TWI833906B - Hardening resin composition - Google Patents

Abstract

[Problem] To provide a curable resin composition whose cured product has excellent heat resistance and dielectric properties, its cured product, and prepregs, circuit boards, build-up films, and semiconductor packaging materials that have these properties. , and semiconductor devices. [Solution] The curable resin composition of the present invention is characterized by containing maleimide (A) having an indene skeleton, a polyphenylene ether compound (B), and an epoxy resin (C).

Description

Hardening resin composition

The present invention relates to a curable resin composition, a cured product obtained from the curable resin composition, a prepreg, a circuit board, a build-up film, a semiconductor packaging material, and a semiconductor device.

As a material for circuit boards used in electronic instruments, it is widely used: Pre-preg is obtained by impregnating glass fiber cloth with thermosetting resins such as epoxy resin and BT (bismaleimide-trimethacrylate) resin, and then heating and drying them. object; a laminated board made by heating and hardening the prepreg; a multi-layer board made by combining the laminated board and the prepreg and heating and hardening. Among other things, as semiconductor package substrates are becoming thinner, warpage of the package substrate during mounting has become a problem. Therefore, in order to suppress this, materials exhibiting high heat resistance are being pursued.

In addition, in recent years, signals have been developed at higher speeds and higher frequencies, and it is desired to provide thermosetting properties for hardened materials that can maintain a sufficiently low dielectric constant and exhibit a sufficiently low dielectric loss tangent in such environments. Resin composition.

Especially recently, in various electrical material applications, especially in advanced material applications, further improvements in performance represented by heat resistance and dielectric properties, and materials and compositions that have both of these are being pursued.

In response to these demands, maleimide resin has attracted attention as a material that has both heat resistance, low dielectric constant and low dielectric loss tangent. However, although conventional maleimide resins have shown high heat resistance, their dielectric constant and dielectric loss tangent values have not reached the level required for cutting-edge material applications. In addition, they are poorly soluble in solvents and Due to poor workability, there is a strong desire to develop a resin that exhibits further low dielectric constant and low dielectric loss tangent while maintaining heat resistance, and also has excellent solvent solubility.

On the other hand, as a cyanate-based material that has both high dielectric properties and heat resistance, a mixture of phenol novolac-type cyanate ester resin, bisphenol A cyanate ester resin, and non-halogen cyclic ring is known. A resin composition made of oxygen resin (see Patent Document 1).

However, although the resin composition described in the aforementioned Patent Document 1 improves the heat resistance and dielectric properties of the cured product to some extent, the heat resistance is still not up to the level required in recent years. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2004-182850

[Problem to be solved by the invention]

Therefore, the problem to be solved by the present invention is to provide a curable resin composition whose cured product has both excellent heat resistance and dielectric properties, and its cured product, as well as a prepreg, a circuit board, and a circuit board having these properties. Build-up films, semiconductor packaging materials, and semiconductor devices. [Means used to solve problems]

Therefore, the present inventors intensively studied in order to solve the above-mentioned problems, and as a result, they discovered the curability of a maleimide (A) having an indene skeleton, a polyphenylene ether compound (B), and an epoxy resin (C). The resin composition enables the cured product to have a low dielectric constant and low dielectric loss tangent, as well as excellent heat resistance, thus completing the present invention.

That is, the present invention relates to a curable resin composition characterized by containing maleimide (A) having an indene skeleton, a polyphenylene ether compound (B), and an epoxy resin (C).

The curable resin composition of the present invention is preferably one in which the maleimide (A) is represented by the following general formula (1). (In formula (1), Ra each independently represents an alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group or arylthio group having 6 to 10 carbon atoms, or an alkyl group having 3 to 10 carbon atoms. cycloalkyl group, halogen atom, nitro group, hydroxyl group or mercapto group, q represents an integer value from 0 to 4. When q is 2 to 4, Ra can be the same or different in the same ring. Rb each independently represents the carbon number An alkyl group, alkoxy group or alkylthio group with 1 to 10 carbon atoms, an aryl group, aryloxy group or arylthio group with 6 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group, r Indicates an integer value of 0 to 3. When r is 2 to 3, Rb can be the same or different in the same ring. n is the average number of repeating units, representing a value of 0.5 to 20).

The cured material of the present invention is preferably a curing reaction of the aforementioned curable resin composition.

The prepreg of the present invention is preferably a semi-hardened product having a reinforcing base material and the curable resin composition impregnated into the reinforcing base material.

The circuit board of the present invention is preferably obtained by laminating the prepreg and copper foil and subjecting them to heat and pressure bonding molding.

The build-up film of the present invention preferably contains the aforementioned curable resin composition.

The semiconductor packaging material of the present invention preferably contains the aforementioned curable resin composition.

The semiconductor device of the present invention preferably contains a cured product obtained by heating and curing the semiconductor packaging material. [Effects of the invention]

The curable resin composition according to the present invention has both excellent heat resistance and dielectric properties in the cured product obtained from the aforementioned curable resin composition, and can provide a curable resin composition having both of these properties. Cured products, prepregs, circuit boards, build-up films, semiconductor packaging materials, and semiconductor devices obtained from the curable resin composition are useful.

The present invention will be described in detail below. The present invention relates to a curable resin composition characterized by containing maleimide (A) having an indene skeleton (hereinafter sometimes referred to as "(A) component"), and a polyphenylene ether compound (B) (hereinafter referred to as "component (B)"), and epoxy resin (C) (hereinafter referred to as "component (C)"). Among them, the maleimide (A) is preferably represented by the following general formula (1). By having an indene skeleton, the maleimide (A) has a smaller proportion of polar functional groups in the structure of the maleimine (A) than conventional maleimines. Therefore, it is preferable because of its excellent dielectric properties. In addition, cured products using conventional maleimide resins tend to be brittle and may have poor brittleness resistance. However, the maleimide (A) has excellent flexibility because it has an indene skeleton. , it is also expected to improve the brittleness resistance and is better.

In the above general formula (1), Ra each independently represents an alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group or arylthio group having 6 to 10 carbon atoms, or an alkyl group having 3 to 10 carbon atoms. 10 (preferably 5 to 10) cycloalkyl groups, halogen atoms, nitro groups, hydroxyl groups or mercapto groups, and q represents an integer value of 0 to 4. When q is 2 to 4, Ra can be the same or different in the same ring. Rb each independently represents an alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group or arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a halogen atom. , hydroxyl group or mercapto group, r represents an integer value from 0 to 3. When r is 2 to 3, Rb can be the same or different in the same ring. n is the average number of repeating units, indicating a value from 0.5 to 20. In addition, when the aforementioned r and the aforementioned q are 0, Ra and Rb respectively refer to a hydrogen atom.

Ra in the general formula (1) is preferably any one of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. The alkyl groups of numbers 1 to 4, etc., reduce the planarity and crystallinity near the maleimide group, thereby improving the solvent solubility without impairing the reactivity of the maleimide group. Get the ideal form of the hardened object.

As for q in the above general formula (1), 2 to 3 are preferred, and 2 is more preferred. When q is 2, the influence of steric hindrance is small and the electron density on the aromatic ring is increased, which is ideal in the production (synthesis) of maleimide.

In the above general formula (1), it is preferred that r is 0 and Rb is a hydrogen atom, and r is 1 to 3 and Rb is selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and cycloalkanes having 3 to 6 carbon atoms. group and at least one of the group of aryl groups having 6 to 10 carbon atoms is preferred, especially when r is 0 and Rb is a hydrogen atom, and the indene skeleton in maleimide is formed, The reduction in steric hindrance is advantageous and ideal for the production (synthesis) of maleimide.

＜Production method of maleimide (A) having indene skeleton＞ The method for producing the aforementioned maleimide (A) will be described below.

The following general formula (2) is that Rc each independently represents a monovalent functional group selected from the group including the following general formulas (3) and (4), and the ortho position of at least one Rc of the two Rc is a hydrogen atom, Rb and r represent the same compounds as above.

In the following general formula (5), at least one of the ortho and para positions of the amine group is a hydrogen atom, and Ra and q respectively represent the same aniline or derivatives thereof as mentioned above. By making the above general formula (2 ), react with a compound of the following general formula (5) in the presence of an acid catalyst to obtain an intermediate amine compound represented by the following general formula (6). In addition, Ra, Rb, q, and r in the following general formula (6) represent the same ones as above.

In the intermediate amine compound represented by the above general formula (6), when in the aniline or its derivative represented by the above general formula (5), q is 3 or less, and at least one of the ortho and para positions of the amine group is When two are hydrogen atoms, the structure includes the following general formula (7) having an indene skeleton and becomes a structure represented by the following general formula (8). However, Ra, Rb, q and r in the following general formula (8) are the same as mentioned above, and m is the number of repeating units and represents an integer value of 1 to 20. In addition, the structure represented by the following general formula (8) may also be included in the structure of the above-mentioned general formula (6).

Among the characteristic indene skeletons of the maleimide (A) used in the present invention (refer to the above general formula (7)), in order to have a low melting point (low softening point), low melt viscosity, and excellent workability , the average repeating unit number n is 0.5 to 20 in terms of the average repeating unit number n (average), preferably 0.7 to 10.0, more preferably 0.95 to 10.0, further preferably 0.98 to 9.0, further preferably 0.99 to 8.0, more preferably 1.0 to 7.0, further preferably 1.0 to 6.0. By having an indene skeleton in the structure of the maleimide (A), it has excellent solvent solubility compared to the maleimide used hitherto, which is ideal. In addition, as long as n is less than 0.5, the content ratio of the high melting point substance in the structure of the maleimide (A) becomes high, and the solvent solubility is poor. Furthermore, the high molecular weight component that contributes to flexibility is As the proportion becomes lower, the brittleness resistance of the obtained hardened material decreases, and the flexibility and softness may also decrease, which is not preferable. Furthermore, if n is greater than 20, the heat resistance may be deteriorated. Furthermore, the high molecular weight component may be too much and the fluidity may be reduced when the cured product is molded, resulting in poor workability, which is undesirable. In addition, from the viewpoint of high thermal deformation temperature, high glass transition temperature, etc., the value of n is preferably 0.5 to 10.0, and more preferably 0.95 to 10.0.

The compound represented by the general formula (2) (hereinafter referred to as "compound (a)") used in the present invention is not particularly limited. Typically, p- and m-diisopropenylbenzene, p- and m-diisopropenylbenzene are used. m-Bis(α-hydroxyisopropyl)benzene, 1-(α-hydroxyisopropyl)-3-isopropenylbenzene, 1-(α-hydroxyisopropyl)-4-isopropenylbenzene or this etc. mixture. In addition, nuclear alkyl substituents of these compounds can also be used, such as: diisopropenyltoluene and bis(α-hydroxyisopropyl)toluene, etc. Furthermore, nuclear halogen substituents can also be used, such as: chlorobis Isopropenylbenzene and chlorobis(α-hydroxyisopropyl)benzene, etc.

In addition, examples of the compound (a) include: 2-chloro-1,4-diisopropenylbenzene, 2-chloro-1,4-bis(α-hydroxyisopropyl)benzene, 2 -Bromo-1,4-diisopropenylbenzene, 2-bromo-1,4-bis(α-hydroxyisopropyl)benzene, 2-bromo-1,3-diisopropenylbenzene, 2-bromo- 1,3-bis(α-hydroxyisopropyl)benzene, 4-bromo-1,3-diisopropylbenzene, 4-bromo-1,3-bis(α-hydroxyisopropyl)benzene, 5- Bromo-1,3-diisopropenylbenzene, 5-bromo-1,3-bis(α-hydroxyisopropyl)benzene, 2-methoxy-1,4-diisopropenylbenzene, 2-methyl Oxy-1,4-bis(α-hydroxyisopropyl)benzene, 5-ethoxy-1,3-diisopropenylbenzene, 5-ethoxy-1,3-bis(α-hydroxyisopropyl) Propyl)benzene, 2-phenoxy-1,4-diisopropenylbenzene, 2-phenoxy-1,4-bis(α-hydroxyisopropyl)benzene, 2,4-diisopropenyl Benzenethiol, 2,4-bis(α-hydroxyisopropyl)benzenethiol, 2,5-diisopropenylbenzenethiol, 2,5-bis(α-hydroxyisopropyl)benzenethiol, 2-Methylthio-1,4-diisopropenylbenzene, 2-methylthio-1,4-bis(α-hydroxyisopropyl)benzene, 2-phenylthio-1,3-diisopropylene benzene, 2-phenylthio-1,3-bis(α-hydroxyisopropyl)benzene, 2-phenyl-1,4-diisopropenylbenzene, 2-phenyl-1,4-bis( α-Hydroxyisopropyl)benzene, 2-cyclopentyl-1,4-diisopropenylbenzene, 2-cyclopentyl-1,4-bis(α-hydroxyisopropyl)benzene, 5-naphthyl -1,3-diisopropenylbenzene, 5-naphthyl-1,3-bis(α-hydroxyisopropyl)benzene, 2-methyl-1,4-diisopropenylbenzene, 2-methyl -1,4-bis(α-hydroxyisopropyl)benzene, 5-butyl-1,3-diisopropenylbenzene, 5-butyl-1,3-bis(α-hydroxyisopropyl)benzene , 5-cyclohexyl-1,3-diisopropenylbenzene, 5-cyclohexyl-1,3-bis(α-hydroxyisopropyl)benzene, etc.

In addition, the substituent contained in the aforementioned compound (a) is not particularly limited, and the compounds exemplified above can be used. However, the case of a substituent with a large steric hindrance is less likely to occur than a substituent with a small steric hindrance. The resulting stacking of maleimines makes it difficult to crystallize maleimines. In other words, the solvent solubility of maleimines is improved, which is an ideal state.

In addition, as the compound represented by the above general formula (5) (hereinafter referred to as "compound (b)"), typically other than aniline, for example, dimethylaniline, diethylaniline, and diisopropylaniline can be used , ethylmethylaniline, chloroaniline, dichloroaniline, toluidine, dimethylaniline, phenylaniline, nitroaniline, aminophenol and cyclohexylaniline, etc. Furthermore, examples include methoxyaniline, ethoxyaniline, phenoxyaniline, naphthoxyaniline, aminothiol, methylthioaniline, ethoxyaniline, and phenylthioaniline.

In addition, when the maleimine group is directly bonded to the benzene ring as in conventional maleimines (such as N-phenylmaleimine), since the five members of the benzene ring and maleimine The state in which the rings are arranged on the same plane is stable, so they become easy to stack and exhibit high crystallinity. This causes poor solvent solubility. On the other hand, in the case of the present invention, the compound (b) is not particularly limited, and the compounds exemplified above can be used. For example, when 2,6-dimethylaniline has a methyl group as a substituent, The benzene ring and the five-membered ring of maleimide adopt a twisted configuration due to the steric hindrance of the methyl group, making it difficult to stack. Therefore, the crystallinity is reduced and the solvent solubility is improved, making it an ideal form. However, if the steric hindrance is too large, the reactivity may be inhibited during the synthesis of maleimide. Therefore, for example, it is preferable to use a compound (b) having an alkyl group having 2 to 4 carbon atoms.

In the method for producing the intermediate amine compound represented by the general formula (6) used in the present invention, the aforementioned compound (a) and the aforementioned compound (b) are expressed in terms of the aforementioned compound (b) relative to the aforementioned compound (a). The molar ratio (compound (b)/compound (a)) is preferably 0.1 to 2.0, more preferably 0.2 to 1.0. After adding and reacting (the first stage), the aforementioned compound (b) is added to The molar ratio of the previously added compound (a) is preferably 0.5 to 20.0, more preferably 0.7 to 5.0, and is further added to react (the second stage), whereby an indene-containing compound (a) can be obtained. The skeleton is maleimide (A). In addition, this two-stage reaction also provides ideal results from the viewpoints of completion of the reaction and operability. In addition, in the reaction of the first stage, by setting the aforementioned compound (b) to a molar ratio (compound (b)/compound (a)) relative to the previously added compound (a), it is better to It is 0.10 to 0.49, more preferably 0.15 to 0.40, and even more preferably 0.20 to 0.39. Since it has a wide molecular weight distribution, and the content ratio of low molecular weight high melting point substances becomes lower and the ratio of high molecular weight components becomes higher, it can It is preferable to obtain an intermediate amine compound and maleimide which have excellent solvent solubility and can further contribute to flexibility and brittleness resistance.

Examples of acid catalysts used in the aforementioned reaction include inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluomethanesulfonic acid, activated clay, acidic catalysts, etc. Clay, silica, zeolite, solid acids such as strong acidic ion exchange resins, heterogeneous polysaccharides, etc. From the perspective of operability, solid acids that can easily remove the catalyst by filtration after the reaction are Preferably, when using another acid, it is preferable to neutralize with an alkali and wash with water after the reaction.

The blending amount of the aforementioned acid catalyst is 100 parts by mass of the total amount of the aforementioned compound (a) and the aforementioned compound (b) as the initially input raw materials. The acid catalyst is blended in the range of 5 to 40 parts by mass. From the viewpoint of operability and economy, 5 to 30 parts by mass is preferred. The reaction temperature is usually in the range of 100 to 300°C. In order to suppress the formation of isomer structures and avoid side reactions such as thermal decomposition, 150 to 230°C is preferred.

The reaction time is usually in the range of a total of 2 to 48 hours under the aforementioned reaction temperature conditions, since the reaction cannot proceed completely in a short time, and side reactions such as thermal decomposition of the product may occur if it is a long time. , and preferably a total of 2 to 24 hours, more preferably a total of 4 to 24 hours, further preferably a total of 4 to 12 hours, in order to reduce low molecular weight components and increase high molecular weight components, a total of 8 to 12 hours For the better.

In the aforementioned method for producing an intermediate amine compound, since aniline or its derivatives can also serve as a solvent, other solvents may not necessarily be used, and a solvent may be used. For example, in the case of a reaction system that also has a dehydration reaction, specifically a case where a compound having an α-hydroxypropyl group is reacted as a raw material, azeotropic dehydration using toluene, xylene, or chlorobenzene can be used. After the dehydration reaction is completed, the solvent is distilled off, and the reaction is carried out within the above reaction temperature range.

The maleimide (A) used in the present invention can be obtained by putting the intermediate amine compound represented by the above general formula (6) obtained by the above method into a reactor, and dissolving it in an appropriate solvent. It is obtained by reacting in the presence of acid anhydride and catalyst. After the reaction, unreacted maleic anhydride and other impurities are removed by washing with water, and the solvent is removed by reducing pressure. In addition, a dehydrating agent can be used during the reaction.

The maleimide (A) used in the present invention has the skeleton of the above general formula (1) and contains the structure represented by the above general formula (7) having an indene skeleton. When q is 3 or less and the amine When at least two of the ortho and para positions of the group are hydrogen atoms, the structure corresponding to the above general formula (8), that is, the structure represented by the following general formula (9) also includes the structure represented by the above general formula (1). Representation structure.

Ra, Rb, q, r and m in the above general formula (9) represent the same ones as above.

Examples of the organic solvent used in the maleyl imidization reaction for synthesizing the maleimide (A) include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexane. Ketones, acetophenone and other ketones, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylstyrene, N-methyl-2-pyrrolidinone, acetonitrile, Aprotic solvents such as cyclobutane, cyclic ethers such as dimethane and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, aromatic solvents such as benzene, toluene and xylene, etc., and these can be used individually Can also be mixed.

In the maleyl imidization reaction, the intermediate amine compound and maleic anhydride are blended at an equivalent ratio of maleic anhydride to the amine equivalent of the intermediate amine compound in the range of 1 to 1.5. Preferably, it is more preferably 1.1 to 1.2, and it is in the organic solvent at a mass ratio of 0.5 to 50, preferably 1 to 5, relative to the total amount of the intermediate amine compound and maleic anhydride. Make it react in a better way.

Catalysts used in the maleyl imidization reaction include inorganic salts such as acetates, chlorides, bromides, sulfates, and nitrates of nickel, cobalt, sodium, calcium, iron, lithium, manganese, etc. , Inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluomethanesulfonic acid and other organic acids, such as activated clay, acidic clay, silica aluminum, zeolite, strongly acidic ion exchange Resin-like solid acids, heterogeneous multiple acid salts, etc., and toluenesulfonic acid is particularly ideal.

Examples of the dehydrating agent used in the maleyl imidization reaction include lower aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, oxides such as phosphorus pentoxide, calcium oxide and barium oxide, sulfuric acid, etc. Inorganic acids, porous ceramics such as molecular sieves, etc., and acetic anhydride is preferably used.

The amount of catalyst and dehydrating agent used in the aforementioned maleyl imidization reaction is not particularly limited, but is usually 1 equivalent of the amine group of the intermediate amine compound, and the catalyst energy is 0.0001 to 1.0 mol, which is relatively Preferably, it is used at 0.001-0.5 mol, and more preferably, it is used at 0.01-0.3 mol. The dehydrating agent can be used at 1-3 mol, preferably 1-1.5 mol.

As the reaction conditions for the aforementioned maleyl imidization, the above-mentioned intermediate amine compound and maleic anhydride can be put in and reacted at a temperature range of 10 to 100°C (preferably 30 to 50°C) for 0.5 to 12 hours. (Preferably 1 to 8 hours), add the aforementioned catalyst, and react at a temperature range of 90 to 130°C (preferably 105 to 120°C) for 2 to 24 hours (preferably 4 to 10 hours) , in order to reduce low molecular weight components and increase high molecular weight components, 6 to 10 hours is better. In addition, after the reaction, unreacted maleic anhydride and other impurities are removed by washing with water, and low molecular weight components are reduced and high molecular weight components are increased by heating and aging.

From the viewpoint of being excellent in low dielectric constant and low dielectric loss tangent, the maleimide (A) is based on the molecular weight distribution (weight average molecular weight (Mw) calculated from gel permeation chromatography (GPC) measurement). )/number average molecular weight (Mn)) is preferably in the range of 1.0 to 10.0, more preferably 1.1 to 9.0, further preferably 1.1 to 8.0, further preferably 1.2 to 5.0, further preferably 1.2 to 4.0, It is further preferably 1.3 to 3.8, particularly preferably 1.3 to 3.6, and most preferably 1.3 to 3.4. In addition, according to the GPC chart obtained from the above-mentioned GPC measurement, when the molecular weight distribution is over a wide range and there are many high molecular weight components, the proportion of high molecular weight components that contribute to flexibility increases. Therefore, compared with the conventional method using horse The cured product of leimide can suppress brittleness and obtain a cured product with excellent flexibility and softness, making it an ideal form.

＜GPC Measurement＞ The molecular weight distribution (Mw/Mn) of maleimide (A) was measured based on gel permeation chromatography (GPC) under the following conditions. Measuring device: "HLC-8320 GPC" manufactured by Tosoh Co., Ltd. Column: Protection column "HXL-L" made by Tosoh Co., Ltd. + "TSK-GEL G2000HXL" made by Tosoh Co., Ltd. + "TSK-GEL G2000HXL" made by Tosoh Co., Ltd. + "TSK-GEL G3000HXL" made by Tosoh Co., Ltd. + Tosoh Co., Ltd. "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Co., Ltd. Measurement conditions: Column temperature 40℃ Development solvent Tetrahydrofuran Flow rate 1.0ml/minute Standard: According to the measurement manual of the aforementioned "GPC Workstation EcoSEC-WorkStation", the following known monodisperse polystyrene is used for molecular weight. (Polystyrene used) Made by Tosoh Co., Ltd. "A-500" Made by Tosoh Co., Ltd. "A-1000" Made by Tosoh Co., Ltd. "A-2500" Made by Tosoh Co., Ltd. "A-5000" Tosoh Co., Ltd. "F-1" Tosoh Co., Ltd. "F-2" Tosoh Co., Ltd. "F-4" Tosoh Co., Ltd. "F-10" Made by Tosoh Co., Ltd. "F-20" Made by Tosoh Co., Ltd. "F-40" Made by Tosoh Co., Ltd. "F-80" Made by Tosoh Co., Ltd. "F-128" Sample: A tetrahydrofuran solution in which the resin solid content of maleimide obtained in the synthesis example was converted into 1.0% by mass and filtered with a microfilter (50 μl).

<Polyphenylene ether compound (B)> The curable resin composition of the present invention is characterized by containing a polyphenylene ether compound (B) (hereinafter sometimes referred to as "component (B)"). The polyphenylene ether (PPE) contained in the structure of the polyphenylene ether compound (B) has excellent dielectric properties such as dielectric constant and dielectric loss tangent, so even in the high frequency band (high frequency range) from the MHz band to the GHz band ), it is also possible to prepare a curable resin composition that can produce a cured product that exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant. Therefore, it can be used as a molding material for high frequencies and is useful. In addition, by reacting with the aforementioned maleimide (A) having an indene skeleton, it functions as a curing agent and can generate three-dimensional cross-linking, thereby obtaining a cured product that is also excellent in heat resistance, which is an ideal aspect. . In addition, a cured product using a maleimide resin is generally poor in brittleness resistance, but has a tendency to improve brittleness by reaction with the polyphenylene ether compound (B), so it is preferred. Furthermore, in relation to the epoxy resin (C) described in detail below, it functions as a hardener and improves the adhesion to copper, and is useful in manufacturing circuit boards using copper foil, for example.

The polyphenylene ether compound (B) is not particularly limited, but may have a structure represented by the following general formula (10) or (11), for example.

Rd in the above general formulas (10) and (11) can each be independently enumerated: hydrogen atom, alkyl group having 1 to 5 carbon atoms, alkenyl group having 1 to 5 carbon atoms, cycloalkyl group having 3 to 5 carbon atoms, carbon Alkoxy group with 1 to 5 carbon atoms, thioether group with 1 to 5 carbon atoms, alkylcarbonyl group with 2 to 5 carbon atoms, alkoxycarbonyl group with 2 to 5 carbon atoms, alkylcarbonyloxy group with 2 to 5 carbon atoms, carbon Alkanesulfonyl groups with numbers 1 to 5, etc. In addition, s represents an integer value of 1 to 30, and t and u also represent an integer value of 1 to 30.

The alkyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, Propyl etc.

The alkenyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include vinyl, 1-propenyl, 1-butenyl, 1-pentenyl, isopropenyl, and the like.

The cycloalkyl group having 3 to 5 carbon atoms is not particularly limited, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, methylcyclobutyl, and the like.

The alkoxy group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, and the like.

The thioether group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, pentylthio group, and the like.

The alkylcarbonyl group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include a methylcarbonyl group, an ethylcarbonyl group, a propcarbonyl group, an isopropylcarbonyl group, a butylcarbonyl group, and the like.

The alkoxycarbonyl group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, and the like.

The alkylcarbonyloxy group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include methylcarbonyloxy, ethylcarbonyloxy, propcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, and the like.

The alkane sulfonyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include methanesulfonyl group, ethyl sulfonyl group, propyl sulfonyl group, isopropyl sulfonyl group, butyl sulfonyl group, and pentyl sulfonyl group. Jiji et al.

Among these, the aforementioned Rd is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 3 to 5 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Atoms, methyl groups, and ethyl groups are more preferred, and hydrogen atoms and methyl groups are particularly preferred.

Examples of Y in the above (11) include a divalent aromatic group derived from an aromatic compound having two phenolic hydroxyl groups.

The aromatic compound having two phenolic hydroxyl groups is not particularly limited, and examples thereof include catechol, resorcinol, hydroquinone, 1,4-dihydroxynaphthalene, and 1,5-dihydroxynaphthalene. , 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol B, bisphenol BP, bisphenol C, bisphenol F, tetramethyl bisphenol A etc. Among these, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol E, and bisphenol F are preferred. 4 , 4'-biphenol, bisphenol A, and tetramethylbisphenol A are more preferred.

Since the two phenolic hydroxyl groups of the aromatic compound having two phenolic hydroxyl groups form a phenyl ether bond (two oxygen atoms bonded to Y), Y is derived from the aromatic compound having two phenolic hydroxyl groups. The divalent aromatic group of the compound.

In addition, the terminal structure of the above-mentioned general formulas (10) and (11) usually becomes an aryloxy group having a phenolic hydroxyl group. The aforementioned phenolic hydroxyl group can be modified into other structural parts.

Examples of the structural moiety obtained by modifying the phenolic hydroxyl group include groups containing polymerizable unsaturated bonds such as (meth)acryloxy group, allyloxy group, and vinyloxy group. The epoxy compound is reacted with Structural parts derived from phenolic hydroxyl groups, etc. Among them, a phenolic hydroxyl group or a group containing a polymerizable unsaturated bond is preferred from the viewpoint of achieving a curable composition with an excellent balance between dielectric properties and heat resistance in the cured product.

Furthermore, the polyphenylene ether compound (B) used in the present invention can also be used as an alloyed polymer with polystyrene or the like. Examples of the alloyed polymer include alloyed polymers of poly(2,6-dimethyl-1,4-phenylene) ether and polystyrene, poly(2,6-dimethyl-1 , 4-phenylene) ether and styrene-butadiene copolymer alloy polymer, etc.

In addition to the resins listed above, the polyphenylene ether compound (B) used in the present invention can be used in a range that does not impair the characteristics of the present invention: the polyphenylene ether compound and the phenolic compound are reacted in the presence of a reaction initiator. Various modified polyphenylene ether compounds such as polyphenylene ether compounds obtained by decomposition and rearrangement reactions and polyphenylene ether compounds modified with polybutadiene polymers can be used alone or in mixture.

The weight average molecular weight (Mw) of the polyphenylene ether compound (B) is preferably 1,000 to 5,000, more preferably 1,200 to 4,000, and still more preferably 1,400 to 3,000. As long as the weight average molecular weight of the compound (B) is within the above range, a cured product having a balance of excellent dielectric properties and heat resistance can be more reliably obtained, which is an ideal aspect. In addition, the weight average molecular weight (Mw) here only needs to be measured by a common molecular weight measurement method, and specific examples thereof include values measured using the above-mentioned GPC.

＜Epoxy resin(C)＞ The curable resin composition of the present invention is characterized by containing epoxy resin (C) (hereinafter sometimes referred to as "component (C)"). The epoxy resin (C) is useful in preparing a curable resin composition that can provide a cured product having good fluidity when preparing a curable resin composition and excellent adhesion. In addition, when the polyphenylene ether compound (B) and the epoxy resin (C) are used, the adhesion to copper is improved, and it is useful in manufacturing circuit boards using copper foil, for example.

The epoxy resin (C) is not particularly limited, and examples thereof include: phenol novolak type epoxy resin, cresol novolac type epoxy resin, α-naphthol novolak type epoxy resin, β-naphthalene Novolak-type epoxy resins such as phenol novolak-type epoxy resin, bisphenol A novolak-type epoxy resin, and biphenyl novolak-type epoxy resin; phenol aralkyl type epoxy resin, naphthol aralkyl type ring Aralkyl epoxy resins such as oxy resin, phenol biphenyl aralkyl epoxy resin and other aralkyl epoxy resins; bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type Epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type Bisphenol-type epoxy resins such as epoxy resin; biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, epoxy resins with biphenyl skeleton and diepoxypropyloxybenzene skeleton, etc. Epoxy resin; naphthalene-type epoxy resin; binaphthol-type epoxy resin; binaphthyl-type epoxy resin; dicyclopentadiene-phenol-type epoxy resin and other dicyclopentadiene-type epoxy resins; tetraepoxypropyldi Aminodiphenylmethane type epoxy resin, tripoxypropyl p-aminophenol type epoxy resin, diamino diphenyl ester epoxypropylamine type epoxy resin and other epoxypropylamine type epoxy resins Oxygen resin; 2,6-naphthalene dicarboxylic acid dialpoxypropyl ester type epoxy resin, hexahydrophthalic anhydride glycidyl ester type epoxy resin and other diepoxypropyl ester type epoxy resin; diphenyl Benzopyran type epoxy resins such as hexamethyldibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. These may be used individually, or 2 or more types may be used together.

Among these, phenol aralkyl type epoxy resin, biphenyl novolak type epoxy resin, and naphthol novolak type epoxy resin containing a naphthalene skeleton are used from the viewpoint of obtaining a cured product with excellent heat resistance. , naphthol aralkyl epoxy resin, naphthol-phenol novolak-type epoxy resin, naphthol-cresol novolak-type epoxy resin, crystalline biphenyl-type epoxy resin, tetramethyl Biphenyl-based epoxy resin, dibenzopyran-based epoxy resin, aromatic ring-modified novolak-type epoxy resin containing alkoxy groups (formaldehyde is used to link the aromatic ring containing epoxypropyl groups and containing alkoxy groups Compounds with aromatic rings) are particularly preferred.

The curable resin composition of the present invention may also contain a curing agent other than the polyphenylene ether compound (B) within a range that does not impair the curing of the present invention. In addition, the polyphenylene ether compound (B) is preferably 50 mass% or more, more preferably 60 mass% or more, more preferably 70 mass% or more, and 80 mass% or more relative to 100 mass% of the total amount of the hardener. The above is particularly good, and more than 90% by mass is the best.

Examples of curing agents other than the polyphenylene ether compound (B) include amine compounds, amide compounds, acid anhydride compounds, phenol compounds, cyanate ester compounds, and compounds having a substituent containing an unsaturated double bond. compounds, diene polymers, etc. These hardeners may be used alone or in combination of two or more types.

Examples of the amine compound include: diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylthione, isophoronediamine, imidazole, and _BF3 -aminezole. compounds, guanidine derivatives, etc.

Examples of the amide-based compound include dicyandiamine, a polyamide resin synthesized from a dimer of perilla oleic acid and ethylenediamine, and the like.

Examples of the acid anhydride-based compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Hydrophthalic anhydride, etc.

Examples of the phenolic compound include phenol novolak resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Xylok resin) , Polyvalent phenol novolak resin, naphthol aralkyl resin, trimethylolmethane resin, tetrahydroxyphenylethane resin, naphthalene resin, which is synthesized from polyvalent hydroxyl compounds represented by resorcinol novolac resin and formaldehyde. Phenol novolak resin, naphthol-phenol novolak resin, naphthol-cresol novolac resin, biphenyl-modified phenol resin (a polyvalent phenol compound with a bismethylene group linking the phenol core), biphenyl Modified naphthol resin (a polyvalent naphthol compound with a phenol core linked by bismethylene), amino tris-modified phenol resin (a polyvalent phenol compound with a phenol core linked by melamine, benzoguanamine, etc.), containing Polyvalent phenol compounds such as alkoxy aromatic ring-modified novolak resin (a polyvalent phenol compound with formaldehyde connected to the phenol core and an aromatic ring containing alkoxy groups).

Examples of the cyanate ester compound include bisphenol A-type cyanate ester resin, bisphenol F-type cyanate ester resin, bisphenol E-type cyanate ester resin, bisphenol S-type cyanate ester resin, and bisphenol vulcanized resin. Physical type cyanate ester resin, phenylene ether type cyanate ester resin, naphthyl ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin , phenol novolak type cyanate ester resin, cresol novolak type cyanate ester resin, triphenylmethane type cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolac type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-novolak type cyanate ester resin , naphthol-cresol co-novolak type cyanate ester resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate ester resin, biphenyl modified novolak type cyanate ester resin, anthracene type cyanate ester resin, etc. .

The compound having an unsaturated double bond-containing substituent is not particularly limited as long as it has two or more unsaturated bond-containing substituents in the molecule. Examples thereof include allyl groups and isopropenyl groups. , 1-propenyl, acrylyl, methacrylyl, styryl, styrylmethyl, etc. as the aforementioned compounds containing substituents of unsaturated bonds.

Examples of the diene polymer include non-modified diene polymers that have not been modified with polar groups. Here, the polar group refers to a functional group that affects the dielectric properties, and examples include: phenol group, amine group, epoxy group, etc. The diene polymer is not particularly limited, and examples thereof include 1,2-polybutadiene, 1,4-polybutadiene, and the like.

As the diene polymer, homopolymers and derivatives thereof of butadiene in which more than 50% of the butadiene units in the polymer chain are 1,2-bonds can also be used.

Since the epoxy resin (C) is used in the present invention, a curing accelerator can be appropriately used in combination with the curable resin composition of the present invention as needed. Various types of hardening accelerators can be used, and examples thereof include phosphorus-based compounds, tertiary amines, imidazole, organic acid metal salts, Lewis acids, amine salts, and the like. Especially when used as semiconductor packaging materials, from the viewpoint of excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc., phosphorus-based compounds such as triphenylphosphine and tertiary amine-based compounds such as 1,8-di Acridinebicyclo-[5.4.0]-undecene (DBU) is preferred. These hardening accelerators may be used alone or in combination of two or more types. Moreover, the addition amount of the said hardening accelerator is preferably used in the range of 1-10 mass parts with respect to 100 mass parts of the said epoxy resin (C), for example.

＜Preparation of curable resin composition＞ The curable resin composition of the present invention is characterized by containing maleimide (A) having an indene skeleton, a polyphenylene ether compound (B), and an epoxy resin (C). Since the maleimide (A) has an indene skeleton, it has excellent solvent solubility compared to conventional maleimines, making it easy to prepare a curable resin composition and having excellent workability. The structure of lymide (A) has a small proportion of polar functional groups, so a cured product with excellent dielectric properties can be obtained. In addition, the polyphenylene ether compound (B) mentioned above functions as a hardener, and the polyphenylene ether (PPE) in its structure can contribute to dielectric properties such as dielectric constant and dielectric loss tangent. Furthermore, the above-mentioned epoxy The resin (C) system has good fluidity when preparing a curable resin composition, and a cured product with excellent adhesion can be obtained. Furthermore, the polyphenylene ether compound (B) acting as a hardener reacts with the maleimide (A) and the epoxy resin (C) to produce three-dimensional cross-linking, thereby obtaining a product with excellent heat resistance. The hardened object becomes the ideal form. In addition, cured products using maleimide resin generally have poor brittleness resistance, but the brittleness is improved by reaction with the polyphenylene ether compound (B), and the adhesion to copper is improved. For example, in It is useful for manufacturing circuit boards using copper foil.

The blending ratio (parts by mass) of the component (A), the component (B) and the component (C) is 90:10 to (A): ((B) + (C)). 10:90 is preferred, 80:20-20:80 is more preferred, 65:35-35:65 is further preferred, and 55:45-45:55 is particularly preferred. By formulating the blending ratio within the aforementioned range, heat resistance, low dielectric constant, and low dielectric loss tangent can be achieved, which is preferable.

The blending ratio (parts by mass) of the polyphenylene ether compound (B) and the epoxy resin (C) in the curable resin composition of the present invention is not particularly limited, but it is from the viewpoint of good properties of the obtained cured product. See, the (B) component: (C) component is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and further preferably 65:35 to 35:65. By formulating the blending ratio within the aforementioned range, heat resistance, low dielectric constant, and low dielectric loss tangent can be achieved, which is preferable.

The curable resin composition of the present invention may also contain alkenyl-containing compounds within a range that does not impair the purpose, such as bismaleimines and allyl ethers other than the aforementioned maleimide (A). compounds, allylamine compounds, triallyl cyanurate, alkenylphenol compounds, vinyl-containing polyolefin compounds, etc. In addition, other thermosetting resins may be appropriately blended according to the purpose, such as thermosetting polyimide resin, phenol resin, active ester resin, benzophenone resin, cyanate resin, etc.

The curable resin composition of the present invention may be blended with a non-halogen flame retardant that does not substantially contain halogen atoms in order to achieve flame retardancy within a range that does not impair the purpose. Examples of the non-halogen flame retardant include: phosphorus flame retardants, nitrogen flame retardants, polysiloxane flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc. Can be used alone or in combination.

The curable resin composition of the present invention may be blended with inorganic fillers as needed. Examples of the inorganic filler include fused silica, crystallized silica, alumina, silicon nitride, aluminum hydroxide, and the like. When the blending amount of the inorganic filler is particularly large, it is preferable to use fused silica. The aforementioned fused silica can be used in either crushed or spherical form. However, in order to increase the blending amount of fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use spherical ones. good. Furthermore, in order to increase the blending amount of spherical silica, it is better to appropriately adjust the particle size distribution of spherical silica. Taking the flame retardancy into consideration, the filling rate is preferably higher, and is particularly preferably 20% by mass or more based on the total amount of the curable resin composition. In addition, when the aforementioned curable resin composition is used for a conductive paste, etc. described in detail below, conductive fillers such as silver powder and copper powder can be used.

The curable resin composition of the present invention can be added with various blending agents such as silane coupling agents, release agents, pigments, and emulsifiers as needed.

＜hardened material＞ The cured product of the present invention is preferably one in which the curable resin composition undergoes a curing reaction. The curable resin composition can be obtained by uniformly mixing the above-mentioned components, and a cured product can be easily produced by the same method as a conventionally known method. Examples of the cured product include molded cured products such as laminates, molded products, adhesive layers, coating films, and films.

The aforementioned hardening (thermal hardening) reaction can be easily carried out without a catalyst. However, to make the reaction faster, a polymerization initiator such as an organic peroxide, an azo compound, or a phosphine-based compound is added. , tertiary amine-like alkaline catalysts are effective. Examples include: benzyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazoles, etc. The blending amount is based on the entire curable resin composition. 0.05 to 5% by mass is preferred.

＜Prepreg＞ The prepreg of the present invention is preferably a semi-hardened product having a reinforcing base material and the curable resin composition impregnated into the reinforcing base material. As a method for producing the prepreg, a known method can be used, and the prepreg can be produced by impregnating a reinforcing base material with a resin varnish in which the curable resin composition is dissolved (diluted) in an organic solvent, The reinforcing base material impregnated with the resin varnish is heat-treated to semi-harden (or unharden) the curable resin composition.

As the aforementioned organic solvent, for example, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, methylethyl Ketone (MEK), methyl isobutyl ketone, dihexane, tetrahydrofuran, etc. are used alone or as a mixed solvent of two or more kinds.

As the reinforcing base material for impregnating the aforementioned resin varnish, it is woven fabric, non-woven fabric, mat, paper, etc. made of inorganic fibers or organic fibers such as glass fiber, polyester fiber, polyamide fiber, etc., which can be used alone or in combination. use.

The mass ratio of the curable resin composition and the reinforcing base material in the prepreg is not particularly limited, but usually the curable resin composition (resin component) in the prepreg is 20 to 60% by mass. The method of preparation is better.

The conditions for the heat treatment of the prepreg can be appropriately selected according to the types and amounts of organic solvents, catalysts, various additives used, etc., but are usually at a temperature of 80 to 220°C and a time of 3 to 30 minutes. conduct.

＜Heat-resistant materials and electronic materials＞ Since the cured product obtained from the curable resin composition of the present invention has excellent heat resistance and dielectric properties, it can be ideally used for heat-resistant members and electronic members. Especially ideal for use in: circuit boards, semiconductor packaging materials, semiconductor devices, build-up films, build-up substrates, adhesives, photoresist materials, etc. In addition, it can be ideally used as a matrix resin for fiber-reinforced resin, and is particularly suitable as a highly heat-resistant prepreg. Furthermore, since the maleimide (A) having the indene skeleton contained in the curable resin composition exhibits excellent solubility in various solvents, it can be used as a paint. The heat-resistant members and electronic members thus obtained can be ideally used in various applications, such as: industrial machine parts, general machine parts, automobile, railway, vehicle and other parts, space and aviation-related parts, electronic and electrical parts, and building materials. , containers and packaging components, daily necessities, sports and leisure products, casing components for wind power generation, etc., but are not limited to these.

Examples of representative products produced using the curable resin composition of the present invention will be described below.

＜Circuit board＞ In the present invention, the circuit board is preferably obtained by laminating the prepreg and copper foil and subjecting them to heat and pressure bonding molding. Specifically, as a method of obtaining a circuit board from the curable resin composition of the present invention, the above-mentioned prepreg is laminated by a common method, copper foil is overlapped appropriately, and the pressure is 1 to 10 MPa at 170 This is a method of heating and crimping at ~300°C for 10 minutes to 3 hours.

＜Semiconductor packaging materials＞ In the present invention, the semiconductor packaging material preferably contains the aforementioned curable resin composition. Specifically, a method for obtaining a semiconductor packaging material from the curable resin composition of the present invention includes using an extruder, a kneader, a roller machine, etc. as necessary, and combining the aforementioned curable resin composition with further This is a method in which blending agents such as hardening accelerators and inorganic fillers of any component are fully melted and mixed until they become uniform. In this case, fused silica is usually used as an inorganic filler. However, when used as a highly thermally conductive semiconductor packaging material for power transistors and power ICs, crystalline silica with a higher thermal conductivity than fused silica is used. , highly filled with alumina, silicon nitride, etc., or fused silica, crystalline silica, alumina, silicon nitride, etc. are preferred. The filling rate is preferably in the range of 30 to 95 parts by mass per 100 parts by mass of the curable resin composition. In order to improve flame retardancy, moisture resistance, welding crack resistance, and reduce linear expansion Coefficient, of which 70 parts by mass or more is more preferred, and 80 parts by mass or more is still more preferred.

＜Semiconductor Device＞ In the present invention, the semiconductor device preferably contains a cured product obtained by heating and curing the semiconductor packaging material. Specifically, as a semiconductor package molding method for obtaining a semiconductor device from the curable resin composition of the present invention, the above-mentioned semiconductor package material is molded using an injection molding or transfer molding machine, an injection molding machine, etc., and further at 50 to 250 ℃, heating and hardening method between 2 to 10 hours.

＜Build-up substrate＞ Examples of a method for obtaining a build-up substrate from the curable resin composition of the present invention include steps 1 to 3. In step 1, first, the curable resin composition suitably blended with rubber, filler, etc. is applied to the circuit board on which the circuit is formed using a spray coating method, a curtain coating method, or the like, and then is cured. In step 2, if necessary, drill predetermined through holes and the like on the circuit board coated with the curable resin composition, treat it with a roughening agent, and wash its surface with hot water. , forming unevenness on the aforementioned substrate, and performing plating treatment on metals such as copper. In step 3, the operations of steps 1 to 2 are repeated sequentially according to the requirements, and the resin insulating layer and the conductor layer of the prescribed circuit pattern are alternately layered to form the layered substrate. In addition, in the aforementioned steps, it is preferable that the drilling of the through-hole portion is performed after the outermost resin insulating layer is formed. Furthermore, the build-up substrate in the present invention can also be obtained by heating and press-bonding a copper foil with resin in which the resin composition is semi-hardened on the copper foil to a wiring substrate on which a circuit is formed at 170 to 300°C. A roughened surface is formed, the plating step is omitted, and a build-up substrate is produced.

＜Build-up film＞ The build-up film of the present invention preferably contains the aforementioned curable resin composition. As a method of obtaining a build-up film from the curable resin composition of the present invention, for example, the curable resin composition is coated on a support film, dried, and a resin composition layer is formed on the support film. method. When the curable resin composition of the present invention is used in a build-up film, the most important thing for the film is that it softens under the temperature conditions of the lamination in the vacuum lamination method (usually 70°C to 140°C), and When the circuit boards are laminated, the resin present in the through-holes or through-holes of the circuit board is filled with fluidity (resin flow), and it is preferable to blend the above-mentioned components in a manner that exhibits such characteristics. In addition, in order to prevent the resulting build-up film and circuit board (copper-clad laminate, etc.) from showing locally different characteristic values due to phase separation, etc., and to express certain performance in any part, Appearance uniformity is required.

Here, the diameter of the through hole of the circuit board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually better to enable resin filling within this range. In addition, when laminating both sides of a circuit board, it is desirable to fill approximately 1/2 of the through hole.

A specific method for producing the aforementioned build-up film includes preparing a resin composition in which an organic solvent is blended and varnished, and then coating the varnished resin composition on the surface of the supporting film (Y). A method of drying an organic solvent by heating or hot air blowing to form a resin composition layer (X).

Examples of organic solvents used here include acetone, methyl ethyl ketone, ketones such as cyclohexanone, ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, and carboxylate. Acetate esters such as alcohol acetate, carbitols such as cellulose and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N- Methylpyrrolidone and the like are preferred, and the non-volatile component is preferably used in a ratio of 30 to 60% by mass.

In addition, the thickness of the aforementioned resin composition layer (X) usually needs to be greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, so the thickness of the resin composition layer (X) is preferably 10 to 100 μm. In addition, the resin composition layer (X) in the present invention can be protected by a protective film described below. By protecting it with a protective film, it is possible to prevent waste and the like from adhering to and damaging the surface of the resin composition layer.

Examples of the aforementioned support film and protective film include: polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polycarbonate; Examples of polyimide include release paper, copper foil, aluminum foil and other metal foils. In addition, in addition to matting treatment and corona treatment, the support film and protective film can be subjected to mold release treatment. The thickness of the supporting film is not particularly limited, but is usually 10 to 150 μm, preferably 25 to 50 μm. In addition, the thickness of the protective film is preferably 1 to 40 μm.

The support film (Y) is peeled off after the circuit boards are laminated or after an insulating layer is formed by heating and hardening. As long as the support film (Y) is peeled off after heating and hardening of the resin composition layer constituting the build-up film, adhesion of waste and the like during the hardening step can be prevented. In the case of peeling after hardening, a release treatment is usually applied to the support film in advance.

In addition, a multilayer printed circuit board can be produced from the build-up film obtained as described above. For example, when a protective film is used to protect the resin composition layer (X), after peeling off the resin composition layer (X), the resin composition layer (X) is laminated in direct contact with the circuit board, for example, by a vacuum lamination method. Layer on one or both sides of the circuit board. The laminating method can be a batch type or a continuous type using rollers. In addition, the build-up film and circuit board can be heated (preheated) according to need before lamination. The lamination conditions are preferably a crimping temperature (lamination temperature) of 70 to 140°C and a crimping pressure of 1 to 11kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ² ) is preferred, and it is preferred to laminate under reduced pressure of 20mmHg (26.7hPa) or less.

＜Conductive Paste＞ An example of a method for obtaining a conductive paste from the curable resin composition of the present invention is a method of dispersing conductive particles in the composition. The above-mentioned conductive paste can be made into a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of conductive particles used. [Example]

The present invention will be specifically explained below through examples and comparative examples. However, the following “parts” and “%” are based on mass unless otherwise specified. In addition, the softening point, amine equivalent, GPC, and FD-MS mass spectrometry were measured and evaluated under the following conditions.

1)Softening point Measuring method: According to JIS K7234 (ball and ball method), the softening point (°C) of the intermediate amine compound obtained in the synthesis example shown below is measured.

2) Amine equivalent The amine equivalent of the intermediate amine compound is measured by the following measurement method. In a 500 mL Erlenmeyer flask with a co-stopper, approximately 2.5 g of the intermediate amine compound, 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine were accurately weighed, and a cooling tube was installed and placed in an oil bath set to 120°C. Heat and reflux for 150 minutes. After cooling, 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran were added, and titration was performed by potentiometric titration with a 0.5 mol/L potassium hydroxide-ethanol solution. Use the same method to perform a blank test and make corrections. Amine equivalent (g/eq.)=(S×2,000)/(Blank-A) S: Amount of sample (g) A: Consumption of 0.5mol/L potassium hydroxide-ethanol solution (mL) Blank: Consumption of 0.5mol/L potassium hydroxide-ethanol solution in the blank test (mL)

3)GPC measurement The following measurement equipment and measurement conditions were used to measure, and the GPC chart of the maleimide obtained in the synthesis example shown below was obtained (Figs. 1 to 9). From the results of the aforementioned GPC chart, the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) was measured and calculated based on the number average molecular weight (Mn), and the dihydrogen in the maleimide contributed to The average number of repeating units of the indene skeleton is "n". Specifically, for compounds with n=0 to 4, the theoretical molecular weight and the measured value molecular weight in GPC are plotted on a scatter diagram, and an approximate straight line is drawn, which is represented by the measured value Mn(1) on the straight line. Point and find the number average molecular weight (Mn), and calculate n. Measuring device: "HLC-8320 GPC" manufactured by Tosoh Co., Ltd. Column: Protection column "HXL-L" made by Tosoh Co., Ltd. + "TSK-GEL G2000HXL" made by Tosoh Co., Ltd. + "TSK-GEL G2000HXL" made by Tosoh Co., Ltd. + "TSK-GEL G3000HXL" made by Tosoh Co., Ltd. + Tosoh Co., Ltd. "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Co., Ltd. Measurement conditions: Column temperature 40℃ Development solvent Tetrahydrofuran Flow rate: 1.0ml/minute Standard: According to the measurement manual of the aforementioned "GPC Workstation EcoSEC-WorkStation", the following known monodisperse polystyrene is used for molecular weight. (Using polystyrene) Made by Tosoh Co., Ltd. "A-500" Made by Tosoh Co., Ltd. "A-1000" Made by Tosoh Co., Ltd. "A-2500" Made by Tosoh Co., Ltd. "A-5000" Tosoh Co., Ltd. "F-1" Tosoh Co., Ltd. "F-2" Tosoh Co., Ltd. "F-4" Tosoh Co., Ltd. "F-10" Made by Tosoh Co., Ltd. "F-20" Made by Tosoh Co., Ltd. "F-40" Made by Tosoh Co., Ltd. "F-80" Made by Tosoh Co., Ltd. "F-128" Sample: A tetrahydrofuran solution in which the resin solid content of maleimide obtained in the synthesis example was converted into 1.0% by mass and filtered with a microfilter (50 μl).

4)FD-MS mass spectrometry FD-MS mass spectrometry was measured using the following measurement equipment and measurement conditions. Measuring device: JMS-T100GC AccuTOF Measurement conditions Measuring range: m/z=4.00～2000.00 Change rate: 51.2mA/min Final current value: 45mA Cathode voltage: -10kV Recording interval: 0.07sec

[Synthesis Example 1] Synthesis of Maleimine Compound A-1 (1) Synthesis of Intermediate Amine Compound 2,6-dimethyl was put into a 1L flask equipped with a thermometer, a cooling tube, a Dean-Stark separator, and a stirrer. Add 48.5g (0.4mol) of aniline, 272.0g (1.4mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 280g of xylene and 70g of activated clay, and heat to 120°C while stirring. Furthermore, while removing the distilled water with a Dean-Stark tube, the temperature was raised to 210°C and allowed to react for 3 hours. Thereafter, the mixture was cooled to 140°C, 145.4 g (1.2 mol) of 2,6-dimethylaniline was added, and then the temperature was raised to 220°C and allowed to react for 3 hours. After the reaction, the air was cooled to 100°C, diluted with 300 g of toluene, and the activated clay was removed by filtration. The solvent and low molecular weight substances such as unreacted substances were distilled off under reduced pressure to obtain the following general formula (A-1 364.1g of the intermediate amine compound represented by ). The amine equivalent weight is 298 and the softening point is 70°C.

(2) Maleic imidization In a 2L flask equipped with a thermometer, cooling tube, Dean-Stark separator, and stirrer, 131.8 g (1.3 mol) of maleic anhydride and 700 g of toluene were added and stirred at room temperature. Next, a mixed solution of 364.1 g of reactant (A-1) and 175 g of DMF was added dropwise over 1 hour. After the dripping was completed, the reaction was further carried out at room temperature for 2 hours. 37.1 g of p-toluenesulfonic acid monohydrate was added, and the reaction liquid was heated to cool and separate the azeotropic water and toluene under reflux. Then, only toluene was returned to the system and a dehydration reaction was performed for 8 hours. After the air was cooled to room temperature, it was concentrated under reduced pressure to dissolve the brown solution in 600g of ethyl acetate, washed three times with 150g of ion-exchange water and three times with 150g of 2% sodium bicarbonate aqueous solution, and dried after adding sodium sulfate. , the reaction product obtained by concentrating under reduced pressure was vacuum dried at 80° C. for 4 hours to obtain 413.0 g of a product containing maleimide compound A-1. In the FD-MS mass spectrum of the maleimide compound A-1, peaks of M+=560, 718, and 876 were confirmed, and each peak corresponds to the case where n is 0, 1, and 2. In addition, when GPC is used to determine the value of the number n of repeating units (based on the number average molecular weight) in the indene skeleton part of the maleimide A-1, the GPC chart is shown in Figure 1, n=1.47 , molecular weight distribution (Mw/Mn)=1.81.

[Synthesis Example 2] Synthesis of Maleimine Compound A-2 (1) Synthesis of Intermediate Amine Compound Put 2,6-dimethyl in a 1L flask equipped with a thermometer, cooling tube, Dean-Stark separator, and stirrer. 48.5g (0.4mol) of aniline, 233.2g (1.2mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 230g of xylene and 66g of activated clay were heated to 120°C while stirring. Furthermore, while removing the distilled water with a Dean-Stark tube, the temperature was raised to 210°C and allowed to react for 3 hours. Thereafter, the mixture was cooled to 140°C, 145.4 g (1.2 mol) of 2,6-dimethylaniline was added, and then the temperature was raised to 220°C and allowed to react for 3 hours. After the reaction, air cool to 100°C, dilute with 300g of toluene, remove activated clay by filtration, and distill off low molecular weight substances such as solvent and unreacted matter under reduced pressure to obtain the following general formula (A-2 278.4g of the intermediate amine compound represented by ). The amine equivalent weight is 294 and the softening point is 65°C.

(2) Maleic imidization In a 2L flask equipped with a thermometer, cooling tube, Dean-Stark separator, and stirrer, 107.9 g (1.1 mol) of maleic anhydride and 600 g of toluene were added and stirred at room temperature. Next, a mixed solution of 278.4 g of reactant (A-2) and 150 g of DMF was added dropwise over 1 hour. After the dripping was completed, the reaction was further carried out at room temperature for 2 hours. 27.0 g of p-toluenesulfonic acid monohydrate was added, and the reaction liquid was heated to cool and separate the azeotropic water and toluene under reflux. Then, only toluene was returned to the system and dehydration reaction was performed for 8 hours. After the air was cooled to room temperature, it was concentrated under reduced pressure to dissolve the brown solution in 500g of ethyl acetate, washed three times with 120g of ion-exchange water and three times with 120g of 2% sodium bicarbonate aqueous solution, and dried after adding sodium sulfate. , the reaction product obtained by concentrating under reduced pressure was vacuum dried at 80° C. for 4 hours to obtain 336.8 g of a product containing maleimine compound A-2. In the FD-MS mass spectrum of the maleimide compound A-2, peaks of M+=560, 718, and 876 were confirmed, corresponding to the cases where n is 0, 1, and 2, respectively. In addition, when GPC is used to determine the value of the number n of repeating units (based on the number average molecular weight) in the indene skeleton part of the aforementioned maleimide A-2, the GPC chart is shown in Figure 2, n=1.25 , molecular weight distribution (Mw/Mn)=3.29.

[Synthesis Example 3] Synthesis of Maleimine Compound A-3 (1) Synthesis of Intermediate Amine Compound Put 2,6-dimethyl in a 2L flask equipped with a thermometer, cooling tube, Dean-Stark separator, and stirrer. Add 48.5g (0.4mol) of aniline, 388.6g (2.0mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 350g of xylene and 123g of activated clay, and heat to 120°C while stirring. Furthermore, while removing the distilled water with a Dean-Stark tube, the temperature was raised to 210°C and allowed to react for 3 hours. Thereafter, the mixture was cooled to 140°C, 145.4 g (1.2 mol) of 2,6-dimethylaniline was added, and then the temperature was raised to 220°C and allowed to react for 3 hours. After the reaction, air cool to 100°C, dilute with 500g of toluene, remove activated clay by filtration, and distill off low molecular weight substances such as solvent and unreacted matter under reduced pressure to obtain the following general formula (A-3 402.1g of the intermediate amine compound represented by ). The amine equivalent weight is 306 and the softening point is 65°C.

(2) Maleic imidization In a 2L flask equipped with a thermometer, cooling tube, Dean-Stark separator, and stirrer, 152.1 g (1.5 mol) of maleic anhydride and 700 g of toluene were added and stirred at room temperature. Next, a mixed solution of 402.1 g of reactant (A-3) and 200 g of DMF was added dropwise over 1 hour. After the dripping was completed, the reaction was further carried out at room temperature for 2 hours. 37.5 g of p-toluenesulfonic acid monohydrate was added, and the reaction liquid was heated to cool and separate the azeotropic water and toluene under reflux. Then, only toluene was returned to the system and dehydration reaction was performed for 8 hours. After the air was cooled to room temperature, it was concentrated under reduced pressure to dissolve the brown solution in 800g of ethyl acetate, washed three times with 200g of ion-exchange water and three times with 200g of 2% sodium bicarbonate aqueous solution, and dried after adding sodium sulfate. , the reaction product obtained by concentrating under reduced pressure was vacuum dried at 80° C. for 4 hours to obtain 486.9 g of a product containing maleimine compound A-3. In the FD-MS mass spectrum of the maleimide compound A-3, peaks of M+=560, 718, and 876 were confirmed, corresponding to the cases where n is 0, 1, and 2, respectively. In addition, when GPC is used to determine the value of the repeating unit number n (based on the number average molecular weight) in the indene skeleton part of the aforementioned maleimide A-3, the GPC chart is shown in Figure 3, n=1.96 , molecular weight distribution (Mw/Mn)=1.52.

[Synthesis Example 4] Synthesis of Maleimine Compound A-4 (1) Synthesis of Intermediate Amine Compound Put 2,6-diethyl in a 2L flask equipped with a thermometer, cooling tube, Dean-Stark separator, and stirrer. 59.7g (0.4mol) of aniline, 272.0g (1.4mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 350g of xylene and 94g of activated clay were heated to 120°C while stirring. Furthermore, while removing the distilled water with a Dean-Stark tube, the temperature was raised to 210°C and allowed to react for 3 hours. Thereafter, the mixture was cooled to 140°C, 179.1 g (1.2 mol) of 2,6-diethylaniline was added, and then the temperature was raised to 220°C and allowed to react for 3 hours. After the reaction, the air was cooled to 100°C, diluted with 500g of toluene, and the activated clay was removed by filtration. The solvent and low molecular weight substances such as unreacted substances were distilled off under reduced pressure to obtain the following general formula (A-4 342.1 g of the intermediate amine compound represented by ). The amine equivalent weight is 364 and the softening point is 47°C.

(2) Maleic imidization In a 2L flask equipped with a thermometer, cooling tube, Dean-Stark separator, and stirrer, 107.9 g (1.1 mol) of maleic anhydride and 600 g of toluene were added and stirred at room temperature. Next, a mixed solution of 342.1 g of reactant (A-4) and 180 g of DMF was added dropwise over 1 hour. After the dripping was completed, the reaction was further carried out at room temperature for 2 hours. 26.8 g of p-toluenesulfonic acid monohydrate was added, and the reaction liquid was heated to cool and separate the azeotropic water and toluene under reflux. Then, only toluene was returned to the system and dehydration reaction was performed for 8 hours. After the air was cooled to room temperature, it was concentrated under reduced pressure, and the brown solution was dissolved in 500g of ethyl acetate, washed three times with 200g of ion-exchange water, and three times with 200g of 2% sodium bicarbonate aqueous solution, and dried after adding sodium sulfate. , the reaction product obtained by concentrating under reduced pressure was vacuum dried at 80° C. for 4 hours to obtain 388.1 g of a product containing maleimine compound A-4. In the FD-MS mass spectrum of the maleimide compound A-4, peaks of M+=616, 774, and 932 were confirmed, which correspond to the cases where n is 0, 1, and 2 respectively. In addition, when GPC is used to determine the value of the number n of repeating units (based on the number average molecular weight) in the indene skeleton part of the maleimide A-4, the GPC chart is shown in Figure 4, n=1.64 , molecular weight distribution (Mw/Mn)=1.40.

[Synthesis Example 5] Synthesis of Maleimine Compound A-5 (1) Synthesis of Intermediate Amine Compound 2,6-diiso is placed in a 1L flask equipped with a thermometer, a cooling tube, a Dean-Stark separator, and a stirrer. 70.9g (0.4mol) of propylaniline, 272.0g (1.4mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 350g of xylene and 97g of activated clay were heated to 120°C while stirring. Furthermore, while removing the distilled water with a Dean-Stark tube, the temperature was raised to 210°C and allowed to react for 3 hours. Thereafter, the mixture was cooled to 140°C, 212.7 g (1.2 mol) of 2,6-diisopropylaniline was added, and then the temperature was raised to 220°C and allowed to react for 3 hours. After the reaction, the air was cooled to 100°C, diluted with 500g of toluene, filtered to remove activated clay, and low molecular weight substances such as solvent and unreacted matter were distilled off under reduced pressure to obtain the following general formula (A-5 317.5g of the intermediate amine compound represented by ). The amine equivalent weight is 366 and the softening point is 55°C.

(2) Maleic imidization In a 2L flask equipped with a thermometer, cooling tube, Dean-Stark separator, and stirrer, 107.9 g (1.1 mol) of maleic anhydride and 600 g of toluene were added and stirred at room temperature. Next, a mixed solution of 317.5 g of reactant (A-5) and 175 g of DMF was added dropwise over 1 hour. After the dripping was completed, the reaction was further carried out at room temperature for 2 hours. 24.8 g of p-toluenesulfonic acid monohydrate was added, and the reaction liquid was heated to cool and separate the azeotropic water and toluene under reflux. Then, only toluene was returned to the system and dehydration reaction was performed for 8 hours. After the air was cooled to room temperature, it was concentrated under reduced pressure to dissolve the brown solution in 600g of ethyl acetate, washed three times with 200g of ion-exchange water and three times with 200g of 2% sodium bicarbonate aqueous solution, and dried after adding sodium sulfate. , the reaction product obtained by concentrating under reduced pressure was vacuum dried at 80° C. for 4 hours to obtain 355.9 g of a product containing maleimide compound A-5. In the FD-MS mass spectrum of the maleimide compound A-5, peaks of M+=672, 830, and 988 were confirmed, which correspond to the cases where n is 0, 1, and 2 respectively. In addition, when GPC is used to determine the value of the number n of repeating units (based on the number average molecular weight) in the indene skeleton part of the maleimide A-5, the GPC chart is shown in Figure 5, n=1.56 , molecular weight distribution (Mw/Mn)=1.24.

[Synthesis Example 6] Synthesis of Maleimine Compound A-9 (1) Synthesis of Intermediate Amine Compound In the aforementioned synthesis method of the intermediate amine compound A-1, the reaction time at 210°C was changed to 6 hours. The reaction time at 220° C. was changed to 3 hours and the same operation was performed to obtain 345.2 g of an intermediate amine compound represented by the following general formula (A-9). The amine equivalent weight is 348 and the softening point is 71°C.

(2) Maleimide compound A-9 was synthesized from the above synthesis method of maleimine compound A-1 by substituting the intermediate for A-9 and proceeding in the same manner. Material 407.6g. In the FD-MS mass spectrum of the maleimide compound A-9, peaks of M+=560, 718, and 876 were confirmed, and each peak corresponds to the case where n is 0, 1, and 2. In addition, when GPC is used to determine the value n of the repeating unit number (based on the number average molecular weight) in the indene skeleton part of the aforementioned maleimide A-9, the GPC chart is shown in Figure 6, n=2.59 , molecular weight distribution (Mw/Mn)=1.49.

[Synthesis Example 7] Synthesis of Maleimine Compound A-10 In addition to the above synthesis method of the intermediate amine compound A-1, the reaction time at 210°C was changed to 6 hours, and the reaction time at 220°C was changed to The same operation was performed for 3 hours, and the dehydration reaction under reflux in the maleyl imidization reaction was set to other than 10 hours for the intermediate amine compound (amine equivalent: 347, softening point: 71°C). Under the same conditions as the synthesis method of maleimine compound A-1, 415.6 g of a product containing maleimine compound A-10 was obtained. In the FD-MS mass spectrum of the maleimide compound A-10, peaks of M+=560, 718, and 876 were confirmed, and each peak corresponds to the case where n is 0, 1, and 2. In addition, when GPC is used to determine the value of the number n of repeating units (based on the number average molecular weight) in the indene skeleton part of the aforementioned maleimide A-10, the GPC chart is shown in Figure 7, n=2.91 , molecular weight distribution (Mw/Mn)=1.64.

[Synthesis Example 8] Synthesis of Maleimine Compound A-11 In addition to the above synthesis method of the intermediate amine compound A-1, the reaction time at 210°C was changed to 9 hours, and the reaction time at 220°C was changed to The same operation was performed for 3 hours, and the dehydration reaction under reflux in the maleyl imidization reaction was set to other than 10 hours for the intermediate amine compound (amine equivalent: 342, softening point: 69°C). The conditions were the same as the synthesis method of maleimine compound A-1, and 398.7 g of a product containing maleimine compound A-11 was obtained. In the FD-MS mass spectrum of the maleimide compound A-11, peaks of M+=560, 718, and 876 were confirmed, and each peak corresponds to the case where n is 0, 1, and 2. In addition, when GPC is used to determine the value n of the repeating unit number (based on the number average molecular weight) in the indene skeleton part of the aforementioned maleimide A-11, the GPC chart is shown in Figure 8, n=3.68 , molecular weight distribution (Mw/Mn)=2.09.

[Synthesis Example 9] Synthesis of Maleimine Compound A-12 In addition to the above synthesis method of the intermediate amine compound A-1, the reaction time at 210°C was changed to 9 hours, and the reaction time at 220°C was changed to The same operation was performed for 3 hours. For the intermediate amine compound (amine equivalent weight: 347, softening point: 70°C) to be synthesized, the dehydration reaction under reflux in the maleyl imidization reaction was set to other than 12 hours. Under the same conditions as the synthesis method of maleimine compound A-1, 422.7 g of a product containing maleimine compound A-12 was obtained. In the FD-MS mass spectrum of the maleimide compound A-12, peaks of M+=560, 718, and 876 were confirmed, and each peak corresponds to the case where n is 0, 1, and 2. In addition, when GPC is used to determine the value of the repeating unit number n (based on the number average molecular weight) in the indene skeleton part of the aforementioned maleimide A-12, the GPC chart is shown in Figure 9, n=4.29 , molecular weight distribution (Mw/Mn)=3.02.

[Examples 1 to 9 and Comparative Example 1] ＜Solvent solubility of maleimide＞ The maleimides (A-1) to (A-5), (A-9) to (A-12) obtained in Synthesis Examples 1 to 9, and the commercially available maleimide ( A-6) Evaluation of the solubility of (4,4'-diphenylmethane bismaleimide, "BMI-1000" manufactured by Yamato Chemical Industry Co., Ltd.) to toluene and methyl ethyl ketone (MEK) , the evaluation results are shown in Table 1. As a method for evaluating solvent solubility, each maleimide obtained in the above synthesis examples and comparative examples was used to prepare toluene such that the non-volatile content became 10, 20, 30, 40, 50, 60, and 70% by mass. solution, and methyl ethyl ketone (MEK) solution. Specifically, small glass bottles containing each maleimide obtained in the above synthesis examples and comparative examples were placed at room temperature (25°C) for 60 days, and each solution composed of each non-volatile component was uniformly The evaluation (visual inspection) of the case of dissolution (no insoluble matter) is 0, and the evaluation (visual inspection) of the case of dissolution (presence of insoluble matter) is ×. In addition, when the non-volatile component is 20% by mass or more, it is practically preferable as long as it is soluble in the solvent.

[Examples 10 to 18 and Comparative Examples 2 to 4] ＜Preparation of curable resin composition＞ The maleimide (A-1) to (A-5), (A-9) to (A-12) obtained in Synthesis Examples 1 to 9, and the comparative maleimide (A-6) ( 4,4'-diphenylmethane bismaleimide, "BMI-1000", manufactured by Daiwa Chemical Industry Co., Ltd.), maleimide (A-7) for comparison (bisphenol A diphenyl ether Bismaleimide, "BMI-4000" manufactured by Yamato Chemical Industry Co., Ltd.), maleimide for comparison (A-8) (1,6'-bismaleimide-(2,2 , 4-trimethyl)hexane, "BMI-TMH" manufactured by Yamato Chemical Industry Co., Ltd.), polyphenylene ether compound (B-1) ("SA-90", manufactured by SABIC Corporation, Mw: 1700), ring Oxygen resin (C-1) (BPA type epoxy resin "850-S", equivalent weight: 188g/eq, manufactured by DIC Co., Ltd.), and hardening accelerator (D-1) (triphenylphosphine, Tokyo Chemical Industry Co., Ltd. Co., Ltd.) at the ratio shown in Table 2 to prepare a curable resin composition.

[Examples 10, 15 to 18, and Comparative Examples 2 to 4] ＜Uniformity of film appearance＞ In Examples 10, 15 to 18, and Comparative Examples 2 to 4, 14.81 g of methyl ethyl ketone (MEK) was mixed and dissolved in the ratio shown in Table 2 to obtain a curable resin composition. 5 g of each curable resin composition was applied to a release PET film (thickness after drying: 295 μm), dried (heated) at 80°C for 1 hour, and then dried (heated) at 120°C for 1 hour. A formed film was produced, and the appearance of the obtained formed film was visually confirmed. The case where the film appearance is uniform is evaluated as 0, and the case where the film appearance is uneven is evaluated as × (for example, when turbidity, insoluble matter, etc. are confirmed). The evaluation results are shown in Table 3.

<Preparation of hardened product (molded product)>

A cured product (molded product) is produced by subjecting the above-mentioned curable resin composition to the following conditions.

Hardening conditions: After heating at 200°C for 2 hours, it was further heated and hardened at 250°C for 2 hours.

The thickness of the hardened product (molded product) after molding: 2.4mm

Various physical properties and characteristics of the obtained hardened product were evaluated using the following methods. The evaluation results are shown in Table 4.

<Glass transition temperature (Tg)>

The hardened material with a thickness of 2.4 mm was cut into a size of 5 mm in width and 54 mm in length, and this was used as a test piece. A viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "DMS6100" manufactured by Hitachi High-Tech Science Co., Ltd., deformation mode: dual-hold bending, measurement mode: sine wave vibration, frequency 1Hz, temperature rise rate 3°C/ minutes), and the temperature at which the elastic coefficient change becomes the maximum (the tan δ change rate is the maximum) is evaluated as the glass transition temperature Tg (°C). In addition, from the viewpoint of heat resistance, the glass transition temperature Tg is preferably 135°C or higher, and more preferably 140°C or higher.

<Thermal decomposition resistance>

The hardened material with a thickness of 2.4 mm was finely cut, and measured in a nitrogen atmosphere using a thermogravimetric analyzer (thermal gravimetric measuring device "TGA/DSC1" of METTLER TOLEDO Co., Ltd.) with the temperature rising rate set to 5°C/min. , and the temperature at which the weight decreases by 5% is regarded as the thermal decomposition temperature (Td5) (°C) for evaluation.

＜Dielectric properties＞ According to JIS-C-6481, the network analyzer "E8362C" manufactured by Agilent Technologies Co., Ltd. was used and the cavity resonance method was used to measure the 1GHz frequency of the test piece after being stored in a room at 23°C and 50% humidity for 24 hours after absolute drying. The dielectric constant and dielectric loss tangent below. In addition, as the dielectric constant and the dielectric loss tangent, from the viewpoint of reducing transmission loss as an electronic material, the dielectric constant is preferably 2.75 or less, and more preferably 2.70 or less. In addition, the dielectric loss tangent is preferably 0.020 or less, and more preferably 0.018 or less.

[Table 1] Solvent solubility evaluation Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative example 1 maleimide A-1 A-2 A-3 A-4 A-5 A-9 A-10 A-11 A-12 A-6 Toluene solution non-volatile components 10% ○ ○ ○ ○ ○ ○ ○ ○ ○ × 20% ○ ○ ○ ○ ○ ○ ○ ○ ○ × 30% ○ × ○ ○ ○ ○ ○ ○ ○ × 40% × × ○ ○ ○ ○ ○ ○ ○ × 50% × × ○ ○ ○ ○ ○ ○ ○ × 60% × × ○ × ○ ○ ○ ○ ○ × 70% × × ○ × × ○ ○ ○ ○ × MEK solution non-volatile components 10% ○ ○ ○ ○ ○ ○ ○ ○ ○ × 20% ○ ○ ○ ○ ○ ○ ○ ○ ○ × 30% ○ ○ ○ ○ ○ ○ ○ ○ ○ × 40% ○ ○ ○ ○ ○ ○ ○ ○ ○ × 50% ○ ○ ○ ○ ○ ○ ○ ○ ○ × 60% × × ○ ○ ○ ○ ○ ○ ○ × 70% × × ○ ○ ○ ○ ○ ○ ○ ×

[Table 2] Blending amount (number of grams) Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Comparative example 2 Comparative example 3 Comparative example 4 A-1 11.00 A-2 11.00 A-3 11.00 A-4 11.00 A-5 11.00 A-6 11.00 A-7 11.00 A-8 11.00 A-9 11.00 A-10 11.00 A-11 11.00 A-12 11.00 B-1 6.60 6.60 6.60 6.60 6.60 6.60 6.60 6.60 6.60 6.60 6.60 6.60 C-1 4.40 4.40 4.40 4.40 4.40 4.40 4.40 4.40 4.40 4.40 4.40 4.40 D-1 0.22 0.22 0.22 0.22 0.22 0.22 0.22 0.22 0.22 0.22 0.22 0.22

[table 3] Example 10 Example 15 Example 16 Example 17 Example 18 Comparative example 2 Comparative example 3 Comparative example 4 Uniformity of film appearance ○ ○ ○ ○ ○ × × ×

[Table 4] Physical property evaluation unit Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Comparative example 2 Glass transition temperature Tg(DMA) ℃ 158 170 145 152 151 150 149 146 145 133 Thermal decomposition temperature (Td5/nitrogen environment) ℃ 320 342 323 331 328 324 320 322 325 317 Dielectric constant (1GHz) - 2.65 2.68 2.67 2.68 2.67 2.68 2.67 2.65 2.67 Unable to make Dielectric loss tangent (1GHz) - 0.0154 0.0176 0.0158 0.0164 0.0159 0.0165 0.0158 0.0157 0.0154 Unable to make

From the evaluation results in Table 1 above, it was confirmed that in Examples 1 to 9, since maleimide having an indene skeleton was used, when the toluene solution was prepared, even if the non-volatile content was 20 mass % It is soluble and can be dissolved even when the non-volatile content is 50% by mass when preparing a MEK solution. It has excellent solvent solubility. On the other hand, it was confirmed that the commercially available maleimide used in Comparative Example 1 does not have an indene skeleton in its structure and has poor solvent solubility.

From the evaluation results in Table 3 above, it was confirmed that the films obtained by applying and drying the curable resin composition solution (varnish) containing maleimide having an indene skeleton in Examples 10 and 15 to 18 It has a uniform appearance and can be used in applications such as circuit boards (copper-clad laminates, etc.) including build-up films that require a uniform appearance of the resulting film. On the other hand, in Comparative Examples 2 to 4, it was confirmed that since commercially available maleimide without an indene skeleton was used, the appearance of the film was uneven and it was difficult to use it in build-up films and circuit boards ( Copper-clad laminates, etc.) and other uses.

From the evaluation results in Table 4 above, it can be confirmed that in Examples 10 to 18, by adding an epoxy resin in addition to the maleimide having an indene skeleton and using it as a hardener, it is also helpful. A polyphenylene ether compound with excellent dielectric properties, high glass transition temperature and thermal decomposition resistance, and excellent heat resistance and thermal decomposition resistance. In addition, the dielectric constant and the dielectric loss tangent were also suppressed to be low, and it was confirmed that the dielectric characteristics were excellent. On the other hand, in Comparative Example 2, it was confirmed that the glass transition temperature and thermal decomposition resistance were lower than those in the Examples, the heat resistance and thermal decomposition resistance were inferior, and the dielectric constant and dielectric loss tangent were hardened. Due to the influence of the brittleness of the material, it was not possible to prepare samples for evaluation in the first place. [Possibility of industrial application]

Since the cured product of the curable resin composition of the present invention has excellent heat resistance and dielectric properties, it can be ideally used in heat-resistant components and electronic components. In particular, it can be ideally used in semiconductor packaging materials, circuit boards, and build-up films. , build-up substrate, etc., adhesives, photoresist materials. In addition, it can also be ideally used as a matrix resin for fiber-reinforced resin and is suitable as a highly heat-resistant prepreg.

without.

Figure 1 is a GPC chart of the maleimide compound (A-1) obtained in Synthesis Example 1. Figure 2 is a GPC chart of the maleimide compound (A-2) obtained in Synthesis Example 2. Figure 3 is a GPC chart of the maleimide compound (A-3) obtained in Synthesis Example 3. Figure 4 is a GPC chart of the maleimide compound (A-4) obtained in Synthesis Example 4. Figure 5 is a GPC chart of the maleimide compound (A-5) obtained in Synthesis Example 5. Figure 6 is a GPC chart of the maleimide compound (A-9) obtained in Synthesis Example 6. Figure 7 is a GPC chart of the maleimide compound (A-10) obtained in Synthesis Example 7. Figure 8 is a GPC chart of the maleimide compound (A-11) obtained in Synthesis Example 8. Figure 9 is a GPC chart of the maleimide compound (A-12) obtained in Synthesis Example 9.

without.

Claims (7)

A curable resin composition containing maleimide (A) having an indene skeleton, a polyphenylene ether compound (B), and an epoxy resin (C), wherein the maleimide (A) It is represented by the following general formula (1),

(In formula (1), Ra each independently represents an alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group or arylthio group having 6 to 10 carbon atoms, or an alkyl group having 3 to 10 carbon atoms. cycloalkyl group, halogen atom, nitro group, hydroxyl group or mercapto group, Ra can be the same or different in the same ring; Rb each independently represents an alkyl group, alkoxy group or alkylthio group with 1 to 10 carbon atoms, and the number of carbon atoms Aryl groups, aryloxy groups or arylthio groups with 6 to 10 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, halogen atoms, hydroxyl groups or mercapto groups, r represents an integer value of 0 to 3; when r is 2 to 3, Rb They can be the same or different within the same ring; n is the average number of repeating units, indicating a value from 0.95 to 10.0). A cured product characterized in that it is obtained by curing the curable resin composition of claim 1. A prepreg characterized by having a reinforcing base material and a semi-hardened product impregnated with the curing resin composition of Claim 1 in the reinforcing base material. A circuit board characterized by being as specified in claim 3 It is obtained by laminating impregnated materials and copper foil and heating and pressing them. A build-up film characterized by containing the curable resin composition of claim 1. A semiconductor packaging material, characterized by containing the curable resin composition according to claim 1. A semiconductor device characterized by comprising a cured product obtained by heating and curing the semiconductor packaging material according to claim 6.