KR20210137514A - curable resin composition - Google Patents

Abstract

A curable resin composition having excellent heat resistance and dielectric properties in the cured product, the cured product, a prepreg having these properties, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device provides Curable resin composition of this invention contains the maleimide (A) which has an indane skeleton, and the polyphenylene ether compound (B) which has a reactive double bond, It is characterized by the above-mentioned.

Description

curable resin composition

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

As a material for circuit boards for electronic devices, glass cloth is impregnated with a thermosetting resin such as an epoxy resin or BT (bismaleimide-triazine) resin and heat-dried; a prepreg obtained by heating and curing the prepreg; A multilayer board obtained by combining the laminate and the prepreg and heat-hardening is widely used. Among them, since the thickness of the semiconductor package substrate progresses and warpage of the package substrate at the time of mounting becomes a problem, in order to suppress this, the material which expresses high heat resistance is calculated|required.

Furthermore, in recent years, as the signal speed and high frequency increase, it is required to provide a thermosetting resin composition that provides a cured product exhibiting a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant under these environments.

In particular, in recent years, in various electrical material applications, particularly high-tech material applications, further improvement in performance typified by heat resistance and dielectric properties, and materials and compositions having both of these are required.

In response to these demands, maleimide resins are attracting attention as a material having both heat resistance and low dielectric constant and low dielectric loss tangent. However, the conventional maleimide resin exhibits high heat resistance, but its dielectric constant and dielectric loss tangent value do not reach the level required for advanced material applications. There is a strong demand for the development of a resin that exhibits a low dielectric constant and a low dielectric loss tangent and is also excellent in solvent solubility.

Among these, as a cyanate ester material having high dielectric properties and heat resistance, a resin composition comprising a phenol novolac-type cyanate ester resin, a bisphenol A cyanate ester resin, and a non-halogen epoxy resin is used. It is known (refer patent document 1).

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

Japanese Patent Laid-Open No. 2004-182850

Therefore, the problem to be solved by the present invention is a curable resin composition having both excellent heat resistance and dielectric properties in the cured product, a cured product thereof, a prepreg having these performances, a circuit board, a build-up film, and a semiconductor encapsulant , and to provide a semiconductor device.

Then, in order to solve the said subject, the present inventors studied intensively, As a result, the curable resin composition containing the maleimide (A) which has an indane skeleton, and the polyphenylene ether compound (B) which has a reactive double bond is , the cured product has a low dielectric constant and a low dielectric loss tangent, and found that it is possible to have both excellent heat resistance and complete the present invention.

That is, the present invention relates to a curable resin composition comprising a maleimide (A) having an indane skeleton and a polyphenylene ether compound (B) having a reactive double bond.

As for the curable resin composition of this invention, it is preferable that the said maleimide (A) is represented by following General formula (1).

(In the formula (1), each Ra is independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group or an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group, or an arylthio group having 3 to 10 carbon atoms. represents a cycloalkyl group, a halogen atom, a nitro group, a hydroxyl group or a mercapto group, and q represents an integer value of 0 to 4. When q is 2 to 4, Ra may be the same or different within the same ring. Independently, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group or alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or arylthio group, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group ;

It is preferable that the hardened|cured material of this invention makes hardening reaction of the said curable resin composition, and is formed.

It is preferable that the prepreg of this invention has a reinforcing base material and the semi-hardened|cured material of the said curable resin composition impregnated in the said reinforcing base material.

It is preferable that the circuit board of this invention is obtained by laminating|stacking the said prepreg and copper foil, and carrying out thermocompression-bonding shaping|molding.

It is preferable that the buildup film of this invention contains the said curable resin composition.

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

It is preferable that the semiconductor device of this invention contains the hardened|cured material which heat-hardened the said semiconductor sealing material.

According to the curable resin composition of the present invention, in the cured product obtained from the curable resin composition, it has excellent heat resistance and dielectric properties, and a curable resin composition having these properties, a cured product obtained from the curable resin composition, a preprep It is useful because it can provide a leg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device.

BRIEF DESCRIPTION OF THE DRAWINGS It is a GPC chart diagram of the maleimide compound (A-1) obtained by Synthesis Example 1.
Fig. 2 is a GPC chart of the maleimide compound (A-2) obtained in Synthesis Example 2;
Fig. 3 is a GPC chart of the maleimide compound (A-3) obtained in Synthesis Example 3;
Fig. 4 is a GPC chart of the maleimide compound (A-4) obtained in Synthesis Example 4;
Fig. 5 is a GPC chart of the maleimide compound (A-5) obtained in Synthesis Example 5;
Fig. 6 is a GPC chart of the maleimide compound (A-8) obtained in Synthesis Example 6.
Fig. 7 is a GPC chart of the maleimide compound (A-9) obtained in Synthesis Example 7.
Fig. 8 is a GPC chart of the maleimide compound (A-10) obtained in Synthesis Example 8;
Fig. 9 is a GPC chart of the maleimide compound (A-11) obtained in Synthesis Example 9;

Hereinafter, the present invention will be described in detail.

The present invention relates to a curable resin composition comprising a maleimide (A) having an indane skeleton and a polyphenylene ether compound (B) having a reactive double bond. Especially, it is preferable that the said maleimide (A) is represented by the following general formula (1). Since the maleimide (A) has an indane skeleton, the proportion of polar functional groups in the structure of the maleimide (A) is small compared to the maleimides up to this point, and therefore the dielectric properties are excellent, which is preferable. In addition, the cured product using the conventional maleimide resin tends to be brittle, and there is a concern that the brittleness resistance is inferior. improvement is also expected and desirable.

In the general formula (1), each Ra is independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group or an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group, or an arylthio group having 3 to 10 carbon atoms. A cycloalkyl group, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group of (preferably 5-10) is represented, and q represents the integer value of 0-4. When q is 2 to 4, Ra may be the same or different within the same ring. Rb is each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group or alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or arylthio group, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or A mercapto group is shown, and r shows the integer value of 0-3. When r is 2 to 3, Rb may be the same or different within the same ring. n is an average number of repeating units, and represents the numerical value of 0.5-20. Moreover, when said r and said q are 0, Ra and Rb each point out a hydrogen atom.

Ra in the general formula (1) is preferably any one of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and as an alkyl group having 1 to 4 carbon atoms, etc., It becomes a preferable aspect which can obtain hardened|cured material without impairing the reactivity of a maleimide group while solvent solubility improves by the fall of planarity and crystallinity fall in the vicinity of a maleimide group.

It is preferable that it is 2-3, and, as for q in the said General formula (1), it is more preferable that it is 2. When the said q is 2, the influence of a steric hindrance is small, the electron density on an aromatic ring improves, In manufacture (synthesis) of a maleimide, WHEREIN: It becomes a preferable aspect.

In the general formula (1), r is 0, Rb is preferably a hydrogen atom, r is 1 to 3, Rb is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and , it is preferably at least one selected from the group consisting of an aryl group having 6 to 10 carbon atoms, and in particular, when r is 0 and Rb is a hydrogen atom, steric hindrance is reduced in the formation of the indane skeleton in maleimide, , it is advantageous in the production (synthesis) of maleimide, and is a preferred embodiment.

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

The manufacturing method of the said maleimide (A) is demonstrated below.

In the following general formula (2), each Rc independently represents a monovalent functional group selected from the group consisting of the following general formulas (3) and (4), and at least one of Rc's ortho position is a hydrogen atom, , Rb and r are the same compounds as above.

In the following general formula (5), at least one of the ortho position and the para position of the amino group is a hydrogen atom, and Ra and q are aniline or a derivative thereof, each representing the same as above, and a compound of the general formula (2) By reacting with the compound of the following general formula (5) in the presence of an acid catalyst, an intermediate amine compound represented by the following general formula (6) can be obtained. In addition, Ra, Rb, q, and r in the following general formula (6) represent the same thing as the above.

In the intermediate amine compound represented by the general formula (6), the following general formula (7) having an indane skeleton is included in the structure, but among the aniline or its derivatives represented by the general formula (5), q is 3 or less , and when at least two of the ortho and para positions 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 as described above, m is the number of repeating units, and represents an integer value of 1 to 20. In addition, the structure represented by the following general formula (8) may also be included in the structure of the said general formula (6).

In the indane skeleton (refer to the above general formula (7)), which is a characteristic of the maleimide (A) used in the present invention, the average number of repeating units n is a low melting point (low softening point), a low melt viscosity, and handleability In order to make this excellent, the average number of repeating units n (average value) is 0.5 to 20, preferably 0.7 to 10.0, more preferably 0.95 to 10.0, further preferably 0.98 to 9.0, further preferably It is 0.99-8.0, More preferably, it is 1.0-7.0, More preferably, it is 1.0-6.0. By having an indane skeleton in the structure of the said maleimide (A), it is excellent in solvent solubility compared with the maleimide used until this time, and it becomes a preferable aspect. In addition, when n is less than 0.5, the content of the high-melting-point substance in the structure of the maleimide (A) is high, the solvent solubility is poor, and the ratio of the high molecular weight component contributing to the flexibility is low. There is a possibility that brittleness resistance falls and there exists a possibility that a flexibility and softness|flexibility also fall, and it is unpreferable. Moreover, when n exceeds 20, there is concern that heat resistance is inferior, and high molecular weight components increase too much, and when molding a cured product, fluidity is lowered, and handling properties are concerned, which is not preferable. Moreover, as a value of said n, from viewpoints, such as a high heat distortion temperature and a high glass transition temperature, 0.5-10.0 are preferable, More preferably, it is 0.95-10.0.

Although the compound represented by the said General formula (2) (henceforth "compound (a)") used in this invention is not specifically limited, Typically, p- and m-diisopropenylbenzene, p- and m-bis(α-hydroxyisopropyl)benzene, 1-(α-hydroxyisopropyl)-3-isopropenylbenzene, 1-(α-hydroxyisopropyl)-4-isopropenylbenzene or mixtures of these are used. In addition, nuclear alkyl group substituents of these compounds, for example, diisopropenyltoluene and bis(α-hydroxyisopropyl)toluene, etc. can also be used, and further nuclear halogen substituents such as chlorodiisopropenylbenzene and Chlorobis(α-hydroxyisopropyl)benzene and the like can also be used.

In addition, as the compound (a), for example, 2-chloro-1,4-diisopropenylbenzene, 2-chloro-1,4-bis(α-hydroxyisopropyl)benzene, 2-bro Parent-1,4-diisopropenylbenzene, 2-bromo-1,4-bis(α-hydroxyisopropyl)benzene, 2-bromo-1,3-diisopropenylbenzene, 2-bromo parent-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-hydroxy Roxyisopropyl)benzene, 2-phenoxy-1,4-diisopropenylbenzene, 2-phenoxy-1,4-bis(α-hydroxyisopropyl)benzene, 2,4-diisopropenylbenzene Thiol, 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-cyclo Pentyl-1,4-diisopropenylbenzene, 2-cyclopentyl-1,4-bis(α-hydroxyisopropyl)benzene, 5-naphthyl-1,3-diisopropenylbenzene, 5-naph tyl-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 can be exemplified.

Moreover, as a substituent contained in the said compound (a), there is no restriction|limiting in particular, Although the compound of the said illustration can be used, In the case of a substituent with a large steric hindrance, compared with a substituent with a small steric hindrance, stacking of the maleimides obtained This is less likely to occur, and crystallization of maleimides does not occur easily, that is, the solvent solubility of maleimides is improved, which is a preferable aspect.

Further, as the compound represented by the general formula (5) (hereinafter referred to as "compound (b)"), typically, other than aniline, for example, dimethylaniline, diethylaniline, diisopropylaniline, ethylmethylaniline, chloro aniline, dichloroaniline, toluidine, xylidine, phenylaniline, nitroaniline, aminophenol, cyclohexylaniline and the like can be used. Further, methoxyaniline, ethoxyaniline, phenoxyaniline, naphthoxyaniline, aminothiol, methylthioaniline, ethylthioaniline and phenylthioaniline can be exemplified.

Also, as in the case of a conventional maleimide (eg, N-phenylmaleimide), when a maleimide group is directly bonded to a benzene ring, the state in which the benzene ring and the 5-membered ring of the maleimide are arranged on the same plane is stable. Therefore, it becomes easy to stack, and high crystallinity will be expressed. Therefore, it becomes a cause of inferior solvent solubility. On the other hand, in the case of the present invention, the compound (b) is not particularly limited, and the compounds of the above examples can be used. For example, as in 2,6-dimethylaniline, as a substituent, a methyl group is When it has, the benzene ring and the 5-membered ring of maleimide take a twisted configuration from steric hindrance of the methyl group, and stacking becomes difficult, so that the crystallinity decreases, the solvent solubility improves, and it becomes a preferable aspect. However, when the steric hindrance is too large, there is a concern that the reactivity at the time of synthesis of maleimide may be inhibited. For example, it is preferable to use the compound (b) having an alkyl group having 2 to 4 carbon atoms.

In the method for producing the intermediate amine compound represented by the general formula (6) for use in the present invention, the compound (a) and the compound (b) are in a molar ratio of the compound (b) to the compound (a). (Compound (b)/Compound (a)), preferably 0.1 to 2.0, more preferably 0.2 to 1.0, after the introduction reaction (first step), the compound (b) is further added to the above Maleimide (A) having an indane skeleton can be obtained by further adding an amount of preferably 0.5 to 20.0, more preferably 0.7 to 5.0, in a molar ratio with respect to compound (a) and reacting (2nd step). have. In addition, this two-step reaction gives desirable results in order to complete the reaction or in terms of handling properties and the like. Further, in the reaction of the first step, the compound (b) is added above as a molar ratio (compound (b)/compound (a)) to the compound (a), preferably 0.10 to 0.49, more preferably is 0.15 to 0.40, more preferably 0.20 to 0.39, has a wide molecular weight distribution, the content of low-molecular-weight high-melting-point substances is low, and the ratio of high-molecular-weight components is high, so solvent solubility is excellent. Moreover, the intermediate amine compound and maleimide which can contribute to flexibility and brittle resistance can be obtained, and it is preferable.

Examples of the acid catalyst used in the 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, fluoromethanesulfonic acid, activated clay, acid clay, Examples of solid acids such as silica alumina, zeolite, and strongly acidic ion exchange resins, heteropolyhydrochloric acid, etc., but a solid acid that can easily remove the catalyst by filtration after the reaction is preferable from the viewpoint of handling properties, and when using other acids, after the reaction , it is preferable to perform neutralization with a base and washing with water.

The compounding amount of the acid catalyst is 5 to 40 parts by mass of the acid catalyst with respect to 100 parts by mass of the total amount of the compound (a) and the compound (b) of the raw material to be charged first, but from the viewpoint of handling properties and economical efficiency. , preferably 5 to 30 parts by mass. The reaction temperature may normally be in the range of 100 to 300°C, but 150 to 230°C is preferable in order to suppress the formation of an isomer structure and to avoid side reactions such as thermal decomposition.

As the reaction time, the reaction does not proceed completely in a short time, and side reactions such as thermal decomposition of the product occur when it is prolonged for a long time. Therefore, under the reaction temperature conditions, it is usually in the range of 2 to 48 hours in total, but preferably Preferably, it is a total of 2 to 24 hours, more preferably, a total of 4 to 24 hours, and still more preferably, a total of 4 to 12 hours. A total of 8 to 12 hours is more preferable.

In the manufacturing method of the said intermediate amine compound, since aniline or its derivative(s) also serves as a solvent, although it is not necessarily necessary to use another solvent, it is also possible to use a solvent. For example, in the case of a reaction system that also serves as a dehydration reaction, specifically, when a compound having an α-hydroxypropyl group is reacted as a raw material, a solvent capable of azeotropic dehydration such as toluene, xylene, or chlorobenzene is used. After completion of the dehydration reaction, the solvent is distilled off, and then a method of performing the reaction within the above reaction temperature range may be employed.

The maleimide (A) used in the present invention is prepared by adding the intermediate amine compound represented by the general formula (6) obtained by the above method to a reactor, dissolving it in a suitable solvent, and then reacting in the presence of maleic anhydride and a catalyst. After the reaction, unreacted maleic anhydride and other impurities are removed by washing with water or the like, and the solvent is removed under reduced pressure. Moreover, you may use a dehydrating agent at the time of reaction.

Maleimide (A) used in the present invention has a skeleton of the general formula (1) and includes a structure represented by the general formula (7) having an indane skeleton, but q is 3 or less and an amino group ortho When at least two of the position and the para position are hydrogen atoms, a structure corresponding to the above general formula (8), that is, a structure represented by the following general formula (9) is also included as the structure represented by the above general formula (1).

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

Examples of the organic solvent used in the maleimidization reaction for synthesizing the maleimide (A) include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone and acetophenone, N,N-dimethyl Aprotic solvents such as formamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, acetonitrile and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; acetic acid Esters, such as ethyl and butyl acetate, aromatic solvents, such as benzene, toluene, and xylene, etc. are mentioned, Moreover, these may be used individually or in mixture.

In the maleimidization reaction, it is preferable to mix the intermediate amine compound and maleic anhydride in an equivalent ratio of maleic anhydride to the amino equivalent of the intermediate amine compound in the range of 1 to 1.5, more preferably 1.1 -1.2, it becomes a preferable aspect to make it react in the organic solvent of 0.5-50 mass ratio, Preferably 1-5 mass ratio with respect to the total amount of an intermediate amine compound and maleic anhydride.

Examples of the catalyst used in the maleimidization reaction include inorganic salts such as acetates, chlorides, bromides, sulfates and nitrates, such as nickel, cobalt, sodium, calcium, iron, lithium, and manganese, and inorganic acids such as phosphoric acid, hydrochloric acid and sulfuric acid. , organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid, activated clay, acid clay, silica alumina, zeolite, solid acids such as strongly acidic ion exchange resins, heteropolyhydrochloric acid, etc. However, toluenesulfonic acid is particularly preferably used.

Examples of the dehydrating agent used in the maleimidization reaction include lower aliphatic carboxylic anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, oxides such as phosphorus pentoxide, calcium oxide and barium oxide, inorganic acids such as sulfuric acid, and porous ceramics such as molecular sieves etc. are mentioned, Preferably acetic anhydride can be used.

There is no particular limitation on the amount of the catalyst and dehydrating agent used in the maleimidization reaction, but usually, the amount of the catalyst is 0.0001 to 1.0 mole, preferably 0.001 to 0.5 mole, more preferably based on 1 equivalent of the amino group of the intermediate amine compound. 0.01 to 0.3 mol, and 1 to 3 mol of the dehydrating agent, preferably 1 to 1.5 mol.

As the reaction conditions for maleimidization, the intermediate amine compound and maleic anhydride are added, and the temperature range is 10 to 100°C, preferably 30 to 50°C, for 0.5 to 12 hours, preferably 1 to 8 hours. After the reaction, by adding the catalyst, the reaction can be carried out in a temperature range of 90 to 130 ° C., preferably 105 to 120 ° C., for 2 to 24 hours, preferably 4 to 10 hours, reducing low molecular weight components, high In order to increase the molecular weight component, 6 to 10 hours are more preferable. In addition, after the reaction, unreacted maleic anhydride and other impurities are removed by washing with water or the like, and the low molecular weight component decreases and the high molecular weight component increases even by heating and aging.

The maleimide (A) has a molecular weight distribution calculated from gel permeation chromatography (GPC) measurement (weight average molecular weight (Mw)/number average molecular weight (Mn)) of 1.0 because it is excellent in low dielectric constant and low dielectric loss tangent. It is preferable that it is in the range of -10.0, More preferably, it is 1.1-9.0, More preferably, it is 1.1-8.0, More preferably, it is 1.2-5.0, More preferably, it is 1.2-4.0, More preferably, it is 1.3 to 3.8, particularly preferably 1.3 to 3.6, and most preferably 1.3 to 3.4. In addition, from the GPC chart obtained from the GPC measurement, when the molecular weight distribution is over a wide range and there are many high molecular weight components, since the ratio of the high molecular weight components contributing to flexibility increases, compared with the conventional cured product using maleimide. Therefore, brittleness is suppressed, the hardened|cured material excellent in flexibility and softness|flexibility can be obtained, and it becomes a preferable aspect.

<GPC measurement>

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

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

Column: Tosoh Corporation Guard Column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK" -GEL G3000HXL" + "TSK-GEL G4000HXL" made by Tosoh Corporation

Detector: RI (Differential Refractometer)

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

Measurement conditions: Column temperature 40℃

Developing solvent tetrahydrofuran

Flow rate 1.0ml/min

Standard: Based on the measurement manual of the "GPC Work Station EcoSEC-WorkStation", the following monodisperse polystyrene having a known molecular weight was used.

(Use polystyrene)

"A-500" made by Tosoh Corporation

"A-1000" made by Tosoh Corporation

"A-2500" made by Tosoh Corporation

"A-5000" made by Tosoh Corporation

"F-1" made by Tosoh Corporation

"F-2" made by Tosoh Corporation

"F-4" made by Tosoh Corporation

"F-10" made by Tosoh Corporation

"F-20" made by Tosoh Corporation

"F-40" made by Tosoh Corporation

"F-80" made by Tosoh Corporation

"F-128" made by Tosoh Corporation

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

<Polyphenylene ether compound having a reactive double bond (B)>

The curable resin composition of this invention contains the polyphenylene ether compound (B) which has a reactive double bond in addition to the maleimide (A) which has the said indane skeleton, It is characterized by the above-mentioned. Polyphenylene ether (PPE) contained in the structure of the polyphenylene ether compound (B) having a reactive double bond has excellent dielectric properties such as dielectric constant and dielectric loss tangent, region), a curable resin composition capable of obtaining a cured product exhibiting a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant can be prepared, so that it can be used as a molding material for high frequency use and is useful. Further, by reaction with the maleimide (A) having an indane skeleton, it acts as a curing agent, can cause three-dimensional crosslinking, and can obtain a cured product excellent in heat resistance, which is a preferable aspect.

The polyphenylene ether compound (B) having a reactive double bond is not particularly limited as long as it is a polyphenylene ether compound having a reactive double bond in the molecule. For example, it is represented by the following general formula (10) or (11) has a structure that is displayed.

Rd in the general formulas (10) and (11) is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms. group, a thioether group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 5 carbon atoms, an alkyloxycarbonyl group having 2 to 5 carbon atoms, an alkylcarbonyloxy group having 2 to 5 carbon atoms, and an alkylsulfonyl group having 1 to 5 carbon atoms. can The general formulas (10) and (11) have a reactive double bond-containing group in the terminal structure of the structure, and as the reactive double bond-containing group, for example, an alkenyl group having 1 to 5 carbon atoms, (meth) An acryloyl group, a styryl group, a styryl methyl group, etc. are mentioned. In addition, s is an integer value of 1-30, and t and u are also integer values of 1-30.

Although it does not restrict|limit especially as said C1-C5 alkyl group, A methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, propyl group, etc. are mentioned.

Although it does not restrict|limit especially as said C1-C5 alkenyl group, A vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, isopropenyl group, etc. are mentioned.

Although it does not restrict|limit especially as said C3-C5 cycloalkyl group, A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a methylcyclobutyl group, etc. are mentioned.

Although it does not restrict|limit especially as said C1-C5 alkoxy group, A methoxy group, an ethoxy group, a propyloxy group, isopropyloxy group, a butoxy group, pentyloxy group, etc. are mentioned.

Although it does not restrict|limit especially as said C1-C5 thioether group, A methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, pentylthio group, etc. are mentioned.

Although it does not restrict|limit especially as said C2-C5 alkylcarbonyl group, A methylcarbonyl group, ethylcarbonyl group, propylcarbonyl group, isopropylcarbonyl group, butylcarbonyl group, etc. are mentioned.

Although it does not restrict|limit especially as said C2-C5 alkyloxycarbonyl group, A methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butyloxycarbonyl group, etc. are mentioned.

Although it does not restrict|limit especially as said C2-C5 alkylcarbonyloxy group, A methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, etc. are used. can be heard

Although it does not restrict|limit especially as said C1-C5 alkylsulfonyl group, A methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, etc. are mentioned.

Among these, Rd is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 3 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a hydrogen atom, a methyl group, or an ethyl group It is more preferable that it is a hydrogen atom, and it is especially preferable that they are a methyl group.

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

The aromatic compound having two phenolic hydroxyl groups is not particularly limited, but catechol, resorcinol, hydroquinone, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxy naphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol B, bisphenol BP, bisphenol C, bisphenol F, tetramethylbisphenol A, and the like. Among these, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol E, and bisphenol F are preferable, and 4,4'-ratio It is more preferable that they are phenol, bisphenol A, and tetramethylbisphenol A.

Since the two phenolic hydroxyl groups of the aromatic compound having two phenolic hydroxyl groups form a phenylene ether bond (two oxygen atoms bonding to Y), Y is a divalent compound derived from an aromatic compound having two phenolic hydroxyl groups. become aromatic.

As a weight average molecular weight (Mw) of the polyphenylene ether compound (B) which has the said reactive double bond, Preferably it is 1000-5000, More preferably, it is 1200-4000, More preferably, it is 1400-3000. am. If it is in the said range, the hardened|cured material with the more reliably outstanding dielectric characteristic and heat resistance balanced can be obtained, and it becomes a preferable aspect. In addition, the weight average molecular weight (Mw) here should just be what was measured by the general molecular weight measuring method, The value measured using GPC mentioned above specifically, etc. are mentioned.

To the curable resin composition of the present invention, a curing agent other than the polyphenylene ether compound (B) having a reactive double bond may be added to the curable resin composition of the present invention in a range not impairing the curing of the present invention. Moreover, 50 mass % or more of the polyphenylene ether compound (B) which has the said reactive double bond is preferable with respect to 100 mass % of hardening|curing agent whole quantity, 60 mass % or more is more preferable, and 70 mass % or more is still more preferable. and 80 mass % or more is especially preferable, and 90 mass % or more is the most preferable.

Examples of the curing agent other than the polyphenylene ether compound (B) having a reactive double bond include an amine compound, an amide compound, an acid anhydride compound, a phenol compound, a cyanate ester compound, an unsaturated double bond-containing substituent and a compound having a , a diene-based polymer, and the like. These hardening|curing agents may be independent, and two or more types of combined use may be sufficient as them.

Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, and guanidine derivatives.

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

Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methyl Hexahydrophthalic anhydride, etc. are mentioned.

Examples of the phenolic compound include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol addition type resin, phenol aralkyl resin (xylok resin), resorcinno Polyhydric phenol novolak resins synthesized from polyhydric hydroxy compounds represented by rock resins and formaldehyde, naphthol aralkyl resins, trimethylolmethane resins, tetraphenylolethane resins, naphthol novolac resins, naphthol-phenol coaxial novolac resins, Naphthol-cresol coaxial novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound in which a phenol nucleus is connected to a bismethylene group), biphenyl-modified naphthol resin (a polyvalent naphthol compound in which a phenol nucleus is connected to a bismethylene group), aminotriazine Polyhydric phenols such as modified phenol resins (polyhydric phenol compounds in which phenol cores are linked with melamine, benzoguanamine, etc.) or aromatic ring-modified novolac resins containing alkoxy groups (polyhydric phenol compounds in which phenol cores and alkoxy group-containing aromatic rings are linked with formaldehyde) compounds can be mentioned.

Examples of the cyanate ester compound include bisphenol A cyanate ester resin, bisphenol F cyanate ester resin, bisphenol E cyanate ester resin, bisphenol S cyanate ester resin, and bisphenol sulfide cyanate ester. Resin, phenylene ether type cyanate ester resin, naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenolo Volac cyanate ester resin, cresol novolak cyanate ester resin, triphenylmethane cyanate ester resin, tetraphenylethane cyanate ester resin, dicyclopentadiene-phenol addition reaction cyanate ester resin, phenolaral Kill type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol coaxial novolak type cyanate ester resin, naphthol-cresol coaxial novolak type cyanate ester resin, aromatic hydrocarbon form Aldehyde resin-modified phenol resin-type cyanate ester resin, biphenyl-modified novolac-type cyanate ester resin, anthracene-type cyanate ester resin, etc. are mentioned.

The compound having an unsaturated double bond-containing substituent is not particularly limited, for example, as long as it is a compound having two or more unsaturated bond-containing substituents in the molecule. Examples of the unsaturated bond-containing substituent include an allyl group, isopropenyl group, 1-propyl group. The compound which has a phenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styryl methyl group, etc. is mentioned.

As said diene-type polymer, the unmodified diene-type polymer which is not modified|denatured with a polar group is mentioned, for example. Here, a polar group is a functional group which affects a dielectric property, For example, a phenol group, an amino group, an epoxy group, etc. are mentioned. It does not specifically limit as said diene polymer, For example, 1,2- polybutadiene, 1, 4- polybutadiene, etc. can be used.

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

<Preparation of curable resin composition>

The curable resin composition of the present invention comprises a maleimide (A) having an indane skeleton (hereinafter sometimes referred to as “component (A)”), and a polyphenylene ether compound (B) having a reactive double bond (hereinafter referred to as “component (A)”). , "(B) component" is sometimes referred to). The said component (B) can generate|occur|produce three-dimensional crosslinking by reaction with the said (A) component, can obtain the hardened|cured material excellent in dielectric properties and heat resistance, and becomes a preferable aspect.

As a compounding ratio (mass part) of said (A) component and said (B) component, it is preferable that (A) component: (B) component is 90:10-10:90, More preferably, 80 :20-20:80, More preferably, it is 65:35-35:65, Especially preferably, it is 55:45-45:55. By preparing the compounding ratio in the above range, it is excellent in heat resistance, low dielectric constant, and low dielectric loss tangent, and since flexibility can be expressed, it is preferable.

In the curable resin composition of the present invention, alkenyl group-containing compounds such as bismaleimides other than the maleimide (A), allyl ether compounds, allylamine compounds, triallyl Anurate, an alkenylphenol-based compound, a vinyl group-containing polyolefin compound, or the like may be added. Moreover, it is also possible to mix|blend other thermosetting resins, for example, thermosetting polyimide resin, an epoxy resin, a phenol resin, an active ester resin, benzoxazine resin, cyanate resin, etc. suitably according to the objective.

To the curable resin composition of the present invention, a non-halogen-based flame retardant substantially containing no halogen atom can be blended in order to exhibit flame retardancy within a range not impairing the object. Examples of the non-halogen-based flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organometallic salt-based flame retardants, and these can be used alone or in combination.

An inorganic filler can be mix|blended with curable resin composition of this invention as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When making the compounding quantity of the said inorganic filler especially large, it is preferable to use fused silica. The fused silica may be either crushed or spherical. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use the spherical one. Moreover, in order to raise the compounding quantity of a spherical silica, it is preferable to adjust the particle size distribution of a spherical silica suitably. The filling factor considers a flame retardance, the higher one is preferable, and 20 mass % or more is especially preferable with respect to the whole quantity of curable resin composition. In addition, when using the said curable resin composition for uses, such as an electrically conductive paste mentioned in full detail below, conductive 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 hardening accelerator, a silane coupling agent, a mold release agent, a pigment, and an emulsifier, as needed.

<Cured material>

It is preferable that the hardened|cured material of this invention makes hardening reaction of the said curable resin composition, and is formed. The said curable resin composition is obtained by mixing each component mentioned above uniformly, and can be easily set as hardened|cured material by the method similar to the method known conventionally. As said hardened|cured material, molded hardened|cured material, such as a laminated material, a cast, an adhesive layer, a coating film, and a film, is mentioned.

The curing (thermal curing) reaction is easily carried out in the absence of a catalyst. However, if a faster reaction is desired, the addition of a polymerization initiator such as an organic peroxide or an azo compound, or a basic catalyst such as a phosphine-based compound or a tertiary amine is effective. am. For example, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazole, etc. exist, as a compounding quantity, 0.05-5 mass % of the whole curable resin composition is preferable. do.

<Prepreg>

It is preferable that the prepreg of this invention has a reinforcing base material and the semi-hardened|cured material of the said curable resin composition impregnated in the said reinforcing base material. As a method for producing the prepreg, a known method can be used. The reinforcing substrate is impregnated with a resin varnish obtained by dissolving (diluted) the curable resin composition in an organic solvent, and the reinforcing substrate impregnated with the resin varnish is subjected to heat treatment. , It can be set as a prepreg by semi-hardening (or non-hardening) the said curable resin composition.

Examples of the organic solvent include toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone (MEK), and methyl isobutyl. In ketone, dioxane, tetrahydrofuran, etc., it can be used individually or as 2 or more types of mixed solvent.

Examples of the reinforcing substrate impregnated with the resin varnish include inorganic fibers such as glass fibers, polyester fibers, and polyamide fibers, woven or nonwoven fabrics made of organic fibers, mats, papers, and the like, and these can be used alone or in combination. can

Although it does not specifically limit as a mass ratio of the curable resin composition in the said prepreg and a reinforcing base material, Usually, it is preferable to prepare so that the curable resin composition in a prepreg (resin content in) may become 20-60 mass %.

The conditions for the heat treatment of the prepreg are appropriately selected depending on the type and usage of the organic solvent, catalyst, and various additives to be used, but is usually carried out at a temperature of 80 to 220°C and under conditions such as 3 minutes to 30 minutes.

<Heat-resistant materials and electronic materials>

Since the hardened|cured material obtained by the curable resin composition of this invention is excellent in heat resistance and dielectric property, it can be used suitably for a heat-resistant member and an electronic member. In particular, it can be suitably used for a circuit board, a semiconductor sealing material, a semiconductor device, a build-up film, a build-up board|substrate, an adhesive agent, a resist material, etc. Moreover, it can use suitably also for the matrix resin of fiber reinforced resin, and is especially suitable as a high heat-resistant prepreg. Moreover, since the maleimide (A) which has the said indane skeleton contained in the said curable resin composition shows the outstanding solubility to various solvents, it can be made into a paint. The heat-resistant member or electronic member obtained in this way can be suitably used for various uses, for example, industrial machine parts, general machine parts, automobile, railway, vehicle, etc. parts, space/aviation related parts, electronic/electric parts, Building materials, containers/packaging members, household goods, sports/leisure articles, and casing members for wind power generation may be mentioned, but are not limited thereto.

Hereinafter, an example is given and demonstrated about the typical product manufactured using the curable resin composition of this invention.

<circuit board>

In this invention, as a circuit board, the thing obtained by laminating|stacking the said prepreg and copper foil, and carrying out thermocompression-bonding shaping|molding is preferable. Specifically, as a method of obtaining a circuit board from the curable resin composition of the present invention, the prepreg is laminated by a conventional method, and copper foils are stacked on top of each other, and under a pressure of 1 to 10 MPa, at 170 to 300° C. for 10 minutes. For 3 hours, the method of thermocompression-molding is mentioned.

<Semiconductor encapsulant>

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 encapsulant from the curable resin composition of the present invention, a curing accelerator as an optional component and a compounding agent such as an inorganic filler are further added to the curable resin composition as needed with an extruder, a kneader, a roll, etc. A method of sufficiently melting and mixing until uniform is mentioned using In that case, fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, high filling of crystalline silica, alumina, silicon nitride, or the like, which has higher thermal conductivity than fused silica, or fused silica Silica, crystalline silica, alumina, silicon nitride, etc. may be used. The filling rate is preferably in the range of 30 to 95 parts by mass of the inorganic filler per 100 parts by mass of the curable resin composition, and among them, in order to improve flame retardancy, moisture resistance and solder crack resistance, and to reduce the coefficient of linear expansion, 70 mass parts or more are more preferable, and it is still more preferable that it is 80 mass parts or more.

<Semiconductor device>

In this invention, it is preferable that the hardened|cured material which heat-hardened the said semiconductor sealing material is included as a semiconductor device. Specifically, as a semiconductor package molding for obtaining a semiconductor device from the curable resin composition of the present invention, the semiconductor encapsulant is molded using a mold or a transfer molding machine, an injection molding machine, etc., and further at 50 to 250 ° C., 2 A method of curing by heating for ∼10 hours is mentioned.

<Build-up board>

As a method of obtaining a buildup board|substrate from curable resin composition of this invention, the method of passing through processes 1-3 is mentioned. In step 1, first, the said curable resin composition which mix|blended rubber, a filler, etc. suitably is apply|coated to the circuit board in which the circuit was formed using the spray coating method, the curtain coating method, etc., and then hardened. In step 2, if necessary, after drilling a predetermined through-hole portion or the like in the circuit board to which the curable resin composition has been applied, the substrate is treated with a roughening agent and the surface is washed with hot water. Concavities and convexities are formed on the surface, and a metal such as copper is plated. In step 3, the operations of steps 1 and 2 are sequentially repeated as desired, and the resin insulating layer and the conductor layer having a predetermined circuit pattern are alternately built up to form a build-up substrate. Moreover, in the said process, what is necessary is just to perform the drilling of a through-hole part after formation of the resin insulating layer of an outermost layer. Moreover, the buildup board|substrate in this invention forms a roughened surface by thermocompression-bonding at 170-300 degreeC on the wiring board which formed the circuit on the copper foil with resin which made the said resin composition semi-hardened on copper foil, It is also possible to omit the process of a plating process and to produce a build-up board|substrate.

<Build-up film>

It is preferable that the buildup film of this invention contains the said curable resin composition. As a method of obtaining a buildup film from curable resin composition of this invention, after apply|coating curable resin composition on a support film, for example, it dries and the method of forming a resin composition layer on a support film is mentioned. When the curable resin composition of the present invention is used for a build-up film, the film is softened at the temperature conditions of lamination in the vacuum lamination method (usually 70° C. to 140° C.), and simultaneously with the circuit board lamination. It is important to exhibit fluidity (resin flow) that allows resin filling in existing via holes or through holes, and it is preferable to blend each of the above components so as to express such characteristics. In addition, in the resulting build-up film or circuit board (copper clad laminate, etc.), a phenomenon such as locally different characteristic values due to phase separation or the like does not occur, and a certain performance is expressed in an arbitrary site. For this purpose, appearance uniformity is required.

Here, the diameter of the through hole of the circuit board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to enable resin filling within this range. Moreover, when laminating the both surfaces of a circuit board, it is preferable to fill about 1/2 of a through hole.

As a specific method of manufacturing an above-mentioned buildup film, after preparing the resin composition which mix|blended the organic solvent and varnished, the said varnished resin composition is apply|coated to the surface of the support film (Y), and further heated, or The method of drying the organic solvent by hot air spraying etc. and forming the resin composition layer (X) is mentioned.

Examples of the organic solvent used herein include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate. , Cellosolve, it is preferable to use carbitols such as butylcarbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and a nonvolatile content of 30 It is preferable to use it in the ratio used as -60 mass %.

Moreover, it is necessary to make the thickness of the said resin composition layer (X) to be formed more than the thickness of a conductor layer normally. Since the thickness of the conductor layer which a circuit board has is the range of 5-70 micrometers normally, it is preferable that the thickness of the said resin composition layer (X) has a thickness of 10-100 micrometers. Moreover, the said resin composition layer (X) in this invention may 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, and a damage|wound can be prevented.

The support film and protective film described above include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonate, polyimide, or release paper, copper foil, aluminum foil, etc. of metal foil, etc. are mentioned. Moreover, a support film and a protective film may give the mold release process other than a mad process and corona treatment. Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in the range of 25-50 micrometers. Moreover, as for the thickness of a protective film, it is preferable to set it as 1-40 micrometers.

The said support film Y peels, after laminating on a circuit board, or after forming an insulating layer by heat-hardening. When the support film Y is peeled off after the resin composition layer which comprises a buildup film heat-hardens, adhesion of dust etc. in a hardening process can be prevented. When peeling after hardening, a mold release process is previously performed normally to a support film.

Moreover, a multilayer printed circuit board can be manufactured from the buildup film obtained by making it above. For example, when the resin composition layer (X) is protected with a protective film, after peeling them, on one or both sides of the circuit board, for example, the layer (X) of the resin composition is in direct contact with the circuit board. For example, it is laminated by the vacuum lamination method. The method of lamination may be a batch type or a continuous type with rolls may be sufficient as it. Moreover, as needed, before laminating, you may heat (preheat) a buildup film and a circuit board as needed. As for the conditions of lamination, it is preferable that the crimping temperature (laminate temperature) is 70 to 140° C., and the crimping pressure is preferably 1 to 11 kgf/cm 2 (9.8×10 ^{4 to} 107.9×10 ⁴ N/m 2), It is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or less with an air pressure.

<Conductive paste>

As a method of obtaining an electrically conductive paste from curable resin composition of this invention, the method of disperse|distributing electroconductive particle in the said composition is mentioned, for example. The said electrically conductive paste can be set as the paste resin composition for circuit connection, or an anisotropic electrically conductive adhesive according to the kind of electroconductive particle to be used.

(Example)

Next, although an Example and a comparative example demonstrate this invention concretely, below, "part" and "%" are based on mass, unless it specifically limits. In addition, a softening point, an amine equivalent, GPC, and FD-MS spectrum were measured and evaluated on the following conditions.

1) softening point

Measurement method: Based on JISK7234 (ring-and-ball method), the softening point (degreeC) of the intermediate amine compound obtained by 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.

About 2.5 g of an intermediate amine compound as a sample, 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine were precisely weighed in a 500 mL Erlenmeyer flask with an idler, and a cooling tube was attached to 120 Heat and reflux for 150 minutes in an oil bath set at °C.

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 a 0.5 mol/L potassium hydroxide-ethanol solution by potentiometric titration. A blank test was performed in the same manner and corrected.

Amine equivalent weight (g/eq.)=(S×2,000)/(Blank-A)

S: amount of sample (g)

A: Consumption (mL) of 0.5 mol/L potassium hydroxide-ethanol solution

Blank: Consumption (mL) of 0.5 mol/L potassium hydroxide-ethanol solution in blank test

3) GPC measurement

It measured using the following measuring apparatus and measurement conditions, and obtained the GPC chart (FIG. 1-9) of the maleimide obtained by the synthesis example shown below. From the results of the GPC chart, the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)), and the average number of repeating units "n" contributing to the indane skeleton in maleimide were calculated as the number average molecular weight (Mn) Based on this, it was measured and calculated. Specifically, for compounds of n=0 to 4, the theoretical molecular weight and the molecular weight of each measured value in GPC are plotted on the scatter diagram, an approximate straight line is drawn, and the number from the point indicated by the measured value Mn(1) on the straight line The average molecular weight (Mn) was calculated|required, and n was computed.

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

Column: Tosoh Corporation Guard Column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK" -GEL G3000HXL" + "TSK-GEL G4000HXL" made by Tosoh Corporation

Detector: RI (Differential Refractometer)

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

Measurement conditions: Column temperature 40℃

Developing solvent tetrahydrofuran

Flow rate 1.0ml/min

Standard: Based on the measurement manual of the "GPC Work Station EcoSEC-WorkStation", the following monodisperse polystyrene having a known molecular weight was used.

(Use polystyrene)

"A-500" made by Tosoh Corporation

"A-1000" made by Tosoh Corporation

"A-2500" made by Tosoh Corporation

"A-5000" made by Tosoh Corporation

"F-1" made by Tosoh Corporation

"F-2" made by Tosoh Corporation

"F-4" made by Tosoh Corporation

"F-10" made by Tosoh Corporation

"F-20" made by Tosoh Corporation

"F-40" made by Tosoh Corporation

"F-80" made by Tosoh Corporation

"F-128" made by Tosoh Corporation

Sample: A 1.0 mass % tetrahydrofuran solution in terms of the 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 measuring apparatus and measurement conditions.

Measuring device: JMS-T100GC AccuTOF

Measuring conditions

Measurement range: m/z=4.00 to 2000.00

Rate of change: 51.2mA/min

Final current value: 45mA

Cathode voltage: -10kV

Recording Interval: 0.07sec

[Synthesis Example 1] Synthesis of maleimide compound A-1

(1) Synthesis of intermediate amine compounds

48.5 g (0.4 mol) of 2,6-dimethylaniline, α,α'-dihydroxy-1,3-diiso in a 1L flask equipped with a thermometer, cooling tube, Dean-Stark trap, and stirrer 272.0 g (1.4 mol) of propylbenzene, 280 g of xylene, and 70 g of activated clay were added and heated to 120° C. while stirring. Further, while removing the effluent with a Dean-Stark tube, the temperature was raised to 210°C, and the reaction was carried out for 3 hours. After that, it was cooled to 140°C, 145.4 g (1.2 mol) of 2,6-dimethylaniline was added, and then the temperature was raised to 220°C and reacted for 3 hours. After the reaction, air-cooled to 100° C., diluted with 300 g of toluene, filtered to remove activated clay, and distilled off low molecular weight substances such as solvents and unreacted substances under reduced pressure to obtain the following general formula (A-1) 364.1 g of the indicated intermediate amine compound was obtained. The amine equivalent weight was 298 and the softening point was 70°C.

(2) Maleimidization

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 cooling tube, a Dean-Stark trap, and a stirrer, and the mixture was stirred at room temperature. Next, 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 carried out at room temperature for 2 hours. After adding 37.1 g of p-toluenesulfonic acid monohydrate, heating the reaction solution to cool and separate azeotropic water and toluene under reflux, only toluene was returned to the system and dehydration reaction was performed for 8 hours. After air cooling to room temperature, concentration under reduced pressure, the brown solution was dissolved in 600 g of ethyl acetate, washed 3 times with 150 g of ion-exchanged water, 3 times with 150 g of 2% aqueous sodium hydrogen carbonate solution, dried by adding sodium sulfate, and then concentrated under reduced pressure to obtain the reaction product It vacuum-dried at 80 degreeC for 4 hours, and obtained 413.0g of products containing maleimide compound A-1. In the FD-MS spectrum of this maleimide compound A-1, the peaks of M+=560, 718, 876 are confirmed, and each peak corresponds when n is 0, 1, 2. Further, when the value of the number of repeating units n (based on the number average molecular weight) in the indane skeleton portion in the maleimide A-1 was determined by GPC, the GPC chart is shown in FIG. (Mw/Mn) = 1.81.

[Synthesis Example 2] Synthesis of maleimide compound A-2

(1) Synthesis of intermediate amine compounds

2,6-dimethylaniline 48.5 g (0.4 mol), α,α'-dihydroxy-1,3-diisopropylbenzene 233.2 g ( 1.2 mol), 230 g of xylene, and 66 g of activated clay were added and heated to 120° C. while stirring. Further, while removing the effluent with a Dean-Stark tube, the temperature was raised to 210°C, and the reaction was carried out for 3 hours. After that, it was cooled to 140°C, 145.4 g (1.2 mol) of 2,6-dimethylaniline was added, and then the temperature was raised to 220°C and reacted for 3 hours. After the reaction, air-cooled to 100° C., diluted with 300 g of toluene, filtered to remove activated clay, and distilled off low molecular weight substances such as solvents and unreacted substances under reduced pressure to obtain the following general formula (A-2) 278.4 g of the indicated intermediate amine compound was obtained. The amine equivalent weight was 294 and the softening point was 65°C.

(2) Maleimidization

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 cooling tube, a Dean-Stark trap, and a stirrer, and the mixture was stirred at room temperature. Next, the reaction material (A-2) was dripped over 1 hour by the mixed solution of 278.4 g and DMF 150g.

After completion of the dropwise addition, the reaction was further carried out at room temperature for 2 hours. After adding 27.0 g of p-toluenesulfonic acid monohydrate, heating the reaction solution to cool and separate azeotropic water and toluene under reflux, only toluene was returned to the system and dehydration reaction was performed for 8 hours. After air cooling to room temperature, concentration under reduced pressure, the brown solution was dissolved in 500 g of ethyl acetate, washed 3 times with 120 g of ion-exchanged water, 3 times with 120 g of 2% aqueous sodium hydrogen carbonate solution, dried by adding sodium sulfate, and then concentrated under reduced pressure to obtain the reaction product It vacuum-dried at 80 degreeC for 4 hours, and 336.8g of products containing maleimide compound A-2 were obtained. In the FD-MS spectrum of this maleimide compound A-2, the peaks of M+=560, 718, 876 are confirmed, and it corresponds when n is 0, 1, and 2, respectively. In addition, the value of the number of repeating units n (based on the number average molecular weight) in the indane skeleton portion in the maleimide A-2 was determined by GPC. (Mw/Mn) = 3.29.

[Synthesis Example 3] Synthesis of maleimide compound A-3

(1) Synthesis of intermediate amine compounds

2,6-dimethylaniline 48.5 g (0.4 mol), α,α'-dihydroxy-1,3-diisopropylbenzene 388.6 g ( 2.0 mol), 350 g of xylene and 123 g of activated clay were added, and heated to 120° C. while stirring. Further, while removing the effluent with a Dean-Stark tube, the temperature was raised to 210°C, and the reaction was carried out for 3 hours. After that, it was cooled to 140°C, 145.4 g (1.2 mol) of 2,6-dimethylaniline was added, and then the temperature was raised to 220°C and reacted for 3 hours. After the reaction, air-cooled to 100° C., diluted with 500 g of toluene, removed activated clay by filtration, and distilled off low molecular weight substances such as solvents and unreacted substances under reduced pressure to obtain the following general formula (A-3) 402.1 g of the indicated intermediate amine compound was obtained. The amine equivalent weight was 306 and the softening point was 65°C.

(2) Maleimidization

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

After completion of the dropwise addition, the reaction was further carried out at room temperature for 2 hours. After adding 37.5 g of p-toluenesulfonic acid monohydrate, heating the reaction solution to cool and separate azeotropic water and toluene under reflux, only toluene was returned to the system and dehydration reaction was performed for 8 hours. After air cooling to room temperature, concentration under reduced pressure, the brown solution was dissolved in 800 g of ethyl acetate, washed 3 times with 200 g of ion-exchanged water, 3 times with 200 g of 2% aqueous sodium hydrogen carbonate solution, dried by adding sodium sulfate, and then concentrated under reduced pressure to obtain the reaction product It vacuum-dried at 80 degreeC for 4 hours, and obtained 486.9g of products containing maleimide compound A-3. In the FD-MS spectrum of this maleimide compound A-3, the peaks of M+=560, 718, 876 are confirmed, and it corresponds when n is 0, 1, and 2, respectively. Further, the value of the number of repeating units n (based on the number average molecular weight) in the indane skeleton portion in the maleimide A-3 was determined by GPC. (Mw/Mn) = 1.52.

[Synthesis Example 4] Synthesis of maleimide compound A-4

(1) Synthesis of intermediate amine compounds

2,6-diethylaniline 59.7g (0.4mol), α,α'-dihydroxy-1,3-diisopropylbenzene 272.0g in a 2L flask equipped with a thermometer, cooling tube, Dean-Stark trap, and stirrer (1.4 mol), 350 g of xylene, and 94 g of activated clay were added and heated to 120° C. while stirring. Further, while removing the effluent with a Dean-Stark tube, the temperature was raised to 210°C, and the reaction was carried out for 3 hours. After that, the mixture was cooled to 140° C., and 179.1 g (1.2 mol) of 2,6-diethylaniline was added thereto, followed by heating to 220° C. and reacting for 3 hours. After the reaction, air cooled to 100° C., diluted with 500 g of toluene, filtered to remove activated clay, and distilled off low molecular weight substances such as solvents and unreacted substances under reduced pressure to obtain the following general formula (A-4) 342.1 g of the indicated intermediate amine compound was obtained. The amine equivalent weight was 364 and the softening point was 47°C.

(2) Maleimidization

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 cooling tube, a Dean-Stark trap, and a stirrer, and the mixture was stirred at room temperature. Next, a mixed solution of 342.1 g of the reaction product (A-4) and 180 g of DMF was added dropwise over 1 hour.

After completion of the dropwise addition, the reaction was further carried out at room temperature for 2 hours. After adding 26.8 g of p-toluenesulfonic acid monohydrate, heating the reaction solution and cooling and separating azeotropic water and toluene under reflux, only toluene was returned to the system and dehydration reaction was performed for 8 hours. After air cooling to room temperature, concentration under reduced pressure, the brown solution was dissolved in 500 g of ethyl acetate, washed 3 times with 200 g of ion-exchanged water, 3 times with 200 g of 2% aqueous sodium hydrogen carbonate solution, dried by adding sodium sulfate, and then concentrated under reduced pressure to obtain the reaction product It vacuum-dried at 80 degreeC for 4 hours, and obtained 388.1g of products containing maleimide compound A-4. In the FD-MS spectrum of this maleimide compound A-4, the peaks of M+=616, 774, and 932 are confirmed, and it corresponds when n is 0, 1, and 2, respectively. In addition, the value of the number of repeating units n (based on the number average molecular weight) in the indane skeleton portion in the maleimide A-4 was determined by GPC. (Mw/Mn) = 1.40.

[Synthesis Example 5] Synthesis of maleimide compound A-5

(1) Synthesis of intermediate amine compounds

70.9 g (0.4 mol) of 2,6-diisopropylaniline, α,α'-dihydroxy-1,3-diisopropylbenzene 272.0 in a 1L flask equipped with a thermometer, cooling tube, Dean-Stark trap, and stirrer g (1.4 mol), 350 g of xylene, and 97 g of activated clay were added and heated to 120° C. while stirring. Further, while removing the effluent with a Dean-Stark tube, the temperature was raised to 210°C, and the reaction was carried out for 3 hours. After that, the mixture was cooled to 140°C and 212.7 g (1.2 mol) of 2,6-diisopropylaniline was added thereto, followed by heating to 220°C and reacting for 3 hours. After the reaction, it is cooled to 100° C. in air, diluted with 500 g of toluene, filtered to remove activated clay, and low molecular weight substances such as solvents and unreacted substances are distilled off under reduced pressure to obtain the following general formula (A-5) 317.5 g of the indicated intermediate amine compound was obtained. The amine equivalent weight was 366 and the softening point was 55°C.

(2) Maleimidization

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 cooling tube, a Dean-Stark trap, and a stirrer, and the mixture was stirred at room temperature. Next, a mixed solution of 317.5 g of the reaction product (A-5) and 175 g of DMF was added dropwise over 1 hour.

After completion of the dropwise addition, the reaction was further carried out at room temperature for 2 hours. 24.8 g of p-toluenesulfonic acid monohydrate was added, and the reaction solution was heated to cool and separate azeotropic water and toluene under reflux, then only toluene was returned to the system and dehydration reaction was performed for 8 hours. After air cooling to room temperature, concentration under reduced pressure, the brown solution was dissolved in 600 g of ethyl acetate, washed 3 times with 200 g of ion-exchanged water, 3 times with 200 g of 2% aqueous sodium hydrogen carbonate solution, dried by adding sodium sulfate, and concentrated under reduced pressure to obtain the reaction product It vacuum-dried at 80 degreeC for 4 hours, and obtained 355.9g of products containing maleimide compound A-5. In the FD-MS spectrum of this maleimide compound A-5, the peaks of M+=672, 830, and 988 are confirmed, and it corresponds when n is 0, 1, and 2, respectively. Further, when the value of the number of repeating units n (based on the number average molecular weight) in the indane skeleton portion in the maleimide A-5 was determined by GPC, the GPC chart is shown in FIG. (Mw/Mn) = 1.24.

[Synthesis Example 6] Synthesis of maleimide compound A-8

(1) Synthesis of intermediate amine compounds

In the method for synthesizing the intermediate amine compound A-1, the same operation was performed by changing the reaction time at 210°C to 6 hours and the reaction time at 220°C to 3 hours, and the intermediate amine represented by the following general formula (A-8) Compound 345.2 g was obtained. The amine equivalent weight was 348 and the softening point was 71°C.

(2) Maleimidization

From the above-mentioned method for synthesizing maleimide compound A-1, the intermediate was changed to A-8 and the same operation was performed to obtain 407.6 g of a product containing maleimide compound A-8. In the FD-MS spectrum of this maleimide compound A-8, the peaks of M+=560, 718, 876 are confirmed, and each peak corresponds when n is 0, 1, and 2. Further, the value of the number of repeating units n (based on the number average molecular weight) in the indane skeleton portion in the maleimide A-8 was determined by GPC. (Mw/Mn) = 1.49.

[Synthesis Example 7] Synthesis of maleimide compound A-9

In the synthesis method of the intermediate amine compound A-1, the reaction time of 210 ° C. is changed to 6 hours and the reaction time of 220 ° C. is changed to 3 hours, and the same operation is performed, and the synthesized intermediate amine compound (amine equivalent weight is 347, softening point is 71 ° C.), except that the dehydration reaction under reflux in the maleimidization reaction is 10 hours, by subjecting to the same conditions as the synthesis method of the maleimide compound A-1, the maleimide compound A-9 415.6 g of the product containing was obtained. In the FD-MS spectrum of this maleimide compound A-9, the peaks of M+=560, 718, 876 are confirmed, and each peak corresponds when n is 0, 1, 2. Further, when the value of the number of repeating units n (based on the number average molecular weight) in the indane skeleton portion in the maleimide A-9 was determined by GPC, the GPC chart is shown in Fig. 7, n = 2.91, and molecular weight distribution (Mw/Mn)=1.64.

[Synthesis Example 8] Synthesis of maleimide compound A-10

In the method for synthesizing the intermediate amine compound A-1, the same operation was performed by changing the reaction time at 210 ° C. to 9 hours and the reaction time at 220 ° C. to 3 hours, and the synthesized intermediate amine compound (amine equivalent is 342, softening point is 69 ° C.), except that the dehydration reaction under reflux in the maleimidization reaction is 10 hours, by subjecting to the same conditions as the method for synthesizing the maleimide compound A-1 above, the maleimide compound A-10 is 398.7 g of the product containing was obtained. In the FD-MS spectrum of this maleimide compound A-10, the peaks of M+=560, 718, 876 are confirmed, and each peak corresponds when n is 0, 1, 2. Further, the value of the number of repeating units n (based on the number average molecular weight) in the indane skeleton portion in the maleimide A-10 was determined by GPC. (Mw/Mn) = 2.09.

[Synthesis Example 9] Synthesis of maleimide compound A-11

In the method for synthesizing the intermediate amine compound A-1, the intermediate amine compound (amine equivalent weight is 347, softening point is 70° C.), except that the dehydration reaction under reflux in the maleimidization reaction is set to 12 hours, the maleimide compound A-11 is obtained by subjecting to the same conditions as the method for synthesizing the maleimide compound A-1 above. 422.7 g of the product containing was obtained. In the FD-MS spectrum of this maleimide compound A-11, the peaks of M+=560, 718, 876 are confirmed, and each peak corresponds when n is 0, 1, 2. Further, the value of the number of repeating units n (based on the number average molecular weight) in the indane skeleton portion in the maleimide A-11 was determined by GPC. (Mw/Mn) = 3.02.

[Examples 1 to 9 and Comparative Example 1]

<Solvent solubility of maleimide>

Maleimides (A-1) to (A-5), (A-8) to (A-11) obtained in Synthesis Examples 1 to 9, and commercially available maleimides for comparison (A-6) (4, 4'-diphenylmethane bismaleimide, "BMI-1000" Yamato Kasei Kogyo Co., Ltd. product) evaluated the solubility with respect to toluene and methyl ethyl ketone (MEK), and the evaluation result was shown in Table 1.

As a solvent solubility evaluation method, using each maleimide obtained in the said synthesis example and comparative example, a toluene solution and methyl so that a non-volatile content may be 10, 20, 30, 40, 50, 60, and 70 mass %. An ethyl ketone (MEK) solution was prepared.

Specifically, when the vials containing each maleimide obtained in the above Synthesis Examples and Comparative Examples were left at room temperature (25°C) for 60 days and uniformly dissolved in each solution of each nonvolatile matter composition (no insoluble matter) ) was evaluated (visually) with ○ and not dissolving (there was an insoluble matter) as ×. Moreover, if a non-volatile matter can melt|dissolve in a solvent when it is 20 mass % or more, it is practically preferable.

[Examples 10 to 18 and Comparative Example 2]

<Preparation of curable resin composition>

Maleimides (A-1) to (A-5), (A-8) to (A-11) obtained in Synthesis Examples 1 to 9, maleimide (A-6) for comparison (4,4'-diphenyl) Methanebismaleimide, "BMI-1000" manufactured by Yamato Chemical Industries, Ltd.), a polyphenylene ether compound having a reactive double bond (B-1) ("SA-9000", manufactured by SABIC, Mw: 1700) was mix|blended in the ratio shown in Table 2, and curable resin composition was prepared.

<Preparation of cured product (molded product)>

A cured product (molded product) was produced by subjecting the curable resin composition to the following conditions.

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

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

About the obtained hardened|cured material, the following method evaluated various physical properties and characteristics. Table 3 shows the evaluation results.

[Examples 19 to 24 and Comparative Examples 3 to 4]

<Preparation of curable resin composition>

Maleimide (A-1), (A-8) to (A-11) obtained in Synthesis Example 1 and Synthesis Examples 6 to 9, maleimide for comparison (A-7) (3,3'-dimethyl-5; 5'-diethyl-4,4'-diphenylmethane bismaleimide, "BMI-5100" manufactured by Yamato Chemical Industries, Ltd.), a polyphenylene ether compound having a reactive double bond (B-1) ( "SA-9000", manufactured by SABIC, Mw: 1700), a vinylbenzylated polyphenylene ether compound (B-2), and methyl ethyl ketone (MEK) were blended in the proportions shown in Table 4 to prepare a curable resin composition . Moreover, about the said compound (B-2), it synthesize|combined based on Example 1 of Unexamined-Japanese-Patent No. 6147538.

<Varnish solubility and uniformity of film appearance>

In Examples 19-24 and each curable resin composition of Comparative Examples 3-4, it confirmed visually whether it was melt|dissolving uniformly (confirmation of varnish solubility). A case in which it was uniformly dissolved was evaluated as ○, a case in which it was not uniformly dissolved or not dissolved at all was evaluated as × (for example, when an insoluble matter exists).

In addition, 5 g of each curable resin composition is applied on a release PET film (thickness after drying: 295 μm), dried at 80° C. for 1 hour (heating), and further dried (heated) at 120° C. for 1 hour, A film molded product was produced, and the appearance of the obtained film molded product was visually confirmed. The case where the film appearance was uniform was evaluated as ○, and the case where the film appearance was non-uniform was evaluated as × (for example, when turbidity or insoluble matter can be confirmed). Table 4 shows the evaluation results.

<Glass transition temperature (Tg)>

A cured product having 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. This test piece was subjected to a change in elastic modulus using a viscoelasticity measuring device (DMA: Hitachi High-Tech Sciences Co., Ltd. solid viscoelasticity measuring device “DMS6100”, deformation mode: both-side bending, measurement mode: sinusoidal vibration, frequency 1 Hz, temperature increase rate 3° C./min). The temperature at which α becomes the maximum (the rate of change of tan δ is greatest) was evaluated as the glass transition temperature Tg (°C). Moreover, from a heat resistant viewpoint, as glass transition temperature Tg, 250 degreeC or more (high Tg-ization) is preferable, More preferably, it is 260 degreeC or more.

<Thermal decomposition resistance>

The cured product having a thickness of 2.4 mm is finely cut, and using a thermogravimetric analyzer (thermogravimetric measuring device "TGA/DSC1" manufactured by METTLER TOREDO), the temperature increase rate is 5 ° C./min. Measurement is performed in a nitrogen atmosphere, The temperature at which the weight decreases by 5% was evaluated as the thermal decomposition temperature (Td5) (°C).

<Thermal Expansibility>

A cured product having a thickness of 2.4 mm was cut out to a size of 5 mm in width and 5 mm in length, and this was used as a test piece. The thermal expansion coefficient CTE (ppm) of this test piece was measured in the range of 40-60 degreeC using the thermal analysis apparatus ("TMA/SS6100" made by SII Nanotechnology Co., Ltd., temperature increase rate 3 degreeC/min). Moreover, from a viewpoint of heat resistance, prevention of warpage, etc., as a thermal expansion coefficient, 60 ppm or less is preferable, More preferably, it is 55 ppm or less.

<Genetic Characteristics>

In accordance with JIS-C-6481, using a network analyzer "E8362C" manufactured by Agilent Technologies Co., Ltd., using a cavity resonance method, after drying in a room at 23°C and 50% humidity for 24 hours. The dielectric constant and dielectric loss tangent at 1 GHz of the test piece were measured. Moreover, as for dielectric constant and dielectric loss tangent, from a viewpoint of transmission loss reduction as an electronic material, 2.60 or less are preferable and, as for the dielectric constant, 2.55 or less are more preferable. Moreover, 0.0020 or less are preferable and, as for a dielectric loss tangent, 0.0015 or less are more preferable.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

From the evaluation results in Table 1, in Examples 1 to 9, since maleimide having an indane skeleton was used, when a toluene solution was prepared, it could be dissolved even if the nonvolatile matter was 20 mass%, and MEK solution was prepared. When it did, it could melt|dissolve even if a non-volatile matter was 50 mass %, and it has confirmed that it was excellent in solvent solubility. On the other hand, it was confirmed that the commercially available maleimide used in Comparative Example 1 did not have an indane skeleton in the structure and was poor in solvent solubility.

From the evaluation results in Table 3 above, in Examples 10 to 18, in addition to maleimide having an indane skeleton, a polyphenylene ether compound having a reactive double bond containing polyphenylene ether contributing also to dielectric properties in its structure ( By using B), the glass transition temperature and thermal decomposition resistance were high, and the thermal expansion coefficient was suppressed to be small, so it was confirmed that the heat resistance and thermal decomposition resistance were excellent. In addition, the dielectric constant and dielectric loss tangent were also suppressed to be low, and it was confirmed that the dielectric properties were excellent. On the other hand, in Comparative Example 2, the glass transition temperature or thermal decomposition temperature is low, and the thermal expansion coefficient is high, so it is confirmed that the heat resistance and thermal decomposition resistance are inferior, and the dielectric constant and dielectric loss tangent is low with respect to the Example. It could not be suppressed, and it was confirmed that it is inferior also about a dielectric property.

From the evaluation results in Table 4, in Examples 19 to 24, it was confirmed that the curable resin composition solution (varnish) containing maleimide having an indane skeleton was uniformly dissolved, and the curable resin composition solution (varnish) The film obtained by coating and drying has a uniform appearance, and it was confirmed that it can be used for applications such as circuit boards (copper-clad laminates, etc.), including build-up films in which the appearance uniformity of the obtained film is required. On the other hand, in Comparative Examples 3 to 4, since maleimide having no indan skeleton is used, which is a commercially available product, the appearance of the film is non-uniform, making it difficult to use for applications such as build-up films and circuit boards (copper clad laminates, etc.) that was confirmed

The curable resin composition of the present invention is suitable for use in heat-resistant members and electronic members since the cured product is excellent in heat resistance and dielectric properties, and in particular, semiconductor encapsulants, circuit boards, build-up films, and build-up substrates It can be used suitably for an adhesive agent or a resist material. Moreover, it can use suitably also for the matrix resin of fiber reinforced resin, and is suitable as a high heat-resistant prepreg.

Claims (8)

A curable resin composition comprising a maleimide (A) having an indane skeleton and a polyphenylene ether compound (B) having a reactive double bond. According to claim 1,
The said maleimide (A) is represented by following General formula (1), Curable resin composition characterized by the above-mentioned.

(In formula (1), each Ra is independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group or an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group, or an arylthio group having 3 to 10 carbon atoms. represents a cycloalkyl group, a halogen atom, a nitro group, a hydroxyl group or a mercapto group, and q represents an integer value of 0 to 4. When q is 2 to 4, Ra may be the same or different within the same ring. Independently, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group or alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or arylthio group, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group ; A cured product formed by curing the curable resin composition according to claim 1 or 2 to a curing reaction. A prepreg comprising a reinforcing base material and a semi-cured product of the curable resin composition according to claim 1 or 2 impregnated in the reinforcing base material. It is obtained by laminating|stacking the prepreg of Claim 4, and copper foil, and thermocompression-bonding, The circuit board characterized by the above-mentioned. The buildup film characterized by containing the curable resin composition in any one of Claims 1-3. The curable resin composition in any one of Claims 1-3 is contained, The semiconductor sealing material characterized by the above-mentioned. A semiconductor device comprising a cured product obtained by heating and curing the semiconductor encapsulant according to claim 7 .

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