JPH11268217A - Laminated molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated molded product excellent in weatherability and water resistance and hard to generate a defect such as lifting or the like on the surface of a gel coat layer at the time of production. SOLUTION: A laminated molded product has a fiber reinforced plastic layer and the gel coat layer formed on the surface thereof. The gel coat layer comprises a cured material of a gel coat resin compsn. containing (A) an unsaturated polyester obtained by the condensation reaction of an acid component based on an unsaturated dibasic acid and/or an anhydride thereof and an alicyclic saturated dibasic acid and/or an anhydride thereof and polyhydric alcohol and an unsaturated polyester resin for a gel coat containing a polymerizable monomer as essential components. The fiber reinforced plastic layer comprises a cured material of a fiber-containing resin compsn. containing (B) an unsaturated polyester having dicyclopentenyl group and an unsaturated polyester resin for fiber reinforced plastic containing a polymerizable monomer as essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated molded article in which a gel coat layer is formed on a fiber reinforced plastic layer.

[0002]

2. Description of the Related Art Fiber-reinforced plastic moldings have high strength and are therefore used for various products such as bathtubs, unit baths, boats, tanks and the like. The outermost layer is usually provided with a gel coat layer for improving physical properties such as weather resistance and water resistance. As the resin for the gel coat layer, an unsaturated polyester obtained by subjecting an acid component containing an unsaturated dibasic acid and / or an anhydride to a polyhydric alcohol to a condensation reaction and an unsaturated polyester containing a polymerizable monomer Although resins are generally used, there is a problem that the formed gel coat layer has low weather resistance. The problem is that hexahydrophthalic anhydride (HHPA) is used as the acid component.
It is solved by using an alicyclic saturated dibasic acid and / or an anhydride thereof in combination with an unsaturated dibasic acid and / or an anhydride thereof. Further, as the polyhydric alcohol, a glycol having a main chain consisting only of carbon atoms and two or more side chains and having a large steric hindrance that may be bonded to each other, such as neopentyl glycol The use of an essential component such as (NPG) further improves the weather resistance of the gel coat layer.

[0003]

However, when producing a laminated molded article, an unsaturated dibasic acid and / or an anhydride thereof and an alicyclic saturated dibasic acid and / or an anhydride thereof are used in combination as acid components. A gel coat resin composition containing an unsaturated polyester resin containing an unsaturated polyester obtained as an essential component is applied to a mold surface and cured to form a gel coat layer, and a polymerizable monomer such as styrene is formed on the gel coat layer. When a fiber-containing resin composition containing an unsaturated polyester resin containing a monomer and an unsaturated polyester as an essential component is laminated, a phenomenon in which the gel coat layer shrinks, so-called lifting, occurs, and a defect occurs on the surface of the gel coat layer. For this reason, after demolding, it is necessary to remove the portion where lifting occurred, reapply the gel coat resin composition there, and partially repair the gel coat layer by smoothing the surface by polishing or the like. Productivity decline was inevitable. Further, the occurrence of this lifting is further exacerbated when the glycol having a large steric hindrance is used as the polyhydric alcohol as a raw material of the unsaturated polyester used in the gel coat resin composition.

[0004] The occurrence of this lifting is prevented by increasing the thickness of the gel coat layer. However, when the gel coat layer is thickened, the weather resistance is reduced and cracks are observed during lamination. The problem to be solved by the present invention is to provide a laminated molded article which is excellent in weather resistance and water resistance and is less likely to cause defects such as lifting on the surface of a gel coat layer during production.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and repeated experiments, and as a result, have found that an unsaturated dibasic acid and / or its anhydride and an alicyclic system as an acid component. The above laminated molded article having a gel coat layer formed using a gel coat resin composition containing, as an essential component, an unsaturated polyester resin containing an unsaturated polyester obtained by using a saturated dibasic acid and / or an anhydride thereof in combination In, if the unsaturated polyester contained in the fiber-containing resin composition used for forming the fiber-reinforced plastic layer, a polyester having a dicyclopentenyl group is used,
Experiments have confirmed that the above problems can be solved at once, and have completed the present invention.

That is, the laminated molded product according to the present invention is:
In the laminated molded article provided with a fiber-reinforced plastic layer and a gel coat layer formed on the surface thereof, the gel coat layer comprises an unsaturated dibasic acid and / or an anhydride thereof and an alicyclic saturated dibasic acid and / or Gel coat containing, as an essential component, an unsaturated polyester resin for gel coat containing an unsaturated polyester (A) obtained by a condensation reaction of an acid component essentially containing the anhydride and a polyhydric alcohol and a polymerizable monomer. The fiber reinforced plastic layer comprises a cured product of a resin composition, and the fiber reinforced plastic layer comprises, as an essential component, an unsaturated polyester resin for fiber reinforced plastic comprising an unsaturated polyester (B) having a dicyclopentenyl group and a polymerizable monomer. And a cured product of a fiber-containing resin composition containing

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The unsaturated polyester (A) used in the present invention is obtained by a condensation reaction between the following acid components and a polyhydric alcohol. The acid component essentially contains an unsaturated dibasic acid and / or an anhydride thereof and an alicyclic saturated dibasic acid and / or an anhydride thereof.

The unsaturated dibasic acid and / or anhydride thereof is not particularly restricted but includes, for example, α, β- such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, aconitic acid and itaconic acid. Unsaturated dibasic acids;
Β, γ-unsaturated dibasic acids such as dihydromuconic acid. These may be used alone or in combination of two or more. Among these, maleic acid, maleic anhydride,
Fumaric acid is preferred because it is readily available.

The alicyclic saturated dibasic acid and / or its anhydride are not particularly limited, but include, for example, hexahydrophthalic acid, hexahydrophthalic anhydride, methylhexahydrophthalic acid, methylhexahydrophthalic anhydride. Acid, 1,2-cyclohexanedicarboxylic acid,
Examples thereof include 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. These may be used alone or in combination of two or more.

As the acid component for obtaining the unsaturated polyester (A), the unsaturated dibasic acid and / or anhydride thereof and the alicyclic saturated dibasic acid and / or anhydride thereof must be used. However, if necessary, other acid components may be used in combination therewith. Other acid components that can be used in combination are not particularly limited, but include, for example, malonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid,
Glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3,3-diethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid Aliphatic saturated dibasic acids such as, sebacic acid and 1,12-dodecane diacid;
Phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid,
Aromatic dibasic acids such as 2,3-naphthalenedicarboxylic anhydride and 4,4′-biphenyldicarboxylic acid; tetrahydrophthalic anhydride, dimer acid and the like. Further, a monobasic acid such as benzoic acid or cyclohexanecarboxylic acid can be used for terminal blocking of the unsaturated polyester (A). The other acid components may be used alone or in combination of two or more.

In the raw material for the reaction of the unsaturated polyester (A),
The usage ratio of the unsaturated dibasic acid and / or anhydride thereof to the entire acid component is not particularly limited, but is preferably 15 to 90 mol%, more preferably 30 to 80 mol%. In the reaction raw material of the unsaturated polyester (A),
Alicyclic saturated dibasic acid and / or
Alternatively, the use ratio of the anhydride is not particularly limited, but is preferably 20 to 70 mol%, more preferably 30 to 70 mol%.
６０60 mol%. If this ratio is less than 20 mol%,
The weather resistance of the gel coat layer tends to decrease, and if it exceeds 70 mol%, the strength of the gel coat layer tends to decrease.

The polyhydric alcohol used for obtaining the unsaturated polyester (A) is not particularly limited, but is, for example, a glycol having a main chain consisting only of carbon atoms and two or more side chains. It is preferable that the glycol which the side chains may bond to each other is essential. Since such a glycol has a steric hindrance and a bulky structure, the weather resistance and water resistance of the gel coat layer formed of a cured product of the gel coat resin composition containing the unsaturated polyester (A) obtained by using the glycol further increase. (Hereinafter, the glycol may be referred to as “bulky glycol”).

The above-mentioned glycol having a bulky structure is not particularly limited. For example, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propane Diol,
1,4-cyclohexanedimethanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,
Examples include 1,4-cyclohexanediol, hydrogenated bisphenol A, and the like. These may be used alone or in combination of two or more.

The polyhydric alcohol is not limited to the above-mentioned glycol having a bulky structure, and other polyhydric alcohols can be used instead of or in combination with the glycol. Examples of other polyhydric alcohols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methylpropane
Diols such as 1,3-diol; bisphenol A
Adducts of alkylene oxides such as ethylene oxide and propylene oxide; triols such as trimethylolpropane; alkylene oxides such as ethylene oxide and propylene oxide. Further, a monohydric alcohol such as benzyl alcohol can be used for blocking the terminal of the unsaturated polyester (A). The above alcohols may be used alone or in combination of two or more.

In the raw material for the reaction of the unsaturated polyester (A),
The proportion of the glycol having the bulky structure to the entire polyhydric alcohol is not particularly limited, but is preferably 4%.
It is 0 to 100 mol%, more preferably 50 to 80 mol%. The ratio of the amounts used for the condensation reaction between the acid component and the polyhydric alcohol in order to obtain the unsaturated polyester (A) is not particularly limited.
The polyhydric alcohol is preferably 0.90 to 1.10 equivalents, more preferably 0.95 to 1.05 equivalents.

The raw material for the reaction of the unsaturated polyester (A) may contain other components, if necessary, in addition to the acid component and the polyhydric alcohol. The other components are not particularly limited, but include, for example, a catalyst for accelerating the condensation reaction, an antifoaming agent, and a polymerization inhibitor for preventing gelation. Even if only one of these other components is used, 2
More than one species may be used in combination.

The reaction conditions for obtaining the unsaturated polyester (A) by the condensation reaction between the acid component and the polyhydric alcohol are not particularly limited. For example, the reaction temperature and reaction time may be appropriately set so that the above reaction is completed, and are not particularly limited. The condensation reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or helium. The inert gas may be supplied into the reaction system by, for example, so-called bubbling.

The number average molecular weight of the unsaturated polyester (A) is not particularly limited, but is preferably from 1,000 to 1,000.
8,000. If the number average molecular weight of the unsaturated polyester (A) is less than 1,000, the weather resistance and water resistance of the gel coat layer tend to decrease, and if it exceeds 8,000,
The viscosity of the gel coat resin composition containing the unsaturated polyester (A) tends to increase, and the handleability tends to decrease.

The acid value of the unsaturated polyester (A) is not particularly limited. The thickness of the gel coat layer is not particularly limited, but is preferably 0.05 to 0.70 mm, more preferably 0.10 to 0.50 mm, and still more preferably 0.15 to 0.35 mm. If the thickness is less than 0.05 mm, the fibers of the fiber-reinforced plastic layer tend to be transparent or the water resistance tends to decrease. If the thickness exceeds 0.70 mm, the weather resistance decreases or cracks are observed during lamination. Or tend to.

The unsaturated polyester (B) used in the present invention is an unsaturated polyester having a dicyclopentenyl group. In the present invention, the substituent represented by the following formula 1 and the substituent represented by the following formula 2 are collectively referred to as a dicyclopentenyl group.

[0021]

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[0022]

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The unsaturated polyester (B) may have only one of the substituent represented by Formula 1 and the substituent represented by Formula 2 as a dicyclopentenyl group. However, both may be provided. The method for synthesizing the unsaturated polyester (B) is not particularly limited. For example, the following methods (1) and (2) disclosed in JP-A-9-111108 and the following method (3) And the like.

(1) a method of introducing a dicyclopentenyl group into an unsaturated polyester by replacing at least a part of an acid component and a polyhydric alcohol which are raw materials of a general unsaturated polyester with a compound having a dicyclopentenyl group; For example, a method in which part of the acid component is replaced with an unsaturated polybasic acid adduct of dicyclopentadiene, or a part of the polyhydric alcohol is replaced with glycol adducts of dicyclopentadiene or hydroxydicyclopentadiene.

(2) A method for producing a compound having a dicyclopentenyl group by addition of an acid component or a polyhydric alcohol to dicyclopentadiene during the condensation reaction between the acid component and the polyhydric alcohol, for example, a method for producing a compound having a general unsaturated content Either the acid component and the polyhydric alcohol used for the synthesis of the polyester are mixed with dicyclopentadiene to carry out the condensation reaction, or the acid component and the polyhydric alcohol are mixed to initiate the condensation reaction, and then the dicyclopentadiene is added. A method of adding and denaturing.

(3) A method in which after a condensation reaction between an acid component and a polyhydric alcohol is performed, dicyclopentadiene is mixed and added to terminal carboxylic acid residues or hydroxyl residues. In addition,
Any two or more of the above methods can be used in combination. The unsaturated polybasic acid adduct of dicyclopentadiene used in the above synthesis method (1) is not particularly limited, but an adduct obtained by adding an unsaturated polybasic acid to dicyclopentadiene, for example, dicyclopentadiene Unsaturated dibasic acid adduct of dicyclopentadiene such as maleic acid adduct of pentadiene; maleic acid half ester adduct of dicyclopentadiene and the like.

In the above synthesis method (1), among the compounds having a dicyclopentenyl group used for substituting an acid component or a part of a polyhydric alcohol, an unsaturated dibasic acid adduct of dicyclopentadiene is preferable. Maleic acid adduct of dicyclopentadiene is particularly preferred.
When these are used, an unsaturated polyester (B) exhibiting excellent surface smoothness, dimensional stability, hot water resistance and the like when formed into a laminated molded article can be obtained. The maleic acid adduct of dicyclopentadiene can be produced by adding dicyclopentadiene and maleic acid in the presence of water.

As the acid component and the polyhydric alcohol used in the synthesis of the unsaturated polyester (B), the same ones as used in the conventional unsaturated polyester can be used, and there is no particular limitation. An unsaturated dibasic acid and / or an anhydride thereof may be used as an essential component, and if necessary, further containing another acid component. As these unsaturated dibasic acids, anhydrides and other acid components, those exemplified above as those used in the synthesis of the unsaturated polyester (A) can be used. As for the polyhydric alcohol, those exemplified above can be used as those used in the synthesis of the unsaturated polyester (A).

When synthesizing the unsaturated polyester (B),
The ratio of the amount of the acid component to the amount of the dicyclopentadiene used is preferably 0.1 to 1.0 mol, more preferably 0.3 to 0.8 mol, per mol of the acid component. . If the amount of dicyclopentadiene used is less than 0.1 mol, lifting tends to occur in the gel coat layer having a certain thickness or less, and if it exceeds 1.0 mol, the fiber containing the unsaturated polyester (B) is used. The curability of the containing resin composition tends to decrease.

When the unsaturated polyester (B) is synthesized, the ratio of the amount of the acid component to the amount of the polyhydric alcohol used and the reaction conditions are as follows:
The same applies to the case of the unsaturated polyester (A), and there is no particular limitation. In addition, the synthesis of the unsaturated polyester (B) is performed, for example, by using Technical Processin.
gs, 36th Annual Conference
e, Reinforced Plastics / Com
positions Institute, The Soc
iety of the Plastics Indu
try Inc. , Session 7-E (198
It can also be performed by the conventionally known method shown in 1).

The content of dicyclopentenyl groups in the unsaturated polyester (B) is preferably at least 20% by weight, more preferably 20 to 40% by weight. When the content of the dicyclopentenyl group is less than 20% by weight, lifting tends to occur easily in the gel coat layer having a certain thickness or less. The dicyclopentenyl group content of the unsaturated polyester (B) can be determined, for example, by the following method.

First, from the total weight of an acid component and a polyhydric alcohol (including a compound having a dicyclopentenyl group) which are components forming an ester chain, a component which is eliminated by a condensation reaction between the acid component and the polyhydric alcohol. And the obtained value is defined as the total weight of the unsaturated polyester (B). In addition, the molecular weight of the dicyclopentenyl group (1
The value obtained by multiplying by 33) is defined as the weight of the dicyclopentenyl group. The value obtained by dividing the weight of the dicyclopentenyl group by the total weight of the unsaturated polyester (B) is defined as the content of the dicyclopentenyl group to be determined.

When a compound having a dicyclopentenyl group is formed during the condensation reaction, the weight of the compound having a dicyclopentenyl group is calculated from the weight of the raw materials used for forming the compound having a dicyclopentenyl group. What is necessary is just to calculate the theoretical amount. A calculation example is shown below. That is,
For example, 1 mol of dicyclopentadiene (132 g), 1 mol of maleic anhydride (98 g) and 1 mol of water (18 g)
And the maleic acid adduct of dicyclopentadiene produced by using
When dehydration condensation is carried out with g), the following is obtained. First, since the theoretical amount of the maleic acid adduct of dicyclopentadiene to be formed is 1 mol, the weight is 132 g + 98.
g + 18 g = 248 g. The water desorbed by the condensation has a hydroxyl group of 1.2 mol and a carboxyl group of 1 mol.
Since it is 1 mole, the weight is 18 ×
1 = 18 g. Therefore, the content of the dicyclopentenyl group is 133 g / (248 g + 37.2 g-18)
g) Δ × 100 = 49.8% by weight.

The number average molecular weight of the unsaturated polyester (B) is not particularly limited, but is preferably from 350 to 6.0.
00, more preferably 600 to 3,000, even more preferably 800 to 2,000. When the number average molecular weight of the unsaturated polyester (B) is less than 350, the water resistance of the laminated molded article tends to decrease, and when it exceeds 6,000,
The viscosity of the fiber-containing resin composition containing the unsaturated polyester (B) tends to increase, and the handleability tends to decrease.

The acid value of the unsaturated polyester (B) is not particularly limited. The thickness of the fiber-reinforced plastic layer is not particularly limited as long as the laminated molded product has a thickness sufficient to have a desired strength, and is not particularly limited.
１００100 mm, more preferably 2-50 mm.
If it is less than 0.5 mm, the strength of the laminated molded article tends to be insufficient.

For the formation of the gel coat layer, a gel coat resin composition containing an unsaturated polyester resin for gel coat containing an unsaturated polyester (A) and a polymerizable monomer as an essential component is used. For the formation, a fiber-containing resin composition containing, as an essential component, an unsaturated polyester resin for a fiber-reinforced plastic containing an unsaturated polyester (B) and a polymerizable monomer is used.

The polymerizable monomer is not particularly restricted but includes, for example, styrene, α-methylstyrene,
Divinylbenzene, vinyltoluene, paramethylstyrene, t-butylstyrene, diallylphthalate, methyl (meth) acrylate, butyl (meth) acrylate,
Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methoxydiethylene glycol (Meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like. These polymerizable monomers may be used alone or in combination of two or more. Of these polymerizable monomers, styrene is preferred because it is relatively inexpensive and easy to obtain and has excellent copolymerizability with unsaturated polyester.

The amount of the polymerizable monomer is not particularly limited, but is, for example, preferably 25 to 400 parts by weight, more preferably 40 to 250 parts by weight, and still more preferably 100 parts by weight of the unsaturated polyester. 55 to 150 parts by weight. If the amount of the polymerizable monomer is less than 25 parts by weight, the viscosity of the composition tends to be high, and the handleability tends to decrease. If it exceeds 400 parts by weight, the curability of the composition tends to decrease. is there.

It is preferable that the gel coat resin composition and the fiber-containing resin composition further contain a thixotropy-imparting agent, a polymerization inhibitor, a curing accelerator and the like. They are,
One type may be used alone, or two or more types may be used in combination. The thixotropic agent is not particularly limited, but includes, for example, colloidal silica, fused silica, silica airgel, organically modified clay, clay, silica powder, cellulose acetate, Aerosil (trade name of Nippon Aerosil Co., Ltd.), Thixogel (trade name of Yokohama Kasei Co., Ltd.), Dispalon (trade name of Kusumoto Kasei Co., Ltd.), Leolo Seal (Tokuyama Soda Co., Ltd.)
Trade name).

The amount of the thixotropy imparting agent is not particularly limited, but is preferably, for example, 0.25 to 5 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the unsaturated polyester resin. It is. If the compounding amount of the thixotropy imparting agent is less than 0.25 parts by weight, the thixotropy is not sufficient,
When the composition is applied to a mold surface having a vertical surface, sagging tends to occur, and when it exceeds 5 parts by weight, the viscosity of the composition tends to be high and handleability tends to decrease.

The polymerization inhibitor is not particularly restricted but includes, for example, hydroquinone, methylhydroquinone, pt-butylcatechol, t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, methoxyhydroquinone, trimethylhydroquinone, , 5-di-t-butylhydroquinone, phenothiazine, copper naphthenate and the like.

The amount of the polymerization inhibitor is not particularly limited. The curing accelerator is not particularly limited, but includes, for example, cobalt naphthenate, cobalt octenoate, divalent acetylacetonate cobalt, trivalent acetylacetone cobalt, potassium octenoate, zirconium naphthenate, zirconium acetyl acetate, vanadium naphthenate, Organic metal salts such as vanadium octenoate, vanadium acetate and lithium acetylacetonate; amine compounds such as dimethylaniline; phosphorus-containing compounds such as triphenylphosphine; methyl acetoacetate, ethyl acetoacetate, acetylacetone, N-morpholinoacetoa Β-diketone compounds such as cetamide and the like.

The amount of the curing accelerator is not particularly limited. If necessary, the gel coat resin composition may further contain a pigment for coloring. Examples of the pigment include, but are not particularly limited to, for example, titanium white, titanium yellow, cadmium yellow, molybdenum orange, cadmium orange, cadmium sulfoselenide orange, bengala, cadmium red, condensed azo red, quinacridone red, cobalt violet, and quinacridone violet. , Phthalocyanine green, chrome oxide green, ultramarine, cobalt blue,
Examples include phthalocyanine blue, ultramarine, carbon black, iron black, ultramarine green, isoindolinone, aluminum powder, and bronze powder.

Although the amount of the pigment is not particularly limited,
For example, unsaturated polyester resin 100 for gel coating
The amount is preferably 1 to 40 parts by weight, more preferably 5 to 30 parts by weight based on parts by weight. The gel coat resin composition and the fiber-containing resin composition are usually used by blending at least one curing agent for curing.

The curing agent is not particularly limited, but
For example, diisopropyl peroxydicarbonate,
Benzoyl peroxide, lauroyl peroxide, acetyl peroxide, di-t-butyl peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, t-butyl peroxy-2-ethylhexanoate, 1,1,3,3-tetra Methyl butyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethyl hexanoate, t-butyl hydroperoxide, t-butyl peroxy neodikenate, t-butyl peroxy benzoate, cumene hydro Organic peroxides such as peroxides; and azo compounds such as azobis (iso) butyronitrile and azobisdiethylvaleronitrile.

The amount of the curing agent is not particularly limited.
Gel coat resin composition and fiber-containing resin composition,
If necessary, at least one additional material (additive)
Etc. may be blended. The auxiliary materials (additives) are not particularly limited, but include, for example, dyes, extenders, ultraviolet absorbers, antioxidants, plasticizers, leveling agents, defoamers, silane coupling agents, antistatic agents, Examples include fuel agents, lubricants, viscosity reducing agents, low-shrinkage agents, inorganic fillers, organic fillers, drying agents such as wax, and dispersants. The amounts of these components are not particularly limited.

As the material of the reinforcing fibers used in the fiber-containing resin composition, those used in conventionally known fiber-reinforced plastics can be used, and there is no particular limitation. For example, inorganic fibers such as glass fibers and carbon fibers can be used. Organic fibers such as vinylon, phenol, nylon, Teflon, aramid, and polyester. The shape is not particularly limited, for example, mats such as cloth and chop strand mat, preformable mat, continuous strand mat, surfacing mat,
Chop shape, roving shape and the like can be mentioned.

The proportion of the reinforcing fibers is preferably from 10 to 50% by weight, more preferably from 15 to 40% by weight, based on the total weight of the fiber-containing resin composition. The fiber-containing resin composition is obtained, for example, by impregnating an unsaturated polyester resin containing an unsaturated polyester (B) and a polymerizable monomer into a reinforcing fiber such as a mat or a reinforcing fiber such as a chop. The mixture can be obtained by mixing fibers for use with the unsaturated polyester resin.

It should be noted that the laminated molded article is not limited to only the two layers of the gel coat layer and the fiber reinforced plastic layer. For example, one or more other layers may be laminated as a backup material for the fiber reinforced plastic layer. The method for producing a laminated molded product is not particularly limited, but is performed, for example, as follows.

First, the gel coat resin composition is applied to the surface of a molding die by a known method such as spray gun coating or brush coating, and cured to form a gel coat layer on the die surface. Next, on the formed gel coat layer,
Hand lay-up molding, spray-up molding, resin injection molding, pressure pack molding, by known methods such as vacuum pack molding, laminating the fiber-containing resin composition,
By curing, a fiber reinforced plastic layer is formed on the gel coat layer. In this case, if necessary, one or more other layers may be laminated on the fiber reinforced plastic layer.

Thereafter, a laminate containing at least the gel coat layer and the fiber reinforced plastic layer is released from the mold to obtain a laminate molded product. As a molding die used for producing a laminated molded product, a mold used for producing a conventionally known laminated molded product can be used, and is not particularly limited. Examples thereof include a steel mold, an FRP mold, a thermal spray mold, and an electroforming mold. No.

In the production of the laminated molded product, a release agent may be used, if necessary. The release agent may be applied to the mold surface in advance, or may be included in the gel coat resin composition. As the release agent, those used in the production of conventionally known laminated molded products can be used, and there is no particular limitation.

The laminated molded article of the present invention can be used, for example, in a bathtub,
Waterproof pan, unit bath, kitchen counter, wash basin,
Ships, boats, septic tanks, tanks, linings, pools,
It can be used for various applications such as vehicles, vehicle parts, housings, containers and the like.

[0054]

The present invention will be described in detail below with reference to examples and comparative examples. In the following examples, “parts” means “parts by weight” and “%” means “% by weight” unless otherwise specified. In addition, this invention is not limited to a following example. (Production of unsaturated polyester resin for gel coating)
The production example of the unsaturated polyester resin used for the gel coat is shown below. <Resin Production Example A1> 728 parts of neopentyl glycol and ethylene glycol 211 were placed in a four-necked flask equipped with a thermometer, a stirrer, an inert gas injection pipe, and a reflux condenser.
And 616 parts of hexahydrophthalic anhydride, and reacted at 210 ° C. until the acid value reached 10 while blowing nitrogen gas. Cool to 100 ° C and add maleic anhydride 58
8 parts were charged, heated to 210 ° C., and reacted for 10 hours to obtain an unsaturated polyester (A1) having an acid value of 7.8 and a number average molecular weight of 3,960.

By adding 1309 parts of styrene and 0.36 parts of hydroquinone to the unsaturated polyester (A1), an unsaturated polyester resin (A1) having a nonvolatile content of 60% and a viscosity of 500 mPa · s was obtained. <Resin Production Example A2> In a four-necked flask similar to Resin Production Example A1, 728 parts of neopentyl glycol, 211 parts of ethylene glycol, 946 parts of 1,4-cyclohexanedicarboxylic acid, and 441 parts of maleic anhydride were charged. The mixture was heated to 210 ° C. while blowing, and reacted for 13 hours to obtain an acid value of 12, and a number average molecular weight of 5,030.
(A2) was obtained.

By adding 1384 parts of styrene and 0.35 part of hydroquinone to the unsaturated polyester (A2), an unsaturated polyester resin (A2) having a nonvolatile content of 60% and a viscosity of 920 mPa · s was obtained. <Comparative resin production example a1> In a four-necked flask similar to resin production example A1, 938 parts of dipropylene glycol, 211 parts of ethylene glycol and 664 parts of isophthalic acid were charged, and the acid value was 10 at 210 ° C while blowing nitrogen gas. The reaction was continued until The mixture was cooled to 100 ° C., charged with 588 parts of maleic anhydride, heated to 210 ° C., and reacted for 13 hours to obtain an acid value of 8.0 and a number average molecular weight of 3,
820 of Comparative Unsaturated Polyester (a1) was obtained.

This unsaturated polyester for comparison (a1)
To this were added 1433 parts of styrene and 0.36 part of hydroquinone to obtain a nonvolatile content of 60% and a viscosity of 480 mPa.
* Comparative unsaturated polyester resin (a1) of s was obtained. (Preparation of gel coat resin composition) Next, using the unsaturated polyester resin obtained above, a gel coat resin composition was prepared according to the following preparation examples. <Composition Preparation Example A1> 100 parts of the unsaturated polyester resin (A1) obtained in Resin Production Example A1, Aerosil # 20
0 (manufactured by Nippon Aerosil Co., Ltd.), 25 parts of titanium white (CR-90, manufactured by Ishihara Sangyo Co., Ltd.), 0.5 part of cobalt naphthenate (Co concentration 6%) and styrene 15
Part is kneaded with three rolls to obtain a viscosity of 2.6 Pa.
A gel coat resin composition (A1) having a s and degree of thixotropicity of 5.7 was obtained. <Composition preparation example A2> In the composition preparation example A1, a resin production example A2 was used instead of the unsaturated polyester resin (A1).
In the same manner as in Composition Preparation Example A1, except that the same amount of the unsaturated polyester resin (A2) obtained in the above was used and the amount of Aerosil # 200 was changed to 2 parts, the viscosity was 3.
Gel coat resin composition (A)
2) was obtained. <Comparative composition preparation example a1> In composition preparation example A1,
Instead of the unsaturated polyester resin (A1), the comparative unsaturated polyester resin (a) obtained in Comparative Resin Production Example a1 was used.
A gel coat resin composition (a1) for comparison having a viscosity of 2.4 Pa · s and a degree of thixotropicity of 4.8 was obtained in the same manner as in Composition Preparation Example A1, except that 1) was used in the same amount. (Production of unsaturated polyester resin for fiber reinforced plastic) Next, unsaturated polyester resin used for fiber reinforced plastic was produced according to the following production example. <Resin Production Example B1> In a four-necked flask similar to Resin Production Example A1, 784 parts of maleic anhydride, 1,112 parts of dicyclopentadiene (purity: 95%), and 144 deionized water were placed.
Then, an addition reaction was performed at 130 ° C. for 3 hours while blowing nitrogen gas to obtain a maleic acid adduct of dicyclopentadiene. To this, 337 parts of phthalic anhydride, 304 parts of propylene glycol and 416 parts of neopentyl glycol were added and mixed, and the mixture was heated to 200 ° C. while blowing nitrogen gas and reacted for 8 hours to obtain an acid value of 28 and a number average molecular weight. An unsaturated polyester (B1) having a molecular weight of 2,891 and a dicyclopentenyl group content of 37% was obtained. The ratio between the acid component and dicyclopentadiene in synthesizing the unsaturated polyester was 1: 0.7 in molar ratio.

To the obtained unsaturated polyester (B1),
By adding 1,069 parts of styrene and 0.4 parts of hydroquinone, the non-volatile content is 63% and the viscosity is 516 mPa · s.
(B1) was obtained. <Resin Production Example B2> In a four-necked flask similar to Resin Production Example A1, 686 parts of maleic anhydride, 278 parts of dicyclopentadiene (95% purity), 496 parts of isophthalic acid, and 798 parts of propylene glycol were charged, and nitrogen gas was added. After stirring at 140 ° C. for 7.5 hours while blowing water, the mixture was further heated to 215 ° C. and reacted for 8 hours to obtain an acid value of 20, a number average molecular weight of 2,060 and a dicyclopentenyl group content of 13%. A saturated polyester (B2) was obtained. The ratio between the acid component and the dicyclopentadiene in synthesizing the unsaturated polyester is 1: 1:
0.2.

To the obtained unsaturated polyester (B2),
By adding 1258 parts of styrene and 0.32 parts of hydroquinone, the non-volatile content is 62% and the viscosity is 480 mPa · s.
(B2) was obtained. <Resin Production Example B3> A four-necked flask similar to Resin Production Example A1 was charged with 196 parts of maleic anhydride, 278 parts of dicyclopentadiene (95% purity) and 36 parts of deionized water, and charged with 130 g of nitrogen gas. By carrying out the addition reaction at 3 ° C. for 3 hours, a maleic acid adduct of dicyclopentadiene was obtained. In addition, phthalic anhydride 296
, 125 parts of propylene glycol and 172 parts of neopentyl glycol were added and mixed, and the mixture was heated to 200 ° C. while blowing nitrogen gas and reacted for 8 hours to obtain an acid value of 25, a number average molecular weight of 1,230, Unsaturated polyester having a pentenyl group content of 26% (B3)
I got The ratio between the acid component and the dicyclopentadiene in synthesizing the unsaturated polyester is 1: 1:
0.5.

To the obtained unsaturated polyester (B3),
By adding 442 parts of styrene and 0.31 part of hydroquinone, an unsaturated polyester resin (B3) having a nonvolatile content of 70% and a viscosity of 540 mPa · s was obtained. <Comparative resin production example b1> In a four-necked flask similar to resin production example A1, 392 parts of maleic anhydride and phthalic anhydride 8 were added.
88 parts, 228 parts of propylene glycol and 453 parts of ethylene glycol were charged, the temperature was raised to 210 ° C. while blowing nitrogen gas, and the reaction was carried out for 8 hours.
An unsaturated polyester for comparison (b1) having an acid value of 12, a number average molecular weight of 1,910, and a dicyclopentenyl group content of 0% was obtained.

This unsaturated polyester for comparison (b1)
Of styrene and 0.30 part of hydroquinone were added to obtain a non-volatile content of 60% and a viscosity of 540 mPa.
-The comparative unsaturated polyester resin (b1) of s was obtained. (Preparation of resin composition for forming fiber-reinforced plastic layer) Next, using the unsaturated polyester resin for fiber-reinforced plastic obtained above, a resin composition for forming a fiber-reinforced plastic layer was prepared according to the following preparation examples. <Composition Preparation Examples B1 to B3 and Comparative Composition Preparation Example b1
> To 100 parts of each unsaturated polyester resin obtained in Resin Production Examples B1 to B3 and Comparative Resin Production Example b1, 0.7 parts of Aerosil # 200 (manufactured by Nippon Aerosil Co., Ltd.) was added,
After sufficiently stirring with a homomixer, 0.3 parts of cobalt octenoate and 10 parts of styrene are additionally added and mixed well, whereby resin compositions (B1) to (B3) for forming a fiber-reinforced plastic layer and a fiber for comparison Thus, a resin composition (b1) for forming a reinforced plastic layer was obtained. (Production of laminated molded article and performance evaluation) Using the gel coat resin composition and the resin composition for forming a fiber-reinforced plastic layer obtained above, according to the following Examples and Comparative Examples,
Laminated articles were manufactured and their performance was evaluated. <Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4>
20cm long, 20cm wide, 2mm thick with release agent applied
A gel coat resin composition to which 1% of a curing agent (Kayamec BUY, manufactured by Kayaku Akzo Co., Ltd.) is added is applied to a glass plate having a thickness of 0.10 mm, 0.20 mm, and 0.30 mm with an applicator. Then, the mixture was cured at 25 ° C. for 8 hours to form a gel coat layer.

Next, a curing agent (Kayamec M-55Y,
A resin composition for forming a fiber-reinforced plastic layer to which 1% of Kayaku Akzo Co., Ltd.) is added is impregnated into three chop strand mats (CM-455FA, manufactured by Asahi Fiber Co., Ltd.) having a size of 20 cm × 20 cm. Fiber-containing resin composition (chop strand mat: resin composition for forming a fiber-reinforced plastic layer containing a curing agent (weight ratio) = 3)
0:70) on the gel coat layer,
After curing for 5 hours to form a fiber reinforced plastic layer having a thickness of 3 mm, the laminate was demolded to obtain a laminate molded product.

The degree of lifting of the obtained laminated molded product was visually observed and evaluated according to the following criteria. Lifting evaluation criteria: ○… No lifting. Δ: Lifting slightly occurred.

×: Lifting occurred. <Examples 2-1 to 2-6 and Comparative examples 2-1 to 2-4>
20cm long, 20cm wide, 2mm thick with release agent applied
A gel coat resin composition to which 1% of a curing agent (Kayamec BUY, manufactured by Kayaku Akzo Co., Ltd.) is added is applied to a glass plate having a thickness of 0.25 mm using an applicator.
The coating was cured at 25 ° C. for 24 hours to form a gel coat layer.

Next, a curing agent (Kayamec M-55Y,
A resin composition for forming a fiber-reinforced plastic layer to which 1% of Kayaku Akzo Co., Ltd.) is added is impregnated into three chop strand mats (CM-455FA, manufactured by Asahi Fiber Co., Ltd.) having a size of 20 cm × 20 cm. Fiber-containing resin composition (chop strand mat: resin composition for forming a fiber-reinforced plastic layer containing a curing agent (weight ratio) = 3)
0:70) on the gel coat layer,
After curing for 4 hours to form a fiber reinforced plastic layer having a thickness of 3 mm, the laminate was removed from the mold to obtain a laminate molded product.

The obtained laminated molded product was subjected to a weather resistance test by the following method. 50mm x 50 from laminated molded product
mm test piece was cut out and sunshine weatherometer (WEL-SUN-HC-B type, Suga Test Instruments Co., Ltd.)
Was used for the acceleration test. The test pieces were taken out at predetermined time intervals, and the color difference (ΔE) was measured as a value of discoloration from the initial value using a color difference meter (# 90, manufactured by Nippon Denshoku Industries Co., Ltd.), and the gloss was measured with a gloss meter (measuring angle 60 °). ) To determine the gloss retention from the beginning.

Tables 1 to 4 show the results.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

[Table 4]

[0072]

Industrial Applicability The laminated molded article of the present invention is an excellent laminated molded article which is excellent in weather resistance and water resistance and hardly causes defects such as lifting on the surface of the gel coat layer during production.

Claims (4)

[Claims] 1. A laminated molded article comprising a fiber reinforced plastic layer and a gel coat layer formed on the surface thereof, wherein the gel coat layer comprises an unsaturated dibasic acid and / or an anhydride thereof and an alicyclic saturated dibasic acid. An unsaturated polyester resin for gel coating containing an unsaturated polyester (A) obtained by condensation reaction of an acid component essentially comprising a basic acid and / or an anhydride thereof and a polyhydric alcohol and a polymerizable monomer is used. The fiber-reinforced plastic layer comprises a cured product of a gel coat resin composition containing as an essential component, and the fiber-reinforced plastic layer comprises an unsaturated polyester (B) having a dicyclopentenyl group and a polymerizable monomer. A laminated molded article comprising a cured product of a fiber-containing resin composition containing a polyester resin as an essential component. 2. The polyhydric alcohol is a glycol having a main chain consisting only of carbon atoms and two or more side chains, and the glycol which may be bonded to the side chains is essential. Item 2. The laminated molded article according to Item 1. 3. The laminated molded article according to claim 1, wherein the unsaturated polyester (B) has a dicyclopentenyl group content of 20% by weight or more. 4. The unsaturated polyester (B) may contain dicyclopentadiene in an amount of 0.1 to 1.0 based on 1 mol of the acid component.
The laminated molded product according to any one of claims 1 to 3, which is synthesized using a molar ratio.