TW202415729A - Resin composition, resin sheet, multilayer printed wiring board, and semiconductor device - Google Patents

Abstract

Provided are a resin composition that does not inhibit a photocuring reaction in an exposure step and that can provide excellent alkali developability in a development step, and a resin sheet, a multilayer printed wiring board, and a semiconductor device using the same. A resin composition comprising a bismaleimide compound (A) represented by general formula (1), a compound (B) containing one or more carboxy groups, and a photocuring initiator (C). (In formula (1), R3 independently represent a tetravalent organic group containing a cyclic structure. R2 independently are a C6-200 divalent hydrocarbon group. R1 independently are represented by formula (2) (R5 each independently represent a hydrogen atom, a C1-6 linear or branched alkyl group, a halogen atom, a hydroxy group, or a C1-6 linear or branched alkoxy group. I each independently represent an integer of 1-4.). R4 is R1 or R2. m is 1-100 and n is 0-100. Also, the order of each repeating unit bracketed by m and n is not limited, and the bonding pattern may be alternate, block, or random.).

Description

Resin composition, resin sheet, multilayer printed wiring board, and semiconductor device

The present invention relates to a resin composition, a resin sheet, a multilayer printed wiring board, and a semiconductor device.

In recent years, especially with the progress in the field of cutting-edge materials, there is a demand for the development of higher performance materials. For example, for materials suitable for large-capacity communication equipment, antenna modules for smartphones, and cable systems for laptops; materials suitable for millimeter wave radar; and equipment related to automatic braking devices in cars, there is a growing demand for electronic circuit substrates with better dielectric properties, heat resistance, low stress, water resistance, and adhesion.

Previously, cyanate resins are widely known as thermosetting resins that have excellent heat resistance, low dielectric constant, and low dielectric loss. For example, Patent Document 1 discloses a phenol novolac-type cyanate resin as a resin that has excellent heat resistance and storage stability. However, although the cured product obtained by using the phenol novolac-type cyanate resin described in Patent Document 1 has excellent thermal expansion resistance, it has a large water absorption rate and sometimes has deteriorated dielectric properties.

In addition, due to the miniaturization and high density of multi-layer printed wiring boards, research on thinning the laminates used in multi-layer printed wiring boards is prevalent. With the thinning, the insulating layer is also required to be thinner, and resin sheets that do not contain glass cloth are required. The resin composition used as the material of the insulating layer is mainly thermosetting resin, and the opening for achieving conduction between the insulating layers is generally performed by laser processing.

On the other hand, the problem of drilling holes by laser processing is that the more holes there are in a high-density substrate, the longer the processing time. Therefore, in recent years, a resin sheet that can perform batch drilling processing in the exposure and development steps has been sought by using a resin composition in which the exposed part is hardened by irradiation with light or the like (exposure step) and the unexposed part can be removed (development step).

As an exposure method, a method of using a mercury lamp as a light source and exposing through a photomask is used, and a material that can be properly exposed in the light source of the mercury lamp is sought. The exposure method using the mercury lamp as a light source uses GHI mixed rays (G-ray wavelength 436 nm, H-ray wavelength 405 nm, I-ray wavelength 365 nm), etc., so that a universal photocuring initiator can be selected. In addition, in recent years, as an exposure method, the introduction of a direct drawing exposure method is also being promoted. The direct drawing exposure method is based on the digital data of the pattern and is directly drawn on the photosensitive resin composition layer without a photomask. Compared with the exposure method with a photomask, the direct drawing exposure method has good positioning accuracy and can obtain a high-precision pattern. Therefore, it is particularly promoted in substrates that need to form high-density wiring. The light source used is monochromatic light such as laser. In the digital micro mirror device (DMD) type device that can form a high-precision resist pattern, a light source with a wavelength of 405 nm (h-ray) is used.

As a developing method, alkaline development can be used in order to obtain a high-definition pattern.

In the photosensitive resin composition used for such a laminate or resin sheet, a compound having an ethylenically unsaturated group such as (meth)acrylate is used in order to enable rapid hardening in the exposure step. For example, Patent Document 2 describes a photosensitive thermosetting resin composition comprising a carboxyl-modified epoxy (meth)acrylate resin, a biphenyl-type epoxy resin, a photohardening initiator, and a diluent. The carboxyl-modified epoxy (meth)acrylate resin is obtained by reacting a bisphenol-type epoxy resin with (meth)acrylic acid and then reacting an acid anhydride.

In addition, Patent Document 3 describes a resin composition comprising: a photocurable binder polymer, a photopolymerizable compound having an ethylenic unsaturated bond, a photopolymerization (curing) initiator, a sensitizer, and a diallylnadic imide compound and a dimaleimide compound as a thermal curing agent.

Patent Document 4 describes a resin composition containing a bismaleimide compound (curable resin) and a photoradical polymerization initiator (curing agent) as a photosensitive resin composition for use in laminates or resin sheets.

Patent document 5 describes a resin composition including a compound containing a polycarboxyl group and a curable resin such as an epoxy resin, wherein the polycarboxyl group-containing compound is obtained by reacting dimaleimide with a monoamine and then reacting with an acid anhydride. Patent document 5 also describes a polycarboxyl group-containing compound that can produce a cured product having alkaline developability. [Prior art document] [Patent document]

[Patent Document 1] Japanese Patent Publication No. 11-124433 [Patent Document 2] Japanese Patent Publication No. 2005-62450 [Patent Document 3] Japanese Patent Publication No. 2010-204298 [Patent Document 4] WO2018/56466A1 [Patent Document 5] Japanese Patent Publication No. 2015-229734

[Problems to be solved by the invention] However, the cured products using the conventional (meth)acrylate resins cannot obtain sufficient physical properties and have limitations in forming excellent protective films and interlayer insulation layers. In addition, the alkaline developability of the cured products is insufficient, and high-precision anti-etching patterns cannot be obtained, which poses a problem when used in high-density printed wiring boards.

The hardened material obtained from the resin composition described in Patent Document 1 also has insufficient alkali developability and cannot obtain a high-precision resist pattern, which causes problems when used in high-density printed wiring boards.

Patent Document 2 describes the use of a bismaleimide compound, but it is described as a thermosetting agent, and (meth)acrylate is used as a photopolymerizable compound. Therefore, the hardened material obtained from the resin composition has insufficient alkali developability, and a high-precision anti-corrosion pattern cannot be obtained, which is problematic when used in high-density printed wiring boards.

Since the resin composition of Patent Document 3 has insufficient alkaline developability, unexposed resin composition remains even after development. Therefore, in Patent Document 3, a high-precision resist pattern cannot be obtained, and the resin composition cannot be used in the manufacture of high-density printed wiring boards.

The polycarboxyl group-containing compound described in Patent Document 4 needs to be obtained by reacting bismaleimide with a monoamine and then reacting an acid anhydride, so the steps are complicated. In addition, since an aromatic amine compound is used as the monoamine, the polycarboxyl group-containing compound contains an amide group having an aromatic ring in its structure. Therefore, the polycarboxyl group-containing compound has poor light transmittance and hinders the photocuring reaction, so it is difficult to use it in a photosensitive resin composition in practice.

Therefore, the present invention is made in view of the above-mentioned problems, and provides a resin composition, a resin sheet using the resin composition, a multilayer printed wiring board, and a semiconductor device. When the resin composition is used to manufacture a printed wiring board, it does not hinder the photocuring reaction in the exposure step and has excellent photocurability, and can provide excellent alkali development in the development step. [Means for solving the problem]

The inventors of the present invention have found that the above-mentioned problems can be solved by using a resin composition comprising a specific bismaleimide compound (A), a compound having one or more carboxyl groups (B), and a photocuring initiator (C), thereby completing the present invention.

That is, the present invention includes the following contents. [1] A resin composition comprising: a dimaleimide compound (A) represented by the following general formula (1), a compound (B) containing one or more carboxyl groups, and a photocuring initiator (C).

[Chemistry 1]

(In formula (1), R ₃ independently represents a tetravalent organic group containing a cyclic structure; R ₂ independently represents a divalent alkyl group having 6 to 200 carbon atoms; R ₁ independently represents a tetravalent alkyl group having 6 to 200 carbon atoms;

[Chemistry 2]

( _R5 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms; l each independently represents an integer of 1 to 4); _R4 is _R1 or _R2 ; m is 1 to 100, and n is 0 to 100; in addition, the order of each repeating unit enclosed by m and n is not limited, and the bonding pattern may be alternating, block, or random) [2] The resin composition as described in [1], wherein the compound (B) containing one or more carboxyl groups is at least one compound selected from the group consisting of a compound represented by the following formula (3), a compound represented by the following formula (4), a compound represented by the following formula (5), and a compound represented by the following formula (6).

[Chemistry 3]

(In formula (3), R ₆ each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group or an aminomethyl group; o each independently represents an integer from 1 to 5; in formula (3), when there are two or more carboxyl groups, these groups may be linked to form an acid anhydride)

[Chemistry 4]

(In formula (4), _R7 each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group or an aminomethyl group; p each independently represents an integer of 1 to 9; in formula (4), when there are two or more carboxyl groups, these groups may be linked to form an acid anhydride; in formula (4), when there is a carboxymethyl group, a carboxymethyl group and a carboxyl group may be linked to form an acid anhydride)

[Chemistry 5]

(In formula (5), _R8 each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group or an aminomethyl group; q each independently represents an integer of 1 to 9; in formula (5), when there are two or more carboxyl groups, these groups may be linked to form an acid anhydride; in formula (5), when there is a carboxymethyl group, a carboxymethyl group and a carboxyl group may be linked to form an acid anhydride)

[Chemistry 6]

(In formula (6), _R9 each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group or an aminomethyl group; r each independently represents an integer of 1 to 5; in formula (6), when there are one or more carboxyl groups, the acid anhydride formed by a carboxymethyl group and a carboxyl group bonded to each other may be used; in formula (6), when there are two or more carboxyl groups, the acid anhydride formed by a bonded group thereof may be used; in formula (6), when there are two or more carboxylmethyl groups, the acid anhydride formed by a bonded group thereof may be used). [3] The resin composition according to [1] or [2], comprising a bismaleimide compound (A) represented by the following formula (1), wherein the organic group represented by _R3 is any one of the tetravalent organic groups represented by the following structural formulas (7) to (15).

[Chemistry 7]

(In formula (1), R ₃ independently represents a tetravalent organic group containing a cyclic structure; R ₂ independently represents a divalent alkyl group having 6 to 200 carbon atoms; R ₁ independently represents a tetravalent alkyl group having 6 to 200 carbon atoms;

[Chemistry 8]

(R ₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms; l each independently represents an integer of 1 to 4); R ₄ is R ₁ or R ₂ ; m is 1 to 100, and n is 0 to 100; in addition, the order of each repeating unit enclosed by m and n is not limited, and the bonding pattern may be alternating, block, or random)

[Chemistry 9]

(In formula (11), Y represents C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond or the following formula (16) [Chemical 10]

The divalent linking group represented by

-* in the structural formula represents a bond, and in formula (1), it is bonded to the carbonyl carbon forming the cyclic imide structure. [4] The resin composition as described in any one of [1] to [3], wherein the photocuring initiator (C) comprises a compound represented by the following formula (17).

[Chemistry 11] (In formula (17), _R10 each independently represents a substituent represented by the following formula (18) or a phenyl group)

[Chemistry 12]

(In formula (18), -* represents a bond, and R ₁₁ each independently represents a hydrogen atom or a methyl group). [5] A resin sheet comprising: a support; and a resin layer disposed on one or both surfaces of the support, wherein the resin layer comprises a resin composition as described in any one of [1] to [4]. [6] A resin sheet as described in [5], wherein the thickness of the resin layer is 1 μm to 50 μm. [7] A multilayer printed wiring board comprising: an insulating layer; and a conductive layer formed on one or both surfaces of the insulating layer, wherein the insulating layer comprises a resin composition as described in any one of [1] to [4]. [8] A semiconductor device comprising the resin composition described in any one of [1] to [4]. [Effects of the Invention]

The present invention can provide a resin composition, a resin sheet using the resin composition, a multilayer printed wiring board, and a semiconductor device. When the resin composition is used to manufacture a multilayer printed wiring board, it does not hinder the photocuring reaction in the exposure step and has excellent photocurability, and can provide excellent alkali developability in the development step.

The following is a detailed description of a method for implementing the present invention (hereinafter referred to as "this embodiment"). The following this embodiment is an example for explaining the present invention, and the present invention is not limited to the following content. The present invention can be appropriately modified and implemented within the scope of its gist.

In addition, the term "(meth)acryloxy" in this specification refers to both "acryloxy" and its corresponding "methacryloxy", the term "(meth)acrylate" refers to both "acrylate" and its corresponding "methacrylate", and the term "(meth)acrylic acid-" refers to both "acrylic acid-" and its corresponding "methacrylic acid-".

[Resin composition] The resin composition of this embodiment includes a specific dimaleimide compound (A), a compound containing one or more carboxyl groups (B), and a photocuring initiator (C). Each component is described below.

<Bismaleimide compound (A)> The bismaleimide compound (A) of the present invention is a compound having two maleimide groups, and is represented by the following general formula (1)

[Chemistry 13]

(In formula (1), R ₃ independently represents a tetravalent organic group containing a cyclic structure; R ₂ independently represents a divalent alkyl group having 6 to 200 carbon atoms; R ₁ independently represents a tetravalent alkyl group having 6 to 200 carbon atoms;

[Chemistry 14]

(R ₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms; l each independently represents an integer of 1 to 4); R ₄ is R ₁ or R ₂ ; m is 1 to 100, and n is 0 to 100; in addition, the order of each repeating unit enclosed by m and n is not limited, and the bonding pattern may be alternating, block, or random).

In the above formula (2), R ₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms.

The linear or branched alkyl group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. Among these, alkyl groups having 1 to 4 carbon atoms are preferred, and methyl, ethyl, n-propyl, and isopropyl are more preferred, in terms of excellent adhesion to wafers and substrates, good solubility in solvents, low melting points, low water absorption, and good compatibility with other resins. Halogen atoms include fluorine, chlorine, bromine, and iodine atoms. The linear or branched alkoxy group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy, and tert-butoxy. Among these, alkoxy groups having 1 to 4 carbon atoms are preferred, and methoxy, ethoxy, n-propoxy, and isopropoxy are more preferred, in terms of excellent adhesion to chips and substrates, good solubility in solvents, low melting points, low water absorption, and good compatibility with other resins. As R ₅ , in addition to exhibiting excellent adhesion to chips and substrates, etc., it also exhibits good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. Preferably, it is a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, a methoxy group, and an ethoxy group. More preferably, it is a hydrogen atom, a methyl group, and a hydroxyl group. Still more preferably, it is a hydrogen atom.

In the formula (2), l each independently represents an integer of 1 to 4. As l, in order to exhibit excellent adhesion to a wafer, a substrate, etc., as well as good solubility in a solvent, a low melting point, low water absorption, and good compatibility with other resins, it is preferred that all R ₅ are hydrogen atoms, and thus 4 is preferred.

Specific examples of R ₁ in the formula (1) include the following formulas (19) to (21). Preferred is the following formula (19) derived from m-xylylenediamine (MXDA: manufactured by Mitsubishi Gas Chemical Co., Ltd.) which is easily available as a commercial product.

[Chemistry 15]

[Chemistry 16]

[Chemistry 17]

The maleimide compound of the present embodiment is not particularly limited as long as it can exert the effects of the present invention, but in terms of good solubility in solvents, low melting point, low water absorption and good compatibility with other resins, the weight average molecular weight is preferably 100 to 100,000, more preferably 500 to 30,000. In addition, in the present embodiment, the so-called "weight average molecular weight" refers to the weight average molecular weight obtained by gel permeation chromatography (GPC) and converted to polystyrene standards.

Generally, maleimide compounds have poor light transmittance. Therefore, if the resin composition described later contains the maleimide compound, light does not sufficiently reach the photocuring initiator dispersed in the resin composition, and the photocuring initiator is difficult to generate free radicals. Therefore, generally speaking, the photoradical reaction of the maleimide compound is difficult to proceed, and even if the free radical polymerization or dimerization reaction of the maleimide monomer proceeds, its reactivity is very low. However, the dimaleimide compound (A) has very excellent light transmittance because the maleimide group is bonded to the aromatic ring via the methylene group and the conjugation length is short. Therefore, light sufficiently reaches the photocuring initiator, thereby efficiently inducing the photoradical reaction of the maleimide. Furthermore, when a chloroform solution containing the maleimide compound at 1 mass% is prepared and the light transmittance of the chloroform solution is measured using light having a wavelength of 405 nm (h-ray), the transmittance is 3% or more, showing very excellent light transmittance. Therefore, for example, when a printed wiring board having a high-density and high-precision wiring formation (pattern) is manufactured using a direct writing exposure method, the photo-radical reaction of the maleimide is efficiently induced even when an active energy ray containing a wavelength of 405 nm (h-ray) is used.

When active energy rays including a wavelength of 405 nm (h-rays) are used, if the photocuring initiator does not absorb the light of the wavelength of 405 nm (h-rays) and generate free radicals, polymerization does not proceed. Therefore, in this case, as the photocuring initiator described later, it is preferable to use a photocuring initiator having an absorbance of 0.1 or more at a wavelength of 405 nm (h-rays) and showing very excellent absorption of light at a wavelength of 405 nm (h-rays).

Since the bismaleimide compound (A) has excellent light transmittance as described above, for example, when light with a wavelength of 405 nm is used, the light also fully reaches the photocuring initiator, and the free radicals generated by the photocuring initiator are used to perform a free radical reaction, and photocuring can also be performed in a resin composition containing a large amount of maleimide compounds. In addition, the cured product containing the resin composition has excellent light curing properties, heat resistance and thermal stability, so a protective film and an insulating layer can be appropriately formed.

The independent divalent hydrocarbon group having 6 to 200 carbon atoms represented by R ₂ in the formula (1) is a divalent residue obtained by removing two carboxyl groups from a dicarboxylic acid contained in the dimer acid.

In the present specification, dimer acid refers to an acid obtained by dimerizing the unsaturated bonds of unsaturated carboxylic acids such as linoleic acid, oleic acid, and linolenic acid, followed by distillation purification, and mainly contains dicarboxylic acids having 36 carbon atoms, usually contains tricarboxylic acids having 54 carbon atoms up to about 5% by mass, and contains monocarboxylic acids up to about 5% by mass. The diamine derived from the dimer acid of the present invention (hereinafter referred to as a dimer acid-derived diamine as the case may be) is a diamine obtained by replacing two carboxyl groups possessed by each dicarboxylic acid contained in the dimer acid with amino groups, and is usually a mixture. In the present invention, examples of such a dimer acid-derived diamine include diamines such as [3,4-bis(1-aminoheptyl)6-hexyl-5-(1-octenyl)]cyclohexane, or diamines containing diamines in which unsaturated bonds are saturated by further hydrogenating these diamines.

As the divalent hydrocarbon derived from the dimer acid of the present invention to be introduced into the bismaleimide compound using the diamine derived from the dimer acid, it is preferred to be a residue after removing two amine groups from the diamine derived from the dimer acid. In addition, when the bismaleimide compound of the present invention is obtained using the diamine derived from the dimer acid, the diamine derived from the dimer acid may be used alone or in combination of two or more diamines having different compositions. Furthermore, as such a diamine derived from the dimer acid, for example, commercial products such as "PRIAMINE 1074" and "PRIAMINE 1075" (manufactured by Croda Japan Co., Ltd.) having a diamine having a C36 skeleton as a main component may be used.

The organic groups represented by _R3 in the formula (1) are tetravalent organic groups each independently containing a cyclic structure and are derived from a tetrabasic acid dianhydride used in the synthesis of the bismaleimide resin of the present invention. The tetrabasic acid dianhydride is not particularly limited as long as it has two anhydride groups in one molecule. Specific examples of the tetrabasic acid dianhydride include pyromellitic anhydride, ethylene glycol-bis(trimellitic anhydride), glycerol-bis(trimellitic anhydride) monoacetate, 1,2,3,4-butanetetracarboxylic anhydride, 3,3',4,4'-diphenylsulfonic acid tetracarboxylic anhydride, 3,3',4,4'-benzophenonetetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 3,3',4,4'-diphenylethertetracarboxylic anhydride, 5-(2,5-dioxotetrahydro-3-furyl)-3-methylcyclohexene-1,2-dicarboxylic anhydride, 3a,4,5,9b-tetrahydro-5-(tetrahydro-2 ,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, biscyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and biscyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 5,5'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-bisphenol A dianhydride, etc. Among them, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, and 4,4'-bisphenol A dianhydride are preferred in terms of solvent solubility and adhesion to the substrate. These may be used alone or in combination of two or more.

From the viewpoint of the solvent solubility of the finally obtained bismaleimide resin, the organic group represented by _R3 in the above formula (1) is particularly preferably any one of the tetravalent organic groups represented by the following formulas (7) to (15).

[Chemistry 18]

In formula (11), Y represents C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond, or a divalent linking group represented by formula (16).

[Chemistry 19]

The -* in the structural formula represents a bond, and in formula (1) it is bonded to the carbonyl carbon forming the cyclic imide structure.

In the present invention, the tetravalent organic group represented by R ₃ in the formula (1) is preferably the following formula (22) to formula (26).

[Chemistry 20]

[Chemistry 21]

[Chemistry 22]

[Chemistry 23]

[Chemistry 24]

In the resin composition, the content of the photocuring initiator (A) is preferably 25 to 99 parts by mass, more preferably 30 to 97 parts by mass, and even more preferably 50 to 95 parts by mass, based on 100 parts by mass of the total of the bismaleimide compound (A), the compound containing one or more carboxyl groups (B), and the photocuring initiator (C), from the viewpoint of sufficiently proceeding the photocuring of the maleimide compound and sufficiently insolubilizing the exposed portion in terms of alkali developability.

<Method for producing bismaleimide compound (A)> The method for producing the bismaleimide compound (A) is not particularly limited, and it can be produced efficiently by, for example, the method shown below. As a basic process, through step A of synthesizing acylamine using tetrabasic acid dianhydride and diamine, and performing ring-closure dehydration, then reacting maleic anhydride to synthesize maleic acid, and finally performing ring-closure dehydration to cap the molecular chain end with maleimide group, step B, thereby obtaining a bismaleimide compound.

In the production method, each step can be roughly divided into two types: the synthesis reaction of acylamine or maleic acid and the ring-closing dehydration reaction, which are described in detail below.

In step A, first, acylamine is synthesized by reacting a specific tetrabasic acid dianhydride with a specific diamine. The reaction is generally carried out in an organic solvent (e.g., a nonpolar solvent or a high-boiling-point aprotic polar solvent) at room temperature (25°C) to 100°C. Then, the ring-closing dehydration reaction of acylamine is carried out at 90°C to 120°C while removing the water produced as a by-product of the condensation reaction from the system. In order to promote the ring-closing dehydration reaction, an organic solvent (e.g., a nonpolar solvent, a high-boiling-point aprotic polar solvent, etc.) or an acid catalyst may be added.

As organic solvents, toluene, xylene, anisole, biphenyl, naphthalene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc. can be listed. These can be used alone or in combination of two or more. In addition, as acid catalysts, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc. can be listed. These can be used alone or in combination of two or more. The molar ratio of diamine to tetrabasic acid dianhydride is preferably set to diamine/tetrabasic acid dihydrate = 2.5 to 1.02/1.0, and more preferably set to diamine/tetrabasic acid dianhydride = 2.0 to 1.15/1.0. By mixing at this ratio, a copolymer containing amino groups at both ends can be synthesized.

In step B, maleic acid is synthesized by reacting the diamine having amino groups at both ends obtained in step B with maleic anhydride at room temperature (25°C) to 100°C, and finally, the water in the system generated as a by-product under the condition of 95°C to 120°C is removed and closed-loop dehydration is performed, thereby using maleimide groups to cap the ends of the molecular chain, and the target bismaleimide compound can be obtained. If the capping reaction of the ends of the molecular chain using maleimide groups is performed below 120°C, it is difficult to produce side reactions or high molecular weight bodies, so it is better. If this manufacturing method is used, the obtained bismaleimide compound has a block copolymer structure, so it can be uniform and improve the compatibility of the synthesized resin.

The compound of the present invention may be purified by a conventional method, and reprecipitation or the like may be used.

The mixing ratio of the raw materials in the reaction is preferably such that (the total molar number of the aromatic diamine contributing to the structure of _R1 and the non-aromatic organic diamine containing a divalent hydrocarbon having 6 to 200 carbon atoms contributing to the structure of _R2 ): (the total molar number of the tetrabasic acid dianhydride ( _R3 ) + 1/2 of the molar number of maleic anhydride) is 1:1. In addition, when the organic diamine ( _R2 ) is used, from the viewpoint of the tendency to obtain a composition with better photocurability, the ratio of (the molar number of the organic diamine ( _R2 )): (the molar number of the aromatic diamine ( _R1 )) is preferably 0.1 or more. Furthermore, when the organic diamine (R ₂ ) is used, the polymerization form of the amide unit comprising the aromatic diamine (R ₁ ) and tetracarboxylic dianhydride (R ₃ ) and the amide unit comprising the organic diamine (R ₂ ) and tetracarboxylic dianhydride (R ₃ ) may be random polymerization or block polymerization.

[Compound (B) containing one or more carboxyl groups] The resin composition of the present embodiment contains a compound (B) containing one or more carboxyl groups (also referred to as component (B) or compound (B)). The compound (B) is not particularly limited as long as it contains one or more carboxyl groups in the compound. The carboxyl group may be a salt such as a sodium salt or a potassium salt. When the molecule contains two or more carboxyl groups, it may be an acid anhydride formed by the mutual linkage of these groups. The compound (B) may be used alone or in combination of two or more.

The compound (B) can be photocured together with the dimaleimide compound (A) of the present embodiment and the photocuring initiator (C) described later using various active energy rays to obtain a cured product. In addition, according to the present embodiment, a resin composition containing the compound (B) can be obtained in the unexposed portion. When a 1% by mass N-methylpyrrolidone solution containing the compound (B) is prepared and the transmittance of the 1% by mass N-methylpyrrolidone solution containing the compound (B) is measured using active energy rays having a wavelength of 365 nm (i-rays), the transmittance is preferably 5% or more. Such a compound (B) shows very excellent light transmittance. In addition, when the transmittance of a 1 mass % N-methylpyrrolidone solution containing the compound (B) is measured using active energy rays containing a wavelength of 405 nm (h-rays), the transmittance is preferably 5% or more, which also shows very excellent light transmittance. If such a compound (B) is used, for example, when a printed wiring board having a high-density and high-precision wiring formation (pattern) is manufactured using a direct writing exposure method, a photoradical reaction of maleimide is efficiently induced even when active energy rays containing a wavelength of 405 nm (h-rays) are used. For obtaining a resin composition with better photocurability, the preferred range of transmittance at a wavelength of 365 nm (i-rays) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more, respectively. For a resin composition that can obtain better photocurability, the preferred range of transmittance at a wavelength of 405 nm (h-ray) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more. Furthermore, the upper limits of the transmittance at a wavelength of 365 nm (i-ray) and the transmittance at a wavelength of 405 nm (h-ray) are, for example, 99.9% or less, and may be 100% or less.

In the present embodiment, from the viewpoint of obtaining more excellent alkali developing property, it is preferred that the compound (B) contains 1 to 4 carboxyl groups in the molecule.

In order to further improve the developing property, the molecular weight of the compound (B) is preferably 50 to 1,000, more preferably 100 to 800.

Examples of the compound (B) include formic acid, aliphatic compounds containing one or more carboxyl groups, aromatic compounds containing one or more carboxyl groups, and hetero compounds containing one or more carboxyl groups. These compounds (B) may be used alone or in combination of two or more.

(Aliphatic compounds containing one or more carboxyl groups) Examples of aliphatic compounds containing one or more carboxyl groups include chain aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, chain aliphatic polycarboxylic acids, and alicyclic polycarboxylic acids. These compounds may also have hydrogen atoms, and substituents such as alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl groups in the molecule. In addition, when these compounds have two or more carboxyl groups in the molecule, they may be acid anhydrides formed by these groups being linked to each other. When these compounds have carboxylalkyl groups in the molecule, they may be acid anhydrides formed by carboxylalkyl groups and carboxyl groups being linked to each other. When these compounds have two or more carboxylalkyl groups in the molecule, they may be acid anhydrides formed by these groups being linked to each other.

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-hexyl, and 2-methylpropoxy. Examples of the aryloxy group include phenoxy and p-tolyloxy. Examples of the aryl group include phenyl, toluyl, benzyl, methylbenzyl, xylyl, mesityl, naphthyl, and anthracenyl. Examples of the aminoalkyl group include aminomethyl, aminoethyl, aminopropyl, aminodimethyl, aminodiethyl, aminodipropyl, aminobutyl, aminohexyl, and aminononyl. Examples of carboxyalkyl groups include carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxyhexyl, and carboxynonyl.

Examples of the chain aliphatic monocarboxylic acid include saturated fatty acids such as acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, valeric acid, caproic acid, lactic acid, succinic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid; and unsaturated fatty acids such as oleic acid, elaidic acid, erucic acid, nervonic acid, linolenic acid, stearidonic acid, eicosapentaenoic acid, linoleic acid, and linolenic acid.

Examples of the alicyclic monocarboxylic acid include monocyclic carboxylic acids such as cyclopropanecarboxylic acid, cyclopropenecarboxylic acid, cyclobutanecarboxylic acid, cyclobutenecarboxylic acid, cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexenecarboxylic acid, cycloheptanecarboxylic acid, cycloheptenecarboxylic acid, cyclooctanecarboxylic acid, and cyclooctenecarboxylic acid; and polycyclic or bridged alicyclic carboxylic acids such as norbornanecarboxylic acid, tricyclodecanecarboxylic acid, tetracyclododecanecarboxylic acid, adamantanecarboxylic acid, methyladamantanecarboxylic acid, ethyladamantanecarboxylic acid, and butyladamantanecarboxylic acid.

Examples of the chain aliphatic polycarboxylic acid include carboxylic acids obtained by adding one or more carboxyl groups to a chain aliphatic monocarboxylic acid, such as propane diacid, octanedioic acid, nonane diacid, decanedioic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, and octadecanedioic acid.

Examples of the alicyclic polycarboxylic acid include carboxylic acids obtained by further adding one or more carboxyl groups to an alicyclic monocarboxylic acid. Examples include cyclopropane dicarboxylic acid, cyclopropylene dicarboxylic acid, cyclopropane tricarboxylic acid, cyclopropylene tricarboxylic acid, cyclobutane dicarboxylic acid, cyclobutene dicarboxylic acid, cyclobutane tricarboxylic acid, cyclobutene tricarboxylic acid, cyclobutane tetracarboxylic acid, cyclobutene tetracarboxylic acid, cyclopentane dicarboxylic acid, cyclopentene dicarboxylic acid, cyclopentane tricarboxylic acid, cyclopentene tricarboxylic acid, cyclopentane tetracarboxylic acid, cyclopentene tetracarboxylic acid, cyclopentane pentacarboxylic acid, cyclopentene pentacarboxylic acid, cyclobutane tetracarboxylic acid, cyclopentane pentacarboxylic acid, cyclopentene pentacarboxylic acid, cyclobutane tetracarboxylic acid, cyclopentane pentacarboxylic acid, cyclopentene pentacarboxylic acid, cyclopent ... Monocyclic carboxylic acids such as hexanedicarboxylic acid, cyclohexenedicarboxylic acid, cyclohexanetricarboxylic acid, cyclohexenetricarboxylic acid, cyclohexanetetracarboxylic acid, cyclohexenetetracarboxylic acid, cyclohexanepentacarboxylic acid, cyclohexenepentacarboxylic acid, cyclohexanehexacarboxylic acid, cyclohexenehexacarboxylic acid, cycloheptanedicarboxylic acid, cycloheptenedicarboxylic acid, cyclooctanedicarboxylic acid, and cyclooctenedicarboxylic acid; polycyclic or bridged aliphatic ring dicarboxylic acids such as norbornanedicarboxylic acid and adamantanedicarboxylic acid, etc.

(Aromatic compounds containing one or more carboxyl groups) Examples of the parent skeleton of aromatic compounds containing one or more carboxyl groups include benzoic acid, phenylacetic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, pentacarboxybenzene, hexacarboxybenzene, naphthalenecarboxylic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, anthracene carboxylic acid, anthracene dicarboxylic acid, anthracene tricarboxylic acid, anthracene tetracarboxylic acid, anthracene pentacarboxylic acid, etc. Aromatic compounds may also have substituents such as hydrogen atoms, and alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxyalkyl groups on the aromatic rings of these parent skeletons. In addition, when these compounds have two or more carboxyl groups in the molecule, they may be acid anhydrides formed by the mutual linkage of these groups. When these compounds have carboxyalkyl groups in the molecule, they may be acid anhydrides formed by the mutual linkage of carboxyalkyl and carboxyl groups. When these compounds have two or more carboxyalkyl groups in the molecule, they may also be acid anhydrides formed by the mutual linkage of these groups. For these substituents, please refer to the above description.

(Hetero compounds containing one or more carboxyl groups) As the parent skeleton of the hetero compound containing one or more carboxyl groups, for example, there can be listed compounds containing one or more carboxyl groups in hetero rings such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thione, phenothiazine, phenothiazine, xanthine, acridine, phenazine, and carbazole. The hetero compound may also have substituents such as hydrogen atoms, and alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl groups on these parent skeletons. In addition, when these compounds have two or more carboxyl groups in the molecule, they may also be acid anhydrides formed by the mutual linkage of these groups. When these compounds have a carboxyalkyl group in the molecule, they may also be an acid anhydride formed by the carboxyalkyl group and the carboxyl group being linked to each other. When these compounds have two or more carboxyalkyl groups in the molecule, they may also be an acid anhydride formed by the carboxyalkyl group and the carboxyl group being linked to each other. For these substituents, please refer to the above description.

As the compound (B), from the viewpoint of imparting better alkali development property to the resin composition, the compound represented by formula (3), the compound represented by formula (4), the compound represented by formula (5), and the compound represented by formula (6) are preferred. From the viewpoint of alkali development property, the compound represented by formula (4), the compound represented by formula (5), and the compound represented by formula (6) are more preferred.

The compound represented by formula (3) is as follows.

[Chemistry 25]

In formula (3), R ₆ each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group or an aminomethyl group. In addition, when the compound represented by formula (3) has two or more carboxyl groups, they may also be an acid anhydride formed by linking these groups to each other. In formula (3), the upper limit of the number of carboxyl groups is 6. In terms of alkali development, R ₆ is preferably each independently a hydrogen atom, a hydroxyl group, a carboxyl group or an amino group, and in terms of obtaining better alkali development, it is more preferably to include a carboxyl group. In addition, o each independently represents an integer of 1 to 5.

As the compound represented by the formula (3), a compound represented by the formula (27) is preferred in terms of obtaining better alkali developing properties.

[Chemistry 26]

In formula (27), R ₆ each independently represents a hydrogen atom, a hydroxyl group, an amino group or an aminomethyl group. In terms of showing better alkali development, R ₆ is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom. In addition, o' each independently represents an integer from 0 to 4. The number of carboxyl groups s represents an integer from 5 to o. In terms of showing better alkali development, the number of carboxyl groups s is preferably an integer from 1 to 3. In this case, the number o of R ₆ is an integer from 5 to s and is an integer from 2 to 4. The compound represented by formula (27) contains two or more carboxyl groups, and may also be an acid anhydride formed by these groups being linked to each other.

Examples of the compound represented by formula (27) include 4-aminobenzoic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, 4-aminomethylbenzoic acid, and anhydrides thereof. Examples of the anhydrides include phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. As the compound represented by formula (27), phthalic acid, trimellitic acid, pyromellitic acid, and anhydrides thereof are preferred in terms of obtaining better alkali developing properties.

The compound represented by formula (4) is as follows.

[Chemistry 27]

In formula (4), _R7 each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a carboxylmethyl group, an amino group or an aminomethyl group. In addition, when the compound represented by formula (4) has two or more carboxyl groups, these groups may be linked to form an acid anhydride. In formula (4), the upper limit of the number of carboxyl groups is 10. When the compound represented by formula (4) has a carboxylmethyl group, it may be a carboxylmethyl group and a carboxyl group are linked to form an acid anhydride. In terms of alkali development, _R7 is preferably each independently a hydrogen atom, a hydroxyl group, a carboxyl group, or an amino group, and in terms of obtaining better alkali development, it is more preferably to contain a carboxyl group. In addition, p each independently represents an integer of 1 to 9. Furthermore, piperidinecarboxylic acid tends to have poor alkali development compared to other compounds (B) containing one or more carboxyl groups.

When R ₇ contains a carboxyl group, the number of carboxyl groups p is preferably 1 to 3 from the viewpoint of alkali developability. R ₇ other than a carboxyl group is preferably independently a hydrogen atom or a hydroxyl group, more preferably a hydrogen atom. When the compound represented by formula (4) contains 1 to 3 carboxyl groups, the number of R ₇ other than a carboxyl group is 7 to 9.

Examples of the compound represented by formula (4) include piperidinecarboxylic acid, 1,2-piperidinedicarboxylic acid, and piperidinedicarboxylic anhydride.

The compound represented by formula (5) is as follows.

[Chemistry 28]

In formula (5), _R8 each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group, or an aminomethyl group. In addition, when the compound represented by formula (5) has two or more carboxyl groups, these groups may be linked to each other to form an acid anhydride. In formula (5), the upper limit of the number of carboxyl groups is 10. When the compound represented by formula (5) has a carboxymethyl group, it may be an acid anhydride formed by a carboxymethyl group and a carboxyl group linked to each other. In terms of alkali development, _R8 is preferably each independently a hydrogen atom, a hydroxyl group, a carboxyl group, or an amino group, and in terms of obtaining better alkali development, it is more preferably to contain a carboxyl group. In addition, q each independently represents an integer of 1 to 9.

As the compound represented by the formula (5), a compound represented by the formula (28) is preferred in terms of obtaining better alkali developing properties.

[Chemistry 29]

In formula (28), _R8 each independently represents a hydrogen atom, a hydroxyl group, a carboxymethyl group, an amino group or an aminomethyl group. In terms of showing better alkali development, _R8 is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom. In addition, q' each independently represents an integer of 0 to 8. The number of carboxyl groups t represents an integer of 9-q. In terms of showing better alkali development, the number of carboxyl groups t is preferably an integer of 1 to 3. In this case, the number q of _R8 is an integer of 9-t and an integer of 6 to 8. The compound represented by formula (28) contains two or more carboxyl groups, and may also be an acid anhydride formed by these groups being linked to each other. In addition, when the compound represented by formula (28) has a carboxymethyl group, it may also be an acid anhydride formed by the carboxymethyl group and the carboxyl group being linked to each other.

Examples of the compound represented by formula (28) include 3-cyclohexene-1-carboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and cis-4-cyclohexene-1,2-dicarboxylic anhydride. In terms of obtaining better alkali developing properties, the compound represented by formula (28) is preferably cis-4-cyclohexene-1,2-dicarboxylic acid and cis-4-cyclohexene-1,2-dicarboxylic anhydride.

The compound represented by formula (6) is as follows.

[Chemistry 30]

In formula (6), R ₉ each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a carboxylmethyl group, an amino group, or an aminomethyl group. In addition, when the compound represented by formula (6) has one or more carboxyl groups, it may be an acid anhydride formed by a carboxylmethyl group and a carboxyl group linked to each other. In addition, in formula (6), when there are two or more carboxyl groups, it may be an acid anhydride formed by these groups linked to each other. In formula (6), the upper limit of the number of carboxyl groups is 5. In formula (6), when there are two or more carboxylmethyl groups, it may be an acid anhydride formed by these groups linked to each other. In formula (6), the upper limit of the number of carboxylmethyl groups is 6. In terms of alkali development, R ₉ is preferably each independently a hydrogen atom, a hydroxyl group, a carboxyl group, or an amino group, and in terms of obtaining better alkali development, it is more preferable to contain a carboxyl group. In addition, r each independently represents an integer from 1 to 5.

As the compound represented by the formula (6), a compound represented by the formula (29) is preferred in terms of obtaining better alkali developing properties.

[Chemistry 31]

In formula (29), R ₉ each independently represents a hydrogen atom, a hydroxyl group, a carboxymethyl group, an amino group or an aminomethyl group. In terms of showing better alkali development, R ₉ is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom. In addition, r' each independently represents an integer of 0 to 4. The number of carboxyl groups u represents an integer of 5-r'. In terms of showing better alkali development, the number of carboxyl groups u is preferably an integer of 1 to 3. In this case, the number of R ₉ r' is an integer of 5-u and an integer of 2 to 4. In formula (29), it may be an acid anhydride formed by the carboxymethyl group and the carboxyl group being linked to each other. When the compound represented by formula (29) has two or more carboxyl groups, it may also be an acid anhydride formed by the two groups being linked to each other. In formula (29), the upper limit of the number of carboxyl groups is 5. When the compound represented by formula (29) has two or more carboxymethyl groups, these groups may be linked to each other to form an acid anhydride. In formula (29), the upper limit of the number of carboxymethyl groups is 6.

As the compound represented by formula (29), for example, phenylacetic acid, 1,2-phenyldiacetic acid, 1,3-phenyldiacetic acid, 1,4-phenyldiacetic acid, and their anhydrides can be listed. As their anhydrides, for example, 1,2-phenyldiacetic acid anhydride can be listed. As the compound represented by formula (29), 1,2-phenyldiacetic acid is preferred in terms of obtaining better alkali development properties. These compounds (B) containing one or more carboxyl groups can also be used alone or in combination of two or more.

In the resin composition, the content of the compound (B) containing one or more carboxyl groups is preferably 0.01 to 50 parts by mass, more preferably 1 to 50 parts by mass, based on 100 parts by mass of the total of the bismaleimide compound (A), the compound (B) containing one or more carboxyl groups, and the photocuring initiator (C) described later, in order to impart better alkali developability to the resin composition. Further preferably, it is 1 to 35 parts by mass. If the amount of the compound (B) containing one or more carboxyl groups is small, the crosslinking density becomes high, thereby becoming a composition with excellent curing properties such as heat resistance and low dielectric properties.

[Photocuring initiator (C)] The resin composition includes a photocuring initiator (C) (also referred to as component (C)). The photocuring initiator (C) is not particularly limited, and a known one generally used in a photocurable resin composition can be used. The photocuring initiator (C) can be used to perform photocuring together with a dimaleimide compound (A) and a compound (B) containing one or more carboxyl groups using various active energy rays.

Examples of the photocuring initiator (C) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; organic peroxides such as benzoyl peroxide, lauryl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, and di-tert-butyl diperoxyphthalate; 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, benzoyl-diphenyl-phosphine oxide, and bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide; Phosphine and other phosphine oxides; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propane-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 and other acetophenones; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and anthraquinones such as 2-amylanthraquinone; thiocones such as 2,4-diethylthiocone, 2-isopropylthiocone, and 2-chlorothiocone; ketones such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-bismethylaminobenzophenone; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], and ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1- Free radical photocuring initiators such as oxime esters such as (O-acetyl oxime), or diazonium salts of Lewis acids such as p-methoxyphenyldiazonium fluorophosphonate and N,N-diethylaminophenyldiazonium hexafluorophosphonate; iodine salts of Lewis acids such as diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantiphonate; coronium salts of Lewis acids such as triphenylzirconium hexafluorophosphonate and triphenylzirconium hexafluoroantiphonate; phosphonium salts of Lewis acids such as triphenylphosphonium hexafluoroantiphonate; other halides; triazine initiators; borate initiators; other cationic photocuring initiators such as photoacid generators.

As the light curing initiator (C), a commercial product may be used. Examples of commercial products include: Omnirad (registered trademark) 369 (trade name) manufactured by IGM Resins B.V., Omnirad (registered trademark) 819 (trade name) manufactured by IGM Resins B.V., Omnirad (registered trademark) 819DW (trade name) manufactured by IGM Resins B.V., and Omnirad (registered trademark) 819DW (trade name) manufactured by IGM Resins B.V. Omnirad (registered trademark) 907 (trade name) manufactured by IGM Resins B.V., Omnirad (registered trademark) TPO (trade name) manufactured by IGM Resins B.V., Omnirad (registered trademark) TPO-G (trade name) manufactured by IGM Resins B.V., Omnirad (registered trademark) 784 (trade name) manufactured by IGM Resins B.V., BASF Japan Irgacure (registered trademark) OXE01 (trade name) manufactured by BASF Japan Co., Ltd., Irgacure (registered trademark) OXE02 (trade name) manufactured by BASF Japan Co., Ltd., Irgacure (registered trademark) OXE03 (trade name) manufactured by BASF Japan Co., Ltd., and Irgacure (registered trademark) OXE04 (trade name) manufactured by BASF Japan Co., Ltd., etc. The light curing initiator (C) can also be used alone or in combination of two or more.

When the photocuring initiator (C) is prepared to contain 0.01 mass % of the photocuring initiator (C) in chloroform solution, and the absorbance of the chloroform solution containing 0.01 mass % of the photocuring initiator (C) is measured using active energy rays having a wavelength of 365 nm (i-ray), the absorbance is preferably 0.1 or more, and the photocuring initiator (C) shows very excellent light absorption. In addition, when the absorbance of the chloroform solution containing 0.01 mass % of the photocuring initiator (C) is measured using active energy rays having a wavelength of 405 nm (h-ray), the absorbance is preferably 0.1 or more, and in this case, the photocuring initiator (C) also shows very excellent light absorption. If such a photocuring initiator (C) is used, for example, when a printed wiring board having a high-density and high-precision wiring formation (pattern) is manufactured by a direct writing exposure method, even when an active energy ray including a wavelength of 405 nm (h-ray) is used, a photoradical reaction of maleimide is efficiently induced. Furthermore, in order to obtain a resin composition with better photocurability, the absorbance at a wavelength of 365 nm (i-ray) is preferably 0.15 or more. In order to obtain a resin composition with better photocurability, the absorbance at a wavelength of 405 nm (h-ray) is preferably 0.15 or more. Furthermore, the upper limit of each of the absorbance at a wavelength of 365 (i-ray) and the absorbance at a wavelength of 405 nm (h-ray) is, for example, 99.9 or less.

As such a photocuring initiator (C), a compound represented by formula (17) is preferred.

[Chemistry 32]

In formula (17), R ₁₀ each independently represents a substituent represented by formula (18) or a phenyl group.

[Chemistry 33]

In formula (18), R ₁₁ each independently represents a hydrogen atom or a methyl group. In formula (7), -* represents a bond with the phosphorus atom (P) in formula (17).

When a chloroform solution containing the compound represented by formula (17) is prepared at 0.01 mass % and the absorbance of the chloroform solution is measured using active energy rays containing a wavelength of 365 nm (i-ray), the absorbance is 0.1 or more and shows very excellent absorptivity with respect to light of a wavelength of 365 nm (i-ray). Therefore, the compound appropriately generates free radicals with respect to light of a wavelength of 365 nm (i-ray). The absorbance is preferably 0.15 or more. The upper limit value is, for example, 10.0 or less, 5.0 or less, or 2.0 or less.

In addition, when a chloroform solution containing the compound at 0.01 mass % is prepared and the absorbance of the chloroform solution is measured using active energy rays containing a wavelength of 405 nm (h-ray), the absorbance is 0.1 or more and shows very excellent absorptivity with respect to light of a wavelength of 405 nm (h-ray). Therefore, the compound appropriately generates free radicals with respect to light of a wavelength of 405 nm (h-ray). The absorbance is preferably 0.15 or more. The upper limit value is, for example, 10.0 or less, 5.0 or less, or 2.0 or less.

In formula (17), R ₁₀ each independently represents a substituent represented by formula (18) or a phenyl group. Among R ₁₀ , preferably one or more are substituents represented by formula (18). In formula (18), R ₁₁ each independently represents a hydrogen atom or a methyl group. Among R ₁₁ , preferably one or more are methyl groups, and more preferably all are methyl groups.

Examples of the compound represented by formula (17) include acyl phosphine oxides such as 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide. Among these, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide is preferred in terms of excellent light transmittance. These compounds may be used alone or in combination of two or more.

Acylphosphine oxides show very excellent absorption properties for active energy rays including a wavelength of 405 nm (h-rays), and for example, can suitably perform radical polymerization of a bismaleimide compound (A) having a transmittance of 5% or more at a wavelength of 405 nm (h-rays). Therefore, a resin composition having excellent photocurability without inhibiting a photocuring reaction in an exposure step, and having excellent alkali developability in a developing step, can be suitably produced, particularly when used for producing a multilayer printed wiring board, and a resin sheet, a multilayer printed wiring board, and a semiconductor device using the resin composition.

In the resin composition, the content of the photocuring initiator (C) is preferably 0.5 to 25 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total of the bismaleimide compound (A), the compound (B) containing one or more carboxyl groups, and the photocuring initiator (C), from the viewpoint of sufficiently proceeding the photocuring of the maleimide compound and sufficiently insolubilizing the exposed portion in terms of alkali developability.

Preferably, when the bismaleimide compound (A) is 40 to 99 parts by mass, the compound (B) containing one or more carboxyl groups is 0.01 to 50 parts by mass, and the photocuring initiator (C) is 0.50 to 25 parts by mass. More preferably, when the bismaleimide compound (A) is 50 to 97 parts by mass, the compound (B) containing one or more carboxyl groups is 1 to 35 parts by mass, and the photocuring initiator (C) is 0.5 to 15 parts by mass. Further preferably, when the bismaleimide compound (A) is 60 to 96 parts by mass, the compound (B) containing one or more carboxyl groups is 2 to 35 parts by mass, and the photocuring initiator (C) is 0.5 to 10 parts by mass.

[Maleimide compound (D) other than bismaleimide compound (A)] In the resin composition of the present embodiment, a maleimide compound (D) other than the bismaleimide compound (A) of the present embodiment (also referred to as component (D)) may be included as long as the effect of the present invention is exerted. The bismaleimide compound (A) has very excellent light transmittance, so even if the maleimide compound (D) is used, light can fully reach the photocuring initiator, thereby efficiently inducing the photoradical reaction of the maleimide, and photocuring can be performed using various active energy rays. Therefore, for example, even when using active energy rays with a wavelength of 365 nm or 405 nm, the light can fully reach the photocuring initiator, and the free radicals generated by the photocuring initiator can be used to perform a free radical reaction, and photocuring can be performed in the composition containing the maleimide compound (D). The maleimide compound (D) is described below.

The maleimide compound (D) is not particularly limited as long as it is a compound other than the maleimide compound (A) and has one or more maleimide groups in the molecule. Specific examples thereof include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimidocaproic 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, alkane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene bis(hexaconimide), m-phenylene bis(hexaconimide), p-phenylene bis(hexaconimide), 2,2-bis( 4-(4-maleimidephenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane dimaleimide, 4-methyl-1,3-phenylene dimaleimide, 1,2-dimaleimideethane, 1,4-dimaleimidebutane, 1,5-dimaleimide Amine pentane, 1,5-bismaleimide-2-methylpentane, 1,6-bismaleimide hexane, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 1,8-bismaleimide-3,6-dioxahedane, 1,11-bismaleimide-3,6,9-trioxahedane, 1 ,3-bis(maleimidemethyl)cyclohexane, 1,4-bis(maleimidemethyl)cyclohexane, 4,4-diphenylether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, 4,4- Diphenylmethane bis(octaconimide), 2,2-bis[4-(4-octaconimidephenoxy)phenyl]propane, bis(3,5-dimethyl-4-octaconimidephenyl)methane, bis(3-ethyl-5-methyl-4-octaconimidephenyl)methane, bis(3,5-diethyl-4-octaconimidephenyl)methane, polyphenylmethane maleimide, maleimide compounds represented by polyphenylmethane maleimide formula (13), maleimide compounds represented by formula (14), fluorescein-5-maleimide, prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds, etc. These maleimide compounds (D) may be used alone or in combination of two or more.

As the maleimide compound represented by formula (30), a commercial product may be used, for example, BMI-2300 (trade name) manufactured by Yamato Chemical Industries, Ltd. As the maleimide compound represented by formula (31), a commercial product may be used, for example, MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. As the maleimide compound represented by formula (32), a commercial product may be used, for example, MIR-5000 (trade name) manufactured by Nippon Kayaku Co., Ltd.

[Chemistry 34]

In formula (30), R ₁₂ each independently represents a hydrogen atom or a methyl group. n represents an integer of 1 or greater, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.

[Chemistry 35]

In formula (31), _R13 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, l each independently represents an integer of 1 to 3, and n represents an integer of 1 to 10. Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, and neopentyl.

[Chemistry 36]

In formula (32), _R14 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, l2 each independently represents an integer of 1 to 3, and n represents an integer of 1 to 10. Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, and neopentyl.

In this embodiment, in order to efficiently induce the photoradical reaction of the bismaleimide compound (A), when a chloroform solution containing the maleimide compound (D) at 1 mass% is prepared and the transmittance of the chloroform solution is measured using active energy rays containing a wavelength of 365 nm (i-rays), it is preferred to show a light transmittance of 5% or more. The transmittance in this case is more preferably 8% or more, and further preferably 10% or more. In addition, in the present embodiment, in order to efficiently cause the photoradical reaction of the bismaleimide compound (A), when a chloroform solution containing the maleimide compound (D) at 1 mass% is prepared and the transmittance of the chloroform solution is measured using active energy rays having a wavelength of 405 nm (h-rays), it is preferred that the transmittance is 5% or more. By using such a maleimide compound (D), for example, when a printed wiring board having a high-density and high-precision wiring formation (pattern) is manufactured using a direct writing exposure method, the photoradical reaction of the maleimide is efficiently caused even when active energy rays having a wavelength of 405 nm (h-rays) are used. In order to obtain a resin composition with better photocurability, the light transmittance is preferably 8% or more, and further preferably 10% or more.

Examples of such maleimide compounds (D) include maleimide compounds represented by formula (33), maleimide compounds represented by formula (34), maleimide compounds represented by formula (35), maleimide compounds represented by formula (36), maleimide compounds represented by formula (37), maleimide compounds represented by formula (38), maleimide compounds represented by formula (39), 1,6-bismaleimide-(2,2,4-trimethyl)hexane (maleimide compound represented by formula (40)), maleimide compounds represented by formula (41), and luciferin-5-maleimide.

[Chemistry 37]

In the formula (33), n (average) is 1 or more, preferably 1 to 21, and more preferably 1 to 16 from the viewpoint of exhibiting excellent photocurability.

[Chemistry 38]

In formula (34), the number of x is 10 to 35. In formula (34), the number of y is 10 to 35.

[Chemistry 39]

In formula (35), ^Ra represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. ^Ra is preferably a linear or branched alkyl group, and more preferably a linear alkyl group in terms of excellent photocurability. The number of carbon atoms in the alkyl group is preferably 4 to 12 in terms of excellent photocurability. The number of carbon atoms in the alkenyl group is preferably 4 to 12 in terms of excellent photocurability.

As the linear or branched alkyl group, reference may be made to R ₃ in the bismaleimide compound (A). Among these, n-heptyl, n-octyl, and n-nonyl are preferred, and n-octyl is more preferred, in terms of showing excellent photocurability. As the linear or branched alkenyl group, reference may be made to R ₃ in the bismaleimide compound (A). Among these, 2-heptenyl, 2-octenyl, and 2-nonenyl are preferred, and 2-octenyl is more preferred, in terms of showing excellent photocurability.

In formula (35), R ^b represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. As R ^b , a linear or branched alkyl group is preferred, and a linear alkyl group is more preferred in terms of excellent photocurability. As the carbon number of the alkyl group, 4 to 12 is preferred in terms of excellent photocurability. As the carbon number of the alkenyl group, 4 to 12 is preferred in terms of excellent photocurability.

As a specific example of the alkyl group, the alkyl group in ^Ra can be referred to. Among them, in terms of showing excellent photocurability, n-heptyl, n-octyl, and n-nonyl are preferred, and n-octyl is more preferred. As a specific example of the alkenyl group, the alkenyl group in ^Rb can be referred to. Among them, in terms of showing excellent photocurability, 2-heptenyl, 2-octenyl, and 2-nonenyl are preferred, and 2-octenyl is more preferred.

In the formula (35), the number of _na is 1 or more, preferably 2 to 16, and more preferably 3 to 14 from the viewpoint of exhibiting excellent photocurability.

In the formula (35), the number of n _b is 1 or more, preferably 2 to 16, and more preferably 3 to 14 from the viewpoint of exhibiting excellent photocurability.

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

[Chemistry 40]

In the formula (36), n (average) is 0.5 or more, preferably 0.8 to 10, and more preferably 1 to 8 from the viewpoint of exhibiting excellent photocurability.

[Chemistry 41]

In formula (37), n represents an integer greater than or equal to 1, and preferably represents an integer from 1 to 10.

[Chemistry 42]

In formula (38), n represents an integer greater than or equal to 1, and preferably represents an integer from 1 to 10.

[Chemistry 43]

[Chemistry 44]

(In the formula (40), R ₁₅ each independently represents a hydrogen atom, a methyl group or an ethyl group, and R ₁₆ each independently represents a hydrogen atom or a methyl group)

The maleimide compound (D) may also be a commercially available product. Examples of the maleimide compound represented by formula (33) include BMI-1000P (trade name, n=13.6 (average) in formula (33)) manufactured by K.I Chemical Co., Ltd., BMI-650P (trade name, n=8.8 (average) in formula (33)) manufactured by K.I Chemical Co., Ltd., BMI-250P (trade name, n=3 to 8 (average) in formula (33)) manufactured by K.I Chemical Co., Ltd., and CUA-4 (trade name, n=1 in formula (33)) manufactured by K.I Chemical Co., Ltd., etc. Examples of maleimide compounds represented by formula (34) include BMI-6100 (trade name, x=18, y=18 in formula (34)) manufactured by Designer Molecules Inc. Examples of maleimide compounds represented by formula (35) include BMI-689 (trade name, formula (41), functional group equivalent: 346 g/eq.) manufactured by Designer Molecules Inc.

[Chemistry 45]

As the maleimide compound represented by formula (36), for example, BMI-1500 (trade name, n=1.3 in formula (36), functional group equivalent: 754 g/eq.) manufactured by Designer Molecules Inc. can be cited. As the maleimide compound represented by formula (37), commercially available products can also be used, for example, BMI-1700 (trade name) manufactured by Designer Molecules Inc. (DMI) can be cited. As the maleimide compound represented by formula (38), commercial products can also be used, for example, BMI-3000 (trade name) manufactured by DMI, BMI-3000J (trade name) manufactured by DMI, BMI-5000 (trade name) manufactured by DMI, and BMI-9000 (trade name) manufactured by DMI. As the maleimide compound represented by formula (39), commercial products can also be used, for example, BMI-TMH manufactured by Yamato Chemical Industries, Ltd. can be used. As the maleimide compound represented by formula (40), commercial products can also be used, for example, BMI-70 (trade name) manufactured by K.I Chemical (K.I Chemical) can be used. These maleimide compounds (D) can be used alone or in combination of two or more.

In the resin composition, the content of the maleimide compound (D) is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 50 to 125 parts by mass, based on 100 parts by mass of the total of the bismaleimide compound (A), the compound (B), and the photocuring initiator (C), from the viewpoint of obtaining a cured product having the maleimide compound as a main component and further improving the photocurability.

In the resin composition, from the viewpoint of obtaining a cured product having the maleimide compound as a main component and further improving the light curing property, the mixing ratio of the bismaleimide compound (A) to the maleimide compound (D) ((A):(D)) is preferably 1-99:99-1 on a mass basis, more preferably 5-95:95-5, and even more preferably 10-90:90-10.

In the resin composition, the total content of the dimaleimide compound (A) and the maleimide compound (D) is preferably 40 to 99 parts by mass, more preferably 50 to 97 parts by mass, and even more preferably 60 to 96 parts by mass, based on 100 parts by mass of the total of the dimaleimide compound (A), the compound (B), the photocuring initiator (C), and the maleimide compound (D), from the viewpoint of obtaining a cured product having the maleimide compound as a main component and further improving the photocurability.

[Filler (E)] In order to improve the coating properties, heat resistance and other properties, the resin composition may contain a filler (E) (also referred to as component (E)). As the filler (E), it is preferred that it has insulating properties and does not block the permeability of various active energy rays used in photocuring, and it is more preferred that it does not block the permeability of active energy rays including a wavelength of 365 nm (i-rays) and/or a wavelength of 405 nm (h-rays).

Examples of the filler (E) include silicon dioxide (e.g., natural silicon dioxide, fused silicon dioxide, amorphous silicon dioxide, and hollow silicon dioxide), aluminum compounds (e.g., alumina, aluminum hydroxide, aluminum oxide, and aluminum nitride), boron compounds (e.g., boron nitride), magnesium compounds (e.g., magnesium oxide, and magnesium hydroxide), calcium compounds (e.g., calcium carbonate), and molybdenum compounds (e.g., molybdenum oxide, and zinc molybdate). , barium compounds (e.g., barium sulfate and barium silicate), talc (e.g., natural talc and calcined talc), mica, glass (e.g., glass short fibers, spherical glass, glass fine powder, E glass, T glass, and D glass), silicone powder, fluororesin fillers, urethane resin fillers, (meth) acrylic resin fillers, polyethylene fillers, styrene-butadiene rubber, and silicone rubber, etc. These fillers (E) can be used alone or in combination of two or more.

Among these, preferred are silica, alumina, barium sulfate, silicone powder, fluororesin fillers, urethane resin fillers, (meth)acrylic resin fillers, polyethylene fillers, styrene-butadiene rubber, and silicone rubber. These fillers (E) can also be surface treated using the silane coupling agent described below.

From the viewpoint of improving the heat resistance of the cured product and obtaining good coating properties, silicon dioxide is preferred, and fused silicon dioxide is more preferred. Specific examples of silicon dioxide include SFP-130MC (trade name) manufactured by Denka Co., Ltd., SC2050-MB (trade name), SC1050-MLE (trade name), YA010C-MFN (trade name), and YA050C-MJA (trade name) manufactured by Admatechs Co., Ltd.

From the viewpoint of the ultraviolet light transmittance of the resin composition, the particle size of the filler (E) is generally 0.005 μm to 10 μm, preferably 0.01 μm to 1.0 μm.

In the resin composition, the content of the filler (E) is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and even more preferably 100 parts by mass or less, based on 100 parts by mass of the total of the bismaleimide compound (A), the compound (B), and the light curing initiator (C), from the viewpoint of improving the light transmittance of the resin composition and the heat resistance of the cured product. The upper limit may be 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less. When the filler (E) is contained, from the viewpoint of obtaining the effect of improving coating properties, heat resistance and other properties, the lower limit is usually 1 part by mass based on 100 parts by mass of the total of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C).

[Silane coupling agent and wetting dispersant] In the resin composition of the present embodiment, a silane coupling agent and/or a wetting dispersant may be used in combination to improve the dispersibility of the filler and the bonding strength between the polymer and/or resin and the filler. As these silane coupling agents, there is no particular limitation as long as they are silane coupling agents generally used for surface treatment of inorganic materials. Specific examples include 3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, 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; γ-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl triethoxysilane, 3-glycidyloxypropyl dimethoxymethylsilane, 3-glycidyloxypropyl diethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, and [8-(glycidyloxy)-n-octyl]trimethoxysilane; epoxysilanes such as vinyl tri(2-methoxyethoxy)silane, vinyl trimethoxysilane, vinyl triethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxy Vinyl silanes such as methoxy(7-octen-1-yl)silane and trimethoxy(4-vinylphenyl)silane; methacryl silanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane; acryl silanes such as γ-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane; isocyanate silanes such as 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane; tris-(trimethoxysilylpropyl)isocyanurate, etc. Isocyanurate silane series; 3-butylenepropyltrimethoxysilane, 3-butylenepropyldimethoxymethylsilane and other butylene silane series; 3-ureidopropyltriethoxysilane and other ureido silane series; p-phenylenetrimethoxysilane and other phenylene silane series; N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane Cationic silane systems such as hydrochlorides; anhydride systems such as [3-(trimethoxysilyl)propyl]succinic anhydride; phenylsilane systems such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, and p-tolyltrimethoxysilane; arylsilane systems such as trimethoxy(1-naphthyl)silane. These silane coupling agents can be used alone or in combination of two or more.

In the resin composition of the present embodiment, the content of the silane coupling agent is usually 0.1 to 10 parts by mass relative to 100 parts by mass of the total of the dimaleimide compound (A), the compound (B) and the photocuring initiator (C). As a wetting dispersant, there is no particular limitation as long as it is a dispersing stabilizer used for coating applications. As specific examples, we can cite DISPERBYK (registered trademark)-110 (trade name), 111 (trade name), 118 (trade name), 180 (trade name), 161 (trade name), BYK (registered trademark)-W996 (trade name), W9010 (trade name), W903 (trade name) and other wetting dispersants manufactured by BYK Chemie Japan (Co., Ltd.). These wetting dispersants can be used alone or in combination of two or more. In the resin composition of this embodiment, the content of the wetting dispersant is usually 0.1 to 10 parts by mass relative to 100 parts by mass of the total of the dimaleimide compound (A), the compound (B) and the photocuring initiator (C).

[Cyanate compounds, phenol resins, cyclohexane resins, benzoxazine compounds, epoxy resins, and other compounds] In the present embodiment, as long as the effects of the present invention are exerted, the resin composition of the present embodiment may contain various types of compounds and resins such as cyanate compounds, phenol resins, cyclohexane resins, benzoxazine compounds, epoxy resins, and other compounds in addition to the dimaleimide compound (A), the compound containing one or more carboxyl groups (B), the photocuring initiator (C), and the maleimide compound (D) of the present embodiment, depending on the flame retardancy, heat resistance, and thermal expansion characteristics of the cured product after curing. In addition, the compounds and resins are preferably: when exposed to active energy rays including a wavelength of 365 nm (i-rays) and/or active energy rays including a wavelength of 405 nm (h-rays), the resin composition of the present embodiment is photosensitive and photocured. These compounds and resins can also be used alone or in combination of two or more.

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

For example, we can cite what is represented by equation (42).

[Chemistry 46]

In formula (42), Ar ₁ represents a benzene ring, a naphthalene ring, or two benzene rings bonded by a single bond. When there are multiple Ar _1s , 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 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a group formed by an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms. The aromatic ring in Ra may have a substituent, and the substituent in Ar ₁ and Ra may be selected at any position. p represents the number of cyano groups bonded to Ar ₁ , and each independently represents an integer of 1 to 3. q represents the number of Ra bonded to Ar ₁ , and is 4-p when Ar ₁ is a benzene ring, 6-p when Ar ₁ is a naphthyl ring, and 8-p when Ar ₁ is a single-bonded group of two benzene rings. t represents the average number of repetitions, and is an integer from 0 to 50. The cyanate compound may be a mixture of compounds having different t. When there are a plurality of X, each of them independently represents a single bond, a divalent organic group having 1 to 50 carbon atoms (the hydrogen atom may be substituted with a heteroatom), a divalent organic group having 1 to 10 nitrogen atoms (for example, -NRN- (where R represents an organic group)), a carbonyl group (-CO-), a carboxyl group (-C(=O)O-), a carbonyl dioxide (-OC(=O)O-), a sulfonyl group (-SO ₂ -), a divalent sulfur atom, or a divalent oxygen atom.

The alkyl group in Ra of formula (25) may have any of a linear or branched chain structure and a cyclic structure (e.g., a cycloalkyl group). In addition, the hydrogen atom in the alkyl group in formula (25) and the aryl group in Ra may be substituted by a halogen atom such as a fluorine atom or a chlorine atom; an alkoxy group such as a methoxy group or a phenoxy group; or a cyano group.

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

Specific examples of the divalent organic group having 1 to 50 carbon atoms in X of formula (25) include methylene, ethyl, trimethylene, cyclopentyl, cyclohexyl, trimethylcyclohexyl, biphenylmethylene, dimethylmethylene-phenyl-dimethylmethylene, fluorene diyl, and phthalide diyl. The hydrogen atom in the divalent organic group may be substituted by a halogen atom such as a fluorine atom or a chlorine atom; an alkoxy group such as a methoxy group or a phenoxy group; or a cyano group. Specific examples of the divalent organic group having 1 to 10 nitrogen atoms in X of formula (42) include an imide group, a polyimide group, and the like.

In addition, examples of the organic group represented by X in formula (42) include organic groups having structures represented by formula (43) or formula (44).

[Chemistry 47]

In formula (43), Ar ₂ represents a benzene diyl group, a naphthalene diyl group or a biphenyl diyl group, and when u is an integer greater than 2, Ar ₂ may be the same as or different from each other. 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 group having at least one phenolic hydroxyl group. Rd and Re each independently represent any one selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. u represents an integer from 0 to 5.

[Chemistry 48]

In formula (44), Ar ₃ represents a benzene diyl group, a naphthalene diyl group or a biphenyl diyl group, and when v is an integer greater than 2, Ar ₃ may be the same as or different from each other. 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 alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a trifluoromethyl group, or at least one substituted aryl group selected from the group consisting of a cyano group. v represents an integer from 0 to 5, but may be a mixture of compounds having different v.

Furthermore, as X in formula (42), a divalent group represented by the formula:

[Chemistry 49]

Here, in the formula, z represents an integer of 4 to 7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of Ar ₂ of formula (43) and Ar ₃ of formula (44) include: a benzene diyl group in which two carbon atoms shown in formula (43) or two oxygen atoms shown in formula (44) are bonded to the 1,4 position or the 1,3 position; a biphenyl diyl group in which two carbon atoms or two oxygen atoms are bonded to the 4,4' position, 2,4' position, 2,2' position, 2,3' position, 3,3' position, or 3,4'position; and a naphthalene diyl group in which two carbon atoms or two oxygen atoms are bonded to the 2,6 position, 1,5 position, 1,6 position, 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 in formula (43) and Ri and Rj in formula (44) have the same meanings as the alkyl group and aryl group in formula (42).

Specific examples of the cyano-substituted aromatic compound represented by formula (42) include cyanobenzene, 1-cyano-2-methylbenzene, 1-cyano-3-methylbenzene, 1-cyano-4-methylbenzene, 1-cyano-2-methoxybenzene, 1-cyano-3-methoxybenzene, 1-cyano-4-methoxybenzene, 1-cyano-2,3-dimethylbenzene, 1-cyano-2,4-dimethylbenzene, 1-cyano-2,5-dimethylbenzene, 1 -2,6-cyanodimethylbenzene, 1-cyano-3,4-dimethylbenzene or 1-cyano-3,5-dimethylbenzene, cyanoethylbenzene, cyanobutylbenzene, cyanooctylbenzene, cyanononylbenzene, 2-(4-cyanophenyl)-2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyano-4-cyclohexylbenzene, 1-cyano-4-vinylbenzene, 1-cyano-2-chlorobenzene or 1-cyano-3-chlorobenzene, 1-cyano-2,6 -dichlorobenzene, 1-cyano-2-methyl-3-chlorobenzene, cyanonitrobenzene, 1-cyano-4-nitro-2-ethylbenzene, 1-cyano-2-methoxy-4-allylbenzene (cyanate of eugenol), methyl (4-cyanophenyl) sulfide, 1-cyano-3-trifluoromethylbenzene, 4-cyanobiphenyl, 1-cyano-2-acetylbenzene or 1-cyano-4-acetylbenzene, 4-cyanobenzaldehyde, 4-cyanobenzoic acid methyl ester, 4-cyano benzoic acid phenyl ester, 1-cyano-4-acetamidobenzene, 4-cyanobenzophenone, 1-cyano-2,6-di-tert-butylbenzene, 1,2-dicyanobenzene, 1,3-dicyanobenzene, 1,4-dicyanobenzene, 1,4-dicyano-2-tert-butylbenzene, 1,4-dicyano-2,4-dimethylbenzene, 1,4-dicyano-2,3,4-dimethylbenzene, 1,3-dicyano-2,4,6-trimethylbenzene, 1,3-dicyano 1-cyano-naphthalene or 2-cyano-naphthalene, 1-cyano-4-methoxy-naphthalene, 2-cyano-6-methoxy-naphthalene, 2-cyano-7-methoxy-naphthalene, 2,2'-dicyano-1,1'-binaphthyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyano-naphthalene, 2,2'- or 4,4'-dicyanobiphenyl, 4,4'-dicyanooctafluorobiphenyl, 2,4 '- or 4,4'-dicyanodiphenylmethane, bis(4-cyano-3,5-dimethylphenyl)methane, 1,1-bis(4-cyanophenyl)ethane, 1,1-bis(4-cyanophenyl)propane, 2,2-bis(4-cyanophenyl)propane, 2,2-bis(4-cyanophenyl-3-methylphenyl)propane, 2,2-bis(2-cyano-5-biphenyl)propane, 2,2-bis(4-cyanophenyl)hexafluoropropane, 2,2-bis(4-cyanophenyl) 1,1-bis(4-cyanophenyl)-3,5-dimethylphenyl)propane, 1,1-bis(4-cyanophenyl)butane, 1,1-bis(4-cyanophenyl)isobutane, 1,1-bis(4-cyanophenyl)pentane, 1,1-bis(4-cyanophenyl)-3-methylbutane, 1,1-bis(4-cyanophenyl)-2-methylbutane, 1,1-bis(4-cyanophenyl)-2,2-dimethylpropane, 2,2-bis(4-cyanophenyl)butane, 2,2- Bis(4-cyanophenyl)pentane, 2,2-bis(4-cyanophenyl)hexane, 2,2-bis(4-cyanophenyl)-3-methylbutane, 2,2-bis(4-cyanophenyl)-4-methylpentane, 2,2-bis(4-cyanophenyl)-3,3-dimethylbutane, 3,3-bis(4-cyanophenyl)hexane, 3,3-bis(4-cyanophenyl)heptane, 3,3-bis(4-cyanophenyl)octane, 3,3-bis(4-cyanophenyl) 3,3-Bis(4-cyanophenyl)-2-methylpentane, 3,3-Bis(4-cyanophenyl)-2-methylhexane, 3,3-Bis(4-cyanophenyl)-2,2-dimethylpentane, 4,4-Bis(4-cyanophenyl)-3-methylheptane, 3,3-Bis(4-cyanophenyl)-2-methylheptane, 3,3-Bis(4-cyanophenyl)-2,2-dimethylhexane, 3,3-Bis(4-cyanophenyl)-2,4-dimethylhexane, 3,3-Bis( 4-cyanophenyl)-2,2,4-trimethylpentane, 2,2-bis(4-cyanophenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-cyanophenyl)phenylmethane, 1,1-bis(4-cyanophenyl)-1-phenylethane, bis(4-cyanophenyl)biphenylmethane, 1,1-bis(4-cyanophenyl)cyclopentane, 1,1-bis(4-cyanophenyl)cyclohexane, 2,2-bis(4-cyanophenyl)-3-isopropylphenyl )propane, 1,1-bis(3-cyclohexyl-4-cyanophenyl)cyclohexane, bis(4-cyanophenyl)diphenylmethane, bis(4-cyanophenyl)-2,2-dichloroethylene, 1,3-bis[2-(4-cyanophenyl)-2-propyl]benzene, 1,4-bis[2-(4-cyanophenyl)-2-propyl]benzene, 1,1-bis(4-cyanophenyl)-3,3,5-trimethylcyclohexane, 4-[bis(4-cyanophenyl)methyl] Benzene, 4,4-dicyanobenzophenone, 1,3-bis(4-cyanophenyl)-2-propene-1-one, bis(4-cyanophenyl) ether, bis(4-cyanophenyl) sulfide, bis(4-cyanophenyl) sulfide, 4-cyanophenyl-4-cyanobenzoate (4-cyanophenyl-4-cyanobenzoate), bis-(4-cyanophenyl) carbonate, 1,3-bis(4-cyanophenyl)adamantane, 1,3-bis(4-cyanophenyl)- 5,7-dimethyladamantane, 3,3-bis(4-cyanophenyl)isobenzofuran-1(3H)-one (cyanate of phenolphthalein), 3,3-bis(4-cyano-3-methylphenyl)isobenzofuran-1(3H)-one (cyanate of o-cresolphthalein), 9,9'-bis(4-cyanophenyl)fluorene, 9,9-bis(4-cyano-3-methylphenyl)fluorene, 9,9-bis(2-cyano-5-biphenyl)fluorene, tris(4-cyanophenyl) 1,1,1-tris(4-cyanophenyl)ethane, 1,1,3-tris(4-cyanophenyl)propane, α,α,α'-tris(4-cyanophenyl)-1-ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis(4-cyanophenyl)ethane, tetrakis(4-cyanophenyl)methane, 2,4,6-tris(N-methyl-4-cyanophenylamino)-1,3,5-triazine, 2,4-bis(N-methyl-4-cyanophenylamino)- 6-(N-methylanilino)-1,3,5-triazine, bis(N-4-cyano-2-methylphenyl)-4,4'-oxydiphenylene dicarboxamide, bis(N-3-cyano-4-methylphenyl)-4,4'-oxydiphenylene dicarboxamide, bis(N-4-cyanophenyl)-4,4'-oxydiphenylene dicarboxamide, bis(N-4-cyanophenyl)-2-methylphenyl)-4,4'-(hexafluoroisopropylidene)diphenylene dicarboxamide, tris(3,5 -dimethyl-4-cyanobenzyl) isocyanurate, 2-phenyl-3,3-bis(4-cyanophenyl)benzylformamide, 2-(4-methylphenyl)-3,3-bis(4-cyanophenyl)benzylformamide, 2-phenyl-3,3-bis(4-cyanophenyl)benzylformamide, 1-methyl-3,3-bis(4-cyanophenyl)indolin-2-one, and 2-phenyl-3,3-bis(4-cyanophenyl)indolin-2-one.

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

As another specific example of the cyanate compound represented by formula (42), there can be cited the following phenol resins which are cyanated by the same method as above, and prepolymers thereof, etc.: phenol novolac resins and cresol novolac resins (phenol, alkyl-substituted phenol or halogen-substituted phenol, and formaldehyde such as formalin or paraformaldehyde are reacted with each other by a known method); Compounds are reacted in an acidic solution), trisphenol novolac resins (formed by reacting hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), fluorene novolac resins (formed by reacting a fluorenone compound with 9,9-bis(hydroxyaryl)fluorene in the presence of an acidic catalyst), phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins and biphenyl aralkyl resins (formed by reacting a hydroxybenzaldehyde and phenol in the presence of an acidic catalyst by a known method). A dihalogenated methyl compound represented by _{Ar 4} -(CH ₂ Y) ₂ (Ar ₄ represents a phenyl group, Y represents a halogen atom; the same shall apply in the following paragraph) is reacted with a phenol compound in the presence of an acidic catalyst or in the absence of a catalyst; a bis(alkoxymethyl) compound represented by Ar ₄ -(CH ₂ OR) ₂ (R represents an alkyl group) is reacted with a phenol compound in the presence of an acidic catalyst; or a di(alkoxymethyl) compound represented by Ar ₄ -(CH ₂ OH) ₂ and a phenol compound in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound and a phenol compound are condensed), a phenol-modified xylene formaldehyde resin (formed by a known method by reacting a xylene formaldehyde resin and a phenol compound in the presence of an acidic catalyst), a modified naphthalene formaldehyde resin (formed by a known method by reacting a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound in the presence of an acidic catalyst), a phenol-modified dicyclopentadiene resin, a phenol resin having a polynaphthalene ether structure (formed by dehydrating and condensing a polyhydroxynaphthalene compound having two or more phenolic hydroxyl groups in one molecule in the presence of an alkaline catalyst by a known method), and the like. These cyanate compounds may be used alone or in combination of two or more.

The production method of these cyanate ester compounds is not particularly limited, and a known method can be used. As an example of the production method, the following method can be cited: a hydroxyl group-containing compound having a desired skeleton is obtained or synthesized, and the hydroxyl group is modified by a known method to be cyanated. As a method for cyanating a hydroxyl group, for example, the method described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins", Blackie Academic & Professional can be cited.

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

In the resin composition of the present embodiment, the content of the cyanate compound is usually 0.01 to 40 parts by mass relative to 100 parts by mass of the total of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C).

(Phenol resin) As the phenol resin, any generally known phenol resin can be used as long as it has two or more hydroxyl groups in one molecule. For example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac type phenol resin, Varnish resin, multifunctional naphthol resin, anthracene phenol resin, naphthalene skeleton modified novolac phenol resin, phenol aralkyl phenol resin, naphthol aralkyl phenol resin, dicyclopentadiene phenol resin, biphenyl phenol resin, alicyclic phenol resin, polyol phenol resin, phosphorus-containing phenol resin, polymerizable unsaturated hydrocarbon-containing phenol resin, and hydroxyl-containing silicone resins. These phenol resins can be used alone or in combination of two or more.

In the resin composition of the present embodiment, the content of the phenol resin is usually 0.01 to 40 parts by mass relative to 100 parts by mass of the total of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C).

(Oxycyclobutane resin) As the oxycyclobutane resin, generally known ones can be used. For example, alkyl cyclooxybutanes such as cyclooxybutane, 2-methylcyclooxybutane, 2,2-dimethylcyclooxybutane, 3-methylcyclooxybutane, 3,3-dimethylcyclooxybutane, 3-methyl-3-methoxymethylcyclooxybutane, 3,3-bis(trifluoromethyl)perfluorocyclooxybutane, 2-chloromethylcyclooxybutane, 3,3-bis(chloromethyl)cyclooxybutane, biphenyl-type cyclooxybutane, OXT-101 (trade name, manufactured by Toagosei Co., Ltd.), OXT-121 (trade name, manufactured by Toagosei Co., Ltd.), and OXT-221 (trade name, manufactured by Toagosei Co., Ltd.). These cyclohexane oxybutane resins can be used alone or in combination of two or more.

In the resin composition, the content of the cyclohexane oxybutane resin is usually 0.01 to 40 parts by mass relative to 100 parts by mass of the total of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C).

(Benzoxazine compound) As the benzoxazine compound, any generally known compound having two or more dihydrobenzoxazine rings in one molecule can be used. For example, bisphenol A type benzoxazine BA-BXZ (manufactured by Konishi Chemical Industry Co., Ltd., trade name), bisphenol F type benzoxazine BF-BXZ (manufactured by Konishi Chemical Industry Co., Ltd., trade name), bisphenol S type benzoxazine BS-BXZ (manufactured by Konishi Chemical Industry Co., Ltd., trade name), phenolphthalein type benzoxazine, etc. These benzoxazine compounds can be used alone or in combination of two or more.

In the resin composition of the present embodiment, the content of the benzoxazine compound is usually 0.01 to 40 parts by mass relative to 100 parts by mass of the total of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C).

(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, Epoxy resin, polyfunctional phenol epoxy resin, naphthalene epoxy resin, naphthalene skeleton modified novolac epoxy resin, naphthalene ether epoxy resin, phenol aralkyl epoxy resin, anthracene epoxy resin, trifunctional phenol epoxy resin, tetrafunctional phenol epoxy resin, triglycidyl isocyanuric acid esters, glycidyl ester type epoxy resins, alicyclic epoxy resins, dicyclopentadiene novolac type epoxy resins, biphenyl novolac type epoxy resins, phenol aralkyl novolac type epoxy resins, naphthol aralkyl novolac type epoxy resins, aralkyl novolac type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, polyol type epoxy resins, phosphorus-containing epoxy resins, glycidyl amine, compounds obtained by epoxidizing double bonds of butadiene and the like, compounds obtained by reacting hydroxyl-containing silicone resins with epichlorohydrin, and halides thereof. These epoxy resins can be used alone or in combination of two or more.

As the epoxy resin, a commercial product may be used. Examples of commercial products include an epoxy resin represented by formula (45) (NC-3000FH (trade name) manufactured by Nippon Kayaku Co., Ltd., where n is approximately 4 in formula (45)) and a naphthalene-based epoxy resin represented by formula (46) (HP-4710 (trade name) manufactured by DIC Corporation).

[Chemistry 50]

[Chemistry 51]

These epoxy resins may be used alone or in combination of two or more.

In the resin composition of the present embodiment, the content of the epoxy resin is usually 0.01 to 40 parts by mass relative to 100 parts by mass of the total of the dimaleimide compound (A), the compound (B) and the photocuring initiator (C).

(Other compounds) As other compounds, there can be listed: vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrenes such as styrene, methyl styrene, ethyl styrene, and divinylbenzene; triallyl isocyanurate, trimethylallyl isocyanurate, and diallyl nadic acid imide, etc. These compounds can also be used alone or in combination of two or more. In the resin composition of the present embodiment, the content of other compounds is usually 0.01 to 40 parts by mass relative to 100 parts by mass of the total of the dimaleimide compound (A), the compound (B), and the photocuring initiator (C).

[Organic solvent] The resin composition of the present embodiment may contain an organic solvent as needed. If an organic solvent is used, the viscosity of the resin composition can be adjusted during preparation. There is no particular limitation on the type of organic solvent as long as it can dissolve a part or all of the resin in the resin composition. Examples of organic solvents include: ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alicyclic ketones such as cyclopentanone and cyclohexanone; solvent-based solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester-based solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxy isobutyrate, and γ-butyrolactone; polar solvents such as amides such as dimethylacetamide and dimethylformamide; non-polar solvents such as aromatic hydrocarbons such as toluene, xylene, and anisole. These organic solvents can be used alone or in combination of two or more.

[Other components] In the resin composition of the present embodiment, various polymer compounds such as thermosetting resins, thermoplastic resins, and oligomers thereof, and elastomers that have not been listed heretofore, flame retardant compounds that have not been listed heretofore, and additives, etc., can also be used in combination within the scope that does not impair the characteristics of the present embodiment. These are not particularly limited if they are general users. For example, flame retardant compounds can include nitrogen-containing compounds such as melamine and benzoguanamine, compounds containing oxazine rings, and phosphoric acid ester compounds of phosphorus compounds, aromatic condensed phosphates, halogen-containing condensed phosphates, etc. As additives, there can be listed: ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface conditioners, gloss agents, polymerization inhibitors, thermosetting accelerators, etc. These components can also be used alone or in a suitable mixture of two or more. In the resin composition of the present embodiment, the content of other components is usually 0.1 to 10 parts by mass relative to the total of 100 parts by mass of the dimaleimide compound (A), the compound (B) and the photocuring initiator (C).

[Method for producing resin composition] The resin composition of the present embodiment is prepared by appropriately mixing a bismaleimide compound (A), a compound (B), a photocuring initiator (C), and, if necessary, a maleimide compound (D) other than the bismaleimide compound (A), a filler (E), and other resins, other compounds, additives, etc. The resin composition can be suitably used as a varnish when producing a resin sheet of the present embodiment described later. In addition, the organic solvent used in the preparation of the varnish is not particularly limited, and its specific example is as described above.

The method for producing the resin composition includes, for example, mixing the above-mentioned components into a solvent in sequence and stirring the mixture thoroughly. The resin composition has excellent photocurability, good solubility in organic solvents, and excellent alkali developability.

When manufacturing the resin composition, known treatments (stirring, mixing, kneading treatments, etc.) for uniformly dissolving or dispersing the components may be performed as necessary. Specifically, by performing a stirring and dispersing treatment using a stirring tank equipped with a stirrer having an appropriate stirring capacity, the dispersibility of the components in the resin composition can be improved. Stirring, mixing, and kneading treatments may be appropriately performed using known devices such as stirring devices for the purpose of dispersion, such as ultrasonic homogenizers, devices for the purpose of mixing, such as three-rollers, ball mills, bead mills, sand mills, and mixing devices of a revolving or rotating type. In addition, an organic solvent may be used as necessary when preparing the resin composition. The type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples thereof are as described above.

The resin composition can be suitably used as a varnish when preparing the resin sheet of the present embodiment described later. The varnish can be obtained by a known method. For example, the varnish can be obtained by adding 10 to 900 parts by mass of an organic solvent to 100 parts by mass of the components other than the organic solvent in the resin composition of the present embodiment, and performing the known mixing treatment (stirring, kneading treatment, etc.).

[Applications] The resin composition can be preferably used for applications where insulation is required. For example, it can be used for photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (for laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die attach materials, semiconductor sealing materials, hole filling resins, and component embedding resins. Among these, the resin composition has excellent photocurability because it does not hinder the photocuring reaction in the exposure step, and can be given excellent alkali development in the development step, so it can be suitably used as an insulating layer for multilayer printed wiring boards or solder resists.

[Cured material] The cured material is obtained by curing the resin composition of the present embodiment. The cured material can be obtained, for example, by melting or dissolving the resin composition in a solvent, pouring the mixture into a mold, and curing the mixture under normal conditions using light. Regarding the wavelength range of the light, it is preferred to cure the mixture within a range of 100 nm to 500 nm, which is a range where curing is efficiently performed using a photopolymerization initiator or the like.

[Resin sheet] The resin sheet of the present embodiment is a resin sheet with a support, which has a support and a resin layer disposed on one or both sides of the support, and the resin layer contains the resin composition of the present embodiment. The resin sheet can be manufactured by applying the resin composition on the support and drying it. The resin layer in the resin sheet has excellent light curing property and alkali developing property.

The support body may be a known one, but 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, polyvinyl alcohol film, and triacetate film. Among these, PET film is preferred.

In order to facilitate peeling from the resin layer, the resin film is preferably coated with a peeling agent on the surface. The thickness of the resin film is preferably in the range of 5 μm to 100 μm, and more preferably in the range of 10 μm to 50 μm. If the thickness is less than 5 μm, the support tends to be easily broken when the support is peeled off before alkaline development, and if the thickness exceeds 100 μm, the resolution tends to decrease when exposing from the support.

In order to reduce light scattering during exposure, the resin film is preferably a film with excellent transparency.

Furthermore, in the resin sheet of the present embodiment, the resin layer can also be protected by a protective film. By protecting the side of the resin layer with a protective film, dust or the like can be prevented from being attached to the surface of the resin layer or from being damaged. 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 preferably in the range of 1 μm to 50 μm, and more preferably in the range of 5 μm to 40 μm. When the thickness is less than 1 μm, the operability of the protective film tends to be reduced, and if it exceeds 50 μm, the cost performance tends to be poor. Furthermore, the protective film is preferably such that the adhesion between the resin layer and the protective film is smaller than the adhesion between the resin layer and the support.

The method for producing the resin sheet of the present embodiment can be exemplified by the following method, for example: the resin composition of the present embodiment is applied to a support such as a PET film, and the organic solvent is removed by drying to produce the resin sheet. Regarding the coating method, for example, it can be carried out by a known method using a roller coater, a comma coater, a gravure coater, a die coater, a rod coater, a lip coater, a blade coater, and an extrusion coater. Drying can be carried out, for example, by heating in a dryer at 60°C to 200°C for 1 minute to 60 minutes.

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

The resin sheet can be preferably used for manufacturing the insulating layer of a multi-layer printed wiring board.

[Multi-layer printed wiring board] The multi-layer printed wiring board of the present embodiment has an insulating layer and a conductive layer formed on one or both sides of the insulating layer, and the insulating layer contains the resin composition of the present embodiment. For example, the insulating layer can be obtained by stacking and curing more than one resin sheet. There is no particular limitation on the number of layers of the insulating layer and the conductive layer, and the number of layers can be appropriately set according to the target use. In addition, there is no particular limitation on the order of the insulating layer and the conductive layer. As the conductive layer, it can be a metal foil used for various printed wiring board materials, for example, metal foils such as copper and aluminum can be listed. Examples of copper metal foils include rolled copper foil and electrolytic copper foil. The thickness of the conductor layer is usually 1 μm to 100 μm. Specifically, it can be produced by the following method.

(Lamination step) In the lamination step, a vacuum lamination press is used to press the resin layer side of the resin sheet onto one or both sides of the circuit substrate. Examples of the circuit substrate include glass epoxy substrates, metal substrates, ceramic substrates, silicon substrates, semiconductor sealing resin substrates, polyester substrates, polyimide substrates, bismaleimide triazine (BT) resin substrates, and thermosetting polyphenylene ether substrates. Furthermore, the so-called circuit substrate refers to a substrate having a patterned conductive layer (circuit) formed on one or both sides of the substrate as described above. In addition, in a multilayer printed wiring board formed by alternately laminating a conductor layer and an insulating layer, a substrate in which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits) is also included in the circuit substrate. Furthermore, the insulating layer laminated on the multilayer printed wiring board may be an insulating layer obtained by laminating and curing one or more resin sheets of the present embodiment, or may be an insulating layer obtained by laminating one or more resin sheets of the present embodiment and a known resin sheet different from the resin sheet of the present embodiment. Furthermore, there is no particular limitation on the method of overlapping the resin sheet of the present embodiment with a known resin sheet different from the resin sheet of the present embodiment. The surface of the conductor layer may also be roughened in advance by blackening and/or copper etching. In the lamination step, if the resin sheet has a protective film, the resin sheet and the circuit substrate are preheated as needed after the protective film is peeled off and removed, and the resin layer of the resin sheet is pressed and connected to the circuit substrate while being pressurized and heated. In the present embodiment, a method of pressing the resin layers of the resin sheet to the circuit substrate under reduced pressure by vacuum lamination can be appropriately used.

Regarding the conditions of the lamination step, for example, it is preferred to set the pressing temperature (lamination temperature) to 50°C to 140°C, set the pressing pressure to 1 kgf/ ^cm2 to 15 kgf/ ^cm2 , set the pressing time to 5 seconds to 300 seconds, and perform the lamination under reduced pressure with the air pressure set to 20 mmHg or less. In addition, the lamination step may be a batch type or a continuous type using a roll. The vacuum lamination method can be performed using a commercially available vacuum lamination press. As a commercially available vacuum lamination press, for example, a 2-stage build-up laminator (trade name) manufactured by Nikko Materials (Co., Ltd.) can be listed.

(Exposure step) In the exposure step, after the resin layer is provided on the circuit substrate by the lamination step, the resin layer is irradiated with active energy rays as a light source to harden the resin layer in the irradiated part. The irradiation may be performed via a mask pattern or by a direct drawing method of direct irradiation. Examples of active energy rays include ultraviolet rays, visible rays, electron beams, and X-rays. The wavelength of the active energy rays is, for example, in the range of 200 nm to 600 nm. When ultraviolet rays are used, the irradiation amount is approximately 10 mJ/cm ² to 1000 mJ/cm ² . In addition, when a printed wiring board having a high-density and high-precision wiring formation (pattern) is manufactured using a stepper exposure method, it is preferable to use an active energy ray including a wavelength of 365 nm (i-ray), for example. When using an active energy ray including a wavelength of 365 nm (i-ray), the irradiation amount is approximately 10 mJ/cm ² to 10,000 mJ/cm ² . When a printed wiring board having a high-density and high-precision wiring formation (pattern) is manufactured using a direct writing exposure method, it is preferable to use an active energy ray including a wavelength of 405 nm (h-ray), for example. When using an active energy ray including a wavelength of 405 nm (h-ray), the irradiation amount is approximately 10 mJ/cm ² to 10,000 mJ/cm ² . There are two methods of exposure through a mask pattern: a contact exposure method in which the mask pattern is brought into close contact with the multi-layer printed wiring board, and a non-contact exposure method in which exposure is carried out using parallel light without close contact. Either method may be used. In addition, when a support is present on the resin layer, exposure may be carried out from the support, or exposure may be carried out after the support is peeled off.

(Alkali development step) When there is no support on the resin layer, the uncured portion (unexposed portion) is directly removed by alkali development after the exposure step to form a pattern of the insulating layer. In addition, when there is a support on the resin layer, after the exposure step, the uncured portion (unexposed portion) is removed by alkali development after the support is removed to form a pattern of the insulating layer. The unexposed resin layer of the resin composition of the present embodiment has excellent alkali developability, so a printed wiring board with a high-precision pattern can be obtained.

In the case of alkaline development, the developer is not particularly limited as long as it is a developer that selectively dissolves the unexposed portion, and alkaline developers such as tetramethylammonium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium hydroxide aqueous solution, and potassium hydroxide aqueous solution can be used. In this embodiment, it is particularly preferred to use tetramethylammonium hydroxide aqueous solution. These alkaline developers can also be used alone or in combination of two or more.

In addition, as an alkaline developing method, for example, it can be carried out by a known method such as immersion, coating, spraying, shaking immersion, brushing, scraping, etc. In the pattern formation of this embodiment, these developing methods can also be used in combination as needed. In addition, as a developing method, when a high-pressure spray is used, the resolution will be further improved, so it is suitable. When the spray method is adopted, the spray pressure is preferably 0.02 MPa to 0.5 MPa.

(Post-baking step) In the present embodiment, a post-baking step is performed after the alkaline development step is completed to form an insulating layer (hardened material). As the post-baking step, there can be cited a step of ultraviolet irradiation using a high-pressure mercury lamp, a step of heating using a clean oven, etc., and these steps can also be used in combination. In the case of ultraviolet irradiation, the irradiation amount can be adjusted as needed, for example, the irradiation amount can be about 50 mJ/ ^cm2 to 10,000 mJ/ ^cm2 . The heating conditions can be appropriately selected as needed, but are preferably in the range of 150° C. to 220° C. and 20 minutes to 180 minutes, and more preferably in the range of 160° C. to 200° C. and 30 minutes to 150 minutes.

(Conductor layer formation step) After forming the insulating layer (hardened material), a conductor layer is formed on the surface of the insulating layer by dry plating. As dry plating, known methods such as evaporation, sputtering, and ion plating can be used. Evaporation (vacuum evaporation) is, for example, a method of placing a multi-layer printed wiring board in a vacuum container and heating the metal to evaporate, thereby forming a metal film on the insulating layer. Sputtering is, for example, a method of placing a multi-layer printed wiring board in a vacuum container, introducing an inert gas such as argon, and applying a DC voltage to cause the ionized inert gas to collide with the target metal, and using the knocked-out metal to form a metal film on the insulating layer.

Then, a conductive layer is formed by electroless plating or electrolytic plating, etc. As a method for subsequent patterning, for example, a subtractive method, a semi-additive method, etc. can be used.

[Semiconductor device] The semiconductor device of the present embodiment includes the resin composition of the present embodiment. Specifically, it can be manufactured by the following method. The semiconductor device can be manufactured by mounting a semiconductor chip on a conductive part of a multilayer printed wiring board. Here, the conductive part refers to a part in the multilayer printed wiring board where an electrical signal is transmitted, and the place may be a surface or an embedded part. In addition, the semiconductor chip is not particularly limited as long as it is an electrical circuit element made of semiconductor.

As long as the semiconductor chip functions effectively, there is no particular limitation on the mounting method of the semiconductor chip when manufacturing the semiconductor device. Specifically, there are wire bonding mounting method, flip chip mounting method, mounting method using bumpless build-up layer (BBUL), mounting method using anisotropic conductive film (ACF), and mounting method using non-conductive film (NCF).

In addition, a semiconductor device can be manufactured by forming an insulating layer containing a resin composition on a semiconductor chip or a substrate carrying a semiconductor chip. The shape of the substrate carrying the semiconductor chip can be a wafer or a panel. After forming the insulating layer, the same method as a multi-layer printed wiring board can be used for manufacturing. [Example]

Hereinafter, the present invention will be described in more detail based on embodiments and comparative examples, but the present invention is not limited to the following embodiments.

The molecular weight determination conditions are as follows. Model: GPC TOSOH HLC-8220GPC Column: Super HZM-N Solvent: tetrahydrofuran (THF); 0.35 ml/min, 40°C Detector: differential refractometer (refractive index, RI) Molecular weight standard: polystyrene

<Synthesis of bismaleimide compound (A)> As bismaleimide compound (A), the following four compounds were prepared. [Synthesis Example 1 (A-1)] In a 1 L round bottom flask equipped with a thermometer, a reflux cooler, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet, and a stirring apparatus, 165 g of toluene and 165 g of N-methylpyrrolidone were placed. Then, 26.6 g (0.20 mol) of m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 11.7 g (0.02 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) were added, and then 20.9 g (0.22 mol) of methanesulfonic acid was slowly added to form a salt. The mixture was stirred for about 10 minutes to mix, and then 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (48.2 g, 0.11 mol) was slowly added to the stirred mixture. The mixture was heated and refluxed for 6 hours to form an amine-terminated diimide. At this point, the theoretical amount of water generated from the condensation was obtained. The reaction mixture was cooled to below room temperature, and 25.5 g (0.26 mol) of maleic anhydride was added to the flask. The mixture was further refluxed for 8 hours to obtain the desired amount of water generated. After cooling to room temperature, the organic layer was washed with water (100 ml × five times) to remove the salt and unreacted raw materials, and a varnish of a bismaleimide compound was obtained. Thereafter, the varnish was added dropwise to 1,000 g of methanol to perform a reprecipitation step, remove the solvent and dry it, thereby obtaining 72 g (yield 72%, Mw=4,000) of the target light brown solid bismaleimide compound.

[Synthesis Example 2 (A-2)] In a 1 L round-bottom flask equipped with a thermometer, reflux cooler, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirring apparatus, 162 g of toluene and 162 g of N-methylpyrrolidone were placed. Then, 32.4 g (0.24 mol) of m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added, and then 22.9 g (0.24 mol) of methanesulfonic acid was slowly added to form a salt. The mixture was stirred for about 10 minutes to mix, and then 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (52.8 g, 0.12 mol) was slowly added to the stirred mixture. The mixture was heated to reflux for 6 hours to form an amine-terminated diimide. At this point, the theoretical amount of water generated from the condensation was obtained. The reaction mixture was cooled to below room temperature, and 28.0 g (0.29 mol) of maleic anhydride was added to the flask. The mixture was further refluxed for 8 hours to obtain the desired amount of water. After cooling to room temperature, the organic layer was washed with water (100 ml × five times) to remove the salt and unreacted raw materials to obtain a varnish of the bismaleimide compound. Thereafter, the varnish was added dropwise to 1,000 g of methanol, and a reprecipitation step was performed to remove the solvent and dry it, thereby obtaining 78 g of the target light brown solid bismaleimide compound (yield 78%, Mw=3,600).

[Synthesis Example 3 (A-3)] In a 1 L round-bottom flask equipped with a thermometer, reflux cooler, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirring device, 170 g of toluene and 170 g of N-methylpyrrolidone were placed. Then, 20.2 g (0.15 mol) of m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 20.0 g (0.04 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) were added, and then 17.8 g (0.19 mol) of methanesulfonic acid was slowly added to form a salt. The mixture was stirred for about 10 minutes to mix, and then 4,4'-bisphenol A dianhydride (48.3 g, 0.09 mol) was slowly added to the stirred mixture. The mixture was heated and refluxed for 6 hours to form an amine-terminated diimide. At this point, the theoretical amount of water generated from the condensation was obtained. The reaction mixture was cooled to below room temperature, and 21.8 g (0.22 mol) of maleic anhydride was added to the flask. The mixture was further refluxed for 8 hours to obtain the desired amount of water generated. After cooling to room temperature, the organic layer was washed with water (100 ml × five times) to remove the salt and unreacted raw materials, and a varnish of a bismaleimide compound was obtained. Thereafter, the varnish was added dropwise to 1,000 g of methanol to perform a reprecipitation step, remove the solvent and dry it, thereby obtaining 68 g (yield 68%, Mw=4,200) of the target white solid bismaleimide compound.

<Synthesis of a compound (B) containing one or more carboxyl groups> As a compound (B) containing one or more carboxyl groups, the following four compounds were prepared. [Synthesis Example 5 (B-1)] 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid (ACHA-MI) Manufactured by Tokyo Chemical Industry Co., Ltd. [Synthesis Example 6 (B-2)] 6-maleimidocaproic acid (MCA) Manufactured by Tokyo Chemical Industry Co., Ltd. [Compound (B-3)] cis-4-cyclohexene-1,2-dicarboxylic acid (TH-W) Manufactured by Shin Nippon Chemical Co., Ltd., product name "Rikacid TH-W" [Compound (B-4)] 4-aminobenzoic acid Manufactured by Tokyo Chemical Industry Co., Ltd.

<Photopolymerization initiator (C)> As the photopolymerization initiator (C), the following two compounds were prepared. Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime) (manufactured by BASF Japan, "IRGACURE OXE-02") Bis(2,4,6-trimethylbenzyl)phenylphosphine oxide (manufactured by BASF Japan, "Omnirad 819")

(Example 1 to Example 6) The components (A) to (C) in the amounts (parts by mass) shown in Table 1 and 103 parts by mass of cyclopentanone as an organic solvent (G) were mixed to prepare the photosensitive resin compositions of Examples 1 to 6.

<Evaluation of properties> The following properties were measured for the prepared curable resin composition and cured film. The results are shown in Table 1.

[Compatibility] Visual compatibility refers to the state of the curable resin composition after mixing and stirring components (A) to (G). Good compatibility means that there is no precipitate and it can be applied to the base material, while poor compatibility means that there is precipitate and it is difficult to apply to the base material. (Evaluation criteria) ○: No precipitate ×: Precipitate

[Evaluation of photocurability and alkaline development properties] The photosensitive resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were spin-coated on a silicon substrate and heated at 95°C for 2 minutes to form a coating having a thickness of 10 μm to 15 μm. Subsequently, a light source capable of irradiating active energy rays having a wavelength of 405 nm (USHIO UX-1000SM-HJ01 (trade name)) was used to irradiate from the support at an irradiation dose of 2000 mJ/ ^cm2 , exposing half of the coating and leaving the remaining portion unexposed. After exposure, heat at 150°C for 15 minutes and oscillate in a 2.38% tetramethyl ammonium hydroxide (TMAH) aqueous solution (developer, manufactured by Tokuyama Co., Ltd.) for 60 to 180 seconds. Then, for the undissolved portion of the unexposed part, develop it with propylene glycol monomethyl ether glycol to confirm the photocurability. For the laminate obtained after development, the photocurability and alkali developability are evaluated by visual inspection according to the following criteria. (Alkali developability judgment criteria) ○: The exposed part is insoluble, but the unexposed part is dissolved during 60 seconds to 3 minutes of oscillation. ×: Both the exposed and unexposed parts are insoluble. In addition, the curability is also judged by whether there is a pattern remaining after development. (Criteria for determination of photocurability) ○: After development, a pattern remains ×: After development, no pattern remains The results of alkali developability and photocurability are shown in Table 1.

[Table 1] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 A-1 Synthesis Example 1 90 90 90 90 A-2 Synthesis Example 2 90 A-3 Synthesis Example 3 90 B-1 ACHA-MI 10 10 B-2 MCA 10 10 10 B-3 TH-W 10 C-1 OXE02 3 3 3 3 3 C-2 Omnirad 3 D CP 103 103 103 103 103 103 Evaluation results compatibility ○ ○ ○ ○ ○ ○ Light hardening ○ ○ ○ ○ ○ ○ Alkali Development ○ ○ ○ ○ ○ ○

As clearly shown in Table 1, according to this embodiment, when exposed to any of active energy rays including a wavelength of 405 nm (h-rays) and active energy rays including a wavelength of 200 nm to 600 nm, good photosensitivity and photocuring can be performed. In addition, according to this embodiment, as shown in Table 1, a cured product with excellent alkali developability can be obtained. [Industrial Applicability]

The resin composition of the present embodiment has excellent photocurability and alkali developability and can be effectively used in industry, for example, it can be used for photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (for laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die attach materials, semiconductor sealing materials, hole filling resins, parts embedding resins, fiber-reinforced composite materials, etc.

without

Claims (8)

A resin composition comprising: a bismaleimide compound (A) represented by the following general formula (1), a compound (B) containing one or more carboxyl groups, and a photocuring initiator (C); (In formula (1), R ₃ independently represents a tetravalent organic group including a cyclic structure; R ₂ independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms; R ₁ independently represents the following formula (2); R ₄ is R ₁ or R ₂ ; m is 1 to 100, and n is 0 to 100; in addition, the order of the repeating units enclosed by m and n is not limited, and the bonding pattern may be alternating, block, or random); (R ₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms; l each independently represents an integer of 1 to 4). The resin composition according to claim 1, wherein the compound (B) containing one or more carboxyl groups is at least one compound selected from the group consisting of a compound represented by the following formula (3), a compound represented by the following formula (4), a compound represented by the following formula (5), and a compound represented by the following formula (6); (In formula (3), R ₆ each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group or an aminomethyl group; o each independently represents an integer of 1 to 5; in formula (3), when there are two or more carboxyl groups, these groups may be linked to form an acid anhydride); (In formula (4), _R7 each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group or an aminomethyl group; p each independently represents an integer of 1 to 9; in formula (4), when there are two or more carboxyl groups, these groups may be linked to form an acid anhydride; in formula (4), when there is a carboxymethyl group, a carboxymethyl group and a carboxyl group may be linked to form an acid anhydride); (In formula (5), _R8 each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group or an aminomethyl group; q each independently represents an integer of 1 to 9; in formula (5), when there are two or more carboxyl groups, these groups may be linked to form an acid anhydride; in formula (5), when there is a carboxymethyl group, a carboxymethyl group and a carboxyl group may be linked to form an acid anhydride); (In formula (6), _R9 each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group or an aminomethyl group; r each independently represents an integer from 1 to 5; in formula (6), when there are more than one carboxyl group, it may be an acid anhydride formed by a carboxymethyl group and a carboxyl group linked to each other; in formula (6), when there are more than two carboxyl groups, it may be an acid anhydride formed by these groups linked to each other; in formula (6), when there are more than two carboxymethyl groups, it may be an acid anhydride formed by these groups linked to each other). A resin composition as claimed in claim 1 or 2, comprising a bismaleimide compound (A) represented by the following formula (1), wherein the organic group represented by _R3 is any one of the tetravalent organic groups represented by the following structural formulas (7) to (15); (In formula (1), R ₃ independently represents a tetravalent organic group including a cyclic structure; R ₂ independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms; R ₁ independently represents the following formula (2); R ₄ is R ₁ or R ₂ ; m is 1 to 100, and n is 0 to 100; in addition, the order of the repeating units enclosed by m and n is not limited, and the bonding pattern may be alternating, block, or random); ( _R5 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms; l each independently represents an integer of 1 to 4); (In formula (11), Y represents C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond, or a divalent linking group represented by the following formula (16)); The -* in the structural formula represents a bond, and in formula (1) it is bonded to the carbonyl carbon forming the cyclic imide structure. The resin composition according to claim 1 or 2, wherein the photocuring initiator (C) comprises a compound represented by the following formula (17); (In formula (17), _R9 each independently represents a substituent represented by the following formula (18) or a phenyl group); (In formula (18), -* represents a bond, and R ₁₀ each independently represents a hydrogen atom or a methyl group). A resin sheet having: a support body; and a resin layer disposed on one side or both sides of the support body, wherein the resin layer comprises the resin composition as described in claim 1 or 2. The resin sheet as described in claim 5, wherein the thickness of the resin layer is 1 μm to 50 μm. A multilayer printed wiring board comprising: an insulating layer; and a conductive layer formed on one or both sides of the insulating layer, wherein the insulating layer comprises the resin composition as described in claim 1 or 2. A semiconductor device comprising the resin composition as described in claim 1 or 2.