JP2021021027A - Maleimide compound and method for producing the same, amide acid compound and method for producing the same, resin composition, cured product, resin sheet, prepreg, metal foil-clad laminate, printed wiring board, sealing material, fiber-reinforced composite material, adhesive, and semiconductor device - Google Patents

Abstract

To provide a maleimide compound that expresses excellent adhesiveness to a chip, a substrate or the like, and a method of producing the same.SOLUTION: The present invention relates to a maleimide compound represented by the formula (1) (where, R1 independently represent a hydrogen atom, a C1-6 linear or branched alkyl group, a halogen atom, a hydroxy group, or a C1-6 linear or branched alkoxy group, R2 is a hydrogen atom, or a C1-6 linear or branched alkyl group, R3 and R4 independently represent a hydrogen atom, a halogen atom, a C1-6 linear or branched alkyl group, or a C1-6 linear or branched alkenyl group. n is an integer of 1-30 and m independently represent an integer of 1-4).SELECTED DRAWING: None

Description

The present invention relates to a maleimide compound and its production method, an amic acid compound and its production method, a resin composition, a cured product, a resin sheet, a prepreg, a metal foil-clad laminate, a printed wiring board, a sealing material, and a fiber-reinforced composite material. , Adhesives, and semiconductor devices.

In recent years, the high integration and miniaturization of semiconductors widely used in electronic devices, communication devices, personal computers, etc. are accelerating. Along with this, various characteristics required for a laminated board for a semiconductor package used for a printed wiring board are becoming more and more severe. The required characteristics include, for example, adhesiveness to chips and substrates, low water absorption, heat resistance, flame retardancy, electrical characteristics (for example, low dielectric constant and low dielectric loss tangent), low coefficient of thermal expansion, heat resistance, and resistance. Examples include chemical properties and high plating peel strength.

Among them, maleimide compounds are known as resins or compounds for printed wiring boards having excellent heat resistance, electrical properties, and moisture resistance, and resin compositions in which a maleimide compound is used in combination with an epoxy resin or the like are used for semiconductor plastic packages and the like. Widely used as a material for highly functional printed wiring boards.
For example, Patent Document 1 describes that a resin composition containing a maleimide compound having a specific structure and other components is excellent in properties such as heat resistance, electrical properties, and moisture resistance.

JP-A-11-124488

However, the resin composition described in Patent Document 1 still has room for improvement from the viewpoint of adhesiveness to chips, substrates and the like. If the adhesiveness to chips and substrates is not sufficient, it is difficult to apply it to insulating materials used for printed wiring boards and the like, and applications that require high adhesion strength such as resin sheets.

The present invention has been made in view of the above problems, and a maleimide compound and a method for producing the same, an amic acid compound and the method for producing the same, a resin composition, and curing, which exhibit excellent adhesiveness to chips and substrates. It is an object of the present invention to provide an object, a resin sheet, a prepreg, a metal foil-clad laminate, a printed wiring board, a sealing material, a fiber-reinforced composite material, an adhesive, and a semiconductor device.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be achieved by a maleimide compound having a specific structure, and have completed the present invention.

That is, the present invention includes the following aspects.
[1] A maleimide compound represented by the following formula (1).

In formula (1), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. Alternatively, it indicates a branched alkoxy group, R ₂ indicates a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ each independently represent a hydrogen atom. , A halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 30, and m represents an integer of 1 to 4 independently of each other.
[2] The maleimide compound according to [1], which is represented by the following formula (2).

In the formula (2), n represents an integer of 1 to 30.
[3] The maleimide compound according to [1] or [2], which is a maleimide compound of an amine compound represented by the following formula (3).

In formula (3), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. Alternatively, it indicates a branched alkoxy group, and R ₂ indicates a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 30, and m represents an integer of 1 to 4 independently of each other.
[4] A method for producing a maleimide compound represented by the following formula (1), which comprises a step of dehydrating and ring-closing the amic acid compound represented by the following formula (4).

In formula (4), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. Alternatively, it indicates a branched alkoxy group, R ₂ indicates a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ each independently represent a hydrogen atom. , A halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 30. m represents an integer of 1 to 4 independently of each other.

In formula (1), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. Alternatively, it indicates a branched alkoxy group, R ₂ indicates a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ each independently represent a hydrogen atom. , A halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 30. m represents an integer of 1 to 4 independently of each other.
[5] An amic acid compound represented by the following formula (4).

In formula (4), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. Alternatively, it indicates a branched alkoxy group, R ₂ indicates a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ each independently represent a hydrogen atom. , A halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 30. m represents an integer of 1 to 4 independently of each other.
[6] An amic acid compound represented by the following formula (4), which comprises a step of addition-reacting an amine compound represented by the following formula (3) with an acid anhydride represented by the following formula (5). Production method.

In formula (3), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. Alternatively, it indicates a branched alkoxy group, and R ₂ indicates a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 30, and m represents an integer of 1 to 4 independently of each other.

In formula (5), R ₃ and R ₄ are independently hydrogen atoms, halogen atoms, linear or branched alkyl groups having 1 to 6 carbon atoms, or linear or branched alkyl groups having 1 to 6 carbon atoms. Shows a branched alkenyl group.

In formula (4), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. Alternatively, it indicates a branched alkoxy group, R ₂ indicates a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ each independently represent a hydrogen atom. , A halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 30, and m represents an integer of 1 to 4 independently of each other.
[7] A resin composition containing the maleimide compound according to any one of [1] to [3].
[8] Maleimide compounds other than the maleimide compound according to any one of [1] to [3], cyanate ester compounds, phenol resins, epoxy resins, oxetane resins, benzoxazine compounds, carbodiimide compounds, and ethylenically unsaturated groups. The resin composition according to [7], further comprising one or more selected from the group consisting of compounds having.
[9] The resin composition according to [7] or [8], further comprising a photocuring initiator.
[10] The resin composition according to any one of [7] to [9], further comprising a filler.

[11] A cured product containing the resin composition according to any one of [7] to [10].
[12] The support has a support and a resin layer arranged on one side or both sides of the support, and the resin layer contains the resin composition according to any one of [7] to [10]. Resin sheet.
[13] A prepreg containing a base material and the resin composition according to any one of [7] to [10], which is impregnated or coated on the base material.
[14] A layer containing at least one selected from the group consisting of the resin sheet according to [12] and the prepreg according to [13], and a metal foil arranged on one or both sides of the layer. A metal leaf-clad laminate in which the layer contains a cured product of the resin composition.
[15] It has an insulating layer and a conductor layer formed on one side or both sides of the insulating layer, and the insulating layer contains the resin composition according to any one of [7] to [10]. Multi-layer printed wiring board.

[16] A sealing material containing the resin composition according to any one of [7] to [10].
[17] A fiber-reinforced composite material containing the resin composition according to any one of [7] to [10] and reinforcing fibers.
[18] An adhesive containing the resin composition according to any one of [7] to [10].
[19] A semiconductor device having the resin composition according to any one of [7] to [10].

According to the present invention, a maleimide compound and a method for producing the same, an amic acid compound and the method for producing the same, a resin composition, a cured product, a resin sheet, a prepreg, and a metal foil covering, which exhibit excellent adhesiveness to chips and substrates. Laminated boards, printed wiring boards, sealing materials, fiber reinforced composite materials, adhesives, and semiconductor devices can be provided.

FIG. 1 is a ¹ H-NMR chart of the amic acid compound (MA-G328) obtained in Example 1. FIG. 2 is a ¹ H-NMR chart of the maleimide compound (BMI-G328) obtained in Example 1.

Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail, but the present invention is not limited thereto, and various modifications are made without departing from the gist thereof. Is possible.
As used herein, the term "(meth) acrylic" means both "acrylic" and the corresponding "methacrylic". "(Meta) acrylate" means both "acrylate" and its corresponding "methacrylate". "(Meta) allele" means both "allyl" and its corresponding "methallyl". Further, in the present embodiment, "resin solid content" or "resin solid content in the resin composition" refers to the photocuring initiator, additive, solvent and filler in the resin composition unless otherwise specified. The excluded components, and "100 parts by mass of resin solid content" means that the total of the components excluding the photocuring initiator, additives, solvent and filler in the resin composition is 100 parts by mass. And.

[Maleimide compound]
The maleimide compound of the present embodiment has a structure represented by the following formula (1). By having such a structure, the maleimide compound of the present embodiment can exhibit excellent adhesiveness to chips, substrates and the like. The maleimide compound of the present embodiment may be in the form of one type alone or a mixture of two or more types.

In the above formula (1), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. Shows a shaped or branched alkoxy group.

The linear or branched alkyl group having 1 to 6 carbon atoms is not particularly limited, and for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group, an isobutyl group, or sec-butyl. Examples include groups and tert-butyl groups. Among these, in addition to excellent adhesion to chips and substrates, it exhibits good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, and therefore has a high number of carbon atoms. Alkyl groups 1 to 4 are preferable, and methyl group, ethyl group, n-propyl group, and i-propyl group are more preferable.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The linear or branched alkoxy group having 1 to 6 carbon atoms is not particularly limited, and for example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a 2-methylpropoxy group. Groups include 1-methylpropoxy groups and tert-butoxy groups. Among these, in addition to excellent adhesion to chips and substrates, etc., it exhibits good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, and therefore has a high number of carbon atoms. Alkoxy groups 1 to 4 are preferable, and methoxy group, ethoxy group, n-propoxy group, and iso-propoxy group are more preferable.
As R ₁ , in addition to excellent adhesion to chips and substrates, hydrogen has good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. Atomic, methyl, ethyl, hydroxy, methoxy, and ethoxy groups are preferred, hydrogen atoms, methyl, and hydroxy groups are more preferred, and hydrogen atoms are even more preferred.

In the formula (1), R ₂ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.
As the linear or branched alkyl group having 1 to 6 carbon atoms, the above description of R ₁ can be referred to including a preferable embodiment.
As R ₂ , in addition to excellent adhesiveness to chips and substrates, hydrogen has good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. Atoms, methyl groups, and ethyl groups are preferred, hydrogen atoms and methyl groups are more preferred, and hydrogen atoms are even more preferred.

In the above formula (1), R ₃ and R ₄ are independently hydrogen atom, halogen atom, linear or branched alkyl group having 1 to 6 carbon atoms, or linear chain having 1 to 6 carbon atoms. Alternatively, it indicates a branched alkenyl group. R ₃ and R ₄ may all be the same or different.
As the halogen atom and the linear or branched alkyl group having 1 to 6 carbon atoms, the above description of R ₁ can be referred to.
The linear or branched alkenyl group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include a vinyl group, an allyl group, a 4-pentenyl group, an isopropenyl group, and an isopentyl group.
R ₃ and R ₄ exhibit good solubility in a solvent, low melting point, low water absorption, and good compatibility with other resins, in addition to excellent adhesion to chips and substrates. Therefore, each independently preferably has a hydrogen atom and a methyl group, and more preferably all of R ₃ and R ₄ are hydrogen atoms.

In the formula (1), n represents an integer of 1 to 30. As n, in addition to excellent adhesiveness to chips and substrates, it exhibits good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. An integer of 27 is preferable, and an integer of 1 to 25 is more preferable.

In the above equation (1), m independently represents an integer of 1 to 4. As m, in addition to excellent adhesiveness to chips and substrates, it exhibits good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. Therefore, R ₁ Is preferably a hydrogen atom, and therefore is preferably 4.

The maleimide compound of the present embodiment is not particularly limited as long as it exhibits the effects of the present invention, but has a mass average molecular weight in terms of good solubility in a solvent, low melting point, low water absorption, and good compatibility with other resins. However, it is preferably 100 to 100,000, and more preferably 500 to 30,000. In the present embodiment, the "mass average molecular weight" means the polystyrene standard equivalent mass average molecular weight by the gel permeation chromatography (GPC) method.

Normally, the maleimide compound has poor light transmittance. Therefore, when the resin composition described later contains the maleimide compound, the light does not sufficiently reach the photocuring initiator dispersed in the resin composition, and the photocuring initiator is used. It is difficult to generate radicals. Therefore, in general, the photoradical reaction of the maleimide compound is difficult to proceed, and even if the radical polymerization or dimerization reaction of the maleimide alone proceeds, the reactivity is very low. However, in the maleimide compound according to the present embodiment, the maleimide group is bonded to the aromatic ring via the methylene group, and the light transmittance is very excellent because the conjugate length is short. Therefore, the photocuring initiator Sufficient light reaches up to, and the photoradical reaction of maleimide occurs efficiently. When a chloroform solution containing 1% by mass of the maleimide compound was prepared and the light transmittance of this chloroform solution was measured using light with a wavelength of 405 nm (h line), the transmittance was 3% or more. Shows very good light transmittance. Therefore, for example, when a printed wiring board having a high-density and high-definition wiring formation (pattern) is manufactured by using the direct drawing exposure method, even when an active energy ray containing a wavelength of 405 nm (h line) is used. The photoradical reaction of maleimide occurs efficiently.

When an active energy ray containing a wavelength of 405 nm (h line) is used, the polymerization does not proceed unless the photocuring initiator absorbs the light having a wavelength of 405 nm (h line) and generates a radical. Therefore, in this case, as the photocuring initiator described later, the photocuring exhibiting an absorbance of 0.1 or more at a wavelength of 405 nm (h line) and extremely excellent absorption to light having a wavelength of 405 nm (h line). It is preferable to use an initiator.

Since the maleimide compound of the present embodiment has excellent light transmission as described above, for example, even when light having a wavelength of 405 nm is used, the light sufficiently reaches the photocuring initiator and the radicals generated from the photocuring initiator. The radical reaction using the above proceeds, and even a resin composition containing a large amount of maleimide compound can be photocured.
Since the cured product obtained by containing the resin composition of the present embodiment is excellent in photocurability, heat resistance and thermal stability, a protective film and an insulating layer can be suitably formed.

The maleimide compound of the present embodiment exhibits good solubility in a solvent, low melting point, low water absorption, and good compatibility with other resins, in addition to better adhesion to chips and substrates. Therefore, it is preferably expressed by the following formula (2). Further, the maleimide compound of the present embodiment has good solubility in a solvent, low melting point, low water absorption, and good compatibility with other resins, in addition to better adhesion to chips and substrates. Since it is expressed, it is also preferable that it is a maleimided product of an amine compound represented by the following formula (3).

In the formula (2), n represents an integer of 1 to 30. The preferred embodiment of n is the same as n in the above formula (1).

In the above formula (3), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. It represents a state or branched alkoxy group, and R ₂ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 30. m represents an integer of 1 to 4 independently of each other.
R ₁ , R ₂ , n, and m are the same as those in the above formula (1), including preferred embodiments.

[Method for producing maleimide compound]
The maleimide compound represented by the formula (1) of the present embodiment is not particularly limited, but is represented by, for example, the amine compound represented by the formula (3) and the following formula (5) as described later. By including the step of addition reaction with the acid anhydride, the amic acid compound represented by the following formula (4) is obtained, and then the obtained amic acid compound is dehydrated and ring-closed. be able to.

In the above formula (5), R ₃ and R ₄ are independently hydrogen atom, halogen atom, linear or branched alkyl group having 1 to 6 carbon atoms, or linear chain having 1 to 6 carbon atoms. Alternatively, it indicates a branched alkenyl group.
R ₃ and R ₄ are the same as those in the above formula (1), including preferred embodiments.

In the above formula (4), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. R ₂ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ each independently represent hydrogen. It indicates an atom, a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 30, and m represents an integer of 1 to 4 independently of each other.
R _{1 to} R ₄ , n, and m are the same as those in the above formula (1), including preferred embodiments.

By having a specific structure, the amic acid represented by the formula (4) can exhibit excellent adhesiveness to chips, substrates and the like.

(Method for synthesizing an amine compound represented by the above formula (3))
The amine compound represented by the formula (3) is not particularly limited, but can be obtained, for example, by the following synthetic method. That is, the excess diamine represented by the following formula (6) is reacted with epihalohydrin represented by the following formula (7) in the presence of an alkali metal hydroxide having a stoichiometry or higher, and the above formula (3) Synthesize the amino compound represented by.

In the above formula (6), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. Shows a shaped or branched alkoxy group. m represents an integer of 1 to 4 independently of each other.
R ₁ and m are the same as those in the above formula (1), including preferred embodiments.

In the formula (7), R ₂ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and X represents a chlorine atom or a bromine atom.
R ₂ is the same as the above formula (1) including a preferable embodiment.

The amount of diamine is usually 1 mol or more and preferably 1.5 mol or more and 6 mol or less with respect to 1 mol of epihalohydrin. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. These may be solid or aqueous solutions. The amount of alkali metal hydroxide is usually 1 mol or more and preferably 1 mol or more and 1.1 mol or less with respect to 1 mol of epihalohydrin. Since the reaction between diamine and epihalohydrin is usually an exothermic reaction, a method of dropping epihalohydrin into the diamine is preferable, and the reaction temperature is usually 50 ° C. or higher and 120 ° C. or lower, and 100 ° C. or higher and 120 ° C. or lower. Is preferable.

After completion of the reaction, primary alcohols such as butanol, pentanol, hexanol, heptanol, and octanol are added to the reaction system in combination with water, if desired, to dissolve the polyamino compound in the alcohol layer and the alkali metal halide in the aqueous layer. , Perform liquid separation. The amount of alcohol used for the liquid separation is not particularly limited, but is preferably 1 mol or more and 5 mol or less, and the amount of water is preferably 20 mol or more and 50 mol or less with respect to 1 mol of epihalohydrin. After adding alcohol and water to the reaction system, stirring may be carried out for the purpose of dissolving the alkali metal halide. After the liquid separation, alcohol is distilled off from the upper liquid layer to obtain an amine compound represented by the above formula (3). As the primary alcohol, one type may be used alone or two or more types may be used in combination, if necessary.

(Method for synthesizing an amic acid compound represented by the above formula (4))
The amic acid compound represented by the formula (4) is not particularly limited, but can be obtained by, for example, the following synthetic method. That is, it can be obtained by an addition reaction between the amine compound represented by the formula (3) obtained by the above synthesis method and the acid anhydride represented by the formula (5).

The acid anhydride represented by the formula (5) is not particularly limited, and is, for example, maleic anhydride, 3-methylmaleic anhydride, 3-ethylmaleic anhydride, 3,4-dimethylmaleic anhydride, 3 , 4-diethyl maleic anhydride, 3-chloromaleic anhydride, 3,4-dichloromaleic anhydride, and the like. These acid anhydrides may be used alone or in combination of two or more.
The amount of the acid anhydride represented by the formula (5) is usually 1.5 to 3.0 with respect to 1 mol of the amine compound represented by the formula (3) obtained by the above synthesis method. It is double molars, preferably 1.8 to 2.2 times moles.

In the addition reaction, the amine compound and the acid anhydride may be charged in the entire amount from the beginning, but since the reaction between the diamine compound and the acid anhydride is an exothermic reaction, excessive heat generation is performed by adding either one in small amounts. It is preferable to react while suppressing. More preferably, the acid anhydride is dissolved in a solvent, and the mixture is stirred under normal pressure (1 atm) so that the internal temperature of the reaction vessel is maintained in the range of 100 ° C. or lower, preferably 30 to 100 ° C. However, the amine compound is added dropwise. At this time, the amine compound of the raw material to be dropped may be dissolved in the same solvent as the reaction solvent. The dropping time of the raw material amine compound is preferably 5 to 180 minutes, but more preferably the entire amount is dropped in the range of 30 to 120 minutes. Further, the addition reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen, helium and argon.

Immediately after the completion of dropping the amine compound as a raw material, a dehydration ring-closing reaction of the produced amic acid compound may be carried out, but it is preferable to age the amic acid compound at 30 to 120 ° C. for about 0.5 to 3.0 hours. , 50 to 100 ° C. for 1.0 to 2.0 hours, and then dehydration ring closure reaction is more preferable.

The addition reaction is preferably carried out in an organic solvent. The organic solvent is not particularly limited, but for example, saturated hydrocarbons such as pentane, hexane, heptane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; dichloromethane, chloroform, carbon tetrachloride. , Dichloroethane, chlorobenzene, and halogenated hydrocarbons such as dichlorobenzene; diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane. , Bis [2- (2-methoxyethoxy) ethyl] ethers, tetrahirodofuran, 1,3-dioxane, 1,4-dioxane, and ethers such as anisole; phenol, o-chlorophenol, m-chlorophenol , P-chlorophenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, Solvents such as 3,4-xylenol, and 3,5-xylenoal; N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, And amides such as hexamethylphosphoramide; lactams such as N-methylpyrrolidone (NMP) and N-methylcaprolactam; sulfur-containing solvents such as dimethylsulfoxide, diphenylsulfoxide, dimethylsulfone, diphenylsulfone, and sulfolane; Examples thereof include 1,3-dimethyl-2-imidazolidinone. These organic solvents may be used alone or in combination of two or more.

In addition, the following solvents may coexist with these organic solvents. Examples of such organic solvents include benzene, toluene, o-xylene, m-xylene, p-xylene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, and m-bromotoluene. , P-Bromotoluene, chlorobenzene, bromobenzene and the like. They act as an azeotropic solvent for removing (dehydrating) the water produced in the reaction solution. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent used is not particularly limited and varies depending on the solvent type and composition used, but is usually 1 to 1000 parts by mass, preferably 1 part by mass with respect to 1 part by mass of the total of the amine compound and the acid anhydride as raw materials. ~ 100 parts by mass. The reaction solvent is preferably a solution in which the raw materials are dissolved, but the reaction may be carried out in a slurry state.

(Method for synthesizing maleimide compound represented by the above formula (1))
The maleimide compound represented by the formula (1) is not particularly limited, but can be obtained, for example, by the following synthetic method. That is, it can be obtained by dehydrating and ring-closing the amic acid compound represented by the formula (4) obtained by the above synthesis method. The dehydration ring closure reaction is preferably carried out in an organic solvent. As the organic solvent, the solvent used in the addition reaction can be referred to, and it may be the same as or different from the solvent used in the addition reaction.

The dehydration ring closure reaction is preferably carried out in the presence of an organic base catalyst, an acid catalyst, or an imidizing agent, if necessary.

Examples of the organic base catalyst include triethylamine, tributylamine, trypentylamine, N, N-dimethylaniline, N, N-diethylaniline, pyridine, α-picoline, β-picoline, γ-picoline, and 2,4-lutidine. Included are 2,6-lutidine, quinoline, and isoquinoline. One of these organic base catalysts can be used alone or in combination of two or more.
Acid catalysts include, for example, inorganic acids such as hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, anhydrous sulfuric acid, nitrate, phosphoric acid, phosphite, phosphoric acid, and molybdenum phosphate; methanesulfonic acid, ethanesulfonic acid. Sulfonic acids such as acids, trifluoromethanesulfonic acids, benzenesulfonic acids, and p-toluenesulfonic acids; carboxylic acids such as acetic acid and oxalic acid; chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, difluoroacetic acid, and trifluoro Examples thereof include halogenated carboxylic acids such as acetic acid; solid acids such as silica, alumina, and active white clay; cationic ion exchange resins and the like. Further, these acid catalysts may be salts with a diamine compound. Of these, sulfuric acid, phosphoric acid, and p-toluenesulfonic acid are preferred. These acid solvents may be used alone or in combination of two or more.
The amount of the organic base catalyst and the acid catalyst used is not particularly limited as long as the reaction rate of the dehydration ring closure reaction is substantially improved, but is usually 0.001 to 10 times the molar amount of the amine compound as a raw material. It is preferably 005 to 5 times mol, more preferably 0.01 to 1 time mol.

As the imidizing agent, for example, a known method in which acetic anhydride or the like is used as a dehydrating agent and the reaction is carried out in an organic solvent in the presence of a catalyst and a base (for example, Japanese Patent Publication No. 46-23250, Japanese Patent Publication No. 49-40231). No. and the method described in Japanese Patent Publication No. 59-52660) can be used. Further, as the imidizing agent, a condensing agent such as polyphosphoric acid and dicyclohexylcarbodiimide can also be used.

When a dehydrating agent (acetic anhydride or the like) is used as the imidizing agent, the amount used is not particularly limited, but is usually 1.0 to 10 times the molar amount of 1 mol of the raw material amine compound. It is preferably 1.8 to 6.0 times the molar amount, more preferably.
Examples of the catalyst include oxides of alkaline earth metals, iron (II and III), nickel (II), manganese (II and III), copper (I and II) or cobalt (II and III) carbonates. Examples include salts, sulfates, phosphates, acetates and the like. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is not particularly limited, but is usually 5 × 10 ^{-4 to} 0.1 mol per 1 mol of the amic acid compound.
Examples of the base include sodium acetate, potassium acetate, trimethylamine, triethylamine, tributylamine and the like. These bases can be used alone or in combination of two or more. The amount of the base used is not particularly limited, but is usually 0.05 to 1.1 mol with respect to 1 mol of the amic acid compound.

The reaction temperature and reaction time in the dehydration ring closure reaction vary depending on the type of raw material used, the type of solvent, the type of catalyst, the type and amount of azeotropic dehydration solvent, and the type and amount of imidizing agent. 1 to 24 hours in the range of 20 to 180 ° C. The reaction pressure is not particularly limited, but may be usually atmospheric pressure. The reaction atmosphere is not particularly limited, but is usually under an air, nitrogen, helium, neon, or argon atmosphere, and the reaction is preferably carried out under an inert gas such as nitrogen or argon.

The method for isolating the target maleimide compound from the reaction mixture containing the maleimide compound is not particularly limited, but when the target product is precipitated from the reaction solvent, it can be isolated by filtration or centrifugation. .. On the other hand, when the target product is dissolved in the reaction solvent, the solvent is distilled off under reduced pressure, an appropriate poor solvent is added to the reaction mixture, or the reaction mixture is discharged into the poor solvent to cause precipitation. It can be isolated by filtration or centrifugation.
When it is necessary to further purify the isolated maleimide compound, it may be purified by a known method. Examples of such a method include a distillation purification method, a recrystallization method, a column chromatography method, a sludge treatment, and an activated carbon treatment.

The obtained maleimide compound can be identified by a known method such as NMR (nuclear magnetic resonance analysis). The purity of the maleimide compound can be analyzed by, for example, liquid chromatography or IR spectral method. Volatile components such as by-products and residual solvents in the maleimide compound can be quantitatively analyzed by, for example, gas chromatography. The halogen compound remaining in the maleimide compound can be identified by, for example, a liquid chromatograph mass spectrometer, and can be quantified by ion chromatography after potentiometric titration using a silver nitrate solution or decomposition by a combustion method. .. The polymerization reactivity of the maleimide compound can be evaluated by, for example, the reaction enthalpy by differential scanning calorimetry and the gelation time by the hot plate method or the torque measurement method.

[Resin composition]
The resin composition of the present embodiment contains the maleimide compound of the present embodiment. Since it is configured in this way, the resin composition of the present embodiment can exhibit excellent adhesiveness to chips, substrates and the like. In the present embodiment, from the viewpoint of obtaining better adhesiveness to chips, substrates and the like, the content of the maleimide compound of the present embodiment is 5 parts by mass or more with respect to 100 parts by mass of the resin composition of the present embodiment. It is preferably, more preferably 10 parts by mass or more. The content of the maleimide compound of the present embodiment is not particularly limited, but is, for example, 90 parts by mass or less.

[Resin or compound]
The resin composition of the present embodiment is a resin or a compound other than the maleimide compound of the present embodiment, which is a maleimide compound (hereinafter, also referred to as “another maleimide compound”), a cyanate ester compound, a phenol resin, an epoxy resin, or oxetane. Further, one or more selected from the group consisting of a resin, a benzoxazine compound, a carbodiimide compound, and a compound having an ethylenically unsaturated group can be further contained. Hereinafter, each of these components will be described.

(Other maleimide compounds)
The other maleimide compound is not particularly limited as long as it is a compound other than the maleimide compound of the present embodiment and has one or more maleimide groups in the molecule. Specific examples include, for example, N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-carboxyphenylmaleimide, N- (4-carboxy-3-hydroxyphenyl) maleimide, 6-maleimidehexanoic acid, 4 -Maleimide butyric acid, bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, 4,4-diphenylmethanebismaleimide, bis (3,5-dimethyl-4-4) Maleimidephenyl) methane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene Bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis (4- (4-maleimide phenoxy) -phenyl) propane, 3 , 3-Dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,2-bismaleimideethane, 1,4-bismaleimidebutane, 1,6 -Bismaleimide hexane, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 1,8-bismaleimide-3,6-dioxaoctane, 1,11-bismaleimide-3,6,9 -Trioxaundecane, 1,3-bis (maleimidemethyl) cyclohexane, 1,4-bis (maleimidemethyl) cyclohexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylsulphon bismaleimide, 1,3-bis ( 3-Maleimide phenoxy) benzene, 1,3-bis (4-maleimide phenoxy) benzene, 4,4-diphenylmethane biscitraconimide, 2,2-bis [4- (4-citraconimide phenoxy) phenyl] propane, bis ( 3,5-Dimethyl-4-citraconimidephenyl) methane, bis (3-ethyl-5-methyl-4-citraconimidephenyl) methane, bis (3,5-diethyl-4-citraconimidephenyl) methane, polyphenyl Methanemaleimide, polyphenylmethanemaleimide, maleimide compound represented by the following formula (8), maleimide compound represented by the following formula (9), represented by the following formula (10). Maleimide compounds represented by the following formula (11), maleimide compounds represented by the following formula (18), and other maleimide compounds represented by the following formula (12), represented by the following formula (13). Maleimide compound, maleimide compound represented by the following formula (14), maleimide compound represented by the following formula (15), 1,6-bismaleimide- (2,2,4-trimethyl) hexane (following formula (16)) (Maleimide compound represented by), a maleimide compound represented by the following formula (17), fluorescein-5-maleimide, a prepolymer of these maleimide compounds, a prepolymer of a maleimide compound and an amine compound, and the like. These other maleimide compounds may be used alone or in admixture of two or more.

In the formula (8), the plurality of R _5, each independently, represent a hydrogen atom or a methyl group. n ₁ represents an integer of 1 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.

In the formula (9), a plurality of R ₆ each independently represent a hydrogen atom or a methyl group. n ₂ represents an integer of 1 or more, preferably an integer of 1-5.

In the formula (10), n ₃ (average) is 1 or more, preferably 1 to 21, and more preferably 1 to 16 from the viewpoint of exhibiting excellent photocurability.

In the formula (11), the number of x is 10 to 35.
In the formula (11), the number of y is 10 to 35.

In the formula (12), Ra represents ^a linear or branched alkyl group having 1 to 16 carbon atoms or a linear or branched alkenyl group having 1 to 16 carbon atoms. R ^a is preferably ^a linear or branched alkyl group, and more preferably a linear alkyl group because it exhibits excellent photocurability.
The number of carbon atoms of the alkyl group is preferably 1 to 16, and more preferably 4 to 12 because it exhibits excellent photocurability.
The number of carbon atoms of the alkenyl group is preferably 1 to 16, and more preferably 4 to 12 because it exhibits excellent photocurability.

As the linear or branched alkyl group, the description of R ₁ in the above formula (1) can be referred to. Among these, an n-heptyl group, an n-octyl group, and an n-nonyl group are preferable, and an n-octyl group is more preferable, because they exhibit excellent photocurability.
As the linear or branched alkenyl group, the description of R ₁ in the above formula (1) can be referred to. Among these, 2-heptenyl group, 2-octenyl group and 2-nonenyl group are preferable, and 2-octenyl group is more preferable, because they show excellent photocurability.

In the formula (12), R ^b represents a linear or branched alkyl group having 1 to 16 carbon atoms or a linear or branched alkenyl group having 1 to 16 carbon atoms. R ^b is preferably a linear or branched alkyl group, and more preferably a linear alkyl group because it exhibits excellent photocurability.
The number of carbon atoms of the alkyl group is preferably 1 to 16, and more preferably 4 to 12 because it exhibits excellent photocurability.
The number of carbon atoms of the alkenyl group is preferably 1 to 16, and more preferably 4 to 12 because it exhibits excellent photocurability.

As a specific example of the alkyl group, the alkyl group in ^Ra can be referred to. Among these, an n-heptyl group, an n-octyl group, and an n-nonyl group are preferable, and an n-octyl group is more preferable, because they exhibit excellent photocurability.
As a specific example of the alkenyl group, the alkenyl group in ^Ra can be referred to. Among these, 2-heptenyl group, 2-octenyl group and 2-nonenyl group are preferable, and 2-octenyl group is more preferable, because they show excellent photocurability.

In the formula (12), the number of n _a is 1 or more, preferably 2 to 16, and more preferably 3 to 14 from the viewpoint of exhibiting excellent photocurability.

In the formula (12), the number of n _b is 1 or more, preferably 2 to 16, and more preferably 3 to 14 from the viewpoint of exhibiting excellent photocurability.

The numbers n _a and n _b may be the same or different.

In the formula (13), n ₄ (average) is 0.5 or more, preferably 0.8 to 10, and more preferably 1 to 8 from the viewpoint of exhibiting excellent photocurability.

In equation (14), n ₅ represents an integer of 1 or more, preferably an integer of 1-10.

In equation (15), n ₆ represents an integer of 1 or more, preferably an integer of 1-10.

(In the above formula (17), R ₇ independently represents a hydrogen atom, a methyl group, or an ethyl group, and R ₈ independently represents a hydrogen atom or a methyl group.)

Commercially available products can also be used as other maleimide compounds.
Examples of the maleimide compound represented by the formula (8) include BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd.
Examples of the maleimide compound represented by the formula (9) include MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd.
The maleimide compound represented by the formula (10), for example, KI Kasei Co., Ltd. BMI-1000P (trade name, n ₃ = 13.6 (average in formula (10))), KI BMI-650P manufactured by Kasei Co., Ltd. (trade name, n ₃ = 8.8 (average) in formula (10)), BMI-250P manufactured by KI Kasei Co., Ltd. (trade name, formula (10)) N ₃ = 3 to 8 (average)), CUA-4 manufactured by KI Kasei Co., Ltd. (trade name, n ₃ = 1 in formula (10)) and the like.
Examples of the maleimide compound represented by the formula (11) include Designer Moleculars Inc. BMI-6100 manufactured by BMI-6100 (trade name, x = 18, y = 18 in the formula (11)) and the like can be mentioned.
Examples of the maleimide compound represented by the formula (12) include Designer Molecules Inc. BMI-689 (trade name, the following formula (18), functional group equivalent: 346 g / eq.) And the like can be mentioned.

Examples of the maleimide compound represented by the formula (13) include Designer Moleculars Inc. BMI-1500 manufactured by BMI-1500 (trade name, n ₄ = 1.3 in the formula (13), functional group equivalent: 754 g / eq.) And the like can be mentioned.
As the maleimide compound represented by the formula (14), a commercially available product can also be used, and for example, Designer Molecules Inc. BMI-1700 (trade name) manufactured by (DMI) can be mentioned.
As the maleimide compound represented by the formula (15), a commercially available product can also be used, and for example, Designer Molecules Inc. (DMI) BMI-3000 (trade name), Designer Moleculars Inc. BMI-5000 (trade name) manufactured by (DMI), Designer Moleculars Inc. BMI-9000 (trade name) manufactured by (DMI) can be mentioned.
As the maleimide compound represented by the formula (16), a commercially available product can also be used, and examples thereof include BMI-TMH (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd.
As the maleimide compound represented by the formula (17), a commercially available product can also be used, and examples thereof include BMI-70 (trade name) manufactured by KI Kasei Co., Ltd.
These other maleimide compounds may be used alone or in admixture of two or more.

In the resin composition according to the present embodiment, the total content of the other maleimide compounds other than the maleimide compound of the present embodiment is not particularly limited, but from the viewpoint of obtaining better adhesiveness to the chip, the substrate and the like. The resin solid content in the resin composition of the present embodiment is preferably 0.01 to 95 parts by mass, more preferably 1 to 90 parts by mass with respect to 100 parts by mass of the resin solid content.

(Cyanic acid ester compound)
The cyanate ester compound is not particularly limited as long as it is a resin having an aromatic moiety in the molecule in which at least one cyanato group (cyanic acid ester group) is substituted.

For example, the one represented by the equation (19) can be mentioned.

In formula (19), Ar ₁ represents a benzene ring, a naphthalene ring, or a single bond of two benzene rings. When there are a plurality of them, they may be the same or different from each other. Ra independently has a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and 1 to 6 carbon atoms. Indicates a group in which an alkyl group and an aryl group having 6 to 12 carbon atoms are bonded. The aromatic ring in Ra may have a substituent, and the substituent in Ar ₁ and Ra can be selected at any position. p indicates the number of cyanato groups attached to Ar ₁ , and each is an integer of 1 to 3 independently. q represents the number of Ra to bind to Ar _1, the 4-p when Ar ₁ is a benzene ring, when the naphthalene ring when those 6-p, 2 one benzene ring is a single bond is 8-p .. t indicates the average number of repetitions and is an integer of 0 to 50, and the cyanate ester compound may be a mixture of compounds having different t. If there are a plurality of X, each of them is independently a single bond, a divalent organic group having 1 to 50 carbon atoms (the hydrogen atom may be replaced with a hetero atom), and a divalent group having 1 to 10 nitrogen atoms. Organic group (for example, -N-RN- (where R indicates an organic group)), carbonyl group (-CO-), carboxy group (-C (= O) O-), carbonyl dioxyside group ( -OC (= O) O-), sulfonyl group (-SO _2- ), divalent sulfur atom or divalent oxygen atom.

The alkyl group in Ra of the formula (19) may have either a linear or branched chain structure or a cyclic structure (for example, a cycloalkyl group).
Further, even if the hydrogen atom in the alkyl group in the formula (19) and the aryl group in Ra is substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group. Good.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group and 2,2-dimethylpropyl group. Examples thereof include a group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a trifluoromethyl group and the like.
Specific examples of the alkenyl group include vinyl group, (meth) allyl group, isopropenyl group, 1-propenyl group, 2-butenyl group, 3-butenyl group, 1,3-butandienyl group and 2-methyl-2-propenyl. , 2-Pentenyl group, 2-hexenyl group and the like.
Specific examples of the aryl group include phenyl group, xsilyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group and trifluorophenyl. Groups, methoxyphenyl groups, o-, m- or p-tolyl groups and the like can be mentioned.
Examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like.

Specific examples of the divalent organic group having 1 to 50 carbon atoms in X of the formula (19) include methylene group, ethylene group, trimethylene group, cyclopentylene group, cyclohexylene group, trimethylcyclohexylene group and biphenylylmethylene. Examples thereof include a group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluorinatedyl group, a phthalidodiyl group and the like. The hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group or the like.
Examples of the divalent organic group having a nitrogen number of 1 to 10 in X of the formula (19) include an imino group and a polyimide group.

Further, examples of the organic group of X in the formula (19) include those having a structure represented by the following formula (20) or the following formula (21).

In the formula (20), Ar ₂ represents a benzenediyl group, a naphthalenediyl group or a biphenyldiyl group, and when u is 2 or more, they may be the same or different from each other. Rb, Rc, Rf, and Rg each independently have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or an aryl having at least one phenolic hydroxy group. Indicates a group. Rd and Re are independently selected from one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a hydroxy group. .. u represents an integer from 0 to 5.

In the formula (21), Ar ₃ represents a benzenediyl group, a naphthalenediyl group or a biphenyldiyl group, and when v is 2 or more, they may be the same or different from each other. Ri and Rj are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, benzyl groups, alkoxyl groups having 1 to 4 carbon atoms, hydroxy groups, trifluoromethyl groups, respectively. Alternatively, it indicates an aryl group in which at least one cyanato group is substituted. v represents an integer from 0 to 5, but may be a mixture of compounds in which v is different.

Further, as X in the formula (19), a divalent group represented by the following formula can be mentioned.

Here, in the formula, z represents an integer of 4 to 7. Each Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
As specific examples of Ar _{2 of the} formula (20) and Ar ₃ of the formula (21), two carbon atoms represented by the formula (20) or two oxygen atoms represented by the formula (21) are 1,4. A benzenediyl group bonded to the position or 1,3 position, the two carbon atoms or two oxygen atoms at the 4,4'position, the 2,4'position, the 2,2'position, the 2,3'position, The biphenyldiyl group bonded to the 3,3'position or the 3,4'position and the two carbon atoms or two oxygen atoms are located at the 2,6, 1,5, 1,6 positions, Examples thereof include a naphthalenediyl group bonded to the 1,8, 1,3, 1,4, or 2,7 positions.
The alkyl and aryl groups in Rb, Rc, Rd, Re, Rf and Rg of formula (20) and Ri and Rj of formula (21) are synonymous with those in formula (19).

Specific examples of the cyanato-substituted aromatic compound represented by the above formula (19) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1-. Sianato-2-,1-Cyanato-3-, or 1-Cyanato-4-methoxybenzene, 1-Cyanato-2,3-,1-Cyanato-2,4-,1-Cyanato-2,5-,1 -Cyanato-2,6-, 1-Cyanato-3,4- or 1-Cyanato-3,5-dimethylbenzene, Cyanatoethylbenzene, Cyanatobutylbenzene, Cyanatooctylbenzene, Cyanatononylbenzene, 2-( 4-Cianaphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-2- or 1-cyanato -3-Chlorobenzene, 1-Cyanato-2,6-dichlorobenzene, 1-Cyanato-2-methyl-3-chlorobenzene, Cyanatonitrobenzene, 1-Cyanato-4-nitro-2-ethylbenzene, 1-Cyanato-2- Methoxy-4-allylbenzene (cyanate of eugenol), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl, 1-cyanato-2- or 1-cyanato- 4-Acetylbenzene, 4-Cyanatobenzaldehyde, 4-Cyanato benzoic acid methyl ester, 4-Cyanato benzoic acid phenyl ester, 1-Cyanato-4-acetaminobenzene, 4-Cyanatobenzophenone, 1-Cyanato-2,6 -Di-tert-butylbenzene, 1,2-disyanatobenzene, 1,3-disyanatobenzene, 1,4-disyanatobenzene, 1,4-disyanato-2-tert-butylbenzene, 1,4-disianato -2,4-dimethylbenzene, 1,4-disyanato-2,3,4-dimethylbenzene, 1,3-disyanato-2,4,6-trimethylbenzene, 1,3-disyanato-5-methylbenzene, 1 -Cyanato or 2-cyanatonaphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methoxynaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2'-disicanato-1,1'-binaphthyl, 1,3-,1,4-,1,5-,1,6-,1,7-,2,3-,2,6- or 2,7-disianatocinaphthalene, 2,2'-or 4,4'-Je Cyanatobiphenyl, 4,4'-disianato octafluorobiphenyl, 2,4'-or 4,4'-disianatodiphenylmethane, bis (4-cyanato-3,5-dimethylphenyl) methane, 1,1-bis (4-Cyanatophenyl) ethane, 1,1-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanato-3-methyl) Phenyl) propane, 2,2-bis (2-cyanato-5-biphenylyl) propane, 2,2-bis (4-cyanatophenyl) hexafluoropropane, 2,2-bis (4-cyanato-3,5) -Dimethylphenyl) Propane, 1,1-bis (4-cyanatophenyl) butane, 1,1-bis (4-cyanatophenyl) isobutane, 1,1-bis (4-cyanatophenyl) pentane, 1, 1-bis (4-Cyanatophenyl) -3-methylbutane, 1,1-bis (4-Cyanatophenyl) -2-methylbutane, 1,1-bis (4-Cyanatophenyl) -2,2-dimethyl Propane, 2,2-bis (4-cyanatophenyl) butane, 2,2-bis (4-cyanatophenyl) pentane, 2,2-bis (4-cyanatophenyl) hexane, 2,2-bis ( 4-Cyanatophenyl) -3-methylbutane, 2,2-bis (4-cyanatophenyl) -4-methylpentane, 2,2-bis (4-cyanatophenyl) -3,3-dimethylbutane, 3 , 3-bis (4-cyanatophenyl) hexane, 3,3-bis (4-cyanatophenyl) heptane, 3,3-bis (4-cyanatophenyl) octane, 3,3-bis (4-si) Anatophenyl) -2-methylpentane, 3,3-bis (4-cyanatophenyl) -2-methylhexane, 3,3-bis (4-cyanatophenyl) -2,2-dimethylpentane, 4,4 -Bis (4-Cyanatophenyl) -3-methylheptane, 3,3-bis (4-Cyanatophenyl) -2-methylheptane, 3,3-bis (4-Cyanatophenyl) -2,2- Dimethylhexane, 3,3-bis (4-cyanatophenyl) -2,4-dimethylhexane, 3,3-bis (4-cyanatophenyl) -2,2,4-trimethylpentane, 2,2-bis (4-Cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-cyanatophenyl) phenylmethane, 1,1-bis (4-cyanatophenyl) -1- Phenyl ethane, bis ( 4-Cyanatophenyl) biphenylmethane, 1,1-bis (4-cyanatophenyl) cyclopentane, 1,1-bis (4-cyanatophenyl) cyclohexane, 2,2-bis (4-cyanato-3-3) Isopropylphenyl) Propane, 1,1-bis (3-cyclohexyl-4-cyanatophenyl) cyclohexane, bis (4-cyanatophenyl) diphenylmethane, bis (4-cyanatophenyl) -2,2-dichloroethylene, 1, 3-Bis [2- (4-Cyanatophenyl) -2-propyl] benzene, 1,4-Bis [2- (4-Cyanatophenyl) -2-propyl] benzene, 1,1-Bis (4- Cyanatophenyl) -3,3,5-trimethylcyclohexane, 4- [bis (4-cyanatophenyl) methyl] biphenyl, 4,4-disianatobenzophenone, 1,3-bis (4-cyanatophenyl)- 2-Propen-1-one, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) sulfone, 4-cyanato benzoic acid-4-cyanatophenyl ester (4-Cyanatophenyl-4-Cyanatobenzoate), bis- (4-Cyanatophenyl) carbonate, 1,3-bis (4-Cyanatophenyl) adamantan, 1,3-bis (4-Cyanatophenyl) ) -5,7-Dimethyladamantan, 3,3-bis (4-cyanatophenyl) isobenzofuran-1 (3H) -one (cyanate of phenolphthaline), 3,3-bis (4-cyanato-3-) Methylphenyl) Isobenzofuran-1 (3H) -one (cyanate of o-cresolphthaline), 9,9'-bis (4-cyanatophenyl) fluorene, 9,9-bis (4-cyanato-3-methyl) Phenyl) fluorene, 9,9-bis (2-cyanato-5-biphenylyl) fluorene, tris (4-cyanatophenyl) methane, 1,1,1-tris (4-cyanatophenyl) ethane, 1,1 , 3-Tris (4-Cyanatophenyl) Propane, α, α, α'-Tris (4-Cyanatophenyl) -1-ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis (4- Cyanatophenyl) ethane, tetrakis (4-cyanatophenyl) methane, 2,4,6-tris (N-methyl-4-cyanatoanilino) -1,3,5-triazine, 2,4-bis (N-methyl) -4-Cyanatoanilino) -6- (N-methylani) Reno) -1,3,5-triazine, bis (N-4-cyanato-2-methylphenyl) -4,4'-oxydiphthalimide, bis (N-3-cyanato-4-methylphenyl) -4, 4'-oxydiphthalimide, bis (N-4-cyanatophenyl) -4,4'-oxydiphthalimide, bis (N-4-cyanato-2-methylphenyl) -4,4'-(hexafluoroisopropi) Liden) diphthalimide, tris (3,5-dimethyl-4-cyanatobenzyl) isocyanurate, 2-phenyl-3,3-bis (4-cyanatophenyl) phthalimidine, 2- (4-methylphenyl) -3 , 3-Bis (4-Cyanatophenyl) Phenylimidine, 2-Phenyl-3,3-Bis (4-Cyanato-3-methylphenyl) Phenylimidine, 1-Methyl-3,3-Bis (4-Cyanatophenyl) Indolin-2-one and 2-phenyl-3,3-bis (4-cyanatophenyl) indolin-2-one can be mentioned.

These cyanate ester compounds may be used alone or in admixture of two or more.

As another specific example of the cyanate ester compound represented by the formula (19), a phenol novolac resin, a cresol novolak resin (by a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin, paraformaldehyde, etc.) Formaldehyde compound of (reacted in an acidic solution), trisphenol novolac resin (reacted hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), fluorennovolak resin (fluorenone compound and 9,9- bis (hydroxyaryl) that the fluorenes were reacted in the presence of an acid catalyst), phenol aralkyl resins, cresol aralkyl resin, naphthol aralkyl resin and a biphenyl aralkyl resin (by known _{methods, Ar 4 - (CH 2 Y} ) ₂ (Ar ₄ indicates a phenyl group and Y indicates a halogen atom. The same shall apply hereinafter in this paragraph.) A reaction of a bishalogenomethyl compound and a phenol compound as represented by an acidic catalyst or no catalyst. _{, Ar 4 - (CH 2 oR} ) 2 as (where. R is showing an alkyl group) obtained by reacting a bis as represented by (alkoxymethyl) compound and a phenol compound in the presence of an acidic catalyst, or, Ar ₄ - (CH ₂ OH) bis (hydroxymethyl) as represented by _two things compound and a phenol compound is reacted in the presence of an acidic catalyst, or a heavy and aromatic aldehyde compound and aralkyl compound with a phenol compound Condensed), phenol-modified xyleneformaldehyde resin (reacted xyleneformaldehyde resin and phenolic compound in the presence of an acidic catalyst by a known method), modified naphthaleneformaldehyde resin (naphthaleneformaldehyde resin by a known method) And a hydroxy-substituted aromatic compound reacted in the presence of an acidic catalyst), a phenol-modified dicyclopentadiene resin, and a phenol resin having a polynaphthylene ether structure (a phenolic hydroxy group is contained in one molecule by a known method). Phenolic resins such as those obtained by dehydrating and condensing two or more polyvalent hydroxynaphthalene compounds in the presence of a basic catalyst) are cyanated by the same method as described above, and these prepolymers and the like are mentioned. Be done. These are not particularly limited. These cyanate ester compounds may be used alone or in admixture of two or more.

The method for producing these cyanate ester compounds is not particularly limited, and known methods can be used. An example of such a production method is a method in which a hydroxy group-containing compound having a desired skeleton is obtained or synthesized, and the hydroxy group is modified by a known method to cyanate. Examples of the method for cyanating a hydroxy group include the methods described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins," Blackie Academic & Professional.

The cured resin product using these cyanate ester compounds has excellent properties such as glass transition temperature, low thermal expansion property, and plating adhesiveness.

In the resin composition according to the present embodiment, the total content of the cyanate ester compound is not particularly limited, but is preferably 0.01 to 100 parts by mass of the resin solid content in the resin composition of the present embodiment. It is 60 parts by mass.

(Phenol resin)
As the phenol resin, generally known phenol resins can be used as long as they have two or more hydroxyl groups in one molecule. For example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl Aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolak type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type Phenolic resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, polymerizable unsaturated hydrocarbon group-containing phenol resin, hydroxyl group-containing silicone resin, etc. These are mentioned, but are not particularly limited. These phenol resins can be used alone or in admixture of two or more.

In the resin composition according to the present embodiment, the total content of the phenol resin is not particularly limited, but is preferably 0.01 to 60 mass by mass in 100 parts by mass of the resin solid content in the resin composition of the present embodiment. It is a department.

(Epoxy resin)
The epoxy resin is not particularly limited, and generally known epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Xylene novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, trifunctional phenol type epoxy resin 4, Functional phenol type epoxy resin, triglycidyl isocyanurate, glycidyl ester type epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, phenol aralkylnovolac type epoxy resin, naphthol aralkylnovolac type Epoxy resin, aralkyl novolac type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, compound with epoxidized double bond such as glycidylamine, butadiene, hydroxyl group-containing silicone Examples thereof include compounds obtained by reacting resins with epichlorohydrin, and epoxies thereof. These epoxy resins can be used alone or in admixture of two or more.

In the resin composition according to the present embodiment, the total content of the epoxy resin is not particularly limited, but is preferably 0.01 to 60 mass by mass in 100 parts by mass of the resin solid content in the resin composition of the present embodiment. It is a department.

(Oxetane resin)
As the oxetane resin, generally known ones can be used. For example, alkyl oxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di (trifluoro). Methyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (manufactured by Toa Synthetic Co., Ltd., trade name), and OXT-121 (Toa Synthetic Co., Ltd.) Manufactured, trade name), etc. are not particularly limited. These oxetane resins can be used alone or in admixture of two or more.

In the resin composition according to the present embodiment, the total content of the oxetane resin is not particularly limited, but is preferably 0.01 to 40 mass by mass in 100 parts by mass of the resin solid content in the resin composition of the present embodiment. It is a department.

(Benzooxazine compound)
As the benzoxazine compound, a generally known compound can be used as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol F type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol S type benzoxazine BS-BXZ (Konishi). Chemical Co., Ltd., trade name), phenolphthaline-type benzoxazine, etc., but are not particularly limited. These benzoxazine compounds may be used alone or in admixture of two or more.

In the resin composition according to the present embodiment, the total content of the benzoxazine compound is not particularly limited, but is preferably 0.01 to 40 in 100 parts by mass of the resin solid content in the resin composition of the present embodiment. It is a mass part.

(Carbodiimide compound)
The carbodiimide compound is not particularly limited as long as it has at least one or more carbodiimide groups in the molecule, and generally known compounds can be used. For example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, N, N'-di-2,6 Polycarbodiimides such as -diisopropylphenylcarbodiimide, 2,6,2', 6'-tetraisopropyldiphenylcarbodiimide, cyclic carbodiimide, carbodilite (registered trademark: manufactured by Nisshinbo Chemical Co., Ltd.), and stavaxol (registered trademark: LANXESS Deutschland GmbH). And so on. These carbodiimide compounds may be used alone or in admixture of two or more.

In the resin composition according to the present embodiment, the total content of the carbodiimide compound is not particularly limited, but is preferably 0.01 to 40 mass by mass in 100 parts by mass of the resin solid content in the resin composition of the present embodiment. It is a department.

(Compound with ethylenically unsaturated group)
The compound having an ethylenically unsaturated group is not particularly limited as long as it is a compound having one or more ethylenically unsaturated groups in one molecule, and generally known compounds can be used. For example, a compound having a (meth) acryloyl group, a vinyl group and the like can be mentioned.

Examples of the compound having a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, and polyethylene glycol (meth) acrylate monomethyl ether. , Phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol Di (meth) acrylate, epoxy di (meth) acrylate of adipate, bisphenolethylene oxide di (meth) acrylate, hydride bisphenolethylene oxide (meth) acrylate, bisphenoldi (meth) acrylate, ε-caprolactone-modified neopenglycolate hydroxypivalate Di (meth) acrylate, ε-caprolactone-modified dipentaerythritol hexa (meth) acrylate, ε-caprolactone-modified dipentaerythritol poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, trimethylpropantri (meth) acrylate, Trietyrole propantri (meth) acrylate and its ethylene oxide adduct; pentaerythritol tri (meth) acrylate and its ethylene oxide adduct; pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and its Examples include ethylene oxide adducts.

In addition, urethane (meth) acrylates having a (meth) acryloyl group and a urethane bond in the same molecule; polyester (meth) acrylates having a (meth) acryloyl group and an ester bond in the same molecule; epoxy. Epoxy (meth) acrylates derived from a resin and also having a (meth) acryloyl group; reactive oligomers in which these bonds are used in combination can also be mentioned.

Examples of urethane (meth) acrylates include reaction products of hydroxyl group-containing (meth) acrylates, polyisocyanates, and other alcohols used as needed. For example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; glycerin (meth) acrylate such as glycerin mono (meth) acrylate and glycerin di (meth) acrylate. ) Alacrylates; sugar alcohol (meth) acrylates such as pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and toluene diisocyanate. , Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexanemethylene diisocyanate, and polyisocyanates such as their isocyanurates and burette reactants. Meta) acrylates can be mentioned.

Examples of polyester (meth) acrylates include caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, and caprolactone-modified tetrahydro. Monofunctional (poly) ester (meth) acrylates such as furfuryl (meth) acrylate; hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, epichlorohydrin-modified Di (poly) ester (meth) acrylates such as phthalic acid di (meth) acrylate; 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone and δ-valerolactone per mol of trimetylolpropane or glycerin. Examples thereof include mono, di or tri (meth) acrylates of triol obtained by addition.

A triol mono obtained by adding 1 mol or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone to 1 mol of pentaerythritol, dimethylolpropane, trimethylolpropane, or tetramethylolpropane. Triol mono or poly (di, triol or tetra (meth) acrylate, triol obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone to 1 mol of dipentaerythritol. Examples thereof include mono (meth) acrylate and poly (meth) acrylate of polyhydric alcohols such as triol, tetraol, pentaol or hexaol of meta) acrylate.

Furthermore, diol components such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, and hexanediol, and maleic acid and fumal. With polybasic acids such as acids, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebatic acid, azelaic acid, 5-sodium sulfoisophthalic acid, and anhydrides thereof. (Meta) acrylate of polyester polyol which is the reaction product of the above; (meth) of cyclic lactone-modified polyester diol composed of the diol component, polybasic acid, these anhydrides, ε-caprolactone, γ-butyrolactone, δ-valerolactone and the like. Examples thereof include polyfunctional (poly) ester (meth) acrylates such as acrylates.

Epoxy (meth) acrylates are carboxylate compounds of a compound having an epoxy group and (meth) acrylic acid. For example, phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, trishydroxyphenylmethane type epoxy (meth) acrylate, dicyclopentadienephenol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate. , Bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol A novolak type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal type epoxy (meth) acrylate, heterocyclic epoxy ( Examples thereof include meta) acrylates and the like, and these acid anhydride-modified epoxy acrylates and the like.

Examples of the compound having a vinyl group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether and ethylene glycol divinyl ether. Examples of styrenes include styrene, methylstyrene, ethylstyrene, divinylbenzene and the like. Examples of other vinyl compounds include triallyl isocyanurate, trimetaallyl isocyanurate, and bisallyl nadiimide.

These compounds having an ethylenically unsaturated group can be used alone or in admixture of two or more.

In the resin composition according to the present embodiment, the total content of the compounds having an ethylenically unsaturated group is not particularly limited, but is preferably in 100 parts by mass of the resin solid content in the resin composition of the present embodiment. It is 0.01 to 40 parts by mass.

[Photocuring initiator]
The resin composition of the present embodiment may further contain a photocuring initiator. The photocurable initiator is not particularly limited, and those known in the field generally used in the photocurable resin composition can be used.

Examples of the photocuring initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, and parachlorobenzoyl peroxide. And organic peroxides exemplified by di-tert-butyl-di-perphthalate, etc .; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphos Phosphine oxides such as finoxide, ethoxyphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyncrohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Acetophenones such as morpholino-propane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2-ethylanthraquinone, 2-t-butylanthraquinone, 2 -Antraquinones such as chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; acetophenone dimethyl ketal, and ketals such as benzyl dimethyl ketal; benzophenone , 4-Benzoyl-4'-methyldiphenylsulfide, and benzophenones such as 4,4'-bismethylaminobenzophenone; 1,2-octanedione, and 1- [4- (phenylthio)-, 2- (O-). Benzoyl oxime)] and other radical photocuring initiators such as oxime esters,
Diazonium salts of Lewis acids such as p-methoxyphenyldiazonium fluorophosphonate and N, N-diethylaminophenyldiazonium hexafluorophosphonate; iodonium salts of Lewis acids such as diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate; triphenyl Sulfonium salts of Lewis acids such as sulfonium hexafluorophosphonate and triphenylsulfonium hexafluoroantimonate; phosphonium salts of Lewis acids such as triphenylphosphonium hexafluoroantimonate; other halides; triazine initiators; borate initiators ; Other cationic photopolymerization initiators such as photoacid generators can be mentioned.

Commercially available products can also be used as the photocuring initiator, for example, IGM Resins B.I. V. Omnirad® 369, IGM Resins B. et al. V. Omnirad® 819, IGM Resins B. et al. V. Omnirad® 907, IGM Resins B. et al. V. Omnirad® TPO G, IGM Resins B. et al. V. Omnirad (registered trademark) TPO LG and the like.
These photo-curing initiators can be used alone or in admixture of two or more.

In the present embodiment, the photocuring initiator has an absorbance of 0.1 or more of the photocuring initiator having a wavelength of 405 nm (h line) in order to efficiently cause the photoradical reaction of the maleimide compound of the present embodiment. Is preferable. By using such a photocuring initiator, for example, when a printed wiring board having a high-density and high-definition wiring formation (pattern) is manufactured by using a direct drawing exposure method, a wavelength of 405 nm (h line) is included. Even when active energy rays are used, the photoradical reaction of maleimide occurs efficiently. When the absorbance at a wavelength of 405 nm (h line) is 0.1 or more, a chloroform solution containing 0.01% by mass of a photoinitiator is prepared and light with a wavelength of 405 nm (h line) is used. When the absorbance of this chloroform solution is measured, it means that the absorbance is 0.1 or more.

As such a photocuring initiator, a compound represented by the following formula (22) is preferable.

In the formula (22), a plurality of R ₉ each independently represent a substituent or a phenyl group represented by the following formula (23).

In formula (23), each of the plurality of R _10s independently represents a hydrogen atom or a methyl group. In the formula (23), − * indicates a bond with the phosphorus atom (P) in the formula (22).

The compound represented by the formula (22) is a case where a chloroform solution containing 0.01% by mass of this compound is prepared and the absorbance of the chloroform solution is measured using light having a wavelength of 405 nm (h line). With an absorbance of 0.1 or more, it exhibits extremely excellent absorbency for light having a wavelength of 405 nm (h line). Therefore, this compound preferably generates radicals for light having a wavelength of 405 nm (h line).

The absorbance is preferably 0.2 or more. The upper limit is not particularly limited, but is, for example, 2.0.

In the formula (22), a plurality of R ₉ each independently represent a substituent or a phenyl group represented by the formula (23). Of the plurality of R ₉ , one or more is preferably a substituent represented by the above formula (23).
In the above formula (23), each of the plurality of R _10s independently represents a hydrogen atom or a methyl group. Of the plurality of R ₁₀ , it is preferable that one or more are methyl groups, and it is more preferable that all of them are methyl groups.

Examples of the compound represented by the formula (22) include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and ethoxyphenyl (2,4,6-trimethylbenzoyl). Acylphosphine oxides such as 2,4,6-trimethylbenzoyl) -phosphine oxide can be mentioned. These compounds may be used alone or in admixture of two or more.

The acylphosphine oxides of the present embodiment show extremely excellent absorption to active energy rays including a wavelength of 405 nm (h line) and have a transmittance of 5% or more at a wavelength of 405 nm (h line). The maleimide compound can be suitably radically polymerized. Therefore, according to this embodiment, a resin composition and a resin sheet having excellent photocurability, heat resistance, and thermal stability, particularly when used for a multilayer printed wiring board, and a multilayer printed wiring board using them, and It becomes possible to suitably manufacture a semiconductor device.

In the resin composition of the present embodiment, the content of the photocuring initiator is not particularly limited, but from the viewpoint of obtaining better adhesion to chips, substrates and the like, 100 parts by mass of the resin composition of the present embodiment is used. On the other hand, the total content of the photocuring initiator is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass.

(Curing accelerator)
If necessary, the resin composition of the present embodiment may contain a curing accelerator for appropriately adjusting the curing rate. The curing accelerator is not particularly limited, and those generally used as a curing accelerator such as a cyanate ester compound and an epoxy resin can be preferably used. Examples of the curing accelerator include organic metal salts such as zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetone, nickel octylate, manganese octylate, phenol, xylenol, cresol, resorcin, catechol, etc. Phenolic compounds such as octylphenol and nonylphenol, alcohols such as 1-butanol and 2-ethylhexanol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1 -Imidazoles such as cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and carboxylic acids of these imidazoles or Derivatives such as adducts of the acid anhydrides, amines such as dicyandiamide, benzyldimethylamine, 4-methyl-N, N-dimethylbenzylamine, phosphine compounds, phosphine oxide compounds, phosphonium salt compounds, diphosphins Phosphor compounds such as compounds, epoxy-imidazole adduct compounds, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropylperoxycarbonate, peroxides such as di-2-ethylhexylperoxycarbonate. , Or an azo compound such as azobisisobutyronitrile. These can be used individually by 1 type or in combination of 2 or more types.
In the resin composition of the present embodiment, the content of the curing accelerator is not particularly limited, but from the viewpoint of obtaining better adhesiveness to the chip, the substrate and the like, 100 parts by mass of the resin composition of the present embodiment The total content of the curing accelerator is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass.

[Filler]
The resin composition of the present embodiment may further contain a filler in order to improve various properties such as coating film property and heat resistance. The filler preferably has insulating properties and does not hinder the permeability to a wavelength of 405 nm (h line). The filler is not particularly limited, but for example, silica (for example, natural silica, fused silica, amorphous silica, hollow silica, etc.), aluminum compound (for example, boehmite, aluminum hydroxide, alumina, aluminum nitride, etc.), boron compound, etc. (For example, boron nitride, etc.), magnesium compounds (for example, magnesium oxide, magnesium hydroxide, etc.), calcium compounds (for example, calcium carbonate, etc.), molybdenum compounds (for example, molybdenum oxide, zinc molybdate, etc.), barium compounds (for example, magnesium oxide, etc.) , Barium sulfate, barium silicate, etc.), talc (eg, natural talc, fired talc, etc.), mica (mica), glass (eg, short fibrous glass, spherical glass, fine powder glass (eg, E glass, T glass, etc.) , D glass, etc.), silicone powder, fluororesin-based filler, urethane resin-based filler, (meth) acrylic resin-based filler, polyethylene-based filler, styrene / butadiene rubber, silicone rubber, and the like. These fillers can be used alone or in admixture of two or more.

Among these, it is composed of silica, boehmite, barium sulfate, silicone powder, fluororesin-based filler, urethane resin-based filler, (meth) acrylic resin-based filler, polyethylene-based filler, styrene-butadiene rubber, and silicone rubber. It is preferably one or more selected from the group.
These fillers may be surface-treated with a silane coupling agent or the like described later.

Silica is preferable, and fused silica is more preferable, from the viewpoint of improving the heat resistance of the cured product obtained by curing the resin composition of the present embodiment and obtaining good coating film properties. Specific examples of silica include SFP-130MC manufactured by Denka Co., Ltd., SC2050-MB, SC1050-MLE, YA010C-MFN, and YA050C-MJA manufactured by Admatex Co., Ltd.

The particle size of the filler is not particularly limited, but is usually 0.005 to 100 μm, preferably 0.01 to 50 μm.

In the resin composition of the present embodiment, the content of the filler is not particularly limited, but from the viewpoint of improving the heat resistance of the cured product, 1000 parts by mass of the resin solid content in the resin composition. The amount is preferably parts by mass or less, more preferably 500 parts by mass or less, and most preferably 300 parts by mass or less. When the filler is contained, the lower limit is not particularly limited, but from the viewpoint of obtaining the effect of improving various properties such as coating film property and heat resistance, the resin solid content in the resin composition is 100 parts by mass. On the other hand, it is usually 1 part by mass.

<Silane coupling agent and wet dispersant>
In the resin composition of the present embodiment, a silane coupling agent and / or a wet dispersant may be used in combination in order to improve the dispersibility of the filler and the adhesive strength between the polymer and / or the resin and the filler. It is possible.
The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic substances. Specific examples include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N- (2-aminoethyl) -3. -Aminopropyltrimethoxylane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, N- (2-aminoethyl)- 3-Aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, [3- (6-aminohexylamino) propyl] trimethoxysilane, and [3- (N, N-dimethylamino) -propyl] Aminosilanes such as trimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethyl Epoxysilanes such as silane, 3-glycidoxypropyldiethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and [8- (glycidyloxy) -n-octyl] trimethoxysilane; Vinyltris (2-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxy (7-octen-1-yl) silane, trimethoxy (4-vinylphenyl) silane, etc. Vinylsilane series; methacrylsilane series such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane, 3-acryloxy Acrylicsilanes such as propyltrimethoxysilane and 3-acryloxypropyltriethoxysilane; isocyanatesilanes such as 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane; tris- (trimethoxysilylpropyl) Isocyanuratesilanes such as isocyanurates; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyldimethoxymethylsilane; 3-ureidopropyltriethoxysila Ureidosilanes such as p-styryltrimethoxysilanes; Cationicsilanes such as N- [2- (N-vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane hydrochloride; [3- (Trimethoxysilyl) propyl] Acid anhydride system such as succinic acid anhydride; phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, p-tolyltrimethoxysilane, etc. Phenylsilane system; arylsilane system such as trimethoxy (1-naphthyl) silane can be mentioned. These silane coupling agents may be used alone or in admixture of two or more.

In the resin composition of the present embodiment, the content of the silane coupling agent is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
The wet dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints. Specific examples include wet dispersants such as DISPERBYK (registered trademark) -110, 111, 118, 180, 161 and BYK (registered trademark) -W996, W9010, W903 manufactured by Big Chemie Japan Co., Ltd. .. These wet dispersants can be used alone or in admixture of two or more.
In the resin composition of the present embodiment, the content of the wet dispersant is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

<Organic solvent>
The resin composition of the present embodiment may contain an organic solvent, if necessary. When an organic solvent is used, the viscosity of the resin composition at the time of preparation can be adjusted. The type of the organic solvent is not particularly limited as long as it can dissolve a part or all of the resin in the resin composition. Specific examples thereof are not particularly limited, but for example, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alicyclic ketones such as cyclopentanone and cyclohexanone; propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. Cellosolve solvents such as: ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, and ester solvents such as γ-butyrolactone; dimethylacetamide, and dimethylformamide. Polar solvents such as amides such as; non-polar solvents such as aromatic hydrocarbons such as toluene and xylene can be mentioned.
These organic solvents may be used alone or in admixture of two or more.

<Other ingredients>
The resin composition of the present embodiment includes various polymers such as thermosetting resins, thermoplastic resins, and oligomers and elastomers thereof, which have not been mentioned so far, as long as the characteristics of the present embodiment are not impaired. Compounds; Flame-retardant compounds not listed so far; Additives and the like can be used in combination. These are not particularly limited as long as they are generally used. For example, flame-retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, phosphate compounds of phosphorus compounds, aromatic condensed phosphoric acid esters, halogen-containing condensed phosphoric acid esters, and the like. Additives include UV absorbers, antioxidants, optical brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface conditioners, brighteners, polymerization inhibitors, and cure promoters. Agents and the like can be mentioned. These components may be used alone or in admixture of two or more.
In the resin composition of the present embodiment, the content of other components is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

<Manufacturing method of resin composition>
The resin composition of the present embodiment is prepared by appropriately mixing the maleimide compound of the present embodiment with a resin or compound, a photocuring initiator, a filler, other components, additives and the like, if necessary. To. The resin composition of the present embodiment can be suitably used as a varnish for producing the resin sheet of the present embodiment described later.

The method for producing the resin composition of the present embodiment is not particularly limited, and examples thereof include a method in which each of the above-mentioned components is sequentially added to a solvent and sufficiently stirred.

At the time of producing the resin composition, if necessary, a known treatment (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing each component can be performed. Specifically, the dispersibility of the filler in the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank equipped with a stirring machine having an appropriate stirring ability. The stirring, mixing, and kneading treatment may be performed on, for example, a stirring device for dispersing an ultrasonic homogenizer, a device for mixing three rolls, a ball mill, a bead mill, a sand mill, or a revolution or rotation type. It can be appropriately performed using a known device such as a mixing device. Further, when preparing the resin composition of the present embodiment, an organic solvent can be used if necessary. The type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples thereof are as described above.

<Use>
The resin composition of the present embodiment can be used for applications in which an insulating resin composition is required, and is not particularly limited, but is a photosensitive film, a photosensitive film with a support, a prepreg, a resin sheet, and a circuit. It can be used for substrates (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component embedding resins, fiber reinforced composite materials, etc. .. Among them, the resin composition of the present embodiment has excellent heat resistance and thermal stability as well as better adhesiveness to chips and substrates, and therefore is used for an insulating layer of a multilayer printed wiring board or for a solder resist. Can be suitably used as.

[Cured product]
The cured product of the present embodiment is obtained by curing the resin composition of the present embodiment. The cured product is not particularly limited, but can be obtained, for example, by melting or dissolving the resin composition in a solvent, pouring it into a mold, and curing it under normal conditions using heat, light, or the like. In the case of thermosetting, the curing temperature is not particularly limited, but is preferably in the range of 120 ° C. to 300 ° C. from the viewpoint of efficient curing and prevention of deterioration of the obtained cured product. In the case of photocuring, the wavelength region of light is not particularly limited, but it is preferable to cure in the range of 100 nm to 500 nm in which curing is efficiently promoted by a photopolymerization initiator or the like.

[Resin sheet]
The resin sheet of the present embodiment has a support and resin layers arranged on one or both sides of the support, and the resin layer is a resin with a support containing the resin composition of the present embodiment. It is a sheet. The resin sheet can be produced by applying the resin composition on the support and drying it. The resin layer in the resin sheet of the present embodiment has excellent heat resistance and thermal stability as well as excellent adhesiveness to chips and substrates.

As the support, known ones can be used, and the support is not particularly limited, but is preferably a resin film. Examples of the resin film include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, and polyvinyl alcohol. Examples include a film and a triacetyl acetate film. Among them, PET film is preferable.

As the resin film, in order to facilitate peeling from the resin layer, a resin film having a peeling agent coated on the surface can be preferably used. The thickness of the resin film is preferably in the range of 5 to 100 μm, more preferably in the range of 10 to 50 μm. If the thickness is less than 5 μm, the support tends to be torn easily when the support is peeled off, and if the thickness exceeds 100 μm, the resolution when exposed from above the support tends to decrease.

Further, in order to reduce light scattering during exposure, it is preferable that the resin film has excellent transparency.

Further, in the resin sheet of the present embodiment, the resin layer may be protected by a protective film.
By protecting the resin layer side with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin layer and scratches. As the protective film, a film made of the same material as the resin film can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 to 50 μm, and more preferably in the range of 5 to 40 μm. If the thickness is less than 1 μm, the handleability of the protective film tends to decrease, and if it exceeds 50 μm, the cost tends to be inferior. The protective film preferably has a smaller adhesive force between the resin layer and the protective film than the adhesive force between the resin layer and the support.

The method for producing the resin sheet of the present embodiment is not particularly limited, but for example, the resin composition of the present embodiment is applied to a support such as a PET film and dried to remove the organic solvent to remove the resin. Examples thereof include a method of manufacturing a sheet.
The coating method can be performed by a known method using, for example, a roll coater, a comma coater, a gravure coater, a die coater, a bar coater, a lip coater, a knife coater, a squeeze coater, or the like. The drying can be performed, for example, by heating in a dryer at 60 to 200 ° C. for 1 to 60 minutes.

The amount of the organic solvent remaining in the resin layer is preferably 5% by mass or less with respect to the total mass of the resin layer from the viewpoint of preventing the diffusion of the organic solvent in a later step. The thickness of the resin layer is preferably 1 to 50 μm from the viewpoint of improving handleability.

The resin sheet of the present embodiment can be used for manufacturing an insulating layer of a multilayer printed wiring board.

[Prepreg]
The prepreg of the present embodiment includes a base material and a resin composition impregnated or coated on the base material. The method for producing the prepreg of the present embodiment is not particularly limited as long as it is a method for producing the prepreg by combining the resin composition of the present embodiment and the base material. For example, the resin composition of the present embodiment is impregnated or coated on a base material, and then semi-cured (B-staged) by a method of drying in a dryer at 120 to 220 ° C. for about 2 to 15 minutes. The prepreg of the present embodiment can be manufactured. At this time, the amount of the resin composition adhered to the substrate, that is, the content of the resin composition (including the filler) with respect to 100 parts by mass of the prepreg after semi-curing may be in the range of 20 to 99 parts by mass. preferable.

As the base material used in producing the prepreg of the present embodiment, known materials used for various printed wiring board materials can be used. The base material is not particularly limited, and examples thereof include inorganic fibers other than glass such as glass fibers and quartz; organic fibers such as polyimide, polyamide and polyester; and woven fabrics such as liquid crystal polyester. As the shape of the base material, woven cloth, non-woven fabric, roving, chopped strand mat, surfaceing mat and the like are known, and any of these may be used. As the base material, one type can be used alone or two or more types can be used in combination. Among the woven fabrics, a woven fabric that has been subjected to a super-spreading treatment or a filling treatment is particularly suitable from the viewpoint of dimensional stability. The liquid crystal polyester woven fabric is preferable from the viewpoint of electrical characteristics. The thickness of the base material is not particularly limited, but is preferably in the range of 0.01 to 0.2 mm for laminated board applications.

[Metal leaf laminated board]
The metal leaf-clad laminate of the present embodiment includes a layer containing at least one selected from the group consisting of the resin sheet of the present embodiment and the prepreg of the present embodiment, and the metal foil arranged on one or both sides of the layer. And, the layer contains a cured product of the resin composition according to the present embodiment. When a prepreg is used, for example, a metal foil such as copper or aluminum is arranged on one side or both sides of the above-mentioned one prepreg or a plurality of prepregs stacked, and laminated molding is performed. It can be produced by. The metal foil used here is not particularly limited as long as it is used as a material for a printed wiring board, but copper foil such as rolled copper foil and electrolytic copper foil is preferable. The thickness of the metal foil is not particularly limited, but is preferably 2 to 70 μm, and more preferably 3 to 35 μm. As the molding conditions, a method used when manufacturing a normal laminated board for a printed wiring board and a multilayer board can be adopted. For example, using a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like, laminating molding is performed under the conditions of a temperature of 180 to 350 ° C., a heating time of 100 to 300 minutes, and a surface pressure of 20 to 100 kg / cm ^2. This makes it possible to manufacture the metal foil-clad laminate of the present embodiment. Further, a multilayer plate can also be produced by laminating and molding the above-mentioned prepreg in combination with a separately produced wiring plate for an inner layer. As a method for manufacturing a multilayer plate, for example, a copper foil of 35 μm is arranged on both sides of one of the above-mentioned prepregs, laminated and formed under the above conditions, an inner layer circuit is formed, and the circuit is blackened. The inner layer circuit board is formed. Further, the inner layer circuit board and the prepreg are alternately arranged one by one, and a copper foil is further arranged on the outermost layer, and laminating molding is preferably performed under the above conditions under vacuum. In this way, the multilayer board can be produced.

The metal foil-clad laminate of the present embodiment can be suitably used as a printed wiring board by further forming a pattern. The printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. The following is an example of a method for manufacturing a printed wiring board.
First, the metal leaf-clad laminate is prepared. Next, an inner layer substrate is produced by etching the surface of the metal foil-clad laminate to form an inner layer circuit. The inner layer circuit surface of the inner layer substrate is subjected to surface treatment to increase the adhesive strength, if necessary, and then the required number of the above prepregs are laminated on the inner layer circuit surface. Further, a metal foil for an outer layer circuit is laminated on the outside thereof, and integrally molded by heating and pressurizing. In this way, a multi-layer laminated board in which an insulating layer made of a base material and a cured product of a thermosetting resin composition is formed between an inner layer circuit and a metal foil for an outer layer circuit is manufactured. Next, after drilling holes for through holes and via holes in the multilayer laminated plate, a plated metal film for conducting the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of the holes. Further, the printed wiring board is manufactured by forming the outer layer circuit by etching the metal foil for the outer layer circuit.

The printed wiring board obtained in the above-mentioned production example has an insulating layer and a conductor layer formed on one side or both sides of the insulating layer, and the insulating layer contains the resin composition of the present embodiment. For example, the prepreg of the present embodiment (the base material and the resin composition of the present embodiment impregnated or coated therein), and the layer of the resin composition of the metal leaf-clad laminate of the present embodiment (the resin composition of the present embodiment). A layer made of) can constitute an insulating layer containing the resin composition of the present embodiment.

[Multilayer printed wiring board]
The multilayer printed wiring board of the present embodiment has an insulating layer and a conductor layer formed on one side or both sides of the insulating layer, and the insulating layer contains the resin composition of the present embodiment. The insulating layer can also be obtained, for example, by stacking one or more resin sheets and curing them. The prepreg of the present embodiment may be used instead of the resin sheet of the present embodiment. The multilayer printed wiring board of the present embodiment can be manufactured according to a conventional method, and the manufacturing method thereof is not particularly limited. The following is an example of a method for manufacturing a multilayer printed wiring board.
First, the metal leaf-clad laminate is prepared. Next, an inner layer substrate is produced by etching the surface of the metal foil-clad laminate to form an inner layer circuit. The inner layer circuit surface of the inner layer substrate is subjected to surface treatment to increase the adhesive strength, if necessary, and then the required number of the above prepregs are laminated on the inner layer circuit surface. Further, a metal foil for an outer layer circuit is laminated on the outside thereof, and integrally molded by heating and pressurizing. In this way, a multi-layer laminated board in which an insulating layer made of a base material and a cured product of a resin composition is formed between an inner layer circuit and a metal foil for an outer layer circuit is manufactured. Next, after drilling holes for through holes and via holes in the multilayer laminated plate, a plated metal film for conducting the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of the holes. Further, a multilayer printed wiring board is manufactured by forming an outer layer circuit by etching a metal foil for an outer layer circuit.

The printed wiring board obtained in the above-mentioned production example has an insulating layer and a conductor layer formed on one side or both sides of the insulating layer, and the insulating layer contains the resin composition of the present embodiment. For example, the prepreg of the present embodiment (the base material and the resin composition of the present embodiment impregnated or coated therein), and the layer of the resin composition of the metal leaf-clad laminate of the present embodiment (the resin composition of the present embodiment). A layer made of) can constitute an insulating layer containing the resin composition of the present embodiment.

[Encapsulation material]
The sealing material of the present embodiment includes the resin composition of the present embodiment. As a method for producing a sealing material, a generally known method can be appropriately applied and is not particularly limited. For example, a sealing material can be produced by mixing the resin composition of the present embodiment with various known additives or solvents generally used for sealing materials using a known mixer. it can. The method for adding the maleimide compound, various additives, and the solvent of the present embodiment at the time of mixing can be appropriately applied to a generally known method, and is not particularly limited.

[Fiber reinforced composite material]
The fiber-reinforced composite material of the present embodiment includes the resin composition of the present embodiment and the reinforcing fibers. As the reinforcing fiber, generally known fibers can be used and are not particularly limited. For example, glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, spherical glass; carbon fiber; aramid fiber; boron fiber; PBO fiber; high-strength polyethylene fiber; Alumina fiber; Examples include silicon carbide fiber. The form and arrangement of the reinforcing fibers are not particularly limited, and can be appropriately selected from woven fabrics, non-woven fabrics, mats, knits, braids, unidirectional strands, rovings, chopped and the like. In addition, as a form of reinforcing fibers, a preform (a laminated woven base fabric made of reinforcing fibers, a sewn-integrated one with stitch threads, or a fiber structure such as a three-dimensional woven fabric or a braid) is applied. You can also.

As a method for producing these fiber-reinforced composite materials, generally known methods can be appropriately applied and are not particularly limited. For example, a liquid composite molding method, a resin film infusion method, a filament winding method, a hand layup method, and a pull-fusion method can be mentioned. Among these, in the resin transfer molding method, which is one of the liquid composite molding methods, materials other than preforms such as metal plates, foam cores, and honeycomb cores can be set in advance in the molding die. Since it can be used for various purposes, it is preferably used when a composite material having a relatively complicated shape is mass-produced in a short time.

[adhesive]
The adhesive of the present embodiment contains the resin composition of the present embodiment. As a method for producing the adhesive, a generally known method can be appropriately applied and is not particularly limited. For example, an adhesive can be produced by mixing the resin composition of the present embodiment with various known additives or solvents generally used for adhesive applications using a known mixer. The method for adding the maleimide compound, various additives, and the solvent of the present embodiment at the time of mixing can be appropriately applied to a generally known method, and is not particularly limited.

[Semiconductor device]
The semiconductor device of this embodiment has the resin composition of this embodiment. Specifically, it can be produced by the following method. A semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of the multilayer printed wiring board of the present embodiment. Here, the conductive portion is a portion of the multilayer printed wiring board that transmits an electric signal, and the location may be a surface or an embedded portion. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The mounting method of the semiconductor chip when manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build. Examples thereof include a mounting method using an up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

A semiconductor device can also be manufactured by forming a semiconductor chip or an insulating layer containing the resin composition of the present embodiment on a substrate on which the semiconductor chip is mounted. The shape of the substrate on which the semiconductor chip is mounted may be a wafer shape or a panel shape. After the formation, it can be manufactured by the same method as the above-mentioned multilayer printed wiring board.

Hereinafter, the present embodiment will be described in more detail with reference to Examples and Comparative Examples. The present embodiment is not limited to the following examples.

[Example 1] Synthesis of maleimide compound (hereinafter, abbreviated as BMI-G328) BMI-G328 represented by the following formula (24) was synthesized as described below.
(24)

<Synthesis of amic acid compound (hereinafter abbreviated as MA-G328)>
First, MA-G328 represented by the following formula (25) was synthesized by the following method.

8.96 parts by mass (91.3 mmol) of maleic anhydride and 70 mL of N-methylpyrrolidone (NMP) in a 500 mL four-necked flask equipped with an argon inlet, Dean-Stark apparatus, Dimroth condenser, and thermometer. In addition, maleic anhydride was completely dissolved by stirring at room temperature under an argon stream. A mixed solution of 10.0 parts by mass of gascamine (registered trademark) 328 (manufactured by Mitsubishi Gas Chemical Company, Inc., adduct of metaxylylenediamine and epichlorohydrin, trade name) and 80 mL of NMP was added dropwise to this solution, and the mixture was stirred at room temperature for 17 hours. did.
A part of the reaction solution was separated, ethanol was added, and the mixture was shaken. The precipitated solid was collected by filtration and washed with ethanol. ¹ H-NMR measurement (500 MHz, DMSO-d6) was carried out on the solid after washing with ethanol, and it was confirmed that the solid was MA-G328 represented by the formula (25).
A ¹ H-NMR chart of the amic acid compound (MA-G328) is shown in FIG. A peak attributed to terminal carboxyl group hydrogen was observed at 9.4 ppm. In addition, a peak (6.2-6.5 ppm) attributed to alkene hydrogen was observed.

<Synthesis of BMI-G328>
1.16 parts by mass (6.1 mmol) of p-toluenesulfonic acid monohydrate was added to the above reaction solution, and the mixture was heated under reflux at 130 ° C. for 20 hours. After cooling to room temperature, 900 mL of ethanol was added to the cooled reaction solution, and the mixture was stirred for 20 minutes. The precipitated solid was collected by filtration and washed with 200 mL of water and 200 mL of ethanol. The obtained solid was finely pulverized and washed with 200 mL of water. The solid was collected by filtration and dried under reduced pressure at 60 ° C. to obtain 12.67 parts by mass of the reaction product. When the obtained reaction product was subjected to ^{1 1} H-NMR measurement (500 MHz, DMSO-d6), it was expressed in BMI-G328 represented by the formula (24) (a mixture of n in the formula (24) of 1 to 20). I confirmed that there was.
A ¹ H-NMR chart of the maleimide compound (BMI-G328) is shown in FIG. As shown in FIG. 2, the peak (6.2-6.5 ppm) attributed to alkene hydrogen observed by ¹ H-NMR of MA-G328 disappeared, and the peak attributed to alkene hydrogen of the maleimide ring (peak). 6.5 ppm) was newly observed.

<Preparation of cured product>
[Example 2]
100 parts by mass of the maleimide compound (BMI-G328) obtained in Example 1 and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Registered Trademark) manufactured by IGM Resins B.V. as a photoinitiator. ) 819) was mixed with 5 parts by mass and 400 parts by mass of dimethylacetamide, and the mixture was stirred with an ultrasonic homogenizer to prepare a varnish. This varnish was dropped onto a Si wafer (manufactured by Kunshan Sino Silicon Technology Co., Ltd.), and a coating film was formed by spin coating (700 rpm for 10 seconds, then 1000 rpm for 30 seconds). After drying at 120 ° C. for 5 minutes using a hot plate, a wavelength of 405 nm (h line) is used at an exposure rate of 10,000 mJ / cm ² using an exposure machine (manufactured by ORC Manufacturing Co., Ltd., HMW-201GX (trade name)). The coating film was cured by irradiating it with active energy rays containing. Further, heat treatment was performed at 180 ° C. for 60 minutes to obtain a cured product with a Si wafer.

[Comparative Example 1]
Instead of 100 parts by mass of the maleimide compound (BMI-G328) obtained in Example 1, 100 parts by mass of a maleimide compound (manufactured by Designer Molecules Inc., trade name "BMI-689") was used, and 400 parts by mass of dimethylacetamide was used. A cured product with a Si wafer was obtained in the same manner as in Example 2 except that the mass portion was changed to 80 parts by mass.

<Evaluation of adhesiveness>
In order to evaluate the adhesiveness, a cross-cut test was performed according to JIS-K5600-5-6. Specifically, in the cured products with Si wafers obtained in Example 2 and Comparative Example 1, six cuts were made at 1 mm intervals in each of the vertical and horizontal directions so as to be orthogonal to each other, and a right-angle grid of 25 squares was formed. A pattern was made. A pressure cooker (temperature: 121 ° C., humidity: 100% RH, pressure: 2 atm) is applied to the notched cured product with a Si wafer for up to 3 hours, 5 hours, and 24 hours, respectively. After the pressure-moisture absorption treatment, a peeling test of a cured product from a Si wafer was performed with a transparent adhesive tape (manufactured by Cortec Co., Ltd., trade name "SP3209") in a room temperature environment.
The number of residual cured products (coating film) before and after the peeling test was visually counted. The results are shown in Table 1.

As is clear from Table 1, it was confirmed that the maleimide compound of the present embodiment has excellent adhesiveness to chips, substrates and the like.

The maleimide compound of the present invention is industrially useful because it exhibits excellent adhesion to chips, substrates, etc., and is, for example, a photosensitive film, a photosensitive film with a support, a prepreg, a resin sheet, a circuit board ( It can be used for laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component embedding resins, fiber reinforced composite materials, and the like.

Claims (19)

A maleimide compound represented by the following formula (1).
(In the formula (1), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. R ₂ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ each independently represent hydrogen. It represents an atom, a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 1 to 6 carbon atoms. N represents an integer of 1 to 30. , M each independently represents an integer of 1 to 4). The maleimide compound according to claim 1, which is represented by the following formula (2).
(In equation (2), n represents an integer of 1 to 30.). The maleimide compound according to claim 1 or 2, which is a maleimide compound of an amine compound represented by the following formula (3).
(In the formula (3), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. Indicates a state or branched alkoxy group, R ₂ indicates a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms. N indicates an integer of 1 to 30, and m. Independently indicate an integer of 1 to 4). A method for producing a maleimide compound represented by the following formula (1), which comprises a step of dehydrating and ring-closing the amic acid compound represented by the following formula (4).
(In formula (4), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. R ₂ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ each independently represent hydrogen. It represents an atom, a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 1 to 6 carbon atoms. N represents an integer of 1 to 30. .M represents an integer of 1 to 4 independently of each other).
(In the formula (1), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. R ₂ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ each independently represent hydrogen. It represents an atom, a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 1 to 6 carbon atoms. N represents an integer of 1 to 30. .M represents an integer of 1 to 4 independently of each other). An amic acid compound represented by the following formula (4).
(In formula (4), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. R ₂ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ each independently represent hydrogen. It represents an atom, a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 1 to 6 carbon atoms. N represents an integer of 1 to 30. .M represents an integer of 1 to 4 independently of each other). A method for producing an amic acid compound represented by the following formula (4), which comprises a step of addition-reacting an amine compound represented by the following formula (3) with an acid anhydride represented by the following formula (5).
(In the formula (3), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. Indicates a state or branched alkoxy group, R ₂ indicates a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms. N indicates an integer of 1 to 30, and m. Independently indicate an integer of 1 to 4).
(In the formula (5), R ₃ and R ₄ are independently hydrogen atom, halogen atom, linear or branched alkyl group having 1 to 6 carbon atoms, or linear chain having 1 to 6 carbon atoms. Alternatively, it indicates a branched alkenyl group.)
(In formula (4), R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. R ₂ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ each independently represent hydrogen. It represents an atom, a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 1 to 6 carbon atoms. N represents an integer of 1 to 30. , M each independently represents an integer of 1 to 4). A resin composition containing the maleimide compound according to any one of claims 1 to 3. Maleimide compounds other than the maleimide compound according to any one of claims 1 to 3, cyanate ester compounds, phenol resins, epoxy resins, oxetane resins, benzoxazine compounds, carbodiimide compounds, and compounds having an ethylenically unsaturated group. The resin composition according to claim 7, further comprising one or more selected from the group consisting of. The resin composition according to claim 7 or 8, further comprising a photocuring initiator. The resin composition according to any one of claims 7 to 9, further comprising a filler. A cured product containing the resin composition according to any one of claims 7 to 10. With the support
It has a resin layer arranged on one side or both sides of the support.
The resin layer contains the resin composition according to any one of claims 7 to 10.
Resin sheet. With the base material
The resin composition according to any one of claims 7 to 10, which is impregnated or coated on the base material.
Including prepreg. A layer containing at least one selected from the group consisting of the resin sheet according to claim 12 and the prepreg according to claim 13.
With the metal foil arranged on one side or both sides of the layer,
Have,
A metal leaf-clad laminate in which the layer contains a cured product of the resin composition. Insulation layer and
With the conductor layer formed on one side or both sides of the insulating layer,
Have,
A multilayer printed wiring board in which the insulating layer contains the resin composition according to any one of claims 7 to 10. A sealing material containing the resin composition according to any one of claims 7 to 10. The resin composition according to any one of claims 7 to 10 and
Reinforcing fiber and
Including fiber reinforced composite material. An adhesive comprising the resin composition according to any one of claims 7 to 10. A semiconductor device having the resin composition according to any one of claims 7 to 10.