KR102314333B1 - Thermosetting resin composition, prepreg, and cured product thereof - Google Patents

Abstract

[식(1) 중, 복수 존재하는 R₁은 각각 독립적으로 존재하고, 수소 원자, 탄소수 1~10개의 알킬기 또는 방향족기를 나타낸다. a는 1~3을 나타낸다. n은 정수이며, 그 평균값은 1<n≤5를 나타낸다]Provided is a thermosetting resin composition that can be molded and processed at a relatively low temperature, and is excellent in heat resistance, mechanical strength, toughness, and thermal decomposition properties after curing. The compound (A) which has a maleimide group represented by following formula (1), and the compound (B) which has an allyl group or metaallyl group are contained.

[In Formula (1), _{two or more R<1>} exists each independently, and represents a hydrogen atom, a C1-C10 alkyl group, or an aromatic group. a represents 1-3. n is an integer, and the average value represents 1 < n ≤ 5]

Description

Thermosetting resin composition, prepreg, and cured product thereof

INDUSTRIAL APPLICABILITY The present invention can be used for various purposes such as aerospace materials, machine tool member uses, and electrical/electronic materials, and is particularly useful in fields such as fiber-reinforced composite materials requiring heat resistance and sealing materials for electrical and electronic components. It relates to a resin composition, a prepreg, and its hardened|cured material.

A fiber-reinforced composite material consists of a matrix resin and reinforcing fibers such as carbon fiber, glass fiber, alumina fiber, boron fiber, and aramid fiber, and is generally lightweight and has high strength. Such fiber-reinforced composite materials are used as insulating materials and laminates for electrical and electronic components (printed wiring boards, build-up boards, etc.), aerospace materials such as aircraft aircraft and wings, machine tool members represented by robot handarms, and construction and civil engineering repair materials. It is widely used in various applications, such as golf shafts and leisure equipment applications such as tennis rackets. In particular, carbon fiber-reinforced composite materials (hereinafter referred to as CFRP) in aerospace materials such as aircraft aircraft and wings, and machine tool members typified by robot handarms have heat resistance that maintains rigidity in the temperature range from room temperature to about 200°C. , mechanical properties, long-term reliability, that is, a sufficiently high thermal decomposition temperature and a low water absorption are required. As a matrix resin of a fiber-reinforced composite material, an epoxy-based resin has been widely used in the prior art, but the epoxy-based resin has low heat resistance, making it unsuitable for use in aerospace materials or machine tool members.

On the other hand, a maleimide resin is widely known as a matrix resin which has high heat resistance and can withstand a use environment of 200°C or higher. Although a bismaleimide compound is generally used as a main agent of maleimide resin, hardening alone is bad and a molded article becomes brittle. In order to improve this, various modifiers have been developed. As a solution, various modifications have been made, for example, blending a modified butadiene-based resin in which a meta (acryloyl) group is introduced into a cyanic acid ester-based resin composition (Patent Document 1), butadiene-acrylonitrile air Addition of coalescing (Patent Document 2) or an epoxy resin added thereto (Patent Document 3), etc. are known. However, although these methods reduce brittleness, there is a problem that heat resistance and water resistance are unavoidable.

A method of modifying a maleimide resin with an allyl compound known as an additive such as a reactive diluent, a crosslinking agent and a flame retardant of the maleimide resin is also known. For example, Patent Document 4 is a resin obtained by heating and melting liquid o,o'-diallylbisphenol A in 4,4'-diphenylmethanebismaleimide at room temperature and mixing it, It is possible to impregnate.

Japanese Patent Laid-Open No. 57-153045 Japanese Patent Laid-Open No. 57-153046 Japanese Patent Laid-Open No. 56-157424 Japanese Patent Laid-Open No. 9-87460

However, according to Patent Document 4, the obtained 4-4'bismaleimidediphenylmethane has no mechanical strength or toughness due to its rigid skeleton, and even if modified with o,o'-diallylbisphenol A, the obtained resin does not obtain sufficient strength and is molded. Many cracks are observed in one CFRP.

In view of the above circumstances, an object of the present invention is to provide a thermosetting resin composition that can be molded and processed at a relatively low temperature and is excellent in heat resistance after curing, water supply characteristics, mechanical strength, and thermal decomposition characteristics.

As a result of intensive studies in view of the above-described actual conditions, the present inventors have found that a thermosetting resin composition containing a compound having a specific maleimide group and a compound having an allyl group or a metaallyl group can be molded and processed at a relatively low temperature, and further It was excellent in sclerosis|hardenability, and by using this, even if it was a short post-curing process, it discovered that the hardened|cured material excellent in characteristics, such as heat resistance, was obtained, and came to complete this invention.

That is, the present invention is

[One]

Thermosetting resin composition containing the compound (A) which has a maleimide group represented by following formula (1), and the compound (B) which has an allyl group or metaallyl group;

[In Formula (1), _{two or more R<1>} exists each independently, and represents a hydrogen atom, a C1-C10 alkyl group, or an aromatic group. a represents 1-3. n is an integer, and the average value represents 1 < n ≤ 5]

[2]

The thermosetting resin composition according to [1], wherein the compound (B) having an allyl group or a metaallyl group has a weight average molecular weight (Mw) of 350 to 1200;

[3]

The thermosetting resin composition according to the above [1] or [2], which further contains a catalyst;

[4]

A prepreg in which the thermosetting resin composition according to any one of [1] to [3] is held on a sheet-like fiber substrate;

[5]

It relates to the thermosetting resin composition according to any one of [1] to [3] or a cured product of the prepreg according to the above [4].

(Effects of the Invention)

The thermosetting resin composition of the present invention can be molded and processed at a relatively low temperature, and has excellent effects in heat resistance after curing, water supply characteristics and mechanical strength, and thermal decomposition characteristics.

The thermosetting resin composition of this invention is demonstrated below.

The thermosetting resin composition of the present invention comprises a compound (A) having a maleimide group represented by the following formula (1) (also simply referred to as “maleimide compound (A)”) and a compound (B) having an allyl group or metaallyl group contains

[In Formula (1), _{two or more R<1>} exists each independently, and represents a hydrogen atom, a C1-C10 alkyl group, or an aromatic group. a represents 1-3. n is an integer, and the average value represents 1 < n ≤ 5]

_{Examples of the alkyl group having 1 to 10 carbon atoms in R 1} in the formula (1) include a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, and sec-butyl group. 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. Among them, a methyl group is preferable.

_{Examples of the aromatic group for R 1} in the formula (1) include an aromatic hydrocarbon group such as a phenyl group, a biphenyl group, an indenyl group, a naphthyl group, an anthryl group, a fluorenyl group, and a pyrenyl group, a furanyl group, a thienyl group, and a thienothiene group. a nyl group, a pyrrolyl group, an imidazolyl group, a pyridyl group, a pyradyl group, a pyrimidyl group, a quinolyl group, an indolyl group, a carbazolyl group, etc. are mentioned.

In addition, the value of n in Formula (1) is an integer, and the average value ≤5 of 1<n is shown. It is preferable that n is 1-10, It is more preferable that it is 2-8, It is especially preferable that it is 2-4. In addition, although the value of n can be calculated from the value of the weight average molecular weight calculated|required by the measurement of the gel permeation chromatography (GPC) of the maleimide compound (A), it is calculated from the measurement result of GPC of the compound which is a raw material approximately. It can be thought of as almost equivalent to the value of n.

The manufacturing method of the said maleimide compound (A) is not specifically limited, You may manufacture by any well-known method as a synthesis method of a maleimide compound. For example, Japanese Patent Laid-Open No. 3-100016 and Japanese Patent Application Laid-Open No. Hei 8-16151 describe the reaction of anilines with a dihalogenomethyl compound or a dialkoxymethyl compound. The compound of formula (2) is obtained by employing the method of and reacting aniline with bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls.

[In formula (2), two or more R's exist each independently, and represent a hydrogen atom, a C1-C10 alkyl group, or an aromatic group. n is an integer and represents an average value of 1 < n ≤ 5]

Examples of the alkyl group having 1 to 10 carbon atoms in R in the formula (2) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a n-butyl group, an iso-butyl group, a tert-butyl group, and a 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, etc. are mentioned.

As an aromatic group in R in said Formula (2), aromatic hydrocarbon groups, such as a phenyl group, a biphenyl group, an indenyl group, a naphthyl group, an anthryl group, a fluorenyl group, a pyrenyl group, a furanyl group, a thienyl group, a thienothienyl group , a pyrrolyl group, an imidazolyl group, a pyridyl group, a pyradyl group, a pyrimidyl group, a quinolyl group, an indolyl group, and a carbazolyl group.

Examples of the anilines used in the preparation of the maleimide compound include aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, and 2,3-dimethylaniline. , 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2-propylaniline, 3-propylaniline, 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-diethylaniline, 2-isopropyl-6-methylaniline, 4-pentylaniline, etc. alkyl-substituted aniline having one or more C1-C5 alkyl groups; and phenylaniline having a phenyl group such as 2-aminobiphenyl and 4-aminobiphenyl. These may be used independently and may use 2 or more types together.

Examples of the bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls used include 4,4'-bis(chloromethyl)biphenyl, 4,4'-bis(bromomethyl)biphenyl, 4,4'- Bis(fluoromethyl)biphenyl, 4,4'-bis(iodmethyl)biphenyl, 4,4'-dimethoxymethylbiphenyl, 4,4'-diethoxymethylbiphenyl, 4,4'-dipe Ropoxymethylbiphenyl, 4,4'-diisopropoxymethylbiphenyl, 4,4'-diisobutoxymethylbiphenyl, 4,4'-dibutoxymethylbiphenyl, 4,4'-di-tert -butoxymethylbiphenyl, etc. are mentioned. These may be used independently and may use 2 or more types together. The usage-amount of bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls is 0.05-0.8 mol normally with respect to 1 mol of anilines used, Preferably it is 0.1-0.6 mol.

The maleimide compound (A) is, for example, obtained by reacting maleic anhydride with a raw material compound as in the above formula (2) in the presence of a solvent and a catalyst. For example, Japanese Patent Laid-Open No. 3-100016 B, the method described in Japanese Patent Application Laid-Open No. 61-229863 may be employed.

As the solvent used in the reaction, it is necessary to remove the water generated during the reaction from the inside of the system, so 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 Although ketone solvents, such as a ketone and cyclopentanone, etc. are mentioned, It is not limited to these, You may use 2 or more types together.

Moreover, in addition to the said water-insoluble solvent, an aprotic polar solvent can also be used together. For example, dimethylsulfone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc. are mentioned, Even if 2 or more types are used together good. When using an aprotic polar solvent, it is preferable to use a thing with a higher boiling point than the water-insoluble solvent used together.

The catalyst is not particularly limited as an acid catalyst, and examples thereof include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, phosphoric acid and the like. For example, maleic acid is dissolved in toluene, an N-methylpyrrolidone solution of the compound of formula (2) is added under stirring, and then p-toluenesulfonic acid is added thereto, and water generated under reflux conditions is discharged into the system. The reaction is carried out while removing from

As the maleimide compound (A), one having a melting point and a softening point may be used. In particular, when it has a melting point, it is preferably 200°C or less, and when it has a softening point, it is preferably 150°C or less. If the melting point or softening point is too high, the possibility of gelation may increase during mixing.

The content of the maleimide compound (A) in the thermosetting resin composition of the present invention is preferably 30 to 70 mass % with respect to the total amount of the composition from the viewpoint of the fluidity of the thermosetting resin composition and the heat resistance of a cured product obtained by curing the same, 35 It is more preferable that it is -60 mass %. By setting the content of the maleimide compound (A) to 30 to 70 mass % with respect to the total amount of the composition, a thermosetting resin composition having a viscosity capable of relatively low-temperature moldability is easily obtained, and a cured product having high heat resistance is easily obtained. tends to

The thermosetting resin composition of the present invention is a compound (A) having a maleimide group represented by the formula (1), and a compound (B) having an allyl group or a metaallyl group (also referred to as “(meth)allyl group-containing compound (B)”) indicated). The compound (B) having an allyl group or a metaallyl group acts as a curing agent for the maleimide compound (A).

Examples of the compound (B) having an allyl group or metaallyl group include 4,4'-bisphenol A diallyl ether, 4,4'-bisphenol F diallyl ether, and 4,4'-bisphenol F dimethallyl ether. , tri(meth)allylisocyanurate, 2,2-di(4-acetyloxy-3-(meth)allylphenyl)propane, di(4-acetyloxy-3-(meth)allylphenyl)methane, di (4-acetyloxy-3-(meth)allylphenyl)sulfone, 2,2-di(4-benzoyloxy-3-(meth)allylphenyl)propane, di(4-benzoyloxy-3-(meth)allyl Phenyl) methane, di(4-benzoyloxy-3-(meth)allylphenyl)sulfone, 2,2-di(4-toluyloxy-3-(meth)allylphenyl)propane, di(4-toluyloxy -3-(meth)allylphenyl)methane, di(4-toluyloxy-3-(meth)allylphenyl)sulfone, 2,2-di(4-propionyloxy-3-(meth)allylphenyl)propane , di(4-propionyloxy-3-(meth)allylphenyl)methane, di(4-propionyloxy-3-(meth)allylphenyl)sulfone, 2,2-di(4-butyryloxy-3 -(meth)allylphenyl)propane, 2,2-di(4-isobutyryloxy-3-(meth)allylphenyl)propane allylchloride, allyl alcohol, allylethyl ether, allyl-2-hydroxyethyl ether , allyl glycidyl ether, methacryl glycidyl ether, diallyl phthalate, trimethylol propane diallyl ether, pentaerythritol triallyl ether, and triallyl isocyanurate. Preferably, (meth)allyl ether resin represented by the following general formula (3) or (meth)allyl phenol resin represented by following formula (4) is mentioned.

[In formula (3), _{two or more R 1} and R 2 each independently exist and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group. a represents 1-3. n is an integer, and the average value represents 1 < n ≤ 5]

[In formula (4), _{two or more R 1} and R 2 each independently exist and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group. a represents 1-3. n is an integer, and the average value represents 1 < n ≤ 5]

_{Examples of the alkyl group having 1 to 10 carbon atoms in R 1} and R ₂ in the formulas (3) and (4) include a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, 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. Among them, a methyl group is preferable.

_{Examples of the aromatic group for R 1} and R ₂ in the formulas (3) and (4) include an aromatic hydrocarbon group such as a phenyl group, a biphenyl group, an indenyl group, a naphthyl group, an anthryl group, a fluorenyl group, and a pyrenyl group, fura nyl group, thienyl group, thienothienyl group, pyrrolyl group, imidazolyl group, pyridyl group, pyradyl group, pyrimidyl group, quinolyl group, indolyl group, carbazolyl group, etc. are mentioned.

In the formulas (3) and (4), R ₂ adjacent to each other on the same ring may be bonded to each other to form a condensed ring. Examples of the condensed ring formed in this case include naphthalene, anthracene, and phenanthrene.

A part of a plurality of (meth)allyl groups in the formulas (3) and (4) may be substituted with a hydrogen atom. For example, it is not necessary for all phenolic hydroxyl groups in Formula (3) to be allyl-etherified, and you may have the hydroxyl group which is not allyl-etherified.

In addition, the value of n in Formula (3) and Formula (4) is an integer, and represents 1<n average value <=5. It is preferable that n is 1-10, It is more preferable that it is 2-8, It is especially preferable that it is 2-4.

In addition, although the value of n can be calculated from the value of the weight average molecular weight calculated|required by the measurement of gel permeation chromatography (GPC), it is approximately equivalent to the value of n calculated from the measurement result of GPC of the compound which is a raw material. you may think that

350-1200 are preferable for the weight average molecular weight (Mw) of the compound (B) which has the said allyl group or metaallyl group. More preferably, it is 400-1000, Especially preferably, it is 440-800. When the molecular weight is less than 350, molding of the cured product becomes difficult due to volatility, and when the molecular weight exceeds 1200, high viscosity or compatibility with a solvent is very difficult, so that molding of the cured product becomes difficult in some cases.

In addition, a weight average molecular weight can be measured by the gel permeation chromatography method (GPC).

The total amount of chlorine in the compound (B) having an allyl group or metaallyl group is preferably 500 ppm or less, more preferably 300 ppm or less, and particularly preferably 100 ppm or less.

It is preferable that the softening point of the compound (B) which has the said allyl group or metaallyl group is 120 degrees C or less. When the softening point exceeds 120° C., since compatibility with a solvent is very difficult, it is difficult to remove the salt by washing or the like, and corrosion is sometimes considered in fields requiring electrical reliability.

The compound (B) having an allyl group or metaallyl group has excellent flame retardancy compared to resins such as general cresol novolac, and a composition capable of expressing flame retardancy without adding halogen as a flame retardant can be prepared, and the environmental load It is useful for this purpose, and can stop the movement of ions such as chlorine, which are contained to some extent from the hydrophobicity of the system, and has high electrical reliability as well as low halogen and a combination of these structures is important as a material for electrical and electronic components.

The method for producing the compound (B) having an allyl group or a metaallyl group in the thermosetting resin composition of the present invention is not particularly limited, and any known method for synthesizing an allyl ether compound may be used. For example, Japanese Patent Laid-Open No. 2003-104923 discloses a method for obtaining allyl ether by reacting a polyhydric phenol compound with a base such as an alkali metal hydroxide to react allyl chloride, allyl bromide, or allyl halide such as methyl allyl chloride. has been Alternatively, the (meth)allyl group-containing phenol resin represented by the formula (4) can also be obtained by subjecting the (meth)allyl ether resin represented by the formula (3) to a Clijen potential reaction.

For example, it is obtained by reaction of a phenol resin with an allyl (methallyl) halide. As a raw material phenol resin, phenols (phenol, C1-C4 alkyl-substituted phenol), 4,4'-bis(chlormethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl) )-1,1'-biphenyl is preferred. Particularly preferred are phenol, cresol or naphthol and 4,4'-bis(chlormethyl)-1,1'-biphenyl or 4,4'-bis(methoxymethyl)-1,1'-biphenyl is the reactant.

As for the allyl (methallyl) halide (eg, allyl chloride), it is preferable to use a small amount of the polymer. For example, allyl chloride tends to polymerize with each other to become polyallyl chloride.

The residual polyallyl chloride not only increases the total chlorine content, but also contributes to an increase in the molecular weight of the allyl ether resin, and may leave a trace amount of gel at the time of commercialization. In addition, in order to reduce the amount of chlorine, it is necessary to add a significant amount of a basic substance, which is not only undesirable industrially, but also produces allyl alcohol with high toxicity in the system.

These polyallyl chloride compounds can be easily identified by gas chromatography, etc., and as a specific amount, it is preferable that the polymer is 1 area % or less based on the area ratio of the allyl chloride monomer, more preferably 0.5 area %, more Preferably it is 0.2 area% or less, Especially preferably, it is 0.05 area% or less.

Moreover, as a purity of allyl (methallyl) chloride, 90 area% or more is preferable, 97 area% or more is more preferable, and 99 area% or more is especially preferable.

The amount of the allyl (methallyl) chloride used is usually 1.0 to 1.15 moles, preferably 1.0 to 1.10 moles, more preferably 1.0 to 1 mole of hydroxyl groups of the raw material phenol resin (hereinafter simply referred to as raw material phenol resin). ~1.05 moles.

As the base that can be used for etherification of allyl (methallyl) chloride, an alkali metal hydroxide is preferable, and specific examples thereof include sodium hydroxide and potassium hydroxide. A solid substance may be used or an aqueous solution thereof may be used, but In the present invention, it is particularly preferable to use a solid material formed into flakes from the viewpoint of solubility and handling.

The usage-amount of an alkali metal hydroxide is 1.0-1.15 mol normally with respect to 1 mol of hydroxyl groups of a raw material phenol resin, Preferably it is 1.0-1.10 mol, More preferably, it is 1.0-1.05 mol.

In order to accelerate the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride may be added as a catalyst. As the usage-amount of a quaternary ammonium salt, it is 0.1-15 g normally with respect to 1 mol of hydroxyl groups of a raw material phenol resin, Preferably it is 0.2-10 g.

In this reaction, an aprotic polar solvent such as dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetamide, dimethylimidazolidinone, or N-methylpyrrolidone may be used as needed. In particular, dimethyl sulfoxide may be used. It is preferable to use it as a solvent.

The amount of the aprotic polar solvent used is preferably 20 to 300% by weight, more preferably 25 to 250% by weight, and particularly preferably 25 to 200% by weight relative to the total weight of the phenol resin. Since the aprotic polar solvent is not useful for purification such as washing with water, it is not preferable to use it in a large amount. Moreover, since the boiling point is high and the removal of a solvent is difficult, a lot of energy is consumed, and it is not preferable to use too much.

In addition, in this reaction, it is also possible to use another solvent. When using, it is preferable to use together C1-C5 alcohol. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol.

Moreover, non-aqueous solvents, such as methyl ethyl ketone, methyl isobutyl ketone, and toluene, can also be used together. In this case, it is preferable to use 100% by weight or less based on dimethyl sulfoxide, and particularly preferably 0.5 to 50% by weight. If a non-aqueous solvent such as methyl ethyl ketone, methyl isobutyl ketone, or toluene is used excessively, cligen transition begins to occur during the reaction, and the remaining phenolic hydroxyl groups increase, resulting in insufficient allyl chloride content in the system. Otherwise, something other than the target structure may arise, or not all phenolic hydroxyl groups may be allyl-etherified.

Reaction temperature is 30-90 degreeC normally, Preferably it is 35-80 degreeC. In particular, in the present invention, it is preferable to increase the reaction temperature by dividing it into two or more steps in order to achieve higher purity allyl etherification. 35-50 degreeC of 1st stage, 45-70 degreeC of 2nd stage are especially preferable. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 5 hours. When the reaction time is short, the reaction does not proceed to the end, and when the reaction time is long, by-products are generated, which is not preferable.

After completion of the reaction, the solvents are distilled off under reduced pressure under heating. The salt which precipitates at the time of reaction does not matter as it is. The recovered allyl ether resin is dissolved in a ketone compound having 4 to 7 carbon atoms (eg, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.) as a solvent, and 40° C. to 90° C. ℃, more preferably, it is washed with water until the water layer reaches pH 5 to 8 in a state heated to 50 to 80 °C. At this time, when water washing is stopped at pH 8 or higher, if a reaction such as epoxidation is performed later, the reaction may not proceed properly because the catalyst system is broken.

In the allyl etherification reaction, it is preferable to blow an inert gas such as nitrogen (in air or in a liquid). When there is no blowing of an inert gas, coloring may generate|occur|produce in the resin obtained. Although the amount of blowing of the inert gas varies depending on the volume of the reaction vessel, blowing of the inert gas in an amount capable of replacing the volume of the reaction vessel in 0.5 to 20 hours is preferable.

Moreover, by heating the allyl ether resin obtained by the above process and making a Kleizen relocation reaction, an allyl ether group is translocated to a phenol nucleus, and an allyl group containing phenol resin can be obtained. 150-250 degreeC is preferable, as for the temperature of this rearrangement reaction, 180-230 degreeC is more preferable, 180-200 degreeC is especially preferable. By setting the reaction temperature to 150°C or higher, the progress of the clizen potential reaction can be accelerated, and by setting the reaction temperature to 250°C or lower, decomposition of a raw material, a target substance, or the like can be prevented.

Content of the compound (B) which has an allyl group or metaallyl group in the thermosetting resin composition of this invention can be set suitably according to the kind of compound to be used, and is not specifically limited. From the viewpoint of the fluidity of the thermosetting resin composition and the heat resistance of a cured product obtained by curing the same, the content ratio of the compound (B) having an allyl group or metaallyl group to the total amount of the composition is preferably 5 to 30% by mass, and 7 to 25% by mass % is more preferable. By setting the content of the compound (B) having an allyl group or metaallyl group to 5 to 30 mass % with respect to the total amount of the composition, relatively low temperature moldability is possible, and a thermosetting resin composition having a viscosity is easy to be obtained, and also has high heat resistance. There exists a tendency for the hardened|cured material which has it to be easy to be obtained.

The thermosetting resin composition of this invention can use a catalyst (or also called a "hardening accelerator") as needed. Specific examples of the catalyst that can be used include a basic (anionic) polymerization catalyst and a radical polymerization catalyst. Examples of the basic polymerization catalyst include pyridine, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, imidazole, triazole, 1-methylimidazole, and 2-methyl. Midazole, 2-ethylimidazole, 2-butylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2,4,5-triphenylimidazole, tetra Zole 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenyl Midazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl Imidazole, 2,4-diamino-6 (2'-methylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6 (2'-undecylimidazole ( 1′))ethyl-s-triazine, 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, 2:3 adduct of 2-methylimidazole isocyanuric acid, 2-phenylimida Zolisocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl Heterocyclic compounds such as various types of -3,5-dicyanoethoxymethylimidazole, and amides such as these heterocyclic compounds and dicyandiamide, 1,8-diaza-bicyclo (5.4.0 ) diaza compounds such as undecene-7 and their salts such as tetraphenylborate and phenol novolac, salts of the above polyhydric carboxylic acids or phosphinic acids, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra Propylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetra Ammonium salts such as methylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodine, tetramethylammonium acetate, and trioctylmethylammonium acetate, triphenylphosphine, tri(toluyl)phosphine, tetraphenylphosphonium bromide, tetra Phosphines such as phenylphosphonium tetraphenylborate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, amine adact, metal carboxylate salts (2-ethylhexanoic acid, stearic acid, behenic acid, Zinc salts, such as myristic acid, tin salts, and zirconium salts), phosphoric acid ester metals (zinc salts such as octyl phosphoric acid and stearyl phosphoric acid), alkoxy metal salts (tributyl aluminum, tetrapropyl zirconium, etc.), acetylacetone salts (acetylacetone) and metal compounds such as zirconium chelate and acetylacetone titanium chelate). Particularly in the present invention, phosphonium salts, ammonium salts, and metal compounds are preferable in terms of coloration during curing and changes thereof. In addition, when a quaternary salt is used, a salt with a halogen leaves a halogen in the cured product, which is not preferable from the viewpoint of electrical reliability and environmental problems.

Examples of the radical polymerization catalyst include benzoin compounds such as benzoin and benzoinmethyl; acetophenone compounds such as acetophenone and 2,2'-dimethoxy-2-phenylacetophenone; thioxanthone; Thioxanthone-based compounds such as oxanthone, 4,4'-diazide chalcone, 2,6-bis(4'-azidebenzal)cyclohexanone, and bisazide compounds such as 4,4'-diazidebenzophenone , azo compounds such as azobisisobutyronitrile, 2,2'-azobispropane, hydrazone, 2,5-dimethyl-2,6-di(t-butylperoxy)hexane, 2,5'-dimethyl and organic peroxides such as -2,5'-di(t-butylperoxy)hexyne-3 and dicumyl peroxide.

A catalyst can be used individually by 1 type or in combination of 2 or more type. It is preferable that they are an anion and a radical polymerization initiator from a sclerosis|hardenability viewpoint of the thermosetting resin obtained.

The content of the catalyst in the thermosetting resin composition can be appropriately set according to the kind of catalyst to be used, and is not particularly limited. It is preferable that the content rate of the catalyst is 0.01-5 mass parts with respect to 100 mass parts of thermosetting resin composition from a viewpoint of making the hardening acceleration effect and the heat resistance of hardened|cured material compatible, More preferably, it is 0.05-4 mass parts, More preferably, 0.1- 3 parts by mass. When there are too few catalysts, it will cause hardening failure, and when too large, it may exert a bad influence on the hardened|cured material property of a resin composition.

The thermosetting resin composition of the present invention may contain a cyanic acid ester compound. The cyanic acid ester compound is a compound represented by the general formula R-O-CN (wherein R is an organic group). As the type of the cyanic acid ester compound, there are, for example, those in which a plurality of cyanates are introduced into bisphenols, those in which a plurality of cyanates are introduced into phenol novolacs, and the like, and specific examples thereof include, for example, phenol novolacs. Polycyanate ester, bisphenol A dicyanate ester, bisphenol E dicyanate ester, tetramethylbisphenol F dicyanate ester, bisphenol F dicyanate ester, dicyclopentadiene bisphenol A dicyanate ester, etc. are mentioned, , but is not particularly limited to these. A cyanic acid ester compound can be used individually by 1 type or in combination of 2 or more type. From the viewpoint of fluidity of the obtained thermosetting resin composition, the cyanate ester compound has a viscosity at 100°C of 100 mPa·s or less, for example, phenol novolac polycyanate ester, bisphenol A dicyanate ester, bisphenol E dicyanate ester. It is preferable to be

Content of a cyanate ester compound can be suitably set according to the kind of compound to be used, and is not specifically limited. From the viewpoint of the fluidity and curability of the thermosetting resin composition and the heat resistance of a cured product obtained by curing it, the content of the cyanate ester compound is preferably 20 to 50% by mass, more preferably 22 to 45% by mass, based on the total amount of the composition. do. By setting the content of the cyanic acid ester compound to 20 to 50 mass % with respect to the total amount of the composition, a thermosetting resin composition having a viscosity and curing rate that can be molded at a relatively low temperature is easy to obtain, and a cured product having high heat resistance can be obtained. tends to be easy.

In addition, a well-known additive can be mix|blended with this invention as needed. Specific examples of the additives that can be used include epoxy resins, curing agents for epoxy resins, polybutadiene and its modified products, modified acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, and maleimide-based compounds. , cyanate ester compounds, silicone gel, silicone oil, silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder, etc. Coloring agents, such as an inorganic filler and the surface treatment agent of fillers like a silane coupling agent, a mold release agent, carbon black, phthalocyanine blue, and phthalocyanine green, are mentioned. Preferably the compounding quantity of these additives is 1,000 weight part or less with respect to 100 weight part of thermosetting resin composition, More preferably, it is the range of 700 weight part or less.

The method for adjusting the thermosetting resin composition of the present invention can be suitably applied to a known method, and is not particularly limited, but may be obtained by uniformly mixing each component or may be prepolymerized.

As an example of a preferable preparation method, the following method is mentioned, for example. In this preparation method, first, the maleimide compound (A) and the compound (B) having an allyl group or metaallyl group are melt-mixed at 120 to 160° C. for 30 minutes to 6 hours, and then the temperature of the obtained molten mixture is adjusted to 100° C. or less. After pouring, a catalyst is added to the mixture as needed, and this thermosetting resin composition is prepared by melt-mixing this uniformly.

Otherwise, the maleimide compound (A) and the compound (B) having an allyl group or metaallyl group are prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent. Similarly, the maleimide compound (A), the compound (B) having an allyl group or metaallyl group, and if necessary, a curing agent such as an amine compound, a cyanate ester compound, a phenol resin, an acid anhydride compound, and other additives are added to the prepolymer. It's okay to be reconciled In the absence of a solvent, for mixing or prepolymerization of each component, for example, an extruder, a kneader, a roll, etc. are used, and in the presence of a solvent, a reaction vessel equipped with a stirring device or the like is used.

An organic solvent can be added to the thermosetting resin composition of the present invention to obtain a varnish-like composition (hereinafter simply referred to as varnish). If necessary, the thermosetting resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone to form an epoxy resin composition varnish. and a prepreg obtained by heat-drying and impregnating a fiber base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper by hot press molding to obtain a cured product of the epoxy resin composition of the present invention have. In this case, the solvent is usually 10 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent, preferably 15 to 70% by weight. Moreover, if it is a liquid composition, the hardened|cured material containing carbon fiber can also be obtained as it is, for example by RTM system.

Moreover, the thermosetting resin composition of this invention can be used also as a modifier of a film-form composition.

Specifically, it can be used in the case of improving the flexibility and the like in the B-stage. Such a film-type resin composition is obtained as a sheet-like adhesive by applying the thermosetting resin composition of the present invention as the resin composition varnish on a release film, removing the solvent under heating, and then performing B-staging. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

The thermosetting resin composition of the present invention is heat-melted, and the viscosity is lowered and impregnated with a sheet-like fiber base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, etc. You can get prepreg.

Moreover, the prepreg of this invention can also be obtained by making a fiber base hold|maintain the said varnish and heat-drying.

After the prepreg is cut into a desired shape and, if necessary, laminated with copper foil, etc., a laminate can be obtained by heating and curing the epoxy resin composition for a laminate while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method, etc. have.

Moreover, a circuit is formed in the laminated board which laminated|stacked copper foil on the surface, and a prepreg, copper foil, etc. are superimposed on it, and the said operation is repeated, and a multilayer circuit board can be obtained.

A hardened|cured material (thermosetting resin molded object) is obtained by heat-hardening the thermosetting resin composition of this invention mentioned above. The curing method of the thermosetting resin composition is not particularly limited. For example, the thermosetting resin composition is heated to 80° C., cast between two glass plates subjected to release treatment using a 1.5 mm-thick spacer, and primary curing is performed at 170 to 200° C. for 2 hours, and then from the glass plate A hardened|cured material (thermosetting resin molded object) can be obtained by isolate|separating a primary hardened|cured material and performing post-curing at 230-260 degreeC for 2 hours.

The thermosetting resin composition of the present invention is applicable to various uses, and the use is not particularly limited. In particular, since the thermosetting resin composition of the present invention is excellent in heat resistance, strength, handleability and manufacturing efficiency, such performance is required, for example, in the field of matrix resins for fiber-reinforced composite materials or sealants for electrical and electronic components. It is particularly useful, and is particularly suitable as a matrix resin for fiber-reinforced composite materials.

Example

Next, although an Example demonstrates this invention further more concretely, below, unless otherwise indicated, a part is "mass part". In addition, this invention is not limited to these Examples.

Various analysis methods used in Examples are described below.

Absorption liquid: 20 ml of 0.1% hydrogen peroxide

The obtained feed solution was measured by ion chromatography.

・Hydroxyl equivalent: according to JIS K0070

・Epoxy equivalent: according to JIS K 7236 (ISO 3001)

・Amine equivalent: according to the method described in JIS K-7236 Annex A

Diphenylamine content: measured by gas chromatography

・ICI melt viscosity: according to JIS K 7117-2 (ISO 3219)

・Softening point: Conforms to JIS K 7234

・Total chlorine: conforms to JIS K 7243-3 (ISO 21672-3)

Gel permeation chromatography (GPC):

Analysis conditions

Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2)

The connection eluent was tetrahydrofuran, and the flow rate was 0.5 ml/min.

Column temperature is 40 ℃, detection: RI (differential refraction detector)

High-speed liquid chromatography (HPLC):

Analysis conditions

Column ODS2 eluent is acetonitrile-water gradient,

Column temperature 40° C. detection UV 274 nm, flow rate 1.0 ml/min.

·Gas Chromatography (GC):

Analysis conditions

Column HP-5 30m×0.32mm×0.25㎛

Carrier gas helium 1.0ml/min Split 1/50

Injector temperature 300℃

Detector temperature 300℃

Oven temperature program After holding at 50℃ for 5 minutes, increase the temperature from 50℃ to 300℃ at 10℃/min and keep it at 300℃ for 5 minutes.

Curing exotherm: Measurement of curing start temperature, curing exothermic peak top temperature and exothermic end temperature by MDSC measurement

Analysis conditions

Analysis mode: MDSC measurement

Measuring instrument: Q2000 made by TA Instruments Japan Inc.,

Temperature increase rate: 3°C/min

(Synthesis Example 1)

40 parts of water, 400 parts of dimethyl sulfoxide, and 210 parts of phenol biphenylene resin (hydroxyl equivalent: 210 g/eq. softening point of 74 ° C.) were added while nitrogen purging to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 45 The temperature was raised to °C, dissolved, cooled to 38-40 °C, and 44.4 parts of flake-like sodium hydroxide (purity 99% manufactured by Tosoh Corporation) (1.1 molar equivalents with respect to 1 molar equivalent of hydroxyl groups in phenol biphenylene resin) was added over 60 minutes. and, thereafter, further allyl chloride (purity 98.7 area%, commercially available allyl chloride is separated by distillation. Allyl chloride polymer content <0.2 area% confirmed by gas chromatography (GC)) 101.5 parts (phenol biphenylene resin) 1.3 molar equivalents with respect to 1 molar equivalent of hydroxyl groups, 1.18 times moles with respect to 1 mole of sodium hydroxide) were added dropwise over 60 minutes, and the reaction was performed as it is at 38-40°C for 5 hours and at 60-65°C for 1 hour.

After completion of the reaction, water or dimethyl sulfoxide was distilled off under heating and reduced pressure at 135° C. or lower with a rotary evaporator, 740 parts of methyl isobutyl ketone was added, washed with water repeatedly to confirm that the water layer became neutral, and then from the oil layer 240 parts of compound (B) (AEP1) having an allyl group was obtained by distilling off solvents while bubbling with nitrogen under reduced pressure using a rotary evaporator. The total chlorine of the obtained resin was 15 ppm. In addition, the obtained resin was semi-solid. And the number average molecular weight (Mn) obtained by GPC measurement was 579, and the weight average molecular weight (Mw) was 805.

(Synthesis Example 2)

25 mass parts of water, 500 mass parts of dimethyl sulfoxide, 500 mass of phenol resin (phenol-biphenylene type hydroxyl equivalent 200 g/eq. softening point 65 degreeC), performing nitrogen purge to the flask provided with a stirrer, a reflux cooling tube, and a stirring device. parts were added, and it heated up to 45 degreeC and made it melt|dissolve. Then, it cooled to 38-40 degreeC, and 130.0 mass parts (1.3 molar equivalent with respect to 1 molar equivalent of hydroxyl groups of a phenol resin) of flake-form caustic soda (purity 99% made from Tosoh Corporation) was added as it is over 60 minutes. Thereafter, 294.3 parts by mass of methacryl chloride (purity 99%, manufactured by Tokyo Chemical Industry Co., Ltd.) (1.3 molar equivalents with respect to 1 molar equivalent of hydroxyl groups in the phenol resin) was added dropwise over 60 minutes, and at 38 to 40°C as it was. It reacted at 60-65 degreeC for 5 hours and 1 hour.

After completion of the reaction, water, dimethyl sulfoxide, and the like were distilled off under reduced pressure by heating at 125°C or lower using a rotary evaporator. And 740 mass parts of methyl isobutyl ketone was added, water washing was repeated, and it confirmed that the water layer became neutral. Then, 600 mass parts of compounds (B) (MEP1) having a metaallyl group were obtained by distilling off solvents from the oil layer while bubbling with nitrogen under reduced pressure using a rotary evaporator. And the number average molecular weight (Mn) obtained by GPC measurement was 591, and the weight average molecular weight (Mw) was 826.

(Synthesis Example 3)

To a flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation trap, and a stirrer, 372 parts of aniline and 200 parts of toluene were charged, and 146 parts of 35% hydrochloric acid were added dropwise at room temperature in 1 hour. After completion of the dropwise addition, cooling and liquid separation of water and toluene, which were heated and azeotroped, were returned to the system and only toluene as an organic layer was returned to the system to perform dehydration. Then, 125 parts of 4,4'-bis(chloromethyl)biphenyl was added over 1 hour, maintaining 60-70 degreeC, and reaction was performed at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while the temperature was raised, the system inside was set to 195 to 200°C, and the reaction was performed at this temperature for 15 hours. Thereafter, while cooling, 330 parts of a 30% sodium hydroxide aqueous solution was slowly added dropwise so as not to reflux vigorously in the system. The separated lower aqueous layer was removed, and washing of the reaction solution with water was repeated until the washing solution became neutral. Then, 173 parts of aromatic amine resins (a1) were obtained by distilling off excess aniline and toluene from the oil layer under heating and reduced pressure (200 degreeC, 0.6 KPa) with a rotary evaporator. The diphenylamine content in the aromatic amine resin (a1) was 2.0%.

The obtained resin was further heated with a rotary evaporator under reduced pressure (200°C, 4 KPa), and water was added dropwise instead of steam blowing. As a result, 166 parts of aromatic amine resins (A1) were obtained. The softening point of the obtained aromatic amine resin (A1) was 56 degreeC, the melt viscosity was 0.035 Pa*s, and the diphenylamine was 0.1 % or less.

(Synthesis Example 4)

147 parts of maleic anhydride and 300 parts of toluene are poured into a flask equipped with a thermometer, cooling tube, Dean-Stark azeotropic distillation trap, and stirrer, and after cooling and separating the azeotropic water and toluene by heating, only toluene, which is an organic layer, is returned into the system. dehydration was performed. Next, the resin solution which melt|dissolved 195 parts of aromatic amine resin (A1) obtained by the synthesis example 3 in 195 parts of N-methyl- 2-pyrrolidone was dripped over 1 hour, maintaining the system inside at 80-85 degreeC. After completion of the dropwise addition, the reaction is carried out at the same temperature for 2 hours, 3 parts of p-toluenesulfonic acid is added, the condensate and toluene azeotroped under reflux conditions are cooled and liquid-separated. time reaction was performed. After completion of the reaction, 120 parts of toluene was added, washing with water was repeated to remove p-toluenesulfonic acid and excess maleic anhydride, and heating was performed to remove water from the system by azeotroping. Then, the reaction solution was concentrated to obtain a resin solution containing 70% of maleimide resin (MT1).

(Example 1)

44 parts by weight of the compound having an allyl group (AEP1) obtained in Synthesis Example 1 and 56 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 were blended and stirred uniformly at 150° C. to obtain the thermosetting resin composition of the present invention got it Table 1 shows the results of curing heat of the obtained thermosetting resin composition.

(Example 2)

44 parts by weight of the compound having an allyl group (AEP1) obtained in Synthesis Example 1 (AEP1) and 56 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 were mixed and uniformly stirred at 150°C, followed by triphenyl as an anionic curing accelerator 1 part by weight of phosphine (TPP JUNSEI CHEMICAL CO., LTD. reagent) was blended and uniformly stirred under the conditions of 100° C. to obtain a thermosetting resin composition of the present invention. Table 1 shows the results of curing heat of the obtained thermosetting resin composition.

(Example 3)

44 parts by weight of the compound having an allyl group (AEP1) obtained in Synthesis Example 1 (AEP1) and 56 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 were mixed and uniformly stirred at 150° C., and then dicumyl, a radical-based curing accelerator 1 part by weight of peroxide (manufactured by DCP KAYAKU AKZO CO., LTD.) was blended and uniformly stirred under the conditions of 100° C. to obtain the thermosetting resin composition of the present invention. Table 1 shows the results of curing heat of the obtained thermosetting resin composition.

From Table 1, it can be confirmed that the thermosetting resin composition of the present invention can be molded at a relatively low temperature, and if it contains an anionic polymerization catalyst and a radical polymerization catalyst, it can be molded and processed at a relatively low temperature due to the curing accelerating action. that can be checked

(Example 4)

44 parts by weight of the compound having an allyl group (AEP1) obtained in Synthesis Example 1 and 56 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 were blended, and uniformly stirred at 150° C. to obtain the thermosetting resin composition of the present invention got it This thermosetting resin composition was cured under curing conditions of 200° C.×2 hours and 250° C.×2 hours to obtain a cured product of the present invention. The measurement results of the physical properties of the cured product are shown in Tables 2 to 4.

(Example 5)

44 parts by weight of the compound having an allyl group (AEP1) obtained in Synthesis Example 1 (AEP1) and 56 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 were mixed and uniformly stirred at 150°C, followed by triphenylphosphine (TPP JUNSEI) CHEMICAL CO., LTD. reagent) 1 part by weight was blended and uniformly stirred under the conditions of 100° C. to obtain a thermosetting resin composition of the present invention. This thermosetting resin composition was cured under curing conditions of 200° C.×2 hours and 250° C.×2 hours to obtain a cured product of the present invention. Table 2 shows the measurement results of the physical properties of the cured product.

(Example 6)

45 parts by weight of the compound having a metaallyl group (MEP1) obtained in Synthesis Example 2 (MEP1) and 55 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 were blended, stirred uniformly at 150°C, and the thermosetting resin composition of the present invention got This thermosetting resin composition was cured under curing conditions of 200°C x 2 hours and 250°C x 2 hours to obtain a cured product of the present invention. Table 2 shows the measurement results of the physical properties of the cured product.

(Example 7)

45 parts by weight of the compound having a metaallyl group (MEP1) obtained in Synthesis Example 2 and 55 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 were mixed and uniformly stirred at 150° C., followed by triphenylphosphine (TPP) JUNSEI CHEMICAL CO., LTD. reagent) 1 part by weight was blended, and the mixture was uniformly stirred under the conditions of 100° C. to obtain a thermosetting resin composition of the present invention. This thermosetting resin composition was cured under curing conditions of 200° C.×2 hours and 250° C.×2 hours to obtain a cured product of the present invention. Table 2 shows the measurement results of the physical properties of the cured product.

(Example 8)

45 parts by weight of the compound having an allyl group (AEP1) obtained in Synthesis Example 1 (AEP1) and 55 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 were mixed and uniformly stirred at 150° C., and then dicumyl peroxide (DCP KAYAKU) 1 part by weight (manufactured by AKZO CO., LTD.) was blended and uniformly stirred under the conditions of 100°C to obtain the thermosetting resin composition of the present invention. This thermosetting resin composition was cured under curing conditions of 200° C.×2 hours and 250° C.×2 hours to obtain a cured product of the present invention. Table 2 shows the measurement results of the physical properties of the cured product.

(Example 9)

45 parts by weight of the compound having a metaallyl group (MEP1) obtained in Synthesis Example 2 (MEP1) and 55 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 were mixed and uniformly stirred at 150° C., and then dicumyl peroxide (DCP) 1 part by weight (manufactured by KAYAKU AKZO CO., LTD.) was blended and uniformly stirred under the conditions of 100°C to obtain the thermosetting resin composition of the present invention. This thermosetting resin composition was cured under curing conditions of 200° C.×2 hours and 250° C.×2 hours to obtain a cured product of the present invention. Table 2 shows the measurement results of the physical properties of the cured product.

(Example 10)

45 parts by weight of the compound having an allyl group (AEP1) obtained in Synthesis Example 1, 54 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4, and 1 part by weight of dicumyl peroxide (DCP KAYAKU AKZO CO., LTD.) It mixed using methyl ethyl ketone as a solvent, and obtained the uniform varnish of 50 mass % of resin content. Next, the said varnish was impregnated and apply|coated to the E glass cloth of thickness 0.2mm, it heat-dried at 160 degreeC for 10 minutes, and obtained the prepreg of 62 mass % of resin content. It confirmed that the residual solvent rate of this prepreg was 0.5 % or less. This prepreg was cut to a size of 150 mm x 250 mm, 4 sheets were stacked, 32 μm electrolytic copper foil was placed up and down, and a kapron film was placed, pressure of 2.5 MPa, 200 ° C. x 2 hours, 250 ° C. x 2 hours. was pressed to obtain a copper clad laminate. The weight loss rate of the hardening process of the obtained copper clad laminated body was measured. Table 5 shows the measurement results.

(Example 11)

45 parts by weight of the compound having a metaallyl group (MEP1) obtained in Synthesis Example 2 (MEP1) and 55 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 were mixed and uniformly stirred at 150° C., and then dicumyl peroxide (DCP) 1 part by weight (manufactured by KAYAKU AKZO CO., LTD.) was mixed and uniformly stirred under the conditions of 100° C., and then pre-cured at 180° C. × 30 minutes. The pre-cured resin was pinched|interposed on the PET film, and it was set as the 300-micrometer-thick sheet|seat with a 180 degreeC laminator. The PET film of the finished sheet was peeled off on one side, the resin part was placed up and down on the twill carbon fiber sheet, and the carbon fiber prepreg was created by pressing under a pressure of 0.1 MPa. Four of these prepregs were piled up, the kapron film was arrange|positioned up and down, the pressure of 2.5 Mpa, 200 degreeC x 2 hours, 250 degreeC x 2 hours was pressed, and the carbon fiber reinforced plastics laminated body was obtained. The weight reduction rate of the hardening process of the obtained carbon fiber reinforced plastics laminated body was measured. Table 5 shows the measurement results.

(Comparative Example 1)

61 parts by weight of EPPN-502H, (Nippon Kayaku Co., Ltd. epoxy equivalent 179 g/eq.), phenol novolac (Meiwa Plastic Industries, Ltd. hydroxyl equivalent 106 g/eq.) 38 parts by weight, TPP ( JUNSEI CHEMICAL CO., LTD. reagent) 1 part by weight, kneaded at 100°C, tableted, and transferred to prepare a resin molded body, and cured at 160°C × 2 hours 180°C × 6 hours to obtain a comparative cured product got it The measurement results of the physical properties of the cured product are shown in Tables 2 and 3.

(Comparative Example 2)

35 parts by weight of the compound having an allyl group (AEP1) obtained in Synthesis Example 1, and 65 parts by weight of 4,4'-bismaleimide diphenylmethane (manufactured by MT2 Tokyo Chemical Industry Co., Ltd.) were blended at 150° C. After uniformly stirring, 1 part by weight of dicumyl peroxide (manufactured by DCP KAYAKU AKZO CO., LTD.) was blended and uniformly stirred under the conditions of 100° C. to obtain a comparative thermosetting resin composition. This thermosetting resin composition was cured under curing conditions of 200°C x 2 hours and 250°C x 2 hours to obtain a cured product for comparison. Table 2 shows the measurement results of the physical properties of the cured product.

(Comparative Example 3)

35 parts by weight of the compound having a metaallyl group (MEP1) obtained in Synthesis Example 2 and 65 parts by weight of 4,4'-bismaleimide diphenylmethane (MT2) were mixed and uniformly stirred at 150° C., followed by dicumyl perox. 1 part by weight of a seed (manufactured by DCP KAYAKU AKZO CO., LTD.) was blended and uniformly stirred under the conditions of 100°C to obtain a comparative thermosetting resin composition. This thermosetting resin composition was cured under curing conditions of 200°C x 2 hours and 250°C x 2 hours to obtain a cured product for comparison. Table 2 shows the measurement results of the physical properties of the cured product.

(Comparative Example 4)

32 parts by weight of diallylbisphenol A (reagent) and 68 parts by weight of 4,4'-bismaleimide diphenylmethane (MT2) were mixed and uniformly stirred at 150°C, followed by triphenylphosphine (TPP JUNSEI CHEMICAL CO) ., LTD. reagent) 1 part by weight was blended and uniformly stirred under the conditions of 100°C to obtain a comparative thermosetting resin composition. This thermosetting resin composition was cured under curing conditions of 200°C x 2 hours and 250°C x 2 hours to obtain a cured product for comparison. Table 4 shows the measurement results of the physical properties of the cured product.

(Comparative Example 5)

37 parts by weight of diallylbisphenol A (reagent) and 63 parts by weight of 4,4'-bismaleimide diphenylmethane (MT2) were blended, and 1 part by weight of dicumyl peroxide (manufactured by DCP KAYAKU AKZO CO., LTD.) After mix|blending and stirring uniformly on the conditions of 100 degreeC, it pre-hardened at 180 degreeC x 30 minutes. The pre-cured resin was pinched|interposed on the PET film, and it was set as the 300-micrometer-thick sheet|seat with a 180 degreeC laminator. The PET film of the finished sheet was peeled off on one side, the resin part was placed up and down on the twill carbon fiber sheet, and the carbon fiber prepreg was created by pressing under a pressure of 0.1 MPa. Four of these prepregs were piled up, the kapron film was arrange|positioned up and down, the pressure of 0.5 MPa, 200 degreeC x 2 hours, 250 degreeC x 2 hours was pressed, and the carbon fiber reinforced plastics laminated body was obtained. The weight reduction rate of the hardening process of the obtained carbon fiber reinforced plastics laminated body was measured. Table 5 shows the measurement results.

In addition, the physical property of hardened|cured material was measured in the following way.

<Heat resistance>

·Tg: The peak point (tanδ MAX) of Tanδ in the DMA measurement was defined as Tg.

Analysis conditions

Dynamic viscoelasticity measuring instrument: TA Instruments Japan Inc., Q-800

Measuring temperature range: 30℃~280℃

On-rate: 2℃/min

Test piece size: What was cut out to 5 mm x 50 mm was used (thickness is about 800 micrometers).

<Bending Test>

- Based on JIS K6911, the test was done at room temperature and 120 degreeC.

· Bending strength: measured at 30°C according to JIS-6481 (bending strength).

<Dielectric constant test, dielectric loss tangent test>

· The test was conducted by the cavity resonator perturbation method using a 1 GHz cavity resonator manufactured by Kanto Electronic Application and Development Inc. However, the sample size made the width 1.7 mm x length 100 mm, and thickness tested it with 1.7 mm.

<Absorption rate>

Water absorption: Weight increase% of cured product immersed at 100°C×24h

<Ratio of weight reduction in curing process>

- It measured with the following formula|equation.

(Formed prepreg x 4 sheets sandwiched with kapron tape up and down: weight of (1)) weight)/(1)×100

From Table 2, it can be seen that the cured product of the thermosetting resin composition of the present invention exhibits higher heat resistance, low water absorption, and low dielectric properties compared to the cured product of a commonly used thermosetting resin composition. In addition, it can be seen from Table 3 that the cured product of the thermosetting resin composition of the present invention has excellent mechanical strength and thermal decomposition characteristics as well as heat resistance after curing.

Moreover, it can be confirmed from Table 4 that in the thermosetting resin composition for comparison, bubbles are not present in the cured product of the thermosetting resin composition of the present invention, while bubbles are present in the cured product. The presence of air bubbles in the cured product means that the resin composition is highly volatile, and in order to prepare a cured product having excellent mechanical strength, it can be assumed that a rapid temperature rise is avoided and a molding method for a long time is required.

In addition, from Table 5, it can be confirmed that the weight loss is small even in the curing process at a high temperature at the time of making glass fiber reinforced plastic (GFRP) or CFRP, and there are few volatile components. It is expected that the laminate molded with a resin effective in suppressing the generation of voids during the curing process due to volatile components exhibits excellent adhesion and mechanical properties, and also has a low yield. That is, the thermosetting resin composition of the present invention is a material suitable for a fiber-reinforced composite material.

Although this invention was demonstrated in detail with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction are possible without deviating from the mind and range of this invention.

In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2016-074500) for which it applied on April 1, 2016, The whole is used by reference. Also, all references cited herein are incorporated in their entirety.

Claims (5)

The thermosetting resin composition containing the compound (A) which has a maleimide group represented by following formula (1), and the compound (B) which has a metaallyl group.

[In Formula (1), _{two or more R<1>} exists each independently, and represents a hydrogen atom, a C1-C10 alkyl group, or an aromatic group. a represents 1-3. n is an integer, and the average value represents 1<n≤5.] The method of claim 1,
The weight average molecular weight (Mw) of the compound (B) which has the said metaallyl group is 350-1200 thermosetting resin composition. 3. The method according to claim 1 or 2,
A thermosetting resin composition further containing a catalyst. The prepreg which hold|maintained the thermosetting resin composition of Claim 1 or 2 on the sheet-like fiber base material. A cured product of the thermosetting resin composition according to claim 1 or the prepreg according to claim 4.