JP2002256038A - Pultruded resin composition and pultruded product - Google Patents

Abstract

(57) [Abstract] [Problem] A pultrudable molding resin composition comprising a radical copolymerizable unsaturated resin, which has both excellent storage stability and low shrinkage during curing of a prepreg. And to provide a pultruded product with little dimensional change using the same. SOLUTION: The radical copolymerizable unsaturated resin composition comprising a radical copolymerizable unsaturated resin composition, a polymer-based low-shrinking agent, and a compatibilizer as essential components, wherein the compatibilizer is:
A styrene monomer as a main component as a chain (C1);
A chain (C) having a skeleton obtained by a polymerization reaction and comprising a polyether, polyester and / or polycarbonate composed of polyoxyalkylene ether as a main component;
A pultrusion resin composition comprising a radical copolymerizable unsaturated resin composition as an essential component, which is the graft copolymer according to 2), and a pultruded article obtained by impregnating the resin composition with a fiber reinforcement.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for pultrusion molding and a pultruded product using the same.

[0002]

2. Description of the Related Art In a pultrusion method or a pultrusion method in which a resin is impregnated into a fibrous reinforcing material and molded, a radical copolymerizable resin such as an unsaturated polyester resin composition or a vinyl ester resin composition is used as a resin component. An unsaturated resin composition has been used.

[0003] However, these radical copolymerizable unsaturated resin compositions are compositions comprising a radical copolymerizable unsaturated resin and a radical copolymerizable monomer as main components. Because it has the property of shrinking,
In particular, due to the difference in the amount of contraction between the longitudinal direction and the direction perpendicular to the molded product, the vertical and horizontal dimensions do not match, and after curing, the molded product is warped, deformed, and in some cases, cracked.

[0004] Therefore, in order to solve the above-mentioned problems, a measure has been taken to further add a thermoplastic resin such as polystyrene as a low shrinkage agent to the radical copolymerizable unsaturated resin composition.

However, these low-shrinkage agents have poor compatibility with the radically copolymerizable unsaturated resin composition, and it is difficult to make the resin composition one-pack. For this reason, the storage stability of the resin composition for pultrusion molding is poor, the impregnation of the resin composition for pultrusion into a fiber reinforcement is difficult, or a fibrous reinforcing material impregnated with resin (hereinafter referred to as prepreg). ) Was separated, and the impregnation and curing were non-uniform.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a pultruding resin composition comprising a radical copolymerizable unsaturated resin, which has both excellent storage stability and low shrinkage during curing of a prepreg. A pultrusion molding composition and a pultruded article using the same with little dimensional change.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, as a resin composition for pultrusion molding, a radical copolymerizable unsaturated resin and a thermoplastic resin have been used. The inventors have found that the above-mentioned problems can be solved by blending a specific compatibilizing agent with the low-shrinkage agent, thereby completing the invention.

That is, the present invention provides a radical copolymerizable unsaturated resin composition (A), a polymeric low-shrinkage agent (B), and the unsaturated resin (A) and the low-shrinkage agent (B). A radical copolymerizable unsaturated resin composition containing a compatibilizer (C) for compatibilization as an essential component, wherein the compatibilizer (C) comprises:
A styrene monomer as a main component as a chain (C1);
A chain (C) having a skeleton obtained by a polymerization reaction and comprising a polyether, polyester and / or polycarbonate composed of polyoxyalkylene ether as a main component;
A pultruding resin composition comprising a radical copolymerizable unsaturated resin composition as an essential component, which is a graft copolymer according to 2), and a pultruded product obtained by impregnating the resin composition with a fiber reinforcing material. provide.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The resin composition for pultrusion molding of the present invention will be described.

The radical copolymerizable unsaturated resin composition (A) used in the present invention comprises a radical copolymerizable unsaturated resin (A1) and a polymerizable unsaturated monomer (A2). . If necessary, a polymerization inhibitor, a curing agent, a filler, a reinforcing agent, an internal release agent, a colorant, and other additives can be added. Radical copolymerizable unsaturated resin (A
Examples of 1) include an unsaturated polyester resin, a vinyl ester resin, a vinyl urethane resin, and an acrylic resin.

First, the unsaturated polyester resin used as the radical copolymerizable unsaturated resin (A1) in the present invention will be described.

The composition of the unsaturated polyester used in the present invention is not particularly limited, and may be an α, β-unsaturated carboxylic acid or an α, β-containing unsaturated carboxylic acid.
It is obtained from a β-unsaturated carboxylic acid and a polyhydric alcohol.

Examples of the α, β-unsaturated carboxylic acid include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, chloromaleic acid, and dimethyl esters thereof. . These α, β-unsaturated carboxylic acids may be used alone or in combination of two or more. Further, as the saturated carboxylic acid, for example, phthalic acid,
Examples thereof include phthalic anhydride, isophthalic acid, terephthalic acid, hexic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, adipic acid, sebacic acid, and azelaic acid. These saturated carboxylic acids may be used alone or in combination of two or more.

On the other hand, polyhydric alcohols include, for example,
Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,
6-hexanediol, cyclohexanediol, neopentyl glycol, 2,2,4-trimethyl-1,3
-Diols such as glycols such as pentanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, alkylene oxide adducts of hydrogenated bisphenol A, alkylene oxide adducts of bisphenol A, and triols such as trimethylolpropane And tetraols such as pentaerythritol. These polyhydric alcohols may be used alone or in combination of two or more.

Further, the obtained unsaturated polyester is treated with epoxy compounds such as glycidyl methacrylate and bisphenol A type epoxy, toluene diisocyanate,
It may be modified with isocyanate compounds such as isopropenyl-dimethyl-benzyl isocyanate.

Further, a dicyclopentadiene unsaturated polyester obtained by adding dicyclopentadiene and reacting with the above α, β-unsaturated carboxylic acid, saturated carboxylic acid and polyhydric alcohol can also be used.

Further, a glycol decomposition product obtained by reacting recovered polyethylene terephthalate (PET) with a polyhydric alcohol at a high temperature is used as a main raw material, and is reacted with the above α, β-unsaturated carboxylic acid, saturated carboxylic acid and polyhydric alcohol. The resulting PET-based unsaturated polyester can also be used without problems if the present invention is applied.

Next, the vinyl ester resin used as the radical copolymerizable unsaturated resin (A1) in the present invention will be described. The vinyl ester resin is a reaction product obtained by reacting an epoxy resin with an unsaturated monobasic acid.

Examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin. Glycidyl ethers of phenols such as brominated epoxy resins of these resins, dipropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl ether of alkylene oxide adduct of bisphenol A, hydrogenated bisphenol A
Glycidyl ethers of polyhydric alcohols such as diglycidyl ether of 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4
Alicyclic epoxy resins such as epoxycyclohexane,
Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl-p-oxybenzoic acid, glycidyl dimer, tetraglycidyl diaminodiphenylmethane, tetraglycidyl-m-xylene diamine, triglycidyl-p-amino Examples include phenol, glycidylamines such as N, N-diglycidylaniline, and heterocyclic epoxy resins such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate. These epoxy resins may be used alone or in combination of two or more.

Examples of unsaturated monobasic acids include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethyl malate, monomethyl fumarate,
Monocyclohexyl fumarate, sorbic acid and the like can be mentioned. These acids may be used alone or in combination of two or more.

Further, the obtained vinyl ester may be modified with acid anhydrides such as maleic anhydride and succinic anhydride, and isocyanate compounds such as toluene diisocyanate and isopropenyl-dimethyl-benzyl isocyanate.

Next, the vinyl urethane resin used as the radical copolymerizable unsaturated resin (A1) in the present invention will be described. The vinyl urethane resin is an oligomer obtained from a polyol compound, an organic polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate. The polyol compound is a general term for a compound having a plurality of hydroxyl groups in the molecule, but a functional group having an active hydrogen capable of reacting with an isocyanate group instead of a hydroxyl group, for example, a compound having a carboxyl group, an amino group, or a mercapto group. I do not care. Such polyol compounds include, for example, polyester polyols, polyether polyols, acrylic polyols, polycarbonate polyols, polyolefin polyols, castor oil polyols,
Caprolactone-based polyols and the like can be mentioned, and each can be used alone or in combination of two or more. As the organic polyisocyanate compound, those described below can be used.

As typical examples of the organic polyisocyanate compound, only typical ones can be mentioned, for example, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthalene. Diisocyanate, 1,4-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, or
Multimers obtained by isocyanurating various isocyanate compounds are exemplified. These may be used alone or in combination of two or more.

Next, the acrylic resin used as the radical copolymerizable unsaturated resin (A1) in the present invention will be described. The acrylic resin is composed of a thermoplastic acrylic polymer derived from a polymerizable unsaturated monomer having (meth) acrylate and (meth) acrylate as main components, and a polymerizable unsaturated monomer. Things.
It is obtained by polymerizing the monomer solution by using (meth) acrylic acid ester as an essential component and optionally using another polymerizable unsaturated monomer copolymerizable with the above (meth) acrylic acid ester. Things. Because this acrylic polymer is used in the form of a syrup dissolved in the polymerizable monomer,
Those having a molecular weight of 100,000 or less are preferable and can be obtained by a general polymerization method such as suspension polymerization and solution polymerization. A syrup obtained by prepolymerizing 10 to 40% by weight of the monomer can be used as it is.

The polymerizable unsaturated monomer (A) which can be used in the radical copolymerizable unsaturated resin composition (A) used in the present invention.
If only typical examples are exemplified as 2), styrenes, acrylic esters, methacryl esters,
Known materials such as diallyl phthalate esters, vinyl carboxylate, and vinyl ethers can be used. However, the present invention is not limited thereto, and various unsaturated monomers can be appropriately selected and used according to the use of the resin liquid and required performance.

The polymerizable unsaturated monomer (A1) for the radical copolymerizable unsaturated resin (A1) such as the unsaturated polyester resin, vinyl ester resin, vinyl urethane resin or acrylic resin in the composition (A) used in the present invention. The blending amount of A2) is not particularly limited, but the radical copolymerizable unsaturated resin (A1) and the polymerizable unsaturated monomer (A2)
Of the polymerizable unsaturated monomer (A
2) is preferably in the range of 10 to 70 parts by weight,
More preferably, it is within the range of 50 parts by weight.

The polymerization inhibitor that can be used in the resin composition of the present invention is not particularly limited, and a conventionally known polymerization inhibitor can be used. Specific examples include hydroquinone, trimethylhydroquinone, pt-butylcatechol, t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate, copper chloride and the like. One of these polymerization inhibitors may be used alone, or two or more of them may be used by mixing at appropriate times. The amount of the polymerization inhibitor is not particularly limited.

The curing agent that can be used in the resin composition of the present invention is not particularly limited, and a conventionally known curing agent can be used. For example, one or more types selected from a thermal curing agent, an ultraviolet curing agent, an electron beam curing agent, and the like are included. The amount of the curing agent to be used is preferably 0.1 to 10 parts by weight, particularly preferably 1 to 5 parts by weight, based on 100 parts by weight of the resin composition.

Examples of the thermosetting agent include organic peroxides. Specific examples include diacyl peroxide-based, peroxyester-based, hydroperoxide-based, ketone peroxide-based, alkyl perester-based, and percarbonate-based compounds. And the like can be used, and can be appropriately selected according to molding conditions.

The ultraviolet curing agent is a photosensitizer. Specifically, known compounds such as acylphosphine oxide-based, penzoin ether-based, penzophenone-based, acetophenone-based, and thioxanthone-based compounds can be used, and can be appropriately selected according to molding conditions. Examples of the electron beam curing agent include halogenated alkylbenzenes and disulfide compounds.

The additives (curing accelerators) which are used in combination with the above-mentioned curing agents to accelerate the curing are not particularly limited. For example, metal salts such as cobalt naphthenate and cobalt octenoate; N, N-dimethylaniline,
Tertiary amines such as N, N-di (hydroxyethyl) paratoluidine, dimethylacetoacetamide and the like can be mentioned, and they can be selectively used if necessary.

The polymeric low-shrinkage agent (B) used in the present invention is not particularly limited, but those which exhibit the desired effect of reducing shrinkage and improving physical properties (fracture toughness) can be used for molding. Can be appropriately selected and used according to conditions and the like. In particular, if only typical ones are exemplified, a polystyrene-based resin containing styrene as a main component, for example, polystyrene, a copolymer of styrene and (meth) acrylate, a styrene-conjugated diene block copolymer styrene-hydrogenated Conjugated diene block copolymers and the like can be mentioned. In addition, styrene-free (meth) acrylate polymers such as polymethyl methacrylate and poly (n-butyl acrylate) can be used. Further, those obtained by reacting a double bond in these polymers with another compound can also be used.

The above-mentioned styrene-conjugated diene-based block copolymer is a block copolymer comprising a styrene component and a conjugated diene component obtained by polymerizing styrene and a conjugated diene. Butadiene, isoprene, 1,3-pentadiene or the like is used. Further, a styrene-hydrogenated conjugated diene block copolymer obtained by hydrogenating the styrene-conjugated diene block copolymer may be used. The structural unit of the block copolymer is not particularly limited, and includes a repeating unit of styrene and conjugated diene such as styrene-conjugated diene, styrene-conjugated diene-styrene, and conjugated diene-styrene-conjugated diene. Specific examples include a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, a styrene-ethylene / butylene block copolymer, and a styrene-ethylene / propylene block copolymer.

The above-mentioned polymer-based low-shrinkage agent (B) may contain a polymerizable unsaturated monomer, if necessary. Examples of the polymerizable unsaturated monomer that can be used in combination here include the above-mentioned polymerizable unsaturated monomer (A2). The blending amount of the polymer-based low-shrinkage agent (B) and the polymerizable unsaturated monomer is not particularly limited, but the polymer-based low-shrinkage agent (B) and the polymerizable unsaturated monomer are not limited. The amount of the polymerizable unsaturated monomer (A2) is preferably from 10 to 70 parts by weight, more preferably from 20 to 50 parts by weight, based on 100 parts by weight of the total.

Radical copolymerizable unsaturated resin composition (A)
The blending amount of the polymer and the polymer-based low-shrinkage agent (B) is not particularly limited, but the total amount of the radical copolymerizable unsaturated resin composition (A) and the polymer-based low-shrinkage agent (B) is 100. The polymer-based low-shrinkage agent (B) is used in parts by weight (per solid),
The range is preferably 2 to 22 parts by weight (per solid), and more preferably 3 to 13 parts by weight.

Next, the compatibilizer (C) used in the present invention is a polyether comprising a chain (C1) styrene monomer as a main component, having a skeleton obtained by a polymerization reaction, and comprising a polyoxyalkylene ether. It is a resin composition containing, as a main component, a graft copolymer having a chain (C2) containing polyester and / or polycarbonate as a main component, and appropriately dissolved in a polymerizable unsaturated monomer.

As the graft copolymer, a monomer having a polymerizable functional group such as a (meth) acryloyl group at a terminal of a polyether containing ethylene oxide as a main component as an unsaturated monomer (hereinafter referred to as polyether) -Based macromonomer) and styrene-based monomers, (meth)
Copolymers with unsaturated monomers selected from the group of acrylic acid ester monomers are also included.

As the monomer component that can be used to form the above-mentioned chain (C1), only a styrene-based monomer or a styrene-based monomer as a main component, and a (meth) acrylic acid-based monomer or the like as another component is used in combination. It is a mixture consisting of Examples of typical styrene monomers include styrene, vinyltoluene (methylstyrene), p-methylstyrene, t-butylstyrene,
Chlorstyrene, vinylbenzyl alkyl ether and the like can be mentioned. It is desirable that the styrene-based monomer is the main component of the chain (C1) because of excellent compatibility stability.

Representative examples of the (meth) acrylic acid-based monomer that can be used in combination include known (meth) acrylic acid,
Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, glyceryl carbonate (meth) acrylate, isocyanatoethyl methacrylate, (meth) acrylic acid Esters are available. If only typical examples of (meth) acrylic acid esters are shown, methyl, ethyl,
Examples include ester compounds such as propyl, butyl, cyclohexyl, t-butylcyclohexyl, benzyl, phenyl, isobornyl, dicyclopentanyl, stearyl, behenyl, and trifluoroethyl, and are added as necessary.

Chain (C2) in compatibilizer (C) of the present invention
Is one or more chains selected from polyether, polyester, and polycarbonate, and has a number average molecular weight of preferably from 1,000 to 20,000, more preferably from 2,000 to 10,000, and the synthesis method, structure, and the like are particularly limited. Not something. Polyether is preferred as such a chain. The polyether is described later. Examples of the polyester include α, β-unsaturated carboxylic acids, and saturated and / or unsaturated polyesters obtained from saturated carboxylic acids and polyhydric alcohols, and polycaprolactones obtained by ring-opening polymerization of caprolactone and the like. It is. Examples of the polycarbonate include a polycarbonate obtained by reacting a polyhydric alcohol described below with a carbonate compound such as dimethyl carbonate, and a polycarbonate obtained by ring-opening polymerization of a cyclic carbonate compound such as trimethylene carbonate. These can be used alone or in combination of two or more.

Ring-opening polymerizable monomers can be used as a component that can be used to constitute the polyether chain of the chain (C2). Ethylene oxide is used as a component, and ethylene oxide alone or copolymerized with ethylene oxide. It consists of other possible alkylene oxides and other ring-opening copolymerizable cyclic compounds. Other alkylene oxides, propylene oxide, butylene oxide,
Cyclohexene oxide, tetrahydrofuran,
Styrene oxide and the like can be mentioned. Oxyethylene-
A polyether having a unit as a main component is preferable.

Next, the components that can be used to form the ethylene oxide-based polyether chain of the chain (C2) are selected from the group of ring-opening polymerizable monomers. It is composed of other alkylene oxide monomers which can be copolymerized with ethylene oxide alone or other cyclic compounds which can be ring-opened and copolymerized. Examples of other alkylene oxide-based monomers include propylene oxide, butylene oxide, cyclohexene oxide, tetrahydrofuran, styrene oxide and the like.

Other cyclic compounds capable of ring-opening copolymerization include acid anhydrides such as succinic anhydride and phthalic anhydride. In addition, cyclic ester compounds, for example, caprolactone, valerolactone and the like can be mentioned. Further, cyclic carbonate compounds, for example, ethylene carbonate, propylene carbonate, trimethylene carbonate and the like can be mentioned. Other than the cyclic compounds, carbon dioxide which can be copolymerized with the alkylene oxide monomer can also be used.

Chain (C2) in compatibilizer (C) of the present invention
It is desirable in terms of performance and synthesis that the number average molecular weight of the ethylene oxide-based polyether chain forming the polymer is 1,000 to 20,000, and the number average molecular weight is 3,000 to 8,000.
Is particularly desirable.

The structure of the polyether chain of the chain (C2) obtained by copolymerizing these ring-opening polymerizable monomers with ethylene oxide as a component is compatible with the radical copolymerizable unsaturated resin. There is no particular limitation as long as it exerts. For example, random copolymerization or block copolymerization with ethylene oxide may be used. The chain (C2) is extended using an ethylene oxide-based polyether polyol compound or a glycol compound having a molecular weight of 1,000 or less and a dicarboxylic acid compound, a diisocyanate compound, a carbonate compound, a diglycidyl ether compound, or the like. Molecular weight 1000-20
000. The polyether-based chain may be linear or branched.
Linear chains are preferred.

The content of oxyethylene units in the chain (C2) is preferably from 20 to 100% by weight, particularly preferably from 60 to 100% by weight. The remaining components are preferably non-oxyethylene-based polyethers, polyesters and / or polycarbonates.
This is because the oxyethylene chain as the main component is closely coordinated with the radical copolymerizable unsaturated resin by an intermolecular force, acts as an anchor component, and becomes a very important component in stable dispersion. Needless to say, components other than the oxyethylene chain are designed, selected, and used so as to enhance a desired compatibilizing effect or to provide an effect other than the compatibilizing.

The method for producing the graft copolymer is not particularly limited, but generally, a chain (C
A method in which only 1) is previously synthesized, and a separately synthesized chain (C2) is bonded by a polymer reaction to obtain the desired (C).
A method of previously synthesizing only (C1), and subjecting the ring-opening polymerizable monomer constituting (C2) to ring-opening polymerization starting from an active site in (C1), an unsaturated monomer constituting (C1) There is a method of obtaining the desired (C) by addition-copolymerizing a polymerizable macromonomer having a polymerizable functional group at one end as a previously synthesized polyether chain (C2). As a method for producing the compatibilizer of the present invention, a synthesis method using a polyether-based macromonomer, which can easily obtain a homogeneous polymer, is desirable.

The polyether-based macromonomer which can be used in the graft copolymer of the present invention includes the above-mentioned chain (C)
The compound having a polymerizable functional group copolymerizable with the unsaturated monomer constituting the chain (C1) at the terminal of 2). The functional group is generally an ethylenically unsaturated group. Specific examples include a (meth) acryloyl group, a styryl group, a vinyl group, a propenyl group, an allyl group, a vinyl ether group, an allyl ether group, a fumaryl group, and a maleyl group. It is particularly preferable that the compound having these functional groups is chemically bonded only to one terminal of the above-mentioned linear polyether chain.

Specifically, mono (meth) acrylates of polyethylene oxide, monovinyl benzyl ethers of polyethylene oxide, monovinyl ethers of polyethylene oxide, monoallyl ethers of polyethylene oxide, monocrotonate of polyethylene oxide , An equimolar reaction product of isocyanate ethyl methacrylate and polyethylene oxide, a compound obtained by bonding a hydroxyl group-containing unsaturated monomer such as hydroxyethyl (meth) acrylate to polyethylene oxide via a diisocyanate compound such as isophorone diisocyanate Etc. can also be used. In addition, mono- (meth) acrylic acid esters of polycaprolactone and the like as polyester-based macromers, and mono- (meth) acrylic acid esters of polytrimethylene carbonate and the like as polycarbonate-based macromonomers are exemplified. As a result, the detailed chemical structure of the macromonomer is not limited as long as a graft copolymer that functions as a compatibilizer for the purpose of the present invention is obtained.

In the graft copolymer of the present invention, the chemical structure of the free terminal of the polyether chain in the chain (C2) and the terminal group structure other than the terminal having the polymerizable functional group of the polyether macromonomer are particularly Not limited. The terminal derived from polyether chain synthesis conditions may be used as is, or may be chemically converted to another structure. Desirably, it is a hydroxyl group or an alkoxy ether group. In addition, chain (C2)
As for the molecular weight of the polyether chain in the resin, the compatibilizing effect is remarkably exhibited, that is, the content of ethylene oxide chains in the polyether chain does not become low. Polyether chains having a terminal group structure are preferred.

The copolymerizable unsaturated monomers that can be used other than the main group of the styrene monomer and the (meth) acrylate monomer constituting the chain (C1) of the graft copolymer include: Unsaturated carboxylic acid compounds such as (meth) acrylic acid, fumaric acid, and itaconic acid; (meth) acrylate monomers having a functional group such as a hydroxyl group or a glycidyl ether group; and maleimide monomers such as N-phenylmaleimide And vinyl carboxylate monomers such as vinyl benzoate, mono and diester monomers of fumaric acid, mono and diester monomers of itaconic acid, and vinyl ether monomers such as cyclohexyl vinyl ether. These can be appropriately selected and used as needed.

As the main component in the chain (C1), it is desirable to use styrene monomers. The content of the styrene-based monomer is not particularly limited, but from the viewpoint of excellent compatibility, 50% by weight or more of the chain portion excluding the polyether chain in the graft copolymer is a styrene-based monomer. It is particularly preferably 70 to 99% by weight. As the styrene-based monomers, it is desirable to use styrene.

The weight ratio of the chain (C1) to the chain (C2) (C
1 / C2) is 90/10 to 20/80 (% by weight). Desirably, it is 70/30 to 30/70 (% by weight). In addition, a mixture of unsaturated polyester resin and polystyrene can be made into one liquid for a long period of one month or more.
/ 40 to 50/50 (% by weight) is particularly preferred.

The number average molecular weight of the graft copolymer is not particularly limited. However, from the viewpoint that the effect as a compatibilizer is more remarkably exhibited, the number average molecular weight in gel permeation chromatography (GPC) is as follows.
It is desirable to be 2,000 to 100,000.

The synthesis reaction of the graft copolymer used for the compatibilizer (C) may be carried out in a solvent or without using a solvent, but is usually carried out in a solvent from the viewpoint of workability. . The solvent is one in which the compatibilizer is dissolved,
Any material may be used as long as it does not hinder the synthesis of the graft copolymer. After the reaction, the above graft copolymer may be isolated as a solid from the solvent, or may remain in the solution of the reaction solvent. In particular, as long as there is no problem in using as a compatibilizer, it is preferable to use the solution as it is. Further, for the purpose of lowering the viscosity of the solution and improving convenience, it is diluted with an organic solvent other than an unsaturated monomer such as styrene or a reaction solvent, or
It is also possible to redissolve. For example, a composition containing a graft copolymer, an unsaturated monomer and a solvent is used as the compatibilizer composition.

The polymerization initiator used in the synthesis of the graft copolymer is not particularly limited, but is generally a radical copolymerization initiator, for example, an organic peroxide such as benzoyl peroxide or an azo such as AIBN. Compounds are available. As long as the desired polymer is obtained, an anionic or cationic polymerization initiator other than the radical copolymerization system can be used.

As the compatibilizer (C), in addition to the above graft copolymer, a styrene-based resin and a polyether resin obtained mainly from ethylene oxide may be used.
A block copolymer bonded via a diisocyanate compound is also included. At this time, as the diisocyanate compound that can be used, for example, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, 1,4-cyclohexane diisocyanate , 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and the like.

Radical copolymerizable unsaturated resin composition (A)
And the amount of the compatibilizer (C) for compatibilizing the low-shrinkage agent (B) are 100 parts by weight in total of the radical copolymerizable unsaturated resin composition (A) and the low-shrinkage agent (B). From the point that (A) and (B) can be compatibilized for a long time,
It is preferably at least 30 parts by weight from the viewpoint that good cured physical properties can be obtained. Further, the range of 0.5 to 10 parts by weight is particularly preferable.

The resin composition of the present invention can be used by adding a filler if necessary. The filler that can be used in the resin composition of the present invention is not particularly limited, for example,
Calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, perlite, baryta, silica, silica sand, dolomite, limestone, gypsum, aluminum fine powder, hollow balloon, alumina, glass powder, aluminum hydroxide , Dolomite, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide and the like. These fillers are selected in consideration of workability and the strength of the obtained molded article, appearance, economy, etc., but calcium carbonate, aluminum hydroxide, silica, and talc are preferable, and among them, aluminum hydroxide and silica are preferable. Particularly preferred. The fillers include those subjected to surface treatment. For example, surface-treated methylated silica is effective in preventing sedimentation.

Further, the resin composition of the present invention can be used by adding a coloring agent if necessary. The colorant that can be used is not particularly limited, but includes, for example, inorganic pigments such as titanium white and carbon black and organic pigments such as phthalocyanine blue and quinacridone red, and various colorants can be used according to the hue. . In general, a pigment is often added as a toner in which a pigment is uniformly dispersed in a radical copolymerizable unsaturated resin composition such as an unsaturated polyester resin.

If necessary, a flame retardant may be added. The flame retardant that can be used is not particularly limited, and examples thereof include chlorinated paraffins, phosphates, antimony trioxide, and bromine-based flame retardants.
Further, if necessary, various ultraviolet absorbents can be used in combination.

Further, if necessary, an internal release agent may be added and used. Examples of the internal release agent include higher fatty acids such as stearic acid, higher fatty acid salts such as zinc stearate, and alkyl phosphates.

The fiber reinforcing material used in the present invention includes, for example, glass fiber, polyester fiber, phenol fiber, polyvinyl alcohol fiber, aromatic polyamide fiber, nylon fiber, and carbon fiber. Examples of these forms include woven fabrics such as glass cloth, chopped strand mat, roving, and roving cloth. These fiber reinforcing materials are selected in consideration of the viscosity of the composition, the strength of the obtained molded article, and the like.

Next, a method for producing a prepreg obtained by impregnating a fiber reinforcing material with a resin composition for pultrusion molding will be described.

For example, a reinforcing material made of fibrous material is passed through an impregnation tank containing a resin composition for pultrusion molding, impregnated, excess resin is squeezed out, and the resin is hardened by passing through a mold. Basically, it is a drawing method, (1) impregnating the fiber reinforcing material with resin, (2) shaping and curing into a predetermined cross-sectional shape,
(3) It consists of the steps of pulling and cutting.

The pultruded product of the present invention can be obtained, for example, by the above-mentioned methods (1), (2) and (3).

[0067]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. “Parts” in the following text are based on weight unless otherwise specified.

Reference Example 1 (Preparation of Radical Copolymerizable Unsaturated Resin Composition (A)) A flask equipped with a nitrogen inlet tube, a reflux condenser, and a stirrer was charged with 286 parts of neopentyl glycol, 110 parts of propylene glycol, and isophthalic acid. 166 parts and 294 parts of maleic anhydride are charged, and heating is started while stirring under a nitrogen stream. While maintaining the liquid temperature at 210 ° C., a dehydration condensation reaction was performed. When the acid value reached 23 mg-KOH / g, the solution was cooled to 180 ° C and hydroquinone 0.1
And cooled to 150 ° C. to obtain an unsaturated polyester resin (a). Then, styrene was added to the unsaturated polyester resin so as to form a styrene solution having a solid content of 65% by weight to prepare a radical copolymerizable unsaturated resin composition solution (a-1).

Reference Example 2 (Preparation of Low Shrinkage Agent) In a flask provided with a thermometer, a nitrogen inlet tube, a stirrer, a condenser and a dropping port, 600 parts of styrene was charged and heated to 50 ° C. with stirring. 400 parts of polystyrene (Dick Styrene CR-3500, manufactured by Dainippon Ink and Chemicals) having a weight average molecular weight of about 250,000 and 0.1 part of hydroquinone were added and dissolved. A low-shrinkage agent solution (b-1) having a solid content of 40% by weight was obtained.

Reference Example 3 (Preparation of compatibilizer) 200 parts of xylene was charged as a solvent into a flask provided with a thermometer, a nitrogen inlet tube, a stirrer, a condenser and a dropping port, and the temperature was raised to 120 ° C. under a nitrogen stream. did. Next, a premix solution was prepared by dissolving, in 210 parts of styrene, 140 parts of a monomethoxy-polyethylene oxide-monomethacrylate having a polyether chain number average molecular weight of 4000 as a macromonomer and 2.0 parts of AIBN as a polymerization initiator. did. Next, this mixed solution is added to the dropping funnel for about 3 hours.
It was added dropwise over a period of time to carry out addition polymerization. After the dropwise addition, the reaction was further carried out for 8 hours while maintaining the temperature at 120 ° C. to obtain the desired graft copolymer (c). After the reaction, the obtained resin solution is
C., and 30 parts of xylene and 0.1 part of hydroquinone were added thereto, followed by cooling to room temperature. In this way,
Thus, a compatibilizer solution (c-1) containing 60% by weight of the active ingredient was obtained.
This is designated as compatibilizer solution SE-1. The number average molecular weight of the obtained polymer (c) measured by GPC was 12,000.
Met.

Example 1 80 parts of the radical copolymerizable unsaturated resin composition solution (a-1) prepared in Reference Example 1, 20 parts of the low shrinkage agent (b-1) prepared in Reference Example 2, Reference Example 3 0.8 parts of the compatibilizer solution (c-1) prepared in the above was mixed and mixed with a stirrer to obtain a resin mixture (x).

To confirm the stability of one-pack, the obtained resin mixture was allowed to stand at room temperature, and the time required for separation was visually examined. Table 1 shows the obtained results.

Next, the above resin mixture (x) was put into a mold, heated and molded at 120 ° C. to prepare a test piece, and the volume shrinkage was measured. Further, a test piece cured at 120 ° C. by impregnating the glass cloth with the resin mixed solution (x) was prepared, and the warpage was measured by the “method for measuring warpage” described below. Table 1 shows the obtained results.

Measurement method of warpage; thickness 3 mm, width 500 m
m of the molded product was cut into a length of 1000 mm, placed on a flat surface plate, and the lift of the end of the molded product was measured.

Comparative Example 1 (Evaluation by Composition without Addition of Compatibilizer (C)) Example 1 was repeated except that the compatibilizer solution (c-1) was not added.
Although a resin mixture was prepared under the same conditions as in Example 1, the resin mixture was separated in 0.5 to 2 hours, so that the physical properties of the cured product could not be measured.

Comparative Example 2 (Evaluation by Composition without Addition of Low-Shrinkage Agent Solution (B)) Example 1 except that the low-shrinkage agent solution (b-1) was not added.
A resin mixture was prepared and evaluated under the same conditions as described above.

[0077]

[Table 1]

[0078]

The resin composition for pultruding of the present invention can provide a pultruded article having excellent storage stability of the resin solution for impregnation and having both low shrinkage during curing of the pultruded article.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 5/24 CER B29K 67:00 // B29K 67:00 C08L 101: 00 C08L 101: 00 B29C 67/14 DF term (reference) 4F072 AA07 AB04 AB05 AB06 AB07 AB09 AB10 AD34 AD38 AE11 AE13 AF02 AF03 AF04 AF05 AF06 AF15 AG03 AH04 AH31 AJ04 AJ16 AK17 4F205 AA41 AB01 AB15 AG14 HA05 HA27 HA33 HA42 HB02 PA03 PA03 PA03 PA03 PA01 PA03 PA69 PA78 PA79 PB22 PB25 PB40 PC02 PC08 QA03 QA08 QA09 QA20 QB03 QB12 QB19 QB20 QB22 QB24 RA03 RA10 SA01 SA21 SA31 SA64 SA73 SA76 SA83 SA84 UA01 UA03 WA07 XA02 4J027 AA02 AB06 AB07 AB18 AB19 AB18 AB18 AB18 AB15 AB16 AG03 AG04 AG05 AG23 AG24 AG25 AG27 AG33 BA04 BA05 BA07 BA22 CA02 CA10 CC02 CD02

Claims (7)

[Claims] 1. A radical copolymerizable unsaturated resin composition (A), a polymer-based low-shrinking agent (B), and a compatibilizer between the unsaturated resin (A) and the low-shrinking agent (B). A radical copolymerizable unsaturated resin composition comprising a compatibilizer (C) as an essential component, wherein the compatibilizer (C) comprises a chain (C)
As 1), a styrene-based monomer as a main component, a skeleton obtained by a polymerization reaction, and a polyether, polyester and / or polyoxyalkylene ether are used.
Alternatively, a pultruding resin composition comprising a radical copolymerizable unsaturated resin composition as an essential component, which is a graft copolymer having a chain (C2) containing polycarbonate as a main component. 2. The resin composition according to claim 1, wherein the radical copolymerizable unsaturated resin composition (A) comprises an unsaturated polyester resin and / or a vinyl ester resin and styrene. 3. The resin composition according to claim 1, wherein the polymer-based low-shrinkage agent (B) is a styrene-based resin. 4. The weight ratio (C1 / C2) of the chain (C1) and the chain (C2) of the compatibilizer (C) is 90/10 to 2
0/80 (% by weight).
4. The resin composition according to any one of 4. 5. A compatibilizer (C) comprising an unsaturated monomer having a styrene monomer as a main component forming a chain (C1) and a (meth) acryloyl at one end forming a chain (C2). The resin composition according to any one of claims 1 to 4, wherein the resin composition is obtained by addition-copolymerizing a polyether, a polyester, and / or a polycarbonate macromonomer having a group or a styryl group. 6. The resin composition according to claim 1, further comprising a filler and / or a toner. 7. A pultruded product obtained by impregnating a resin composition for pultrusion according to any one of claims 1 to 6 into a fiber reinforcing material, curing and molding.