TW201806985A - Thermosetting resin composition, prepreg and cured product thereof - Google Patents

Abstract

Provided is a thermosetting resin composition which can be molded at relatively low temperatures, and which exhibits excellent heat resistance, mechanical strength, toughness and thermal decomposition properties after curing. This thermosetting resin composition contains: a compound (A) represented by formula (1) and having a maleimide group; and a compound (B) having an allyl group or a methallyl group. (In formula (1), each of the plurality of R1 moieties is independently present and represents a hydrogen atom, an alkyl group having 1-10 carbon atoms or an aromatic group; a represents a number of 1-3; and n represents an integer having an average satisfying 1 < n ≤ 5.).

Description

Thermosetting resin composition, prepreg and cured product thereof

The present invention relates to an application that can be used in various applications such as aerospace materials, tool mechanism parts, and electrical / electronic materials, and is particularly useful in fields such as fiber-reinforced composite materials that require heat resistance or sealing materials for electrical and electronic parts Thermosetting resin composition, prepreg, and cured product thereof.

Fiber-reinforced composite materials are composed of matrix resin and carbon fiber, glass fiber, alumina fiber, boron fiber, or aromatic polyamide fiber, and they are generally lightweight and high-strength. This fiber-reinforced composite material is widely used as insulation materials for electrical and electronic parts, laminated boards (printed wiring boards, build-up substrates, etc.), aerospace materials such as fuselage or wings of passenger aircraft, and tools such as robotic arms. It is used as a mechanism or as a building / civilian maintenance material, and is widely used for recreational applications such as golf clubs and tennis rackets. Especially in aerospace materials such as the fuselage or wings of passenger aircraft, and tool mechanisms such as robotic arms, carbon fiber reinforced composite materials (hereinafter referred to as CFRP) are required to be in a temperature range from room temperature to about 200 ° C. To maintain rigidity, heat resistance, mechanical properties, and long-term reliability, that is, it is required that the thermal decomposition temperature is sufficiently high and the water absorption rate is low. As a matrix resin for fiber-reinforced composite materials, epoxy resins are widely used, but epoxy resins are not suitable for aerospace materials or tool components due to their low heat resistance. way.

On the other hand, as a matrix resin that has high heat resistance and can withstand use environments above 200 ° C, maleimide resin is well known. As the main agent of the maleimide resin, a bismaleimide compound is generally used. However, if only this compound is used, the curability is poor and the molded product becomes brittle. Therefore, various modifiers have been developed to improve this situation. . As a solution, various modifications have been performed. For example, it is known that a modified butadiene-based resin in which a methyl (acrylic acid) group is introduced into a cyanate-based resin composition is incorporated (Patent Document 1) ), Those obtained by adding a butadiene-acrylonitrile copolymer (Patent Literature 2), or those obtained by further adding an epoxy resin (Patent Literature 3), and the like. However, although brittleness is reduced by these methods, there is a problem that the reduction in heat resistance and water resistance cannot be avoided.

Further, a method of modifying a maleimide resin by using a well-known allyl compound as an additive such as a reactive diluent, a cross-linking agent, and a flame retardant of the maleimide resin is also known. For example, Patent Document 4 discloses a resin obtained by heating, melting, and mixing o, o'-diallyl bisphenol A which is liquid at normal temperature, and mixing it with 4,4'-diphenylmethanebismaleimide. It can be impregnated with a carbon fiber sheet in a solvent-free manner.

Prior art literature

Patent literature

Patent Document 1: Japanese Patent Application Laid-Open No. 57-153045

Patent Document 2: Japanese Patent Application Laid-Open No. 57-153046

Patent Document 3: Japanese Patent Application Laid-Open No. 56-157424

Patent Document 4: Japanese Patent Application Laid-Open No. 9-87460

However, the 4,4'-diphenylmethanebismaleimide obtained in Patent Document 4 does not have mechanical strength or toughness due to the rigid skeleton, even with o, o'-diallyl bisphenol A When the modification was performed, the obtained resin did not obtain sufficient strength, and a large number of cracks were observed in the molded CFRP.

In view of the foregoing, an object of the present invention is to provide a thermosetting resin composition that can be formed at a relatively low temperature, and further has excellent heat resistance, water absorption properties, mechanical strength, and thermal decomposition properties after curing.

The present inventors conducted diligent research in view of the above facts, and found that a thermosetting resin composition containing a compound having a specific maleimide group and a compound having an allyl group or a methallyl group can be used in The molding process is performed at a relatively low temperature, and the hardening property is excellent. Furthermore, by using this thermosetting resin composition, a hardened material having excellent properties such as heat resistance can be obtained even after a short-term hardening treatment, thereby completing the present invention. .

That is, this invention relates to [1] a thermosetting resin composition containing the compound (A) which has a maleimide group represented by the following formula (1), and allyl or methene Propyl compound (B),

(In the formula (1), a plurality of existing R ₁ exist independently and represent a hydrogen atom, an alkyl group having 1 to 10 carbons or an aromatic group. A represents 1 to 3. n is an integer, and the average value thereof represents 1 <n ≦ 5); [2] The thermosetting resin composition according to the above item [1], wherein the weight average molecular weight (Mw) of the compound (B) having the allyl or methallyl group is 350 ~ 1200; [3] The thermosetting resin composition as described in the above item [1] or [2], which further contains a catalyst; [4] A prepreg, which makes the above items [1] to [3] [5] A thermosetting resin composition according to any one of the above, obtained by retaining the sheet-like fibrous base material; [5] A hardened material, which is described in any one of the above [1] to [3] A thermosetting resin composition or a cured product of the prepreg according to [4].

The thermosetting resin composition of the present invention has an effect that it can be formed at a relatively low temperature, and further has excellent heat resistance, water absorption properties, mechanical strength, and thermal decomposition properties after curing.

Hereinafter, the thermosetting resin composition of the present invention will be described.

The thermosetting resin composition of the present invention includes a compound (A) having a maleimide group (also referred to as "maleimide compound (A)") represented by the following formula (1), and Allyl or methallyl compound (B).

(In the formula (1), a plurality of existing R ₁ exist independently and represent a hydrogen atom, an alkyl group having 1 to 10 carbons or an aromatic group. A represents 1 to 3. n is an integer, and the average value thereof represents 1 <n ≦ 5)

Examples of the alkyl group having 1 to 10 carbon atoms of R ₁ in the formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, and Dibutyl, n-pentyl, isopentyl, pentyl, n-hexyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, nonyl, decyl and the like. Among them, methyl is preferred.

Examples of the aromatic group of R ₁ in the formula (1) include aromatic hydrocarbon groups such as phenyl, biphenyl, indenyl, naphthyl, anthryl, fluorenyl, and fluorenyl groups, furyl, thienyl, and thiophene. Benzothienyl, pyrrolyl, imidazolyl, pyridyl, pyr Group, pyrimidinyl, quinolinyl, indolyl, and carbazolyl.

In addition, the value of n in the formula (1) is an integer, and represents an average value of 1 <n ≦ 5. n is preferably 1 to 10, more preferably 2 to 8, and even more preferably 2 to 4. The value of n can be calculated from the value of the weight-average molecular weight of the maleimide compound (A) obtained by measurement by gel permeation chromatography (GPC). The values of n calculated from the measurement results of the compounds by GPC were approximately equal.

The manufacturing method of the said maleimide compound (A) is not specifically limited, It can manufacture by any well-known method known as a synthesis method of a maleimide compound. For example, in Japanese Unexamined Patent Publication No. 3-100016 and Japanese Unexamined Patent Publication No. 8-16151, the reactions of anilines with dihalomethyl compounds or dialkoxymethyl compounds are described. In the same way, anilines are reacted with dihalomethylbiphenyls or bisalkoxymethylbiphenyls to obtain compounds of formula (2).

(In the formula (2), a plurality of existing Rs exist independently and represent a hydrogen atom, an alkyl group having 1 to 10 carbons or an aromatic group. N is an integer, and the average value of 1 <n ≦ 5)

Examples of the alkyl group having 1 to 10 carbon atoms of R in the formula (2) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, and second Butyl, n-pentyl, isopentyl, pentyl, n-hexyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, nonyl, decyl and the like.

Examples of the aromatic group of R in the formula (2) include aromatic hydrocarbon groups such as phenyl, biphenyl, indenyl, naphthyl, anthryl, fluorenyl, and fluorenyl, furyl, thienyl, and thieno. Thienyl, pyrrolyl, imidazolyl, pyridyl, pyridine Group, pyrimidinyl, quinolinyl, indolyl, and carbazolyl.

Examples of the anilines used in the production of the above-mentioned maleimidine compounds include anilines; 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-ethylaniline, and 3-ethylaniline. , 4-ethylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethyl Aniline, 3,5-dimethylaniline, 2-propylaniline, 3-propylaniline, 4-propylaniline, 2-isopropylaniline, 3-isopropylaniline, 4-isopropylaniline, 2-ethyl-6-methylaniline, 2-second butylaniline, 2-thirdbutylaniline, 4-butylaniline, 4-secondbutylaniline, 4-thirdbutylaniline, 2 1,6-diethylaniline, 2-isopropyl-6-methylaniline, 4-pentylaniline and other alkyl-substituted anilines having a single or multiple alkyl groups of 1 to 5 carbons; Phenylanilines having a phenyl group, such as benzene and 4-aminobiphenyl, and the like. These may be used alone or in combination of two or more.

Examples of the dihalomethylbiphenyls or bisalkoxymethylbiphenyls used include 4,4'-bis (chloromethyl) biphenyl and 4,4'-bis (bromomethyl). Biphenyl, 4,4'-bis (fluoromethyl) biphenyl, 4,4'-bis (iodomethyl) biphenyl, 4,4'-dimethoxymethylbiphenyl, 4,4'- Diethoxymethyl biphenyl, 4,4'-dipropoxymethyl biphenyl, 4,4'-diisopropoxymethyl biphenyl, 4,4'-diisobutoxymethyl Biphenyl, 4,4'-dibutoxymethyl biphenyl, 4,4'-di-third-butoxymethyl biphenyl, and the like. These may be used alone or in combination of two or more. The amount of dihalomethylbiphenyls or dialkoxymethylbiphenyls used is 1-mole relative to the aniline used, usually 0.05-0.8 mol, preferably 0.1-0.6 mol.

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

Since the solvent used in the reaction needs to remove water generated during the reaction from the system, a water-insoluble solvent is used. Examples include: 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 isocyanate Ketone solvents such as butyl ketone and cyclopentanone are not limited to these, and two or more kinds may be used in combination.

In addition to the above-mentioned water-insoluble solvent, an aprotic polar solvent may be used in combination. Examples include dimethylphosphonium, dimethylphosphonium, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, and the like You can also use 2 or more types together. When an aprotic polar solvent is used, it is preferable to use a solvent having a boiling point higher than that of 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, and an N-methylpyrrolidone solution of a compound of formula (2) is added under stirring, and then p-toluenesulfonic acid is added, and water generated under reflux conditions will be removed from the system. Remove and react while.

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

From the viewpoint of the fluidity of the thermosetting resin composition and the heat resistance of the hardened material obtained by curing the content, the content of the maleimide compound (A) in the thermosetting resin composition of the present invention is relatively The total amount of the composition is preferably 30 to 70% by mass, and more preferably 35 to 60% by mass. By setting the content ratio of the maleimide compound (A) to the composition The total amount is 30 to 70% by mass, and there is a tendency that it is easy to obtain a thermosetting resin composition having a viscosity that can be formed at a relatively low temperature, and it is easy to obtain a hardened material having high heat resistance.

The thermosetting resin composition of the present invention contains the compound (A) having a maleimide group represented by the above formula (1) and the compound (B) having an allyl group or a methallyl group (also expressed as "(Meth) allyl-containing compound (B)"). The compound (B) having an allyl group or a methallyl group functions as a hardener for the maleimide compound (A).

Examples of the compound (B) having an allyl group or a methallyl group include 4,4'-bisphenol A diallyl ether, 4,4'-bisphenol F diallyl ether, and 4,4 '-Bisphenol F dimethylallyl ether, tris (meth) allyl isocyanurate, 2,2-bis (4-acetamido-3- (methyl) allylphenyl) ) Propane, bis (4-ethoxymethyl-3- (methyl) allylphenyl) methane, bis (4-ethoxymethyl-3- (methyl) allylphenyl) fluorene, 2 , 2-bis (4-benzyloxy-3- (methyl) allylphenyl) propane, bis (4-benzyloxy-3- (methyl) allylphenyl) methane , Bis (4-benzyloxy-3- (methyl) allylphenyl) hydrazone, 2,2-bis (4-tolueneoxy-3- (methyl) allylphenyl) Propane, bis (4-toluenyloxy-3- (methyl) allylphenyl) methane, bis (4-toluenyloxy-3- (methyl) allylphenyl) fluorene, 2, 2-bis (4-propioxyl-3- (methyl) allylphenyl) propane, bis (4-propylenoxy-3- (methyl) allylphenyl) methane, bis ( 4-Propanyloxy-3- (meth) allylphenyl) pyrene, 2,2-bis (4-butoxymethyl-3- (methyl) allylphenyl) propane, 2, 2-bis (4-isobutyridyloxy-3- (meth) allylphenyl) propane-allyl , Allyl alcohol, allyl ether, allyl-2-hydroxy ether, allyl glycidyl ether, methyl allyl glycidyl ether, diallyl phthalate, trimethylol Propane diallyl ether, neopentyl alcohol triallyl ether, triallyl isocyanurate. Preferable examples include a (meth) allyl ether resin represented by the following general formula (3) or a (meth) allyl phenol resin represented by the following formula (4).

(In formula (3), a plurality of existing R ₁ and R ₂ exist independently and represent a hydrogen atom, an alkyl group having 1 to 10 carbons or an aromatic group. A represents 1 to 3. n is an integer, and the average (Value represents 1 <n ≦ 5)

(In formula (4), a plurality of existing R ₁ and R ₂ exist independently and represent a hydrogen atom, an alkyl group having 1 to 10 carbons or an aromatic group. A represents 1 to 3. n is an integer, and the average (Value represents 1 <n ≦ 5)

Examples of the alkyl group having 1 to 10 carbon atoms of R ₁ and R _{2 in} the formulae (3) and (4) include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. Base, third butyl, second butyl, n-pentyl, isopentyl, pentyl, n-hexyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, nonyl, decyl and the like. Among them, methyl is preferred.

Examples of the aromatic groups of R ₁ and R _{2 in} the formulae (3) and (4) include aromatic hydrocarbon groups such as phenyl, biphenyl, indenyl, naphthyl, anthryl, fluorenyl, and fluorenyl groups. , Furyl, thienyl, thienothienyl, pyrrolyl, imidazolyl, pyridyl, pyridine Group, pyrimidinyl, quinolinyl, indolyl, and carbazolyl.

In the above formulae (3) and (4), R ₂ existing 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, phenanthrene, and the like.

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 to etherify all the phenolic hydroxyl groups in the formula (3), and it is also possible to have unallylated hydroxyl groups.

In addition, the value of n in formulas (3) and (4) is an integer, and represents the average value of 1 <n ≦ 5. n is preferably 1 to 10, more preferably 2 to 8, and even more preferably 2 to 4.

In addition, the value of n can be calculated from the value of the weight-average molecular weight obtained by the measurement by gel permeation chromatography (GPC), and can be approximated as the value of n calculated from the measurement result of GPC as a raw material compound. Roughly equal.

The weight average molecular weight (Mw) of the compound (B) having an allyl group or a methallyl group is preferably 350 to 1200. More preferably, it is 400 to 1000, and particularly preferably 440 to 800. If the molecular weight is less than 350, the hardened product is difficult to be formed due to volatility, and if the molecular weight exceeds 1200, the hardened product may be difficult to be formed due to high viscosity or very difficult to be miscible with the solvent.

The weight average molecular weight can be measured by gel permeation chromatography (GPC).

The total chlorine content of the compound (B) having an allyl group or a methallyl group is preferably 500 ppm or less, more preferably 300 ppm or less, and even more preferably 100 ppm or less.

The softening point of the compound (B) having an allyl group or a methallyl group is preferably 120 ° C or lower. If the softening point exceeds 120 ° C, it is very difficult to be compatible with the solvent, and therefore it is difficult to remove salts by washing or the like, and there is a concern that corrosion may occur in a field requiring electrical reliability.

The compound (B) having an allyl or methallyl group has superior flame retardancy compared to general resins such as cresol novolac, and can produce a composition that can exhibit flame retardance without adding halogen as a flame retarder. It is useful for environmental loads, and can stop the movement of chlorine and plasma components contained to some extent due to the high hydrophobicity of the system. Not only has high electrical reliability, but also the combination of low halogen and these structures as electrical and electronic parts Materials are more important.

In the thermosetting resin composition of the present invention, the production method of the compound (B) having an allyl group or a methallyl group is not particularly limited, and it can be well-known as a method for synthesizing an allyl ether compound. Made by any method. For example, Japanese Patent Application Laid-Open No. 2003-104923 discloses that a halogenated allyl group such as allyl chloride, allyl bromide, and methallyl chloride is reacted with a polyphenol compound using a base such as an alkali metal hydroxide. And the method of obtaining allyl ether. Alternatively, the (meth) allyl ether resin represented by the formula (3) may be subjected to a Claisen Rearrangement reaction to obtain a (meth) allyl group represented by the formula (4). Phenolic resin.

For example, it is obtained by reacting a phenol-based resin with a halogenated allyl (methallyl). As the phenol resin used as a raw material, phenols (phenol, alkyl-substituted phenol having 1 to 4 carbon atoms) and 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4, 4'-bis (methoxymethyl) -1,1'-biphenyl reactant. Especially preferred are phenol, cresol or naphthol and 4,4'-bis (chloromethyl) -1,1'-biphenyl or 4,4'-bis (methoxymethyl) -1,1'- Reactant of biphenyl.

The halogenated allyl (methallyl) (for example, allyl chloride) is preferably one having a smaller amount of polymers. For example, allyl chloride tends to polymerize with each other to become polyallyl chloride.

The residue of the polyallyl chloride not only becomes a factor that increases the total amount of chlorine, but also increases the molecular weight of the allyl ether resin, and a small amount of gel may remain during the production. Again, for To reduce the amount of chlorine, it is necessary to add a considerable amount of alkaline substances, which is not only industrially unsatisfactory, but also produces allyl alcohol, which is highly toxic in the system.

These polyallyl chloride compounds can be easily confirmed by gas chromatography or the like. As a specific amount, the area ratio is preferably 1 area% or less based on the allyl chloride monomer. The polymer is more preferably 0.5 area%, more preferably 0.2 area% or less, and even more preferably 0.05 area% or less.

The purity of allyl (methallyl) chloride is preferably 90 area% or more, more preferably 97 area% or more, and even more preferably 99 area% or more.

The amount of the allyl (methallyl) chloride used is generally 1.0 to 1.15 moles relative to 1 mol of the hydroxyl group of the phenol resin (hereinafter, also simply referred to as the raw material phenol resin) as the raw material. It is 1.0 to 1.10 moles, and more preferably 1.0 to 1.05 moles.

The alkali that can be used when allyl (methallyl) chloride is etherified is preferably an alkali metal hydroxide. Specific examples thereof include sodium hydroxide and potassium hydroxide, and solid forms can be used. It is also possible to use an aqueous solution thereof. In the present invention, particularly in terms of solubility and operability, it is preferable to use a solid formed into a sheet shape.

The amount of the alkali metal hydroxide used is usually 1.0 to 1.15 mol, preferably 1.0 to 1.10 mol, and more preferably 1.0 to 1.05 mol, relative to 1 mol of the hydroxyl group of the raw phenol resin.

To promote the reaction, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride may be added as a catalyst. The used amount of the quaternary ammonium salt is generally 0.1 to 15 g, preferably 0.2 to 10 g, relative to 1 mole of the hydroxyl group of the raw phenol resin.

In this reaction, if necessary, aprotic poles such as dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetamide, dimethylimidazolidone, and N-methylpyrrolidone can be used. As the solvent, it is particularly preferable to use dimethyl sulfene as the solvent.

The use amount of the aprotic polar solvent is preferably 20 to 300% by weight, more preferably 25 to 250% by weight, and even more preferably 25 to 200% by weight based on the total weight of the phenol resin. Aprotic polar solvents are not useful for purification, such as water washing, and are not good for large-scale use. In addition, since the boiling point is high and it is difficult to remove the solvent, a huge amount of energy is consumed, so the excess is not good.

Moreover, in this reaction, other solvents may be used. When using other solvents, it is preferred to use an alcohol having 1 to 5 carbon atoms in combination. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol, and isopropanol.

In addition, non-aqueous solvents such as methyl ethyl ketone, methyl isobutyl ketone, and toluene may be used in combination. In this case, it is preferable to use 100% by weight or less, more preferably 0.5 to 50% by weight, with respect to dimethyl fluorene. If non-aqueous solvents such as methyl ethyl ketone, methyl isobutyl ketone, toluene, etc. are used excessively, Clesen rearrangement will begin to occur during the reaction, and the residual phenolic hydroxyl groups will increase, not only the allyl groups in the system The amount of chlorine becomes insufficient, and other than the target structure is generated, and not all phenolic hydroxyl groups may be allyl etherified.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. In particular, in the present invention, in order to perform allyl etherification with higher purity, it is preferable to increase the reaction temperature by dividing into two or more stages. Particularly preferred: 35 to 50 ° C in the first stage and 45 to 70 ° C in the second stage. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, and particularly preferably 1 to 5 hours. If the reaction time is short, the reaction is incomplete, and if the reaction time is long, by-products are formed, which is not preferable.

After completion of the reaction, the solvents were distilled off under heating and reduced pressure. The salt precipitated during the reaction can be left as it is. The recovered allyl ether resin is dissolved with a ketone compound having a carbon number of 4 to 7 (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.) as a solvent, In a state of being heated to 40 ° C to 90 ° C, and more preferably 50 to 80 ° C, water washing is performed until the aqueous layer has a pH value of 5 to 8. At this time, when water washing is stopped at a pH of 8 or more, if a reaction such as epoxidation is performed thereafter, the catalyst system may be broken and the reaction may not proceed properly.

In the allyl etherification reaction, an inert gas (in a gas or a liquid) such as nitrogen is preferably blown. When the inert gas is not blown in, the obtained resin may be colored. The blowing amount of the inert gas also varies according to the volume of the reaction container, and it is preferable to blow in the amount of the inactive gas that can replace the volume of the reaction container within 0.5 to 20 hours.

Furthermore, the allyl ether resin obtained by the above steps is heated to cause a Claisen rearrangement reaction, whereby the allyl ether group is rearranged into a phenol core, and an allyl-containing phenol system can be obtained. Resin. The temperature of the rearrangement reaction is preferably 150 to 250 ° C, more preferably 180 to 230 ° C, and even more preferably 180 to 200 ° C. By setting the reaction temperature to 150 ° C or higher, the progress of the Claisen rearrangement reaction can be advanced, and by setting the reaction temperature to 250 ° C or lower, decomposition of raw materials, target materials, and the like can be prevented.

The content of the compound (B) having an allyl group or a methallyl group in the thermosetting resin composition of the present invention can be appropriately set according to the type of the compound used, and is not particularly limited. From the viewpoint of the fluidity of the thermosetting resin composition and the heat resistance of the hardened material obtained by curing it, the compound (B) having an allyl group or a methallyl group relative to the total amount of the composition The content ratio is preferably 5 to 30% by mass, and more preferably 7 to 25% by mass. By setting the content ratio of the compound (B) having an allyl group or a methallyl group to 5 to 30% by mass based on the total amount of the composition, there is a tendency that it is easy to obtain and can be formed at a relatively low temperature. In addition, a thermosetting resin composition having viscosity can easily obtain a hardened material having high heat resistance.

The thermosetting resin composition of the present invention may use a catalyst (or also referred to as a "hardening accelerator") as necessary. Specific examples of usable catalysts include basic (anionic) polymerization catalysts and radical polymerization catalysts. Examples of the basic polymerization catalyst include pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, imidazole, triazole, and 1-methylimidazole , 2-methylimidazole, 2-ethylimidazole, 2-butylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2,4,5-triphenylimidazole, Tetrazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-benzene Imidazole, 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-symmetric tris , 2,4-diamino-6- (2'-undecylimidazole (1 ')) ethyl-symmetric tris , 2,4-diamino-6- (2'-ethyl-4-methylimidazole (1 ')) ethyl-symmetric tris , 2,4-diamino-6- (2'-methylimidazole (1 ')) ethyl-symmetric tris -Isotricyanic acid adduct, 2-methylimidazole isotricyanic acid 2: 3 adduct, 2-phenylimidazole isotricyanic acid adduct, 2-phenyl-3,5 -Bis (hydroxymethyl) imidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-bis (cyanoethoxymethyl) Various isocyclic compounds such as imidazole, and such heterocyclic compounds and diamines such as dicyandiamide, 1,8-diazabicyclo (5.4.0) undecene-7, and other diaza Compounds and salts thereof such as tetraphenylborate, phenolic novolac, and the salts of the above-mentioned polycarboxylic acids or phosphinic acids; tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropyl hydroxide Ammonium, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylhexadecylammonium hydroxide, trimethylammonium hydroxide Ammonium salts such as octylmethylammonium, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate; triphenylphosphine, trimethylammonium Phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, and other phosphine or phosphonium compounds 2,4,6-tris (aminemethyl) phenols and other phenols; amine adducts; metal carboxylic acid salts (2-ethylhexanoic acid, stearic acid, behenic acid, myristic acid, etc. zinc salts, Tin salts, zirconium salts) or phosphate metal salts (zinc salts of octyl phosphate, octadecyl phosphate, etc.), metal alkoxy salts (tributylaluminum, tetrapropylzirconium, etc.), acetamidine acetone (Zirconium acetoacetate chelate, titanium chelate acetoacetate, etc.) and other metal compounds. In the present invention, sulfonium or ammonium salts and metal compounds are particularly preferred in terms of coloring or changes during curing. In the case where a quaternary salt is used, the salt with the halogen leaves halogen in the hardened material, which is not good from the viewpoints of electrical reliability and environmental issues.

As a radical polymerization catalyst, there are benzoin-based compounds such as benzoin and benzoin methyl ether; acetophenone-based compounds such as acetophenone and 2,2'-dimethoxy-2-phenylacetophenone; 9-oxygen sulfur , 2,4-diethyl-9-oxysulfur 9-oxysulfur Series compounds; 4,4'-diazidochalcone, 2,6-bis (4'-azidobenzylidene) cyclohexanone, 4,4'-diazidobenzophenone And other bisazide compounds; azo compounds such as azobisisobutyronitrile, 2,2'-azodipropane; 2,5-dimethyl-2,6-bis (third butylperoxy) hexane Organic peroxides such as alkane, 2,5'-dimethyl-2,5'-bis (third butylperoxy) hexyne-3, and dicumyl peroxide.

The catalyst may be used alone or in combination of two or more. From the viewpoint of the curability of the obtained thermosetting resin, anionic and radical polymerization initiators are preferred.

The content of the catalyst in the thermosetting resin composition can be appropriately set according to the type of the catalyst used, and is not particularly limited. From the viewpoint of considering both the hardening-promoting effect and the heat resistance of the hardened material, the content ratio of the catalyst is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 4 parts by mass relative to 100 parts by mass of the thermosetting resin composition And more preferably 0.1 to 3 parts by mass. If the catalyst is too small, it will cause the hardening failure, and if it is too large, it may adversely affect the hardened physical properties of the resin composition.

The thermosetting resin composition of the present invention may contain a cyanate ester compound. The cyanate ester compound is a compound represented by the general formula R-O-CN (wherein, R is an organic group). As cyanic acid Examples of the type of the ester compound include those obtained by introducing a plurality of cyanate groups into bisphenols, and those obtained by introducing a plurality of cyanate groups into phenol-based novolacs. As specific examples, for example, Phenolic novolac polycyanate, bisphenol A dicyanate, bisphenol E dicyanate, tetramethylbisphenol F dicyanate, bisphenol F dicyanate, dicyclopentadiene di Phenol A dicyanate and the like are not particularly limited thereto. The cyanate ester compound may be used singly or in combination of two or more kinds. From the viewpoint of the fluidity of the obtained thermosetting resin composition, the viscosity of the cyanate compound at 100 ° C is preferably 100 mPa. Those below s are preferably, for example, phenol novolac polycyanate, bisphenol A dicyanate, and bisphenol E dicyanate.

The content of the cyanate ester compound can be appropriately set according to the type of the compound used, and is not particularly limited. From the viewpoint of the fluidity and hardenability of the thermosetting resin composition and the heat resistance of the hardened material obtained by curing, the content ratio of the cyanate compound to the total amount of the composition is preferably 20 to 50 mass%, more preferably 22 to 45 mass%. By setting the content ratio of the cyanate compound to 20 to 50% by mass based on the total amount of the composition, it is easy to obtain a thermosetting resin composition having a viscosity and a curing rate that can be formed at a relatively low temperature. It tends to be easy to obtain a hardened material having high heat resistance.

Furthermore, in the present invention, known additives may be blended as necessary. Specific examples of usable additives include epoxy resins, hardeners for epoxy resins, polybutadiene and modified products thereof, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, and polyethylene , Polyimide, fluororesin, maleimide compound, cyanate compound, polysiloxane gel, polysiloxane; and silica, alumina, calcium carbonate, quartz powder , Aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder and other inorganic fillers; surface treatment agents for fillers such as silane coupling agents; release agents; carbon black , Phthalocyanine blue, Phthalocyanine and other colorants. The blending amount of these additives is preferably in the range of 1,000 parts by weight or less and more preferably 700 parts by weight or less with respect to 100 parts by weight of the thermosetting resin composition.

The method for adjusting the thermosetting resin composition of the present invention may be performed by a known method as appropriate, and is not particularly limited. The components may be uniformly mixed only 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 above-mentioned maleimide compound (A) and the compound (B) having an allyl or methallyl group are melt-mixed at 120 to 160 ° C for 30 minutes to 6 hours, and then, After the temperature of the obtained molten mixture is lowered to 100 ° C. or lower, a catalyst is added to the mixture as needed, and the mixture is uniformly melt-mixed to prepare a thermosetting resin composition.

In addition, in the presence or absence of a catalyst, the presence or absence of a solvent, the above-mentioned maleimide compound (A) and the compound (B) having an allyl group or a methallyl group are subjected to By heating, prepolymerization is performed. Similarly, an amine compound, a cyanate compound, a phenolic resin, an acid anhydride compound, etc. may be added to the maleimide compound (A) and the compound (B) having an allyl group or a methallyl group as necessary. Prepolymerization of hardeners and other additives. For mixing or prepolymerizing the components, an extruder, a kneader, a roll, etc. are used in the absence of a solvent, and a reaction container with a stirring device is used in the presence of a solvent.

An organic solvent can be added to the thermosetting resin composition of the present invention to make a varnish-like composition (hereinafter, simply referred to as a varnish). The thermosetting resin composition of the present invention is dissolved in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N- It can be made into epoxy resin composition varnish in solvents such as methylpyrrolidone, impregnated with glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and dried by heating To obtain a prepreg, and to obtain the prepreg By performing hot pressing, a cured product of the epoxy resin composition of the present invention can be produced. The solvent at this time 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 hardened | cured material containing a carbon fiber can also be obtained, for example directly by the RTM method.

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

Specifically, it can be used in cases where the flexibility and the like in the B-stage are improved. Such a film-type resin composition can be obtained by making the thermosetting resin composition of the present invention into the above-mentioned resin composition varnish, applying it on a release film, removing the solvent under heating, and then performing B stage Into a sheet-like adhesive. This sheet-shaped adhesive can be used as an interlayer insulating layer of a multilayer substrate or the like.

The thermosetting resin composition of the present invention is heated and melted to reduce its viscosity, and it is impregnated and held in a sheet-like fibrous substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber. This can obtain the prepreg of the present invention in a semi-hardened state.

In addition, the varnish may be held on a fiber substrate and dried by heating to obtain the prepreg of the present invention.

The prepreg is cut into a desired shape, and if necessary laminated with copper foil, the pressure is applied to the laminate by a pressure forming method, an autoclave forming method, a sheet winding forming method, or the like, and the laminated plate is used for The epoxy resin composition is cured by heating, whereby a laminated board can be obtained.

Furthermore, a circuit is formed on a laminated board made of copper foil superimposed on the surface, and a prepreg or copper foil is superposed thereon, and the above operations are repeated to obtain a multilayer circuit board.

It is obtained by heat-hardening the thermosetting resin composition of the present invention described above. Hardened material (thermosetting resin molded body). The method for curing the thermosetting resin composition is not particularly limited. For example, the thermosetting resin composition is heated to 80 ° C, and is cast between two glass plates after being demolded using a spacer having a thickness of 1.5 mm, and is cured once at 170 to 200 ° C for 2 hours. Then, the cured product was removed once from the glass plate, and then cured at 230 to 260 ° C for 2 hours, whereby a cured product (thermosetting resin molded body) was obtained.

The thermosetting resin composition of the present invention can be used in various applications, and its application is not particularly limited. In particular, the thermosetting resin composition of the present invention is excellent in heat resistance and strength as well as workability and manufacturing efficiency, and is therefore used for applications requiring such properties, such as matrix resins for fiber-reinforced composite materials or sealants for electrical and electronic parts. It is particularly useful in such fields as it is particularly suitable as a matrix resin for fiber-reinforced composite materials.

Examples

Next, the present invention will be described in more detail with reference to examples. Unless otherwise specified, parts refer to "mass parts". The present invention is not limited to these examples.

Hereinafter, various analysis methods used in the examples will be described.

Absorption liquid: 0.1% hydrogen peroxide 20ml

The obtained water-absorbing liquid 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: determined by gas chromatography

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

． Softening point: According to JIS K 7234

． Total chlorine: according to JIS K 7243-3 (ISO 21672-3)

． Gel Permeation Chromatography (GPC):

Analysis conditions

Columns (Shodex KF-603, KF-602.5, KF-602, KF-601 × 2)

The linked eluent is tetrahydrofuran, and the flow rate is 0.5ml / min.

The column temperature is 40 ° C. Detection: RI (differential refractive index detector)

． High performance liquid chromatography (HPLC):

Analysis conditions

The column is ODS2 and the eluent is an acetonitrile-water gradient.

The column temperature is 40 ° C, the UV detection is 274nm, and the flow rate is 1.0ml / min.

． Gas Chromatography (GC):

Analysis conditions

The column is HP-5, 30m × 0.32mm × 0.25μm

The carrier gas is helium, 1.0mL / min, and the split ratio is 1/50

Ejector temperature: 300 ° C

Detector temperature: 300 ° C

Oven temperature program: After holding at 50 ° C for 5 minutes, the temperature was raised from 50 ° C to 300 ° C at 10 ° C / min, and directly held at 300 ° C for 5 minutes.

． Hardening heat: Use MDSC measurement to measure the hardening start temperature, hardening heat peak temperature, and heat end temperature.

Analysis conditions

Analysis mode: MDSC measurement

Measuring device: Q2000, manufactured by TA-instruments,

Heating rate: 3 ℃ / min

(Synthesis example 1)

For a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, while flushing with nitrogen, 40 parts of water, 400 parts of dimethyl sulfene, and phenol biphenyl resin (210 g / eq. Of hydroxyl equivalent, 74 ° C softening point) 210 parts, dissolve after heating up to 45 ° C, cooling to 38-40 ° C, and directly adding flake-shaped sodium hydroxide (99% purity, manufactured by Tosoh) 44.4 parts (1 mol relative to the hydroxyl group of the phenol extended biphenyl resin) over 60 minutes. Ear equivalent is 1.1 mol equivalent), and then allyl chloride (purity 98.7 area%) was added dropwise over 60 minutes, and the commercially available allyl chloride was separated by distillation. The amount of allyl chloride polymer was <0.2 Area%, confirmed by gas chromatography (GC)) 101.5 parts (1 mol equivalent with respect to 1 mol of hydroxyl group of phenol extended biphenyl resin, 1.18 times mol with respect to 1 mol of sodium hydroxide Ear), directly react at 38 ~ 40 ° C for 5 hours and react at 60 ~ 65 ° C for 1 hour.

After the reaction, the water or dimethyl sulfene was distilled off at 135 ° C or lower under heating and reduced pressure using a rotary evaporator. Then, 740 parts of methyl isobutyl ketone was added and washed repeatedly with water to confirm that the water layer became medium After introducing the nitrogen gas, the solvent was distilled off from the oil layer using a rotary evaporator under reduced pressure, thereby obtaining 240 parts of a compound (B) (AEP1) having an allyl group. The total chlorine of the obtained resin was 15 ppm. The obtained resin had a semi-solid shape. The number average molecular weight (Mn) obtained by GPC measurement was 579, and the weight average molecular weight (Mw) was 805.

(Synthesis example 2)

The flask equipped with a stirrer, a reflux cooling tube and a stirring device is flushed with nitrogen, Add 25 parts by mass of water, 500 parts by mass of dimethyl sulfene, and 500 parts by mass of a phenolic resin (phenol-strene type, hydroxyl equivalent 200g / eq., Softening point 65 ° C), heat up to 45 ° C to dissolve . Subsequently, it was cooled to 38 to 40 ° C, and 130.0 parts by mass of caustic soda (purity: 99%, manufactured by Tosoh) was added directly over 60 minutes (1.3 mol equivalent to 1 mol equivalent of the hydroxyl group of the phenol resin). Thereafter, 294.3 parts by mass of methylallyl chloride (purity: 99%, manufactured by Tokyo Chemical Industry Co., Ltd.) was further added dropwise over 60 minutes (1.3 mol equivalent with respect to 1 mol equivalent of hydroxyl group of phenol resin), directly at 38 The reaction was carried out at ~ 40 ° C for 5 hours and at 60 ~ 65 ° C for 1 hour.

After completion of the reaction, water, dimethyl sulfene, and the like were distilled off using a rotary evaporator under heating and reduced pressure at 125 ° C or lower. Then, 740 parts by mass of methyl isobutyl ketone was added, and water washing was performed repeatedly, and it was confirmed that the water layer became neutral. Thereafter, while introducing nitrogen, the solvent was distilled off from the oil layer using a rotary evaporator under reduced pressure, thereby obtaining 600 parts by mass of a compound (B) (MEP1) having a methallyl group. The number average molecular weight (Mn) obtained by GPC measurement was 591, and the weight average molecular weight (Mw) was 826.

(Synthesis example 3)

In a flask equipped with a thermometer, a cooling pipe, a Dean-Stark azeotropic distillation separator, and a stirrer, 372 parts of aniline and 200 parts of toluene were added, and 146 parts of 35% hydrochloric acid was added dropwise at room temperature over 1 hour. After the completion of the dropwise addition, the azeotropic water and toluene are heated and cooled, and after liquid separation, only toluene as an organic layer is returned to the system and dehydrated. Then, while maintaining the temperature at 60 to 70 ° C., 125 parts of 4,4′-bis (chloromethyl) biphenyl was added over 1 hour, and the reaction was further performed at the same temperature for 2 hours. After the reaction was completed, toluene was distilled off while raising the temperature, and the inside of the system was set at 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 cause a severe reflux in the system, at a temperature below 80 ° C. The toluene that was distilled off during the temperature rise was returned to the system and left to stand at 70 ° C to 80 ° C. The water layer separated from the lower layer was removed, and the reaction solution was repeatedly washed with water until the washing solution became neutral. Then, the excess aniline and toluene were distilled off from the oil layer using a rotary evaporator under heating and reduced pressure (200 ° C., 0.6 KPa), thereby obtaining 173 parts of an aromatic amine resin (a1). The dianiline in the aromatic amine resin (a1) was 2.0%.

For the obtained resin, a rotary evaporator was used under heating and reduced pressure (200 ° C, 4KPa) instead of blowing in water vapor, and a little water was added dropwise one by one. As a result, 166 parts of the aromatic amine resin (A1) was obtained. The softening point of the obtained aromatic amine resin (A1) was 56 ° C, and the melt viscosity was 0.035Pa. s, diphenylamine is 0.1% or less.

(Synthesis example 4)

In a flask equipped with a thermometer, a cooling pipe, a Dean-Stark azeotropic distillation separator, and a stirrer, 147 parts of maleic anhydride and 300 parts of toluene were added, and the heated and azeotropic water and toluene were cooled and separated. After that, only toluene as an organic layer was returned to the system and dehydrated. Next, 195 parts of the aromatic amine resin (A1) obtained in Synthesis Example 3 was dissolved in 195 parts of N-methyl-2-pyrrolidone while the inside of the system was maintained at 80 to 85 ° C over 1 hour. The resulting resin solution. After the dropwise addition, the reaction was performed at the same temperature for 2 hours, 3 parts of p-toluenesulfonic acid was added, and the condensed water and toluene which had been azeotropic under reflux conditions were cooled and separated. After that, only the toluene as the organic layer was returned. It was dehydrated in the system and reacted for 20 hours. After the reaction was completed, 120 parts of benzene was added, followed by washing with water repeatedly, p-toluenesulfonic acid and excess maleic anhydride were removed, and heating was performed to remove water from the system by azeotropy. 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 a maleimide resin (MT1) obtained in Synthesis Example 4 were blended, and uniformly stirred at 150 ° C, and A thermosetting resin composition of the present invention was obtained. Table 1 shows the results of curing heat generation of the obtained thermosetting resin composition.

(Example 2)

44 parts by weight of the compound having allyl groups (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. 1 part by weight of triphenylphosphine (TPP, pure chemistry, reagent) blended as an anionic hardening accelerator, uniformly stirred at 100 ° C. to obtain the thermosetting resin composition of the present invention. Table 1 shows the results of curing heat generation of the obtained thermosetting resin composition.

(Example 3)

44 parts by weight of the compound having allyl groups (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. 1 part by weight of dicumyl peroxide (DCP, manufactured by Kayaku Akzo) blended as a radical hardening accelerator was uniformly stirred at 100 ° C to obtain the thermosetting resin composition of the present invention. Table 1 shows the results of curing heat generation of the obtained thermosetting resin composition.

From Table 1, it can be confirmed that the thermosetting resin composition of the present invention can It is confirmed that the molding process is performed at a low temperature, and when an anionic polymerization catalyst and a radical polymerization catalyst are contained, the molding process can be performed at a relatively low temperature by a hardening promoting effect.

(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 a maleimide resin (MT1) obtained in Synthesis Example 4 were blended, and uniformly stirred at 150 ° C, and A thermosetting resin composition of the present invention was obtained. The thermosetting resin composition was cured at 200 ° C. × 2 hours and 250 ° C. × 2 hours under the curing conditions 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 allyl groups (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. One part by weight of triphenylphosphine (TPP, pure chemistry, reagent) was blended and uniformly stirred at 100 ° C to obtain the thermosetting resin composition of the present invention. The thermosetting resin composition was cured at 200 ° C. × 2 hours and 250 ° C. × 2 hours under the curing conditions 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 methallyl (MEP1) obtained in Synthesis Example 2 and 55 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. The thermosetting resin composition was cured at 200 ° C. × 2 hours and 250 ° C. × 2 hours under the curing conditions 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 methallyl (MEP1) obtained in Synthesis Example 2 and 55 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 were blended, and uniformly stirred at 150 ° C Thereafter, 1 part by weight of triphenylphosphine (TPP, pure chemistry, reagent) was blended, and the mixture was uniformly stirred at 100 ° C to obtain the thermosetting resin composition of the present invention. The thermosetting resin composition was cured at 200 ° C. × 2 hours and 250 ° C. × 2 hours under the curing conditions 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)

After blending 45 parts by weight of the compound having allyl groups (AEP1) obtained in Synthesis Example 1 and 55 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4, and uniformly stirring at 150 ° C, One part by weight of dicumyl peroxide (DCP, manufactured by Kayaku Akzo) was blended and uniformly stirred at 100 ° C. to obtain a thermosetting resin composition of the present invention. The thermosetting resin composition was cured at 200 ° C. × 2 hours and 250 ° C. × 2 hours under the curing conditions 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 methallyl (MEP1) obtained in Synthesis Example 2 and 55 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 were blended, and uniformly stirred at 150 ° C Thereafter, 1 part by weight of dicumyl peroxide (DCP, manufactured by Kayaku Akzo (strand)) was blended, and the mixture was uniformly stirred at 100 ° C to obtain a thermosetting resin composition of the present invention. The thermosetting resin composition was cured at 200 ° C. × 2 hours and 250 ° C. × 2 hours under the curing conditions 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)

Using methyl ethyl ketone as a solvent, the compound having an allyl group obtained in Synthesis Example 1 was used. 45 parts by weight of the product (AEP1), 54 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4, and 1 part by weight of dicumyl peroxide (DCP, manufactured by Kayaku Akzo (stock)) were mixed to obtain The resin composition is a uniform varnish of 50% by mass. Next, the varnish was impregnated and coated on an E glass cloth having a thickness of 0.2 mm, and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 62% by mass. It was confirmed that the residual solvent ratio of the prepreg was 0.5% or less. This prepreg was cut to a size of 150 mm × 250 mm, and four sheets were stacked. A 32 μm electrolytic copper foil was placed on top of it, and then a Caprone film was placed. The pressure was 2.5 MPa at 200 ° C. for 2 hours. Pressure was applied at 250 ° C for 2 hours to obtain a copper clad laminate. The weight reduction rate of the hardening process of the obtained copper-clad laminate was measured. The measurement results are shown in Table 5.

(Example 11)

45 parts by weight of the compound having methallyl (MEP1) obtained in Synthesis Example 2 and 55 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 were blended, and uniformly stirred at 150 ° C After that, 1 part by weight of dicumyl peroxide (DCP, manufactured by Kayaku Akzo Co., Ltd.) was blended and uniformly stirred at 100 ° C, and then pre-cured at 180 ° C for 30 minutes. The pre-cured resin was sandwiched between PET films, and a sheet with a thickness of 300 μm was formed using a 180 ° C. laminator. The PET film of the manufactured sheet was peeled off on one side, and the resin part was arranged on the twill weave carbon fiber sheet up and down, and the pressure bonding was performed at a pressure of 0.1 MPa to prepare a carbon fiber prepreg. Four prepregs were stacked on top of each other, and a capron film was placed on top and bottom of the prepreg, and pressed under conditions of a pressure of 2.5 MPa, 200 ° C. for 2 hours, and 250 ° C. for 2 hours to obtain a carbon fiber reinforced plastic laminate. The weight reduction rate of the hardening process of the obtained carbon fiber reinforced plastic laminate was measured. The measurement results are shown in Table 5.

(Comparative example 1)

Blended with 61 parts by weight of EPPN-502H (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 179g / eq.), 38 parts by weight of phenolic novolac (manufactured by Meiwa Kasei, hydroxyl equivalent of 106g / eq.), And TPP (pure chemical, reagent) 1 part by weight was kneaded and compressed at 100 ° C, and then a resin molded body was prepared by transfer molding, and was cured under conditions of 160 ° C for 2 hours and 180 ° C for 6 hours to obtain a comparatively hardened product. 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 a compound having an allyl group (AEP1) obtained in Synthesis Example 1 and 65 parts by weight of 4,4'-bismaleimide diphenylmethane (MT2, manufactured by Tokyo Chemical Industry Co., Ltd.), After uniformly stirring at 150 ° C, 1 part by weight of dicumyl peroxide (DCP, manufactured by Kayaku Akzo (stock)) was blended and uniformly stirred at 100 ° C to obtain a comparative thermosetting resin.组合 物。 Composition. The thermosetting resin composition was cured at 200 ° C. × 2 hours and 250 ° C. × 2 hours under the curing conditions to obtain a comparatively cured product. Table 2 shows the measurement results of the physical properties of the cured product.

(Comparative example 3)

35 parts by weight of a compound having methallyl (MEP1) obtained in Synthesis Example 2 and 65 parts by weight of 4,4'-bismaleimide diphenylmethane (MT2) were blended at 150 ° C After uniform stirring, 1 part by weight of dicumyl peroxide (DCP, manufactured by Kayaku Akzo (strand)) was blended, and the mixture was uniformly stirred at 100 ° C to obtain a comparative thermosetting resin composition. The thermosetting resin composition was cured at 200 ° C. × 2 hours and 250 ° C. × 2 hours under the curing conditions to obtain a comparatively cured product. Table 2 shows the measurement results of the physical properties of the cured product.

(Comparative Example 4)

32 parts by weight of diallyl bisphenol A (reagent) and 4,4'-bismaleimide diphenylmethane (MT2) 68 parts by weight, after uniformly stirring at 150 ° C, 1 part by weight of triphenylphosphine (TPP, pure chemical, reagent) is blended, and uniformly stirred at 100 ° C to obtain comparative heat. A curable resin composition. The thermosetting resin composition was cured at 200 ° C. × 2 hours and 250 ° C. × 2 hours under the curing conditions to obtain a comparatively cured product. Table 4 shows the measurement results of the physical properties of the cured product.

(Comparative example 5)

37 parts by weight of diallyl bisphenol A (reagent) and 63 parts by weight of 4,4'-bismaleimide diphenylmethane (MT2), and dicumyl peroxide (DCP, Kayaku) 1 part by weight of Akzo (strand), uniformly stirred at 100 ° C, and then pre-cured at 180 ° C for 30 minutes. The pre-cured resin was sandwiched between PET films, and a sheet with a thickness of 300 μm was formed using a 180 ° C. laminator. The PET film of the manufactured sheet was peeled off on one side, and the resin part was arranged on the twill weave carbon fiber sheet up and down, and the pressure bonding was performed at a pressure of 0.1 MPa to prepare a carbon fiber prepreg. Four sheets of this prepreg were stacked, and a capron film was placed on top and bottom of the prepreg, and pressed under the conditions of a pressure of 0.5 MPa, 200 ° C. × 2 hours, and 250 ° C. × 2 hours to obtain a carbon fiber reinforced plastic laminate. The weight reduction rate of the hardening process of the obtained carbon fiber reinforced plastic laminate was measured. The measurement results are shown in Table 5.

The physical properties of the cured product were measured in accordance with the following points.

<Heat resistance>

． Tg: The peak point of Tan δ (tan δ MAX) in the DMA measurement is set to Tg.

Analysis conditions

Dynamic Viscoelasticity Tester: Made by TA-instruments, Q-800

Measurement temperature range: 30 ℃ ~ 280 ℃

Heating rate: 2 ℃ / min

Test piece size: A test piece (thickness of about 800 μm) cut into 5 mm × 50 mm was used.

<Bending test>

． Tested at room temperature and 120 ° C in accordance with JIS K 6911.

． Flexural strength: Measured at 30 ° C in accordance with JIS-6481 (flexural strength).

<Dielectric constant test, dielectric loss tangent test>

． The 1GHz cavity resonator manufactured by Kanto Electronics Application Development Co., Ltd. was used for testing by the cavity resonator vibration method. The test was performed by setting the sample size to 1.7 mm in width × 100 mm in length and 1.7 mm in thickness.

<Water absorption>

． Water absorption rate:% increase of the weight of the hardened product after immersion under the condition of 100 ℃ × 24h

<Weight reduction rate during hardening>

The measurement was performed according to the following formula.

(Kapron tape is placed between the upper and lower sides of the formed prepreg × 4 pieces: (1) weight)-(by 200 ° C × 2h + 250 ° C × 2h, pressurization pressure: 0.1MPa plus (Weight of (1)) ((1) × 100)

According to Table 2, it can be confirmed that the cured product of the thermosetting resin composition of the present invention exhibits higher heat resistance, lower water absorption, and lower dielectric than the cured product of the commonly used thermosetting resin composition. characteristic. Furthermore, from Table 3, it can be confirmed that the cured product of the thermosetting resin composition of the present invention is not only excellent in heat resistance after curing but also excellent in mechanical strength and thermal decomposition characteristics.

Moreover, according to Table 4, it was confirmed that bubbles existed in the hardened | cured material of the comparative thermosetting resin composition, On the other hand, the hardened | cured material of the thermosetting resin composition of this invention does not have air bubbles. Regarding the presence of air bubbles in the hardened material, it is presumed that the resin composition has high volatility, and in order to produce a hardened material excellent in mechanical strength, it requires a long-term molding method to avoid a sudden temperature rise.

Furthermore, according to Table 5, it can be confirmed that even in the process of hardening at high temperature at the time of making glass fiber reinforced plastic (GFRP) or CFRP, the weight reduction is small, and the volatile component is also small. In this case, it can be expected that a laminated body formed from a resin that effectively suppresses voids generated during hardening due to volatile components exhibits excellent adhesion and mechanical properties, and has a high yield. That is, the thermosetting resin composition of the present invention is a material suitable for a fiber-reinforced composite material.

The present invention has been described in detail with reference to specific aspects, but those skilled in the art should understand that various changes and modifications can be made without departing from the spirit and scope of the present invention.

In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2016-074500) filed on April 1, 2016, the entire contents of which are incorporated by reference. Also, all references cited herein are incorporated as a whole.

Claims (5)

A thermosetting resin composition comprising a compound (A) having a maleimide group and a compound (B) having an allyl group or a methallyl group represented by the following formula (1), (In the formula (1), multiple existing R ₁ exist independently and represent a hydrogen atom, an alkyl group having 1 to 10 carbons or an aromatic group; a represents 1 to 3; n is an integer, and the average value thereof represents 1 <n ≦ 5). For example, the thermosetting resin composition according to the first patent application range, wherein the weight average molecular weight (Mw) of the compound (B) having an allyl group or a methallyl group is 350 to 1200. For example, the thermosetting resin composition according to the scope of patent application 1 or 2 further contains a catalyst. A prepreg obtained by holding a thermosetting resin composition according to any one of claims 1 to 3 on a sheet-like fibrous substrate. A hardened body is a hardened body of a thermosetting resin composition according to any one of claims 1 to 3 or a prepreg according to claim 4.