JP2001213967A - Compatibilizer, free-radically copolymerizable unsaturated resin composition, molding material, and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compatibilizer which improves the compatibility between a free-radically copolymerizable unsaturated resin and an addition-polymerized polymer added for reducing shrinkage and improving physical properties, corrects the molding defects in molding caused by the separation of the above two ingredients, and enables a stable dispersion of a resin mixture in a liquid state to be maintained for a long time. SOLUTION: This compatibilizer, for compatibilizing a free-radically copolymerizable unsaturated resin with an addition-polymerized polymer, contains a graft copolymer (A) which is formed by bonding chains (A2) formed mainly from a polyester, a polycarbonate, and/or a polyether consisting of a polyoxyalkylene ether to chains (A1) formed mainly from a styrene monomer by polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel compatibilizing agent, a radical compatibilizer, which can compatibilize a radical copolymerizable unsaturated resin with an addition-polymerized polymer added mainly for the purpose of reducing shrinkage and improving physical properties. The present invention relates to a copolymerizable unsaturated resin composition, a molding material and a molded article. More specifically, the addition of a radical copolymerizable unsaturated resin such as an unsaturated polyester, vinyl ester resin, or vinyl urethane resin, and a thermoplastic resin such as polystyrene, polymethyl methacrylate, styrene butadiene rubber, polyvinyl acetate, and acrylic rubber. The present invention relates to a very effective compatibilizer which remarkably improves the compatibility of two components with a polymer and solves problems in storage and molding caused by poor compatibility. Furthermore, by preventing the resin mixture containing the radical copolymerizable unsaturated resin and the addition-polymerized polymer from being separated, and by enabling a stable dispersion state, that is, one-pack, the added value of the product can be increased. The present invention relates to a compatibilizer, a radical copolymerizable unsaturated resin composition, a molding material, and a molded article which enable the composition to be achieved.

[0002]

2. Description of the Related Art A radical copolymerizable unsaturated resin is suitably used as a raw material resin for a molding material. However, a molding material using a radical copolymerizable unsaturated resin has a serious problem that the volume shrinkage occurring at the time of curing causes the molded product to warp or crack. For the purpose of remedying this problem, various thermoplastic resins, for example, low-shrinkage agents such as polystyrene and styrene-butadiene rubber have been used. However, these low-shrinking agents have low compatibility with the radical copolymerizable unsaturated resin, and the separation over time after mixing is inevitable. Therefore, the dispersion stability of the resin mixture is poor, and it is difficult to make the resin mixture one-pack. It is. Further, in the molded article obtained from the resin mixture, defects in various molded appearances such as scumming and color unevenness due to separation of the low-shrinkage agent are likely to occur.

Accordingly, various methods for adding a compatibilizer as a third component have been studied. For example, US Pat.
No. 36600 discloses an example using a styrene-ethylene oxide block copolymer obtained by a living anionic polymerization method as a compatibilizer. Although this compatibilizer exhibits a high compatibilizing effect and can maintain a stable dispersion state for a long period of time, it is difficult to mass-produce it industrially due to the specificity of the synthesis method.

On the other hand, a method of improving the compatibility by using an addition polymer in which a vinyl acetate block, a saturated polyester block, or the like is introduced as a low-shrinking agent has been studied (for example, Japanese Patent Application Laid-Open No. HEI-3-3). 174424, JP-A-11-92646). Although these improved type low-shrinking agents have the effect of delaying the time until separation, they have essentially not improved the compatibility and obtained a stable dispersion state. Further, the above-mentioned technology is limited to a polymer having a specific structure, and does not provide convenience of appropriately selecting and using various kinds of addition polymers as a low-shrinking agent according to necessary physical properties, applications, and the like. SMC using vinyl ester resin,
A copolymer of styrene / maleic acid half ester / polyethylene glycol has been proposed in US Pat. No. 3,947,422 as a viscosity reducing agent to be added to a molding material such as BMC. However, the remaining carboxyl group derived from maleic acid is adsorbed on a filler such as calcium carbonate when SMC is formed, and the excellent compatibilizing effect of the present invention cannot be obtained. In addition, we have found that experiments with systems containing only unsaturated polyester and polystyrene-free fillers may have little compatibilizing effect. Therefore, it cannot be expected that many kinds of unsaturated resins and addition-polymerized polymers are expected to be one-part liquid, and that the improvement of scumming of molded articles, uniform coloring property, surface smoothness, gloss and the like are expected as the effects of the present invention.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide compatibility between a radical copolymerizable unsaturated resin and an addition polymerization type polymer (thermoplastic resin) added for the purpose of reducing shrinkage and improving physical properties. And to provide a compatibilizer which can improve molding defects at the time of molding accompanying the separation of the two components, or can provide a stable dispersion state for a long time in the state of a resin mixture. That is, by preventing separation of the radical copolymerizable unsaturated resin and the addition-polymerized polymer which could not be achieved by the prior art, the resin mixture can be made into one liquid, and defects (scumming) during molding due to the separation can be caused. It is an object of the present invention to provide a practical compatibilizer capable of eliminating uniform coloring, smoothness, and gloss), a radical copolymerizable unsaturated resin composition containing the same, a molding material and a molded article.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on these problems, and as a result, have found that a graft copolymer having a specific structure is extremely useful as the above-mentioned compatibilizer. Reached.

That is, the present invention is a compatibilizing agent for making a radical copolymerizable unsaturated resin compatible with an addition-polymerized polymer, and comprises a chain obtained by a polymerization reaction using a styrene-based monomer as a main component. A1) a compatibilizer, which is a graft copolymer (A) in which a chain (A2) mainly composed of polyoxyalkylene ether, polyester and / or polycarbonate is bonded. The present invention relates to a radical copolymerizable unsaturated resin composition, a molding material and a molded article containing the same.

Further, the present invention relates to a graft copolymer (A)
The graft copolymer (A) in which the chain (A2) is linked to the chain (A1) through a (meth) acryloyl group or styryl group, preferably the chain (A2) has a number average molecular weight of 1
The graft copolymer (A) having a weight ratio (A1 / A2) of the chain (A1) to the chain (A2) of from 90/10 to 20/80, preferably from 000 to 20,000. (A), preferably chain (A1)
Graft copolymerization obtained by addition-copolymerizing an unsaturated monomer containing a styrene-based monomer as a main component and a macromonomer having a (meth) acryloyl group or styryl group at one end to form a chain (A2). A useful radical copolymerizable unsaturated resin composition comprising a compatibilizer containing the union (A), a radical copolymerizable unsaturated resin, a polymerizable unsaturated monomer and / or an addition polymerization type polymer, The present invention relates to a molding material containing a radical copolymerizable unsaturated resin composition and a molded article thereof. Hereinafter, the present invention will be described in detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The compatibilizer of the present invention contains a polyoxyalkylene ether chain as a main component in a chain (A1) of a copolymer obtained by addition polymerization of a styrene monomer as a main component. It contains a graft copolymer (A) in which a chain (A2) composed mainly of a polyether series composed mainly of oxyethylene units and a polyester and / or polycarbonate (A2) is bonded. is there. The chain (A2) is preferably bonded to the chain (A1) via (meth) acryloyl group or styryl group (vinylbenzyl group) in (A2).

As the monomer component which can be used to form the chain (A1), only a styrene monomer or a styrene monomer as a main component, and a (meth) acrylic acid monomer or the like as another component is used in combination. It is a mixture. Styrene, vinyl toluene (methyl styrene), p-methyl styrene, t-butyl styrene, chlorostyrene, vinyl benzyl alkyl ether and the like can be mentioned as typical styrene monomers. It is desirable that the styrene-based monomer is the main component of the chain (A1) because of excellent compatibility stability.

Representative examples of (meth) acrylic acid-based monomers 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 representative 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.

The chain (A2) is one or more chains selected from polyether, polyester and polycarbonate, and preferably has a number average molecular weight of 1,000 to 2,
0000, more preferably 2,000 to 10,000, and there is no particular limitation on the synthesis method, structure, and the like.
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 a saturated carboxylic acid and a polyhydric alcohol, and polycaprolactone 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.

As a component which can be used to constitute the polyether chain of the chain (A2), a ring-opening polymerizable monomer can be used. 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 include propylene oxide, butylene oxide,
Cyclohexene oxaiside, tetrahydrofuran,
Styrene oxide and the like can be mentioned. Oxyethylene-
A polyether having a unit as a main component is preferable. The polyether chain has a number average molecular weight of preferably from 1,000 to 20,000, more preferably from 2,000 to 20,000.
000.

The other ring compounds capable of ring-opening copolymerization include acid anhydride compounds such as succinic anhydride and phthalic anhydride. Cyclic ester compounds, for example, caprolactone, valerolactone and the like. Furthermore, 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 can also be used.

[0015] The structure of the polyether of the chain (A2) obtained by copolymerizing the cyclic compound containing ethylene oxide as a main component is one that exhibits compatibility with the radical copolymerizable unsaturated resin. If there is, there is no particular limitation.
The chain (A2) may be, for example, a random copolymer or a block copolymer of ethylene oxide and another cyclic compound. Further, the chain (A2) may be extended using an ethylene oxide-based polyether polyol compound or a glycol compound having a molecular weight of less than 1,000 and a dicarboxylic acid compound, a diisocyanate compound, a carbonate compound, a diglycidyl ether compound, or the like. . The polyether chain (A2) may be linear or branched, but is preferably linear in terms of the synthesis method.

The number average molecular weight of the polyether of the chain (A2) is preferably in the range of 1,000 to 20,000. Within this range, the performance as a compatibilizer is high,
Further, the composition becomes easy. Particularly desirable is a number average molecular weight of 3,000 to 8,000.

The content of oxyethylene units in the chain (A2) 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 of 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 the desired compatibilizing effect or to impart an effect other than the compatibilizing effect.

The method for producing the graft copolymer (A) of the present invention is not particularly limited.
1) A method in which only the chain (A1) is synthesized in advance, and the separately synthesized chain (A2) is bonded by a polymer reaction to obtain the target (A). 2) Only (A1) is synthesized in advance, and A method of polymerizing the ring-opening polymerizable monomer or the like constituting A2) starting from the active site in (A1), 3) constituting a chain (A2) with the unsaturated monomer constituting (A1) There is a method of obtaining the target (A) by addition-copolymerizing a previously synthesized macromonomer having a polymerizable functional group at one terminal.
As a method for producing the compatibilizer of the present invention, the synthesis method 3) using a macromonomer that can easily obtain a homogeneous polymer is desirable.

The macromonomer which can be used in the graft copolymer (A) of the present invention includes an unsaturated monomer constituting a chain (A1) at one end of the polyether, polyester and / or polycarbonate chain (A2). It has a polymerizable functional group copolymerizable with the monomer. The functional group is preferably an ethylenically unsaturated group. Specifically, from the viewpoint of polymerizability, a (meth) acryloyl group and a styryl group are preferable, and other vinyl groups, propenyl groups,
Examples thereof include an allyl group, a vinyl ether group, and an allyl ether group. Compounds having these functional groups chemically bonded only to one terminal of the above-mentioned chain (A2) are representative examples of the macromonomer that can be used in the present invention.

Specifically, mono (meth) acrylates of polyethylene oxide, monovinyl benzyl ether of polyethylene oxide, monovinyl ether of polyethylene oxide, monoallyl ether of polyethylene oxide as polyether macromers,
Monoisocyanate of polyethylene oxide, equimolar reaction product of isocyanate ethyl methacrylate and polyethylene oxide, diisocyanate compound such as isophorone diisocyanate and polyethylene oxide with hydroxyl group-containing unsaturated monomer such as hydroxyethyl (meth) acrylate Can be used.
Other examples include polyester-based macromers such as poly (caprolactone) mono (meth) acrylate and polycarbonate-based macromonomers such as polytrimethylene carbonate mono (meth) acrylate. As a result, as long as the graft copolymer (A) which functions as the compatibilizer for the purpose of the present invention is obtained, the detailed chemical structure of the entire macromonomer is not limited, but the above-mentioned half ester of polyethylene oxide and maleic acid is used. Use of the compound is not preferable in terms of performance.

In the graft copolymer (A), the chemical structure of the free terminal of the chain (A2) and the other terminal group structure other than the terminal having the polymerizable functional group of the macromonomer are as follows:
There is no particular limitation. The terminal derived from the chain synthesis conditions may be used as is, or may be chemically converted to another structure. The terminal functional group is desirably a hydroxyl group, an alkoxy ether group, or an alkoxy ester group. When the molecular weight of the terminal group is significantly increased, the content of the oxyethylene unit (unit) in the chain (A2) is reduced, so that the compatibilizing effect may be unstable. Therefore, in terms of carbon number, 20
And a chain (A2) having a terminal group structure with a molecular weight of 500 or less.

Other than the styrene monomer as the main component constituting the chain (A1) of the graft copolymer (A), copolymerizable unsaturated monomers that can be used include (meth) acrylic acid, fumaric acid, Unsaturated carboxylic acid compounds such as itaconic acid, (meth) acrylate monomers having a functional group such as a hydroxyl group or a glycidyl ether group, maleimide monomers such as N-phenylmaleimide, acrylamide monomers such as acrylamide, Examples thereof include vinyl carboxylate monomers such as vinyl benzoate, 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 (A1), it is desirable to use a styrene monomer. The content is not particularly limited, but is usually 50% by weight or more, preferably 70 to 99% by weight of the styrene monomer. Particularly, use of a styrene monomer is desirable. Usually, chain (A1)
Is an unsaturated monomer containing 70 to 99.9% by weight of a styrene monomer and (meth) acrylic acid ester.
Consists of 1 to 30% by weight. The constituent components of the chain (A1) are appropriately changed according to the synthesis method and the required performance.

Chain (A1) in graft copolymer (A)
And the weight% ratio (A1 / A2) of the chain (A2) is preferably 90/10 to 20/80, more preferably 80/20.
２０20/80, more preferably 70 / 30-30.
/ 70 (% by weight). Especially 60 / 40-50 / 50
It has been confirmed that the graft copolymer (A) having a composition in the vicinity of the weight% ratio can convert a mixture of an unsaturated polyester resin and polystyrene into one liquid for a period of one month or more.

The number average molecular weight of the graft copolymer (A) is not particularly limited, but is preferably from 2000 to 1
0000, more preferably 5,000 to 50,000. Within this molecular weight range, the effect as a compatibilizer will be higher. The number average molecular weight in this case is defined as gel permeation chromatography (GP
This is measured in C) using a polystyrene standard.

The synthesis reaction of the graft copolymer (A) of the compatibilizer 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. Any solvent may be used as long as the compatibilizing agent dissolves therein and does not interfere with the synthesis of the graft copolymer. After the reaction, the copolymer (A) may be isolated from the solvent as a solid, or may remain in the solution of the reaction solvent. In particular,
If there is no problem in using as a compatibilizer, it is preferable to use the solution as it is. It is also possible to dilute or redissolve with an unsaturated monomer such as styrene or an organic solvent other than the reaction solvent for the purpose of lowering the solution viscosity and improving convenience. For example, a composition containing the graft copolymer (A), an unsaturated monomer and a solvent is used as the compatibilizer composition.

The polymerization initiator at the time of synthesizing the graft copolymer (A) is not particularly limited, but is generally a radical polymerization initiator such as an organic peroxide such as benzoyl peroxide or AIBN ( Azo compounds such as azobisisobutyronitrile) can be used. As long as the desired polymer is obtained, an anionic or cationic polymerization initiator other than the radical polymerization initiator can be used.

The amount of the compatibilizer added to the radical-copolymerizable unsaturated resin and the addition-polymerized polymer (thermoplastic resin) added as a low-shrinking agent or a physical property-improving agent depends on the amount of the radical copolymerizable resin. Total 10 of unsaturated unsaturated resin and addition polymerization type polymer
The amount is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 3 parts by weight, per 0 parts by weight. With such an amount, the compatibility is higher and the physical properties of the cured product are also preferable.

The radical copolymerizable unsaturated resin composition containing the compatibilizer of the present invention includes, for example, unsaturated polyester,
It is composed of a radical copolymerizable unsaturated resin such as a vinyl ester resin, a vinyl urethane resin, or an acrylic resin, an addition polymerization polymer, and a polymerizable unsaturated monomer.
If necessary, a polymerization inhibitor, a curing agent, a filler, a reinforcing material, an internal mold release agent, a colorant, and other various additives can be added.

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 containing an 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-
Pentanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol A
Alkylene oxide adducts, diols such as glycols such as alkylene oxide adducts of bisphenol A, 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
Glycidyl methacrylate, epoxy compounds such as bisphenol A type epoxy, toluene diisocyanate,
A resin modified with an isocyanate compound such as isopropenyl-dimethyl-benzyl isocyanate may be used.

Further, dicyclopentadiene unsaturated polyester obtained by adding dicyclopentadiene to the above α, β-unsaturated carboxylic acid, saturated carboxylic acid and polyhydric alcohol and reacting them together 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.

The vinyl ester resin used in the present invention is a reaction product obtained by reacting an epoxy resin with an unsaturated monobasic acid. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F
Ether resins, phenol novolak epoxy resin, cresol novolak epoxy resin, brominated epoxy resin, etc., glycidyl ethers of polyhydric phenols, dipropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, alkylene oxide of bisphenol A Glycidyl ether of polyhydric alcohol such as diglycidyl ether of adduct, diglycidyl ether of hydrogenated bisphenol A,
3,4-epoxy-6-methylcyclohexylmethyl-
Alicyclic epoxy resins such as 3,4-epoxy-6-methylcyclohexanecarboxylate and 1-epoxyethyl-3,4-epoxycyclohexane, diglycidyl phthalate, diglycidyl tetrahydrophthalate, and diglycidyl p-oxybenzoate Glycidyl esters such as glycidyl ester of acid and dimer acid, glycidylamines such as tetraglycidyldiaminodiphenylmethane, tetraglycidyl m-xylylenediamine, triglycidyl P-aminophenol, N, N-diglycidylaniline, and 1,3-diglycidyl And heterocyclic epoxy resins such as -5,5-dimethylhydantoin and triglycidyl isocyanurate. These epoxy resins may be used alone or in combination of two or more.

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethyl malate, monomethyl fumarate, and the like.
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 resin is subjected to acid anhydrides such as maleic anhydride, succinic anhydride and acetic anhydride, toluene diisocyanate, isopropenyl-dimethyl-
It may be modified with an isocyanate compound such as benzyl isocyanate.

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 generic name of a compound having a plurality of hydroxyl groups in a 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, and 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, each of which is used alone or in combination of two or more. As the organic polyisocyanate compound, those described below can be used.

Examples of particularly typical organic polyisocyanate compounds include 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and naphthalene diisocyanate. , 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and the like. Other examples include multimers obtained by isocyanurating various isocyanate compounds. These may be used alone or in combination of two or more.

The acrylic resin refers to a thermoplastic acrylic polymer derived from a polymerizable unsaturated monomer having (meth) acrylic acid ester and (meth) acrylic acid ester as a main component and a polymerizable unsaturated monomer. It is composed. It is obtained by polymerizing the monomer solution using (meth) acrylic acid ester as an essential component, and optionally using another polymerizable unsaturated monomer copolymerizable with the (meth) acrylic acid ester. Things. Since this acrylic polymer is used in the form of a syrup dissolved in the polymerizable monomer, it is preferably one having a molecular weight of 100,000 or less, and can be obtained by a general polymerization method such as suspension polymerization or solution polymerization. . Also,
A syrup obtained by prepolymerizing 10 to 40% by weight of the monomer can be used as it is.

Examples of particularly typical polymerizable unsaturated monomers usable in the radical copolymerizable unsaturated resin composition include styrenes, acrylic esters, methacrylic esters, and diallyl phthalate esters. , Carboxylic acid vinyl esters, vinyl ethers and the like 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.

(Modification) The amount of the polymerizable unsaturated monomer relative to the unsaturated polyester, vinyl ester resin, vinyl urethane resin or acrylic resin is not particularly limited, but may be in the range of 10 to 70% by weight. Is preferably, and more preferably in the range of 20 to 50% by weight. Preferably a radical copolymerizable unsaturated resin: polymerizable unsaturated monomer = 30 to 90% by weight: 10 to 70% by weight, more preferably 50 to 80% by weight: 20 to 50% by weight. is there.

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 thereof may be used by mixing them 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, peroxyester, hydroperoxide, ketone peroxide, alkyl perester, and percarbonate compounds. And the like are used, and are appropriately selected according to molding conditions.

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

The additives (curing accelerators) used in combination with the above-mentioned curing agents to promote curing are not particularly limited, but, for example, metal salts such as cobalt naphthenate and cobalt octenoate; , N-dimethylaniline,
Tertiary amines such as N, N-di (hydroxyethyl) paratoluidine and dimethylacetoacetamide;
Selected and used as needed.

As typical examples of fillers usable in the resin composition of the present invention, calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, perlite, Examples thereof include baryta, silica, silica sand, dolomite, limestone, gypsum, aluminum fine powder, hollow balloon, alumina, glass powder, aluminum hydroxide, hydrated water, 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 product, appearance, economy, etc., but usually calcium carbonate or aluminum hydroxide,
Silica, talc and the like are often used. The fillers include those subjected to surface treatment.

The reinforcing material that can be used in the resin composition of the present invention may be one that is usually used as a fiber reinforcing material.
For example, there are glass fiber, polyester fiber, phenol fiber, polyvinyl alcohol fiber, aromatic polyamide fiber, nylon fiber, and carbon fiber. Examples of these forms include chopped strands, chopped strand mats, rovings, and woven fabrics.
These fiber reinforcing materials are selected in consideration of the viscosity of the composition, the strength of the obtained molded article, and the like.

Examples of the internal release agent that can be used in the resin composition of the present invention include higher fatty acids such as stearic acid,
Higher fatty acid salts such as zinc stearate and the like, and alkyl phosphates are exemplified. However, the present invention is not limited to these, and various release agents can be appropriately selected and used according to molding conditions.

As typical colorants that can be used in the resin composition of the present invention, there are inorganic pigments such as titanium white and carbon black, and organic pigments such as phthalocyanine blue and quinacridone red. Various colorants can be used depending on the colorant. Generally, the pigment is often added as a toner in which the pigment is uniformly dispersed in an unsaturated polyester resin or the like.

Other various additives include viscosity modifiers such as a viscosity reducing agent, defoaming agents, silane coupling agents, and air blocking agents such as paraffin, and commercially available products can be used.

Further, a sheet molding compound (hereinafter abbreviated as SMC), a bulk molding compound
When preparing molding materials such as compounds (hereinafter abbreviated as BMC), metal oxides and hydroxides such as magnesium oxide and calcium hydroxide as thickeners, crude M
There are polyfunctional isocyanate compounds such as DI. However, the present invention is not limited to this, and various thickeners can be appropriately selected and used according to the use of the molding material and required performance. Generally, magnesium oxide whose viscosity can be easily controlled is used.

In the present invention, the addition polymerization type polymer (thermoplastic resin) mixed with a radical copolymerizable unsaturated resin
The material is not particularly limited, but a material exhibiting the desired effects of reducing shrinkage and improving physical properties (such as fracture toughness) can be appropriately selected and used according to molding applications, conditions, and the like. If only typical ones are exemplified, polystyrene resins containing styrene as a main component, for example, polystyrene, copolymers of styrene and (meth) acrylate, styrene-conjugated diene block copolymers, styrene- And hydrogenated conjugated diene block copolymers.
In addition, styrene-free (meth) acrylate polymers, such as polymethyl methacrylate and n-butyl polyacrylate, may be mentioned. Further, those obtained by reacting a double bond in these polymers with another compound can also be used.

The styrene-conjugated diene-based block copolymer is a block copolymer composed of 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 resin composition of the present invention can be used as a molding material (SM
It can be used as press molding, spray molding, hand lay-up molding, casting, drawing molding as C and BMC, and as a coating material (paint, putty, Sealink III material, lining material). The molding material of the present invention comprises a resin composition, a polymerization inhibitor, a curing agent, a filler, and a fiber reinforcing material, to which various additives such as an internal release agent and a coloring agent are added as necessary.

The molded article of the present invention includes household equipment such as a bathtub, kitchen counter, vanity stand, waterproof pan, septic tank, and the like.
Examples include artificial marble, panels, corrugated sheets, drawn materials, civil engineering and building materials such as polymer concrete, boats, ships and other vehicles, vehicle parts such as lamp reflectors, buttons, and daily necessities for bowling balls.

According to the present invention, it is possible to improve the compatibility between a radical copolymerizable unsaturated resin and a low-shrinking agent, which has not been easily achieved by the prior art, and to prevent separation, thereby making one-package of a resin mixture possible. And a practical compatibilizer capable of eliminating defects during molding due to separation. Therefore, the resin composition using the compatibilizer of the present invention does not cause separation of the low-shrinkage agent, and the molding material is excellent in homogeneity, has no scumming, uniform colorability, and surface smoothness. A molded article having an excellent surface gloss and the like and extremely high quality can be obtained.

[0060]

EXAMPLES 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. Further, “parts” in the text indicates parts by weight.

Example [Preparation of Compatibilizer <Graft Copolymer (A)> of the Present Invention] (Synthesis Example 1) A 1 L flask equipped with a thermometer, a nitrogen inlet tube, a stirrer, a condenser, and a dropping funnel was prepared. Then, 200 g of xylene was charged as a solvent, and the temperature was raised to 120 ° C. under a nitrogen stream. Next, in 210 g of styrene, 140 g of monomethoxy-polyethylene oxide-monomethacrylic acid ester having a polyether chain number average molecular weight of 4000 as a macromonomer and 2.0 g of AIBN (azobisisobutyronitrile) as a polymerization initiator are dissolved. A premix solution was prepared. Next, this mixed solution was added dropwise from a dropping funnel over about 3 hours 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 a target graft copolymer (A). After the reaction, the obtained resin solution was mixed with 30
C., and 440 g of styrene and 0.1 g of hydroquinone were added thereto, followed by cooling to room temperature. Thus, a compatibilizer solution of 35% by weight of the active ingredient was obtained. This is designated as compatibilizer solution SE-1. The obtained polymer (A)
The number average molecular weight measured by GPC was 12,000.

(Synthesis Example 2) (Synthesis of Compatibilizer) In the same manner as in Synthesis Example 1, xylene 200 g, styrene 1
75 g, monomethoxy-polyethylene oxide-monomethacrylic acid ester having a number average molecular weight of 4000 as a macromonomer and 175 g of AIBN 2.0
Using g as a raw material, addition polymerization was performed at 120 ° C. to obtain a target graft copolymer (A). Further, in the same manner as in Synthesis Example 1, 440 g of styrene and 0.1 g of hydroquinone were added to obtain a compatibilizer solution containing 35% by weight of the active ingredient. This is designated as compatibilizer solution SE-2. The number average molecular weight of the obtained polymer (A) measured by GPC was 11,000.

(Synthesis Example 3) (Synthesis of Compatibilizer) In the same manner as in Synthesis Example 1, 200 g of xylene and styrene 2
10 g, 140 g of monomethoxy-polyethylene oxide-monomethacrylate having a number average molecular weight of 6000 as a macromonomer, AIBN 2.0
Using g as a raw material, addition polymerization was performed at 120 ° C. to obtain a target graft copolymer (A). Further, in the same manner as in Synthesis Example 1, 440 g of styrene and 0.1 g of hydroquinone were added to obtain a compatibilizer solution containing 35% by weight of the active ingredient. This is designated as compatibilizer solution SE-3. The number average molecular weight measured by GPC of the obtained polymer (A) was 13,000.

(Synthesis Example 4) (Synthesis of Compatibilizer) In the same manner as in Synthesis Example 1, 200 g of xylene and styrene 2
10 g, 140 g of monomethoxy-polyethylene oxide-monomethacrylate having a polyether chain number average molecular weight of 2,000 as a macromonomer, AIBN 2.0
Using g as a raw material, addition polymerization was performed at 120 ° C. to obtain a target graft copolymer (A). Further, in the same manner as in Synthesis Example 1, 440 g of styrene and 0.1 g of hydroquinone were added to obtain a compatibilizer solution containing 35% by weight of the active ingredient. This is designated as compatibilizer solution SE-4. The number average molecular weight of the obtained polymer (A) measured by GPC was 11,000.

(Synthesis Example 5) (Synthesis of Compatibilizer) In the same manner as in Synthesis Example 1, 200 g of xylene and styrene 2
10 g, methyl methacrylate 35 g, monomethoxy-polyethylene oxide-monomethacrylic acid ester 105 g having a polyether chain number average molecular weight of 4000 as a macromonomer, and AIBN 2.0 g were subjected to addition polymerization at 120 ° C. Polymer (A) was obtained. Further, in the same manner as in Synthesis Example 1, 440 g of styrene,
0.1 g of hydroquinone was added to obtain a compatibilizer solution of 35% by weight of the active ingredient. This is designated as compatibilizer solution SE-5. The number average molecular weight of the obtained polymer (A) measured by GPC was 10,000.

(Synthesis Example 6) (Synthesis of Compatibilizer) In the same manner as in Synthesis Example 1, 200 g of xylene and styrene 1
75 g, behenyl methacrylate 35 g, number average molecular weight of polyether chain 400 as macromonomer
Using 140 g of monomethoxy-polyethylene oxide-monomethacrylic acid ester of No. 0 and 2.0 g of AIBN as raw materials, addition polymerization was carried out at 120 ° C. to obtain a target graft copolymer (A). Further, in the same manner as in Synthesis Example 1, 440 g of styrene and 0.1 g of hydroquinone were added to obtain a compatibilizer solution containing 35% by weight of the active ingredient. This is designated as compatibilizer solution SE-6. The number average molecular weight of the obtained polymer (A) measured by GPC was 10,500.

(Synthesis Example 7) (Synthesis of Compatibilizer) In the same manner as in Synthesis Example 1, 200 g of xylene and styrene 2
10 g, 140 g of monoethoxy-polyethylene oxide-monovinylbenzyl ether having a polyether chain number average molecular weight of 4000 as a macromonomer, AIBN2.
Using 0 g as a raw material, addition polymerization was performed at 120 ° C. to obtain a target graft copolymer (A). Further, in the same manner as in Synthesis Example 1, 440 g of styrene and 0.1 g of hydroquinone were added to obtain a compatibilizer solution containing 35% by weight of the active ingredient. This is designated as compatibilizer solution SE-7. The number average molecular weight measured by GPC of the obtained polymer (A) was 11,500.

(Synthesis Example 8) (Synthesis of Compatibilizer) In the same manner as in Synthesis Example 1, 200 g of xylene and styrene 2
10 g, monomethoxy-polyethylene having a polyether chain number average molecular weight of 4000 as a macromonomer, and monomethacrylic acid ester 1 of a propylene oxide block
Using 40 g of AIBN and 2.0 g of AIBN as raw materials, addition polymerization was performed at 120 ° C. to obtain a target graft copolymer (A). Further, in the same manner as in Synthesis Example 1, 440 g of styrene and 0.1 g of hydroquinone were added to obtain a compatibilizer solution containing 35% by weight of the active ingredient. This is designated as compatibilizer solution SE-8. The number average molecular weight measured by GPC of the obtained polymer (A) was 11,500. The content of the ethylene oxide chain in the side chain (A2) is 80% by weight.

(Synthesis Example 9) (Synthesis of Compatibilizer) In the same manner as in Synthesis Example 1, 200 g of xylene and styrene 2
10 g, monomethoxy-polyethylene oxide having a number average molecular weight of 4,000 as a side chain (A2) as a macromonomer
Using 140 g of monomethacrylic acid ester of polycaprolactone block and 2.0 g of AIBN as raw materials,
To obtain the desired graft copolymer (A). Further, in the same manner as in Synthesis Example 1, 440 g of styrene,
0.1 g of hydroquinone was added to obtain a compatibilizer solution of 35% by weight of the active ingredient. This is designated as compatibilizer solution SE-9. The number average molecular weight of the obtained polymer (A) measured by GPC was 10,500. The content of the ethylene oxide chain in the side chain (A2) is 80% by weight.

(Synthesis Example 10) (Synthesis of Comparative Compatibilizer) In the same manner as in Synthesis Example 1, 200 g of xylene and styrene 2
10 g, monomethoxy-polyethylene oxide having a number average molecular weight of 600 as a polyether chain as a macromonomer
Monomethacrylic acid ester 140 g, AIBN 2.0 g
Was subjected to addition polymerization at 120 ° C. to obtain a comparative graft copolymer. Further, in the same manner as in Synthesis Example 1, 440 g of styrene and 0.1 g of hydroquinone were added to obtain a comparative compatibilizer solution having a solid content of 35% by weight. This is designated as compatibilizer solution SE-10. The number average molecular weight of the obtained polymer measured by GPC was 9,500.

(Synthesis Example 11) (Synthesis of Comparative Compatibilizer) In the same manner as in Synthesis Example 1, 200 g of xylene and styrene 2
10 g, 140 g of a monomethoxy-polypropylene oxide-monomethacrylic acid ester having a number average molecular weight of 4000 as a macromonomer and a polyether chain, AIBN
Using 2.0 g as a raw material, addition polymerization was performed at 120 ° C. to obtain a comparative graft copolymer. Further, in the same manner as in Synthesis Example 1, 440 g of styrene and 0.1 g of hydroquinone were added to obtain a comparative compatibilizer solution having a solid content of 35% by weight. This is designated as compatibilizer solution SE-11. The number average molecular weight of the obtained polymer measured by GPC was 10,000.

(Synthesis Example 12) (Synthesis of Comparative Compatibilizer) In the same manner as in Synthesis Example 1, 200 g of xylene and styrene 2
12 g of a maleic acid half ester of monomethoxy-polyethylene oxide having a number average molecular weight of 4000 of 140 g and AIBN of 2.0 g were used as raw materials.
Addition polymerization was performed at 0 ° C. to obtain a comparative graft copolymer. Further, in the same manner as in Synthesis Example 1, 440 g of styrene,
0.1 g of hydroquinone was added to obtain a comparative compatibilizer solution having a solid content of 35% by weight. This was used as a compatibilizer solution SE-1.
Let it be 2. The number average molecular weight of the obtained polymer measured by GPC was 9,500.

(Synthesis Example 13) (Preparation of Polystyrene Solution with Low Shrinkage Agent) In a flask similar to that of Synthesis Example 1, 650 g of styrene was charged and heated to 50 ° C. Under stirring, the weight average molecular weight is about 25
350 g of polystyrene (Detic Styrene CR-3500, manufactured by Dainippon Ink and Chemicals) and 0.1 g of hydroquinone were added and dissolved. A resin solution having a solid content of 35% by weight was obtained. This is designated as a low-shrinkage agent solution LP-1.

(Synthesis Example 14) (Preparation of Low Shrinkage Agent-Styrene-Butadiene Rubber Solution) In the same manner as in Synthesis Example 13, 650 g of styrene was charged.
Heat to 50 ° C. Under stirring, styrene / rubber weight ratio 3
350 of 1/69 polymer (KRATON D-1118, SHELL)
g and hydroquinone 0.1 g were added and dissolved. A resin solution having a solid content of 35% by weight was obtained. This is designated as a low-shrinkage agent solution LP-2.

(Synthesis Example 15) (Preparation of Solution with Low Shrinkage Agent-Poly (methyl methacrylate)) In the same manner as in Synthesis Example 13, 650 g of styrene was charged.
Heat to 50 ° C. Under stirring, 350 g of a polymer of methyl methacrylate (Diyanal BR-84, manufactured by Mitsubishi Rayon)
0.1 g of hydroquinone was added and dissolved. Solid content 3
A 5% by weight resin solution was obtained. This is a low-shrinkage agent solution LP
-3.

(Synthesis Example 16) (Preparation of Low Shrinkage Agent-Polyvinyl Acetate Solution) In the same manner as in Synthesis Example 13, 650 g of styrene was charged.
Heat to 50 ° C. Under stirring, 350 g of a vinyl acetate polymer (Tundka ASR, M-5D, manufactured by Denki Kagaku Kogyo) and 0.1 g of hydroquinone were added and dissolved. A resin solution having a solid content of 35% by weight was obtained. This is designated as a low-shrinkage agent solution LP-4.

(Synthesis Example 17) (Preparation of Low Shrinkage Agent-Polybutyl Acrylate Solution) In the same manner as in Synthesis Example 1, 100 g of toluene, 350 g of n-butyl acrylate, and 0.4 g of AIBN were used as raw materials.
Addition polymerization was carried out at 0 to 80 ° C. for about 8 hours while paying attention to heat generation to obtain an acrylic rubber-based polymer. Thereafter, the solvent toluene was distilled off at 90 ° C. under reduced pressure. Next, 640 g of styrene and 0.1 g of hydroquinone were added, and a solid content of 35 g was added.
A weight percent resin solution was obtained. This is used as a low-shrinkage agent solution LP-
5 is assumed.

(Synthesis Example 18) (Preparation of unsaturated resin-unsaturated polyester resin) 2 L equipped with a nitrogen gas inlet tube, a reflux condenser, and a stirrer
Propylene glycol 525 in a glass flask
g and 696 g of fumaric acid, and heating is started under a nitrogen stream. At an internal temperature of 200 ° C., a dehydration-condensation reaction was carried out by a conventional method, and when the acid value reached 26 KOH mg / g,
Cool to 0 ° C. and add 0.15 g of hydroquinone. It was further cooled to 150 ° C. to obtain an unsaturated polyester. Next, this unsaturated polyester was converted to styrene 430.
g) to obtain an unsaturated polyester resin liquid having a solid content of 70% by weight. This is a radical polymerizable unsaturated resin liquid VP
-1.

(Synthesis Example 19) (Preparation of Unsaturated Resin-Unsaturated Polyester Resin) 384 g of recovered PET (polyethylene terephthalate) flakes obtained by mechanically pulverizing a PET bottle into a 2 L flask as in Synthesis Example 18 were prepared. 320 g of propylene glycol and 0.4 g of monobutylstannic acid are charged, and heating is started under a nitrogen stream. PET gradually dissolves during heating,
When the slurry is formed, stirring is started. Internal temperature 210 ° C
When this temperature is reached, the reaction is maintained for about 4 hours while maintaining this temperature. After confirming that the contents have turned into a transparent liquid,
Cool to ° C. At this temperature, 392 g of maleic anhydride are added and heating is started. At an internal temperature of 200 ° C., a dehydration-condensation reaction is carried out in a conventional manner. When the acid value reaches 25 KOH mg / g, the solution is cooled to 180 ° C. and hydroquinone 0.1
Add 5 g. It was further cooled to 150 ° C. to obtain an unsaturated polyester. Next, the unsaturated polyester was dissolved in 457 g of styrene to obtain an unsaturated polyester resin liquid having a solid content of 70% by weight. This is designated as radical polymerizable unsaturated resin liquid VP-2.

(Synthesis Example 20) (Preparation of Unsaturated Resin-Unsaturated Polyester Resin) In a 2 L flask similar to that of Synthesis Example 18, 433 g of propylene glycol, 588 g of maleic anhydride, and 95% purity were prepared.
264 g of dicyclopentadiene was charged under a nitrogen stream,
Start heating. Raise the temperature while paying attention to heat generation. At an internal temperature of 200 ° C., a dehydration-condensation reaction is carried out by an ordinary method,
When it reaches 0 KOH mg / g, it is cooled to 180 ° C. and 0.16 g of hydroquinone is added. Further 15
Cooling to 0 ° C. yielded an unsaturated polyester. Next, this unsaturated polyester is dissolved in 510 g of styrene,
An unsaturated polyester resin liquid having a solid content of 70% by weight was obtained.
This is designated as radical polymerizable unsaturated resin liquid VP-3.

(Synthesis Example 21) (Preparation of Unsaturated Resin-Vinyl Ester Resin) A bisphenol A type epoxy resin (epoxy equivalent 4) was placed in a 2 L four-necked flask equipped with nitrogen and air introduction tubes.
10) 826 g, methacrylic acid 174 g, and hydroquinone 0.4 g were charged, and the temperature was raised to 90 ° C. under a gas flow of a one-to-one mixture of nitrogen and air. Here, 2.0 g of 2-methylimidazole was added, and the temperature was raised to 105 ° C to 10 g.
Allowed to react for hours. Thus, a vinyl ester resin was obtained. Next, this vinyl ester resin was converted to styrene 430.
g) and 0.15 g of toluhydroquinone to obtain a vinyl ester resin solution having a solid content of 70% by weight. This is designated as radical polymerizable unsaturated resin liquid VP-4.

(Synthesis Example 22) (Preparation of Unsaturated Resin-Vinyl Ester Resin) A bisphenol A type epoxy resin (epoxy equivalent) was placed in a 2 L four-necked flask equipped with nitrogen and air introduction tubes.
182) 680 g, methacrylic acid 320 g, and hydroquinone 0.4 g were charged, and the temperature was raised to 90 ° C. under a gas flow in which nitrogen and air were mixed at a ratio of 1: 1. 2.0 g of 2-methylimidazole was added thereto, and the temperature was raised to 105 ° C.
The reaction was performed for 0 hours. Then, after cooling to 90 ° C., 150 g of styrene, 0.7 g of toluhydroquinone and 140 g of maleic anhydride were added, and the mixture was further reacted for 3 hours. Thus, a vinyl ester resin was obtained. Next, 339 g of styrene was mixed therein to obtain a vinyl ester resin solution having a solid content of 70%. This is a radical polymerizable unsaturated resin liquid VP
-5.

(Synthesis Example 23) (Preparation of unsaturated resin-vinyl urethane resin) In a similar flask of Synthesis Example 21, 500 g of an ethylene oxide adduct of bisphenol A (molecular weight: 500) and 448 g of isophorone diisocyanate were charged, and nitrogen and air were added. Were reacted at 80 ° C. for 4 hours under a gas flow of a one-to-one mixture. Here, 273 g of 2-hydroxyethyl methacrylate and 0.15 of hydroquinone were added at 60 ° C., and the mixture was heated to 90 ° C. and reacted for 6 hours. Thus, a vinyl urethane resin was obtained. Next, this vinyl urethane resin was dissolved in 523 g of styrene to obtain a vinyl urethane resin liquid having a solid content of 70% by weight. This is designated as radical polymerizable unsaturated resin liquid VP-6.

[Preparation of resin composition and mixing stability thereof]
(Example 1) The unsaturated resin solution (VP) obtained in Synthesis Example 18
-1) 76 parts, the low-shrinkage agent solution (LP
-1) 20 parts, 4 parts of styrene, and 3 parts (approximately 1 part as an active ingredient) of the compatibilizer solution (SE-1) obtained in Synthesis Example 1 were charged into a 200 cc glass bottle and 2,500 rpm with a stirrer.
m, for 5 minutes to obtain a resin mixture (resin composition).

The obtained resin mixture was allowed to stand at room temperature, and the dispersion stability was visually confirmed. At this time, the separation time and the number of days were classified into six stages and evaluated. During storage in the above-described container, a state in which the phases were separated to a height of about 2 mm or more as viewed from the side was defined as a separation time. (Evaluation of compatibility) 1: After mixing, separation was performed in less than 4 hours. 2: After mixing, separation occurred in 4 hours or more and less than 12 hours. 3: After mixing, separation was performed in 12 hours or more and less than 24 hours. 4: After mixing, the mixture was separated within 24 hours or more and less than 10 days. 5: After mixing, separation occurred in 10 days or more and less than 30 days. 6: After mixing, it was stable without any separation for 30 days or more. The dispersion stability of the composition obtained in Example 1 was 6 to 1
Stable for more than a month.

(Examples 2 to 9) Synthesis of compatibilizer solution in Synthesis Example 2
In the same manner as in Example 1, except that the composition was changed to (SE-2 to 9) obtained in Examples 9 to 9, a resin composition was prepared. The stability of this liquid was evaluated in the same manner as in Example 1, and the results, including Example 1, are shown in Tables 1 and 2.

[0087]

[Table 1]

Comparative Example 1 A resin composition was prepared according to Example 1, except that no compatibilizer solution was added.
The stability of this liquid was evaluated in the same manner as in Example 1. Table 2 shows the results. (Comparative Examples 2-3) Example 1 except that the compatibilizer solution was changed to (SE-10, 11) obtained in Synthesis Examples 10 to 11.
, A resin composition was prepared. The stability of this liquid was evaluated in the same manner as in Example 1, and the results are summarized in Table 2.

[0089]

[Table 2]

<Description of Abbreviations in Table> SM: Styrene, MMA: Methyl methacrylate, VM
A: Behenyl methacrylate, PEO: Polyethylene oxide, PPO: Polypropylene oxide, PE-Block: Polyethylene oxide-block polymer PS: Polystyrene, UP: Unsaturated polyester resin

(Examples 10 to 13) A resin composition was prepared in the same manner as in Example 1 except that the low-shrinkage agent solution was changed to (LP-2 to 5) obtained in Synthesis Examples 14 to 17. did. The stability of this solution was evaluated in the same manner as in Example 1, and the results were shown in Table 3.
It was shown to.

(Comparative Examples 4 to 7) Resin compositions similar to those of Examples 10 to 13 were prepared except that no compatibilizer solution was added. The stability of this liquid was evaluated in the same manner as in Example 1. Table 4 shows the results.

[0093]

[Table 3]

[0094]

[Table 4] <Description of Abbreviations in Table> SM: Styrene, PEO: Polyethylene oxide, PS: Polystyrene, SBR: Styrene butadiene rubber PMMA: Polymethyl methacrylate, PVAc: Polyvinyl acetate, PBA: Polybutyl acrylate, PS: Polystyrene, UP : Unsaturated polyester resin

(Examples 14 to 18) Resin compositions were prepared according to Example 1, except that the unsaturated resin liquid was changed to (VP-2 to 6) obtained in Synthesis Examples 19 to 23. . The stability of this liquid was evaluated in the same manner as in Example 1, and the results are shown in Table 5.

Comparative Examples 8 to 12 Resin compositions were prepared in the same manner as in Examples 14 to 18 except that no compatibilizer solution was added. The stability of this liquid was evaluated in the same manner as in Example 1. Table 6 shows the results.

[0097]

[Table 5]

[0098]

[Table 6]

<Description of Abbreviations in Table> SM: styrene, PEO: polyethylene oxide,
PS: polystyrene, UP: unsaturated polyester resin, VE: vinyl ester resin, VU: vinyl urethane resin

Example 19 (Preparation of molding material and molded article) [0100] 80 parts of the unsaturated resin (VP-1) obtained in Synthesis Example 18 was added to the low-shrinkage agent solution (LP-LP) obtained in Synthesis Example 13. 1) 25
Parts, 3 parts of the compatibilizer solution (SE-1) obtained in Synthesis Example 1,
0.06 parts of parabenzoquinone, 4 parts of zinc stearate,
140 parts of calcium carbonate, pigment toner (Polyton Kure PT-88
09, 10 parts by Dainippon Ink and Chemicals, curing agent BIC-75
1.0 part (manufactured by Kayaku Akzo Co., Ltd.) was mixed and sufficiently stirred until uniformly dispersed to form a compound. One day after the preparation, the compound was added with 1.0 part of magnesium oxide as a thickener, mixed and stirred, and impregnated into glass fiber having a fiber length of 1 inch as a reinforcing material, thereby forming a sheet-like SMC.
(Molding material). Both sides of this SMC are protected with a polyethylene film, and are further packaged and stored in an aluminum evaporated film that does not allow styrene to pass through. Note that this SMC
Was set to 28%.

The SMC (molding material) thus obtained is aged at 40 ° C. for 24 hours, and then left standing and stored at room temperature. Three days after the SMC was manufactured, the mixture was supplied to a mold adjusted to an upper mold of 145 ° C. and a lower mold of 135 ° C., and a pressure of 70 kgf /
30 minutes by maintaining the pressure at 5 cm ² (surface pressure) for 5 minutes.
It was formed into a flat plate having a size of 30 cm and a thickness of 3 mm. Evaluation of scumming, uniform coloring, surface smoothness, and gloss of the obtained molded product was performed by the following methods. The results are shown in Table 7.

[Evaluation of Appearance of Molding] Evaluation of scumming: The presence or absence of scumming was visually determined. Evaluation of uniform coloring property: Along with visual evaluation, a color difference meter (Color Machine # 80 manufactured by Nippon Denshoku Industries Co., Ltd.) is used to measure L values at 12 or more points at 1 cm intervals on an arbitrary straight line of the molded product. The average value of the L values is calculated, and the
The variation (standard deviation) of the value is calculated and used as an index. Evaluation of surface smoothness: visual evaluation and surface distortion measuring machine SURFMATIC
(Tokyo Boeki Co., Ltd.) is used to measure the second derivative of the surface irregularities. Surface gloss: Visual and gloss meter (Murakami Color Research Laboratory: G
M26D) and evaluated by 60 ° gloss.

(Evaluation Criteria): Good ◎> ○> △> × Poor Uniform Colorability: ＝= No color unevenness is observed at all, and the variation (standard deviation) of L value is 0.5 or less. ＝= Although little color unevenness can be visually confirmed, the variation (standard deviation) of the L value is 0.7 or less. Δ: Color unevenness can be visually confirmed, and the variation (standard deviation) of the L value is larger than 0.7 and smaller than 1.0. × = Evident color unevenness can be visually confirmed, and the variation (standard deviation) of the L value is 1.0 or more.

Surface smoothness: ＝= second derivative is 500 or less. ＝= Secondary derivative is 700 or less. Δ = Secondary differential coefficient is greater than 700 and less than 1000. X = Second derivative: 1000 or more.

Surface gloss: ＝= gloss at 60 ° is 90 or more. ＝= Gloss at 60 ° is 85 or more. Δ = 60 ° gloss is 80 or more and less than 85. X = Gloss at 60 ° is less than 80.

Example 20 The procedure of Example 19 was repeated except that the unsaturated resin was changed to (VP-5) obtained in Synthesis Example 22 and the low-shrinkage agent was changed to (LP-2) obtained in Synthesis Example 14. Similarly, SMC was prepared to obtain a molded product. Further, the same evaluation was performed. Table 7 shows the results.

Example 21 An SMC was prepared in the same manner as in Example 19 except that the unsaturated resin was changed to (VP-2) obtained in Synthesis Example 19 to obtain a molded article. Further, the same evaluation was performed. The results are shown in Table 7.

Example 22 The procedure of Example 19 was repeated except that the compatibilizing agent was changed to (SE-6) obtained in Synthesis Example 6 and the unsaturated resin was changed to (VP-3) obtained in Synthesis Example 20. To prepare a molded article.
Further, the same evaluation was performed. The results are shown in Table 7.

Comparative Example 13 An SMC was prepared in the same manner as in Example 19 except that no compatibilizer was used, and a molded product was obtained. Further, the same evaluation was performed. The results are shown in Table 7.

Comparative Example 14 The procedure of Example 19 was repeated, except that the compatibilizer was changed to (SE-12) obtained in Synthesis Example 12 and the unsaturated resin was changed to (VP-3) obtained in Synthesis Example 20. To prepare a molded article. Further, the same evaluation was performed. The results are shown in Table 7.

[0111]

[Table 7]

<Description of Abbreviations in Table> SM: styrene, VMA: behenyl methacrylate, P
EO: polyethylene oxide, PS: polystyrene, SBR: styrene butadiene rubber UP: unsaturated polyester resin, VE: vinyl ester resin

As is clear from the results shown in Tables 1 to 6, the compatibilizer solutions satisfying the conditions of the present invention (SE-1 to SE-1)
In all of Examples 1 to 18 using 9), a high compatibilizing effect was obtained, and separation of the resin liquid was extremely unlikely to occur. On the other hand, when the compatibilizer was not used at all, and Comparative Examples 1 to 12 using the compatibilizer solution (SE-10, 11) not satisfying the conditions of the present invention, a sufficient compatibilizing effect was not obtained. Phase separated within one day. (Comparative Example 6 using LP-4)
except for)

Further, as is apparent from the results of Examples 19 to 22 shown in Table 7, the molding defects associated with the separation of the low-shrinkage agent were all improved by the compatibilizer of the present invention, and no scumming was observed. A molded article excellent in uniform coloring, surface smoothness, and surface gloss was obtained. Since Comparative Examples 13 and 14 did not satisfy the requirements of the present invention, molding defects occurred due to the separation of the low-shrinkage agent, and the practicality of molded products was low.

[0115]

The compatibilizing agent of the present invention improves the compatibility between a radical copolymerizable unsaturated resin and a low-shrinking agent, which has not been easily achieved by the prior art, and prevents separation. The mixture can be liquefied, and defects during molding due to separation can be eliminated. The resin composition using it,
There is no separation of the low shrinkage agent, and the molding material is excellent in homogeneity, so there is no scumming, uniform coloring,
An extremely high-quality molded product having excellent surface smoothness and surface gloss can be obtained.

Continuation of the front page F term (reference) 4F071 AA22 AA43X AA43X AA50 AA50X AA51 AA51X AA77 AA81 BA09 BB03 BC01 4J011 PA65 PA69 PA78 PA88 PA89 PA90 PB40 PC02 4J027 AB02 AB03 AB05 AB06 AB07 AB10 AB18 AB17 AC03 AC04 AC06 AH03 AH05 AJ01 BA05 CA06 CA10 CB03 CC02 CD01 4J031 AA13 AA49 AA50 AA52 AA53 AB01 AC01 AD01 AE13

Claims (10)

[Claims] 1. A compatibilizer for compatibilizing a radical copolymerizable unsaturated resin with an addition-polymerized polymer, comprising a styrene monomer as a main component and a chain (A1) obtained by a polymerization reaction. A compatibilizer comprising a graft copolymer (A) formed by bonding a chain (A2) mainly composed of polyether, polyester and / or polycarbonate composed of polyoxyalkylene ether. 2. The compatibilizer according to claim 1, wherein the chain (A2) is bonded to the chain (A1) via a (meth) acryloyl group or a styryl group. 3. A chain (A2) of the graft copolymer (A)
3. The compatibilizer according to claim 1, wherein the number average molecular weight is from 1,000 to 20,000. 4. 4. The method according to claim 1, wherein the content of the oxyethylene unit in the chain (A2) containing the polyether of the graft copolymer (A) as a main component is 20 to 100% by weight. The compatibilizer according to any one of claims 1 to 3. 5. The chain (A) in the graft copolymer (A)
The weight% ratio (A1 / A2) of 1) to the chain (A2) is 9
2. The ratio is 0/10 to 20/80.
The compatibilizing agent according to claim 4. 6. The graft copolymer (A) has a chain (A)
A) a polyether, polyester and / or polycarbonate based monomer having a (meth) acryloyl group or styryl group at one end which forms a chain (A2) and an unsaturated monomer having a styrene monomer as a main component, which forms 1). The compatibilizer according to any one of claims 1 to 5, which is obtained by addition copolymerization of a macromonomer. 7. The compatibilizer according to claim 1, wherein:
A radical copolymerizable unsaturated resin composition comprising a radical copolymerizable unsaturated resin and a polymerizable unsaturated monomer. 8. The compatibilizer according to claim 1, wherein:
A radical copolymerizable unsaturated resin composition comprising an addition polymerization polymer, a radical copolymerizable unsaturated resin, and a polymerizable unsaturated monomer. 9. A molding material comprising the radical copolymerizable unsaturated resin composition according to claim 7. 10. A molded article using the molding material according to claim 8.