboxylic acid metal salts such as aromatic carboxylic acid metal salts and alicyclic carboxylic acid metal salts; metal chelate complexes can be used. The curing accelerator is preferably used in a range of 0.00001 to 0.5 part by weight based on 100 parts by weight of the radical curable resin. In addition, since many curing accelerators are in the form of powder, they are dissolved in various solvents or crosslinkable monomers in consideration of workability, and a solution having a metal content of 1 to 10% by weight is obtained. May be added to the product.

The above resin composition is usually used after adding a curing agent. As the curing agent, an organic peroxide catalyst generally used in the unsaturated polyester resin industry can be used. Examples of the organic peroxide catalyst include benzoyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, ester peroxide and the like. The curing agent is used in an amount of usually from 0.3 to 7 parts by weight, preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of the radical-curable resin. Further, the resin composition may contain a low-shrinking agent such as polystyrene, if necessary. Further, the resin composition of the present invention can be used as a molding material by blending with a filler or glass fiber. Further, a molded product obtained by curing the resin composition or the molding material of the present invention is one of preferred embodiments.

The method for preparing the resin composition is not particularly limited. For example, the resin composition can be prepared by performing a kneading operation or the like in the same manner as a usual resin composition. The curing conditions of the resin composition may be appropriately set according to the curability of the unsaturated polyester, the crosslinkable monomer or curing agent, the curing accelerator, the type and amount of the polymerization inhibitor, and other conditions, and other conditions. However, there is no particular limitation. For example, the curing temperature is preferably 40 ° C. or higher, more preferably 60 ° C. or higher. The curing time is preferably from 20 seconds to 60 minutes.

The resin composition of the present invention can be applied to both cold curing molding and heat curing molding. However, since the effects of the present invention are sufficiently exerted, it is preferably used in heat curing molding. It is something that can be done. Thus, the resin composition of the present invention used for heat curing is one of the preferred embodiments of the present invention. Since the curing temperature in the heat curing is preferably 40 ° C. or more,
In the present invention, a resin composition used for heat curing at 40 ° C. or higher is a preferred embodiment. Further, the resin composition,
According to the heat-curing method of curing at 40 ° C. or more, a molded article having excellent surface curability and excellent chemical resistance can be formed without heat sealing at the time of heat-curing. Such a heat curing method is also one of the present invention. In the heat curing method of the present invention, it is preferable to cure the resin composition under air contact without an air barrier film.

Using the resin composition of the present invention, the molded product obtained by the above-mentioned heat-curing method by heat-curing molding, in particular, filament winding molding, drawing molding, etc.
Even without a surface seal, it has excellent chemical resistance, facilitating its development for corrosion-resistant applications. Specific examples of molded articles include, for example, civil engineering materials such as concrete forms, tanks,
Used for pipes and the like.

[0037]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. “Parts” means “parts by weight”,
“%” Indicates “% by weight”.

Production Example 1 Preparation of Iso-Unsaturated Polyester Resin 118 parts of propylene glycol, 194 parts of dipropylene glycol, and 145 parts of isophthalic acid were charged into a four-necked flask, heated to 210 ° C., and reacted as usual. Next, 200 parts of maleic anhydride was charged, the temperature was raised to 210 ° C., and the reaction was carried out in the usual manner to obtain an iso-unsaturated polyester having an acid value of 28. The isounsaturated polyester is dissolved at 80 ° C in a solution obtained by dissolving 0.1 part of hydroquinone in 400 parts of styrene monomer.
An iso-unsaturated polyester resin of 5 cm ² / s was obtained.

Production Example 2 Preparation of Unsaturated Polyester Resin Containing Dicyclopentenyl Group (1) 196 parts of maleic anhydride, 278 parts of dicyclopentadiene (purity: 95%) and 36 parts of water were charged into a four-necked flask and charged with nitrogen. The addition reaction was performed at 130 ° C. for 3 hours under an air stream to obtain a maleic acid adduct of dicyclopentadiene.
Next, 90 parts of maleic anhydride, 160 parts of neopentyl glycol, and 50 parts of propylene glycol were added and mixed, and a dehydration condensation reaction was carried out at 200 ° C. for 12 hours in a nitrogen stream as usual to obtain an acid value of 15. And a dicyclopentenyl group-containing unsaturated polyester having a dicyclopentenyl group content of 35%. This dicyclopentenyl group-containing unsaturated polyester was added to a solution obtained by dissolving 0.12 part of hydroquinone in 418 parts of styrene monomer.
Dissolved at 0 ° C., and a dicyclopentenyl-containing unsaturated polyester resin having a viscosity of 4.5 cm ² / s at 25 ° C. (DC
PD-1) was obtained.

Production Example 3 Preparation of Unsaturated Polyester Resin Containing Dicyclopentenyl Group (2) 196 parts of maleic anhydride, 278 parts of dicyclopentadiene (95% purity) and 36 parts of water were charged into a four-necked flask, and nitrogen was charged. The addition reaction was performed at 130 ° C. for 3 hours under an air stream to obtain a maleic acid adduct of dicyclopentadiene.
Next, 133 parts of phthalic anhydride and 230 parts of diethylene glycol are added and mixed.
A dehydration condensation reaction was carried out at 12 ° C. for 12 hours to obtain a dicyclopentenyl group-containing unsaturated polyester having an acid value of 20 and a dicyclopentenyl group content of 33%. The dicyclopentenyl group-containing unsaturated polyester is dissolved at 80 ° C. in a solution obtained by dissolving 0.12 part of hydroquinone in 360 parts of styrene monomer, and the dicyclopentenyl having a viscosity of 4.5 cm ² / s at 25 ° C. A group-containing unsaturated polyester resin (DCPD-2) was obtained.

Production Example 4 Preparation of Unsaturated Polyester Resin Containing Dicyclopentenyl Group (3) 196 parts of maleic anhydride, 278 parts of dicyclopentadiene (purity: 95%), and 36 parts of water were charged into a four-necked flask and charged with nitrogen. The addition reaction was performed at 130 ° C. for 3 hours under an air stream to obtain a maleic acid adduct of dicyclopentadiene.
Next, 980 parts of maleic anhydride, 880 parts of neopentyl glycol, and 266 parts of propylene glycol were added and mixed, and a dehydration-condensation reaction was carried out at 200 ° C. for 12 hours in a nitrogen stream as usual, to obtain an acid value of 20. And a dicyclopentenyl group-containing unsaturated polyester having a dicyclopentenyl group content of 11%. The unsaturated dicyclopentenyl group-containing polyester was treated with hydroquinone 0.39.
Parts to a solution of obtained by dissolving in 1431 parts of styrene monomer, dissolved at 80 ° C., 4.5 cm in viscosity of 25 ° C. ² /
s dicyclopentenyl group-containing unsaturated polyester resin (DCPD-3) was obtained.

Production Example 5 Production of Vinyl Ester Resin Epototo YD901 (manufactured by Toto Kasei Co., Ltd., epoxy equivalent 4
65) 368 parts, 81 parts of Epototo YD127 (manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 185), methacrylic acid 10
8 parts, triethylamine 2.3 parts, hydroquinone 0.
15 parts were charged into a four-necked flask, and the acid value was 4 as usual.
The reaction was continued until the temperature was lowered, and 440 parts of a styrene monomer and 0.2 parts of hydroquinone were charged to obtain a vinyl ester resin having a viscosity of 4.5 cm ² / s at 25 ° C.

Example 1 80 parts of DCPD-1 produced in Production Example 2 and Production Example 5
20 parts of the vinyl ester resin prepared in the above was mixed to obtain a resin composition of Example 1.

Example 2 56 parts of DCPD-1 produced in Production Example 2, 224 parts of DCPD produced in Production Example 3, and 20 parts of vinyl ester resin produced in Production Example 5 were mixed, and the resin composition of Example 2 was mixed. Things.

Example 3 80 parts of DCPD-2 produced in Production Example 3 and Production Example 5
20 parts of the vinyl ester resin prepared in the above was mixed to obtain a resin composition of Example 3.

Example 4 85 parts of DCPD-1 produced in Production Example 2 and Production Example 5
15 parts of the vinyl ester resin prepared in the above was mixed to obtain a resin composition of Example 4.

Example 5 60 parts of DCPD-1 produced in Production Example 2 and Production Example 5
40 parts of the vinyl ester resin prepared in the above was mixed to obtain a resin composition of Example 5.

Comparative Example 1 The iso-unsaturated polyester resin produced in Production Example 1 was used. Comparative Example 2 DCPD-1 produced in Production Example 2 was used.

Comparative Example 3 97 parts of DCPD-1 produced in Production Example 2 and Production Example 5
3 parts of the vinyl ester resin prepared in the above was mixed to obtain a resin composition of Comparative Example 3.

Comparative Example 4 30 parts of DCPD-1 produced in Production Example 2 and Production Example 5
70 parts of the vinyl ester resin prepared in the above was mixed to obtain a resin composition of Comparative Example 4.

Comparative Example 5 80 parts of DCPD-3 produced in Production Example 4 and Production Example 5
20 parts of the vinyl ester resin prepared in the above was mixed to obtain a resin composition of Comparative Example 5.

COMPARATIVE EXAMPLE 6 100 parts of DCPD-1 produced in Production Example 2 were added to BYK-
1 part of LPS6665 (a paraffin wax solution manufactured by Big Chemie) was added to obtain a resin composition of Comparative Example 6.

The resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 6 were evaluated by the following methods. Table 1 shows the results
And Table 2. <Cooking board boiling water resistance> To a resin composition containing 0.3 part of cobalt octenoate having a metal content of 8%, 1.0 part of methyl ethyl ketone peroxide (purity of 55%) was added, and a 3 mm-thick casting was performed. The plate was prepared, and the time until cracks were formed by immersion in hot water at 98 ° C. was defined as the boiling resistance of the cast plate.

<Preparation of Test Piece for Evaluation of Chemical Resistance> A flat plate was prepared on a hot plate, and the chemical resistance was evaluated. A film made of Tetron is placed on a hot plate, and then laminated with a resin containing 1% of benzoyl peroxide. The glass composition is
# 450 chopped strand mat 3 ply, set glass content 30%. Next, only in Comparative Example 1, after blocking the air with a tetron film, the composition was cured at 100 ° C. for 10 minutes to obtain a test piece.

<Evaluation of Surface Curing Property> Acetone was applied in an appropriate amount, and the surface curing property was evaluated by touching the surface with the finger to determine the extent of the surface being damaged by acetone. Degree of surface attack by acetone ○: No stickiness △: Slightly sticky ×: Sticky

<Evaluation of Chemical Resistance> The entire surface was immersed in a 40% aqueous solution of sodium hydroxide at 60 ° C. for 5 hours, 50 hours, and 1 hour.
After the lapse of 00 hours, the weight change rate and the appearance change were observed. Appearance ：: Gloss is unchanged from the initial state △: Gloss is lower than the initial state ×: Glass whitening is observed without gloss

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

Since the resin composition of the present invention has the above-mentioned constitution, it has excellent surface curability at the time of curing, and has excellent chemical resistance even at the time of heat curing without a surface seal such as a Mylar film. Molded products can be formed, especially in heat-curing molding such as filament winding molding and pultrusion molding, and the obtained molded products are suitably applied to a wide range of fields such as civil engineering materials such as concrete forms, tanks, pipes and the like. It is a material that can be

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Daisaku Yamamoto 5-8, Nishiobari-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. F-term (reference) 4J027 AA02 AB04 AB06 AB07 AB08 AB15 AB16 AB17 AB18 AB19 BA05 BA07 BA09 BA20 BA22 BA26 BA27 BA28 CB03 CC02 CD01 CD08

Claims (5)

[Claims] The weight ratio of dicyclopentenyl groups is 20
To 45% by weight of an unsaturated polyester (a), a compound (b) having a (meth) acryloyl group, and a resin composition containing an aromatic monomer (c) having no (meth) acryloyl group And the content ratio is (a) is 3
0 to 80% by weight, (b) 3 to 30% by weight, and
(C) 5 to 60% by weight of the resin composition. 2. The unsaturated polyester (a) is reacted with a mixture containing a reaction product (d) obtained by reacting dicyclopentadiene, maleic anhydride and water with a polyhydric alcohol (e). And the molar ratio of the dicyclopentenyl group to the (meth) acryloyl group in the resin composition is from 97/3 to 55/4.
The resin composition according to claim 1, wherein 3. The resin composition according to claim 1, wherein the compound (b) having a (meth) acryloyl group has a number average molecular weight of 300 to 100,000 and is a vinyl ester. 4. A heat curing method comprising curing the resin composition according to claim 1, at a temperature of 40 ° C. or higher. 5. The method according to claim 4, wherein the resin composition is cured under air contact without an air barrier film.
The heat-curing method as described.