JP7365574B2 - Maleimide compounds and their production methods, amic acid compounds and their production methods, resin compositions, cured products, resin sheets, prepregs, metal foil clad laminates, printed wiring boards, sealing materials, fiber reinforced composite materials, adhesives, and semiconductor devices - Google Patents

Description

The present invention relates to a maleimide compound and its manufacturing method, an amic acid compound and its manufacturing 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.

2. Description of the Related Art In recent years, the integration and miniaturization of semiconductors widely used in electronic devices, communication devices, personal computers, etc. have been accelerating. Along with this, various characteristics required of semiconductor package laminates used in printed wiring boards are becoming increasingly strict. Required properties include, for example, adhesion to chips and substrates, low water absorption, heat resistance, flame retardancy, electrical properties (e.g., low dielectric constant and low dielectric loss tangent), low coefficient of thermal expansion, heat resistance, and Examples include chemical properties and increased plating peel strength.

Among these, maleimide compounds are known as resins or compounds for printed wiring boards that have excellent heat resistance, electrical properties, and moisture resistance.Resin compositions that combine maleimide compounds with epoxy resins are used for semiconductor plastic packages, etc. It is widely used as a material for high-performance printed wiring boards.
For example, Patent Document 1 describes that a resin composition containing a maleimide compound with a specific structure and other components has excellent properties such as heat resistance, electrical properties, and moisture resistance.

Japanese Patent Application Publication No. 11-124488

However, the resin composition described in Patent Document 1 still has room for improvement from the viewpoint of adhesion to chips, substrates, and the like. If the adhesion to chips, substrates, etc. is insufficient, it will be difficult to apply it to applications that require high adhesion strength, such as insulating materials used in printed wiring boards, resin sheets, etc.

The present invention has been made in view of the above problems, and provides a maleimide compound and a method for producing the same, an amic acid compound and a method for producing the same, a resin composition, and a cured resin composition, which exhibit excellent adhesion to chips, substrates, etc. The objective is to provide products, resin sheets, prepregs, metal foil-clad laminates, printed wiring boards, sealing materials, fiber-reinforced composite materials, adhesives, and semiconductor devices.

As a result of intensive studies to solve the above-mentioned problems, the present inventors discovered that the above-mentioned problems could be achieved by using a maleimide compound having a specific structure, and 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 each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a straight chain having 1 to 6 carbon atoms. or a branched alkoxy group, R ₂ is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ are each independently 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 each independently represents an integer of 1 to 4.
[2] The maleimide compound according to [1], which is represented by the following formula (2).

In 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 each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a straight chain having 1 to 6 carbon atoms. or a 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, and m each independently represents an integer of 1 to 4.
[4] A method for producing a maleimide compound represented by the following formula (1), which includes a step of subjecting an amic acid compound represented by the following formula (4) to a dehydration ring-closing reaction.

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

In formula (1), R ₁ is each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a straight chain having 1 to 6 carbon atoms. or a branched alkoxy group, R ₂ is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ are each independently 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 from 1 to 30. m each independently represents an integer of 1 to 4.
[5] Amic acid compound represented by the following formula (4).

In formula (4), R ₁ is each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a straight chain having 1 to 6 carbon atoms. or a branched alkoxy group, R ₂ is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ are each independently 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 from 1 to 30. m each independently represents an integer of 1 to 4.
[6] A method of producing an amidic acid compound represented by the following formula (4), which includes a step of causing an addition reaction between an amine compound represented by the following formula (3) and an acid anhydride represented by the following formula (5). Production method.

In formula (3), R ₁ is each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a straight chain having 1 to 6 carbon atoms. or a 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, and m each independently represents an integer of 1 to 4.

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

In formula (4), R ₁ is each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a straight chain having 1 to 6 carbon atoms. or a branched alkoxy group, R ₂ is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ₃ and R ₄ are each independently 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 each independently represents an integer of 1 to 4.
[7] A resin composition comprising the maleimide compound according to any one of [1] to [3].
[8] Maleimide compounds other than the maleimide compounds described in 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 the following.
[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 comprising the resin composition according to any one of [7] to [10].
[12] having a support and a resin layer disposed on one or both sides of the support, the resin layer containing the resin composition according to any one of [7] to [10]; resin sheet.
[13] A prepreg comprising a base material and the resin composition according to any one of [7] to [10], which is impregnated or applied to the base material.
[14] A layer containing at least one member selected from the group consisting of the resin sheet according to [12] and the prepreg according to [13], and a metal foil disposed on one or both sides of the layer. and a metal foil-clad laminate, wherein the layer includes a cured product of the resin composition.
[15] It has an insulating layer and a conductor layer formed on one or both sides of the insulating layer, and the insulating layer contains the resin composition according to any one of [7] to [10]. Multilayer printed wiring board.

[16] A sealing material comprising the resin composition according to any one of [7] to [10].
[17] A fiber-reinforced composite material comprising the resin composition according to any one of [7] to [10] and reinforcing fibers.
[18] An adhesive comprising the resin composition according to any one of [7] to [10].
[19] A semiconductor device comprising 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 a method for producing the same, a resin composition, a cured product, a resin sheet, a prepreg, a metal foil cladding, which exhibit excellent adhesion to chips, substrates, etc. 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 amidic 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, a mode 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 may be made without departing from the gist thereof. is possible.
In this specification, "(meth)acrylic" means both "acrylic" and its corresponding "methacrylic". "(Meth)acrylate" means both "acrylate" and its corresponding "methacrylate". "(Meta)allyl" means both "allyl" and its corresponding "methallyl". In addition, in this embodiment, "resin solid content" or "resin solid content in the resin composition" refers to the photocuring initiator, additives, solvents, and fillers in the resin composition, unless otherwise specified. "Resin solid content 100 parts by mass" refers to the excluded components, and "100 parts by mass of resin solids" means that the total of the components excluding the photocuring initiator, additives, solvents, and fillers in the resin composition is 100 parts by mass. shall be.

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

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

The linear or branched alkyl group having 1 to 6 carbon atoms is not particularly limited, and includes, for example, methyl group, ethyl group, n-propyl group, i-propyl group, butyl group, isobutyl group, sec-butyl group. and tert-butyl group. Among these, in addition to excellent adhesion with chips and substrates, etc., it exhibits good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. 1 to 4 alkyl groups are preferred, and methyl, ethyl, n-propyl, and i-propyl groups are more preferred.
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 includes, for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, and 2-methylpropoxy group. group, 1-methylpropoxy group, and tert-butoxy group. Among these, in addition to excellent adhesion with chips and substrates, etc., it exhibits good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. 1 to 4 alkoxy groups are preferred, and methoxy, ethoxy, n-propoxy, and iso-propoxy groups are more preferred.
In addition to excellent adhesion with chips and substrates, _R1 exhibits good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. Atom, methyl group, ethyl group, hydroxy group, methoxy group, and ethoxy group are preferable, hydrogen atom, methyl group, and hydroxy group are more preferable, and hydrogen atom is still more preferable.

In the formula (1), R ₂ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.
As for the linear or branched alkyl group having 1 to 6 carbon atoms, the above description of R ₁ can be referred to, including preferred embodiments.
In addition to excellent adhesion with chips and substrates, _R2 exhibits good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. Atom, methyl group, and ethyl group are preferred, hydrogen atom and methyl group are more preferred, and hydrogen atom is even more preferred.

In the formula (1), 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 alkyl group having 1 to 6 carbon atoms. or a branched alkenyl group. R ₃ and R ₄ may all be the same or different.
For 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 includes, for example, a vinyl group, an allyl group, a 4-pentenyl group, an isopropenyl group, and an isopentyl group.
_R3 and _R4 should exhibit good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, in addition to excellent adhesion with chips and substrates, etc. , each independently is preferably a hydrogen atom or 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. n is 1 to 1, since it exhibits excellent adhesion to chips, substrates, etc., as well as good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. An integer of 27 is preferred, and an integer of 1 to 25 is more preferred.

In the formula (1), m each independently represents an integer of 1 to 4. In addition to excellent adhesion with chips and substrates, m has good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, so R ₁ are preferably all hydrogen atoms, so 4 is preferable.

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

Normally, maleimide compounds have poor light transmittance, so if the resin composition described below contains a maleimide compound, light will not sufficiently reach the photocuring initiator dispersed in the resin composition, and the photocuring initiator will Hard to generate radicals. Therefore, in general, photoradical reactions of maleimide compounds are difficult to proceed, and even if radical polymerization or dimerization reactions of maleimide alone proceed, the reactivity is extremely low. However, the maleimide compound according to the present embodiment has a maleimide group bonded to an aromatic ring via a methylene group and has a short conjugation length, so it has excellent light transmittance. Sufficient light reaches the area, and the photoradical reaction of maleimide occurs efficiently. In addition, when a chloroform solution containing the maleimide compound at 1% by mass is prepared and the light transmittance of this chloroform solution is measured using a light beam with a wavelength of 405 nm (h line), the transmittance is 3% or more. Shows excellent light transmittance. Therefore, for example, when manufacturing a printed wiring board with high-density and high-definition wiring formation (pattern) using the direct writing exposure method, even if active energy rays containing a wavelength of 405 nm (h line) are used, The photoradical reaction of maleimide occurs efficiently.

When active energy rays having a wavelength of 405 nm (h line) are used, polymerization will not proceed unless the photocuring initiator absorbs the light with a wavelength of 405 nm (h line) and generates radicals. Therefore, in this case, the photocuring initiator described below has an absorbance of 0.1 or more at a wavelength of 405 nm (h line), and has excellent absorbency for light at a wavelength of 405 nm (h line). Preferably, an initiator is used.

As described above, the maleimide compound of this embodiment has excellent light transmittance, so even when using light with a wavelength of 405 nm, the light sufficiently reaches the photocuring initiator, and the radicals generated from the photocuring initiator A radical reaction using the compound proceeds, and photocuring becomes possible even in a resin composition containing a large amount of maleimide compound.
Since the cured product containing the resin composition of the present embodiment has excellent photocurability, heat resistance, and thermal stability, it is possible to suitably form a protective film and an insulating layer.

The maleimide compound of this embodiment exhibits good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, in addition to superior adhesion to chips, substrates, etc. Therefore, it is preferable to be represented by the following formula (2). In addition to superior adhesion to chips and substrates, the maleimide compound of this embodiment also has good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. Therefore, it is also preferable to use a maleimide compound of an amine compound represented by the following formula (3).

In the formula (2), n represents an integer of 1 to 30. Preferred embodiments of n are the same as n in formula (1) above.

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

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

In the formula (5), 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 straight chain having 1 to 6 carbon atoms. or a branched alkenyl group.
R ₃ and R ₄ are the same as in formula (1) above, including preferred embodiments.

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

By having a specific structure, the amic acid represented by the formula (4) can exhibit excellent adhesiveness with 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 synthesis method. That is, an excess of the diamine represented by the following formula (6) is reacted with an epihalohydrin represented by the following formula (7) in the presence of an alkali metal hydroxide in an amount higher than the stoichiometric amount to obtain the above formula (3). Synthesize the amino compound represented by

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

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

After the reaction is completed, a primary alcohol such as butanol, pentanol, hexanol, heptanol, and octanol is added to the reaction system, optionally in combination with water, to dissolve the polyamino compound into the alcohol layer and the alkali metal halide into the water layer. , perform liquid separation. The amount of alcohol used for liquid separation is not particularly limited, but is preferably 1 mol or more and 5 mol or less per 1 mol of epihalohydrin, and the amount of water is preferably 20 mol or more and 50 mol or less. After adding alcohol and water to the reaction system, stirring may be performed for the purpose of dissolving the alkali metal halide. After separation, the amine compound represented by the formula (3) can be obtained by distilling off the alcohol from the upper liquid layer. Note that the primary alcohols can be used alone or in combination of two or more types, if necessary.

(Method for synthesizing the amidic acid compound represented by the above formula (4))
The amidic acid compound represented by the formula (4) is not particularly limited, but can be obtained, for example, by the following synthesis method. That is, it can be obtained by carrying out 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 above formula (5).

The acid anhydride represented by the formula (5) is not particularly limited, but includes, for example, maleic anhydride, 3-methyl maleic anhydride, 3-ethyl maleic anhydride, 3,4-dimethyl maleic anhydride, 3 , 4-diethyl maleic anhydride, 3-chloromaleic anhydride, and 3,4-dichloromaleic anhydride. These acid anhydrides can be used alone or in combination of two or more.
The amount of the acid anhydride represented by the above formula (5) is usually 1.5 to 3.0 per mole of the amine compound represented by the formula (3) obtained by the above synthesis method. twice the molar amount, preferably 1.8 to 2.2 times the molar amount.

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

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

The addition reaction is preferably carried out in an organic solvent. Examples of organic solvents include, but are not limited to, saturated hydrocarbons such as pentane, hexane, heptane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; dichloromethane, chloroform, and 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]ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, and 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, Phenols such as 3,4-xylenol and 3,5-xylenol; 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 include 1,3-dimethyl-2-imidazolidinone. These organic solvents can be used alone or in combination of two or more.

Moreover, the following solvents may be made to 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, m-bromotoluene. , p-bromotoluene, chlorobenzene, and bromobenzene. These act as an azeotropic solvent for removing (dehydrating) water generated in the reaction solution. These organic solvents can be used alone or in combination of two or more.

The amount of organic solvent used is not particularly limited and varies depending on the type and composition of the solvent used, but is usually 1 to 1000 parts by mass, preferably 1 part by mass, per 1 part by mass of the raw material amine compound and acid anhydride. ~100 parts by mass. Although it is preferable that the reaction solvent dissolves the raw materials to form a solution, the reaction may be carried out in the form of a slurry.

(Method for synthesizing maleimide compound represented by formula (1) above)
The maleimide compound represented by the formula (1) is not particularly limited, but can be obtained, for example, by the following synthesis method. That is, it can be obtained by subjecting the amidic acid compound represented by formula (4) obtained by the above synthesis method to a dehydration ring-closing reaction. Further, the dehydration ring closure reaction is preferably carried out in an organic solvent. As the organic solvent, the solvent used in the above-mentioned 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 organic base catalysts include triethylamine, tributylamine, tripentylamine, N,N-dimethylaniline, N,N-diethylaniline, pyridine, α-picoline, β-picoline, γ-picoline, 2,4-lutidine. , 2,6-lutidine, quinoline, and isoquinoline. These organic base catalysts can be used alone or in combination of two or more.
Examples of acid catalysts include inorganic acids such as hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfuric anhydride, nitric acid, phosphoric acid, phosphorous acid, phosphotungstic acid, and phosphomolybdic acid; methanesulfonic acid, ethanesulfonic acid. acids, sulfonic acids such as trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; carboxylic acids such as acetic acid and oxalic acid; chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, difluoroacetic acid, and trifluoroacetic acid Examples include halogenated carboxylic acids such as acetic acid; solid acids such as silica, alumina, and activated clay; and cationic ion exchange resins. Moreover, these acid catalysts may be salts with diamine compounds. Among these, sulfuric acid, phosphoric acid, and p-toluenesulfonic acid are preferred. These acid solvents can be used alone or in combination of two or more.
The amount of the organic base catalyst and acid catalyst to be used is not particularly limited as long as the reaction rate of the dehydration ring-closing reaction is substantially improved, but it is usually 0.001 to 10 times the mole of the raw material amine compound, and 0. The amount is preferably from 0.005 mol to 5 times the mole, and more preferably from 0.01 to 1 times the mole.

As the imidizing agent, for example, 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. 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 (such as acetic anhydride) is used as an imidizing agent, the amount used is not particularly limited, but it is usually 1.0 to 10 times the mole of the raw amine compound. It is preferably 1.8 to 6.0 times the mole amount.
Examples of catalysts include oxides of alkaline earth metals, carbonates of iron (II and III), nickel (II), manganese (II and III), copper (I and II) or cobalt (II and III). Examples include salts, sulfates, phosphates, and acetates. These catalysts can 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, and tributylamine. 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 per 1 mol of the amic acid compound.

The reaction temperature and reaction time in the dehydration ring-closing reaction vary depending on the type of raw materials used, the type of solvent, the type of catalyst, the type and amount of the azeotropic dehydration solvent, and the type and amount of the imidizing agent, but usually, The temperature is 20 to 180°C for 1 to 24 hours. In addition, the reaction pressure is not particularly limited, but usually atmospheric pressure may be used. Although the reaction atmosphere is not particularly limited, it is usually an atmosphere of air, nitrogen, helium, neon, or argon, and it is preferable to carry out the reaction under an atmosphere of nitrogen or argon, which is an inert gas.

The method for isolating the target maleimide compound from the reaction mixture containing the maleimide compound is not particularly limited, but if the target product precipitates from the reaction solvent, it can be isolated by filtration or centrifugation. . On the other hand, if the target substance is dissolved in the reaction solvent, it can be precipitated by distilling off the solvent under reduced pressure, adding an appropriate poor solvent to the reaction mixture, or discharging the reaction mixture into a poor solvent. It can be isolated by filtration or centrifugation.
If it is necessary to further purify the isolated maleimide compound, it may be purified using a known method. Examples of such methods include distillation purification, recrystallization, column chromatography, sludge treatment, and 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, for example, by liquid chromatography or IR spectroscopy. Volatile components such as by-products and residual solvent in the maleimide compound can be quantitatively analyzed by, for example, gas chromatography. Halogen compounds remaining in maleimide compounds can be identified, for example, with a liquid chromatography mass spectrometer, and can also be quantified by ion chromatography after decomposition by potentiometric titration with a silver nitrate solution or by the combustion method. . The polymerization reactivity of the maleimide compound can be evaluated, for example, by reaction enthalpy by differential scanning calorimetry and gelation time by hot plate method or torque measurement method.

[Resin composition]
The resin composition of this embodiment contains the maleimide compound of this embodiment. With this configuration, the resin composition of this embodiment can exhibit excellent adhesiveness with chips, substrates, and the like. In this embodiment, the content of the maleimide compound of this embodiment is 5 parts by mass or more with respect to 100 parts by mass of the resin composition of this embodiment, from the viewpoint of obtaining better adhesion with chips, substrates, etc. The amount is preferably 10 parts by mass or more, and 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 this embodiment includes a maleimide compound other than the maleimide compound of this embodiment (hereinafter also referred to as "another maleimide compound"), a cyanate ester compound, a phenol resin, an epoxy resin, and an oxetane as the resin or compound. It can further contain one or more selected from the group consisting of resins, benzoxazine compounds, carbodiimide compounds, and compounds having ethylenically unsaturated groups. Each of these components will be explained below.

(Other maleimide compounds)
Other maleimide compounds are not particularly limited as long as they are other than the maleimide compound of this embodiment and have one or more maleimide groups in the molecule. Specific examples include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimidohexanoic acid, 4 -Maleimidobutyric acid, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, 4,4-diphenylmethanebismaleimide, bis(3,5-dimethyl-4- maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m-phenylene Bismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3 ,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,2-bismaleimidoethane, 1,4-bismaleimidobutane, 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(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis( 3-Maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4-diphenylmethane biscitraconimide, 2,2-bis[4-(4-citraconimidophenoxy)phenyl]propane, bis( 3,5-dimethyl-4-citraconimidophenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis(3,5-diethyl-4-citraconimidophenyl)methane, polyphenyl Methane maleimide, polyphenylmethane maleimide, a maleimide compound represented by the following formula (8), a maleimide compound represented by the following formula (9), a maleimide compound represented by the following formula (10), a maleimide compound represented by the following formula (11), A maleimide compound represented by the following formula (12), such as a maleimide compound represented by the following formula (18), a maleimide compound represented by the following formula (13), a maleimide compound represented by the following formula (14), etc. maleimide compound represented by the following formula (15), 1,6-bismaleimido-(2,2,4-trimethyl)hexane (maleimide compound represented by the following formula (16)), the following formula Examples include the maleimide compound represented by (17), fluorescein-5-maleimide, prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds. These other maleimide compounds can be used alone or in a suitable mixture of two or more.

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

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

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

In formula (12), R ^a 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 in the alkyl group is preferably 1 to 16, more preferably 4 to 12 because it exhibits excellent photocurability.
The number of carbon atoms in the alkenyl group is preferably 1 to 16, more preferably 4 to 12 because it exhibits excellent photocurability.

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

In 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 in the alkyl group is preferably 1 to 16, more preferably 4 to 12 because it exhibits excellent photocurability.
The number of carbon atoms in the alkenyl group is preferably 1 to 16, more preferably 4 to 12 because it exhibits excellent photocurability.

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

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

In formula (12), the number 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 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 formula (14), n ₅ represents an integer of 1 or more, preferably an integer of 1 to 10.

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

(In the above formula (17), R ₇ each independently represents a hydrogen atom, a methyl group, or an ethyl group, and R ₈ each 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 formula (8) include BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd.
Examples of the maleimide compound represented by formula (9) include MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd.
Examples of the maleimide compound represented by formula (10) include BMI-1000P (trade name, n ₃ in formula (10) = 13.6 (average)) manufactured by K.I. Kasei Co., Ltd., K.I. BMI-650P manufactured by Kasei Co., Ltd. (product name, n ₃ in formula (10) = 8.8 (average)), BMI-250P manufactured by K-I Kasei Co., Ltd. (product name, formula (10)) n ₃ =3 to 8 (average)), CUA-4 manufactured by K.I. Kasei Co., Ltd. (trade name, n ₃ = 1 in formula (10)), and the like.
Examples of the maleimide compound represented by formula (11) include those manufactured by Designer Molecules Inc. BMI-6100 (trade name, x=18, y=18 in formula (11)) manufactured by Manufacturer Co., Ltd., and the like.
As the maleimide compound represented by formula (12), for example, those manufactured by Designer Molecules Inc. BMI-689 (trade name, formula (18) below, functional group equivalent: 346 g/eq.).

As the maleimide compound represented by formula (13), for example, those manufactured by Designer Molecules Inc. BMI-1500 (trade name, n ₄ in formula (13) = 1.3, functional group equivalent: 754 g/eq.).
As the maleimide compound represented by formula (14), commercially available products can also be used, for example, those available from Designer Molecules Inc. (DMI) BMI-1700 (trade name) is an example.
As the maleimide compound represented by formula (15), commercially available products can also be used, for example, those available from Designer Molecules Inc. (DMI) BMI-3000 (product name), Designer Molecules Inc. (DMI) BMI-5000 (product name), Designer Molecules Inc. (DMI) BMI-9000 (trade name) is an example.
As the maleimide compound represented by formula (16), commercially available products can also be used, such as BMI-TMH (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd.
As the maleimide compound represented by formula (17), commercially available products can be used, such as BMI-70 (trade name) manufactured by K.I. Kasei Co., Ltd.
These other maleimide compounds can be used alone or in a suitable mixture of two or more.

In the resin composition according to this embodiment, the total content of other maleimide compounds other than the maleimide compound of this embodiment is not particularly limited, but from the viewpoint of obtaining better adhesiveness with chips, substrates, etc. The amount is preferably 0.01 to 95 parts by weight, more preferably 1 to 90 parts by weight, based on 100 parts by weight of the resin solid content in the resin composition of the present embodiment.

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

For example, what is represented by formula (19) can be mentioned.

In formula (19), Ar ₁ represents a benzene ring, a naphthalene ring, or a single bond of two benzene rings. If there are more than one, they may be the same or different. Ra each independently represents 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, or an alkyl group having 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 substituents in Ar ₁ and Ra can be selected at arbitrary positions. p represents the number of cyanato groups bonded to Ar ₁ and is each independently an integer of 1 to 3; q indicates the number of Ra bonded to Ar ₁ ; when Ar ₁ is a benzene ring, it is 4-p, when it is a naphthalene ring, it is 6-p, and when two benzene rings are single-bonded, it is 8-p. . t indicates the average repeating number and is an integer from 0 to 50, and the cyanate ester compound may be a mixture of compounds having different t. If there is more than one X, each independently represents a single bond, a divalent organic group having 1 to 50 carbon atoms (the hydrogen atom may be substituted with a hetero atom), a divalent organic group having 1 to 10 nitrogen atoms. Organic groups (for example -N-R-N- (where R represents an organic group)), carbonyl groups (-CO-), carboxyl groups (-C(=O)O-), carbonyl dioxide groups ( -OC(=O)O-), a sulfonyl group (-SO ₂ -), a divalent sulfur atom, or a divalent oxygen atom.

The alkyl group in Ra in formula (19) may have either a linear or branched chain structure or a cyclic structure (for example, a cycloalkyl group).
Further, the hydrogen atom in the alkyl group in formula (19) and the aryl group in Ra 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, or a cyano group. good.

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

Specific examples of the divalent organic group having 1 to 50 carbon atoms in X in formula (19) include methylene group, ethylene group, trimethylene group, cyclopentylene group, cyclohexylene group, trimethylcyclohexylene group, biphenylyl methylene group. group, dimethylmethylene-phenylene-dimethylmethylene group, fluorenediyl group, and phthalidodiyl group. 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 1 to 10 nitrogen atoms for X in formula (19) include an imino group and a polyimide group.

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

In 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. Rb, Rc, Rf, and Rg each independently represent 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 the group. Rd and Re are each independently selected from 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 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. Ri and Rj each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group, Or it represents an aryl group substituted with at least one cyanato group. v represents an integer of 0 to 5, but may be a mixture of compounds with different v.

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

In the formula, z represents an integer from 4 to 7. Each Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
As a specific example of Ar ₂ in formula (20) and Ar ₃ in formula (21), two carbon atoms shown in formula (20) or two oxygen atoms shown in formula (21) are 1,4 a benzenediyl group bonded to the position or the 1,3 position, the two carbon atoms or the two oxygen atoms are the 4,4' position, the 2,4' position, the 2,2' position, the 2,3' position, a biphenyldiyl group bonded to the 3,3'-position or the 3,4'-position, and the two carbon atoms or two oxygen atoms are the 2,6-position, the 1,5-position, the 1,6-position, Examples include naphthalenediyl groups bonded to the 1, 8-position, 1, 3-position, 1, 4-position, or 2, 7-position.
The alkyl group and aryl group in Rb, Rc, Rd, Re, Rf and Rg of formula (20) and Ri and Rj of formula (21) have the same meanings as those in formula (19).

Specific examples of the cyanato-substituted aromatic compound represented by the formula (19) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1- cyanato-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-cyanaphenyl)-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-cyanatobenzoic acid methyl ester, 4-cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetaminobenzene, 4-cyanatobenzophenone, 1-cyanato-2,6 -di-tert-butylbenzene, 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato -2,4-dimethylbenzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1 -cyanato or 2-cyanato-naphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methoxynaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2'-dicyanato-1,1'-binaphthyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanatosinaphthalene, 2,2'- or 4,4'-dicyanatobiphenyl, 4,4'-dicyanatooctafluorobiphenyl, 2,4'- or 4,4'-dicyanatodiphenylmethane, 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-methylphenyl)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-dimethylpropane, 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-cyanatophenyl)-2-methylpentane, 3,3-bis(4-cyanatophenyl)-2-methylhexane, 3,3-bis(4-cyanatophenyl)-2,2-dimethyl Pentane, 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-cyanato phenyl)-1-phenylethane, bis(4-cyanatophenyl)biphenylmethane, 1,1-bis(4-cyanatophenyl)cyclopentane, 1,1-bis(4-cyanatophenyl)cyclohexane, 2, 2-bis(4-cyanato-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-dicyanatobenzophenone, 1,3 -Bis(4-cyanatophenyl)-2-propen-1-one, bis(4-cyanatophenyl) ether, bis(4-cyanatophenyl) sulfide, bis(4-cyanatophenyl) sulfone, 4- Cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl-4-cyanatobenzoate), bis-(4-cyanatophenyl) carbonate, 1,3-bis(4-cyanatophenyl)adamantane, 1 ,3-bis(4-cyanatophenyl)-5,7-dimethyladamantane, 3,3-bis(4-cyanatophenyl)isobenzofuran-1(3H)-one (cyanate of phenolphthalein), 3, 3-bis(4-cyanato-3-methylphenyl)isobenzofuran-1(3H)-one (cyanate of o-cresolphthalein), 9,9'-bis(4-cyanatophenyl)fluorene, 9,9 -bis(4-cyanato-3-methylphenyl)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-methylanilino)-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-cyanato-4-methylphenyl)-4,4'-oxydiphthalimide, bis( N-4-cyanato-2-methylphenyl)-4,4'-(hexafluoroisopropylidene)diphthalimide, tris(3,5-dimethyl-4-cyanatobenzyl)isocyanurate, 2-phenyl-3,3 -bis(4-cyanatophenyl)phthalimidine, 2-(4-methylphenyl)-3,3-bis(4-cyanatophenyl)phthalimidine, 2-phenyl-3,3-bis(4-cyanato-3- methylphenyl)phthalimidine, 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 can be used alone or in an appropriate mixture of two or more.

Other specific examples of the cyanate ester compound represented by the formula (19) include phenol novolak resin and cresol novolac resin (by a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin, paraformaldehyde, etc.) trisphenol novolak resin (reacted with hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), fluorene novolac resin (reacted with fluorenone compound and 9,9- bis(hydroxyaryl)fluorenes in the presence of an acidic catalyst), phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, and biphenylaralkyl resin (by a known method, Ar ₄ -(CH ₂ Y) ₂ (Ar ₄ represents a phenyl group and Y represents a halogen atom. The same applies hereinafter in this paragraph.) A product obtained by reacting a bishalogenomethyl compound and a phenol compound with an acidic catalyst or without a catalyst. , Ar ₄ -(CH ₂ OR) ₂ (R represents an alkyl group) and a phenol compound reacted in the presence of an acidic catalyst, or Ar ₄ - (CH ₂ OH) ₂ A bis(hydroxymethyl) compound and a phenol compound are reacted in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound, and a phenol compound are reacted together. phenol-modified xylene formaldehyde resin (by a known method, xylene formaldehyde resin and a phenol compound are reacted in the presence of an acidic catalyst), modified naphthalene formaldehyde resin (a naphthalene formaldehyde resin by a known method) and a hydroxy-substituted aromatic compound in the presence of an acidic catalyst), phenol-modified dicyclopentadiene resin, and phenol resin having a polynaphthylene ether structure (by a known method, a phenolic hydroxy group is reacted in one molecule). Examples include phenolic resins obtained by dehydration condensation of two or more polyhydric hydroxynaphthalene compounds in the presence of a basic catalyst), which are cyanated by the same method as above, and prepolymers thereof. It will be done. These are not particularly limited. These cyanate ester compounds can be used alone or in an appropriate mixture 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 form cyanate. Examples of the method for cyanating a hydroxy group include the method described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins," Blackie Academic & Professional.

Cured resin products using these cyanate ester compounds have excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.

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

(phenolic 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 novolak resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolak type phenol resin, biphenyl Aralkyl type phenolic resin, cresol novolac type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolak type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type Phenol 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 include, but are not particularly limited to. These phenolic resins can be used alone or in an appropriate mixture of two or more.

In the resin composition according to this embodiment, the total content of phenolic resin is not particularly limited, but is preferably 0.01 to 60 parts by mass in 100 parts by mass of resin solid content in the resin composition of this embodiment. 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 , tetrafunctional 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 aralkyl novolak type epoxy resin, naphthol aralkyl novolac type epoxy resin Epoxy resins, aralkyl novolac type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, polyol type epoxy resins, phosphorus-containing epoxy resins, glycidylamine, compounds with epoxidized double bonds such as butadiene, hydroxyl group-containing silicones Compounds obtained by the reaction of resins and epichlorohydrin, and halides thereof are included. These epoxy resins can be used alone or in an appropriate mixture of two or more.

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

(Oxetane resin)
As the oxetane resin, generally known ones can be used. For example, alkyloxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoro methyl) perfluoroxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (manufactured by Toagosei Co., Ltd., trade name), and OXT-121 (manufactured by Toagosei Co., Ltd.) (product name, product name), etc., but is not particularly limited. These oxetane resins can be used alone or in an appropriate mixture of two or more.

In the resin composition according to this embodiment, the total content of oxetane resin is not particularly limited, but is preferably 0.01 to 40 parts by mass in 100 parts by mass of resin solids in the resin composition of this embodiment. Department.

(Benzoxazine compound)
As the benzoxazine compound, any 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 (manufactured by Konishi Chemical Co., Ltd., trade name). (manufactured by Kagaku Co., Ltd., trade name), phenolphthalein type benzoxazine, etc., but are not particularly limited. These benzoxazine compounds can be used alone or in an appropriate mixture of two or more.

In the resin composition according to this embodiment, the total content of benzoxazine compounds is not particularly limited, but is preferably 0.01 to 40 parts by mass in 100 parts by mass of resin solids in the resin composition of this embodiment. Part by mass.

(Carbodiimide compound)
The carbodiimide compound is not particularly limited as long as it has at least one carbodiimide group 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 Stavaxole (registered trademark: manufactured by LANXESS Deutschland GmbH) etc. These carbodiimide compounds can be used alone or in an appropriate mixture of two or more.

In the resin composition according to this embodiment, the total content of carbodiimide compounds is not particularly limited, but is preferably 0.01 to 40 parts by mass in 100 parts by mass of resin solids in the resin composition of this embodiment. Department.

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

Examples of compounds 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, adipate epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth)acrylate, bisphenol di(meth)acrylate, ε-caprolactone modified hydroxypivalic acid neopene glycol Di(meth)acrylate, ε-caprolactone modified dipentaerythritol hexa(meth)acrylate, ε-caprolactone modified dipentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, Triethylolpropane tri(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, there are also urethane (meth)acrylates that have both a (meth)acryloyl group and a urethane bond in the same molecule; polyester (meth)acrylates that have both a (meth)acryloyl group and an ester bond in the same molecule; and epoxy Also included are epoxy (meth)acrylates derived from resins and having (meth)acryloyl groups; reactive oligomers in which these bonds are used in combination.

Examples of urethane (meth)acrylates include reaction products of hydroxyl group-containing (meth)acrylates, polyisocyanates, and other alcohols used as necessary. For example, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; ) Acrylates; 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, dicyclohexane methylene diisocyanate, isocyanurates thereof, polyisocyanates such as buret reaction products, etc. are reacted, urethane ( Examples include meth)acrylates.

Polyester (meth)acrylates include, for example, caprolactone-modified 2-hydroxyethyl (meth)acrylate, ethylene oxide and/or propylene oxide-modified phthalic acid (meth)acrylate, ethylene oxide-modified succinic acid (meth)acrylate, caprolactone-modified tetrahydrocarbon 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 a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. per 1 mol of trimethylolpropane or glycerin. Examples include mono-, di-, or tri(meth)acrylates of triols obtained by addition.

Monotriol obtained by adding 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mole of pentaerythritol, dimethylolpropane, trimethylolpropane, or tetramethylolpropane; Triol mono- or poly( Mono(meth)acrylates or poly(meth)acrylates of polyhydric alcohols such as triols, tetraols, pentaols, or hexaols of meth)acrylates are mentioned.

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

Epoxy (meth)acrylates are carboxylate compounds of a compound having an epoxy group and (meth)acrylic acid. For example, phenol novolak 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 novolac type epoxy (meth)acrylate, naphthalene skeleton-containing epoxy (meth)acrylate, glyoxal type epoxy (meth)acrylate, heterocyclic epoxy ( Examples include meth)acrylates, and acid anhydride-modified epoxy acrylates thereof.

Examples of compounds 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. Other vinyl compounds include triallyl isocyanurate, trimethallyl isocyanurate, bisallylnadimide, and the like.

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

In the resin composition according to this embodiment, the total content of compounds having ethylenically unsaturated groups is not particularly limited, but preferably in 100 parts by mass of resin solids in the resin composition of this embodiment. The amount is 0.01 to 40 parts by mass.

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

Examples of photocuring initiators include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and di-tert-butyl-di-perphthalate; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphos Phosphine oxides such as fin oxide, 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-hydroxychlorohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2 -morpholino-propan-1-one, and acetophenones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; 2-ethylanthraquinone, 2-t-butylanthraquinone, 2 - Anthraquinones such as chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone , 4-benzoyl-4'-methyldiphenyl sulfide, and benzophenones such as 4,4'-bismethylaminobenzophenone; 1,2-octanedione, and 1-[4-(phenylthio)-,2-(O- Radical photocuring initiators such as oxime esters such as benzoyl oxime),
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; Baurate initiators ; Examples include cationic photopolymerization initiators such as other photoacid generators.

A commercially available photocuring initiator can also be used, for example, IGM Resins B. V. Omnirad® 369 manufactured by IGM Resins B. V. Omnirad® 819 manufactured by IGM Resins B. V. Omnirad® 907 manufactured by IGM Resins B. V. Omnirad® TPO G, IGM Resins B. V. Examples include Omnirad (registered trademark) TPO LG manufactured by Omnirad (registered trademark).
These photocuring initiators can be used alone or in a suitable mixture of two or more.

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

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

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

In formula (23), a plurality of R ₁₀ 's each independently represent a hydrogen atom or a methyl group. In the formula (23), -* represents a bond with the phosphorus atom (P) in the formula (22).

The compound represented by the formula (22) can be determined by preparing a chloroform solution containing 0.01% by mass of this compound and measuring the absorbance of this chloroform solution using a light beam with a wavelength of 405 nm (h line). With an absorbance of 0.1 or more, it exhibits excellent absorption of light with a wavelength of 405 nm (h line). Therefore, this compound appropriately generates radicals with respect to light with a wavelength of 405 nm (h line).

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

In the formula (22), each of the plurality of R ₉ 's independently represents a substituent represented by the formula (23) or a phenyl group. It is preferable that one or more of the plurality of R ₉ 's is a substituent represented by the above formula (23).
In the formula (23), each of the plurality of R ₁₀ 's independently represents a hydrogen atom or a methyl group. It is preferable that one or more of the plurality of R ₁₀ 's is a methyl group, and more preferably 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, ethoxyphenyl( Examples include acylphosphine oxides such as 2,4,6-trimethylbenzoyl)-phosphine oxide. These compounds can be used alone or in an appropriate mixture of two or more.

The acylphosphine oxides of this embodiment exhibit very excellent absorption of active energy rays including wavelength 405 nm (h line), and have a transmittance of 5% or more at wavelength 405 nm (h line). Maleimide compounds can be suitably radically polymerized. Therefore, according to this embodiment, a resin composition, a resin sheet, and a multilayer printed wiring board using the same, which have excellent photocurability, heat resistance, and thermal stability, especially when used in a multilayer printed wiring board, and It becomes possible to suitably manufacture a semiconductor device.

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

(hardening accelerator)
The resin composition of the present embodiment may contain a curing accelerator to appropriately adjust the curing speed, if necessary. The curing accelerator is not particularly limited, and those commonly used as curing accelerators such as cyanate ester compounds and epoxy resins can be suitably used. Examples of hardening accelerators include organic metal salts such as zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetonate, nickel octylate, manganese octylate, phenol, xylenol, cresol, resorcinol, catechol, Phenol 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 or carboxylic acids of these imidazoles Derivatives such as adducts of acid anhydrides, amines such as dicyandiamide, benzyldimethylamine, 4-methyl-N,N-dimethylbenzylamine, phosphine compounds, phosphine oxide compounds, phosphonium salt compounds, diphosphine compounds Peroxides such as phosphorus compounds, epoxy-imidazole adduct compounds, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxy carbonate, di-2-ethylhexyl peroxy carbonate, etc. or azo compounds such as azobisisobutyronitrile. These can be used alone or in combination of two or more.
In the resin composition of this embodiment, the content of the curing accelerator is not particularly limited, but from the viewpoint of obtaining better adhesion with chips, substrates, etc. 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.

[Filling material]
The resin composition of this embodiment can further contain a filler in order to improve various properties such as coating properties and heat resistance. The filler is preferably one that has insulating properties and does not impede transparency to a wavelength of 405 nm (h-line). Examples of the filler include, but are not limited to, silica (e.g., natural silica, fused silica, amorphous silica, hollow silica, etc.), aluminum compounds (e.g., boehmite, aluminum hydroxide, alumina, aluminum nitride, etc.), and boron compounds. (e.g., boron nitride, etc.), magnesium compounds (e.g., magnesium oxide, magnesium hydroxide, etc.), calcium compounds (e.g., calcium carbonate, etc.), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), barium compounds (e.g. , barium sulfate, barium silicate, etc.), talc (e.g. natural talc, calcined talc, etc.), mica (mica), glass (e.g. short fibrous glass, spherical glass, fine powder glass (e.g. E glass, T glass) , D glass, etc.), silicone powder, fluororesin filler, urethane resin filler, (meth)acrylic resin filler, polyethylene filler, styrene-butadiene rubber, and silicone rubber. These fillers can be used alone or in an appropriate mixture of two or more.

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

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

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, the content of the filler is 1000 parts by mass based on 100 parts by mass of the resin solid content in the resin composition. It is preferably at most parts by mass, more preferably at most 500 parts by mass, and most preferably at most 300 parts by mass. In addition, when containing a filler, the lower limit is not particularly limited, but from the viewpoint of obtaining the effect of improving various properties such as coating properties and heat resistance, the resin solid content in the resin composition should be 100 parts by mass. On the other hand, it is usually 1 part by mass.

<Silane coupling agent and wetting and dispersing agent>
In the resin composition of this embodiment, a silane coupling agent and/or a wetting and dispersing agent may be used together in order to improve the dispersibility of the filler and the adhesive strength between the polymer and/or resin and the filler. It is possible.
These silane coupling agents are not particularly limited as long as they are silane coupling agents that are generally used for surface treatment of inorganic materials. Specific examples include 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 Aminosilanes such as [3-(N,N-dimethylamino)-propyl]trimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethyl Epoxysilane systems 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. vinyl silane type; methacrylsilane type such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane, 3-acryloxy Acrylic silanes such as propyltrimethoxysilane and 3-acryloxypropyltriethoxysilane; Isocyanate silanes such as 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane; Tris-(trimethoxysilylpropyl) Isocyanurate silanes such as isocyanurate; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyldimethoxymethylsilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; p-styryltrimethoxysilane Styrylsilanes such as; N-[2-(N-vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane hydrochloride and other cationic silanes; [3-(trimethoxysilyl)propyl]succinic anhydride Acid anhydrides such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, and p-tolyltrimethoxysilane; trimethoxy(1-naphthyl)silane, etc. Examples include arylsilane series. These silane coupling agents can be used alone or in an appropriate mixture 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 based on 100 parts by mass of resin solid content in the resin composition.
The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints. Specific examples include wetting and dispersing agents such as DISPERBYK (registered trademark) -110, 111, 118, 180, 161, BYK (registered trademark) -W996, W9010, W903 manufactured by Big Chemie Japan Co., Ltd. . These wetting and dispersing agents can be used alone or in a suitable mixture of two or more.
In the resin composition of the present embodiment, the content of the wetting and dispersing agent is not particularly limited, but is usually 0.1 to 10 parts by mass based on 100 parts by mass of resin solid content in the resin composition.

<Organic solvent>
The resin composition of this embodiment may contain an organic solvent, if necessary. By using an organic solvent, the viscosity can be adjusted during the preparation of the resin composition. The type of organic solvent is not particularly limited as long as it can dissolve part or all of the resin in the resin composition. Specific examples include, but are not limited to, 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 γ-butyrolactone; ester solvents such as dimethylacetamide and dimethylformamide Polar solvents such as amides such as and non-polar solvents such as aromatic hydrocarbons such as toluene and xylene.
These organic solvents can be used alone or in an appropriate mixture of two or more.

<Other ingredients>
The resin composition of this embodiment may contain various polymers such as thermosetting resins, thermoplastic resins, oligomers thereof, and elastomers that have not been mentioned so far, as long as the characteristics of this embodiment are not impaired. It is also possible to use compounds; flame-retardant compounds not mentioned so far; additives, etc. These are not particularly limited as long as they are commonly used. Examples of flame-retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, phosphate compounds of phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters. Additives include ultraviolet absorbers, antioxidants, optical brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, surface conditioners, brighteners, polymerization inhibitors, and curing accelerators. agents, etc. These components can be used alone or in an appropriate mixture of two or more.
In the resin composition of the present embodiment, the content of the other components is not particularly limited, but is usually 0.1 to 10 parts by mass each based on 100 parts by mass of resin solid content in the resin composition.

<Method for manufacturing resin composition>
The resin composition of this embodiment is prepared by appropriately mixing the maleimide compound of this embodiment with a resin or compound, a photocuring initiator, a filler, other components, additives, etc. as necessary. Ru. The resin composition of this embodiment can be suitably used as a varnish when producing the resin sheet of this embodiment described later.

The method for producing the resin composition of the present embodiment is not particularly limited, and includes, for example, a method in which each of the above-mentioned components is sequentially blended into a solvent and thoroughly stirred.

During production of the resin composition, known treatments (stirring, mixing, kneading, etc.) for uniformly dissolving or dispersing each component can be performed as necessary. Specifically, the dispersibility of the filler in the resin composition can be improved by performing the stirring and dispersion treatment using a stirring tank equipped with a stirrer having an appropriate stirring capacity. The above-mentioned stirring, mixing, and kneading processes can be performed using, for example, a stirring device for dispersion such as an ultrasonic homogenizer, a device for mixing such as a three-roll mill, a ball mill, a bead mill, a sand mill, or a revolving or rotating type. This can be carried out appropriately using a known device such as a mixing device. Moreover, when preparing the resin composition of this embodiment, an organic solvent can be used as necessary. The type of 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.

<Application>
The resin composition of this embodiment can be used for applications requiring an insulating resin composition, including but not limited to photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuits, etc. Can be used for substrates (laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulating materials, hole-filling resins, component embedding resins, fiber-reinforced composite materials, etc. . Among them, the resin composition of the present embodiment has excellent adhesion to chips and substrates, etc., as well as excellent heat resistance and thermal stability, so it can be used for insulating layers of multilayer printed wiring boards or for solder resists. It can be suitably used as

[Cured product]
The cured product of this embodiment is obtained by curing the resin composition of this 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, etc. In the case of thermal curing, the curing temperature is not particularly limited, but is preferably within 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 range of light is not particularly limited, but it is preferable to carry out curing in the range of 100 nm to 500 nm, where curing proceeds efficiently using a photopolymerization initiator or the like.

[Resin sheet]
The resin sheet of the present embodiment includes a support and a resin layer disposed on one or both sides of the support, and the resin layer includes a support-attached resin containing the resin composition of the present embodiment. It is a sheet. A resin sheet can be manufactured by applying a resin composition onto a support and drying it. The resin layer in the resin sheet of this embodiment has excellent adhesion to chips, substrates, etc., as well as excellent heat resistance and thermal stability.

Any known support can be used, and 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. film, triacetylacetate film, and the like. Among them, PET film is preferred.

A resin film whose surface is coated with a release agent can be suitably used in order to facilitate peeling from the resin layer. 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 easily torn when peeled off, and if the thickness exceeds 100 μm, the resolution during exposure from above the support tends to decrease.

Further, in order to reduce scattering of light during exposure, the resin film preferably has excellent transparency.

Furthermore, in the resin sheet in this embodiment, the resin layer may be protected with 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 from scratching it. 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, more preferably in the range of 5 to 40 μm. If the thickness is less than 1 μm, the protective film tends to be difficult to handle, and if it exceeds 50 μm, it tends to be less affordable. Note that the protective film is preferably one in which the adhesive force between the resin layer and the protective film is smaller than the adhesive force between the resin layer and the support.

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

The amount of organic solvent remaining in the resin layer is preferably 5% by mass or less based on the total mass of the resin layer, from the viewpoint of preventing diffusion of the organic solvent in subsequent steps. The thickness of the resin layer is preferably 1 to 50 μm from the viewpoint of improving handleability.

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

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

As the base material used in manufacturing the prepreg of this embodiment, known materials used for various printed wiring board materials can be used. Examples of the base material include, but are not limited to, inorganic fibers other than glass such as glass fiber 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 fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, etc. are known, and any of these may be used. One type of base material can be used alone or two or more types can be used in combination. Among woven fabrics, woven fabrics subjected to super-opening treatment or packing treatment are particularly suitable from the viewpoint of dimensional stability. Liquid crystal polyester woven fabric is preferred from the viewpoint of electrical properties. The thickness of the base material is not particularly limited, but for use in laminates, it is preferably in the range of 0.01 to 0.2 mm.

[Metal foil laminate]
The metal foil-clad laminate of this embodiment includes a layer containing at least one member selected from the group consisting of the resin sheet of this embodiment and the prepreg of this embodiment, and a metal foil disposed on one or both sides of the layer. and the layer includes a cured product of the resin composition according to the present embodiment. When using prepreg, for example, metal foil such as copper or aluminum is placed on one or both sides of one prepreg or a stack of multiple prepregs, and lamination molding is performed. It can be produced by The metal foil used here is not particularly limited as long as it is used for printed wiring board materials, but copper foils such as rolled copper foil and electrolytic copper foil are preferred. The thickness of the metal foil is not particularly limited, but is preferably from 2 to 70 μm, more preferably from 3 to 35 μm. As the molding conditions, methods used in the production of normal printed wiring board laminates and multilayer boards can be adopted. For example, lamination molding is performed using a multi-stage press machine, multi-stage vacuum press machine, continuous molding machine, or autoclave molding machine 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/ ^cm2 . In this manner, the metal foil-clad laminate of this embodiment can be manufactured. Moreover, a multilayer board can also be produced by laminating and molding a combination of the prepreg described above and a separately produced wiring board for an inner layer. As a method for manufacturing a multilayer board, for example, 35 μm copper foil is placed on both sides of the prepreg described above, laminated under the above conditions, an inner layer circuit is formed, and this circuit is subjected to a blackening treatment. to form an inner layer circuit board. Furthermore, this inner layer circuit board and the prepreg described above are alternately arranged one by one, and a copper foil is further arranged as the outermost layer, and lamination molding is performed under the above conditions, preferably under vacuum. In this way, a multilayer board can be produced.

The metal foil-clad laminate of this 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. An example of a method for manufacturing a printed wiring board will be shown below.
First, the metal foil-clad laminate described above is prepared. Next, the surface of the metal foil-clad laminate is etched to form an inner layer circuit, thereby producing an inner layer substrate. The surface of the inner layer circuit of this inner layer substrate is subjected to a surface treatment to increase adhesive strength, if necessary, and then a required number of sheets of the prepreg described above are stacked on the surface of the inner layer circuit. Furthermore, a metal foil for an outer layer circuit is laminated on the outside thereof, and is integrally formed by heating and pressurizing. In this way, a multilayer laminate is produced in which a base material and an insulating layer made of a cured product of a thermosetting resin composition are formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after drilling holes for through holes and via holes in this multilayer laminate, a plated metal film is formed on the wall surface of the hole to conduct the inner layer circuit and the metal foil for the outer layer circuit. Furthermore, a printed wiring board is manufactured by etching the metal foil for the outer layer circuit to form an outer layer circuit.

The printed wiring board obtained in the above manufacturing example has an insulating layer and a conductor layer formed on one or both sides of the insulating layer, and the insulating layer contains the resin composition of this embodiment. For example, the prepreg of this embodiment (the base material and the resin composition of this embodiment impregnated or applied thereto), the layer of the resin composition of the metal foil-clad laminate of this embodiment (the resin composition of this embodiment) ) can constitute an insulating layer containing the resin composition of this embodiment.

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

The printed wiring board obtained in the above manufacturing example has an insulating layer and a conductor layer formed on one or both sides of the insulating layer, and the insulating layer contains the resin composition of this embodiment. For example, the prepreg of this embodiment (the base material and the resin composition of this embodiment impregnated or applied thereto), the layer of the resin composition of the metal foil-clad laminate of this embodiment (the resin composition of this embodiment) ) can constitute an insulating layer containing the resin composition of this embodiment.

[Sealing material]
The sealing material of this embodiment includes the resin composition of this embodiment. The method for producing the sealing material is not particularly limited, and any generally known method can be appropriately applied. For example, a sealing material can be manufactured by mixing the resin composition of the present embodiment with various known additives or solvents commonly used in sealing material applications using a known mixer. can. Note that the method of adding the maleimide compound of this embodiment, various additives, and solvent during mixing is not particularly limited, and generally known methods can be appropriately applied.

[Fiber reinforced composite material]
The fiber reinforced composite material of this embodiment includes the resin composition of this embodiment and reinforcing fibers. Generally known reinforcing 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 fibers include silicon carbide fibers. The form and arrangement of the reinforcing fibers are not particularly limited, and can be appropriately selected from woven fabrics, nonwoven fabrics, mats, knits, braided cords, unidirectional strands, rovings, chopped, and the like. In addition, as a form of reinforcing fiber, a preform (a laminated fabric base fabric made of reinforcing fibers, a fabric that is sewn together with stitch thread, or a fiber structure such as a three-dimensional fabric or a braided fabric) can be applied. You can also do it.

The method for manufacturing these fiber reinforced composite materials is not particularly limited, and generally known methods can be applied as appropriate. Examples include liquid composite molding, resin film infusion, filament winding, hand layup, and pultrusion. Among these, the resin transfer molding method, which is one of the liquid composite molding methods, allows materials other than preforms, such as metal plates, foam cores, and honeycomb cores, to be set in advance in the mold. Since it can be used for various purposes, it is preferably used when mass-producing composite materials with relatively complex shapes in a short period of time.

[glue]
The adhesive of this embodiment includes the resin composition of this embodiment. The method for producing the adhesive is not particularly limited, and any generally known method can be appropriately applied. For example, an adhesive can be produced by mixing the resin composition of the present embodiment with various known additives or solvents commonly used in adhesive applications using a known mixer. Note that the method of adding the maleimide compound of this embodiment, various additives, and solvent during mixing is not particularly limited, and generally known methods can be appropriately applied.

[Semiconductor device]
The semiconductor device of this embodiment has the resin composition of this embodiment. Specifically, it can be manufactured by the following method. A semiconductor device can be manufactured by mounting a semiconductor chip on the conductive portion of the multilayer printed wiring board of this embodiment. Here, the conductive location refers to a location on the multilayer printed wiring board that transmits electrical signals, and the location may be on the surface or may be a buried location. 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 this embodiment is not particularly limited as long as the semiconductor chip functions effectively, but specifically, wire bonding mounting method, flip chip mounting method, bumpless build method, etc. Examples 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).

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

Hereinafter, this embodiment will be described in more detail using Examples and Comparative Examples. This embodiment is not limited in any way by 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 amidic 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) were added to a 500 mL four-necked flask equipped with an argon inlet, a Dean-Stark apparatus, a Dimroth condenser, and a 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 Co., Ltd., an adduct of metaxylylene diamine 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 portion of the reaction solution was taken out, 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 performed on the solid after washing with ethanol, and it was confirmed that it was MA-G328 represented by formula (25).
Incidentally, a ¹ H-NMR chart of the amidic acid compound (MA-G328) is shown in FIG. A peak attributed to terminal carboxyl group hydrogen was observed at 9.4 ppm. Furthermore, 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 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 ground 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 H-NMR measurement (500 MHz, DMSO-d6), it was found to be BMI-G328 represented by formula (24) (a mixture where n in formula (24) is 1 to 20). I confirmed that there is.
Incidentally, a ¹ H-NMR chart of the maleimide compound (BMI-G328) is shown in FIG. As shown in Figure 2, the peak (6.2-6.5 ppm) assigned to the alkene hydrogen observed in ¹ H-NMR of MA-G328 disappeared, and the peak assigned to the alkene hydrogen of the maleimide ring ( 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, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad (registered trademark) manufactured by IGM Resins B.V.) as a photocuring initiator ) 819) and 400 parts by mass of dimethylacetamide were mixed and 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, it was exposed using an exposure machine (manufactured by Oak Seisakusho Co., Ltd., HMW-201GX (trade name)) at a wavelength of 405 nm (H-line) with an exposure amount of 10,000 mJ/cm ² The coating film was cured by irradiation 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 parts by mass were changed to 80 parts by mass.

<Evaluation of adhesion>
In order to evaluate adhesiveness, a cross-cut test was conducted according to JIS-K5600-5-6. Specifically, six incisions were made perpendicularly to each other at 1 mm intervals in each of the vertical and horizontal directions in the cured products with Si wafers obtained in Example 2 and Comparative Example 1 to form a 25-square rectangular grid. A pattern was created. The cured product with the cut Si wafer was heated in a pressure cooker (temperature: 121°C, humidity: 100% RH, pressure: 2 atm) for up to 3 hours, up to 5 hours, and up to 24 hours. After performing the pressure and moisture absorption treatment, a peeling test of the cured product from the Si wafer was performed using a transparent adhesive tape (manufactured by Cortech Co., Ltd., trade name "SP3209") under a room temperature environment.
The number of residual cured products (coating films) before and after the peel test was visually counted. The results are shown in Table 1.

As is clear from Table 1, the maleimide compound of this embodiment was confirmed to have excellent adhesiveness to chips, substrates, and the like.

The maleimide compound of the present invention exhibits excellent adhesion to chips, substrates, etc., and is therefore industrially useful, such as photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards ( It can be used for applications such as laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor sealing materials, hole filling resins, component embedding resins, fiber reinforced composite materials, etc.

Claims (19)

A maleimide compound represented by the following formula (1).

(In formula (1), R ₁ is each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a straight chain having 1 to 6 carbon atoms. represents a linear or branched alkoxy group, 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. 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 represent an integer from 1 to 4). The maleimide compound according to claim 1, which is represented by the following formula (2).

(In formula (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 formula (3), R ₁ is each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a straight chain having 1 to 6 carbon atoms. represents a linear or branched alkoxy group, 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 each independently represents an integer from 1 to 4.) A method for producing a maleimide compound represented by the following formula (1), comprising a step of subjecting an amic acid compound represented by the following formula (4) to a dehydration ring-closing reaction.

(In formula (4), R ₁ is each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a straight chain having 1 to 6 carbon atoms. represents a linear or branched alkoxy group, 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. 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 from 1 to 4).

(In formula (1), R ₁ is each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a straight chain having 1 to 6 carbon atoms. represents a linear or branched alkoxy group, 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. 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 from 1 to 4). An amidic acid compound represented by the following formula (4).

(In formula (4), R ₁ is each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a straight chain having 1 to 6 carbon atoms. represents a linear or branched alkoxy group, 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. 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 from 1 to 4). A method for producing an amic acid compound represented by the following formula (4), which includes the step of subjecting an amine compound represented by the following formula (3) to an addition reaction with an acid anhydride represented by the following formula (5).

(In formula (3), R ₁ is each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a straight chain having 1 to 6 carbon atoms. represents a linear or branched alkoxy group, 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 each independently represents an integer from 1 to 4.)

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

(In formula (4), R ₁ is each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a straight chain having 1 to 6 carbon atoms. represents a linear or branched alkoxy group, 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. 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 represent an integer from 1 to 4). A resin composition comprising the maleimide compound according to any one of claims 1 to 3. A maleimide compound other than the maleimide compound according to any one of claims 1 to 3, a cyanate ester compound, a phenol resin, an epoxy resin, an oxetane resin, a benzoxazine compound, a carbodiimide compound, and a compound 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 comprising the resin composition according to any one of claims 7 to 10. a support and
a resin layer disposed on one or both sides of the support,
The resin layer contains the resin composition according to any one of claims 7 to 10.
resin sheet. base material and
The resin composition according to any one of claims 7 to 10, impregnated or applied to the base material,
Including prepreg. A layer containing at least one member selected from the group consisting of the resin sheet according to claim 12 and the prepreg according to claim 13;
a metal foil disposed on one or both sides of the layer;
has
A metal foil-clad laminate, wherein the layer includes a cured product of the resin composition. an insulating layer;
a conductor layer formed on one or both sides of the insulating layer;
has
A multilayer printed wiring board, wherein the insulating layer contains the resin composition according to any one of claims 7 to 10. A sealing material comprising the resin composition according to any one of claims 7 to 10. The resin composition according to any one of claims 7 to 10,
reinforcing fiber,
fiber-reinforced composite materials, including An adhesive comprising the resin composition according to any one of claims 7 to 10. A semiconductor device comprising the resin composition according to any one of claims 7 to 10.