JP2017137492A - Maleimide resin composition, prepreg and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a maleimide resin composition that can be cured even in a process in which epoxy resin can be cured, has excellent heat resistance and dielectric properties (relative dielectric constant and dielectric loss tangent), and is useful for a printed wiring board for electronic apparatus and the like; a prepreg; and a cured product.SOLUTION: A maleimide resin composition comprises an unsaturated double bond group-containing compound (B) in polymaleimide resin (A) represented by the following formula (Rs independently represent H, a C1-10 alkyl group or aromatic group; n is an integer with its average value of 1<n≤5).SELECTED DRAWING: None

Description

  The present invention relates to a maleimide resin composition, a prepreg and a cured product thereof suitable for use in electric and electronic materials.

Curable resins are widely used for adhesion, casting, coating, impregnation, lamination, molding compounds, and the like. However, in recent years, there are various uses, and depending on the use environment and use conditions, conventionally known curable resins may not be satisfactory. For example, in a laminated board for a printed wiring board used for various electric devices, a material having a low dielectric property is required for the purpose of improving a signal transmission speed with the progress of electronic devices.
On the other hand, in addition to the low dielectric properties, in recent years, higher heat resistance has been demanded for materials due to the effect of an increase in reflow temperature due to the use of lead-free solder. Conventionally, thermosetting resins such as paper-phenol resin based on paper and glass cloth-epoxy resin based on glass cloth are mainly used for such applications. These thermosetting resins exhibit high heat resistance and dimensional stability due to their unique cross-linking structure, so they are widely used in fields that require high reliability such as electronic parts, especially copper-clad laminates. In the board and interlayer insulation materials, due to the recent demand for higher density, high copper foil adhesion for forming fine wiring and mechanical strength and toughness when drilling or punching is required. It is said that. Although epoxy resin has relatively good mechanical strength and heat resistance, it has improved the heat resistance due to the recent high-density mounting of printed wiring boards and the high-layer structure, the improvement of the mechanical strength of the resin by making the board thinner, and the CPU. The semiconductor chip with advanced processing capability is mounted on a laminated board made of polymer material, and as the speed of elements such as CPUs increases and the clock frequency increases, signal propagation delay and transmission loss become a problem. A wiring board is required to have a low dielectric constant and a low dielectric loss tangent.

  Conventionally, a bismaleimide resin has been studied as an impregnation resin instead of an epoxy resin for the purpose of improving the dielectric constant of the resin. For example, in Patent Document 1, a wiring board using BT resin, which is a resin in which a bisphenol A-type cyanate ester compound and a bismaleimide compound are used together, is excellent in heat resistance, chemical resistance, electrical characteristics, etc., and is widely used as a high-performance wiring board. It is used.

Japanese Patent Publication No.54-30440 JP 2009-001783 A JP 2008-208201 A

However, bismaleimide resin, which is a thermosetting resin, is a resin having low dielectric properties, flame retardancy, and heat resistance, but generally has a problem of high curing temperature and low workability compared to epoxy resin. .
As means for solving these problems, resin compositions that can be cured by a curing process equivalent to that of an epoxy resin and have both heat resistance, low water absorption characteristics, and electrical reliability have been developed (Patent Documents 2 and 3). ). However, further improvements such as the development of a resin composition having cured product characteristics balanced in heat resistance and dielectric properties (relative dielectric constant, dielectric loss tangent) and the like are required.

  As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention. That is, the present invention

（式（１）中、複数存在するＲはそれぞれ独立して存在し、水素原子、炭素数１〜１０のアルキル基もしくは芳香族基を表す。ｎは整数でありその平均値は１＜ｎ≦５を表す。）
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不飽和二重結合基含有化合物（Ｂ）がエテニルベンゼン、エテニルベンゼン誘導体、ビニル化合物、（メタ）アクリロイル基を有する化合物、及びビニルエーテル基を有する化合物、マレイミド誘導体、不飽和ポリエステルからなる群から選ばれる１種以上の化合物である前項［１］に記載のマレイミド樹脂組成物、
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さらに触媒を含有する前項［１］又は［２］に記載のマレイミド樹脂組成物、
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難燃剤及びフィラー、金属複合塩、活性炭、層状粘土鉱物、金属酸化物の充填剤等のいずれか一種以上を含有する前項［１］〜［３］のいずれか一項に記載のマレイミド樹脂組成物、
［５］
前項［１］〜［４］のいずれか一項に記載のマレイミド樹脂組成物をシート状の繊維基材に保持し、半硬化状態にあるプリプレグ、
［６］
前項［１］〜［５］のいずれか一項に記載のマレイミド樹脂組成物の硬化物、
に関する。 [1]
A maleimide resin composition containing a polymaleimide resin (A) represented by the following formula (1) and an unsaturated double bond group-containing compound (B);

(In the formula (1), a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group. N is an integer and the average value is 1 <n ≦ 5)
[2]
The unsaturated double bond group-containing compound (B) is selected from the group consisting of ethenylbenzene, ethenylbenzene derivatives, vinyl compounds, compounds having (meth) acryloyl groups, compounds having vinyl ether groups, maleimide derivatives, and unsaturated polyesters. The maleimide resin composition according to item [1], which is one or more selected compounds,
[3]
The maleimide resin composition according to item [1] or [2], further containing a catalyst,
[4]
The maleimide resin composition according to any one of [1] to [3] above, which contains any one or more of flame retardants and fillers, metal composite salts, activated carbon, layered clay minerals, metal oxide fillers, and the like. ,
[5]
A prepreg in which the maleimide resin composition according to any one of [1] to [4] is held on a sheet-like fiber base material and is in a semi-cured state;
[6]
Cured product of the maleimide resin composition according to any one of [1] to [5],
About.

  The maleimide resin composition of the present invention is excellent in curability at low temperature, and since the cured product has heat resistance, water absorption characteristics, electrical reliability and mechanical strength, insulating materials for electrical and electronic parts and laminated boards (printed wiring boards, It is useful for various composite materials such as build-up substrates) and CFRP, adhesives, paints and the like.

The maleimide resin composition of the present invention will be described below.
The maleimide resin composition of the present invention contains a polymaleimide resin (A) represented by the following formula (1) and an unsaturated double bond group-containing compound (B).

(In the formula (1), a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group. N is an integer and the average value is 1 <n ≦ 5)

In the maleimide resin composition of the present invention, the method for producing the polymaleimide resin represented by the formula (1) that can be used is not particularly limited, and any known method known as a method for synthesizing a maleimide compound may be used. .
When producing a polymaleimide resin of the formula (1), a compound of the following formula (2) is required as a precursor thereof. For example, Patent Document A (Japanese Patent Laid-Open No. 3-100016) and Patent Document B (Japanese Patent Publication) 8-16151) describes the reaction of anilines with dihalogenomethyl compounds and dialkoxymethyl compounds, and anilines and bishalogenomethylbiphenyls or bisalkoxys are employed in the same manner as these. A compound of formula (2) is obtained by reacting with methylbiphenyls.

(In Formula (2), a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. N is an integer, and the average value of 1 <n ≦ 5. Represents.)

Examples of anilines used for the production of the compound of formula (2) include aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2-propylaniline, 3-propyl Aniline, 4-propylaniline, 2-isopropylaniline, 3-isopropylaniline, 4-isopropylaniline, 2-ethyl-6-methylaniline, 2-sec-butylaniline, 2-tert-butylaniline, 4-butylaniline, 4-sec-butylaniline, 4-tert-butylaniline, 2,6-di Alkyl-substituted anilines having one or more alkyl groups having 1 to 5 carbon atoms such as tyraniline, 2-isopropyl-6-methylaniline, 4-pentylaniline, phenyl having phenyl groups such as 2-aminobiphenyl, 4-aminobiphenyl, etc. Examples include aniline. These may be used alone or in combination of two or more.
Examples of bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls used include 4,4′-bis (chloromethyl) biphenyl, 4,4′-bis (bromomethyl) biphenyl, and 4,4′-bis (fluoromethyl). Biphenyl, 4,4'-bis (iodomethyl) biphenyl, 4,4'-dimethoxymethylbiphenyl, 4,4'-diethoxymethylbiphenyl, 4,4'-dipropoxymethylbiphenyl, 4,4'-diisopropoxy Examples include methyl biphenyl, 4,4′-diisobutoxymethyl biphenyl, 4,4′-dibutoxymethyl biphenyl, 4,4′-di-tert-butoxymethyl biphenyl, and the like. These may be used alone or in combination of two or more. The amount of bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls used is usually 0.05 to 0.8 mol, preferably 0.1 to 0.6 mol, per 1 mol of anilines used. .

In the reaction, if necessary, an acidic catalyst such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid and the like may be used. These may be used alone or in combination of two or more. The usage-amount of a catalyst is 0.1-0.8 mol normally with respect to 1 mol of anilines used, Preferably it is 0.5-0.7 mol. If it is more than the above range, the viscosity of the reaction solution is too high and stirring becomes difficult, and if it is too small, the progress of the reaction may be slow.
The reaction may be carried out using an organic solvent such as toluene or xylene, if necessary, or without solvent. For example, after adding an acidic catalyst to a mixed solution of anilines and a solvent, when the catalyst contains water, the water is removed from the system by azeotropic distillation. Thereafter, bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls are added at 40 to 100 ° C., preferably 50 to 80 ° C. over 1 to 5 hours, preferably 2 to 4 hours, and then the solvent is removed from the system. The temperature is raised and the reaction is carried out at 180 to 240 ° C., preferably 190 to 220 ° C. for 5 to 30 hours, preferably 10 to 20 hours. After completion of the reaction, neutralize the acidic catalyst with an aqueous alkaline solution, add a water-insoluble organic solvent to the oil layer and repeat washing with water until the wastewater becomes neutral, and distill off excess anilines and organic solvent under heating and reduced pressure. This gives the compound of formula (2). Although not mentioned in Patent Document B (Japanese Patent Publication No. 8-16151) and Patent Document 2 (Japanese Patent Laid-Open No. 2009-001783), diphenylamine, which is a by-product at this stage, is used in a catalytic amount / raw material usage. Although it depends on the ratio, temperature, time, etc., it is usually contained in the resin in an amount of 2 to 10% by weight. Diphenylamine cannot be removed under conditions where aniline is distilled off. Diphenylamine can be removed by blowing steam or an inert gas such as a large amount of nitrogen gas under reduced pressure by heating at a temperature equal to or higher than the boiling point of aniline.

  When diphenylamine is contained in the maleimide resin composition of the present invention, for example, when used for a curing reaction with an epoxy resin, it becomes a terminal end of a molecular chain, and when the content is large, a curing network is not sufficiently formed. There is a possibility that the mechanical strength will be significantly reduced. In addition, when diphenylamine is contained in the aromatic amine resin represented by the formula (2), diphenylamine remains as it is after maleimidation and remains in the cured product as it is without contributing to the reaction. Bleed out and thermal decomposition resistance may decrease. Accordingly, the diphenylamine content is required to be 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.2% by weight or less.

  The softening point of the aromatic amine resin represented by the formula (2) is preferably 65 ° C. or less, and more preferably 60 ° C. or less. When the softening point is higher than 65 ° C., the viscosity of the maleimidized resin becomes high, and it becomes difficult to impregnate carbon fibers or glass fibers. If the dilution solvent is increased to lower the viscosity, the resin may not adhere sufficiently.

  The polymaleimide resin of the formula (1) used in the maleimide resin composition of the present invention can be obtained by reacting the compound of the formula (2) with maleic anhydride in the presence of a solvent and a catalyst. The method described in JP-A-3-100016) and Patent Document C (JP-A 61-229863) may be employed. As the solvent used in the reaction, it is necessary to remove water generated during the reaction from the system, and therefore a water-insoluble solvent is used. For example, aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, methyl isobutyl ketone, and cyclopentanone However, it is not limited to these, and two or more kinds may be used in combination. In addition to the water-insoluble solvent, an aprotic polar solvent may be used in combination. Examples thereof include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone and the like, and two or more kinds may be used in combination. When using an aprotic polar solvent, it is preferable to use a solvent having a higher boiling point than the water-insoluble solvent used in combination. The catalyst is an acidic catalyst and is not particularly limited, and examples thereof include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, and phosphoric acid. For example, maleic acid is dissolved in toluene, an N-methylpyrrolidone solution of the compound of formula (2) is added with stirring, and then p-toluenesulfonic acid is added to remove water generated under reflux conditions from the system. While doing the reaction.

Examples of the alkyl group having 1 to 10 carbon atoms in R in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, Examples include sec-butyl group, n-pentyl group, i-pentyl group, amyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group and the like. .
Moreover, the value of n of Formula (1) is an integer, and represents an average value of 1 <n ≦ 5. The value of n can be calculated from the value of the weight average molecular weight obtained by gel permeation chromatography (GPC) measurement of the polymaleimide resin, but is approximately represented by the formula (2) that is a raw material. It can be considered to be almost equivalent to the value of n calculated from the GPC measurement result of the amine compound.

  In the maleimide resin composition of the present invention, an epoxy resin can be further blended. Examples of the epoxy resin that can be blended with the polymaleimide resin represented by the formula (1) include a novolac type epoxy resin, a bisphenol A type epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin, a phenol aralkyl type epoxy resin, and the like. Is mentioned. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetate Enone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols Solid or liquid epoxy resins such as chemical compounds, alicyclic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins and the like are not limited thereto. These may be used alone or in combination of two or more.

The maleimide resin composition of the present invention contains an unsaturated double bond group-containing compound (B) (hereinafter also simply referred to as “component (B)”). The unsaturated double bond group-containing compound (B) causes a crosslinking reaction with the polymaleimide resin (A) and acts as a curing agent for the maleimide resin. Specific examples of the unsaturated double bond group-containing compound (B) include styrene (ethenylbenzene), a styrene (ethenylbenzene) derivative (B-1), a compound having a vinyl group (B-2), and a vinyl ether group. (B-3), a maleimide derivative (B-4) other than the maleimide compound, a compound (B-5) having a (meth) acryloyl group, an unsaturated polyester (B-6), and the like. In the present specification, “(meth) acryloyl group” means both a methacryloyl group and an acryloyl group.
The compounding amount of the unsaturated double bond group-containing compound (B) is usually 0.01 to 10 times, preferably 0.05 to 5 times, particularly preferably a polymaleimide resin (A) in weight ratio. The range is 0.1 to 2 times. If the amount of the unsaturated double bond group-containing compound (B) is 0.01 times or less that of the polymaleimide resin (A), the curability and dielectric properties may not be sufficiently improved. And adhesiveness may be reduced.

  Styrene (ethenylbenzene) and styrene (ethenylbenzene) derivative (B-1) are not particularly limited, and examples thereof include styrene, α-methylstyrene, p-methoxystyrene, p-phenoxystyrene, and p-tert-butoxy. Styrene, m-methoxystyrene, o-methoxystyrene, p-phenylstyrene, p-chloromethylstyrene, p-tert-butylstyrene, p-trimethylsiloxystyrene, o-chlorostyrene, α-methylstyrene, o-, Examples thereof include m- or p-methylstyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, and the like, and are shown in Patent Document D (Japanese Patent Laid-Open No. 2005-314556). Poly represented by the following formula (3) And vinyl benzyl) ether compound.

(In the formula, each R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group, and each R ₂ independently represents a hydrogen atom or a vinylbenzyl group, provided that The substitution rate of the hydrogen atom to the vinylbenzyl group is 20 to 100%, n is an average value of 1 to 10, and m is a number of 1 to 4.

  Specific examples of the compound (B-2) having a vinyl group include methyl acetate compounds such as vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, ethylene, glycidyl vinyl ether, N-methylolacrylamide, and N-methylolmethacrylamide. And unsaturated vinyl monomers containing N-methylol groups such as methyl, ethyl and butyl ether, unsaturated vinylamides such as acrylamide and methacrylamide, unsaturated vinyl acids such as methacrylic acid, and vinyl esters of persic acid. , Vinylformamide, vinylacetamide, vinylpyrrolidone, vinylcaprolactam, vinylxylene, monochlorostyrene, divinylbenzene, vinylnaphthalene, 1,2-divinylcyclohexane, 1,3-divinylcyclohexane 1,4-divinyl cyclohexane, 1,2,4-trivinyl cyclohexane, 1,3,5-trivinyl cyclohexane, 1,2,4,5-tetramethyl vinyl cyclohexane.

  Specific examples of the compound (B-3) having a vinyl ether group include alkyl vinyl ether (B-3-1) optionally substituted with a halogen atom, hydroxyl group or amino group at the other end, and a halogen atom or hydroxyl group at the other end. Alternatively, an cycloalkyl vinyl ether (B-3-2) which may be substituted with an amino group, an alkyl group, a cycloalkyl group and an aromatic group which are bonded to an alkylene group and further have a substituent. Monovinyl ether, divinyl ether, polyvinyl ether, and the like having a structure in which at least one group selected from the group consisting of and at least one bond selected from the group consisting of an ether bond, a urethane bond, and an ester bond is bonded. (B-3-3 to B-3-5).

  Specific examples of the alkyl vinyl ether (B-3-1) include methyl vinyl ether, hydroxyethyl vinyl ether, chloroethyl vinyl ether, diethylaminoethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 1, Examples include 4-butanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, and the like.

  Examples of the cycloalkyl vinyl ether (B-3-2) include cyclohexyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, cyclohexyl dimethanol divinyl ether, and cyclohexane dimethanol monovinyl ether.

  Examples of the compound having an ether bond (B-3-3) include diethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, dipropylene glycol divinyl ether, and tripropylene. Examples include glycol monovinyl ether, tripropylene glycol divinyl ether, ditetramethylene glycol monovinyl ether, ditetramethylene glycol divinyl ether, and polytetramethylene glycol divinyl ether.

  The compound having a urethane bond (B-3-4) is a compound having (poly) alkylene glycol monovinyl ether (I) having at least one hydroxyl group in one molecule and at least one isocyanate group in one molecule. It can be obtained by the urethanization reaction of (II).

  Examples of monovinyl ether (I) of (poly) alkylene glycol include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexane-1,4-di And methanol monovinyl ether.

  Examples of the compound (II) having at least one isocyanate group in one molecule include m-isopropenyl-α, α-dimethylbenzyl isocyanate, xylylene diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, Aromatic isocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate, lysine diisocyanate, and the like aliphatic and alicyclic isocyanates Etc.

  In addition, polyisocyanates such as one or more dimers or trimers of these isocyanates can also be used, and various ones having two or more isocyanate groups in one molecule among the above isocyanates. Adducts obtained by urethanization with alcohols can also be used.

  As various alcohols used in this adduct, those having at least one hydroxyl group in one molecule can be used. Examples of such alcohols include methanol, ethanol, ethylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, polyethylene glycol, and cyclohexane-1,4-dimethanol. Bisphenol A polyethoxylate diol, hydrogenated bisphenol A, trimethylolpropane, glycerin, polytetramethylene glycol, polyester polyol, polycarbonate polyol and the like.

  The compound (B-3-5) having an ester bond is an alkylene glycol monovinyl ether (III) having at least one hydroxyl group in one molecule and a compound (IV) having at least one carboxyl group in one molecule. Can be obtained by esterification reaction.

  Examples of the monovinyl ether (III) of alkylene glycol having at least one hydroxyl group in one molecule include those described above as the component (I) of the compound having a urethane bond.

  As the compound (IV) having at least one carboxyl group in one molecule, known carboxylic acids and acid anhydrides thereof can be used. Examples of such compounds include maleic acid, succinic acid, tetrahydrophthalic acid, isophthalic acid, terephthalic acid, phthalic acid, dimer acid, adipic acid, sebacic acid, hexahydrophthalic acid, pyromellitic acid, or these acids. An anhydride etc. can be mentioned.

  Examples of maleimide derivatives (B-4) other than the maleimide compound include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-hexylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and the like. Functional maleimides; N, N′-methylene bismaleimide, N, N′-trimethylene bismaleimide, N, N′-dodecamethylene bismaleimide, N, N ′-(4,4′-diphenylmethane) bismaleimide, Examples thereof include bismaleimides such as 1,4-dimaleimidocyclohexane, isophorone bisurethane bis (N-ethylmaleimide), N, N′-P-phenylenebismaleimide, and the like.

  Specific examples of the compound (B-5) having a (meth) acryloyl group include (poly) ester (meth) acrylate (B-5-1), urethane (meth) acrylate (B-5-2), epoxy ( (Meth) acrylate (B-5-3), (poly) ether (meth) acrylate (B-5-4), alkyl (meth) acrylate or alkylene (meth) acrylate (B-5-5), having an aromatic ring (Meth) acrylate (B-5-6), (meth) acrylate (B-5-7) having an alicyclic structure, and the like can be given.

  More specifically, as (poly) ester (meth) acrylate (B-5-1), caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth) acrylate Monofunctional (poly) ester (meth) acrylates such as Hafester, which is a reaction product of 2-hydroethyl (meth) acrylate of succinic anhydride; neopentyl glycol hydroxypivalate di (meth) acrylate, ε-caprolactone modified neopentyl glycol Mono-, di- or tri (meth) acrylate of triol obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone to 1 mol of hydroxypivalate di (meth) acrylate and trimethylolpropane, pentaerythritol (Poly) ester poly (meth) acrylates of polyalcohols such as poly (meth) acrylates in which 1 mol or more of a cyclic lactone compound of ε-caprolactone is added to 1 mol of ditrimethylolpropane or dipentaerythritol;

  (Poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, cyclohexane-1 , 4-dimethanol, trimethylolpropane and other polyol components and maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, isophthalic acid, terephthalic acid, 5-sodium Polyester poly (meth) acrylate which is a reaction product with a polybasic acid such as sulfoisophthalic acid or its anhydride; a cyclic lactone-modified polyester polyol comprising the polyol component, the polybasic acid and ε-caprolactone or δ-valerolactone ( Meta) Acu Examples include (poly) ester poly (meth) acrylates such as relate.

  As a specific example of urethane (meth) acrylate (B-5-2), for example, it can be obtained by a reaction of a polyol, an organic isocyanate, and a hydroxyl group-containing (meth) acrylate.

  Examples of the polyol include (poly) alkylene glycols such as (poly) ethylene glycol, (poly) propylene glycol, and (poly) tetramethylene glycol; ethylene glycol, propylene glycol, tetramethylene glycol, 3-methyl-1,5 -Pentanediol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, ethylene oxide modified product, propylene oxide modified product, butylene oxide modified product, ε-caprolactone modified product of polyhydric alcohols of glycerol, etc .; polybutadiene glycol , Hydrocarbon polyols such as hydrogenated polybutadiene glycol; aliphatic dicarboxylic acids such as adipic acid and dimer acid, and polymers such as neopentyl glycol and 3-methyl-1,5-pentanediol Aliphatic polyester polyols which are esterified products with all; Aromatic polyester polyols which are esterified products of aromatic dicarboxylic acids such as terephthalic acid and polyols such as neopentyl glycol and 3-methyl-1,5-pentanediol Polycarbonate polyols; acrylic polyols and the like.

  Examples of organic isocyanates include aromatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate , 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate, lysine diisocyanate or other aliphatic or alicyclic diisocyanates; one or more burettes of diisocyanates or the above diisocyanates are trimerized And polyisocyanates such as isocyanurate.

  Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxy Butyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, 2- Examples thereof include hydroxy-3-phenoxypropyl (meth) acrylate and caprolactone-modified 2-hydroxyethyl (meth) acrylate.

  Examples of the epoxy (meth) acrylate (B-5-3) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl diglycidyl ether, and 2,2 ′, 6,6′-tetramethyldiphenyl diglycidyl ether. , Aromatic epoxy resins such as phenol / novolac type epoxy resin, cresol / novolac type epoxy resin, trisphenolmethane type epoxy resin; (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, neopentyl glycol (Poly) glycidyl ethers of aliphatic polyhydric alcohols such as glycerin, trimethylolpropane, 1,6-hexanediol, 1,4-butanediol; Glycidyl ether; epoxy resins such as aliphatic epoxy resins such as epoxidized polybutadiene and (meth) reacting the acrylic acid obtained.

  Examples of (poly) ether (meth) acrylate (B-5-4) include butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and 2-ethoxy. Ethyl (meth) acrylate, ethyl carbitol (meth) acrylate, 2-methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) propylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, phenoxy (poly ) Monofunctional (poly) ether (meth) acrylates such as ethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate ;

  Polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate;

  Polyhydric alcohols such as neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and alkylene oxides (eg, ethylene oxide, propylene oxide, Butylene oxide) adduct poly (meth) acrylate;

  Examples include polyfunctional (poly) ether (meth) acrylates such as di (meth) acrylates of alkylene oxide adducts of bisphenols such as bisphenol A and bisphenol F.

  Examples of the alkyl (meth) acrylate or alkylene (meth) acrylate (B-5-5) include 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, and stearyl. Monofunctional (meth) acrylates such as (meth) acrylate and octadecyl (meth) acrylate;

  Ethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 1,9-nonanediol, trimethylolpropane, pentaerythritol, Poly (meth) acrylates of polyhydric alcohols such as ditrimethylolpropane and dipentaerythritol;

  Hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; tribromophenyl (meth) acrylate, tribromophenyloxyethyl ( (Meth) acrylate having a bromine atom, such as (meth) acrylate, tetrabromobisphenol A polyethoxylate di (meth) acrylate;

  Examples of the (meth) acrylate (B-5-6) having an aromatic ring include monofunctional (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; bisphenol A di (meth) acrylate and bisphenol Examples include di (meth) acrylates such as F di (meth) acrylate.

  Examples of the (meth) acrylate (B-5-7) having an alicyclic structure include monofunctional (meth) acrylates having an alicyclic structure such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; hydrogenated bisphenol A, polyfunctional (meth) acrylates having a cyclic structure such as di (meth) acrylate of hydrogenated bisphenols such as hydrogenated bisphenol F, and tricyclodecane dimethylol di (meth) acrylate.

  In addition to the above-described compound (B-5) having a (meth) acryloyl group, for example, a reaction product of a (meth) acrylic acid polymer and glycidyl (meth) acrylate or a glycidyl (meth) acrylate polymer and (meth) acrylic acid Poly (meth) acrylic (meth) acrylates such as reactants thereof; (meth) acrylates having amino groups such as dimethylaminoethyl (meth) acrylate; isocyanurates such as tris ((meth) acryloxyethyl) isocyanurate (meta) ) Acrylate; (meth) acrylate having polysiloxane skeleton; polybutadiene (meth) acrylate; melamine (meth) acrylate; (meth) acrylamides such as acryloylmorpholine, N, N-dimethyl (meth) acrylamide, etc. can also be used. . Among (meth) acryloyl compounds, compounds having 1 to 6 (meth) acryloyl groups in one molecule are preferable.

  Examples of the unsaturated polyester (B-6) include maleic acid esters such as dimethyl maleate and diethyl maleate; fumaric acid esters such as dimethyl fumarate and diethyl fumarate; and polyvalent monomers such as maleic acid and fumaric acid. The esterification reaction product with alcohol is mentioned.

  Particularly preferred unsaturated double bond group-containing compound (B) is low in polarity and can be expected to have low dielectric properties, so that styrene, a styrene derivative (B-1), a compound having an N-vinyl group (B-2) and Examples thereof include a compound having a vinyl ether group (B-3).

In addition to the unsaturated double bond group-containing compound (B) described above, the maleimide resin composition of the present invention can further use a catalyst (also referred to as a curing accelerator) (C). Specific examples of the catalyst include an acidic catalyst, a basic polymerization catalyst, and a radical polymerization catalyst. A basic polymerization catalyst and a radical polymerization catalyst are preferable because curing at a lower temperature can be expected. Specific examples of the acidic polymerization catalyst include anion components such as SbF ₆ ⁻ , BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , CF ₃ SO ₃ ⁻ , B (C ₆ F ₅ ) ₄ ^−, iodine, sulfur, nitrogen, and the like. And an aromatic cation component containing an atom such as phosphorus. Specific examples of the basic polymerization catalyst include pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, imidazole, triazole, tetrazole 2-methylimidazole, 2-phenylimidazole, 2- Undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl- 2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′- Undecylimidazole (1 ')) ethyl-s-tri Azine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl- s-triazine-isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxy Heterocyclic compounds such as methyl-5-methylimidazole and 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and amides such as these heterocyclic compounds and dicyandiamide, Diaza compounds such as 8-diaza-bicyclo (5.4.0) undecene-7 and their tetraphenylbodies Rate, salts such as phenol novolac, salts with the polyvalent carboxylic acids or phosphinic acids, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, Trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium Ammonium salts such as acetate, triphenyl Phosphines such as sphin, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, amine adducts, carboxylic acid metal salts ( 2-ethylhexanoic acid, stearic acid, behenic acid, zinc salts such as mistylic acid, tin salts, zirconium salts), phosphate ester metals (zinc salts such as octyl phosphoric acid, stearyl phosphoric acid), alkoxy metal salts (tributylaluminum) And metal compounds such as acetylacetone salts (acetylacetonezirconium chelate, acetylacetone titanium chelate, etc.).

  In the present invention, phosphonium salts, ammonium salts, and metal compounds are particularly preferable in terms of coloring at the time of curing and changes thereof. Further, when a quaternary salt is used, a salt with a halogen leaves the cured product with a halogen, which is not preferable from the viewpoint of electrical reliability and environmental problems.

Examples of the radical polymerization catalyst include organic peroxides such as benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, and t-butyl perbenzoate.
One or more catalysts or curing accelerators may be used in combination.
If the amount of the catalyst or curing accelerator (C) is too small, it may cause curing failure, and if it is too large, the cured material properties of the resin composition may be adversely affected. Therefore, the compounding amount of the catalyst (C) is preferably 0.01 to 20% by weight based on 100 parts by weight of the total of the polymaleimide resin (A) and the unsaturated double bond group-containing compound (B) component.

  Furthermore, a known additive can be blended in the maleimide resin composition of the present invention as necessary. Specific examples of additives that can be used include curing agents for epoxy resins, polybutadiene and modified products thereof, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compounds, cyanate ester compounds , Silicone gel, silicone oil, inorganic fillers such as silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder, silane cup Coloring agents such as a surface treatment agent for a filler such as a ring agent, a release agent, carbon black, phthalocyanine blue, and phthalocyanine green can be used. The amount of these additives is preferably 1,000 parts by weight or less, more preferably 700 parts by weight or less, with respect to 100 parts by weight of the curable resin composition.

  Although the preparation method of the maleimide resin composition of this invention is not specifically limited, Each component may be mixed evenly or may be prepolymerized. For example, the polymaleimide resin (A) used in the present invention and the unsaturated double bond group-containing compound (B) are prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent. To do. Similarly, in addition to the polymaleimide resin (A) and unsaturated double bond group-containing compound (B) used in the present invention, epoxy resin, if necessary, amine compound, maleimide compound, cyanate ester compound, phenol resin, acid A curing agent such as an anhydride compound and other additives may be added for prepolymerization. For mixing or prepolymerization of each component, for example, an extruder, a kneader, or a roll is used in the absence of a solvent, and a reaction kettle with a stirring device is used in the presence of a solvent.

As a uniform mixing method, mixing is performed by kneading using a device such as a kneader, a roll, or a planetary mixer at a temperature in the range of 50 to 100 ° C. to obtain a uniform resin composition.
The obtained resin composition is pulverized and then molded into a cylindrical tablet with a molding machine such as a tablet machine, or a granular powder, or a powdery molded product, or these compositions are formed on a surface support. It can be melted and molded into a sheet having a thickness of 0.05 mm to 10 mm to form a maleimide resin composition molded body. The obtained molded article becomes a non-sticky molded article at 0 to 20 ° C., and even when stored at −25 to 0 ° C. for one week or longer, the fluidity and curability are hardly lowered.
The obtained molded body can be molded into a cured product using a transfer molding machine or a compression molding machine.

  An organic solvent can be added to the maleimide resin composition of the present invention to obtain a varnish-like composition (hereinafter simply referred to as varnish). If necessary, the maleimide resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone to obtain a maleimide resin composition varnish, and glass fiber. A cured product of the maleimide resin composition of the present invention is obtained by hot press molding a prepreg obtained by impregnating a base material such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and drying by heating. can do. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent. Moreover, if it is a liquid composition, the maleimide resin hardened | cured material which contains a carbon fiber by the RTM system as it is can also be obtained as it is.

  Moreover, the maleimide resin composition of the present invention can also be used as a modifier for a film-type composition. Specifically, it can be used to improve the flexibility of the B-stage. Such a film-type resin composition is formed by applying the maleimide resin composition of the present invention on the release film as the maleimide resin composition varnish, removing the solvent under heating, and then performing B-stage formation. Obtained as an adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

The prepreg of the present invention can be obtained by heating and melting the maleimide resin composition of the present invention, reducing the viscosity, and impregnating the fiber with a reinforcing fiber such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, or alumina fiber. .
Moreover, the prepreg of this invention can also be obtained by impregnating the said varnish in a reinforced fiber and heat-drying.
The above prepreg is cut into the desired shape, laminated with copper foil, etc. if necessary, and the epoxy resin composition for laminates is heat-cured while applying pressure to the laminate by the press molding method, autoclave molding method, sheet winding molding method, etc. By doing so, a laminated board can be obtained.
Furthermore, a circuit can be formed on a laminated board made by superimposing copper foil on the surface, and a multilayer circuit board can be obtained by superimposing a prepreg or copper foil thereon and repeating the above operation.

  The hardened | cured material of this invention can be used for various uses, such as a molding material, an adhesive agent, a composite material, and a coating material. In particular, since the cured product of the maleimide resin composition of the present invention exhibits excellent flame retardancy, it is useful in the electrical and electronic fields such as IC sealing materials, laminated materials, and electrical insulating materials.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
The various analysis methods used in the examples are described below.
Epoxy equivalent: Conforms to JIS K 7236 (ISO 3001). ICI melt viscosity: Conforms to JIS K 7117-2 (ISO 3219). Softening point: Conforms to JIS K 7234. Total chlorine: JIS K 7243-3 (ISO 21672-2. 3) Compliant ・ Iron content: ICP emission spectroscopic analysis ・ GPC:
Analysis conditions Column (Shodex KF-603, KF-602x2, KF-601x2)
The coupled eluent is tetrahydrofuran. The flow rate is 0.5 ml / min.
Column temperature is 40 ° C
Detection: RI (differential refraction detector)
・ HPLC:
Analysis conditions Column: Inertsil ODS-2 (GL Science)
Detector: UV274nm
Temperature: 40 ° C. Eluent: Acetonitrile / water Flow rate: 1.0 ml / min
Injection volume: 5 μl (concentration: about 10 mg / 6 ml)
Gradient program
Acetonitrile / water Start 30/70 Gradient → 28 minutes later 100/0 Keep as it is and judge to complete curing: Measurement of presence or absence of exothermic peak by MDSC measurement of the obtained cured product.

(Synthesis Example 1)
A flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap, and a stirrer was charged with 372 parts of aniline and 200 parts of toluene, and 146 parts of 35% hydrochloric acid was added dropwise at room temperature over 1 hour. After completion of the dropwise addition, the mixture was heated to cool and separate azeotropic water and toluene, and then only the organic layer of toluene was returned to the system for dehydration. Subsequently, 125 parts of 4,4′-bis (chloromethyl) biphenyl was added over 1 hour while maintaining the temperature at 60 to 70 ° C., and the reaction was further performed at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature to bring the inside of the system to 195 to 200 ° C., and the reaction was carried out at this temperature for 15 hours. Thereafter, 330 parts of a 30% aqueous sodium hydroxide solution was slowly added dropwise while cooling so that the system did not circulate vigorously, and the toluene distilled off at a temperature of 80 ° C. or lower was returned to the system and allowed to stand at 70 ° C. to 80 ° C. I put it. The separated lower aqueous layer was removed, and the reaction solution was washed with water until the washing solution became neutral. Subsequently, 173 parts of aromatic amine resin (a1) was obtained by distilling off excess aniline and toluene from the oil layer with a rotary evaporator under heating and reduced pressure (200 ° C., 0.6 KPa). Diphenylamine in the aromatic amine resin (a1) was 2.0%.
The obtained resin was again dripped in small amounts in place of steam blowing in a rotary evaporator under heating and reduced pressure (200 ° C., 4 KPa). As a result, 166 parts of aromatic amine resin (A1) was obtained. The aromatic amine resin (A1) obtained had a softening point of 56 ° C., a melt viscosity of 0.035 Pa · s, and diphenylamine of 0.1% or less.

(Synthesis Example 2)
After adding 147 parts of maleic anhydride and 300 parts of toluene to a flask equipped with a thermometer, condenser, Dean-Stark azeotropic distillation trap, and stirrer, cooling and separating the water and toluene azeotropically heated. Then, only toluene which is an organic layer was returned to the system for dehydration. Next, a resin solution obtained by dissolving 195 parts of the aromatic amine resin (A1) obtained in Synthesis Example 1 in 195 parts of N-methyl-2-pyrrolidone was added over 1 hour while maintaining the system at 80 to 85 ° C. It was dripped. After completion of the dropping, the reaction is carried out at the same temperature for 2 hours, 3 parts of p-toluenesulfonic acid is added, condensed water and toluene azeotroped under reflux conditions are cooled and separated, and only toluene which is an organic layer Was returned to the system and reacted for 20 hours while dehydrating. 120 parts of toluene was added after completion | finish of reaction, water washing was repeated, p-toluenesulfonic acid and excess maleic anhydride were removed, and it heated and removed water from the system by azeotropy. Next, the reaction solution was concentrated to obtain a resin solution containing 70% of maleimide resin (M1).

(Synthesis Example 3)
[Synthesis of epoxy acrylate of bisphenol A type epoxy resin]
282.5 g of bisphenol A type epoxy resin (product name: RE-310S, manufactured by Nippon Kayaku Co., Ltd.) is dissolved in 266.8 g of toluene, and 0.8 g of dibutylhydroxytoluene is added as a polymerization inhibitor to 60 ° C. The temperature rose. Thereafter, 117.5 g of acrylic acid with 100% equivalent of epoxy group was added and the temperature was further raised to 80 ° C., 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, and the mixture was stirred at 98 ° C. for about 30 hours, A reaction solution was obtained. This reaction solution was washed with water and toluene was distilled off to obtain 395 g of the desired bisphenol A type epoxy acrylate (B3).

(Synthesis Example 4)
[Synthesis of epoxy acrylate of bisphenol F epoxy resin]
68.9 g of bisphenol F type epoxy resin (RE-304S, epoxy equivalent 160 g / eq, manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 66.7 g of toluene, and 1500 ppm of dibutylhydroxytoluene was added as a polymerization inhibitor to this solution at 60 ° C. The temperature was raised to. Thereafter, 31.1 g of acrylic acid was added, the temperature was further raised to 80 ° C., 1500 ppm of trimethylammonium chloride as a reaction catalyst was added thereto, and the mixture was stirred at 98 ° C. for about 30 hours. The obtained reaction liquid was washed with water, and toluene was distilled off to obtain an epoxy acrylate (B4) of bisphenol F epoxy.

Example 1
72 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 29 parts by weight of styrene (B1: Reagent made by Wako Pure Chemical Industries) as component (B), 1 weight of triphenylphosphine (reagent made by TPP Junsei Chemical) as a catalyst Parts were blended and stirred uniformly at 100 ° C. to obtain a maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 180 ° C. × 2 hours to obtain a cured product of the present invention.

(Example 2)
72 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 29 parts by weight of styrene (B1: Wako Pure Chemical Reagent) as component (B), and dicumyl mill peroxide (DCP Kayaku Akzo) 1 as a catalyst The maleimide resin composition of this invention was obtained by mix | blending a weight part and stirring uniformly on 100 degreeC conditions. This maleimide resin composition was cured under curing conditions of 180 ° C. × 2 hours to obtain a cured product of the present invention.

(Example 3)
78 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 23 parts by weight of dipentaerythritol (B2: Wako Pure Chemical Reagent) as component (B), and 1 part by weight of DCP (manufactured by Kayaku Akzo) as a catalyst And uniformly stirred at 100 ° C. to obtain a maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 180 ° C. × 2 hours to obtain a cured product of the present invention.

Example 4
64 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 35 parts by weight of acrylated bisphenol A type epoxy resin (B3) obtained in Synthesis Example 3 as component (B), and TPP (manufactured by Pure Chemical) Reagent) 1 part by weight was mixed and stirred uniformly at 100 ° C. to obtain a maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions at 180 ° C. for 2 hours to obtain a cured product of the present invention.

(Example 5)
64 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 35 parts by weight of acrylated bisphenol A type epoxy resin (B3) obtained in Synthesis Example 3 as component (B), and DCP (chemical chemical Akzo as catalyst) 1 part by weight was mixed and stirred uniformly at 100 ° C. to obtain a maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions at 180 ° C. for 2 hours to obtain a cured product of the present invention.

(Example 6)
67 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 32 parts by weight of bisphenol F epoxy epoxy acrylate (B4) obtained in Synthesis Example 4 as component (B), and DCP (manufactured by Kayaku Akzo) as a catalyst ) 1 part by weight was mixed and stirred uniformly at 100 ° C. to obtain a maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 180 ° C. × 2 hours to obtain a cured product of the present invention.

(Example 7)
67 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 35 parts by weight of epoxy acrylate (B4) of bisphenol F epoxy obtained in Synthesis Example 4 as component (B), and TPP (manufactured by Kayaku Akzo) as a catalyst ) 1 part by weight was mixed and stirred uniformly at 100 ° C. to obtain a maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 180 ° C. × 2 hours to obtain a cured product of the present invention.

(Example 8)
67 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 15 parts by weight of styrene (B1: Wako Pure Chemicals Reagent) as component (B), 1,2,4-trivinylcyclohexane (B5: Tokyo Chemical Industry) Kogyo Co., Ltd., reagent) 12 parts by weight and 1 part by weight of DCP (manufactured by Kayaku Akzo) as a catalyst were mixed and stirred uniformly at 100 ° C. to obtain a maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 180 ° C. × 2 hours to obtain a cured product of the present invention.

Example 9
67 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 15 parts by weight of styrene (B1: Reagent manufactured by Wako Pure Chemical Industries) as component (B), diethylene glycol divinyl ether (B6: Tokyo Chemical Industry Co., Ltd., reagent) 12 parts by weight and 1 part by weight of DCP (manufactured by Kayaku Akzo) as a catalyst were blended and stirred uniformly at 100 ° C. to obtain a maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 180 ° C. × 2 hours to obtain a cured product of the present invention.

(Example 10)
67 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 15 parts by weight of styrene (B1: Reagent made by Wako Pure Chemical Industries) as component (B), and diethylene glycol divinyl ether (B6: Tokyo Chemical Industry) as component (B) Co., Ltd., reagent) 12 parts by weight and 1 part by weight of TPP (manufactured by Kayaku Akzo) as a catalyst were mixed and stirred uniformly at 100 ° C. to obtain a maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 180 ° C. × 2 hours to obtain a cured product of the present invention.

(Comparative Example 1)
72 parts of epoxy resin 1 (EP1: Nippon Kayaku NC-3000 epoxy equivalent 277 g / eq. Softening point 57.5 ° C.), phenol novolac (P-2, Meiwa Kasei H-1, hydroxyl equivalent 106 g / eq.) 27 parts by weight and 1 part by weight of TPP (C1 Pure Chemical Reagent) as a catalyst were blended and uniformly mixed and kneaded with a mixing roll using a mixing roll to obtain an epoxy resin composition. After making this epoxy resin composition into a tablet, a resin molded body was prepared by transfer molding and cured under a curing condition of 180 ° C. × 2 hours.

(Comparative Example 2)
61 parts of epoxy resin 2 (EP2: Nippon Kayaku EPPN-502H Epoxy equivalent 169 g / eq. Softening point 67.5 ° C.), phenol novolac (P-2 Meiwa Kasei H-1, hydroxyl equivalent 106 g / eq) .) 38 parts by weight and 1 part by weight of TPP (C1 Pure Chemical Reagent) as a catalyst were mixed and uniformly mixed and kneaded with a mixing roll using a mixing roll to obtain an epoxy resin composition. After making this epoxy resin composition into a tablet, a resin molded body was prepared by transfer molding and cured under a curing condition of 180 ° C. × 2 hours.

(Comparative Example 3)
96 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2 and 1 part by weight of triphenylphosphine (TPP Pure Chemical Reagent) as a catalyst were mixed and stirred uniformly at 100 ° C., and curing conditions were 180 ° C. × 2 Cured with time, a cured product for comparison was obtained.

(Comparative Example 4)
96 parts by weight of the maleimide resin (M1) obtained in Synthesis Example 2 and 1 part by weight of dicumyl peroxide (DCP Kayaku Akzo) as a catalyst were mixed and stirred uniformly at 100 ° C. to obtain a maleimide resin composition Got. This maleimide resin composition was cured under a curing condition of 180 ° C. for 2 hours to obtain a cured product for comparison.

In order to determine whether the cured product thus obtained had been cured, the measurement was performed under the following conditions to confirm the presence or absence of heat generation. The results are shown in Table 1.
・ Analysis condition analysis mode: MDSC measurement
Measuring instrument: Q2000 manufactured by TA-instruments,
Temperature increase rate: 3 ° C / min

(Table 1)

From Table 1, it can confirm that the maleimide resin composition of this invention is a resin composition which can be hardened at 180 degreeC.
The resin composition curable at 180 ° C., that is, the resin composition cured at 180 ° C. means a state in which the reaction of the functional group of the curable resin component in the curable resin composition is substantially completed, for example, Evaluation can be made by measuring the amount of heat generated by the reaction during curing with a differential scanning calorimetry (DSC) apparatus. Specifically, this indicates a state in which this calorific value is hardly detected.

(Examples 11 and 12 and Comparative Examples 5 and 6)
About the hardened | cured material of this invention obtained in Example 1 and Example 2, and the hardened | cured material for comparison obtained in Comparative Example 2 and 3, hardened | cured material property was measured on condition of the following. The results are shown in Table 2.

-Analysis conditions Dynamic viscoelasticity measuring device: TA-instruments Q-800
Measurement temperature range: 30 ° C to 280 ° C
Temperature rate: 2 ° C / min
Test piece size: A material cut into 5 mm × 50 mm was used (thickness was about 800 μm).
Dielectric constant and dielectric loss tangent: (Cavity Resonator Agilent Technologies) Measured at 1 GHz according to K6991 Water absorption: 100 ° C. × 24 h% increase in weight of cured product immersed

(Table 2)

  From Table 2, the cured product of the maleimide resin composition of the present invention has excellent heat resistance, dielectric loss tangent and low water absorption characteristics compared to general high heat-resistant epoxy resins compared to general epoxy resins. It turned out to be a material.

From the results of Tables 1 and 2 above, it was found that the maleimide resin composition of the present invention exhibits equivalent curability (low temperature curability) as compared with general epoxy resins. Further, the obtained cured product was found to be a material having excellent heat resistance, dielectric loss tangent and low water absorption characteristics as compared with general epoxy resins.

Claims (6)

A maleimide resin composition comprising a polymaleimide resin (A) represented by the following formula (1) and an unsaturated double bond group-containing compound (B).

(In the formula (1), a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group. N is an integer and the average value is 1 <n ≦ 5)   When the unsaturated double bond group-containing compound (B) is styrene (ethenylbenzene), styrene (ethenylbenzene) derivative, vinyl compound, compound having (meth) acryloyl group, compound having vinyl ether group, maleimide derivative and The maleimide resin composition according to claim 1, which is one or more compounds selected from the group consisting of saturated polyesters.   The maleimide resin composition according to claim 1 or 2, further comprising a catalyst.   The maleimide resin composition according to any one of claims 1 to 3, comprising any one or more of a flame retardant and a filler, a metal composite salt, activated carbon, a layered clay mineral, a metal oxide filler, and the like.   The prepreg which hold | maintains the maleimide resin composition as described in any one of Claims 1-4 in a sheet-like fiber base material, and is in a semi-hardened state. Hardened | cured material of the maleimide resin composition as described in any one of Claims 1-5.