WO2018012205A1 - Radically curable resin composition and cured product of same - Google Patents

Abstract

The purpose of the present invention is to provide: a radically curable resin composition which is capable of providing a cured product that has achieved lower thermal expansion, while having high dimensional stability, excellent heat resistance and excellent flame retardancy; and a cured product of this radically curable resin composition. The present invention is a radically curable resin composition which contains (A) a radically polymerizable oligomer, (B) a radically polymerizable monomer and (C) a liquid rubber, and wherein: the radically polymerizable oligomer (A) contains a bromine-containing vinyl ester; and the content ratios of the bromine-containing vinyl ester, the radically polymerizable monomer (B) and the liquid rubber (C) relative to 100% by mass of all thermoplastic resins and elastomers including the radically polymerizable oligomer (A), the radically polymerizable monomer (B) and the liquid rubber (C) are 30-65% by mass, 25-50% by mass and 10-30% by mass, respectively. The present invention is also a radically curable resin composition which contains (A) a radically polymerizable oligomer, (B) a radically polymerizable monomer and (E) a thermoplastic resin and/or an elastomer, and wherein: the radically polymerizable oligomer (A) contains a bromine-containing vinyl ester; the thermoplastic resin and/or elastomer (E) contains (C) a liquid rubber and (D) a thermoplastic resin and/or an elastomer other than the liquid rubber (C); and the content ratios of the bromine-containing vinyl ester, the radically polymerizable monomer (B) and the thermoplastic resin and/or elastomer (E) relative to 100% by mass of the total of the radically polymerizable oligomer (A), the radically polymerizable monomer (B) and the thermoplastic resin and/or elastomer (E) are 30-65% by mass, 25-50% by mass and 10-30% by mass, respectively.

Description

Radical curable resin composition and cured product thereof

The present invention relates to a radical curable resin composition and a cured product thereof.

The radical curable resin can be handled in a liquid state, has good workability, and the cured product has excellent performance such as durability, water resistance, strength, etc., and thus is suitably used for various applications. . For example, in addition to lining materials, adhesives, electrical insulating paints, etc., in various fields such as building materials, housings, casting materials, machine parts, electronic / electric parts, vehicle parts, ship parts, aircraft parts, radical curable resins Construction materials and molded bodies are widely used. In recent years, studies for achieving low thermal expansion have been made from the current situation where high performance is required (see, for example, Patent Documents 1 and 2).

JP 2005-7783 A JP-A-8-318593

As described above, radical curable resins are widely used in various fields because they are excellent in various physical properties. In recent years, however, the physical properties required in various fields have become increasingly strict. For example, in the field of electrical and electronic components that are rapidly becoming smaller, lighter, and multifunctional, a higher level of dimensional stability is required than before, and excellent heat resistance is also required. However, the current situation is that conventional radical curable resins cannot sufficiently meet these requirements.

The present invention has been made in view of the above situation, and achieves low thermal expansion, has high dimensional stability, and can provide a cured product having excellent heat resistance and flame retardancy. It aims at providing the resin composition and its hardened | cured material.

The inventor paid attention to the fact that a resin composition containing a radically polymerizable oligomer and a radically polymerizable monomer has good handleability and workability, and that a cured product has various physical properties. And while advancing diligently, making a bromine-containing vinyl ester as a radically polymerizable oligomer essential, and a resin composition containing a radically polymerizable monomer and a liquid rubber in a predetermined ratio, respectively, can achieve low thermal expansion, It has been found that it provides a cured product having high dimensional stability and excellent heat resistance. Such a cured product is also useful in various fields in that it has excellent toughness, flame retardancy, and surface smoothness, and can exhibit various physical properties in a balanced manner while achieving low thermal expansion. . Thus, the inventors have conceived that the above problems can be solved brilliantly, and have completed the present invention.

That is, the first present invention is a radical curable resin composition comprising a radical polymerizable oligomer (A), a radical polymerizable monomer (B), and a liquid rubber (C), wherein the radical polymerizable oligomer (A ) Contains a bromine-containing vinyl ester, and the content ratio of the bromine-containing vinyl ester, the radical polymerizable monomer (B) and the liquid rubber (C) includes the radical polymerizable oligomer (A) and the radical polymerizable monomer. 30 to 65% by mass, 25 to 50% by mass, and 10 to 30% by mass with respect to 100% by mass of the total amount of the body (B) and all the thermoplastic resins and elastomers including the liquid rubber (C), respectively. It is a radical curable resin composition.

The radical curable resin composition further includes a thermoplastic resin and / or an elastomer (D) other than the liquid rubber (C), and the thermoplastic resin and / or the elastomer (D) includes polyvinyl acetate and polystyrene. And at least one selected from the group consisting of (meth) acrylate polymers.

The second aspect of the present invention is a radically curable resin composition comprising a radically polymerizable oligomer (A), a radically polymerizable monomer (B), and a thermoplastic resin and / or an elastomer (E), The radical polymerizable oligomer (A) contains a bromine-containing vinyl ester, and the thermoplastic resin and / or elastomer (E) is a liquid rubber (C) and a thermoplastic resin other than the liquid rubber (C) and / or Containing the elastomer (D), the bromine-containing vinyl ester, the radical polymerizable monomer (B), and the thermoplastic resin and / or the elastomer (E) are contained in a proportion of the radical polymerizable oligomer (A), 30 to 65% by mass and 25 to 50% by mass, respectively, with respect to 100% by mass of the total amount of the radical polymerizable monomer (B) and the thermoplastic resin and / or elastomer (E). And a radical curable resin composition is 10 to 30 mass%.

The thermoplastic resin and / or elastomer (D) is preferably at least one selected from the group consisting of polyvinyl acetate, polystyrene, and (meth) acrylate polymers.

The bromine-containing vinyl ester preferably has a glass transition temperature of 130 to 170 ° C. when the resin cured product contains 30% by mass of styrene.

The liquid rubber (C) preferably has a number average molecular weight of 60,000 or less.

The radical polymerizable monomer (B) preferably contains a compound having two or more polymerizable groups.

The radical polymerizable oligomer (A) further contains a bromine-free vinyl ester having a glass transition temperature of 130 to 170 ° C. and / or 30% by weight of styrene. It is preferable to include an unsaturated polyester having a glass transition temperature of 130 to 250 ° C. of the cured resin.

The present invention is also a cured product obtained by curing the radical curable resin composition.
Hereinafter, in the present specification, the term “the present invention” simply means the matters common to the first and second present inventions.

Since the radical curable resin composition of the present invention is configured as described above, the cured product achieves low thermal expansion, and has high dimensional stability, heat resistance, toughness, flame retardancy, and surface smoothness. Various physical properties such as can be exhibited in a well-balanced manner. Moreover, since it is liquid at normal temperature (25 degreeC), handling property and workability | operativity are favorable. Therefore, for example, in addition to lining materials, adhesives, electrical insulating paints, etc., it contributes greatly in various fields such as building materials, housings, machine parts, electronic / electric parts, vehicle parts, ship parts, aircraft parts, etc. Is.

Although the preferable form of this invention is demonstrated concretely below, this invention is not limited only to the following description, In the range which does not change the summary of this invention, it can change suitably and can apply. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more also corresponds to the preferable form of this invention.

[Radical curable resin composition]
The radical curable resin composition of the present invention (also simply referred to as “resin composition”) includes a radical polymerizable oligomer (A), a radical polymerizable monomer (B), and a liquid rubber (C) ( Hereinafter, it is also abbreviated as “component (A)”.) If necessary, one or more other components may be further contained, and one or two or more of each component may be used.

In the present specification, a mixture of the radical polymerizable oligomer (A) and the radical polymerizable monomer (B) is also collectively referred to as “radical polymerizable resin” or “radical curable resin”. The “total amount of the radical polymerizable oligomer (A), the radical polymerizable monomer (B), and all the thermoplastic resins and elastomers including the liquid rubber (C)” refers to the radical polymerizable oligomer ( A), a radical polymerizable monomer (B), a liquid rubber (C), and a component (D) described later (a thermoplastic resin and / or an elastomer (D) other than the liquid rubber (C)). In the case, it means the total amount of the component (D).

<(A) Radical polymerizable oligomer>
In the resin composition of the present invention, the radically polymerizable oligomer (A) essentially contains a bromine-containing vinyl ester (also referred to as brominated vinyl ester). The content of the bromine-containing vinyl ester is the components (A), (B) and (C) (however, when the component (D) described later is further included, the components (A), (B), (C) and ( The total amount of D)) is 30 to 65% by mass. By being within this range, it is possible to sufficiently exhibit the effects of the present invention. From the viewpoint of further developing the effect, the lower limit of the content ratio of the bromine-containing vinyl ester is preferably 35% by mass or more, more preferably 38% by mass or more, and the upper limit is preferably 63% by mass or less. Is 60% by mass or less.

In the present invention, the components (A), (B) and (C) (however, when the component (D) described later is further included, the components (A), (B), (C) and (D)) It is also preferable that the bromine atom content with respect to the total amount of 100% by mass is 10% by mass or more. Thereby, while being able to achieve low thermal expansion more, the flame retardance of hardened | cured material further improves. More preferably, it is 12 mass% or more, More preferably, it is 14 mass% or more. Moreover, from the viewpoint of increasing the compatibility with the radical polymerizable monomer (B), the upper limit is preferably 45% by mass or less. More preferably, it is 40 mass% or less, More preferably, it is 35 mass% or less.
In the present specification, the bromine content can be determined by the method described in Examples described later.

In the present invention, it is also suitable to use other radical polymerizable oligomers together with the bromine-containing vinyl ester as the radical polymerizable oligomer (A). Here, the bromine-containing vinyl ester preferably occupies 50 to 100% by mass, more preferably 60 to 100% by mass, and still more preferably 60 to 99% by mass in the total amount of 100% by mass of the radical polymerizable oligomer (A). Particularly preferred is 60 to 90% by mass.

Although it does not specifically limit as another radically polymerizable oligomer, From a viewpoint which can achieve low thermal expansion more, a bromine free vinyl ester and unsaturated polyester are preferable. Among these, as will be described later, a bromine-free vinyl ester having a glass transition temperature of 130 to 170 ° C. containing 30% by mass of styrene and a glass transition temperature of 130% by mass of styrene having a glass transition temperature of 130% by mass. An unsaturated polyester having a temperature of ˜250 ° C. is more preferable, and a form containing at least one of these is one of the preferred forms of the present invention.
Hereinafter, each radical polymerizable oligomer will be further described.

-Bromine-containing vinyl ester-
The bromine-containing vinyl ester is a compound in which a bromine atom is introduced into the main chain and / or side chain of the vinyl ester, and among them, a compound in which a bromine atom is introduced into the main chain of the vinyl ester is preferable.

The bromine-containing vinyl ester preferably has a glass transition temperature (also referred to as Tg) of 130 to 170 ° C. of a cured resin product containing 30% by mass of styrene. When such a bromine-containing vinyl ester is contained in the above-described content ratio, the resulting cured product can be further reduced in thermal expansion and further improved in heat resistance and surface smoothness. From the viewpoint of more manifesting this effect, the Tg of the cured product is more preferably 135 ° C. or higher, further preferably 140 ° C. or higher, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.
In the present specification, the Tg of the cured resin containing 30% by mass of styrene means the Tg of the cured product when the resin is composed of 70% by mass of a bromine-containing vinyl ester and 30% by mass of styrene. It can obtain | require by the method as described in the Example mentioned later.

The bromine-containing vinyl ester is, for example, a compound obtained by reaction of an epoxy compound containing bromine (also referred to as brominated epoxy compound or bromine-containing epoxy compound) with an unsaturated monobasic acid, or brominated with a bromine-containing epoxy compound. A compound obtained by reacting an epoxy compound having a high molecular weight with bisphenol A and an unsaturated monobasic acid is preferred. You may use 1 type, or 2 or more types for each raw material used by this reaction. Moreover, you may use together the epoxy compound which does not contain a bromine as needed.

In the reaction of adding an unsaturated monobasic acid to the epoxy compound, the amount of each raw material is set so that the equivalent of the carboxyl group of the unsaturated monobasic acid to the epoxy group of the epoxy compound is 0.9 to 1.2. It is preferable to do. The reaction temperature for the above reaction is not particularly limited, but is preferably 80 to 130 ° C. For the above reaction, a reaction catalyst, a polymerization inhibitor or the like may be appropriately used in the presence of air as necessary.
The above reaction is preferably carried out in substantially the same manner as the vinyl ester synthesis reaction method described in, for example, Japanese Patent No. 4768161 [0028] to [0035].

Although it does not specifically limit as said epoxy compound, The compound which has at least 2 or more epoxy group in a molecule | numerator is suitable. For example, bisphenol type epoxy compound, novolak type epoxy compound, aliphatic type epoxy compound, alicyclic epoxy compound, monocyclic epoxy compound, amine type epoxy compound, etc., such as mechanical strength, corrosion resistance, heat resistance, etc. From the viewpoint, a bisphenol type epoxy compound is preferable. In order to give a bromine-containing vinyl ester, it is preferable to use at least a brominated epoxy compound in which one or more bromine atoms are introduced into these epoxy compounds for the reaction with an unsaturated monobasic acid.

Examples of the bisphenol type epoxy compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol AD type epoxy compound, and a bisphenol S type epoxy compound. Examples of novolak type epoxy compounds include phenol novolac type epoxy compounds and cresol novolac type epoxy compounds. Examples of the aliphatic epoxy compound include a hydrogenated bisphenol A type epoxy compound and a propylene glycol polyglycidyl ether compound. Examples of the alicyclic epoxy compound include alicyclic diepoxy acetal, dicyclopentadiene dioxide, vinyl hexene dioxide, vinyl hexene dioxide, and glycidyl methacrylate. In addition, a phenol compound such as bisphenol A, or an epoxy compound modified with a dibasic acid such as adipic acid, sebacic acid, dimer acid, or liquid nitrile rubber can also be used.

As the brominated epoxy compound, for example, a compound in which one or more bromine atoms are introduced into the above-described epoxy compound is preferable, among which a brominated bisphenol type epoxy compound or a brominated novolak type epoxy compound is more preferable. More preferred is a brominated bisphenol type epoxy compound, and particularly preferred is the following general formula (1):

Wherein Y represents —C (CH ₃ ) ₂ —, —CH ₂ —, —O—, —S— or —S (O) ₂ —, a, b, c and d are bromine atoms And is the same or different and is an integer of 0 to 4, provided that a = b = c = d = 0, and m represents a number of 0 to 5.) It is.

Among the compounds represented by the general formula (1), a compound in which Y represents —C (CH ₃ ) ₂ — (that is, a brominated bisphenol A type epoxy compound) is preferable, and a, b is more preferable. , C and d are all 2 compounds (that is, tetrabromobisphenol A type epoxy compound). An epoxy compound containing a bisphenol skeleton and a brominated bisphenol skeleton in one molecule can also be used as the brominated bisphenol type epoxy compound.

Examples of the unsaturated monobasic acid include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and sorbic acid; dibasic acid anhydrides and alcohols having at least one unsaturated group in the molecule; And the like. Examples of the dibasic acid anhydride include aliphatic or aromatic dicarboxylic acids such as maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Acrylic acid and methacrylic acid are preferable from the viewpoint of achieving low thermal expansion more preferably methacrylic acid.

Among the bromine-containing vinyl esters, particularly preferred is a compound obtained by reacting an epoxy compound containing a compound represented by the above general formula (1) (in particular, a tetrabromobisphenol A type epoxy compound is preferred) with acrylic acid. It is. Since such a compound has many crosslinking points, the cured product Tg can satisfy the preferred range described above. Therefore, in the obtained cured product, low thermal expansion can be further achieved, and heat resistance and surface smoothness are further improved.

The number average molecular weight of the bromine-containing vinyl ester is not particularly limited, but is preferably 300 to 2000, for example. Thereby, in the hardened | cured material obtained, low thermal expansion can be achieved more.

-Bromine-free vinyl ester-
As described above, the resin composition preferably contains a bromine-free vinyl ester in addition to the bromine-containing vinyl ester. A bromine-free vinyl ester is a vinyl ester containing no bromine atom.

The bromine-free vinyl ester preferably has a glass transition temperature (Tg) of 130 to 170 ° C. of the resin cured product containing 30% by mass of styrene. That is, when the resin is composed of 70% by mass of a bromine-free vinyl ester and 30% by mass of styrene, the Tg of the cured product is preferably 130 to 170 ° C. When such a bromine-free vinyl ester is used, the resulting cured product can be further reduced in thermal expansion and further improved in heat resistance and surface smoothness. From the viewpoint of more manifesting this effect, the Tg of the cured product is more preferably 135 ° C. or higher, further preferably 140 ° C. or higher, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.

The bromine-free vinyl ester can be obtained, for example, by a reaction between an epoxy compound and an unsaturated monobasic acid in the same manner as the bromine-containing vinyl ester described above except that a brominated epoxy compound is not used. Preferred conditions for the reaction and preferred examples of the epoxy compound used are as described above.

The number average molecular weight of the bromine-free vinyl ester is not particularly limited, but is preferably 200 to 2000, for example. More preferably, it is 300 to 1000.

-Unsaturated polyester-
As described above, the resin composition preferably contains an unsaturated polyester in addition to the bromine-containing vinyl ester.

The unsaturated polyester preferably has a glass transition temperature (Tg) of 130 ° C. to 250 ° C. of the cured resin product containing 30% by mass of styrene. When such an unsaturated polyester is used, the resulting cured product can be further reduced in thermal expansion and further improved in heat resistance and surface smoothness. From the viewpoint of more manifesting this effect, the Tg of the cured product is more preferably 140 ° C. or higher.

The unsaturated polyester is, for example, a compound obtained by a condensation reaction between a polybasic acid and a polyhydric alcohol. Each raw material used in this reaction may be used alone or in combination of two or more. Further, it may be modified with dicyclopentadiene (DCPD).

In the reaction between the polybasic acid and the polyhydric alcohol, the amount ratio (the total amount of polybasic acid / polyhydric alcohol and epoxy compound) of these may be 10/8 to 10/12 (mol%). Is preferred. Moreover, the said reaction is not specifically limited, What is necessary is just to perform by a normal synthesis means. In general, the reaction is carried out under an inert gas atmosphere under heating, and the reaction proceeds while removing by-product water. Further, in an inert gas atmosphere, heating to a temperature range of 120 to 250 ° C. in the presence or absence of a water azeotropic solvent such as toluene or xylene and an esterification catalyst such as tin oxalate, the desired acid You may dehydrate-condense until it becomes a value or a viscosity (molecular weight). The temperature range is more preferably 150 to 220 ° C.

The polybasic acid preferably contains an α, β-unsaturated dibasic acid. Examples of the α, β-unsaturated dibasic acid include maleic anhydride, maleic acid, fumaric acid, itaconic acid and the like. Of these, maleic anhydride, maleic acid and / or fumaric acid are preferred. Further, it may contain a saturated polybasic acid, and examples of the saturated polybasic acid include malonic acid, succinic acid, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, and heptic acid. Can be mentioned.

Examples of the polyhydric alcohol include glycol (also referred to as diol) and an epoxy compound.
Examples of the glycol include alkyl-substituted alkylene glycols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, and neopentyl glycol; diethylene glycol, dipropylene glycol, triethylene glycol Condensates of alkylene glycols such as bisphenol A, hydrogenated bisphenol A, alkylene oxide adducts of bisphenol A, bisphenols such as alkylene oxide adducts of hydrogenated bisphenol A; trimethylolpropane monoallyl ether, pentaerythritol diallyl Allyl group-containing alcohols such as ethers; Trivalent or higher alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol; And the like.
Examples of the epoxy compound include ethylene oxide, propylene oxide, butylene oxide, allyl glycidyl ether, glycidyl (meth) acrylate, and glycidyl ethers of bisphenol A.

The number average molecular weight of the unsaturated polyester is not particularly limited, but is preferably 600 to 10,000, for example. More preferably, it is 1000 to 5000.

The unsaturated polyester preferably has an ester acid value of 1 to 50 mgKOH / g. More preferably, it is 5 to 30 mg KOH / g.
In this specification, an ester acid value can be calculated | required based on the method of JISK6901: 2008, for example.

<(B) Radical polymerizable monomer>
In the resin composition of the present invention, the content of the radically polymerizable monomer (B) is such that the components (A), (B) and (C) (provided that the component (D) described later is further included) The total amount of (A), (B), (C) and (D)) is 25 to 50% by mass with respect to 100% by mass. Within this range, a low thermal expansion coefficient can be achieved, a high degree of dimensional stability can be achieved, and a cured product with excellent heat resistance, toughness, flame retardancy, and surface smoothness can be provided, and resin Handling property and workability when using the composition are improved. Further, the amount of residual monomer is reduced, and it becomes possible to suppress the emission from the molded product.

The radical polymerizable monomer is not particularly limited, and is a compound having one polymerizable group in one molecule (also referred to as a monofunctional compound) or a compound having two or more polymerizable groups (polyfunctional compound). Any of these may also be used suitably. Among them, it is preferable to use at least a polyfunctional compound from the viewpoints of further improving the toughness and heat resistance of the cured product and further reducing the coefficient of thermal expansion. Thus, the form in which the radical polymerizable monomer includes a compound having two or more polymerizable groups is one of the preferred forms of the present invention. Moreover, it is also preferable to contain styrene as described later, and it is most preferable to use styrene and a polyfunctional compound in combination.
Hereinafter, these radical polymerizable monomers will be further described.

-Monofunctional compounds-
The monofunctional compound is not particularly limited. For example, aromatic monomers such as styrene, α-methylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, and vinyltoluene; non-functional such as (meth) acrylic acid Saturated monocarboxylic acids; vinyl esters such as vinyl acetate and vinyl adipate; monofunctional (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth) acrylate; Can be mentioned. Among these, a monomer containing an aromatic ring is preferable from the viewpoint of excellent polymerization reactivity and compatibility. More preferred is styrene, vinyltoluene and / or benzyl (meth) acrylate, and even more preferred is styrene. Thereby, the hardened | cured material which is further excellent by heat resistance, toughness, a flame retardance, etc. is obtained.

-Multifunctional compounds-
Although it does not specifically limit as a polyfunctional compound, For example, aromatic monomers, such as divinylbenzene, diallyl phthalate, and diallyl benzene phosphonate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di ( (Meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate Di (meth) acrylates of alkane polyols having 2 to 12 carbon atoms: trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, Examples of the trivalent or higher poly (meth) acrylate of an alkane polyol having 3 to 12 carbon atoms such as dipentaerythritol hexa (meth) acrylate; diallyl phthalate, diallyl phthalate prepolymer; triallyl cyanurate; Among these, from the viewpoint of lowering thermal expansion, improving heat resistance and toughness, divalent or higher (meth) acrylates are preferable, and trivalent or higher poly (meth) acrylates are more preferable.

<(C) Liquid rubber>
In the resin composition of the first aspect of the present invention, the content ratio of the liquid rubber (C) is the components (A), (B) and (C) (provided that the component (D) The total amount of A), (B), (C), and (D)) is 10 to 30% by mass with respect to 100% by mass. Within this range, a low thermal expansion coefficient can be achieved, a high degree of dimensional stability can be achieved, and a cured product with excellent heat resistance, toughness, flame retardancy, and surface smoothness can be provided, and resin Handling property and workability when using the composition are improved. From the viewpoint of further manifesting these effects, the lower limit of the content ratio of the component (C) is preferably 11% by mass or more, and the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less. It is.

The liquid rubber (C) preferably has a number average molecular weight of 60,000 or less. Thereby, it is excellent in compatibility with other components, the toughness and surface smoothness of the cured product are further improved, and the resin composition is more excellent in storage stability and handleability. More preferably, it is 50,000 or less. The lower limit of the number average molecular weight is not particularly limited, but is preferably 50 or more, for example. Especially, it is preferable that it is 500 or more from a viewpoint of the toughness improvement of hardened | cured material, More preferably, it is 1500 or more.

The liquid rubber (C) preferably has an 80 ° C. viscosity of 15 Pa · s or less. More preferably, it is 13 Pa.s or less, More preferably, it is 10 Pa.s or less.
In addition, the 80 degreeC viscosity of a compound can be calculated | required by the method as described in the Example mentioned later.

Specifically, the liquid rubber (C) is preferably one that becomes liquid at room temperature (25 ° C.), for example, liquid polyisoprene, liquid polyisobutylene, liquid polybutadiene, liquid butadiene rubber, liquid butyl rubber, liquid styrene butadiene rubber, Examples thereof include liquid nitrile butadiene rubber, liquid acrylonitrile rubber, liquid chloroprene rubber, liquid polysulfide, liquid phenol resin, liquid epoxy resin, and liquid xylene resin. Among these, liquid polyisoprene, liquid polybutadiene, liquid acrylic lithyl rubber, and liquid xylene resin are preferable. Among liquid polybutadienes, compounds having hydroxyl groups and / or carboxylic acid groups at both ends are preferred.
Further, as the liquid rubber (C), a compound obtained by acid-modifying the liquid rubber or a compound obtained by polymerizing an acid component on the liquid rubber is also preferable. Examples thereof include carboxyl group-terminated butadiene acrylonitrile rubber, maleic acid-modified isoprene, and acrylonitrile / butadiene / methacrylic acid copolymer.

<(D) Thermoplastic resin and / or elastomer>
The resin composition of the present invention may also contain one or more thermoplastic resins and / or elastomers (D) (also referred to as component (D)) other than the liquid rubber (C). The elastomer includes rubber and thermoplastic elastomer. Moreover, the composition containing liquid rubber (C) and a thermoplastic resin and / or elastomer (D) is also called a thermoplastic resin and / or elastomer (E).

When the resin composition of this invention contains a component (D), it is preferable that the content rate is 50 mass% or less among 100 mass% of total amounts of a component (C) and (D). In other words, it is preferable that the component (C) is 50% by mass or more in the total amount of 100% by mass of the components (C) and (D). More preferably, it is 75 mass% or more, More preferably, it is 90 mass% or more.

The resin composition of the present invention preferably contains a liquid rubber (C) and a thermoplastic resin and / or an elastomer (D). When the resin composition of the present invention contains the liquid rubber (C) and the thermoplastic resin and / or the elastomer (D), the radically polymerizable oligomer (A) and the radically polymerizable monomer (B). Compatibility is improved, and separation due to aging of these mixtures can be more sufficiently suppressed. Moreover, in order to suppress more fully that liquid rubber (C) isolate | separates and cracks at the time of hardening of a resin composition, the addition amount of liquid rubber (C) may be reduced. Also in this case, when the resin composition contains a thermoplastic resin and / or elastomer (D) having good compatibility, the linear expansion coefficient can be more sufficiently reduced, and the dimensional stability can be further improved. it can.
That is, the second present invention is a radical curable resin composition comprising a radical polymerizable oligomer (A), a radical polymerizable monomer (B), and a thermoplastic resin and / or an elastomer (E). The radical polymerizable oligomer (A) contains a bromine-containing vinyl ester, and the thermoplastic resin and / or elastomer (E) is a liquid rubber (C) and a thermoplastic resin other than the liquid rubber (C) and / or Or the elastomer (D), and the bromine-containing vinyl ester, the radical polymerizable monomer (B), and the thermoplastic resin and / or elastomer (E) are contained in the radical polymerizable oligomer (A). , 30 to 65% by mass and 25 to 5%, respectively, with respect to 100% by mass of the total amount of the radical polymerizable monomer (B) and the thermoplastic resin and / or elastomer (E). It is a radical curable resin composition by mass% and 10 to 30 mass%.

The content of the thermoplastic resin and / or elastomer (E) in the second aspect of the present invention is as follows: radical polymerizable oligomer (A), radical polymerizable monomer (B), thermoplastic resin and / or elastomer (E ) With respect to a total amount of 100% by mass, and preferably 10 to 25% by mass, more preferably 10 to 20% by mass.

The thermoplastic resin and / or elastomer is not particularly limited. For example, polystyrene, polyethylene, polyvinyl acetate, cross-linked polystyrene, polyvinyl acetate-polystyrene block copolymer, polyphase structure polymer such as acrylic / styrene, cross-linked / non-cross-linked From the viewpoint of more fully exhibiting the effects of the present invention, a compound having excellent compatibility with the above-described radical polymerizable oligomer (A) is used. It is preferable. Specifically, at least one compound selected from the group consisting of polyvinyl acetate, polystyrene, and (meth) acrylate polymers is preferable. The polystyrene may be a styrene polymer. Below, a polyvinyl acetate and a (meth) acrylate type polymer are further demonstrated.

-Polyvinyl acetate-
Polyvinyl acetate is not particularly limited. For example, in addition to vinyl acetate homopolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-acrylate copolymer, vinyl acetate-acrylate copolymer Examples thereof include copolymers such as coalescence. Moreover, the modified polyvinyl acetate which carried out the modification process may be sufficient. Among these, vinyl acetate homopolymer and acid-modified polyvinyl acetate (also referred to as acid-modified polyvinyl acetate) are preferable. Polyvinyl acetate which is dissolved in styrene and has improved workability is also preferably used.

-(Meth) acrylate polymer-
Examples of the (meth) acrylate polymer include acrylic resin, methyl methacrylate butadiene styrene copolymer, styrene methyl methacrylate maleic anhydride copolymer, and ethylene acrylate copolymer.

There is no restriction | limiting in particular as said acrylic resin, What was synthesize | combined suitably may be used and a commercial item may be used. Among these, when synthesizing, those obtained by polymerizing or copolymerizing monomers exemplified below can be used.
That is, alkyl acrylate, alkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl, etc.); Hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate; Epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether; acrylic acid and methacrylic acid Carboxy groups such as itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid or salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.) Is a monomer having a salt thereof; acrylamide, methacrylamide, N-alkyl acrylamide, N-alkyl methacrylamide, N, N-dialkyl acrylamide, N, N-dialkyl methacrylate (alkyl groups include methyl, ethyl, n- Propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.), N-alkoxyacrylamide, N-alkoxymethacrylamide, N, N-dialkoxyacrylamide, N, N-dialkoxymethacrylamide (alkoxy groups include methoxy, ethoxy, butoxy, isobutoxy, etc.), acryloylmorpholine, N-methylolacrylamide, N-methylolmethacrylamide, N-phenylacrylic Monomers having an amide group such as amide and N-phenylmethacrylamide; monomers of acid anhydrides such as maleic anhydride and itaconic anhydride; 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, Oxazoline groups such as 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline Containing monomers: methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, vinyl isocyanate, allyl isocyanate, styrene, α-methylstyrene, vinyl methyl ether, vinyl ethyl ether, vinyl trialkoxysilane, alkyl maleic acid monoester Alkyl fumaric acid monoester, alkyl itaconic acid monoester, acrylonitrile, methacrylonitrile, vinylidene chloride, ethylene, propylene, vinyl chloride, vinyl acetate, butadiene and the like. These may be used individually by 1 type and may use 2 or more types together. As commercially available products, for example, Dialnal BR-77 (T), Dialnal BR-106, Dialnal MB-7601, Dialnal MB-7602, Dialnal MB-7603 (all manufactured by Mitsubishi Rayon Co., Ltd.), etc. Can be used.

The resin composition of the present invention is a composition comprising only components (A), (B) and (C) (however, when component (D) is further included, components (A), (B) and (C) And (D) is preferably a composition having a viscosity at 25 ° C. of 50 to 3000 mPa · s. Thereby, workability | operativity and handleability are improved more and it becomes useful by various uses. The lower limit of the 25 ° C. viscosity is more preferably 50 mPa · s or more, still more preferably 100 mPa · s or more, and the upper limit is more preferably 6000 mPa · s or less, and still more preferably 1000 mPa · s or less. The 25 ° C. viscosity of the composition can be determined by, for example, a Brookfield viscometer.

The resin composition of the present invention is preferably used by being cured as a resin component of a molding material. For example, the resin composition can be used as a molding material substantially as it is or as a coating film-forming component. You can do it. In particular, when used as a molding material, it is preferable to mix and use an inorganic filler and / or a fiber reinforcing material. A molding material containing these is excellent in moldability and excellent in physical properties and flame retardancy. This is one of the preferred embodiments of the present invention.

The inorganic filler is not particularly limited. For example, aluminum hydroxide, calcium carbonate, barium sulfate, alumina, metal powder, kaolin, talc, milled fiber, quartz sand, diatomaceous earth, crystalline silica, fused silica, glass powder, clay, etc. And can be selected in a timely manner according to the intended use. Among these, aluminum hydroxide is preferable in that it has excellent moldability and also has an effect of improving flame retardancy.

The inorganic filler is preferably blended in the range of 30 to 400 parts by mass with respect to 100 parts by mass of the radical polymerizable resin.

The material of the fiber reinforcing material is not particularly limited, for example, inorganic fibers such as glass fiber and carbon fiber; polyvinyl alcohol-based, polyester-based, polyamide-based (including wholly aromatic-based), fluororesin-based, phenol-based various organic materials Fibers can be appropriately selected and used. The shape of the fiber reinforcement may be any shape such as cross; mat shape such as chopped strand mat, preformable mat, continuous strand mat, surfacing mat; chop shape; roving shape; nonwoven fabric shape; paper shape; There is no problem.

The fiber reinforcing material is pre-determined according to the shape of the target molded article, and used by impregnating the radical curable resin composition before curing, or chopping into the radical curable resin composition. The reinforcing fibers can be mixed to obtain a molding material, which can be used for molding into a desired shape.

The fiber reinforcement is preferably used in the range of 20 to 300 parts by mass with respect to 100 parts by mass of the radical polymerizable resin. If the amount is less than 20 parts by mass, the molded product may have insufficient strength. If the amount exceeds 300 parts by mass, the water resistance and chemical resistance of the molded product may be deteriorated. A more preferable amount of the fiber reinforcing material is 30 to 250 parts by mass.

When actually curing and using the resin composition of the present invention, a thermal polymerization initiator, a photopolymerization initiator, a photosensitizer, etc. are blended and heated, or ultraviolet rays, electron beams, radiation, etc. It is sufficient to irradiate the active energy ray.

As the thermal polymerization initiator, known ones can be used. Specifically, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxyneodikenate, lauryl peroxide, benzoylper Oxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexanone, cyclohexanone peroxide, t-butylperoxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-teto Methyl butyl hydroperoxide, cumene hydroperoxide, organic peroxides such as t- butyl hydroperoxide; azobisisobutyronitrile, azo compounds such as azo-bis-diethyl valeronitrile and the like.

It is also effective to mix a curing accelerator during thermal polymerization. Typical examples of the curing accelerator include metal soaps such as cobalt naphthenate and cobalt octylate; tertiary amines; and the like. These may be appropriately selected depending on the combination with the thermal polymerization initiator used. The amount of the thermal polymerization initiator used is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the radical polymerizable resin.

Known photopolymerization initiators are not particularly limited and can be used. The amount of the photopolymerization initiator used is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the radical polymerizable resin. Of course, it is also effective to use a known photosensitizer in combination.

In order to cure the radical curable resin composition and the molding material containing the photopolymerization initiator, the molding material may be irradiated with active energy rays such as ultraviolet rays, electron beams, and radiation using a known apparatus. As the ultraviolet irradiation device, a device equipped with a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, or the like can be used. Examples of the electron beam irradiation apparatus include a scanning electro curtain type, a curtain type, a laminar type, an area beam type, a broad beam type, and a pulse beam type.

In using the resin composition of the present invention as a molding material, in addition to the inorganic filler and the fiber reinforcing material described above, a phosphorus-containing compound, a nitrogen-containing compound, red phosphorus, antimony oxide, a boron compound, or the like is used as a flame retardant or flame retardant. It is also possible to mix as an auxiliary agent. Furthermore, pigments, colorants, flame retardants, antifoaming agents, wetting agents, dispersants, rust inhibitors, antistatic agents, ultraviolet absorbers, antioxidants, and the like can be blended as necessary.

[Cured product]
The radical curable resin composition of the present invention can achieve a low coefficient of thermal expansion, has a high degree of dimensional stability, and can give a cured product having excellent heat resistance, toughness, flame retardancy, and surface smoothness. . Therefore, it can be effectively used in various fields such as adhesives and electrical insulating paints, and the resin composition can be used as it is or in combination with the above-mentioned inorganic fillers, fiber reinforcements, etc. It can be used for a wide range of parts such as casting materials, mechanical parts, electronic / electrical parts, vehicles, ships, aircrafts, etc. A cured product obtained by curing such a radical curable resin composition (also referred to as a cured product of the resin composition) is also included in the present invention.

It does not specifically limit as a hardening method of the said resin composition, For example, it is suitable to mix and harden a hardening | curing agent with a resin composition just before construction (or just before shaping | molding). Further, it can be cured at room temperature (room temperature) by a combination of a curing accelerator and a curing agent. Examples of the combination of the curing accelerator and the curing agent include cobalt octenoate and cumene hydroperoxide. Further, it is preferably carried out by heat curing, and the curing temperature is preferably 50 to 190 ° C., more preferably 80 to 180 ° C. The curing time is preferably 1 to 180 minutes, more preferably 10 to 100 minutes. By curing under such conditions, the curing is completed and the unreacted radical polymerizable monomer (B) is consumed.

The cured product preferably has a linear expansion coefficient of 40 × 10 ⁻⁶ / K or less when it is a cured product containing an inorganic filler. More preferably, it is 39 × 10 ⁻⁶ / K or less, further preferably 38 × 10 ⁻⁶ / K or less, and particularly preferably 37 × 10 ⁻⁶ / K or less. By using the resin composition of the present invention, a low expansion coefficient can be achieved in this way, so that a cured product having excellent physical properties such as dimensional stability and smoothness and a high appearance can be provided.
In this specification, the linear expansion coefficient of hardened | cured material can be calculated | required according to the measuring method as described in the Example mentioned later, for example.

Examples of the shape of the cured product include a coating film shape and a molded product (also referred to as a molded product) shape. Below, the method of obtaining these is further demonstrated.

-Coating film-
When the cured product is a coating film, the method for forming the coating film is not particularly limited. For example, a curing agent is mixed with the resin composition, applied to a substrate, and then cured to form a coating film. Method: When a mat-like fiber reinforcing material is used, a curing agent is mixed into the resin composition, the fiber reinforcing material is impregnated by hand layup or the like to form a coating material, and a coating is formed by curing. Method; and the like.

The base material is not particularly limited, and examples thereof include inorganic base materials such as glass, slate, concrete, mortar, ceramic, and stone materials; metals made of aluminum, iron, zinc, tin, copper, titanium, stainless steel, tinplate, tin, and the like. Metal base material such as plate, metal plated with zinc, copper, chromium, etc., metal treated with chromic acid, phosphoric acid, etc .; polyethylene, polyvinyl chloride, ABS (acrylonitrile-butadiene-styrene), FRP ( Textile reinforced plastic), polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polystyrene, polypropylene, polyester, polyolefin, acrylic resin, epoxy resin, nylon resin and other plastic substrates; synthetic leather; cypress, cedar, pine, plywood, etc. ; Organic materials such as fiber and paper; etc. And the like. These substrates may be coated with a commonly used primer or a coating material such as an undercoat, an intermediate coat, or a top coat such as a metallic base before the resin composition is coated.

As a method of applying the resin composition to the substrate, it may be appropriately set depending on the application, etc., but as the coating method, for example, dip coating, brush coating, roll brush coating, spray coating, roll coating, spin coating, Examples include dip coating, spin coating, bar coating, flow coating, electrostatic coating, die coating, film lamination, and gel coating.

-Molding-
When the cured product is a molded product, the method for obtaining the molded product is not particularly limited. For example, a normal casting method, compression molding method, centrifugal molding method, injection molding method, transfer molding method, injection molding method An extrusion method or the like can be employed.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “parts” means “parts by mass (parts by weight)”, and “%” means “% by mass”.
In addition, the measurement / evaluation methods of various physical properties employed in the following examples and the like are described below.

<Physical property evaluation>
1. Glass transition temperature (Tg) of cured resin of component (A) (Tg of cured resin containing 30% by mass of styrene)
After synthesizing the radical polymerizable oligomer (A), styrene as a radical polymerizable monomer was added to prepare a radical polymerizable resin containing 30% styrene. To 100 parts of this radical polymerizable resin, 1.0 part of a curing agent (80% cumene hydroperoxide (Nippon Yushi Co., Ltd., Park Mill H-80)) was added, mixed, and then a 3 mm thick silicon rubber spacer. Was cast into a container sandwiched between two glass plates (70 mm × 150 mm). After heating at 100 ° C. for 60 minutes in a hot air drier, the radical polymerizable resin was cured by further heating at 175 ° C. for 30 minutes to obtain a cured resin product of 65 mm × 140 mm (thickness 3 mm). A test piece of 5 mm × 5 mm × 3 mm was cut from the cured resin, and Tg was measured with a thermomechanical analyzer (manufactured by Hitachi High-Tech Science Co., Ltd., EXSTAR TMA SS7100). The temperature was raised from room temperature to 230 ° C. at a rate of temperature increase of 5 ° C./min, and the glass transition point (Tg) was determined from the inflection point of the measured linear expansion coefficient (α).

2. The bromine content of brominated epoxy compounds (tetrabromobisphenol A type epoxy resin used in Synthesis Examples 1 to 4) and tetrabromobisphenol A (used in Synthesis Example 4), which are raw materials for bromine content, are the test tables for each product. From the values, they were 48.0% and 58.8%, respectively.
From this bromine content and the amount of each raw material used during the synthesis, the bromine content in the radical polymerizable resin comprising the radical polymerizable oligomer (A) (bromine-containing vinyl ester) and 30% styrene (in each synthesis example) And bromine content (described in Table 1 or 2) with respect to 100% by mass of the total amount of components (A) to (D).

3. The compound (or mixture) to be measured for the molecular weight of the compound was dissolved in a THF (tetrahydrofuran) solvent, and the molecular weight was determined by GPC (gel permeation chromatography). At that time, a calibration curve was prepared using a commercially available monodisperse standard polystyrene, and obtained based on the following conversion method.
Apparatus: HLC-8320GPC (manufactured by Tosoh Corporation), detector: differential refractometer column: TSKgelSuperH2000, TSKgelSuperH2500, TSKgelSuperH3000 (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample concentration: 1% by weight in solid content
Mobile phase: THF
Molecular weight conversion: Polystyrene conversion (general-purpose calibration method)

4). Sample 200ml in a 200ml glass bottle with a viscosity lid at 80 ° C for component (C), left in a hot air drier adjusted to 80 ° C for 90 minutes, and after stirring the sample, DV-11 + Pro (manufactured by Brookfield) Was used to measure the viscosity of component (C) at 80 ° C.

5. Evaluation of linear expansion coefficient, flame retardancy, water resistance and surface smoothness of cured compound (1) Linear expansion coefficient (α)
To 100 parts of the resin composition, 150 parts of aluminum hydroxide (Showa Denko, Heidilite H-320) and 1.0 part of 80% cumene hydroperoxide (Nippon Yushi Co., Ltd., Park Mill H-80) are added and mixed. Thereafter, vacuum degassing was performed to prepare a compound.
The compound is added to the above 1. Was cured by the same method as above to obtain a compound cured product having a thickness of 3 mm. The glass transition point (Tg) was measured with a thermomechanical analyzer using a test piece obtained by cutting from the cured product.

(2) Flame retardancy For the cured compound obtained by the above “(1) Linear expansion coefficient (α)”, a combustion test in accordance with UL 94 (Underwriters Laboratories Inc.) UL 94 standard (plastic material flammability test) Went. Those satisfying the V-0 standard were designated as “◯”, and those not satisfying were designated as “x”.

(3) Water resistance A specimen having a length of 75 mm and a width of 25 mm was cut out from the compound cured product obtained in the above “(1) linear expansion coefficient (α)”, and the boiling water absorption rate defined in JIS K6919 (2009) was measured. In accordance with the law, the appearance change of the test piece was visually observed after being immersed in boiling distilled water for 60 minutes. A case where no change in appearance was observed was indicated by “◯”, and a case where an appearance change such as whitening or swelling due to water absorption was observed was indicated by “X”.

(4) Surface smoothness About the compound hardened | cured material obtained by said "(1) linear expansion coefficient ((alpha))", surface smoothness was evaluated by visual observation and finger touch. The case where irregularities were not recognized by both visual observation and finger touch was indicated as “◯”, and the case where irregularities were observed visually or by touch was indicated as “x”.

6). Heat resistance evaluation (cured resin composition)
1 part by weight of 80% cumene hydroperoxide as a curing agent was added to 100 parts of the resin composition and mixed. Above 1. In the same manner as above, casting was performed to obtain a cured resin composition of 65 mm × 140 mm (thickness 3 mm). A glass transition point (Tg) was measured by a thermomechanical analyzer using a test piece obtained by cutting from the cured product. This Tg was used as an index of heat resistance.

Synthesis Example 1: Synthesis of Brominated Vinyl Ester Resin (1) Tetrabromobisphenol A type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd.) was placed in a reaction vessel (flask) equipped with a stirrer, reflux condenser, gas inlet tube and thermometer. "Epototo (R) YDB-400, epoxy equivalent 400) 1200 parts, 260 parts of methacrylic acid, 2.9 parts of triethylamine, and 0.3 parts of hydroquinone were charged and reacted at 110 ° C for 8 hours while introducing air. As a result, a brominated vinyl ester having an acid value of 2.0 mgKOH / g was obtained.
By adding 626 parts of styrene to the resulting brominated vinyl ester, a bromine-containing vinyl ester resin (1) containing 30% by mass of styrene (bromine content: 27.6%) was obtained. The glass transition temperature of the cured resin was 147 ° C.

Synthesis Example 2: Brominated vinyl ester resin (2)
In Synthesis Example 1, a bromine-containing vinyl ester resin (2) (bromine content 27.6%) containing 30% by mass of vinyl toluene was obtained by the same method except that styrene was changed to vinyl toluene. The glass transition temperature of the cured resin was 147 ° C.

Synthesis Example 3: Brominated vinyl ester resin (3)
In Synthesis Example 1, a bromine-containing vinyl ester resin (3) (bromine content 27.6%) containing 30% by mass of vinyl toluene was obtained by the same method except that styrene was changed to benzyl methacrylate. The glass transition temperature of the cured resin was 140 ° C.

Synthesis Example 4: Synthesis of Brominated Vinyl Ester Resin (4) In the same reaction vessel (flask) as in Synthesis Example 1, 285 parts of bisphenol A (BPA; “Bisphenol A” manufactured by Mitsui Chemicals), tetrabromobisphenol A (Tosoh Corporation) 408 parts bisphenol A type epoxy resin (Mitsui Chemicals "Epomic (R) R-139S", epoxy equivalent 185) 920 parts, tetrabromobisphenol A type epoxy resin (new) 804 parts of "Epototo (R) YDB-400" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 400), 5.2 parts of triethylamine, and 0.52 parts of hydroquinone were charged and reacted at 110 ° C. for 4 hours while introducing air. . 263 parts of methacrylic acid was added and further reacted at 110 ° C. for 5 hours to obtain a brominated vinyl ester having an acid value of 4.0 mgKOH / g.
By adding 1149 parts of styrene to this brominated vinyl ester, a bromine-containing vinyl ester resin (4) containing 30% by mass of styrene (bromine content: 16.3%) was obtained. The glass transition temperature of the cured resin was 122 ° C.

Synthesis Example 5: Synthesis of bromine-free vinyl ester resin (1) In the same reaction vessel (flask) as in Synthesis Example 1, 793 parts of epoxy resin (“Epomic® R-139S” manufactured by Mitsui Chemicals), methacrylic acid A vinyl ester having an acid value of 5.6 mg KOH / g was obtained by charging 387 parts, 1 part of hydroquinone and 6 parts of triethylamine and reacting at 110 ° C. for 4 hours while introducing air.
By adding 505 parts of styrene to the obtained vinyl ester, a bromine-free vinyl ester resin (1) (bromine content 0%) containing 30% by mass of styrene was obtained. The glass transition temperature of the cured resin was 146 ° C.

Synthesis Example 6: Synthesis of unsaturated polyester resin (1) In a reaction vessel (flask) equipped with a stirrer, reflux condenser, gas introduction tube, and thermometer, 1026 parts of propylene glycol, 503 parts of dipropylene glycol, maleic anhydride 1470 parts and 0.6 part of hydroquinone were charged, the inside of the container was purged with nitrogen, and a dehydration condensation reaction was carried out at 200 ° C. for 9 hours to obtain an unsaturated polyester having an acid value of 10 mgKOH / g.
By adding 1170 parts of styrene to the obtained unsaturated polyester, an unsaturated polyester resin (1) containing 30% by mass of styrene was obtained. The glass transition temperature of the cured resin was 190 ° C.

Example 1
Brominated vinyl ester resin (1) 55 parts, unsaturated polyester resin (1) 25 parts, trimethylolpropane trimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), liquid rubber (1) (manufactured by Nippon Zeon Co., Ltd., acrylonitrile butadiene rubber) , "Nipol (R) 1312") 15 parts was mixed to prepare a resin composition.
Using this resin composition, the above 5. A cured resin composition is produced by the method described in 6 above, and the above 6. Compound cured products were prepared by the method described in 1. and various physical properties were evaluated by the methods described above. The results are shown in Table 1.

Examples 2 to 12, Comparative Examples 1 to 10
Each resin composition was prepared using the components shown in Table 1 or 2. Using this resin composition, a resin composition cured product and a compound cured product were produced in the same manner as in Example 1, and various physical properties were evaluated. The results are shown in Tables 1 and 2.

In Tables 1 and 2, the blending ratio (% by mass) is component (A), (B) and (C) (however, when component (D) is included, component (A), (B), (C) And (D)) are the content ratios of the bromine-containing vinyl ester, component (B) and component (C), respectively, when the total amount is 100% by mass.

The raw materials described in Tables 1 and 2 are as follows. In addition, the molecular weight and 80 degreeC viscosity of liquid rubber (C) were evaluated or measured by the method mentioned above.

Liquid rubber (1): manufactured by Nippon Zeon Co., Ltd., acrylonitrile butadiene rubber, “Nipol (R) 1312”, Mn: 2500, Mw: 6700, 80 ° C. viscosity: 2.5 Pa · s
Liquid rubber (2): manufactured by Kuraray Co., Ltd., liquid polyisoprene rubber, “Kuraprene (registered trademark) LIR-30”, Mn: 40000, Mw: 49000, 80 ° C. viscosity: 9.2 Pa · s
Liquid rubber (3): Nippon Soda Co., Ltd., both end hydroxyl group polybutadiene, “NISSO-PB G-1000”, Mn: 2100, Mw: 5000, 80 ° C. viscosity: 0.5 Pa · s

Polyvinyl acetate: manufactured by Wacker, acid-modified vinyl acetate, “C-305”, Mn: 20000, Mw: 50000
Polystyrene: manufactured by DIC, polystyrene, "Dick Styrene GPPS CR-3500"
Xylene resin: manufactured by Fudou, “Nikanol (registered trademark) H”, Mn: 60, Mw: 720, 80 ° C. viscosity: 0.4 Pa · s

From the examples and comparative examples described above, the following matters were confirmed.
Each of the resin compositions obtained in Examples 1 to 12 contains a bromine-containing vinyl ester, a radical polymerizable monomer (B), and a liquid rubber (C), the contents of which are specified in the present invention. The resin composition is in the range. All of the compound cured products obtained using this resin composition had a low coefficient of linear expansion and excellent dimensional stability. In addition, the flame retardancy, water resistance and surface smoothness were good, and the glass transition point of the cured resin composition was high, indicating good heat resistance.

On the other hand, Comparative Examples 1 to 3 were examples in which the liquid rubber (C) was not used. In this case, the compound cured product had a high linear expansion coefficient and was inferior in dimensional stability. In Comparative Example 3, the glass transition point of the cured resin composition was further low and the heat resistance was poor. Comparative Examples 4 and 5 are examples in which the liquid rubber (C) is used, but the content is outside the range defined in the present invention. Among these, in the comparative example 4, the linear expansion coefficient of the compound hardened | cured material was high, and it was inferior to dimensional stability. On the other hand, in Comparative Example 5, since the separation of the component (C) occurred remarkably at the time of producing the cured product, the cured product was non-uniform and the surface unevenness was severe, and the physical properties could not be evaluated.

Comparative Examples 6 to 8 are examples in which the liquid rubber (C) was not included, but other components were used in place of the liquid rubber (C). Among these, in Comparative Example 6 using polyvinyl acetate, whitening of the appearance remarkably occurred in the water resistance test, and the water resistance was poor. In Comparative Example 7 using polystyrene, as in Comparative Example 5, since the separation of component (C) occurred remarkably during the preparation of the cured product, the cured product was uneven and surface irregularities were severe, and physical properties could not be evaluated. It was. In Comparative Example 8 using xylene resin, the surface smoothness of the cured product was poor and the flame retardancy did not meet the V-0 standard.

Comparative Example 9 is an example in which the content of the radical polymerizable monomer (B) exceeds the range specified in the present invention. In this case, as in Comparative Examples 5 and 7, the component (C ) Was remarkably separated, the cured product was non-uniform and surface irregularities were severe, and the physical properties could not be evaluated. Comparative Example 10 was an example in which no bromine-containing vinyl ester was used, but in this case, the flame retardancy was inferior and the linear expansion coefficient α was also higher than in Examples 1-12.

Therefore, for the first time by making the resin composition of the configuration of the present invention, the cured product achieves low thermal expansion, and has high dimensional stability, heat resistance, toughness, flame resistance, water resistance, surface smoothness, etc. It was found that various physical properties of can be exhibited in a well-balanced manner.
The composition ratio defined in the present invention (bromine-containing vinyl ester, radical polymerizable monomer (B), and content ratio of liquid rubber (C) are components (A), (B) and (C). (However, when the component (D) is included, 30 to 65% by mass and 25 to 50% by mass, respectively, with respect to 100% by mass of the total amount of the components (A), (B), (C) and (D)). When the varnish cured product was produced with a composition outside the range of 10 to 30% by mass), the compatibility of each component was poor, separation progressed with heat curing, and smoothness was not obtained. In the composition within the above range, each component was uniformly mixed, and even when heat-cured, it did not separate and became a smooth surface.

Claims (7)

1. A radical curable resin composition comprising a radical polymerizable oligomer (A), a radical polymerizable monomer (B) and a liquid rubber (C),
   The radical polymerizable oligomer (A) contains a bromine-containing vinyl ester,
   The bromine-containing vinyl ester, the radical polymerizable monomer (B) and the liquid rubber (C) are contained in proportions of radical polymerizable oligomer (A), radical polymerizable monomer (B), and liquid rubber (C The radical curable resin composition is 30 to 65% by mass, 25 to 50% by mass, and 10 to 30% by mass with respect to a total amount of 100% by mass of all the thermoplastic resins and elastomers including object.
2. A radical curable resin composition comprising a radical polymerizable oligomer (A), a radical polymerizable monomer (B), and a thermoplastic resin and / or an elastomer (E),
   The radical polymerizable oligomer (A) contains a bromine-containing vinyl ester,
   The thermoplastic resin and / or elastomer (E) includes a liquid rubber (C) and a thermoplastic resin and / or elastomer (D) other than the liquid rubber (C),
   The bromine-containing vinyl ester, radical polymerizable monomer (B), and thermoplastic resin and / or elastomer (E) are contained in a proportion of radical polymerizable oligomer (A) and radical polymerizable monomer (B). ) And a thermoplastic resin and / or elastomer (E) of 100% by mass, radical curing, 30 to 65% by mass, 25 to 50% by mass, and 10 to 30% by mass, respectively. Resin composition.
3. The radical according to claim 2, wherein the thermoplastic resin and / or elastomer (D) is at least one selected from the group consisting of polyvinyl acetate, polystyrene, and (meth) acrylate polymers. Curable resin composition.
4. 4. The radical curable resin composition according to claim 1, wherein the bromine-containing vinyl ester has a glass transition temperature of 130 to 170 ° C. when the resin cured product contains 30% by mass of styrene. .
5. 5. The radical curable resin composition according to claim 1, wherein the liquid rubber (C) has a number average molecular weight of 60,000 or less.
6. 6. The radical curable resin composition according to claim 1, wherein the radical polymerizable monomer (B) contains a compound having two or more polymerizable groups.
7. A cured product obtained by curing the radical curable resin composition according to any one of claims 1 to 6.