CN113767117B - Curable resin composition - Google Patents

Abstract

Providing: curable resin composition having excellent heat resistance and dielectric characteristics as cured product thereof, prepreg, circuit board, laminated film, semiconductor sealing material, and semiconductor device having the above properties. The curable resin composition of the present invention is characterized by comprising: maleimide (A) having an indane skeleton, polyphenylene ether compound (B) and epoxy resin (C).

Description

curable resin composition

technical field

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

Background technique

As a material for circuit boards for electronic equipment, it is widely used: epoxy resins, BT (bismaleimide-triazine) resins and other thermosetting resins are impregnated into glass cloth and heated and dried. A prepreg, a laminate obtained by heat-curing the prepreg, and a multilayer board obtained by combining the laminate and the prepreg and heat-cured. Among them, thinning of semiconductor package substrates is progressing, and warping of package substrates during mounting becomes a problem. Therefore, materials exhibiting high heat resistance are required to suppress this.

In addition, in recent years, the high-speed and high-frequency signals are increasing, and it is desired to provide a thermosetting material that can maintain a sufficiently low dielectric constant under these environments and exhibit a sufficiently low dielectric loss tangent. resin composition.

In particular, recently, in various applications of electrical materials, especially in applications of advanced materials, further improvements in performance represented by heat resistance and dielectric properties, and materials and compositions having both of these performances are required.

In response to such requirements, attention is being paid to maleimide resins as materials having both heat resistance and low dielectric constant/low dielectric loss tangent. However, although conventional maleimide resins exhibit high heat resistance, their dielectric constant/dielectric loss tangent values are not at the level required for advanced material applications, and their handling properties are poor due to poor solvent solubility. It is strongly desired to develop a resin that maintains heat resistance, exhibits further low dielectric constant/low dielectric loss tangent, and is also excellent in solvent solubility.

In such a case, as cyanate-based materials having both high dielectric properties and heat resistance, phenol novolac-type cyanate resins, bisphenol A cyanate resins, and non-halogen-based epoxy resins are known. A resin composition obtained by compounding resins (see Patent Document 1).

However, although the heat resistance and dielectric properties of the cured product of the resin composition described in the aforementioned Patent Document 1 have been improved to some extent, the heat resistance has not yet reached the level required in recent years.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2004-182850

Contents of the invention

The problem to be solved by the invention

Therefore, the problem to be solved by the present invention is to provide a curable resin composition having excellent heat resistance and dielectric properties, a cured product thereof, a prepreg, a circuit board, and a product having both the above properties. Layer thin films, semiconductor sealing materials, and semiconductor devices.

solutions to problems

Therefore, the inventors of the present invention conducted intensive studies to solve the above-mentioned problems, and as a result, found that a compound containing a maleimide (A) having an indane skeleton, a polyphenylene ether compound (B) and an epoxy resin (C) The curable resin composition has a low dielectric constant and a low dielectric loss tangent, and its cured product can also have excellent heat resistance, thereby completing the present invention.

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

In the curable resin composition of the present invention, it is preferable that the maleimide (A) is represented by the following general formula (1).

(In the formula (1), Ra each independently represents an alkyl group, an alkoxy group or an alkylthio group with a carbon number of 1 to 10, an aryl group with a carbon number of 6 to 10, an aryloxy group or an arylthio group, a carbon number of 3 to 10 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 is optionally the same or different in the same ring. Rb each independently represents the number of carbons Alkyl, alkoxy or alkylthio of 1 to 10, aryl, aryloxy or arylthio with 6 to 10 carbons, cycloalkyl with 3 to 10 carbons, halogen atom, hydroxyl or mercapto, r Represents an integer value of 0 to 3. When r is 2 to 3, Rb is optionally the same or different in the same ring. n is the average number of repeating units and represents a value of 0.5 to 20.)

The cured product of the present invention is preferably obtained by subjecting the aforementioned curable resin composition to a curing reaction.

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

The circuit board of the present invention is preferably obtained by laminating the aforementioned prepreg and copper foil, followed by thermocompression molding.

The laminated film of the present invention preferably contains the aforementioned curable resin composition.

It is preferable that the semiconductor sealing material of this invention contains the said curable resin composition.

The semiconductor device of the present invention preferably includes a cured product obtained by heating and curing the aforementioned semiconductor encapsulating material.

The effect of the invention

According to the curable resin composition of the present invention, it is possible to provide a cured product obtained from the above-mentioned curable resin composition having excellent heat resistance and dielectric properties, and a curable resin composition having the above-mentioned performances. The cured product obtained from the curable resin composition, a prepreg, a circuit board, a laminate film, a semiconductor sealing material, and a semiconductor device are useful.

Detailed ways

Hereinafter, the present invention will be described in detail.

The present invention relates to a curable resin composition characterized by comprising: a maleimide (A) having an indane skeleton (hereinafter, sometimes referred to as "component (A)"), a polyphenylene ether compound ( B) (Hereinafter, it may be called "(B) component.") and epoxy resin (C) (Hereinafter, it may be called "(C) component."). Among them, the aforementioned maleimide (A) is preferably represented by the following general formula (1). The aforementioned maleimide (A) has an indane skeleton, so compared with conventional maleimides, the proportion of polar functional groups in the structure of the aforementioned maleimide (A) is small, so the dielectric properties Excellent and therefore preferred. In addition, the cured product using the conventional maleimide resin tends to be brittle, and there is a concern that the brittleness resistance is poor, but the above-mentioned maleimide (A) has an indane skeleton, so it is excellent in flexibility, and the brittleness resistance is also expected. Improvement is preferred.

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

Ra in the above-mentioned general formula (1) is preferably any one of an alkyl group having 1 to 4 carbons, a cycloalkyl group having 3 to 6 carbons, and an aryl group having 6 to 10 carbons. Alkyl groups, etc., so that the solvent solubility is improved by the reduction of planarity and crystallinity near the maleimide group, and it is preferable to obtain a cured product without impairing the reactivity of the maleimide group. Way.

q in the above general formula (1) is preferably 2-3, more preferably 2. In the case where q is 2, the influence of steric hindrance is small, and the electron density on the aromatic ring is increased, which is a preferred mode in the production (synthesis) of maleimide.

R in the above general formula (1) is 0, Rb is preferably a hydrogen atom, and r is 1 to 3, and Rb is preferably selected from an alkyl group with 1 to 4 carbons, a cycloalkyl group with 3 to 6 carbons, and at least one of the group consisting of an aryl group having 6 to 10 carbon atoms, especially when the aforementioned r is 0 and Rb is a hydrogen atom, the stereo position of the indane skeleton in maleimide is formed Less resistance change is advantageous for the production (synthesis) of maleimide, and is a preferred mode.

<Method for producing maleimide (A) having an indane skeleton>

Hereinafter, the manufacturing method of the said maleimide (A) is demonstrated.

The following general formula (2) is the following compound: Rc each independently represents a monovalent functional group selected from the group consisting of the following general formulas (3) and (4), and the neighbors of at least one Rc in the two Rc The position is a hydrogen atom, and the representations of Rb and r are the same as above.

The following general formula (5) is: at least one of the ortho-position and para-position of the amino group is a hydrogen atom, and Ra and q represent the same aniline or its derivatives as described above, by making the compound of the above-mentioned general formula (2) The intermediate amine compound represented by the following general formula (6) can be obtained by reacting with a compound of the following general formula (5) in the presence of an acid catalyst. In addition, Ra, Rb, q, and r in following general formula (6) represent the same as above.

Among the intermediate amine compounds represented by the above general formula (6), the following general formula (7) having an indane skeleton is included in the structure, but in the aniline or its derivatives represented by the above general formula (5), q When it is 3 or less, and at least two of the ortho-position and para-position of the amino group are hydrogen atoms, the structure is represented by the following general formula (8). However, Ra, Rb, q, and r in the following general formula (8) are the same as above, m is the number of repeating units, and represents an integer value of 1-20. In addition, the structure represented by the following general formula (8) may also be included in the structure of the said general formula (6).

In the indane skeleton (refer to the above general formula (7)) that is characteristic of the maleimide (A) used in the present invention, for the average number of repeating units n, in order to have a low melting point (low softening point) and melt Those with low viscosity and excellent handleability have an average number of repeating units n (average value) of 0.5 to 20, preferably 0.7 to 10.0, more preferably 0.95 to 10.0, still more preferably 0.98 to 9.0, still more preferably 0.99 to 8.0 , more preferably 1.0 to 7.0, still more preferably 1.0 to 6.0. By having an indane skeleton in the structure of the said maleimide (A), it is a preferable aspect compared with the maleimide used conventionally because it is excellent in solvent solubility. It should be noted that when the above-mentioned n is less than 0.5, the content ratio of the high-melting point substance in the structure of the above-mentioned maleimide (A) becomes high, the solvent solubility is poor, and the ratio of the high-molecular-weight component that contributes to the flexibility becomes smaller. If it is low, the brittle resistance of the obtained cured product may decrease, and furthermore, the flexibility and softness may also decrease, which is not preferable. In addition, when the aforementioned n exceeds 20, there is a fear that the heat resistance will be poor, and the high molecular weight component will become too much, and the flowability of the cured product may be reduced and the handling property may be poor, which is not preferable. In addition, the value of n is preferably from 0.5 to 10.0, more preferably from 0.95 to 10.0, from the viewpoint of a high heat distortion temperature, a high glass transition temperature, and the like.

The compound represented by the above-mentioned general formula (2) used in the present invention (hereinafter, "compound (a)") is not particularly limited, and typically, p-diisopropenylbenzene and m-diisopropenylbenzene, p-diisopropenylbenzene, p-diisopropenylbenzene, p-diisopropenylbenzene, p-diisopropenylbenzene, p-diisopropenylbenzene, (α-hydroxyisopropyl)benzene and m-bis(α-hydroxyisopropyl)benzene, 1-(α-hydroxyisopropyl)-3-isopropenylbenzene, 1-(α-hydroxyisopropyl) - 4-isopropenylbenzene or mixtures thereof. In addition, nuclear alkyl substituents of these compounds, such as diisopropenyltoluene and bis(α-hydroxyisopropyl)toluene, etc., and nuclear halogen substituents, such as chlorodiisopropenylbenzene and chlorine, can also be used. Bis(α-hydroxyisopropyl)benzene and the like.

In addition, as the aforementioned compound (a), for example, 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-methoxy -1,4-bis(α-hydroxyisopropyl)benzene, 5-ethoxy-1,3-diisopropenylbenzene, 5-ethoxy-1,3-bis(α-hydroxyisopropyl ) benzene, 2-phenoxy-1,4-diisopropenylbenzene, 2-phenoxy-1,4-bis(α-hydroxyisopropyl)benzene, 2,4-diisopropenylbenzenesulfide Alcohol, 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-diisopropenylbenzene , 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, and the like.

It should be noted that the substituent contained in the aforementioned compound (a) is not particularly limited, and the compounds exemplified above can be used. In the case of a substituent with a large steric hindrance, compared with a substituent with a small steric hindrance, It is a preferred aspect that the obtained maleimides are less likely to be deposited together, and the maleimides are less likely to cause crystallization, that is, the solvent solubility of the maleimides is improved.

In addition, as the compound represented by the above-mentioned general formula (5) (hereinafter, "compound (b)"), typically, in addition to aniline, for example, dimethylaniline, diethylaniline, diisopropylaniline, Aniline, ethylmethylaniline, chloroaniline, dichloroaniline, toluidine, xylaniline, phenylaniline, nitroaniline, aminophenol and cyclohexylaniline, etc. In addition, methoxyaniline, ethoxyaniline, phenoxyaniline, naphthoxyaniline, aminothiol, methylthioaniline, ethylthioaniline, and phenylthioaniline can also be exemplified.

It should be noted that when the maleimide group is directly bonded to the benzene ring as in conventional maleimide (for example, N-phenylmaleimide), the benzene ring and maleimide The state in which the 5-membered rings of the amine are arranged on the same plane is stable, and thus stacking is easy, and high crystallinity is exhibited. Therefore, it becomes the cause of poor solvent solubility. On the other hand, in the case of the present invention, the aforementioned compound (b) is not particularly limited, and the compounds exemplified above can be used. In addition, for example, those having a methyl group as a substituent such as 2,6-dimethylaniline In this case, the benzene ring and the 5-membered ring of maleimide are in a distorted conformation due to the steric hindrance of the methyl group, and stacking becomes difficult, so the crystallinity is lowered and the solvent solubility is improved, which is a preferred embodiment. Among them, if the steric hindrance is too large, the reactivity may be hindered during the synthesis of maleimide, so it is preferable to use, for example, a compound (b) having an alkyl group having 2 to 4 carbon atoms.

In the production method of the intermediate amine compound represented by the above-mentioned general formula (6) used in the present invention, the aforementioned compound (a) and the aforementioned compound (b) are mixed by moles of the aforementioned compound (b) relative to the aforementioned compound (a). The ratio (compound (b)/compound (a)) is preferably 0.1 to 2.0, more preferably 0.2 to 1.0. After charging and reacting (the first stage), the aforementioned compound (b) is further added to the previously charged aforementioned compound ( The molar ratio of a) is preferably 0.5 to 20.0, more preferably 0.7 to 5.0, and the maleimide (A) having an indane skeleton can be obtained by further adding and reacting (second stage). In addition, the two-step reaction also brings preferable results in order to complete the reaction or from the viewpoint of handleability and the like. It should be noted that, in the reaction of the first stage, the molar ratio (compound (b)/compound (a)) of the aforementioned compound (b) relative to the previously added aforementioned compound (a) is preferably set to 0.10 -0.49, more preferably 0.15-0.40, more preferably 0.20-0.39, so that the molecular weight distribution is wide, the content ratio of low-molecular-weight high-melting-point substances becomes low, and the ratio of high-molecular-weight components becomes high, so solvent solubility can be obtained. Excellent intermediate amine compounds and maleimides that can further contribute to flexibility and brittleness resistance are preferred.

Examples of the acid catalyst used in the above 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 fluoromethanesulfonic acid, activated clay, acid clay, silicon Solid acids such as aluminum, zeolite, strongly acidic ion exchange resins, heteropolyacid salts, etc., after the reaction, solid acids that can easily remove the catalyst by filtration are also preferable from the viewpoint of handleability. When other acids are used, it is preferable to Alkaline-based neutralization and water-based cleaning are performed.

Regarding the compounding amount of the aforementioned acid catalyst, the acid catalyst is compounded in the range of 5 to 40 parts by mass relative to 100 parts by mass of the total amount of the aforementioned compound (a) and the aforementioned compound (b) of the raw materials charged first, and the handling property and From an economical point of view, 5 to 30 parts by mass is preferable. The reaction temperature may generally be in the range of 100 to 300°C, and is preferably 150 to 230°C in order to suppress formation of isomer structures and avoid side reactions such as thermal decomposition.

As the time for the above-mentioned reaction, the reaction will not be completely carried out when the time is short, and side reactions such as the thermal decomposition reaction of the product will be caused when the time is long. Therefore, under the above-mentioned reaction temperature conditions, it is usually in the range of 2 to 48 hours in total. It is 2 to 24 hours, more preferably 4 to 24 hours in total, more preferably 4 to 12 hours in total, and more preferably 8 to 12 hours in total in order to reduce low molecular weight components and increase high molecular weight components.

In the production method of the aforementioned intermediate amine compound, since aniline or its derivatives also serve as a solvent, it is not necessary to use another solvent, but a solvent may be used. For example, in the case of a reaction system having a dehydration reaction, specifically, in the case of reacting a compound having an α-hydroxypropyl group as a raw material, the following method can be adopted: using toluene, xylene, or chlorobenzene, etc. Azeotropically dehydratable solvent, after the dehydration reaction is completed, the solvent is distilled off, and then the reaction is carried out within the range of the above-mentioned reaction temperature.

The maleimide (A) used in the present invention can be obtained as follows: the intermediate amine compound represented by the above-mentioned general formula (6) obtained by the above-mentioned method is dropped into a reactor, and after being dissolved in a suitable solvent, the The reaction is performed in the presence of maleic anhydride and a catalyst, and after the reaction, unreacted maleic anhydride and other impurities are removed by washing with water or the like, 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 includes a structure represented by the above general formula (7) having a skeleton of the above general formula (1) and an indane skeleton, where q is 3 or less and adjacent to the amino group When at least two of the position and the para position are hydrogen atoms, the structure corresponding to the above general formula (8), that is, the structure represented by the following general formula (9) can also be represented by the above general formula (1) included in the structure.

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

Examples of organic solvents used in the maleimidation reaction for the synthesis of the aforementioned maleimide (A) include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, styrene Ketones such as ketones, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, sulfolane and other aprotic solvents, di Cyclic ethers such as oxane and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, aromatic solvents such as benzene, toluene, and xylene, etc., may be used alone or in combination.

In the above-mentioned maleimidation reaction, it is preferable to mix the above-mentioned intermediate amine compound and maleic anhydride so that the equivalent ratio of maleic anhydride to the amino group equivalent of the intermediate amine compound is in the range of 1 to 1.5, more preferably in the range of 1.1 to 1.2 charging, and reacting in an organic solvent having 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 is a preferred embodiment.

Examples of catalysts used in the maleimidation reaction include inorganic salts such as acetates, chlorides, bromides, sulfates, and nitrates of nickel, cobalt, sodium, calcium, iron, lithium, and manganese. , inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid, activated clay, acid clay, silica alumina, zeolite, strong acid ion exchange resin, etc. solid acid, heteropoly acid salt, etc., particularly preferably toluenesulfonic acid.

Examples of the dehydrating agent used in the aforementioned maleimidation 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, and inorganic acids such as sulfuric acid. Acid, porous ceramics such as molecular sieves, etc., preferably acetic anhydride can be used.

The amount of the catalyst and dehydrating agent used in the aforementioned maleimidation reaction is not limited. Usually, with respect to 1 equivalent of the amino group of the intermediate amine compound, the amount of the catalyst is 0.0001 to 1.0 mole, preferably 0.001 to 0.5 mole, more preferably 0.001 to 0.5 mole, more preferably 0.01 to 0.3 moles are used, and the dehydrating agent is used at 1 to 3 moles, preferably 1 to 1.5 moles.

As the reaction conditions for the above-mentioned maleimidization, the above-mentioned intermediate amine compound and maleic anhydride can be put in, and carried out at a temperature range of 10-100° C., preferably 30-50° C., for 0.5-12 hours, preferably 1-8 hours. After 1 hour of reaction, add the aforementioned catalyst, and carry out the reaction for 2 to 24 hours, preferably 4 to 10 hours, at a temperature of 90 to 130°C, preferably 105 to 120°C. In order to reduce low molecular weight components and increase high molecular weight components, More preferably, it is performed for 6 to 10 hours. In addition, after the reaction, unreacted maleic anhydride and other impurities are removed by washing with water or the like, and heat aging is performed to reduce low molecular weight components and increase high molecular weight components.

For the aforementioned maleimide (A), from the excellent aspects of low dielectric constant and low dielectric loss tangent, the molecular weight distribution calculated by gel permeation chromatography (GPC) measurement (weight average molecular weight (Mw)/number Average molecular weight (Mn)) is preferably in the range of 1.0 to 10.0, more preferably 1.1 to 9.0, still more preferably 1.1 to 8.0, still more preferably 1.2 to 5.0, still more preferably 1.2 to 4.0, still more preferably 1.3 to 3.8, especially Preferably it is 1.3-3.6, Most preferably it is 1.3-3.4. It should be noted that, according to the GPC chart obtained by the above-mentioned GPC measurement, when the molecular weight distribution is wide and there are many high molecular weight components, the ratio of the high molecular weight components that contribute to flexibility increases. Compared with the cured product of imide, brittleness can be suppressed, and a cured product excellent in flexibility and softness can be obtained, which is a preferable embodiment.

<GPC measurement>

The molecular weight distribution (Mw/Mn) of the maleimide (A) was measured based on gel permeation chromatography (GPC) under the following conditions.

Measuring device: "HLC-8320GPC" manufactured by Tosoh Corporation

Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GELG2000HXL" manufactured by Tosoh Corporation + "TSK-GELG2000HXL" manufactured by Tosoh Corporation + "TSK-GELG3000HXL" manufactured by Tosoh Corporation + Tosoh Corporation "TSK-GELG4000HXL" manufactured by Co., Ltd.

Detector: RI (differential refractometer)

Data processing: "GPC workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation

Determination conditions: column temperature 40°C

Developing solvent Tetrahydrofuran

Flow rate 1.0ml/min

Standard: According to the measurement manual of the aforementioned "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrene whose molecular weight is known is used.

(using polystyrene)

Tosoh Corporation "A-500"

"A-1000" manufactured by Tosoh Corporation

"A-2500" manufactured by Tosoh Corporation

"A-5000" manufactured by Tosoh Corporation

"F-1" manufactured by Tosoh Corporation

"F-2" manufactured by Tosoh Corporation

"F-4" manufactured by Tosoh Corporation

"F-10" manufactured by Tosoh Corporation

"F-20" manufactured by Tosoh Corporation

"F-40" manufactured by Tosoh Corporation

"F-80" manufactured by Tosoh Corporation

"F-128" manufactured by Tosoh Corporation

Sample: 1.0 mass % tetrahydrofuran solution in terms of resin solid content of the maleimide obtained in the synthesis example was 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, may be referred to as "component (B)"). The polyphenylene ether (PPE) contained in the structure of the polyphenylene ether compound (B) is excellent in dielectric properties such as dielectric constant and dielectric loss tangent, so high A curable resin composition that maintains a sufficiently low dielectric constant in the frequency band (high frequency region) and exhibits a sufficiently low dielectric loss tangent is useful as a high frequency molding material. In addition, by reacting with the above-mentioned maleimide (A) having an indane skeleton, it can function as a curing agent, generate three-dimensional crosslinking, and can obtain a cured product excellent in heat resistance, which is a preferred embodiment. In addition, generally, a cured product using a maleimide resin is poor in brittleness resistance, but the brittleness tends to be improved by reaction with the aforementioned polyphenylene ether compound (B), which is preferable. Furthermore, in relation to the epoxy resin (C) which will be described in detail below, it also functions as a curing agent and improves the adhesion with copper, and is useful, for example, in the production of circuit boards using copper foil.

It does not specifically limit as said polyphenylene ether compound (B), For example, it has the structure represented by following general formula (10) or (11).

Rd in the above general formulas (10) and (11) each independently include a hydrogen atom, an alkyl group having 1 to 5 carbons, an alkenyl group having 1 to 5 carbons, a cycloalkyl group having 3 to 5 carbons, Alkoxy group with 1 to 5 carbons, thioether group with 1 to 5 carbons, alkylcarbonyl with 2 to 5 carbons, alkoxycarbonyl with 2 to 5 carbons, alkylcarbonyl with 2 to 5 carbons An oxy group, an alkylsulfonyl group having 1 to 5 carbon atoms, and the like. In addition, s is an integer value of 1-30, and t and u also represent the integer value of 1-30.

The alkyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, and propyl.

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

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, and pentyloxy.

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

The alkylcarbonyl group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include methylcarbonyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl, and butylcarbonyl.

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 aforementioned alkylcarbonyloxy group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, and butylcarbonyloxy. Base etc.

The alkylsulfonyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and pentylsulfonyl. wait.

Among these, the aforementioned Rd is preferably a hydrogen atom, an alkyl group having 1 to 5 carbons, or a cycloalkyl group having 3 to 5 carbons, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbons, and even more preferably a hydrogen atom. , methyl, ethyl, particularly preferably hydrogen atom, methyl.

As Y in said (11), a divalent aromatic group derived from the aromatic compound which has two phenolic hydroxyl groups is mentioned.

The aforementioned aromatic compound having two phenolic hydroxyl groups is not particularly limited, and examples thereof include catechol, resorcinol, hydroquinone, 1,4-dihydroxynaphthalene, 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 preferable, and more preferably 4,4'-biphenol, bisphenol A, tetramethylbisphenol A.

The two phenolic hydroxyl groups of the above-mentioned aromatic compound having two phenolic hydroxyl groups form a phenylene ether bond (two oxygen atoms bonded to Y), so Y becomes divalent derived from the aromatic compound having two phenolic hydroxyl groups. aromatic groups.

In addition, in the above general formulas (10) and (11), the terminal structure of the structure is usually an aryloxy group having a phenolic hydroxyl group. The aforementioned phenolic hydroxyl groups may be modified into other structural sites.

Examples of structural sites obtained by modifying the aforementioned phenolic hydroxyl groups include groups containing polymerizable unsaturated bonds such as (meth)acryloyloxy groups, allyloxy groups, and vinyloxy groups; A structural site obtained by reacting a compound with a phenolic hydroxyl group, etc. Among them, a phenolic hydroxyl group or the aforementioned polymerizable unsaturated bond-containing group is preferable from the viewpoint of forming a curable composition having an excellent balance between the dielectric properties and heat resistance of the cured product.

In addition, the polyphenylene ether compound (B) used in the present invention can also be used in the form of an alloyed polymer with polystyrene or the like. Examples of the aforementioned alloyed polymers 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 alloyed polymer, etc.

The polyphenylene ether compound (B) used in the present invention can be used in addition to the above-mentioned resins within the range that does not impair the characteristics of the present invention. 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 combination.

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. When the weight average molecular weight of the said compound (B) is in the said range, the hardened|cured material which acquired the balance of the outstanding dielectric characteristic and heat resistance can be obtained more reliably, and it is a preferable aspect. In addition, the weight average molecular weight (Mw) here should just be the value measured by the usual molecular weight measuring method, Specifically, the value measured using the above-mentioned GPC etc. are mentioned.

<Epoxy resin (C)>

The curable resin composition of this invention is characterized by containing an epoxy resin (C) (Hereinafter, it may be called "(C)component."). The above-mentioned epoxy resin (C) has good fluidity at the time of preparation of a curable resin composition, and is useful for preparing a curable resin composition capable of obtaining a cured product having excellent adhesiveness. Moreover, when the said polyphenylene ether compound (B) and the said epoxy resin (C) are used, the adhesiveness with copper improves, For example, it is useful in manufacture of the circuit board etc. which use copper foil.

The epoxy resin (C) is not particularly limited, and examples thereof include phenol novolac epoxy resins, cresol novolac epoxy resins, α-naphthol novolac epoxy resins, and β-naphthol novolak epoxy resins. Novolak-type epoxy resins, bisphenol A novolak-type epoxy resins, biphenyl novolac-type epoxy resins, etc. novolac-type epoxy resins; phenol aralkyl-type epoxy resins, naphthol-aralkyl-type epoxy resins , phenol biphenyl aralkyl epoxy resin and other aralkyl epoxy resins; bisphenol A epoxy resin, bisphenol AP epoxy resin, bisphenol AF epoxy resin, bisphenol B epoxy resin 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 epoxy Resin and other bisphenol-type epoxy resins; biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, epoxy resins with biphenyl skeletons and diglycidyl etheroxybenzene skeletons, etc. ; naphthalene type epoxy resin; binaphthol type epoxy resin; binaphthyl type epoxy resin; dicyclopentadiene phenol type epoxy resin and other dicyclopentadiene type epoxy resins; Glycidyl amine type epoxy resin, triglycidyl p-aminophenol type epoxy resin, glycidyl amine type epoxy resin of diaminodiphenyl sulfone, etc.; 2,6-naphthalene dicarboxylic acid Diglycidyl ester type epoxy resin, glycidyl ester type epoxy resin of hexahydrophthalic anhydride and other diglycidyl ester type epoxy resins; dibenzopyran, hexamethyldibenzopyran, 7- Benzopyran-type epoxy resins such as phenylhexamethyldibenzopyran, etc. These may be used individually or in combination of 2 or more types, respectively.

Among these, from the viewpoint of obtaining a cured product excellent in heat resistance, phenol aralkyl type epoxy resins, biphenyl novolak type epoxy resins, naphthalene skeleton-containing naphthol novolak type epoxy resins, Naphthol aralkyl epoxy resin, naphthol-phenol novolac epoxy resin, naphthol-cresol novolak epoxy resin, crystalline biphenyl epoxy resin, tetramethyl Biphenyl-type epoxy resin, xanthene-type epoxy resin, alkoxy-containing aromatic ring-modified novolac-type epoxy resin (the glycidyl-containing aromatic ring and alkoxy-containing aromatic ring are connected with formaldehyde compound) etc.

The curable resin composition of the present invention may add a curing agent other than the polyphenylene ether compound (B) within a range that does not impair the curing of the present invention. It should be noted that, relative to 100% by mass of the total amount of the curing agent, the aforementioned polyphenylene ether compound (B) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, particularly preferably 80% by mass or more, Most preferably 90% by mass or more.

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

Examples of the aforementioned amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine compounds, guanidine derivatives, etc.

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

Examples of the acid anhydride-based compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, Phthalic anhydride, methyl hexahydrophthalic anhydride, etc.

Examples of the phenolic compound include phenol novolak resins, cresol novolak resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition type resins, phenol aralkyl resins (Xylock resins), Polyhydric phenol novolak resins synthesized from polyhydric hydroxyl compounds and formaldehyde represented by resorcinol novolak resins, naphthol aralkyl resins, trimethylolmethane resins, tetraphenol ethane resins, naphthol novolak resins , naphthol-phenol novolac resin, naphthol-cresol novolac resin, biphenyl modified phenolic resin (polyphenolic compound formed by linking phenolic nuclei with double methylene), biphenyl modified Naphthol resin (a polyhydric naphthol compound obtained by linking phenol cores with a double methylene group), aminotriazine-modified phenolic resin (a polyhydric phenol compound obtained by linking phenol cores with melamine, benzoguanamine, etc.), Polyhydric phenolic compounds such as alkoxy-containing aromatic ring-modified novolac resins (polyphenolic compounds in which a phenol core and an alkoxy-containing aromatic ring are linked with formaldehyde).

Examples of the cyanate compound include bisphenol A cyanate resin, bisphenol F cyanate resin, bisphenol E cyanate resin, bisphenol S cyanate resin, bisphenol sulfur Ether type cyanate resin, phenylene ether type cyanate resin, naphthylene ether type cyanate resin, biphenyl type cyanate resin, tetramethylbiphenyl type cyanate resin, polyhydroxynaphthalene type Cyanate resin, phenol novolak type cyanate resin, cresol novolac type cyanate resin, triphenylmethane type cyanate resin, tetraphenylethane type cyanate resin, dicyclopentadiene- Phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol novolak type Cyanate ester resin, naphthol-cresol co-condensed novolak type cyanate resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type cyanate resin, biphenyl modified novolak type cyanate resin, anthracene type cyanate resin ester resin, etc.

As the aforementioned compound having an unsaturated double bond-containing substituent, for example, it is not particularly limited as long as it is a compound having two or more unsaturated bond-containing substituents in the molecule, and examples of the aforementioned unsaturated bond-containing substituent include Compounds such as allyl, isopropenyl, 1-propenyl, acryloyl, methacryloyl, styryl, and styrylmethyl.

As said diene polymer, the unmodified diene polymer which is not modified with a polar group is mentioned, for example. Here, the polar group is a functional group that affects dielectric properties, and examples thereof include phenolic groups, amino groups, epoxy groups, and the like. It does not specifically limit as said diene polymer, For example, 1, 2- polybutadiene, 1, 4- polybutadiene, etc. can be used.

As the aforementioned diene-based polymer, a homopolymer of butadiene in which 50% or more of the butadiene units in the polymer chain are 1,2-bonds and its derivatives can also be used.

Since the epoxy resin (C) is used in this invention, you may use a hardening accelerator suitably in combination with the curable resin composition of this invention as needed. Various substances can be used as the curing accelerator, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. Especially when used as a sealing material for semiconductors, the phosphorus compound is preferably triphenylphosphine, and among tertiary amines, 1,8-bis Azabicyclo-[5.4.0]-undecene (DBU). These curing accelerators may be used alone or in combination of two or more. Moreover, it is preferable to use the addition amount of the said hardening accelerator in the range of 1-10 mass parts with respect to 100 mass parts of said epoxy resins (C), for example.

<Preparation of Curable Resin Composition>

The curable resin composition of this invention contains the maleimide (A) which has an indane skeleton, a polyphenylene ether compound (B), and an epoxy resin (C), It is characterized by the above-mentioned. The aforementioned maleimide (A) has an indane skeleton, so compared with conventional maleimides, it has excellent solvent solubility, is easy to prepare a curable resin composition, and is excellent in handling properties. Since the proportion of polar functional groups in the structure of the amine (A) is small, a cured product excellent in dielectric properties can be obtained. In addition, the polyphenylene ether (PPE) in the structure of the aforementioned polyphenylene ether compound (B) functioning as a curing agent can contribute to dielectric properties such as dielectric constant and dielectric loss tangent, and the aforementioned epoxy resin ( C) The fluidity becomes favorable at the time of preparation of curable resin composition, and the hardened|cured material excellent in adhesiveness can be obtained. In addition, the aforementioned polyphenylene ether compound (B) functioning as a curing agent reacts with the aforementioned maleimide (A) and the aforementioned epoxy resin (C), whereby three-dimensional crosslinking can occur and heat resistance can be obtained. Excellent cured product is the preferred method. In addition, generally, a cured product using a maleimide resin has poor brittleness resistance, but by reacting with the aforementioned polyphenylene ether compound (B), the brittleness is improved, and the adhesion to copper is improved. For example, in Useful in the manufacture of circuit boards using copper foil.

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

The compounding 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 from the viewpoint that the properties of the obtained cured product are good, ( B) component: 90:10-10:90 are preferable for (C)component, More preferably, it is 80:20-20:80, More preferably, it is 65:35-35:65. By adjusting the compounding ratio within the above-mentioned range, heat resistance, a low dielectric constant, and a low dielectric loss tangent can be achieved, which is preferable.

To the curable resin composition of the present invention, alkenyl-containing compounds such as bismaleimides other than the aforementioned maleimide (A) and allyl ethers may be added within a range that does not impair the purpose. series compounds, allylamine-based compounds, triallyl cyanurate, alkenylphenol-based compounds, vinyl-containing polyolefin compounds, etc. In addition, other thermosetting resins such as thermosetting polyimide resins, phenol resins, active ester resins, benzoxazine resins, cyanate resins, and the like may be appropriately compounded depending on purposes.

In order to exhibit flame retardancy, the curable resin composition of the present invention may contain a non-halogen-based flame retardant that does not substantially contain a halogen atom within a range that does not impair the purpose. Examples of the aforementioned non-halogen-based flame retardants include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic-based flame retardants, organometallic salt-based flame retardants, and the like. use or in combination.

In curable resin composition of this invention, an inorganic filler can be compounded as needed. Examples of the aforementioned inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and the like. In particular, when increasing the compounding quantity of the said inorganic filler, it is preferable to use fused silica. The above-mentioned fused silica can be used in any shape of crushed or spherical. In order to increase the compounding amount of fused silica and suppress the increase of the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. Furthermore, in order to increase the compounding quantity of spherical silica, it is preferable to adjust the particle size distribution of spherical silica suitably. The filling rate is preferably higher in view of flame retardancy, and is particularly preferably 20% by mass or more with respect to the entire amount of the curable resin composition. Moreover, when using the said curable resin composition for uses, such as an electroconductive paste mentioned in detail below, electroconductive fillers, such as silver powder and copper powder, can be used.

The curable resin composition of this invention can add various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, an emulsifier, etc. as needed.

<cured product>

The cured product of the present invention is preferably obtained by subjecting the aforementioned curable resin composition to a curing reaction. The above-mentioned curable resin composition can be obtained by uniformly mixing the above-mentioned components, and can also be easily prepared into a cured product by the same method as a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast molded products, adhesive layers, coating films, and films.

The above-mentioned curing (thermal curing) reaction can also be easily carried out without a catalyst, and when a rapid reaction is desired, a polymerization initiator such as an organic peroxide or an azo compound, a phosphine compound, or a tertiary amine Addition of a basic catalyst is effective. For example, there are benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazoles, etc., and the compounding amount is preferably 0.05% of the curable resin composition as a whole. ~5% by mass.

<prepreg>

The prepreg of the present invention preferably has a reinforcing base material and a semi-cured product of the curable resin composition impregnated into the reinforcing base material. A known method can be used as a method for producing the aforementioned prepreg. A resin varnish prepared by dissolving (diluted) the aforementioned curable resin composition in an organic solvent can be impregnated into a reinforcing base material. The reinforcing base material is heat-treated to semi-cure (or uncure) the aforementioned curable resin composition to form a prepreg.

As the aforementioned organic solvent, for example, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone (MEK), methyl Isobutyl ketone, dioxane, tetrahydrofuran, etc. are used alone or as a mixed solvent of two or more.

As the reinforcing base impregnated with the aforementioned resin varnish, woven fabrics, non-woven fabrics, mats, paper, etc. formed of inorganic fibers such as glass fibers, polyester fibers, and polyamide fibers, and organic fibers can be used alone or in combination. use.

The mass ratio of the curable resin composition in the prepreg to the reinforcing base material is not particularly limited, but usually, it is preferable that the curable resin composition (resin in the prepreg) is 20 to 60% by mass. way to prepare.

The conditions for the heat treatment of the prepreg can be appropriately selected according to the types and amounts of the organic solvent, catalyst, and various additives used, and are usually performed at a temperature of 80 to 220° C. for 3 to 30 minutes.

<Heat-resistant materials and electronic materials>

Since the cured product obtained from the curable resin composition of the present invention is excellent in heat resistance and dielectric properties, it can be suitably used for heat-resistant members and electronic members. In particular, it can be suitably used for circuit boards, semiconductor sealing materials, semiconductor devices, laminated films, laminated substrates, adhesives, resist materials, and the like. In addition, it can also be used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a high heat-resistant prepreg. Moreover, since the said maleimide (A) which has an indane skeleton contained in the said curable resin composition shows excellent solubility in various solvents, it can be made into a paint. The heat-resistant members and electronic members obtained in this way can be suitably used in various applications, for example, industrial machine parts, general machine parts, parts of automobiles/railways/vehicles, space/aerospace-related parts, electronic/electrical parts, Construction materials, containers/packaging members, daily necessities, sports/leisure products, wind power generation casing members, etc., but are not limited to these objects.

Hereinafter, typical products produced using the curable resin composition of the present invention will be described as examples.

<circuit board>

In the present invention, it is preferable that the circuit board is obtained by laminating the above-mentioned prepreg and copper foil, followed by thermocompression molding. Specifically, as a method of obtaining a circuit board from the curable resin composition of the present invention, the method of laminating the above-mentioned prepregs by a conventional method, appropriately stacking copper foils, and pressing them under a pressure of 1 to 10 MPa can be mentioned. Next, thermocompression molding is performed at 170-300° C. for 10 minutes to 3 hours.

<Semiconductor sealing material>

In this invention, it is preferable to contain the said curable resin composition as a semiconductor sealing material. Specifically, as a method of obtaining a semiconductor sealing material from the curable resin composition of the present invention, a method in which a curing accelerator and an inorganic filler are added as optional components to the curable resin composition may be mentioned. Such compounding agents are sufficiently melt-mixed until uniform using an extruder, a kneader, a roll, or the like as necessary. In this case, fused silica is generally used as the inorganic filler, and when used as a high thermal conductivity semiconductor sealing material for power transistors and power ICs, crystalline silica having a higher thermal conductivity than fused silica, Highly filled crystals such as alumina and silicon nitride, or fused silica, crystalline silica, alumina, silicon nitride, and the like are preferable. For the filling ratio, it is preferable to use an inorganic filler in the range of 30 to 95 parts by mass relative to 100 parts by mass of the curable resin composition. The reduction of , more preferably 70 parts by mass or more, still more preferably 80 parts by mass or more.

<Semiconductor device>

In the present invention, the semiconductor device preferably includes a cured product obtained by heating and curing the aforementioned semiconductor encapsulating material. Specifically, as semiconductor encapsulation molding for obtaining a semiconductor device from the curable resin composition of the present invention, the method of casting the above-mentioned semiconductor encapsulating material, or molding using a transfer molding machine, an injection molding machine, etc., and then Heat curing is performed at 50 to 250° C. for 2 to 10 hours.

<Laminated substrate>

As a method of obtaining a laminated board|substrate from the curable resin composition of this invention, the method via process 1-3 is mentioned. In step 1, first, the aforementioned curable resin composition containing rubber, filler, etc. is applied to a circuit board on which a circuit is formed by spray coating, curtain coating, or the like, and then cured. In step 2, if necessary, the circuit board coated with the curable resin composition is drilled with a predetermined through-hole or the like, treated with a roughening agent, and the surface is washed with hot water, thereby making the above-mentioned board Form unevenness and perform plating treatment with metal such as copper. In Step 3, the operations of Steps 1 to 2 are repeated sequentially as desired, and resin insulating layers and conductor layers of predetermined circuit patterns are alternately laminated to form a build-up substrate. It should be noted that, in the above-mentioned steps, it is preferable to drill the via holes after forming the outermost resin insulating layer. In addition, for the build-up substrate in the present invention, the resin-attached copper foil obtained by semi-curing the resin composition on the copper foil may be heat-compressed at 170 to 300° C. to the wiring substrate on which the circuit is formed. , thereby forming a roughened surface, omitting the process of plating treatment, and producing a build-up substrate.

<Laminated film>

The laminated film of the present invention preferably contains the aforementioned curable resin composition. As a method of obtaining a laminated film from the curable resin composition of the present invention, for example, the method of coating the curable resin composition on a support film and drying it to form a resin composition layer on the support film . When the curable resin composition of the present invention is used in a laminated film, it is important that the film exhibits fluidity (resin flow) as follows: under the lamination temperature conditions of the vacuum lamination method (usually 70°C to 140°C ) under softening, while the circuit board is laminated, the via holes or through holes existing in the circuit board can be filled with resin. In order to express such characteristics, it is preferable to compound the above-mentioned components. It should be noted that, in order to avoid the phenomenon of partially displaying different characteristic values due to phase separation or the like in the obtained laminated film and circuit board (copper-clad laminate, etc.), in order to express a certain performance at any part, Uniformity of appearance 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, and resin filling can usually be performed within this range. In addition, when laminating both surfaces of a circuit board, it is desirable to fill about 1/2 of a via hole.

As a specific method for producing the above-mentioned laminated film, the following method is mentioned: mixing an organic solvent to prepare a varnished resin composition, and then coating the above-mentioned varnished resin composition on the surface of the support film (Y) Then, the organic solvent is dried by heating, blowing hot air, or the like to form a resin composition layer (X).

As the organic solvent used here, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol ethyl alcohol, etc., are preferably used. Acetate esters such as acid esters, cellosolves, carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. , In addition, it is preferable to use it in the ratio of 30-60 mass % of non-volatile components.

In addition, the thickness of the said resin composition layer (X) formed needs to be more than the thickness of a conductor layer normally. Since the thickness of the conductor layer which a circuit board has is usually in the range of 5-70 micrometers, it is preferable to have a thickness of 10-100 micrometers about the thickness of the said resin composition layer (X). In addition, the said resin composition layer (X) in this invention can be protected with the protective film mentioned later. By protecting with a protective film, adhesion of dust etc. to the surface of a resin composition layer can be prevented and damage can be prevented.

The aforementioned support film and protective film include polyethylene, polypropylene, polyolefins such as polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonate, etc. Ester, polyimide, release paper, copper foil, aluminum foil and other metal foils. It should be noted that the support film and the protective film may be subjected to matting treatment, corona treatment, and mold release treatment. The thickness of the support film is not particularly limited, but it is usually used in a range of 10 to 150 μm, preferably in a range of 25 to 50 μm. In addition, the thickness of the protective film is preferably 1 to 40 μm.

The said support film (Y) is peeled off after laminating|stacking on a circuit board, or heat-hardening, and forming an insulating layer. When the support film (Y) is peeled off after the resin composition layer constituting the laminated film is heated and cured, it is possible to prevent adhesion of dust and the like during the curing step. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

In addition, a multilayer printed circuit board can be manufactured from the laminated film obtained as mentioned above. For example, when the above-mentioned resin composition layer (X) is protected by a protective film, after peeling them off, the layer (X) of the above-mentioned resin composition is laminated so as to directly contact the circuit board by, for example, a vacuum lamination method. One or both sides of the circuit board. The lamination method may be a batch method or a continuous method using a roll. In addition, the laminated film and the circuit board may be heated (preheated) as needed before lamination. As for lamination conditions, the crimping temperature (lamination temperature) is preferably 70 to 140°C, and the crimping pressure is preferably 1 to 11kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ² ), preferably under a reduced pressure of 20 mmHg (26.7 hPa) or less.

<Conductive paste>

As a method of obtaining an electrically conductive paste from the curable resin composition of this invention, the method of dispersing electroconductive particle in this composition is mentioned, for example. As the conductive paste, a paste resin composition for circuit connection or an anisotropic conductive adhesive can be used depending on the type of conductive particles used.

Example

Next, the present invention will be described concretely with reference to Examples and Comparative Examples. Hereinafter, "parts" and "%" are based on mass unless otherwise specified. In addition, softening point, amine equivalent, GPC, and, FD-MS spectrum were measured and evaluated under the following conditions.

1) softening point

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

2) Amine equivalent

The amine equivalent of the intermediate amine compound was measured by the following measuring method.

After accurately weighing about 2.5 g of intermediate amine compounds, 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine as samples in a 500 mL Erlenmeyer flask with a stopper, install a condenser and set it at 120°C Heated to reflux in an oil bath 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 titrated with 0.5 mol/L potassium hydroxide-ethanol solution by potentiometric titration. Carry out blank test and correction in the same way.

Amine equivalent (g/eq.)=(S×2000)/(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 determination

It measured using the following measuring apparatus and measurement conditions, and obtained the GPC chart (FIG. 1-FIG. 9) of the maleimide obtained in the synthesis example shown below. Based on the results of the aforementioned GPC chart, the molecular weight distribution (weight-average molecular weight (Mw)/number-average molecular weight (Mn)) was measured/calculated and the effect on the indane skeleton in maleimide was measured/calculated based on the number-average molecular weight (Mn). The average number of repeating units "n" contributed. Specifically, for compounds with n = 0 to 4, use the theoretical molecular weight and the molecular weight of each measured value in GPC to draw points on the scatter diagram, draw an approximate straight line, and obtain the number according to the points represented by the measured value Mn(1) on the straight line. Average molecular weight (Mn), calculate n.

Measuring device: "HLC-8320GPC" manufactured by Tosoh Corporation

Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GELG2000HXL" manufactured by Tosoh Corporation + "TSK-GELG2000HXL" manufactured by Tosoh Corporation + "TSK-GELG3000HXL" manufactured by Tosoh Corporation + Tosoh Corporation "TSK-GELG4000HXL" manufactured by Co., Ltd.

Detector: RI (differential refractometer)

Data processing: "GPC workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation

Determination conditions: column temperature 40°C

Developing solvent Tetrahydrofuran

Flow rate 1.0ml/min

Standard: According to the measurement manual of the aforementioned "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrene whose molecular weight is known is used.

(using polystyrene)

Tosoh Corporation "A-500"

"A-1000" manufactured by Tosoh Corporation

"A-2500" manufactured by Tosoh Corporation

"A-5000" manufactured by Tosoh Corporation

"F-1" manufactured by Tosoh Corporation

"F-2" manufactured by Tosoh Corporation

"F-4" manufactured by Tosoh Corporation

"F-10" manufactured by Tosoh Corporation

"F-20" manufactured by Tosoh Corporation

"F-40" manufactured by Tosoh Corporation

"F-80" manufactured by Tosoh Corporation

"F-128" manufactured by Tosoh Corporation

Sample: 1.0 mass % tetrahydrofuran solution in terms of resin solid content of the maleimide obtained in the synthesis example was filtered with a microfilter (50 μl).

4) FD-MS spectrum

The FD-MS spectrum was measured using the following measurement device and measurement conditions.

Measuring device: JMS-T100GCAccuTOF

Measurement conditions

Measuring range: m/z=4.00～2000.00

Rate of change: 51.2mA/min

Final current value: 45mA

Cathode voltage: -10kV

Recording interval: 0.07 seconds

[Synthesis Example 1] Synthesis of Maleimide Compound A-1

(1) Synthesis of intermediate amine compounds

Put 48.5g (0.4mol) of 2,6-dimethylaniline, α,α'-dihydroxy-1 , 272.0g (1.4mol) of 3-diisopropylbenzene, 280g of xylene and 70g of activated clay were heated to 120°C while stirring. Furthermore, distillation waste water was removed using a Dean-Stark tube, and the temperature was raised to 210° C. to perform a reaction for 3 hours. Then, after cooling to 140 degreeC and throwing in 145.4 g (1.2 mol) of 2, 6- dimethyl aniline, it heated up to 220 degreeC, and performed reaction for 3 hours. After the reaction, the air was cooled to 100° C., diluted with 300 g of toluene, the activated clay was removed by filtration, and low molecular weight substances such as solvent and unreacted substances were distilled off under reduced pressure to obtain the following general formula (A-1 ) intermediate amine compound 364.1g. The amine equivalent is 298, and the softening point is 70°C.

(2) Maleimidation

131.8 g (1.3 mol) of maleic anhydride and 700 g of toluene were put into a 2 L flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer, and stirred at room temperature. Subsequently, a mixed solution of 364.1 g of the reactant (A-1) and 175 g of DMF was added dropwise over 1 hour.

After completion of the dropwise addition, the reaction was further performed at room temperature for 2 hours. After adding 37.1 g of p-toluenesulfonic acid monohydrate, the reaction solution was heated, water and toluene azeotroped under reflux were cooled/separated, and only toluene was returned to the system to perform a dehydration reaction for 8 hours. After air cooling to room temperature, concentrate under reduced pressure, dissolve the brown solution in 600 g of ethyl acetate, wash 3 times with 150 g of ion-exchanged water and 150 g of 2% aqueous sodium bicarbonate solution 3 times, add sodium sulfate to dry, Concentration under reduced pressure was carried out, and the obtained reactant 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 spectrum of this 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, or 2. It should be noted that the value of the number n of repeating units in the indane skeleton part in the aforementioned maleimide A-1 was obtained by GPC (based on the number average molecular weight). As a result, the GPC chart is shown in FIG. 1, n=1.47 , molecular weight distribution (Mw/Mn) = 1.81.

[Synthesis Example 2] Synthesis of Maleimide Compound A-2

(1) Synthesis of intermediate amine compounds

Put 48.5g (0.4mol) of 2,6-dimethylaniline, α,α'-dihydroxy-1 , 233.2g (1.2mol) of 3-diisopropylbenzene, 230g of xylene and 66g of activated clay were heated to 120°C while stirring. Furthermore, distillation waste water was removed using a Dean-Stark tube, and the temperature was raised to 210° C. to perform a reaction for 3 hours. Then, after cooling to 140 degreeC and throwing in 145.4 g (1.2 mol) of 2, 6- dimethyl aniline, it heated up to 220 degreeC, and performed reaction for 3 hours. After the reaction, the air was cooled to 100° C., diluted with 300 g of toluene, the activated clay was removed by filtration, and low molecular weight substances such as solvents and unreacted substances were distilled off under reduced pressure to obtain the following general formula (A-2 ) intermediate amine compound 278.4g. The amine equivalent is 294, and the softening point is 65°C.

(2) Maleimidation

107.9 g (1.1 mol) of maleic anhydride and 600 g of toluene were put into a 2 L flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer, and stirred at room temperature. Next, a mixed solution of 278.4 g of the reactant (A-2) and 150 g of DMF was added dropwise over 1 hour.

After completion of the dropwise addition, the reaction was further performed at room temperature for 2 hours. After adding 27.0 g of p-toluenesulfonic acid monohydrate, the reaction solution was heated, water and toluene azeotroped under reflux were cooled/separated, and only toluene was returned to the system to perform a dehydration reaction for 8 hours. After air cooling to room temperature, it was concentrated under reduced pressure, and the brown solution was dissolved in 500 g of ethyl acetate, washed three times with 120 g of ion-exchanged water and three times with 120 g of 2% aqueous sodium bicarbonate solution, and dried by adding sodium sulfate. Concentration under reduced pressure was carried out, and the obtained reactant was vacuum-dried at 80° C. for 4 hours to obtain 336.8 g of a product containing maleimide compound A-2. In the FD-MS spectrum of the maleimide compound A-2, peaks of M+=560, 718, and 876 were confirmed, corresponding to the cases where n was 0, 1, and 2, respectively. It should be noted that the value of the number n of repeating units in the indane skeleton part in the aforementioned maleimide A-2 was obtained by GPC (based on the number average molecular weight). As a result, the GPC chart is shown in Figure 2, n=1.25 , molecular weight distribution (Mw/Mn) = 3.29.

[Synthesis Example 3] Synthesis of Maleimide Compound A-3

(1) Synthesis of intermediate amine compounds

Put 48.5g (0.4mol) of 2,6-dimethylaniline, α,α'-dihydroxy-1 , 388.6g (2.0mol) of 3-diisopropylbenzene, 350g of xylene and 123g of activated clay were heated to 120°C while stirring. Furthermore, distillation waste water was removed using a Dean-Stark tube, and the temperature was raised to 210° C. to perform a reaction for 3 hours. Then, after cooling to 140 degreeC and throwing in 145.4 g (1.2 mol) of 2, 6- dimethyl aniline, it heated up to 220 degreeC, and performed reaction for 3 hours. After the reaction, the air was cooled to 100° C., diluted with 500 g of toluene, the activated clay was removed by filtration, and low molecular weight substances such as solvents and unreacted substances were distilled off under reduced pressure to obtain the following general formula (A-3 ) intermediate amine compound 402.1g. The amine equivalent is 306, and the softening point is 65°C.

(2) Maleimidation

152.1 g (1.5 mol) of maleic anhydride and 700 g of toluene were charged into a 2 L flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer, and stirred at room temperature. Next, a mixed solution of 402.1 g of the reactant (A-3) and 200 g of DMF was added dropwise over 1 hour.

After completion of the dropwise addition, the reaction was further performed at room temperature for 2 hours. After adding 37.5 g of p-toluenesulfonic acid monohydrate, the reaction solution was heated, water and toluene azeotroped under reflux were cooled/separated, and only toluene was returned to the system to perform a dehydration reaction for 8 hours. After air cooling to room temperature, concentrate under reduced pressure, dissolve the brown solution in 800 g of ethyl acetate, wash three times with 200 g of ion-exchanged water and three times with 200 g of 2% aqueous sodium bicarbonate solution, add sodium sulfate to dry, Concentration under reduced pressure was carried out, and the obtained reactant was vacuum-dried at 80° C. for 4 hours to obtain 486.9 g of a product containing maleimide compound A-3. In the FD-MS spectrum of the maleimide compound A-3, peaks of M+=560, 718, and 876 were confirmed, corresponding to the cases where n was 0, 1, and 2, respectively. It should be noted that the value of the number n of repeating units in the indane skeleton part in the aforementioned maleimide A-3 (based on the number average molecular weight) was obtained by GPC. As a result, the GPC chart is shown in FIG. 3, n=1.96 , molecular weight distribution (Mw/Mn) = 1.52.

[Synthesis Example 4] Synthesis of Maleimide Compound A-4

(1) Synthesis of intermediate amine compounds

Put 59.7g (0.4mol) of 2,6-diethylaniline, α,α'-dihydroxy-1 , 272.0g (1.4mol) of 3-diisopropylbenzene, 350g of xylene and 94g of activated clay were heated to 120°C while stirring. Furthermore, distillation waste water was removed using a Dean-Stark tube, and the temperature was raised to 210° C. to perform a reaction for 3 hours. Then, after cooling to 140 degreeC and throwing in 179.1 g (1.2 mol) of 2,6- diethylaniline, it heated up to 220 degreeC, and performed reaction for 3 hours. After the reaction, the air was cooled to 100° C., diluted with 500 g of toluene, the activated clay was removed by filtration, and low molecular weight substances such as solvents and unreacted substances were distilled off under reduced pressure to obtain the following general formula (A-4 ) intermediate amine compound 342.1 g. The amine equivalent is 364, and the softening point is 47°C.

(2) Maleimidation

107.9 g (1.1 mol) of maleic anhydride and 600 g of toluene were put into a 2 L flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer, and stirred at room temperature. Subsequently, a mixed solution of 342.1 g of the reactant (A-4) and 180 g of DMF was added dropwise over 1 hour.

After completion of the dropwise addition, the reaction was further performed at room temperature for 2 hours. After adding 26.8 g of p-toluenesulfonic acid monohydrate, the reaction solution was heated, water and toluene azeotroped under reflux were cooled/separated, and only toluene was returned to the system to perform a dehydration reaction for 8 hours. After air cooling to room temperature, concentrate under reduced pressure, dissolve the brown solution in 500 g of ethyl acetate, wash three times with 200 g of ion-exchanged water and three times with 200 g of 2% aqueous sodium bicarbonate solution, add sodium sulfate to dry, Concentration under reduced pressure was carried out, and the obtained reactant was vacuum-dried at 80° C. for 4 hours to obtain 388.1 g of a product containing maleimide compound A-4. In the FD-MS spectrum of the maleimide compound A-4, peaks of M+=616, 774, and 932 were confirmed, corresponding to the cases where n was 0, 1, and 2, respectively. It should be noted that the value of the number n of repeating units in the indane skeleton part in the aforementioned maleimide A-4 was obtained by GPC (based on the number average molecular weight). As a result, the GPC chart is shown in FIG. 4, n=1.64 , molecular weight distribution (Mw/Mn) = 1.40.

[Synthesis Example 5] Synthesis of Maleimide Compound A-5

(1) Synthesis of intermediate amine compounds

Put 70.9g (0.4mol) of 2,6-diisopropylaniline, α,α'-dihydroxy- 272.0 g (1.4 mol) of 1,3-diisopropylbenzene, 350 g of xylene, and 97 g of activated clay were heated to 120° C. while stirring. Furthermore, distillation waste water was removed using a Dean-Stark tube, and the temperature was raised to 210° C. to perform a reaction for 3 hours. After cooling to 140 degreeC after that, 2, 6- diisopropyl aniline 212.7g (1.2mol) was injected|thrown-in, and it heated up to 220 degreeC, and performed reaction for 3 hours. After the reaction, the air was cooled to 100° C., diluted with 500 g of toluene, the activated clay was removed by filtration, and low molecular weight substances such as solvent and unreacted substances were distilled off under reduced pressure to obtain the following general formula (A-5 ) intermediate amine compound 317.5 g. The amine equivalent is 366, and the softening point is 55°C.

(2) Maleimidation

107.9 g (1.1 mol) of maleic anhydride and 600 g of toluene were put into a 2 L flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer, and stirred at room temperature. Subsequently, a mixed solution of 317.5 g of the reactant (A-5) and 175 g of DMF was added dropwise over 1 hour.

After completion of the dropwise addition, the reaction was further performed at room temperature for 2 hours. After adding 24.8 g of p-toluenesulfonic acid monohydrate, the reaction solution was heated, water and toluene azeotroped under reflux were cooled/separated, and only toluene was returned to the system to perform a dehydration reaction for 8 hours. After air cooling to room temperature, it was concentrated under reduced pressure, and the brown solution was dissolved in 600 g of ethyl acetate, washed three times with 200 g of ion-exchanged water and three times with 200 g of 2% aqueous sodium bicarbonate solution, and dried by adding sodium sulfate. Concentration under reduced pressure was carried out, and the obtained reactant 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 spectrum of the maleimide compound A-5, peaks of M+=672, 830, and 988 were confirmed, corresponding to the cases where n was 0, 1, and 2, respectively. It should be noted that the value of the number n of repeating units in the indane skeleton part in the aforementioned maleimide A-5 was obtained by GPC (based on the number average molecular weight). As a result, the GPC chart is shown in FIG. 5, n=1.56 , molecular weight distribution (Mw/Mn) = 1.24.

[Synthesis Example 6] Synthesis of Maleimide Compound A-9

(1) Synthesis of intermediate amine compounds

In the synthesis method of the aforementioned 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 3 hours, and the following general formula (A-9) was obtained by performing the same operation The indicated intermediate amine compound was 345.2 g. The amine equivalent is 348, and the softening point is 71°C.

(2) Maleimidation

According to the synthesis method of the aforementioned maleimide compound A-1, the intermediate was replaced by A-9, and the same operation was performed to obtain 407.6 g of a product containing the maleimide compound A-9. In the FD-MS spectrum of this 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, or 2. It should be noted that the value of the number n of repeating units in the indane skeleton part in the aforementioned maleimide A-9 was obtained by GPC (based on the number average molecular weight). As a result, the GPC chart is shown in FIG. 6, n=2.59 , molecular weight distribution (Mw/Mn) = 1.49.

[Synthesis Example 7] Synthesis of Maleimide Compound A-10

In the synthesis method of the aforementioned 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 3 hours. The same operation was carried out. For the synthesized intermediate amine compound (amine equivalent 347, the softening point is 71°C), except that the dehydration reaction under reflux in the maleimidation reaction was set to 10 hours, by the same synthesis method as the aforementioned maleimide compound A-1 conditions, thus obtaining 415.6 g of a product containing maleimide compound A-10. In the FD-MS spectrum of this 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, or 2. It should be noted that the value of the number n of repeating units in the indane skeleton part in the aforementioned maleimide A-10 was obtained by GPC (based on the number average molecular weight). As a result, the GPC chart is shown in FIG. 7, n=2.91 , molecular weight distribution (Mw/Mn) = 1.64.

[Synthesis Example 8] Synthesis of Maleimide Compound A-11

In the synthesis method of the aforementioned 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 3 hours, and the same operation was carried out. For the synthesized intermediate amine compound (amine equivalent 342, the softening point is 69°C), except that the dehydration reaction under reflux in the maleimidation reaction was set to 10 hours, by the same synthesis method as the aforementioned maleimide compound A-1 conditions, thus obtaining 398.7 g of a product containing maleimide compound A-11. In the FD-MS spectrum of this 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, or 2. It should be noted that the value (based on the number average molecular weight) of the number n of repeating units in the indane skeleton part in the aforementioned maleimide A-11 was obtained by GPC. As a result, the GPC chart is shown in FIG. 8, n=3.68 , molecular weight distribution (Mw/Mn) = 2.09.

[Synthesis Example 9] Synthesis of Maleimide Compound A-12

In the synthesis method of the aforementioned 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 3 hours. The same operation was carried out, and the synthetic intermediate amine compound (amine equivalent 347, the softening point is 70°C), except that the dehydration reaction under reflux in the maleimidation reaction was set to 12 hours, by the same synthesis method as the aforementioned maleimide compound A-1 conditions, thus obtaining 422.7 g of a product containing maleimide compound A-12. In the FD-MS spectrum of this 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, or 2. It should be noted that the value (based on the number average molecular weight) of the number n of repeating units in the indane skeleton part in the aforementioned maleimide A-12 was obtained by GPC. As a result, the GPC chart is shown in FIG. 9, n=4.29 , molecular weight distribution (Mw/Mn) = 3.02.

[Examples 1 to 9 and Comparative Example 1]

<Solvent Solubility of Maleimide>

Maleimides (A-1) to (A-5), (A-9) to (A-12) obtained in Synthesis Examples 1 to 9, and commercially available maleimides for comparison Evaluation of the solubility of amine (A-6) (4,4'-diphenylmethane bismaleimide, "BMI-1000" manufactured by Yamato Chemical Industry Co., Ltd.) with respect to toluene and methyl ethyl ketone (MEK), Table 1 shows the evaluation results.

As an evaluation method of solvent solubility, toluene was prepared so that the non-volatile content was 10, 20, 30, 40, 50, 60, and 70% by mass using the maleimides obtained in the above synthesis examples and comparative examples. solution and methyl ethyl ketone (MEK) solution.

Specifically, the vials containing the maleimides obtained in the above-mentioned synthesis examples and comparative examples were left to stand at room temperature (25° C.) for 60 days to uniformly dissolve each non-volatile composition in each solution. The case (no insoluble matter) was evaluated as 0, and the case where it was not dissolved (insoluble matter was present) was evaluated as x (visual observation). In addition, when the non-volatile matter is 20 mass % or more, it is practically preferable when it can dissolve in a solvent.

[Examples 10 to 18, and Comparative Examples 2 to 4]

<Preparation of Curable Resin Composition>

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

[Examples 10, 15-18, and Comparative Examples 2-4]

<Uniformity of Film Appearance>

In Examples 10, 15-18, and Comparative Examples 2-4, the ratio shown in Table 2 was mixed/dissolved in 14.81 g of methyl ethyl ketone (MEK), respectively, and curable resin composition was obtained. 5 g of each curable resin composition was applied in the form of 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 , thereby producing a film molded article, and the appearance of the obtained film molded article was confirmed visually. The case where the film appearance was uniform was evaluated as 0, and the case where the film appearance was uneven was evaluated as × (for example, when turbidity, insoluble matter, etc. can be confirmed). Table 3 shows the evaluation results.

<Preparation of cured product (molded product)>

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

Curing conditions: After heating at 200°C for 2 hours, heat curing was further performed at 250°C for 2 hours.

Plate thickness of cured product (formed product) after molding: 2.4mm

The obtained cured products were evaluated for various physical properties/characteristics by the following methods. The evaluation results are shown in Table 4.

<Glass transition temperature (Tg)>

The cured product with a thickness of 2.4 mm was cut out to a size of 5 mm in width and 54 mm in length, and this was used as a test piece. For this test piece, a viscoelasticity measurement device (DMA: solid viscoelasticity measurement device "DMS6100" manufactured by Hitachi High-Tech Science Corporation, deformation mode: double-sided bending, measurement mode: sine wave oscillation, frequency 1 Hz, heating rate 3°C /min), and the temperature at which the change in elastic modulus becomes the largest (the rate of change in tan δ is the largest) is evaluated as the glass transition temperature Tg (° C.). In addition, from a viewpoint of heat resistance, as glass transition temperature Tg, it is preferable that it is 135 degreeC or more, and it is more preferable that it is 140 degreeC or more.

<Thermal decomposition resistance>

The cured product with a thickness of 2.4 mm was cut into smaller pieces, and measured under a nitrogen atmosphere using a thermogravimetric analysis device (thermogravimetric measurement device "TGA/DSC1" manufactured by Mettler Toredo Co., Ltd.) with a heating rate of 5°C/min. , and evaluated by setting the temperature at which the weight decreased by 5% as the heat-resistant decomposition temperature (Td5) (° C.).

<Dielectric properties>

According to JIS-C-6481, using the network analyzer "E8362C" manufactured by Agilent Technologies Co., Ltd., by the cavity resonator method, measured at 1 GHz after the test piece was stored in a room with a humidity of 50% at 23°C for 24 hours after being absolutely dry. The dielectric constant and dielectric loss tangent. In addition, as a dielectric constant and a dielectric loss tangent, from a viewpoint of reducing the transmission loss as an electronic material, a dielectric constant is preferably 2.75 or less, More preferably, it is 2.70 or less. In addition, the dielectric loss tangent is preferably 0.020 or less, more preferably 0.018 or less.

[Table 1]

[Table 2]

[table 3]

[Table 4]

According to the evaluation results in Table 1 above, it can be confirmed that in Examples 1 to 9, maleimide having an indane skeleton was used, so when preparing a toluene solution, the non-volatile matter could be dissolved even at 20% by mass. When preparing the MEK solution, the non-volatile matter can be dissolved even if it is 50% by mass, and the solvent solubility is excellent. On the other hand, it was confirmed that the commercially available maleimide used in Comparative Example 1 did not have indane in its structure and had poor solubility in a skeleton solvent.

From the evaluation results in Table 3 above, it can be confirmed that in Examples 10, 15 to 18, the films obtained by applying and drying the curable resin composition solution (varnish) containing maleimide having an indane skeleton , uniform appearance, especially laminated films that require uniform appearance of the film obtained, and can also be used for circuit boards (copper-clad laminates, etc.) and other applications. On the other hand, it was confirmed that in Comparative Examples 2 to 4, commercially available maleimides that do not have an indane skeleton were used, so the appearance of the films was uneven, and it was difficult to use them for laminated films and circuit boards (coatings). Copper laminated boards, etc.) etc.

According to the evaluation results in Table 4 above, it can be confirmed that in Examples 10 to 18, an epoxy resin was added as a curing agent in addition to the maleimide having an indane skeleton, and the use of an epoxy resin that also contributes to mediation It is a polyphenylene ether compound with electrical characteristics, so its glass transition temperature and thermal decomposition temperature are high, and it is excellent in heat resistance and thermal decomposition resistance. In addition, it was confirmed that the dielectric constant and the dielectric loss tangent were suppressed to be low, and the dielectric characteristics were excellent. On the other hand, it can be confirmed that in Comparative Example 2, the glass transition temperature and thermal decomposition temperature are lower than those of the examples, and the heat resistance and thermal decomposition resistance are lower than those of the examples. Regarding the dielectric constant and the dielectric loss tangent, Due to the influence of the brittleness of the cured product, it was not possible to produce a sample for evaluation at all.

Industrial availability

The curable resin composition of the present invention is excellent in heat resistance and dielectric properties of the cured product, so it can be suitably used for heat-resistant members and electronic members, especially semiconductor sealing materials, circuit boards, laminated films, Laminate substrates, etc., adhesives, resist materials. In addition, it can also be suitably used as a matrix resin of a fiber-reinforced resin, and is suitable as a high heat-resistant prepreg.

Description of drawings

FIG. 1 is a GPC chart of the maleimide compound (A-1) obtained in Synthesis Example 1. FIG.

FIG. 2 is a GPC chart of the maleimide compound (A-2) obtained in Synthesis Example 2. FIG.

FIG. 3 is a GPC chart of the maleimide compound (A-3) obtained in Synthesis Example 3. FIG.

FIG. 4 is a GPC chart of the maleimide compound (A-4) obtained in Synthesis Example 4. FIG.

FIG. 5 is a GPC chart of the maleimide compound (A-5) obtained in Synthesis Example 5. FIG.

FIG. 6 is a GPC chart of the maleimide compound (A-9) obtained in Synthesis Example 6. FIG.

FIG. 7 is a GPC chart of the maleimide compound (A-10) obtained in Synthesis Example 7. FIG.

FIG. 8 is a GPC chart of the maleimide compound (A-11) obtained in Synthesis Example 8. FIG.

FIG. 9 is a GPC chart of the maleimide compound (A-12) obtained in Synthesis Example 9. FIG.

Claims (7)

1. A curable resin composition characterized by comprising: a maleimide (A) having an indane skeleton, a polyphenylene ether compound (B) and an epoxy resin (C), wherein the maleimide (A) is represented by the following general formula (1),

in the formula (1), ra independently represents an alkyl group, an alkoxy group or an alkylthio group having 1 to 10 carbon atoms, an aryl group, an aryloxy group or an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group or a mercapto group, ra is optionally the same or different in the same ring, rb independently represents an alkyl group, an alkoxy group or an alkylthio group having 1 to 10 carbon atoms, an aryl group, an aryloxy group or an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group, r represents an integer of 0 to 3, rb is optionally the same or different in the same ring when r is 2 to 3, and n represents an average repeating unit number of 0.95 to 10.0.

2. A cured product obtained by curing the curable resin composition according to claim 1.

3. A prepreg comprising a reinforcing substrate and a prepreg impregnated with the curable resin composition according to claim 1.

4. A circuit board obtained by laminating the prepreg according to claim 3 and a copper foil and performing thermocompression bonding molding.

5. A laminated film comprising the curable resin composition according to claim 1.

6. A semiconductor sealing material comprising the curable resin composition according to claim 1.

7. A semiconductor device comprising a cured product obtained by heat curing the semiconductor sealing material according to claim 6.