TWI739817B - Thermosetting resin composition, prepreg and its cured product - Google Patents

Abstract

The present invention provides a thermosetting resin composition that can be molded and processed at a relatively low temperature, and further has excellent heat resistance, mechanical strength, toughness, and thermal decomposition characteristics after curing. The thermosetting resin composition of the present invention contains a compound (A) having a maleimide group represented by the following formula (1) and a compound (B) having an allyl group or a methallyl group,

(In formula (1), a plurality of R _1s exist independently and each represents a hydrogen atom, an alkyl group with 1 to 10 carbons or an aromatic group. a represents 1 to 3. n is an integer, and its average value represents 1 <n≦5).

Description

Thermosetting resin composition, prepreg and its cured product

The present invention relates to a kind that can be used in various applications such as aerospace materials, tool mechanism applications, electrical/electronic materials, etc., especially useful in fields such as fiber-reinforced composite materials requiring heat resistance or sealing materials for electrical and electronic parts. Thermosetting resin composition, prepreg and its cured product.

Fiber-reinforced composite materials are composed of matrix resin and reinforcing fibers such as carbon fiber, glass fiber, alumina fiber, boron fiber, or aromatic polyamide fiber, and generally have the characteristics of light weight and high strength. This fiber-reinforced composite material is widely used as insulation materials for electrical and electronic parts and laminates (printed wiring boards, build-up substrates, etc.), aerospace materials such as the fuselage or wings of passenger aircraft, and tools represented by robotic arms. The use of mechanical parts, or construction/civil engineering maintenance materials, and furthermore, are widely used for entertainment products such as golf clubs or tennis rackets. Especially in the aerospace materials such as the fuselage or wings of passenger aircraft, and the tool mechanism represented by robotic arms, for carbon fiber reinforced composite materials (hereinafter referred to as CFRP), it is required to be in the temperature range of room temperature to about 200°C To maintain rigid heat resistance, mechanical properties, and long-term reliability, that is, a sufficiently high thermal decomposition temperature and a low water absorption rate are required. As the matrix resin of fiber-reinforced composite materials, epoxy resins are widely used conventionally, 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 resins are 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, in order to improve this situation, various modifiers have been developed . As a solution, various modifications have been made. For example, it is known that a modified butadiene resin containing a methyl (acryloyl) group is blended into a cyanate resin composition (Patent Document 1 ), those obtained by adding a butadiene-acrylonitrile copolymer (Patent Document 2), or those obtained by further adding an epoxy resin to these (Patent Document 3), and the like. However, although brittleness is reduced by these methods, there is a problem that heat resistance and water resistance cannot be avoided.

Furthermore, the method of modifying the maleimide resin with an allyl compound which is well-known as a reactive diluent, a crosslinking agent, a flame retardant, etc. of the maleimide resin is also known. For example, Patent Document 4 discloses a resin obtained by heating and melting o,o'-diallyl bisphenol A which is liquid at room temperature and mixing it with 4,4'-diphenylmethane bismaleimide , Enabling it to be impregnated in the 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'-diphenylmethane bismaleimide obtained in Patent Document 4 has no mechanical strength or toughness due to its rigid skeleton, even though o,o'-diallyl bisphenol A After modification, the obtained resin does not have sufficient strength, and a large number of cracks are observed in the molded CFRP.

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

In view of the above facts, the inventors conducted diligent studies and found that a thermosetting resin composition containing a compound having a specific maleimide group and a compound having an allyl or methallyl group can be used in The molding process is performed at a relatively low temperature and the curability is excellent. Furthermore, by using the thermosetting resin composition, even if the curing treatment is performed after a short time, a cured product with excellent heat resistance and other properties can be obtained, thereby completing the present invention .

That is, the present invention relates to [1] a thermosetting resin composition comprising: a compound (A) having a maleimide group represented by the following formula (1) and an allyl group or methylene Propyl compound (B),

(In formula (1), multiple R _1s exist independently, and represent a hydrogen atom, an alkyl group with 1 to 10 carbons, or an aromatic group. a represents 1 to 3. n is an integer, and its average value represents 1 <n≦5); [2] The thermosetting resin composition as described in [1] above, wherein the weight average molecular weight (Mw) of the compound (B) having an allyl or methallyl group is 350~1200; [3] The thermosetting resin composition as described in the preceding paragraph [1] or [2], which further contains a catalyst; [4] A prepreg made of the aforementioned [1] to [3] [5] A cured product described in any one of [1] to [3] above A thermosetting resin composition or a cured product of the prepreg described in [4] above.

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

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

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

(In formula (1), multiple R _1s exist independently, and represent a hydrogen atom, an alkyl group with 1 to 10 carbons, or an aromatic group. a represents 1 to 3. n is an integer, and its average value represents 1 <n≦5)

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

基、嘧啶基、喹啉基、吲哚基及咔唑基等。 _{Examples of the aromatic group of R 1} in the above formula (1) include aromatic hydrocarbon groups such as phenyl, biphenyl, indenyl, naphthyl, anthracenyl, stilbene, and pyrenyl, furyl, thienyl, and thiophene. And thienyl, pyrrolyl, imidazolyl, pyridyl, pyridine

Group, pyrimidinyl, quinolinyl, indolyl and carbazolyl, etc.

In addition, the value of n in formula (1) is an integer, which means that 1<n's average value≦5. n is preferably from 1 to 10, more preferably from 2 to 8, and particularly preferably from 2 to 4. Furthermore, the value of n can be calculated from the value of the weight average molecular weight of the maleimide compound (A) obtained by the measurement of gel permeation chromatography (GPC), and can be approximated as the raw material The values of n calculated from the GPC measurement results of the compounds are approximately the same.

The manufacturing method of the said maleimine compound (A) is not specifically limited, It can manufacture by any well-known well-known method as a synthetic method of a maleimine compound. For example, in Japanese Patent Application Publication No. 3-100016 and Japanese Patent Application Publication No. 8-16151, the reaction of anilines with dihalomethyl compounds or dialkoxymethyl compounds is described. In the same way, anilines are reacted with dihalogenated methyl biphenyls or bis alkoxy methyl biphenyls to obtain the compound of formula (2).

(In formula (2), a plurality of Rs exist independently, and represent a hydrogen atom, an alkyl group with 1 to 10 carbons or an aromatic group. n is an integer, which represents 1<n's average value≦5)

As the alkyl group having 1 to 10 carbon atoms in R in the above formula (2), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, second Butyl, n-pentyl, isopentyl, pentyl, n-hexyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, nonyl, decyl, etc.

基、嘧啶基、喹啉基、吲哚基及咔唑基等。 The aromatic group of R in the above formula (2) includes aromatic hydrocarbon groups such as phenyl, biphenyl, indenyl, naphthyl, anthracenyl, stilbene, and pyrenyl, furyl, thienyl, and thieno Thienyl, pyrrolyl, imidazolyl, pyridyl, pyridine

Group, pyrimidinyl, quinolinyl, indolyl and carbazolyl, etc.

Examples of anilines used in the production of the maleimide compound include: aniline; 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-dimethylaniline Aniline, 3,5-dimethylaniline, 2-propylaniline, 3-propylaniline, 4-propylaniline, 2-isopropylaniline, 3-isopropylaniline, 4-isopropylaniline, 2-Ethyl-6-methylaniline, 2-second butyl aniline, 2-tertiary butyl aniline, 4-butyl aniline, 4-second butyl aniline, 4-tertiary butyl aniline, 2 ,6-Diethylaniline, 2-isopropyl-6-methylaniline, 4-pentylaniline and other alkyl-substituted anilines with single or multiple alkyl groups with 1 to 5 carbon atoms; 2-amino group Phenylanilines with phenyl groups such as benzene and 4-aminobiphenyl. These may be used alone, or two or more of them may be used in combination.

As the bishalomethylbiphenyls or bisalkoxymethylbiphenyls used, 4,4'-bis(chloromethyl)biphenyl, 4,4'-bis(bromomethyl) Biphenyl, 4,4'-bis(fluoromethyl)biphenyl, 4,4'-bis(iodomethyl)biphenyl, 4,4'-dimethoxymethylbiphenyl, 4,4'- Diethoxymethylbiphenyl, 4,4'-dipropoxymethylbiphenyl, 4,4'-diisopropoxymethylbiphenyl, 4,4'-diisobutoxymethyl Biphenyl, 4,4'-dibutoxymethylbiphenyl, 4,4'-di-tertiarybutoxymethylbiphenyl, etc. These may be used alone, or two or more of them may be used in combination. The usage amount of dihalogenated methyl biphenyls or bisalkoxy methyl biphenyls is 1 mol relative to the aniline used, usually 0.05 to 0.8 mol, preferably 0.1 to 0.6 mol.

The 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 it uses, for example, Japanese Patent Application Laid-Open No. 3-100016 Or the method described in Japanese Patent Laid-Open No. 61-229863, etc. Can.

Since the solvent used in the reaction needs to remove the water generated in the reaction from the system, a non-water-soluble 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-based solvents such as ethyl acetate and butyl acetate; Ketone-based solvents such as butyl ketone and cyclopentanone, etc.; however, they are not limited to these, and two or more types may be used in combination.

In addition to the above-mentioned water-insoluble solvents, aprotic polar solvents may also be used in combination. For example, dimethyl sulfide, dimethyl sulfide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc. can be cited , Two or more types can also be used in combination. In the case of using an aprotic polar solvent, it is preferable to use a solvent having a boiling point higher than that of the non-water-soluble solvent used in combination.

The catalyst is an acidic catalyst and is not particularly limited, and examples include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, and the like. For example, dissolving maleic acid in toluene, adding the N-methylpyrrolidone solution of the compound of formula (2) under stirring, and then adding p-toluenesulfonic acid, while the water generated under reflux conditions is removed from the system Removal, while reacting.

As the maleimide compound (A), one 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 during mixing may increase.

From the viewpoint of the fluidity of the thermosetting resin composition and the heat resistance of the cured product obtained by curing, 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, more preferably 35 to 60% by mass. By setting the content ratio of the maleimide compound (A) relative 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 with a viscosity that can be molded at a relatively low temperature, and it is easy to obtain a cured product with higher heat resistance.

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

Examples of the compound (B) having an allyl or methallyl group include 4,4'-bisphenol A diallyl ether, 4,4'-bisphenol F diallyl ether, 4,4 '-Bisphenol F dimethyl allyl ether, tris(meth)allyl isocyanurate, 2,2-bis(4-acetoxy-3-(methyl)allylphenyl) ) Propane, bis(4-acetoxy-3-(methyl)allylphenyl)methane, bis(4-acetoxy-3-(methyl)allylphenyl), 2 , 2-bis(4-benzyloxy-3-(methyl)allylphenyl)propane, bis(4-benzyloxy-3-(methyl)allylphenyl)methane , Bis(4-benzyloxy-3-(methyl)allylphenyl) sulfide, 2,2-bis(4-toluyloxy-3-(methyl)allylphenyl) Propane, bis(4-tolyloxy-3-(methyl)allylphenyl)methane, bis(4-tolyloxy-3-(methyl)allylphenyl)methane, 2, 2-bis(4-propionyloxy-3-(methyl)allylphenyl)propane, bis(4-propionyloxy-3-(methyl)allylphenyl)methane, bis( 4-propionyloxy-3-(methyl)allylphenyl) sulfide, 2,2-bis(4-butyryloxy-3-(methyl)allylphenyl)propane, 2, 2-bis(4-isobutyroxy-3-(methyl)allylphenyl)propane-allyl chloride, allyl alcohol, allyl ethyl ether, allyl-2-hydroxy ethyl ether, ene Propyl glycidyl ether, methallyl glycidyl ether, diallyl phthalate, trimethylolpropane diallyl ether, neopentyl erythritol triallyl ether, isocyanuric acid Triallyl ester. Preferably, the (meth)allyl ether resin represented by the following general formula (3) or the (meth)allyl phenol resin represented by the following formula (4) can be preferably cited.

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

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

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

基、嘧啶基、喹啉基、吲 哚基及咔唑基等。 _{Examples of the aromatic groups of R 1} and R _{2 in} the above formula (3) and formula (4) include aromatic hydrocarbon groups such as phenyl, biphenyl, indenyl, naphthyl, anthracenyl, stilbene, and pyrenyl. , Furyl, thienyl, thienothienyl, pyrrolyl, imidazolyl, pyridyl, pyridine

Group, pyrimidinyl, quinolinyl, indolyl and carbazolyl, etc.

In the above formulas (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.

Part of the multiple (meth)allyl groups in the above formula (3) and formula (4) may be substituted with a hydrogen atom. For example, it is not necessary to etherify all the phenolic hydroxyl groups in formula (3), and may have hydroxyl groups that are not allyl etherified.

In addition, the value of n in formula (3) and formula (4) is an integer, which means that the average value of 1<n≦5. n is preferably from 1 to 10, more preferably from 2 to 8, and particularly preferably from 2 to 4.

Furthermore, the value of n can be calculated from the value of the weight average molecular weight obtained by the measurement of gel permeation chromatography (GPC), and can be approximately regarded as the value of n calculated from the GPC measurement result of the compound used as the raw material 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 400~1000, particularly preferably 440~800. If the molecular weight is less than 350, it will be difficult to form the cured product due to volatility. If the molecular weight exceeds 1200, it may be difficult to form the cured product due to high viscosity or very difficult compatibility with the solvent.

Furthermore, 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 particularly 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 less. If the softening point exceeds 120°C, it is very difficult to dissolve in the solvent. Therefore, it is difficult to remove salt by washing or the like, and there is a concern that corrosion may occur in areas requiring electrical reliability.

The compound (B) with allyl or methallyl groups has superior flame retardancy compared to general cresol novolac resins, and can produce a composition that exhibits flame retardancy without adding halogen as a flame retardant It is useful for environmental load, and can stop the movement of the chlorine plasma component contained in the system due to the high hydrophobicity of the system. It not only has high electrical reliability, but also has low halogen and the combination of these structures as electrical and electronic parts The material is more important.

In the thermosetting resin composition of the present invention, the method for producing the compound (B) having an allyl group or methallyl group is not particularly limited, and it can be known as a synthetic method of an allyl ether compound. Manufactured by any method. For example, Japanese Patent Application Laid-Open No. 2003-104923 discloses the use of alkali metal hydroxides and other alkalis to react halogenated allyl groups such as allyl chloride, allyl bromide, and methallyl chloride with polyphenol compounds. And the method of obtaining allyl ether. Alternatively, the (meth)allyl ether resin represented by the above formula (3) may be subjected to Claisen Rearrangement reaction to obtain the (meth)allyl-containing resin represented by the formula (4) The phenolic resin.

For example, it is obtained by the reaction of a phenolic resin and a halogenated allyl group (methallyl). The phenolic resin used as the raw material is preferably phenols (phenol, alkyl substituted phenols with 1 to 4 carbon atoms) and 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4, The reactant of 4'-bis(methoxymethyl)-1,1'-biphenyl. Particularly preferred are phenol, cresol or naphthol and 4,4'-bis(chloromethyl)-1,1'-biphenyl or 4,4'-bis(methoxymethyl)-1,1'- The reactant of biphenyl.

The above-mentioned halogenated allyl (methallyl) (for example, allyl chloride) is preferably one whose polymer is less. For example, allyl chloride has a tendency to polymerize with each other to become polyallyl chloride.

The residue of polyallyl chloride not only causes the increase of the total chlorine content, but also increases the molecular weight of the allyl ether resin, and a small amount of gel may remain during productization. Again, for To reduce the amount of chlorine, it is necessary to add a considerable amount of alkaline substances, which is not only industrially unfavorable, but also generates highly toxic allyl alcohol in the system.

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

In addition, the purity of allyl (methallyl) chloride is preferably 90 area% or more, more preferably 97 area% or more, and particularly preferably 99 area% or more.

The usage amount of the above allyl (methallyl) chloride is 1 mol of the hydroxyl group of the phenolic resin as the raw material (hereinafter also referred to as the raw phenolic resin), usually 1.0 to 1.15 mol, preferably It is 1.0 to 1.10 mol, more preferably 1.0 to 1.05 mol.

The alkali that can be used when etherifying allyl (methallyl) chloride is preferably an alkali metal hydroxide. Specific examples include sodium hydroxide, potassium hydroxide, etc., 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 material formed into a flake shape.

The usage amount of the alkali metal hydroxide 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.

In order to promote the reaction, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride can also be added as catalysts. The usage amount of the quaternary ammonium salt is usually 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, aprotic electrodes such as dimethyl sulfide (DMSO), dimethylformamide, dimethylacetamide, dimethylimidazolidone, N-methylpyrrolidone, etc. can be used as needed. As a neutral solvent, it is particularly preferable to use dimethyl sulfoxide as the solvent.

As the usage amount of the aprotic polar solvent, relative to the total weight of the phenol resin, it is preferably 20 to 300% by weight, more preferably 25 to 250% by weight, and particularly preferably 25 to 200% by weight. Aprotic polar solvents are not useful for refining such as water washing, and it is not good to use them in large amounts. In addition, since the boiling point is high, it is difficult to remove the solvent, which consumes a huge amount of energy, so more than that is not good.

Furthermore, in this reaction, other solvents may also be used. When using other solvents, it is preferable to use an alcohol with 1 to 5 carbon atoms in combination. Alcohols with 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 also be used in combination. In this case, it is preferable to use 100% by weight or less, and particularly preferably 0.5 to 50% by weight relative to dimethyl sulfoxide. If excessive use of non-aqueous solvents such as methyl ethyl ketone, methyl isobutyl ketone, toluene, etc., Claisen 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 the structure other than the target structure is generated. In addition, the phenolic hydroxyl groups may not be allyl etherified.

The reaction temperature is usually 30 to 90°C, preferably 35 to 80°C. Particularly in the present invention, in order to perform allyl etherification of higher purity, it is preferable to divide into two or more stages to increase the reaction temperature. Especially preferred: the first stage is 35~50℃, and the second stage is 45℃~70℃. 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 will not proceed completely, and if the reaction time is long, by-products will be generated, which is not preferable.

After the reaction, the solvents were distilled off under heating and reduced pressure. The salt precipitated during the reaction can be kept as it is. Dissolve the recovered allyl ether resin with a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.) as a solvent, Under the condition of heating to 40℃~90℃, more preferably 50~80℃, wash with water until the pH value of the water layer is 5~8. At this time, when the water washing is stopped when the pH is 8 or higher, if a reaction such as epoxidation is carried out thereafter, the catalyst system may collapse, which may cause the reaction to proceed improperly.

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

Furthermore, the allyl ether resin obtained by the above steps is heated to cause the Claesen rearrangement reaction, whereby the allyl ether groups are rearranged into phenol nuclei, 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 particularly 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, it is possible to prevent the decomposition of the raw material, the target substance, and the like.

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 kind of compound used, and is not particularly limited. From the viewpoint of the fluidity of the thermosetting resin composition and the heat resistance of the cured product obtained by curing, the compound (B) having an allyl group or a methallyl group relative to the total amount of the composition The content ratio is preferably 5-30% by mass, more preferably 7-25% by mass. By setting the content ratio of the compound (B) having an allyl group or methallyl group to 5-30% by mass relative to the total amount of the composition, there is a tendency that it is easy to obtain and can be molded at a relatively low temperature The thermosetting resin composition has viscosity, and it is easy to obtain a cured product with high heat resistance.

、2,4-二胺基-6-(2'-十一烷基咪唑(1'))乙基-對稱三

、2,4-二胺基-6-(2'-乙基-4-甲基咪唑(1'))乙基-對稱三

、2,4-二胺基-6-(2'-甲基咪唑(1'))乙基-對稱三

-異三聚氰酸加成物、2-甲基咪唑異三聚氰酸之2：3加成物、2-苯基咪唑異三聚氰酸加成物、2-苯基-3,5-二(羥甲基)咪唑、2-苯基-4-羥甲基-5-甲基咪唑、1-氰乙基-2-苯基-3,5-二(氰乙氧基甲基)咪唑之各種等雜環式化合物類、以及該等雜環式化合物類與雙氰胺等醯胺類、1,8-二氮雜雙環(5.4.0)十一碳烯-7等二氮雜化合物及該等之四苯基硼酸鹽、酚系酚醛清漆等鹽類、上述多元羧酸類或次膦酸類之鹽類；氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化三甲基乙基銨、氫氧化三甲基丙基銨、氫氧化三甲基丁基銨、氫氧化三甲基十六烷基銨、氫氧化三辛基甲基銨、氯化四甲基銨、溴化四甲基銨、碘化四甲基銨、四甲基乙酸銨、三辛基甲基乙酸銨等銨鹽；三苯基膦、三(甲苯甲醯基)膦、溴化四苯基鏻、四苯基硼酸四苯基鏻等膦類或鏻化合物；2,4,6-三(胺甲基)苯酚等酚類；胺加成物；羧酸金屬鹽(2-乙基己酸、硬脂酸、山萮酸、肉豆蔻酸等之鋅鹽、錫鹽、鋯鹽)或磷酸酯金屬鹽(磷酸辛酯、磷 酸十八烷基酯等之鋅鹽)、烷氧基金屬鹽(三丁基鋁、四丙基鋯等)、乙醯丙酮鹽(乙醯丙酮鋯螯合物、乙醯丙酮鈦螯合物等)等金屬化合物等。於本發明中，就硬化時之著色或其變化之方面而言，尤佳為鏻鹽或銨鹽、金屬化合物類。又，於使用四級鹽之情形時，與鹵素之鹽會於其硬化物中殘留鹵素，就電氣可靠性及環境問題之觀點而言不佳。 The thermosetting resin composition of the present invention may optionally use a catalyst (or also referred to as a "hardening accelerator"). Specific examples of catalysts that can be used include basic (anionic) polymerization catalysts and radical polymerization catalysts. Examples of basic polymerization catalysts include pyridine, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, imidazole, triazole, 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 Ylimidazole, 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 three

, 2,4-Diamino-6-(2'-undecylimidazole (1')) ethyl-symmetric three

, 2,4-Diamino-6-(2'-ethyl-4-methylimidazole (1')) ethyl-symmetric three

, 2,4-Diamino-6-(2'-methylimidazole (1')) ethyl-symmetric three

-Isocyanuric acid adduct, 2:3 adduct of 2-methylimidazole isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5 -Bis(hydroxymethyl)imidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-bis(cyanoethoxymethyl) Various heterocyclic compounds such as imidazole, as well as these heterocyclic compounds and dicyandiamide and other amides, 1,8-diazabicyclo(5.4.0)undecene-7 and other diazanes Compounds and such salts of tetraphenyl borate, phenolic novolac, the above-mentioned polycarboxylic acids or phosphinic acid salts; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl hydroxide Ammonium, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylhexadecylammonium hydroxide, trimethylammonium hydroxide Ammonium salts such as octyl methyl ammonium, tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetramethyl ammonium iodide, tetramethyl ammonium acetate, trioctyl methyl ammonium acetate; triphenyl phosphine, three Phosphine or phosphonium compounds such as (tolyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate; phenols such as 2,4,6-tris(aminomethyl)phenol; amine addition Material; Carboxylic acid metal salt (2-ethylhexanoic acid, stearic acid, behenic acid, myristic acid, etc. zinc salt, tin salt, zirconium salt) or phosphate metal salt (octyl phosphate, octadecane phosphate Zinc salts such as base esters), metal alkoxides (tributylaluminum, tetrapropyl zirconium, etc.), acetylacetonate (acetone zirconium chelate, acetylacetone titanium chelate, etc.) and other metals Compound etc. In the present invention, particularly preferred are phosphonium salts, ammonium salts, and metal compounds in terms of coloration or changes during curing. In addition, in the case of using a quaternary salt, the salt with halogen will leave halogen in its hardened substance, which is not good from the viewpoint of electrical reliability and environmental issues.

、2,4-二乙基-9-氧硫

等9-氧硫

系化合物；4,4'-二疊氮基查爾酮、2,6-雙(4'-疊氮基苯亞甲基)環己酮、4,4'-二疊氮基二苯甲酮等雙疊氮化合物；偶氮二異丁腈、2,2'-偶氮二丙烷等偶氮化合物；2,5-二甲基-2,6-二(第三丁基過氧基)己烷、2,5'-二甲基-2,5'-二(第三丁基過氧基)己炔-3、過氧化二異丙苯等有機過氧化物。 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

Compounds; 4,4'-diazide chalcone, 2,6-bis(4'-azidobenzylidene) cyclohexanone, 4,4'-diazide benzophenone Biazide compounds such as azobisisobutyronitrile, 2,2'-azobispropane and other azo compounds; 2,5-dimethyl-2,6-bis(tertiary butylperoxy) hexane Organic peroxides such as alkane, 2,5'-dimethyl-2,5'-bis(tert-butylperoxy)hexyne-3, and dicumyl peroxide.

A catalyst can be used individually by 1 type or in combination of 2 or more types. 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 catalyst used, and is not particularly limited. From the viewpoint of taking into account both the curing acceleration effect and the heat resistance of the cured product, the content ratio of the catalyst relative to 100 parts by mass of the thermosetting resin composition is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass , And more preferably 0.1 to 3 parts by mass. If the catalyst is too small, it may cause poor curing, and if it is too much, it may adversely affect the cured 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 (in the formula, R is an organic group). As cyanic acid Types of ester compounds include, for example, those obtained by introducing multiple cyanate ester groups into bisphenols, and those obtained by introducing multiple cyanate ester groups into phenolic novolacs. Specific examples thereof include, for example, Phenolic novolac polycyanate, bisphenol A dicyanate, bisphenol E dicyanate, tetramethyl bisphenol F dicyanate, bisphenol F dicyanate, dicyclopentadiene bis Although phenol A dicyanate etc. are not specifically limited to these. A cyanate ester compound can be used individually by 1 type or in combination of 2 or more types. From the viewpoint of the fluidity of the obtained thermosetting resin composition, the cyanate ester compound preferably has a viscosity of 100 mPa at 100°C. Those less than s are, for example, phenol-based 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 compound used, and is not particularly limited. From the viewpoints of the fluidity and curability of the thermosetting resin composition and the heat resistance of the cured product obtained by curing it, the content ratio of the cyanate ester compound relative to the total composition is preferably 20~ 50% by mass, more preferably 22 to 45% by mass. By setting the content ratio of the cyanate ester compound to be 20-50% by mass relative to the total amount of the composition, it is easy to obtain a thermosetting resin composition having a viscosity and a curing speed that can be molded at a relatively low temperature. , There is a tendency to easily obtain hardened products with higher heat resistance.

Furthermore, in the present invention, known additives may be blended as necessary. Specific examples of additives that can be used include epoxy resins, epoxy resin hardeners, polybutadiene and its modified products, acrylonitrile copolymer modified products, polyphenylene ether, polystyrene, polyethylene , Polyimide, fluororesin, maleimide compound, cyanate ester compound, silicone gel, silicone oil; 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 agent for fillers such as silane coupling agent; release agent; carbon black , Phthalocyanine blue, Phthalocyanine green and other colorants. The blending amount of these additives relative to 100 parts by weight of the thermosetting resin composition is preferably 1,000 parts by weight or less, and more preferably in the range of 700 parts by weight or less.

The method for adjusting the thermosetting resin composition of the present invention can appropriately use a known method, and is not particularly limited, and only the components may be uniformly mixed, or they may be prepolymerized.

As an example of a preferable preparation method, for example, the following methods can be cited. In this preparation method, first, the maleimide compound (A) and the compound having an allyl or methallyl group (B) 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, if necessary, a catalyst is added to the mixture, and the mixture is uniformly melted and mixed, thereby preparing a thermosetting resin composition.

In addition, in the presence or absence of a catalyst, in 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 carried out. By heating, prepolymerization is performed. Similarly, amine compounds, cyanate ester compounds, phenolic resins, acid anhydride compounds, etc. may be added to the maleimide compound (A) and the compound having an allyl or methallyl group (B) as necessary. Hardener and other additives are prepolymerized. Regarding the mixing or prepolymerization of the components, for example, an extruder, kneader, roll, etc. are used in the absence of a solvent, and a reaction vessel 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 form a varnish-like composition (hereinafter referred to as a varnish). If necessary, the thermosetting resin composition of the present invention is dissolved in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N- In a solvent such as methylpyrrolidone, an epoxy resin composition varnish is made, which is impregnated with fiber substrates such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper, and then heated and dried , And obtain the prepreg, and enter the obtained prepreg Hot press molding can be used to form a cured product of the epoxy resin composition of the present invention. 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. In addition, if it is a liquid composition, it is also possible to directly obtain a hardened product containing carbon fibers, for example, by the RTM method.

In addition, the thermosetting resin composition of the present invention can also be used as a modifier of a film-type composition.

Specifically, it can be used to improve the flexibility of the B-stage. 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, coating it on a release film, and removing the solvent under heating, and then proceeding to stage B To make a sheet-like adhesive. The sheet-like 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 lower its viscosity, so that it is impregnated and held in a sheet-like fiber 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 described above may be held on a fiber substrate and heated and dried to obtain the prepreg of the present invention.

The above-mentioned prepreg is cut into the desired shape and laminated with copper foil if necessary. While applying pressure to the laminate by pressure forming, autoclave forming, sheet winding forming, etc., the laminate is used for The epoxy resin composition is heated and hardened to obtain a laminated board.

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

By heating and curing the above-mentioned thermosetting resin composition of the present invention, it is obtained Cured product (thermosetting resin molded body). The curing method of the thermosetting resin composition is not particularly limited. For example, heating the above-mentioned thermosetting resin composition to 80°C, casting it between two glass plates after demolding using spacers with a thickness of 1.5mm, and curing at 170~200°C for 2 hours. After that, the cured product is removed from the glass plate once, and cured at 230 to 260°C for 2 hours to obtain a cured product (thermosetting resin molded body).

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 has excellent heat resistance, strength, operability, and manufacturing efficiency, so it is used in applications requiring such properties, such as matrix resins for fiber-reinforced composite materials or sealants for electrical and electronic parts. It is especially useful in fields such as fiber-reinforced composite materials.

Example

Next, the present invention will be explained in detail through examples, and as long as there is no special description below, parts refer to "parts by mass". Furthermore, the present invention is not limited to these embodiments.

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

Absorbent solution: 20ml of 0.1% hydrogen peroxide

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 appendix A

. Diphenylamine content: measured 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

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

The linking solution is tetrahydrofuran and the flow rate is 0.5ml/min.

The column temperature is 40℃, 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,

Column temperature is 40℃, detection UV: 274nm, flow rate is 1.0ml/min.

. Gas chromatography (GC):

Analysis conditions

The column is HP-5, 30m×0.32mm×0.25μm

Carrier gas is helium, 1.0mL/min, split ratio (Split) is 1/50

Injector temperature: 300℃

Detector temperature: 300℃

Oven temperature program: After keeping at 50°C for 5 minutes, increase the temperature from 50°C to 300°C at 10°C/min, and keep it at 300°C for 5 minutes.

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

Analysis conditions

Analysis mode: MDSC measurement

Tester: Q2000, manufactured by TA-instruments company,

Heating rate: 3℃/min

(Synthesis example 1)

To a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, while flushing with nitrogen, add 40 parts of water, 400 parts of dimethyl sulfide, and phenolic biphenyl resin (hydroxyl equivalent 210g/eq., softening point 74℃) 210 parts, heated to 45°C to dissolve, cooled to 38~40°C, directly added flake sodium hydroxide (purity 99%, manufactured by Tosoh) over 60 minutes, 44.4 parts (relative to the hydroxyl group of phenol stretched biphenyl resin) Ear equivalent is 1.1 molar equivalent), and then allyl chloride (purity 98.7 area%) is added dropwise over 60 minutes, and the commercially available allyl chloride is separated by distillation. The amount of allyl chloride polymer is less than 0.2 Area%, confirmed by gas chromatography (GC)) 101.5 parts (1 mole equivalent to the hydroxyl group of phenol stretched biphenyl resin is 1.3 mole equivalent, and 1.18 times mole equivalent to 1 mole of sodium hydroxide Ears), directly react at 38-40°C for 5 hours and at 60-65°C for 1 hour.

After the completion of the reaction, use a rotary evaporator to distill off water or dimethyl sulfide under heating and reduced pressure at a temperature of 135°C or less, then add 740 parts of methyl isobutyl ketone, wash with water repeatedly, and confirm that the water layer becomes medium. After the performance, while blowing in nitrogen, using a rotary evaporator to distill off the solvents from the oil layer under reduced pressure, thereby obtaining 240 parts of allyl-containing compound (B) (AEP1). The total chlorine of the obtained resin was 15 ppm. In addition, the obtained resin was in a semi-solid shape. Furthermore, the number average molecular weight (Mn) obtained by GPC measurement was 579, and the weight average molecular weight (Mw) was 805.

(Synthesis example 2)

Flush the flask with a stirrer, reflux cooling tube, and stirring device with nitrogen at the same time. Add 25 parts by mass of water, 500 parts by mass of dimethyl sulfide, 500 parts by mass of phenolic resin (phenol-biphenyl type, hydroxyl equivalent 200g/eq., softening point 65°C) on one side, and heat to 45°C to dissolve . Then, it was cooled to 38-40° C., and 130.0 parts by mass of flake-like caustic soda (purity 99%, manufactured by Tosoh) was directly added over 60 minutes (1.3 molar equivalent to 1 molar equivalent of the hydroxyl group of the phenol resin). Thereafter, 294.3 parts by mass of methallyl chloride (purity 99%, manufactured by Tokyo Chemical Industry Co., Ltd.) (1.3 molar equivalent relative to 1 molar equivalent of the hydroxyl group of the phenol resin) was added dropwise over 60 minutes, and directly added to 38 React at ~40°C for 5 hours and at 60~65°C for 1 hour.

After the completion of the reaction, use a rotary evaporator to distill off water or dimethyl sulfide under heating and reduced pressure at 125°C or less. Then, 740 parts by mass of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the water layer became neutral. Thereafter, while passing nitrogen gas, a rotary evaporator was used to distill off the solvents from the oil layer under reduced pressure, thereby obtaining 600 parts by mass of the compound (B) (MEP1) having a methallyl group. Moreover, 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 tube, 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 were added dropwise over 1 hour at room temperature. After the dropwise addition is completed, the azeotropic water and toluene are cooled and separated, and then only toluene as the organic layer is returned to the system for dehydration. Then, while maintaining the temperature at 60 to 70°C, 125 parts of 4,4'-bis(chloromethyl)biphenyl was added over 1 hour, and further, the reaction was performed at the same temperature for 2 hours. After the completion of the reaction, the temperature was increased while the toluene was distilled off, the system was set to 195 to 200°C, and the reaction was carried out at this temperature for 15 hours. After that, while cooling, 330 parts of 30% sodium hydroxide aqueous solution was slowly added dropwise without violent reflux in the system, below 80°C The toluene distilled off when the temperature is raised is returned to the system, and it is allowed to stand at 70℃~80℃. Remove the water layer of the separated lower layer, and repeatedly wash the reaction liquid with water until the washing liquid becomes neutral. Then, 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 aromatic amine resin (a1). The diphenylamine in the aromatic amine resin (a1) is 2.0%.

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

(Synthesis example 4)

Add 147 parts of maleic anhydride and 300 parts of toluene to a flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation separator, and a stirrer. The heated azeotropic water and toluene are cooled and separated After that, only toluene as the organic layer was returned to the system for dehydration. Next, while maintaining the system at 80-85°C, 195 parts of the aromatic amine resin (A1) obtained in Synthesis Example 3 was dissolved in 195 parts of N-methyl-2-pyrrolidone while dripping over 1 hour The resulting resin solution. After the dripping, the reaction was carried out at the same temperature for 2 hours, 3 parts of p-toluenesulfonic acid were added, and the azeotropic condensed water and toluene under reflux conditions were cooled and separated, while only the toluene as the organic layer was returned Into the system and dehydrated, while reacting for 20 hours. After the completion of the reaction, 120 parts of benzene was added, repeated washing with water to remove p-toluenesulfonic acid and excess maleic anhydride, and heating to remove water from the system by azeotropy. Then, the reaction solution was concentrated to obtain a resin solution containing 70% maleimide resin (MT1).

(Example 1)

Blending 44 parts by weight of the allyl-containing compound (AEP1) obtained in Synthesis Example 1 and 56 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4, and uniformly stirring at 150°C, and The thermosetting resin composition of the present invention is obtained. Table 1 shows the results of curing heat generation of the obtained thermosetting resin composition.

(Example 2)

After blending 44 parts by weight of the allyl-containing compound (AEP1) obtained in Synthesis Example 1 and 56 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 and uniformly stirring at 150°C, 1 part by weight of triphenylphosphine (TPP, pure chemical, reagent), which is an anionic hardening accelerator, is blended and 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)

After blending 44 parts by weight of the allyl-containing compound (AEP1) obtained in Synthesis Example 1 and 56 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 and uniformly stirring at 150°C, 1 part by weight of dicumyl peroxide (DCP, manufactured by Kayaku Akzo), which is a free radical hardening accelerator, is blended and 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.

According to Table 1, it can be confirmed that the thermosetting resin composition of the present invention is compatible with For molding processing at low temperature, it can be confirmed that if an anionic polymerization catalyst and a radical polymerization catalyst are contained, it can be further molded at a relatively low temperature due to the hardening promotion effect.

(Example 4)

Blending 44 parts by weight of the allyl-containing compound (AEP1) obtained in Synthesis Example 1 and 56 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4, and uniformly stirring at 150°C, and The thermosetting resin composition of the present invention is obtained. The thermosetting resin composition was cured under curing conditions of 200° C.×2 hours and 250° C.×2 hours to obtain the cured product of the present invention. The measurement results of the physical properties of the hardened product are shown in Tables 2 to 4.

(Example 5)

After blending 44 parts by weight of the allyl-containing compound (AEP1) obtained in Synthesis Example 1 and 56 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4 and uniformly stirring at 150°C, Blended with 1 part by weight of triphenylphosphine (TPP, Pure Chemical, reagent) and uniformly stirred at 100°C to obtain the thermosetting resin composition of the present invention. The thermosetting resin composition was cured under curing conditions of 200° C.×2 hours and 250° C.×2 hours to obtain the cured product of the present invention. Table 2 shows the measurement results of the physical properties of the cured product.

(Example 6)

Mix 45 parts by weight of the methallyl-containing compound (MEP1) obtained in Synthesis Example 2 and 55 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4, and stir uniformly at 150°C , And obtain the thermosetting resin composition of the present invention. The thermosetting resin composition was cured under curing conditions of 200° C.×2 hours and 250° C.×2 hours to obtain the cured product of the present invention. Table 2 shows the measurement results of the physical properties of the cured product.

(Example 7)

Mix 45 parts by weight of the methallyl-containing compound (MEP1) obtained in Synthesis Example 2 and 55 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4, and stir uniformly at 150°C After that, 1 part by weight of triphenylphosphine (TPP, Pure Chemical, reagent) is blended and uniformly stirred at 100° C. to obtain the thermosetting resin composition of the present invention. The thermosetting resin composition was cured under curing conditions of 200° C.×2 hours and 250° C.×2 hours to obtain the 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 allyl-containing compound (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, 1 part by weight of dicumyl peroxide (DCP, manufactured by Kayaku Akzo Co., Ltd.) was blended and uniformly stirred at 100°C to obtain the thermosetting resin composition of the present invention. The thermosetting resin composition was cured under curing conditions of 200° C.×2 hours and 250° C.×2 hours to obtain the cured product of the present invention. Table 2 shows the measurement results of the physical properties of the cured product.

(Example 9)

Mix 45 parts by weight of the methallyl-containing compound (MEP1) obtained in Synthesis Example 2 and 55 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4, and stir uniformly 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. to obtain the thermosetting resin composition of the present invention. The thermosetting resin composition was cured under curing conditions of 200° C.×2 hours and 250° C.×2 hours to obtain the 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 with allyl group obtained in Synthesis Example 1 45 parts by weight of the compound (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 Co., Ltd.) were mixed to obtain The resin composition is a uniform varnish of 50% by mass. Next, the above varnish was impregnated and coated on E glass cloth with a thickness of 0.2 mm, and heated and dried at 160° C. for 10 minutes to obtain a prepreg with a resin content of 62% by mass. It was confirmed that the residual solvent rate of the prepreg was 0.5% or less. The prepreg was cut into a size of 150mm×250mm, and 4 pieces were stacked, and a 32μm electrolytic copper foil was placed on top and bottom of the prepreg, and then a Caprone film was placed at a pressure of 2.5MPa, 200°C for 2 hours , 250℃×2 hours, pressurize to obtain copper clad laminate. The weight reduction rate in the hardening process of the obtained copper-clad laminate was measured. The measurement results are shown in Table 5.

(Example 11)

Mix 45 parts by weight of the methallyl-containing compound (MEP1) obtained in Synthesis Example 2 and 55 parts by weight of the maleimide resin (MT1) obtained in Synthesis Example 4, and stir uniformly at 150°C After that, 1 part by weight of dicumyl peroxide (DCP, manufactured by Kayaku Akzo Co., Ltd.) was blended, and the mixture was uniformly stirred at 100° C., and then pre-hardened at 180° C.×30 minutes. The pre-cured resin is sandwiched between the PET films, and a sheet with a thickness of 300μm is formed by a laminating machine at 180°C. The PET film of the finished sheet is peeled off on one side, and the resin part is arranged up and down on the twill weave carbon fiber sheet and crimped at a pressure of 0.1 MPa to form a carbon fiber prepreg. Four sheets of this prepreg were stacked, capron membranes were placed on top and bottom of the prepreg, and pressure was applied under the conditions of 2.5 MPa, 200° C.×2 hours, and 250° C.×2 hours, to obtain a carbon fiber reinforced plastic laminate. The weight reduction rate during the curing 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, epoxy equivalent 179g/eq.), phenolic novolac (manufactured by Meiwa Chemicals, hydroxy equivalent 106g/eq.) 38 parts by weight, TPP (Junsei Chemical, reagent) 1 part by weight, after kneading and tableting at 100°C, a resin molded body was prepared by transfer molding, and cured under the conditions of 160°C×2 hours and 180°C×6 hours to obtain a cured product for comparison. Tables 2 and 3 show the measurement results of the physical properties of the cured product.

(Comparative example 2)

Blending 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 (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 Co., Ltd.) is blended and stirred at 100°C to obtain a thermosetting resin for comparison. Composition. The thermosetting resin composition was cured under curing conditions of 200°C × 2 hours and 250°C × 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)

Blending 35 parts by weight of the methallyl-containing compound (MEP1) obtained in Synthesis Example 2 and 65 parts by weight of 4,4'-bismaleimide diphenylmethane (MT2) at 150°C After uniform stirring, 1 part by weight of dicumyl peroxide (DCP, manufactured by Kayaku Akzo Co., Ltd.) was blended and stirred uniformly at 100°C to obtain a thermosetting resin composition for comparison. The thermosetting resin composition was cured under curing conditions of 200°C × 2 hours and 250°C × 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)

Blended with 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, blending 1 part by weight of triphenylphosphine (TPP, pure chemical, reagent), and stirring uniformly at 100°C to obtain heat for comparison Curable resin composition. The thermosetting resin composition was cured under curing conditions of 200°C × 2 hours and 250°C × 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)

Blended with 37 parts by weight of diallyl bisphenol A (reagent) and 63 parts by weight of 4,4'-bismaleimide diphenylmethane (MT2), and blended with dicumyl peroxide (DCP, Kayaku) 1 part by weight, uniformly stirred at 100°C, and then pre-hardened at 180°C×30 minutes. The pre-cured resin is sandwiched between the PET films, and a sheet with a thickness of 300μm is formed by a laminating machine at 180°C. The PET film of the finished sheet is peeled off on one side, and the resin part is arranged up and down on the twill weave carbon fiber sheet and crimped at a pressure of 0.1 MPa to form a carbon fiber prepreg. Four sheets of this prepreg were stacked, capron membranes were placed on top and bottom of the prepreg, and pressure was applied under the conditions 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 during the curing process of the obtained carbon fiber reinforced plastic laminate was measured. The measurement results are shown in Table 5.

In addition, the physical properties of the cured product are measured in accordance with the following points.

<Heat resistance>

. Tg: Set the peak point of Tan δ (tan δ MAX) in the DMA measurement as Tg.

Analysis conditions

Dynamic viscoelasticity tester: manufactured by TA-instruments, Q-800

Measuring temperature range: 30℃~280℃

Heating rate: 2℃/min

Test piece size: Use a test piece cut into 5mm×50mm (thickness about 800μm).

<Bending test>

. According to JIS K 6911, test at room temperature and 120°C.

. 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. is used for testing by the cavity resonator vibration method. Here, the sample size was set to 1.7 mm in width × 100 mm in length, and the test was performed with a thickness of 1.7 mm.

<Water Absorption>

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

<Weight reduction rate during hardening>

The measurement is performed according to the following formula.

(The capron tape is sandwiched between the top and bottom of the molded prepreg×4 pieces: the weight of (1))-(by 200℃×2h+250℃×2h, pressure: 0.1MPa plus (1) weight made by pressing)/(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, low water absorption, and low dielectric compared with the cured product of the commonly used thermosetting resin composition. characteristic. Furthermore, according to Table 3, it can be confirmed that the cured product of the thermosetting resin composition of the present invention not only has excellent heat resistance after curing, but also has excellent mechanical strength and thermal decomposition characteristics.

In addition, according to Table 4, it can be confirmed that air bubbles are present in the cured product of the thermosetting resin composition for comparison. In contrast, the cured product of the thermosetting resin composition of the present invention does not have air bubbles. Regarding the presence of air bubbles in the cured product, it can be inferred that the resin composition has high volatility, and in order to prepare a cured product with excellent mechanical strength, a long-term molding method is required to avoid a sudden temperature rise.

Furthermore, according to Table 5, it can be confirmed that even in the curing process at high temperature when the glass fiber reinforced plastic (GFRP) or CFRP is made, the weight loss is less and the volatile components are also less. In this case, it can be expected that a laminate formed from a resin that effectively suppresses voids generated during curing caused by volatile components will exhibit excellent adhesion, mechanical properties, and high yield. That is, the thermosetting resin composition of the present invention is suitable as a material for fiber-reinforced composite materials.

The present invention has been described in detail above with reference to specific aspects, but those familiar with 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 a Japanese patent application (Japanese Patent Application 2016-074500) filed on April 1, 2016, and the entire content is used by reference. In addition, all reference systems cited in this text are incorporated as a whole.

Claims (5)

A thermosetting resin composition comprising: a compound (A) having a maleimide group represented by the following formula (1) and a compound (B) having a methallyl group,

(In formula (1), a plurality of R ₁ exists independently, and represents a hydrogen atom, an alkyl group with 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). For example, the thermosetting resin composition of the first item in the scope of the patent application, wherein the weight average molecular weight (Mw) of the above-mentioned methallyl-containing compound (B) is 350 to 1200. For example, the thermosetting resin composition of item 1 or 2 of the scope of patent application further contains a catalyst. A prepreg obtained by holding the thermosetting resin composition of any one of items 1 to 3 in the scope of the patent application on a sheet-like fibrous base material. A hardened product, which is a thermosetting resin composition in any one of the scope of patent application 1 to 3 or a hardened product of a prepreg in the scope of patent application 4.