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

Abstract

The invention provides a resin composition, a resin sheet using the resin composition, a multilayer printed wiring board, and a semiconductor device, the resin composition having excellent photocurability without hindering a photocuring reaction in an exposure step, and being capable of imparting excellent alkali developability in a development step, and a resin sheet, a multilayer printed wiring board, and a semiconductor device using the resin composition. A resin composition contains a bismaleimide compound (A) represented by general formula (1), a compound (B) containing one or more carboxyl groups, and a photocuring initiator (C). (In formula (1), R3 independently represents a tetravalent organic group containing a cyclic structure; r2 is independently a divalent hydrocarbon group having 6 to 200 carbon atoms; r1 is independently represented by formula (2); r4 is R1 or R2; m is 1 to 100, and n is 0 to 100; in addition, the sequence of each repeating unit formed by m and n is not limited, and the bonding pattern can be alternating, can also be a block, and can also be random; (R5) each independently represents a hydrogen atom, a linear or branched alkyl group having 1-6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1-6 carbon atoms; and each l independently represents an integer of 1-4. ()) # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a resin composition, a resin sheet, a multilayer printed wiring board, and a semiconductor device. Background Art

[0002] 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 notebook computers; materials suitable for millimeter wave radars; and equipment related to automatic braking systems for vehicles, there is a growing demand for electronic circuit boards with better dielectric properties, heat resistance, low stress, water resistance, and adhesion.

[0003] In the past, cyanate resins were widely known as thermosetting resins with excellent heat resistance, low dielectric constant and low dielectric loss. For example, in Patent Document 1, a phenol novolac type cyanate resin is disclosed as a resin with excellent heat resistance and storage stability. However, although the hardened material obtained by using the phenol novolac type cyanate resin described in Patent Document 1 is excellent in heat expansion resistance, it has a large water absorption rate and has a situation of dielectric property degradation.

[0004] In addition, due to the miniaturization and high density of multilayer printed wiring boards, research on thinning the laminate used in the multilayer printed wiring boards is prevalent. With the thinning, the insulating layer is also required to be thinner, and thus a resin sheet that does not contain glass cloth is required. The resin composition used as the material of the insulating layer is mainly thermosetting resin, and the opening for obtaining conduction between the insulating layers is generally performed by laser processing.

[0005] On the other hand, the hole opening by laser processing has the problem that the processing time is longer in a high-density substrate with more holes. Therefore, in recent years, a resin sheet that can be processed by batch hole opening in the exposure and development steps is 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).

[0006] As a method of exposure, a method of using a mercury lamp as a light source and exposing through a photomask is used, thereby seeking a material that can be suitably exposed in the light source of the mercury lamp. The exposure method using the mercury lamp as a light source uses a ghi mixed line (a wavelength of 436nm for g-rays, a wavelength of 405nm for h-rays, and a wavelength of 365nm for i-rays), etc., so that a general 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, and 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 alignment accuracy and can obtain a high-precision pattern. Therefore, it is particularly promoted to be introduced in a substrate that needs to form a high-density wiring. Its light source uses monochromatic light such as a laser, wherein, in a device of a digital micromirror device (DMD) method capable of forming a high-precision resist pattern, a light source with a wavelength of 405nm (h-ray) is used.

[0007] As a developing method, alkali development can be used in order to obtain a high-definition pattern.

[0008] 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 curing in the exposure step.

[0009] 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 photocuring 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 the resulting resin with an acid anhydride.

[0010] In addition, Patent Document 3 describes a resin composition comprising: a photocurable binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, a photopolymerization (curing) initiator, a sensitizer, and a bisallylnadic imide compound and a bismaleimide compound as a thermal curing agent.

[0011] 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 a laminate or a resin sheet.

[0012] Patent Document 5 describes a resin composition comprising a polyvalent carboxyl group-containing compound obtained by reacting bismaleimide with a monoamine and then reacting an acid anhydride with the compound, and a curable resin such as an epoxy resin. Patent Document 5 also describes a polyvalent carboxyl group-containing compound that can produce a cured product having alkali developability.

[0013] Prior art literature

[0014] Patent Literature

[0015] Patent Document 1: Japanese Patent Laid-Open No. 11-124433

[0016] Patent Document 2: Japanese Patent Application Publication No. 2005-62450

[0017] Patent Document 3: Japanese Patent Application Publication No. 2010-204298

[0018] Patent Document 4: WO2018 / 56466A1

[0019] Patent Document 5: Japanese Patent Application Publication No. 2015-229734 Summary of the invention

[0020] Problems to be solved by the invention

[0021] However, the hardened materials using the existing (meth)acrylate resins cannot obtain sufficient physical properties and have limitations in forming excellent protective films and interlayer insulating layers. In addition, the hardened materials have insufficient alkali developability and cannot obtain high-definition resist patterns, which causes problems when used in high-density printed wiring boards.

[0022] The cured product obtained from the resin composition described in Patent Document 1 also has insufficient alkali developability and cannot obtain a high-definition resist pattern, which causes problems when used for a high-density printed wiring board.

[0023] Patent Document 2 describes the use of a bismaleimide compound, but it is described as a heat curing agent, and (meth)acrylate is used as a photopolymerizable compound. Therefore, in the cured product obtained from the resin composition, the alkali developability is also insufficient, and a high-definition resist pattern cannot be obtained, which is problematic when used for a high-density printed wiring board.

[0024] Since the resin composition of Patent Document 3 has insufficient alkali developability, unexposed resin composition remains even after development. Therefore, a high-definition resist pattern cannot be obtained in Patent Document 3 either, and the resin composition cannot be used for the production of a high-density printed wiring board.

[0025] The polycarboxyl-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 process is complicated. In addition, since an aromatic amine compound is used as the monoamine, the polycarboxyl-containing compound contains an amide group having an aromatic ring in its structure. Therefore, the polycarboxyl-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.

[0026] 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 process and has excellent photocurability, and can impart excellent alkali developability in the development process.

[0027] Technical means of solving problems

[0028] The present inventors have found that the above-mentioned problems can be solved by using a resin composition containing a specific bismaleimide compound (A), a compound containing one or more carboxyl groups (B), and a photocuring initiator (C), thereby completing the present invention.

[0029] That is, the present invention includes the following contents.

[0030] [1] 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).

[0031] [Chemistry 1]

[0032]

[0033] (In formula (1), R 3 independently represent a tetravalent organic group containing a cyclic structure; R 2 R is independently a divalent hydrocarbon group having 6 to 200 carbon atoms; 1 are independently represented by the following formula (2); R 4 For R 1 or R 2 ; m is 1 to 100, 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;

[0034] [Chemistry 2]

[0035]

[0036] (R 5Each 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)

[0037] [2] A resin composition according to technical solution 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).

[0038] [Chemistry 3]

[0039]

[0040] (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 may be linked to form an acid anhydride)

[0041] [Chemistry 4]

[0042]

[0043] (In formula (4), R 7 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 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)

[0044] [Chemistry 5]

[0045]

[0046] (In formula (5), R 8 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 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)

[0047] [Chemistry 6]

[0048]

[0049] (In formula (6), R 9Each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group or an aminomethyl group; r 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 carboxylmethyl 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 carboxylmethyl groups, it may be an acid anhydride formed by these groups linked to each other).

[0050] [3] The resin composition according to claim 1 or 2, comprising a bismaleimide compound (A) represented by the following formula (1), wherein R 3 The organic group represented is a bismaleimide compound of any one of the tetravalent organic groups represented by the following structural formulas (7) to (15).

[0051] [Chemistry 7]

[0052]

[0053] (In formula (1), R 3 independently represent a tetravalent organic group containing a cyclic structure; R 2 R is independently a divalent hydrocarbon group having 6 to 200 carbon atoms; 1 are independently represented by the following formula (2); R 4 For R 1 or R 2 ; m is 1 to 100, 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;

[0054] [Chemistry 8]

[0055]

[0056] (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)

[0057] [Chemistry 9]

[0058]

[0059] (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)

[0060] [Chemistry 10]

[0061]

[0062] The -* in the above structural formula represents a bonding bond, and in the formula (1), it is bonded to the carbonyl carbon forming the cyclic imide structure.

[0063] [4] The resin composition according to any one of Technical Solutions 1 to 3, wherein the photocuring initiator (C) contains a compound represented by the following formula (17).

[0064] [Chemistry 11]

[0065]

[0066] (In formula (17), R 10 Each independently represents a substituent represented by the following formula (18) or a phenyl group)

[0067] [Chemistry 12]

[0068]

[0069] (In formula (18), -* represents a bonding bond, R 11 each independently represents a hydrogen atom or a methyl group).

[0070] [5] A resin sheet comprising:

[0071] a support; and

[0072] The resin layer is disposed on one or both sides of the support.

[0073] The resin layer comprises the resin composition according to any one of technical solutions 1 to 4.

[0074] [6] The resin sheet according to claim 5, wherein the thickness of the resin layer is 1 μm to 50 μm.

[0075] [7] A multilayer printed wiring board comprising:

[0076] Insulation layer; and

[0077] A conductor layer is formed on one or both sides of the insulating layer.

[0078] The insulating layer comprises the resin composition according to any one of Technical Solutions 1 to 4.

[0079] [8] A semiconductor device comprising the resin composition according to any one of claims 1 to 4.

[0080] Effects of the Invention

[0081] The present invention 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 multilayer printed wiring board, it does not hinder the photocuring reaction in the exposure process and has excellent photocurability, and can impart excellent alkali developability in the development process. DETAILED DESCRIPTION

[0082] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") is described in detail. The following this embodiment is an example for illustrating the present invention, and the main purpose is not to limit the present invention to the following content. The present invention can be implemented by appropriately modifying it within the scope of its gist.

[0083] In addition, the term "(meth)acryloyloxy" in this specification refers to both "acryloyloxy" and its corresponding "methacryloyloxy", 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-".

[0084] [Resin composition]

[0085] The resin composition of the present embodiment contains a specific bismaleimide compound (A), a compound containing one or more carboxyl groups (B), and a photocuring initiator (C). Hereinafter, each component will be described.

[0086] <Bismaleimide compound (A)>

[0087] The bismaleimide compound (A) of the present invention is a compound having two maleimide groups, and is represented by the following general formula (1):

[0088] [Chemistry 13]

[0089]

[0090] (In formula (1), R 3 independently represent a tetravalent organic group containing a cyclic structure; R 2 R is independently a divalent hydrocarbon group having 6 to 200 carbon atoms; 1 are independently represented by the following formula (2); R 4 For R 1 or R 2 ; m is 1 to 100, 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;

[0091] [Chemistry 14]

[0092]

[0093] (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)).

[0094] In the 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.

[0095] 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. Of 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 chips and substrates, good solubility in solvents, low melting points, low water absorption, and good compatibility with other resins.

[0096] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0097] 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.

[0098] As R 5 In terms of showing excellent adhesion to chips and substrates, as well as good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, preferred are hydrogen atoms, methyl groups, ethyl groups, hydroxyl groups, methoxy groups, and ethoxy groups, more preferred are hydrogen atoms, methyl groups, and hydroxyl groups, and still more preferred are hydrogen atoms.

[0099] In the formula (2), each l independently represents an integer of 1 to 4. As l, in terms of exhibiting excellent adhesion to chips and substrates, etc., as well as good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, R is preferred. 5 All of them are hydrogen atoms, so 4 is preferred.

[0100] As R of the formula (1) 1 Specific examples include the following formulas (19) to (21). Preferably, the following formula (19) is derived from m-xylylenediamine (MXDA: manufactured by Mitsubishi Gas Chemical Co., Ltd.) which is easily available as a commercial product.

[0101] [Chemistry 15]

[0102]

[0103] [Chemistry 16]

[0104]

[0105] [Chemistry 17]

[0106]

[0107] The maleimide compound of the present embodiment is not particularly limited as long as it exerts 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, and 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.

[0108] Generally, the light transmittance of maleimide compounds is poor. Therefore, if the resin composition described later contains maleimide compounds, light will not fully reach the photocuring initiator dispersed in the resin composition, and the photocuring initiator is difficult to generate free radicals. Therefore, in general, the photoradical reaction of maleimide compounds is difficult to proceed, and even if the free radical polymerization or dimerization reaction of the maleimide monomer is carried out, its reactivity is very low. However, the bismaleimide compound (A) has excellent light transmittance because the maleimide group is bonded to the aromatic ring via a methylene group and the conjugation length is short. Therefore, light fully reaches the photocuring initiator, thereby efficiently causing the photoradical reaction of maleimide. In addition, when a chloroform solution containing the maleimide compound at 1% by mass is prepared and the light transmittance of the chloroform solution is measured using light with a wavelength of 405nm (h-ray), the transmittance is more than 3%, showing very excellent light transmittance. Therefore, for example, when a printed wiring board having a high-density and high-definition wiring formation (pattern) is manufactured using a direct writing exposure method, a photoradical reaction of maleimide is efficiently induced even when active energy rays including a wavelength of 405 nm (h-rays) are used.

[0109] When using active energy rays including a wavelength of 405 nm (h-rays), if the photocuring initiator does not absorb the light of the wavelength of 405 nm (h-rays) and generate free radicals, polymerization will not proceed. Therefore, in such a case, as the photocuring initiator described later, it is preferable to use a photocuring initiator whose absorbance at a wavelength of 405 nm (h-rays) is 0.1 or more and shows very excellent absorption to light of a wavelength of 405 nm (h-rays).

[0110] 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 can fully reach the photocuring initiator, and free radicals generated by the photocuring initiator can be used to carry out a free radical reaction, so that photocuring can be carried out in a resin composition containing a large amount of maleimide compound.

[0111] Furthermore, a cured product containing the resin composition has excellent light curing property, heat resistance, and thermal stability, and thus can suitably form a protective film and an insulating layer.

[0112] In the formula (1), R 2 The independent divalent hydrocarbon group having 6 to 200 carbon atoms represented here represents a divalent residue obtained by removing two carboxyl groups from a dicarboxylic acid contained in a dimer acid.

[0113] In this specification, dimer acid refers to an acid obtained by dimerizing unsaturated bonds of unsaturated carboxylic acids such as linolenic acid, oleic acid, and linolenic acid, followed by distillation and 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 diamine derived from dimer acid as appropriate) 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 diamines derived from dimer acid 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.

[0114] As the divalent hydrocarbon derived from the dimer acid of the present invention introduced into the bismaleimide compound using this diamine derived from dimer acid, it is preferably a residue after removing two amino groups from the diamine derived from dimer acid. In addition, when the bismaleimide compound of the present invention is obtained using the diamine derived from dimer acid, as the diamine derived from dimer acid, one type can be used alone, or two or more types with different compositions can be used in combination. Furthermore, as such a diamine derived from dimer acid, for example, a commercial product such as "PRIAMINE 1074" (manufactured by Croda Japan Co., Ltd.) can also be used.

[0115] In the formula (1), R 3 The organic groups represented are tetravalent organic groups each independently containing a cyclic structure, and are derived from the tetrabasic acid dianhydride used for 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-furanyl)-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, bicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and bicyclo[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.

[0116] From the viewpoint of solvent solubility of the bismaleimide resin finally obtained, R in the formula (1) 3 The organic group represented is particularly preferably any one of the tetravalent organic groups represented by the following formulae (7) to (15).

[0117] [Chemistry 18]

[0118]

[0119] 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 formula (16).

[0120] [Chemistry 19]

[0121]

[0122] The -* in the structural formula represents a bonding bond, and in formula (1) it is bonded to the carbonyl carbon of the cyclic imide structure. 3 The tetravalent organic group represented is preferably the following formula (22) to formula (26).

[0123] [Chemistry 20]

[0124]

[0125] [Chemistry 21]

[0126]

[0127] [Chemistry 22]

[0128]

[0129] [Chemistry 23]

[0130]

[0131] [Chemistry 24]

[0132]

[0133] 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, relative to 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 performing the photocuring of the maleimide compound and thereby making the exposed portion sufficiently insolubilized in terms of alkali developability.

[0134] <Method for producing bismaleimide compound (A)>

[0135] The method for producing the bismaleimide compound (A) is not particularly limited, and the bismaleimide compound (A) can be efficiently produced by, for example, the method shown below.

[0136] As a basic process, a bismaleimide compound can be obtained by synthesizing amic acid from tetrabasic acid dianhydride and diamine and performing ring-closing dehydration through step A, then reacting maleic anhydride to synthesize maleamic acid, and finally performing ring-closing dehydration to cap the molecular chain end with a maleimide group through step B.

[0137] In the production method, each step can be roughly divided into two types: a synthesis reaction of amic acid or maleamic acid and a ring-closing dehydration reaction, which are described in detail below.

[0138] In step A, first, amic acid is synthesized by reacting a specific tetrabasic acid dianhydride with a specific diamine. The reaction is generally carried out in an organic solvent (eg, a nonpolar solvent or a high-boiling-point aprotic polar solvent) at room temperature (25°C) to 100°C.

[0139] Next, the ring-closing dehydration reaction of the amic acid 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.

[0140] Examples of organic solvents include toluene, xylene, anisole, biphenyl, naphthalene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc. These can be used alone or in combination of two or more. In addition, examples of acid catalysts include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc. These can be used alone or in combination of two or more.

[0141] The molar ratio of diamine to tetrabasic acid dianhydride is preferably diamine / tetrabasic acid dihydrate = 2.5 to 1.02 / 1.0, more preferably diamine / tetrabasic acid dianhydride = 2.0 to 1.15 / 1.0. By mixing at such a ratio, a copolymer containing amino groups at both ends can be synthesized.

[0142] In step B, maleamic 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, water in the system produced as a by-product is removed under the condition of 95°C to 120°C while performing ring-closing dehydration, thereby capping the molecular chain ends with maleimide groups, and the target bismaleimide compound can be obtained. If the capping reaction of the molecular chain ends with maleimide groups is performed at 120°C or below, side reactions or high molecular weight products are less likely to occur, so it is preferred.

[0143] According to such a production method, the obtained bismaleimide compound has a block copolymer structure, and thus the compatibility with the synthesized resin can be uniformly improved.

[0144] The compound of the present invention may be purified by a conventional method, and reprecipitation or the like may be used.

[0145] The mixing ratio of the raw materials in the reaction is preferably such that (contributing to R 1 Aromatic diamines having the structure of 2 Total number of moles of organic diamines other than aromatic diamines having a structure of 6 to 200 carbon atoms and containing divalent hydrocarbons): (tetrabasic acid dianhydride (R 3 ) is 1:1. 2 ), from the viewpoint of the tendency to obtain a composition with better photocurability, it is preferred that (organic diamine (R 2 ) moles): (aromatic diamine (R 1 ) is greater than 0.1. 2 ), containing aromatic diamine (R 1 ) and tetracarboxylic dianhydride (R 3 ) and an amic acid unit containing an organic diamine (R 2 ) and tetracarboxylic dianhydride (R 3 The polymerization form of the amic acid units of ) may be random polymerization or block polymerization.

[0146] [Compounds containing one or more carboxyl groups (B)]

[0147] The resin composition of the present embodiment contains a compound (B) (also referred to as component (B) or compound (B)) containing one or more carboxyl groups. 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 and a potassium salt. In the case where the molecule contains two or more carboxyl groups, it may also be an acid anhydride formed by these mutually linked groups. Compound (B) may also be used alone or in a suitable mixture of two or more.

[0148] The compound (B) can be photocured using various active energy rays together with the bismaleimide compound (A) of this embodiment and the photocuring initiator (C) described later to obtain a cured product. In addition, according to this embodiment, a resin composition containing the compound (B) can be obtained in the unexposed portion.

[0149] The compound (B) is preferably 5% or more when preparing an N-methylpyrrolidone solution containing the compound (B) at 1% by mass and measuring the transmittance of the N-methylpyrrolidone solution containing the compound (B) at 1% by mass using an active energy line containing a wavelength of 365nm (i-ray). Such a compound (B) shows very excellent light transmittance. In addition, when the transmittance of the N-methylpyrrolidone solution containing the compound (B) at 1% by mass is measured using an active energy line containing a wavelength of 405nm (h-ray), the transmittance is preferably 5% or more, and the case 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 drawing exposure method, even when an active energy line containing a wavelength of 405nm (h-ray) is used, a photoradical reaction of maleimide is efficiently induced. For a resin composition having better photocurability, the preferred range of transmittance at a wavelength of 365 nm (i-ray) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more. For a resin composition having 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. In addition, the upper limit of each of the transmittance at a wavelength of 365 nm (i-ray) and the transmittance at a wavelength of 405 nm (h-ray) is, for example, 99.9% or less, or 100% or less.

[0150] In the present embodiment, it is preferred that the compound (B) contain a carboxyl group at an integer of 1 to 4 in the molecule in order to obtain more excellent alkali developability.

[0151] The molecular weight of the compound (B) is preferably 50 to 1,000, more preferably 100 to 800, from the viewpoint of further improving developability.

[0152] 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) can be used alone or in combination of two or more.

[0153] (Aliphatic compounds containing one or more carboxyl groups)

[0154] As aliphatic compounds containing more than one carboxyl group, for example, chain aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, chain aliphatic polycarboxylic acid, and alicyclic polycarboxylic acid can be listed. These compounds may also have substituents such as hydrogen atoms, and alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl in the molecule. In addition, when these compounds have two or more carboxyl groups in the molecule, they may also be acid anhydrides formed by these mutually linked. When these compounds have carboxylalkyl in the molecule, they may also be acid anhydrides formed by carboxylalkyl and carboxyl groups mutually linked. When these compounds have two or more carboxylalkyl in the molecule, they may also be acid anhydrides formed by these mutually linked.

[0155] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.

[0156] Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, an n-hexyloxy group, and a 2-methylpropoxy group.

[0157] Examples of the aryloxy group include a phenoxy group and a p-tolyloxy group.

[0158] Examples of the aryl group include a phenyl group, a toluoyl group, a benzyl group, a methylbenzyl group, a xylyl group, a mesityl group, a naphthyl group, and an anthracenyl group.

[0159] Examples of the aminoalkyl group include an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminodimethyl group, an aminodiethyl group, an aminodipropyl group, an aminobutyl group, an aminohexyl group, and an aminononyl group.

[0160] Examples of the carboxyalkyl group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group, a carboxyhexyl group, and a carboxynonyl group.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] Examples of the alicyclic polycarboxylic acid include carboxylic acids obtained by further adding one or more carboxyl groups to an alicyclic monocarboxylic acid. For example, monocyclic carboxylic acids such as cyclopropanedicarboxylic acid, cyclopropylenedicarboxylic acid, cyclopropylenetricarboxylic acid, cyclobutanedicarboxylic acid, cyclobutenedicarboxylic acid, cyclobutanetricarboxylic acid, cyclobutenetricarboxylic acid, cyclobutanetetracarboxylic acid, cyclobutenetetracarboxylic acid, cyclopentanedicarboxylic acid, cyclopentenedicarboxylic acid, cyclopentanetricarboxylic acid, cyclopentenetricarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentenetetracarboxylic acid, cyclopentanepentacarboxylic acid, cyclopentenepentacarboxylic acid, cyclohexanedicarboxylic 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; and polycyclic or bridged alicyclic dicarboxylic acids such as norbornanedicarboxylic acid and adamantanedicarboxylic acid may be mentioned.

[0165] (Aromatic compounds containing one or more carboxyl groups)

[0166] As the parent skeleton of the aromatic compound containing more than one carboxyl group, for example, benzoic acid, phenylene acetic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, pentacarboxylbenzene, hexacarboxylbenzene, 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 carboxylalkyl on the aromatic rings of these parent skeletons. In addition, these compounds may also be acid anhydrides formed by these mutually linked when they have more than two carboxyl groups in the molecule. These compounds may also be acid anhydrides formed by carboxyl alkyl and carboxyl groups when they have carboxyl alkyl in the molecule. These compounds may also be acid anhydrides formed by these mutually linked when they have more than two carboxyl alkyl in the molecule. Regarding these substituents, reference may be made to the above.

[0167] (Hetero compounds containing more than one carboxyl group)

[0168] As the parent skeleton of the hetero compound containing more than one carboxyl group, for example, furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thiophene, phenothiazine, phenoxathiol, xanthene, acridine, phenazine, and carbazole heterocyclic compounds containing more than one carboxyl group. The hetero compound may also have, for example, hydrogen atoms, and substituents such as alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl on these parent skeletons. In addition, these compounds may also be acid anhydrides formed by these mutually linked when they have two or more carboxyl groups in the molecule. These compounds may also be acid anhydrides formed by the mutual linking of carboxyl alkyl and carboxyl groups when they have carboxyl alkyl in the molecule. These compounds may also be acid anhydrides formed by the mutual linking of carboxyl alkyl and carboxyl groups when they have two or more carboxyl alkyl in the molecule. Regarding these substituents, reference can be made to the above description.

[0169] As the compound (B), from the aspect of being able to impart more excellent alkali developability to the resin composition, preferably, 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). From the viewpoint of alkali developability, more preferably, the compound represented by formula (4), the compound represented by formula (5), and the compound represented by formula (6).

[0170] The compound represented by formula (3) is as follows.

[0171] [Chemistry 25]

[0172]

[0173] 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, these may be linked to form an acid anhydride. In formula (3), the upper limit of the number of carboxyl groups is 6.

[0174] In terms of alkali developability, R 6 Preferably, each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, or an amino group. In terms of obtaining more excellent alkali developability, it is more preferable that the group contains a carboxyl group.

[0175] In addition, o each independently represents an integer of 1-5.

[0176] As the compound represented by the formula (3), a compound represented by the formula (27) is preferred in terms of obtaining more excellent alkali developability.

[0177] [Chemistry 26]

[0178]

[0179] In formula (27), R 6 Each independently represents a hydrogen atom, a hydroxyl group, an amino group or an aminomethyl group. 6 It is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom.

[0180] In addition, o' represents an integer of 0-4 independently.

[0181] The number of carboxyl groups s represents an integer of 5 to 0. In order to show more excellent alkali developability, the number of carboxyl groups s is preferably an integer of 1 to 3. In this case, R 6 The number o is an integer from 5 to s and is an integer from 2 to 4.

[0182] The compound represented by formula (27) contains two or more carboxyl groups, and these carboxyl groups may be linked to each other to form an acid anhydride.

[0183] 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 these anhydrides include phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. In terms of obtaining better alkali developability, the compound represented by formula (27) is preferably phthalic acid, trimellitic acid, pyromellitic acid, and anhydrides thereof.

[0184] The compound represented by formula (4) is as follows.

[0185] [Chemistry 27]

[0186]

[0187] In formula (4), R 7 Each independently represents a hydrogen atom, a hydroxyl, a carboxyl group, a carboxymethyl group, an amino group or an aminomethyl group. In addition, the compound represented by formula (4) may be an acid anhydride formed by these mutually linked when having two or more carboxyl groups. In formula (4), the upper limit of the number of carboxyl groups is 10. The compound represented by formula (4) may be an acid anhydride formed by carboxymethyl group and carboxyl group mutually linked when having a carboxymethyl group.

[0188] In terms of alkali developability, R 7 Preferably, each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, or an amino group. In terms of obtaining more excellent alkali developability, it is more preferable that the group contains a carboxyl group.

[0189] In addition, p each independently represents an integer of 1-9.

[0190] Furthermore, piperidinecarboxylic acid tends to be inferior in alkali developability compared with other compounds (B) containing one or more carboxyl groups.

[0191] As R 7 In the case of containing a carboxyl group, the number p of the carboxyl groups is preferably 1 to 3 in terms of alkali developability. 7 , preferably each independently represents 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, R other than the carboxyl groups 7 The number is 7 to 9.

[0192] Examples of the compound represented by formula (4) include piperidinecarboxylic acid, 1,2-piperidinedicarboxylic acid, and piperidinedicarboxylic anhydride.

[0193] The compound represented by formula (5) is as follows.

[0194] [Chemistry 28]

[0195]

[0196] In formula (5), R 8Each independently represents a hydrogen atom, a hydroxyl, a carboxyl group, a carboxymethyl group, an amino group or an aminomethyl group. In addition, the compound represented by formula (5) may be an acid anhydride formed by these mutually linked when having two or more carboxyl groups. In formula (5), the upper limit of the number of carboxyl groups is 10. The compound represented by formula (5) may be an acid anhydride formed by carboxymethyl group and carboxyl group mutually linked when having a carboxymethyl group.

[0197] In terms of alkali developability, R 8 Preferably, each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, or an amino group. In terms of obtaining more excellent alkali developability, it is more preferable that the group contains a carboxyl group.

[0198] In addition, q each independently represents an integer of 1-9.

[0199] As the compound represented by the formula (5), a compound represented by the formula (28) is preferred in terms of obtaining more excellent alkali developability.

[0200] [Chemistry 29]

[0201]

[0202] In formula (28), R 8 Each independently represents a hydrogen atom, a hydroxyl group, a carboxymethyl group, an amino group or an aminomethyl group. 8 It is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom.

[0203] In addition, q' represents an integer of 0-8 independently.

[0204] The number of carboxyl groups t represents an integer of 9-q. In order to show more excellent alkali developability, the number of carboxyl groups t is preferably an integer of 1 to 3. In this case, R 8 The number q is an integer of 9-t and an integer of 6-8.

[0205] The compound represented by formula (28) contains two or more carboxyl groups, and these groups may be linked to form an acid anhydride. In addition, when the compound represented by formula (28) has a carboxymethyl group, the carboxymethyl group and the carboxyl group may be linked to form an acid anhydride.

[0206] 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 more excellent alkali developability, the compound represented by formula (28) is preferably cis-4-cyclohexene-1,2-dicarboxylic acid and cis-4-cyclohexene-1,2-dicarboxylic anhydride.

[0207] The compound represented by formula (6) is as follows.

[0208] [Chemistry 30]

[0209]

[0210] In formula (6), R 9 Each independently represents a hydrogen atom, a hydroxyl, a carboxyl group, a carboxymethyl group, an amino group or an aminomethyl group. In addition, the compound represented by formula (6) may be an acid anhydride formed by the mutual connection of a carboxyl group and a carboxyl group when having more than one carboxyl group. In addition, in formula (6), when having more than two carboxyl groups, it may be an acid anhydride formed by these mutual connection. In formula (6), the upper limit of the number of carboxyl groups is 5. In formula (6), when having more than two carboxylmethyl groups, it may be an acid anhydride formed by these mutual connection. In formula (6), the upper limit of the number of carboxyl groups is 6.

[0211] In terms of alkali developability, R 9 Preferably, each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, or an amino group. In terms of obtaining more excellent alkali developability, it is more preferable that the group contains a carboxyl group.

[0212] In addition, r each independently represents an integer of 1-5.

[0213] As the compound represented by the formula (6), a compound represented by the formula (29) is preferred in terms of obtaining more excellent alkali developability.

[0214] [Chemistry 31]

[0215]

[0216] In formula (29), R 9 Each independently represents a hydrogen atom, a hydroxyl group, a carboxymethyl group, an amino group or an aminomethyl group. 9 It is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom.

[0217] In addition, r' represents an integer of 0-4 independently.

[0218] The number of carboxyl groups u represents an integer of 5-r'. In order to show more excellent alkali developability, the number of carboxyl groups u is preferably an integer of 1 to 3. In this case, R 9 The number r' is an integer of 5-u and an integer of 2-4.

[0219] In formula (29), it can also be an acid anhydride formed by the mutual connection of a carboxymethyl group and a carboxyl group. When the compound represented by formula (29) has two or more carboxyl groups, it can also be an acid anhydride formed by these mutual connection. 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, it can also be an acid anhydride formed by these mutual connection. In formula (29), the upper limit of the number of carboxymethyl groups is 6.

[0220] Examples of the compound represented by formula (29) include phenyleneacetic acid, 1,2-phenylenedicarboxylic acid, 1,3-phenylenedicarboxylic acid, 1,4-phenylenedicarboxylic acid, and anhydrides thereof. Examples of the anhydrides thereof include 1,2-phenylenedicarboxylic acid anhydride. As the compound represented by formula (29), 1,2-phenylenedicarboxylic acid is preferred in terms of obtaining better alkali developability.

[0221] These compounds (B) containing one or more carboxyl groups can also be used alone or in combination of two or more.

[0222] 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, relative to 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 a more excellent alkali developability to the resin composition. It is further preferably 1 to 35 parts by mass. If the compound (B) containing one or more carboxyl groups is small, the crosslinking density becomes high, and thus a composition having excellent curing properties such as heat resistance and low dielectric properties is obtained.

[0223] 〔Photocuring initiator (C)〕

[0224] The resin composition includes a photocuring initiator (C) (also referred to as component (C)). The photocuring initiator (C) is not particularly limited, and a photocuring initiator generally known in the field of photocuring resin compositions can be used. The photocuring initiator (C) can be used to perform photocuring together with the bismaleimide compound (A) and the compound (B) containing one or more carboxyl groups using various active energy rays.

[0225] 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 exemplified by benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, and di-tert-butyl diperoxyphthalate; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, benzoyl-diphenyl-phosphine oxide, and bisbenzoyl-phenyl 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-hydroxycyclohexyl phenyl ketone, 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 2 anthraquinones such as -pentylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-dimethylaminobenzophenone; 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 dimethoxyphenyl diazonium fluorophosphonate and N,N-diethylaminophenyl diazonium hexafluorophosphonate; iodonium salts of Lewis acids such as diphenyl iodonium hexafluorophosphonate and diphenyl iodonium hexafluoroantimonate; sulfonium salts of Lewis acids such as triphenyl sulfonium hexafluorophosphonate and triphenyl sulfonium hexafluoroantimonate; phosphonium salts of Lewis acids such as triphenyl phosphonium hexafluoroantimonate; other halides; triazine initiators; borate initiators; other cationic photocuring initiators such as photoacid generators.

[0226] As the photocuring initiator (C), commercially available products can also be used. Examples of commercially available products include: Omnirad (registered trademark) 369 (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) 819 (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) 819DW (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) 907 (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) TPO (trade name) manufactured by IGM Resins BV, and Omnirad (registered trademark) 100 (trade name) manufactured by IGM Resins BV. Omnirad (registered trademark) TPO-G (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) 784 (trade name) manufactured by IGM Resins BV, Irgacure (registered trademark) OXE01 (trade name) manufactured by BASF Japan, Irgacure (registered trademark) OXE02 (trade name) manufactured by BASF Japan, Irgacure (registered trademark) OXE03 (trade name) manufactured by BASF Japan, and Irgacure (registered trademark) OXE04 (trade name) manufactured by BASF Japan.

[0227] The photocuring initiator (C) can be used alone or in combination of two or more.

[0228] When the photocuring initiator (C) is prepared as a chloroform solution containing the photocuring initiator (C) at 0.01% by mass and the absorbance of the chloroform solution containing the photocuring initiator (C) at 0.01% by mass is measured using an active energy line having a wavelength of 365nm (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 the photocuring initiator (C) at 0.01% by mass is measured using an active energy line having a wavelength of 405nm (h-ray), the absorbance is preferably 0.1 or more, and in such a case, very excellent light absorption is also shown. 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 using a direct drawing exposure method, even when an active energy line having a wavelength of 405nm (h-ray) is used, a photoradical reaction of maleimide is efficiently induced. In addition, in order to obtain a resin composition with better photocurability, the absorbance at a wavelength of 365 nm (i-ray) is more 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 more preferably 0.15 or more. In addition, the upper limit 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.

[0229] As such a photocuring initiator (C), a compound represented by formula (17) is preferred.

[0230] [Chemistry 32]

[0231]

[0232] In formula (17), R 10 Each independently represents a substituent represented by formula (18) or a phenyl group.

[0233] [Chemistry 33]

[0234]

[0235] In formula (18), R 11 Each independently represents a hydrogen atom or a methyl group. In formula (7), -* represents a bond to the phosphorus atom (P) in formula (17).

[0236] The compound represented by formula (17) has an absorbance of 0.1 or more and shows very excellent absorptivity relative to light of wavelength 365nm (i-ray) when a chloroform solution containing the compound at 0.01% by mass is prepared and the absorbance of the chloroform solution is measured using an active energy line containing a wavelength of 365nm (i-ray). Therefore, the compound appropriately generates free radicals relative to light of wavelength 365nm (i-ray). The absorbance is preferably 0.15 or more. The upper limit is, for example, 10.0 or less, 5.0 or less, or 2.0 or less.

[0237] In addition, the compound represented by formula (17) has an absorbance of 0.1 or more and shows very excellent absorptivity relative to light of wavelength 405nm (h-ray) when preparing a chloroform solution containing the compound at 0.01% by mass and measuring the absorbance of the chloroform solution using an active energy line containing a wavelength of 405nm (h-ray). Therefore, the compound appropriately generates free radicals relative to light of wavelength 405nm (h-ray). The absorbance is preferably 0.15 or more. The upper limit is, for example, 10.0 or less, 5.0 or less, or 2.0 or less.

[0238] In formula (17), R 10 Each independently represents a substituent represented by formula (18) or a phenyl group. 10 In the formula (18), at least one substituent is preferably a substituent represented by the formula (18).

[0239] In formula (18), R 11 Each independently represents a hydrogen atom or a methyl group. 11 Among them, preferably one or more are methyl groups, and more preferably all are methyl groups.

[0240] As the compound represented by formula (17), for example, acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide can be listed. Among these, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is preferred in terms of excellent light transmittance. These compounds can also be used alone or in combination of two or more.

[0241] Acylphosphine oxides show very excellent absorption with respect to active energy rays including a wavelength of 405 nm (h-rays), and for example, a bismaleimide compound (A) having a transmittance of 5% or more at a wavelength of 405 nm (h-rays) can be suitably subjected to free radical polymerization. Therefore, a resin composition having excellent photocurability without hindering the photocuring reaction in the exposure process, especially when used for manufacturing a multilayer printed wiring board, and having excellent alkali developability in the developing process, a resin sheet using the resin composition, a multilayer printed wiring board, and a semiconductor device can be suitably manufactured.

[0242] 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, relative to 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 performing the photocuring of the maleimide compound and thereby making the exposed portion sufficiently insolubilized in terms of alkali developability.

[0243] 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.

[0244] [Maleimide compounds (D) other than bismaleimide compounds (A)]

[0245] In the resin composition of the present embodiment, as long as the effect of the present invention is exerted, a maleimide compound (D) (also referred to as component (D)) other than the bismaleimide compound (A) of the present embodiment may be included. The light transmittance of the bismaleimide compound (A) is very excellent, so even if the maleimide compound (D) is used, the light fully reaches the photocuring initiator, thereby efficiently causing the photoradical reaction of the maleimide, and various active energy lines can be used for photocuring. Therefore, for example, even if an active energy line containing a wavelength of 365nm or an active energy line containing a wavelength of 405nm is used, the light fully reaches the photocuring initiator, and the free radical reaction is carried out using the free radicals generated by the photocuring initiator, and photocuring can be carried out in the composition prepared with the maleimide compound (D). The maleimide compound (D) is described below.

[0246] 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 biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,2-bismaleimidoethane, 1,4-bismaleimidobutane, 1,5-bismaleimidobutane Amine pentane, 1,5-bismaleimide-2-methylpentane, 1,6-bismaleimide hexane, 1,6-bismaleimide-(2,2,4-trimethyl) hexane, 1,8-bismaleimide-3,6-dioxaoctane, 1,11-bismaleimide-3,6,9-trioxaundecane, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4- Diphenylmethane biscitraconimide, 2,2-bis[4-(4-citraconimide phenoxy) phenyl] propane, bis(3,5-dimethyl-4-citraconimide phenyl) methane, bis(3-ethyl-5-methyl-4-citraconimide phenyl) methane, bis(3,5-diethyl-4-citraconimide phenyl) methane, polyphenylmethane maleimide, maleimide compounds represented by polyphenylmethane maleimide formula (13), maleimide compounds represented by formula (14), fluorescein-5-maleimide, and prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds, etc. These maleimide compounds (D) can also be used alone or in combination of two or more.

[0247] As the maleimide compound represented by formula (30), commercial products may be used, for example, BMI-2300 (trade name) manufactured by Yamato Chemical Industries, Ltd. As the maleimide compound represented by formula (31), commercial products may be used, for example, MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. As the maleimide compound represented by formula (32), commercial products may be used, for example, MIR-5000 (trade name) manufactured by Nippon Kayaku Co., Ltd.

[0248] [Chemistry 34]

[0249]

[0250] In formula (30), R 12 Each independently represents a hydrogen atom or a methyl group. n represents an integer of 1 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.

[0251] [Chemistry 35]

[0252]

[0253] In formula (31), R 13 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.

[0254] Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and a neopentyl group.

[0255] [Chemistry 36]

[0256]

[0257] In formula (32), R 14 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.

[0258] Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and a neopentyl group.

[0259] In the present embodiment, in order to efficiently cause the photo-radical reaction of the bismaleimide compound (A), when a chloroform solution containing the maleimide compound (D) by 1% by mass is prepared and the transmittance of the chloroform solution is measured using an active energy line containing a wavelength of 365nm (i-ray), it is preferred to show a light transmittance of 5% or more. The transmittance in the above case is more preferably 8% or more, and further preferably 10% or more.

[0260] In addition, in the present embodiment, in order to efficiently cause the photoradical reaction of the bismaleimide compound (A), when preparing a chloroform solution containing a maleimide compound (D) at 1% by mass and measuring the transmittance of the chloroform solution using an active energy line containing a wavelength of 405nm (h-ray), it is preferred to show a light transmittance of 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 drawing exposure method, even when an active energy line containing a wavelength of 405nm (h-ray) is used, a photoradical reaction of maleimide is efficiently caused. In terms of a resin composition having better photocurability, the transmittance is more preferably 8% or more, and more preferably 10% or more.

[0261] 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 fluorescein-5-maleimide.

[0262] [Chemistry 37]

[0263]

[0264] In the formula (33), n (average) is 1 or more, preferably 1 to 21, and more preferably 1 to 16 from the viewpoint of showing excellent photocurability.

[0265] [Chemistry 38]

[0266]

[0267] In formula (34), the number of x is 10 to 35.

[0268] In formula (34), the number of y is 10 to 35.

[0269] [Chemistry 39]

[0270]

[0271] In formula (35), R a 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. a , preferably a linear or branched alkyl group, and more preferably a linear alkyl group in terms of showing excellent photocurability.

[0272] The number of carbon atoms in the alkyl group is preferably 4 to 12 in order to exhibit excellent photocurability.

[0273] The number of carbon atoms in the alkenyl group is preferably 4 to 12 in order to exhibit excellent photocurability.

[0274] As the linear or branched alkyl group, R in the bismaleimide compound (A) can be referred to. 3 Among these, in terms of showing excellent photocurability, an n-heptyl group, an n-octyl group, and an n-nonyl group are preferred, and an n-octyl group is more preferred.

[0275] As the linear or branched alkenyl group, reference may be made to R in the bismaleimide compound (A). 3 Among these, 2-heptenyl, 2-octenyl, and 2-nonenyl are preferred, and 2-octenyl is more preferred, in terms of showing excellent photocurability.

[0276] 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. b , preferably a linear or branched alkyl group, and more preferably a linear alkyl group in terms of showing excellent photocurability.

[0277] The number of carbon atoms in the alkyl group is preferably 4 to 12 in order to exhibit excellent photocurability.

[0278] The number of carbon atoms in the alkenyl group is preferably 4 to 12 in order to exhibit excellent photocurability.

[0279] As specific examples of the alkyl group, see R a Among them, the alkyl group is preferably an n-heptyl group, an n-octyl group, and an n-nonyl group, and more preferably an n-octyl group, in terms of showing excellent photocurability.

[0280] As specific examples of alkenyl groups, see R bAmong them, 2-heptenyl, 2-octenyl, and 2-nonenyl are preferred, and 2-octenyl is more preferred, in terms of showing excellent photocurability.

[0281] In formula (35), n a The number is 1 or more, preferably 2 to 16, and more preferably 3 to 14 from the viewpoint of showing excellent photocurability.

[0282] In formula (35), n b The number is 1 or more, preferably 2 to 16, and more preferably 3 to 14 from the viewpoint of showing excellent photocurability.

[0283] n a With n b The number may be the same or different.

[0284] [Chemistry 40]

[0285]

[0286] 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.

[0287] [Chemistry 41]

[0288]

[0289] In formula (37), n represents an integer of 1 or more, and preferably represents an integer of 1 to 10.

[0290] [Chemistry 42]

[0291]

[0292] In the formula (38), n represents an integer of 1 or more, and preferably represents an integer of 1 to 10.

[0293] [Chemistry 43]

[0294]

[0295] [Chemistry 44]

[0296]

[0297] (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)

[0298] As the maleimide compound (D), a commercially available product can also be used.

[0299] Examples of the maleimide compound represented by formula (33) include BMI-1000P manufactured by KI Chemical Co., Ltd. (trade name, n=13.6 (average) in formula (33)), BMI-650P manufactured by KI Chemical Co., Ltd. (trade name, n=8.8 (average) in formula (33)), BMI-250P manufactured by KI Chemical Co., Ltd. (trade name, n=3 to 8 (average) in formula (33)), and CUA-4 manufactured by KI Chemical Co., Ltd. (trade name, n=1 in formula (33)).

[0300] Examples of the maleimide compound represented by the formula (34) include BMI-6100 (trade name, x=18, y=18 in the formula (34)) manufactured by Designer Molecules Inc., and the like.

[0301] Examples of the maleimide compound represented by the formula (35) include BMI-689 (trade name, formula (41), functional group equivalent: 346 g / eq.) manufactured by Designer Molecules Inc., and the like.

[0302] [Chemistry 45]

[0303]

[0304] Examples of the maleimide compound represented by the formula (36) include BMI-1500 (trade name, n=1.3 in the formula (36), functional group equivalent: 754 g / eq.) manufactured by Designer Molecules Inc., and the like.

[0305] As the maleimide compound represented by the formula (37), commercially available products may be used, and examples thereof include BMI-1700 (trade name) manufactured by Designer Molecules Inc. (DMI).

[0306] As the maleimide compound represented by formula (38), commercially available products can also be used, for example, BMI-3000 (trade name) manufactured by Demi Molecules Inc. (DMI), BMI-3000J (trade name) manufactured by Demi Molecules Inc. (DMI), BMI-5000 (trade name) manufactured by Demi Molecules Inc. (DMI), and BMI-9000 (trade name) manufactured by Demi Molecules Inc. (DMI).

[0307] As the maleimide compound represented by the formula (39), commercially available products may be used, and examples thereof include BMI-TMH manufactured by Yamato Chemical Industry Co., Ltd.

[0308] As the maleimide compound represented by the formula (40), commercially available products may be used, and examples thereof include BMI-70 (trade name) manufactured by KI Chemical Co., Ltd.

[0309] These maleimide compounds (D) can also be used individually by 1 type or in mixture of 2 or more types as appropriate.

[0310] 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, relative to 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 the main component and further improving the photocurability.

[0311] In the resin composition, from the viewpoint of obtaining a cured product having the maleimide compound as the main component and further improving the photocurability, the blending ratio ((A):(D)) of the bismaleimide compound (A) to the maleimide compound (D) is preferably 1 to 99:99 to 1 on a mass basis, more preferably 5 to 95:95 to 5, and still more preferably 10 to 90:90 to 10.

[0312] In the resin composition, the total content of the bismaleimide 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, relative to 100 parts by mass of the total of the bismaleimide compound (A), the compound (B), the photocuring initiator (C) and the maleimide compound (D), from the viewpoint of obtaining a cured product containing the maleimide compound as the main component and further improving the photocurability.

[0313] 〔Filling material (E)〕

[0314] The resin composition may contain a filler (E) (also referred to as component (E)) in order to improve properties such as coating properties and heat resistance. The filler (E) preferably has insulating properties and does not hinder the permeability to various active energy rays used in photocuring, and more preferably does not hinder the permeability to active energy rays including a wavelength of 365 nm (i-ray) and / or a wavelength of 405 nm (h-ray).

[0315] As filler (E), for example, silica (for example, natural silica, fused silica, amorphous silica, and hollow silica), aluminum compounds (for example, diaspore, aluminum hydroxide, aluminum oxide, and aluminum nitride), boron compounds (for example, boron nitride), magnesium compounds (for example, magnesium oxide, and magnesium hydroxide), calcium compounds (for example, calcium carbonate), molybdenum compounds (for example, molybdenum oxide, and zinc molybdate), barium compounds (for example, barium sulfate, and barium silicate), talc (for example, natural talc, and calcined talc), mica, glass (for example, short glass fibers, spherical glass, glass fine powder, E glass, T glass, and D glass), silicone powder, fluororesin-based fillers, urethane resin-based fillers, (meth) acrylic resin-based fillers, polyethylene-based fillers, styrene-butadiene rubber, and silicone rubber, etc. These fillers (E) can also be used alone or in combination of two or more.

[0316] Among these, preferred are silica, diaspore, barium sulfate, silicone powder, fluororesin-based fillers, urethane resin-based fillers, (meth)acrylic resin-based fillers, polyethylene-based fillers, styrene-butadiene rubber, and silicone rubber.

[0317] These fillers (E) may be surface-treated with a silane coupling agent or the like described below.

[0318] From the viewpoint of improving the heat resistance of the cured product and obtaining good coating properties, silicon dioxide is preferred, and fused silica is more preferred. Specific examples of silicon dioxide include SFP-130MC (trade name) manufactured by Denka (stock), SC2050-MB (trade name), SC1050-MLE (trade name), YA010C-MFN (trade name), and YA050C-MJA (trade name) manufactured by Admatechs (stock), etc.

[0319] The particle size of the filler (E) is usually 0.005 μm to 10 μm, preferably 0.01 μm to 1.0 μm, from the viewpoint of the ultraviolet light transmittance of the resin composition.

[0320] In the resin composition, about the content of filler (E), with respect to the viewpoint that the light transmittance of the resin composition and the heat resistance of the cured product are good, relative to 100 parts by mass of a total of bismaleimide compound (A), compound (B) and light curing initiator (C), it is preferably set to less than 300 parts by mass, more preferably set to less than 200 parts by mass, and then preferably set to less than 100 parts by mass. The upper limit value can be less than 30 parts by mass, or less than 20 parts by mass, or less than 10 parts by mass. In addition, in the case of containing filler (E), with respect to the viewpoint of obtaining the effect of improving the properties such as film coating and heat resistance, relative to 100 parts by mass of a total of bismaleimide compound (A), compound (B) and light curing initiator (C), the lower limit value is usually 1 part by mass.

[0321] 〔Silane coupling agent and wetting and dispersing agent〕

[0322] In the resin composition of the present embodiment, a silane coupling agent and / or a wetting dispersant may be used in combination in order to improve the dispersibility of the filler and the bonding strength between the polymer and / or the resin and the filler.

[0323] There are no particular limitations on these silane coupling agents as long as they are generally used for surface treatment of inorganic substances. 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; epoxysilanes such as γ-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyldimethoxymethylsilane, 3-glycidyloxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and [8-(glycidyloxy)-n-octyl]trimethoxysilane; vinyltri(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxysilane 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, and 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; mercaptosilane series such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyldimethoxymethylsilane; ureidosilane series such as 3-ureidopropyltriethoxysilane; styrylsilane series such as p-styryltrimethoxysilane; cationic silane series such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; acid anhydride series such as [3-(trimethoxysilyl)propyl]succinic anhydride; phenylsilane series such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, and p-tolyltrimethoxysilane; arylsilane series such as trimethoxy(1-naphthyl)silane. These silane coupling agents can be used alone or in combination of two or more.

[0324] In the resin composition of the present embodiment, the content of the silane coupling agent is usually 0.1 to 10 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).

[0325] As a wetting dispersant, there is no particular limitation as long as it is a dispersion stabilizer used for coating applications. As specific examples, there can be mentioned: 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 (stock). These wetting dispersants can also be used alone or in combination of two or more.

[0326] In the resin composition of the present embodiment, the content of the wetting and dispersing agent is usually 0.1 to 10 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).

[0327] [Cyanate compounds, phenol resins, oxetane resins, benzoxazine compounds, epoxy resins and other compounds]

[0328] In the present embodiment, as long as the effects of the present invention are exerted, the resin composition of the present embodiment may include various types of compounds and resins such as cyanate compounds, phenol resins, oxetane resins, benzoxazine compounds, epoxy resins, and other compounds other than the bismaleimide compound (A), the compound (B) containing one or more carboxyl groups, the photocuring initiator (C), and the maleimide compound (D) of the present embodiment, according to the flame retardancy, heat resistance, and thermal expansion characteristics of the cured product after curing. In addition, these compounds and resins are preferably: when exposed to active energy rays containing a wavelength of 365nm (i-rays) and / or active energy rays containing a wavelength of 405nm (h-rays), the resin composition of the present embodiment is photosensitive and photocured.

[0329] These compounds and resins can be used alone or in combination of two or more.

[0330] (Cyanate ester compound)

[0331] The cyanate compound is not particularly limited as long as it is a resin having an aromatic portion substituted with at least one cyano group (cyanate group) in the molecule.

[0332] For example, the compound represented by formula (42) can be mentioned.

[0333] [Chemistry 46]

[0334]

[0335] In formula (42), Ar 1 It means a benzene ring, a naphthalene ring or two benzene rings are connected by a single bond. 1 When there are multiple groups, 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 bonding 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 Ar 1 The substituents in Ra can be selected at any position. p represents a bond to Ar 1 The number of cyano groups is independently an integer of 1 to 3. 1 The number of Ra, and when Ar 1 When it is a benzene ring, it is 4-p. 1 When it is a naphthalene ring, it is 6-p. 1 When two benzene rings are bonded by a single bond, it is 8-p. 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 multiple Xs, each of them is independently a single bond, a divalent organic group having 1 to 50 carbon atoms (hydrogen atoms may be substituted with heteroatoms), 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.

[0336] The alkyl group in Ra of the formula (25) may have any of a linear or branched chain structure and a cyclic structure (eg, a cycloalkyl group).

[0337] Furthermore, the hydrogen atoms in the alkyl group in the 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.

[0338] Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2,2-dimethylpropyl, cyclopentyl, hexyl, cyclohexyl, and trifluoromethyl.

[0339] Specific examples of the alkenyl group include vinyl, (meth)allyl, isopropenyl, 1-propenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 2-methyl-2-propenyl, 2-pentenyl, and 2-hexenyl.

[0340] Specific examples of the aryl group 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, etc. Furthermore, examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy, etc.

[0341] Specific examples of the divalent organic group having 1 to 50 carbon atoms in X of formula (25) include methylene, ethylene, trimethylene, cyclopentylene, cyclohexylene, trimethylcyclohexylene, biphenylmethylene, dimethylmethylene-phenylene-dimethylmethylene, fluorenediyl, and phthalolide diyl. The hydrogen atoms in the divalent organic group may be substituted by halogen atoms such as fluorine atoms and chlorine atoms; alkoxy groups such as methoxy and phenoxy; and cyano groups.

[0342] Examples of the divalent organic group having 1 to 10 nitrogen atoms in X of the formula (42) include an imide group and a polyimide group.

[0343] In addition, examples of the organic group represented by X in the formula (42) include organic groups having structures represented by the formula (43) or the formula (44).

[0344] [Chemistry 47]

[0345]

[0346] In formula (43), Ar 2 represents a phenylenediyl group, a naphthalenediyl group or a biphenylenediyl group, and when u is an integer greater than or equal to 2, Ar 2 They may be the same 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 of 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 of 0 to 5.

[0347] [Chemistry 48]

[0348]

[0349] In formula (44), Ar 3represents a phenylenediyl group, a naphthalenediyl group or a biphenylenediyl group, and when v is an integer greater than 2, Ar 3 They may be the same 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 of 0 to 5, but may also be a mixture of compounds having different v.

[0350] Furthermore, as X in the formula (42), a divalent group represented by the formula:

[0351] [Chemistry 49]

[0352]

[0353] 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.

[0354] As Ar in formula (43) 2 And Ar in formula (44) 3 Specific examples 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.

[0355] The alkyl group and aryl group in Rb, Rc, Rd, Re, Rf and Rg in the formula (43) and Ri and Rj in the formula (44) have the same meanings as the alkyl group and aryl group in the formula (42).

[0356] Specific examples of the cyano-substituted aromatic compound represented by formula (42) include cyanobenzene, 1-cyano-2-methylbenzene, 1-cyano-3-methylbenzene, or 1-cyano-4-methylbenzene, 1-cyano-2-methoxybenzene, 1-cyano-3-methoxybenzene, or 1-cyano-4-methoxybenzene, 1-cyano-2,3-dimethylbenzene, 1-cyano-2,4-dimethylbenzene, 1-cyano-2,5-dimethylbenzene, 1-cyano-2,6-dimethylbenzene, 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-cyanobenzoic acid phenyl ester, 1-cyano-4-acetyl Aminobenzene, 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-5-methylbenzene, 1-cyanonaphthalene or 2-cyanonaphthalene, 1-cyano-4-methoxynaphthalene, 2-cyano-6-methoxynaphthalene, 2-cyano-7-methoxynaphthalene, 2,2'-dicyano-1,1'-binaphthyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3 -, 2,6- or 2,7-dicyanonaphthalene, 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)propane, 2,2-bis(4-cyano-3-methylphenyl)propane, 2,2-bis(2-cyano-5-biphenyl)propane, 2,2-bis(4-cyanophenyl)hexafluoropropane, 2,2-bis(4-cyano-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)-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-cyano-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]biphenyl, 4,4-dicyanobenzophenone, 1,3-bis(4-cyanophenyl)-2-propen-1-one, bis(4-cyanophenyl)ether, bis(4-cyanophenyl)sulfide, bis(4-cyanophenyl)sulfone, 4-cyanobenzoic acid-4-cyanophenyl ester (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-cresolphenolphthalein), 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)methane, 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-cyanoanilino)-1,3,5-triazine, 2,4-bis(N-methyl-4-cyanoanilino)-6-(N-methylanilino)-1,3,5-triazine, bis(N-4 -cyano-2-methylphenyl)-4,4'-oxydiphthalimide, bis(N-3-cyano-4-methylphenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanophenyl)-4,4'-oxydiphthalimide, bis(N-4-cyano-2-methylphenyl)-4,4'-(hexafluoroisopropylidene)diphthalimide, tris(3,5-dimethyl-4-cyanobenzyl) Isocyanurate, 2-phenyl-3,3-bis(4-cyanophenyl)benzylcarboxylic acid, 2-(4-methylphenyl)-3,3-bis(4-cyanophenyl)benzylcarboxylic acid, 2-phenyl-3,3-bis(4-cyanophenyl-3-methylphenyl)benzylcarboxylic acid, 1-methyl-3,3-bis(4-cyanophenyl)indolin-2-one, and 2-phenyl-3,3-bis(4-cyanophenyl)indolin-2-one.

[0357] These cyanate compounds can be used alone or in combination of two or more.

[0358] As another specific example of the cyanate compound represented by formula (42), there can be mentioned cyanate compounds obtained by cyanating the following phenol resins by the same method as above, and prepolymers thereof, etc.: phenol novolac resins and cresol novolac resins (formed by reacting phenol, alkyl-substituted phenol or halogen-substituted phenol with a formaldehyde compound such as formalin or paraformaldehyde in an acidic solution by a known method), trisphenol novolac resins (formed by reacting hydroxybenzaldehyde with 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 phenol such as Ar by a known method). 4 -(CH 2 Y) 2 (Ar4 represents a phenyl group, Y represents a halogen atom; hereinafter, the same in the above paragraph) is reacted with a phenol compound in the presence of an acidic catalyst or without a catalyst to form a dihalogenated methyl compound such as Ar 4 -(CH 2 OR) 2 A bis(alkoxymethyl) compound represented by (R represents an alkyl group) is reacted with a phenol compound in the presence of an acidic catalyst, or a bis(alkoxymethyl) compound represented by Ar 4 -(CH 2 OH) 2 The bis(hydroxymethyl) compound represented by the present invention is reacted with a phenol compound in the presence of an acidic catalyst, or is formed by polycondensing an aromatic aldehyde compound with an aralkyl compound and a phenol compound), phenol-modified xylene formaldehyde resin (formed by reacting a xylene formaldehyde resin with a phenol compound in the presence of an acidic catalyst by a known method), modified naphthalene formaldehyde resin (formed by reacting a naphthalene formaldehyde resin with a hydroxy-substituted aromatic compound in the presence of an acidic catalyst by a known method), phenol-modified dicyclopentadiene resin, phenol resin having a polynaphthalene ether structure (formed by dehydrating and condensing a polyhydroxy naphthalene compound having two or more phenolic hydroxyl groups in one molecule in the presence of a basic catalyst by a known method), etc. These cyanate compounds can also be used alone or in combination of two or more.

[0359] The method for producing these cyanate ester compounds is not particularly limited, and known methods can be used. As an example of the method, the following method can be cited: obtaining or synthesizing a hydroxyl-containing compound having a desired skeleton, and modifying the hydroxyl group by a known method to cyanate the hydroxyl group. As a method for cyanate-esterifying a hydroxyl group, for example, the method described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins", Blackie Academic & Professional can be cited.

[0360] The cured products using these cyanate compounds have excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.

[0361] In the resin composition of the present embodiment, the content of the cyanate compound is usually 0.01 to 40 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).

[0362] (Phenolic resin)

[0363] As phenol resin, as long as it is a phenol resin with more than two hydroxyls in one molecule, generally known phenol resins can be used. 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, multifunctional phenol resin, naphthol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, phenol resin containing polymerizable unsaturated hydrocarbon group, and hydroxy-containing silicone resins etc. can be listed. These phenol resins can also be used alone or in combination of two or more.

[0364] In the resin composition of the present embodiment, the content of the phenol resin is usually 0.01 to 40 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).

[0365] (Oxetane resin)

[0366] As the oxetane resin, generally known oxetane resins can be used. For example, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane and other alkyloxetanes, 3-methyl-3-methoxymethyloxetane, 3,3-bis (trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl)oxetane, biphenyl type oxetane, OXT-101 (manufactured by Toa Gosei (Co., Ltd.), OXT-121 (manufactured by Toa Gosei (Co., Ltd.), and OXT-221 (manufactured by Toa Gosei (Co., Ltd.), trade name) etc. can be listed. These oxetane resins can also be used alone or in combination of two or more.

[0367] In the resin composition, the content of the oxetane resin is usually 0.01 to 40 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).

[0368] (Benzoxazine compounds)

[0369] As the benzoxazine compound, any generally known benzoxazine may be used as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A benzoxazine BA-BXZ (manufactured by Konishi Chemical Industry Co., Ltd., trade name), bisphenol F benzoxazine BF-BXZ (manufactured by Konishi Chemical Industry Co., Ltd., trade name), bisphenol S benzoxazine BS-BXZ (manufactured by Konishi Chemical Industry Co., Ltd., trade name), phenolphthalein benzoxazine, etc. These benzoxazine compounds may be used alone or in combination of two or more.

[0370] In the resin composition of the present embodiment, the content of the benzoxazine compound is usually 0.01 to 40 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).

[0371] (Epoxy resin)

[0372] The epoxy resin is not particularly limited, and generally known epoxy resins can be used. For example, bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol A novolac epoxy resin, biphenyl epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, xylene novolac epoxy resin, multifunctional 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 isocyanurate epoxy resin, Ester, glycidyl ester epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, phenol aralkyl novolac epoxy resin, naphthol aralkyl novolac epoxy resin, aralkyl novolac epoxy resin, naphthol aralkyl novolac epoxy resin, dicyclopentadiene epoxy resin, polyol epoxy resin, phosphorus-containing epoxy resin, glycidyl amine, compounds obtained by epoxidizing double bonds of butadiene, compounds obtained by reacting hydroxyl-containing silicone resins with epichlorohydrin, and halides thereof. These epoxy resins can also be used alone or in combination of two or more.

[0373] Commercially available products may be used as epoxy resins. Examples of commercially available products include epoxy resins represented by formula (45) (NC-3000FH (trade name) manufactured by Nippon Kayaku Co., Ltd., where n is approximately 4 in formula (45)) and naphthalene-type epoxy resins represented by formula (46) (HP-4710 (trade name) manufactured by DIC Corporation).

[0374] [Chemistry 50]

[0375]

[0376] [Chemistry 51]

[0377]

[0378] These epoxy resins can be used alone or in combination of two or more.

[0379] In the resin composition of the present embodiment, the content of the epoxy resin is usually 0.01 to 40 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).

[0380] (Other compounds)

[0381] Other compounds include 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 bisallyl nadic imide, etc. These compounds may be used alone or in combination of two or more.

[0382] In the resin composition of the present embodiment, the content of other compounds is usually 0.01 to 40 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).

[0383] 〔Organic solvent〕

[0384] In the resin composition of the present embodiment, an organic solvent may also be included as needed. If an organic solvent is used, the viscosity of the resin composition during preparation can be adjusted. Regarding the type of organic solvent, as long as it can dissolve part or all of the resin in the resin composition, there is no particular limitation. As an organic solvent, for example, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alicyclic ketones such as cyclopentanone and cyclohexanone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isopentyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, 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.

[0385] These organic solvents can be used alone or in combination of two or more.

[0386] [Other ingredients]

[0387] 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 so far can also be used in combination within the range that does not damage the characteristics of the present embodiment; flame retardant compounds that have not been listed so far; additives, etc. If these are generally used components, there is no particular limitation. 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 phosphate esters, halogen-containing condensed phosphate esters, etc. As additives, they can include: ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface adjusters, gloss agents, polymerization inhibitors, thermosetting accelerators, etc. These components can also be used alone or in appropriate mixtures of two or more.

[0388] In the resin composition of the present embodiment, the content of other components is usually 0.1 to 10 parts by mass, respectively, based on 100 parts by mass of the total of the bismaleimide compound (A), the compound (B), and the photocuring initiator (C).

[0389] [Method for producing resin composition]

[0390] The resin composition of the present embodiment is prepared by appropriately mixing a bismaleimide compound (A), a compound (B), a photocuring initiator (C), and a maleimide compound (D) other than the bismaleimide compound (A) as needed, a filler (E), and other resins, other compounds, additives, etc. The resin composition can be suitably used as a varnish when making 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.

[0391] The method for producing the resin composition includes, for example, a method of sequentially mixing the above-mentioned components in a solvent and stirring the mixture sufficiently. The resin composition has excellent photocurability, good solubility in an organic solvent, and excellent alkali developability.

[0392] When manufacturing resin combination, known treatment (stirring, mixing, kneading treatment, etc.) for making each component uniformly dissolve or disperse can be carried out as needed. Specifically, by using a stirring tank equipped with a stirrer with appropriate stirring ability to carry out stirring and dispersing treatment, the dispersibility of each component in the resin combination can be improved. Stirring, mixing, kneading treatment can be appropriately carried out 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 revolution or autogenous type. In addition, when preparing resin combination, organic solvents can be used as needed. About the type of organic solvent, as long as it can dissolve the resin in the resin combination, it is not particularly limited, and its specific example is as described above.

[0393] The resin composition can be suitably used as a varnish when making 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 the following method: relative to 100 parts by mass of the components other than the organic solvent in the resin composition of the present embodiment, 10 parts by mass to 900 parts by mass of an organic solvent are added, and the known mixing treatment (stirring, kneading treatment, etc.) is performed.

[0394] [use]

[0395] The resin composition can be preferably used for the purpose of the resin composition requiring insulation. As a purpose, for example, it can be used for a photosensitive film, a photosensitive film with a support, a prepreg, a resin sheet, a circuit substrate (laminated board use, multilayer printed wiring board use, etc.), a solder resist, a bottom fill (underfill) material, a crystal bonding material, a semiconductor sealing material, a hole-filling resin, and a component embedding resin, etc. Among these, the resin composition has excellent light curing properties and can be given excellent alkali developability in the developing process, so it can be suitably used as an insulating layer use of a multilayer printed wiring board or a solder resist use.

[0396] [Hardened material]

[0397] The cured product is obtained by curing the resin composition of the present embodiment. The cured product can be obtained, for example, by melting or dissolving the resin composition in a solvent, pouring it into a mold, and curing it under normal conditions using light. Regarding the wavelength region of the light, it is preferably cured within a range of 100 nm to 500 nm, which is efficiently cured by a photopolymerization initiator or the like.

[0398] [Resin sheet]

[0399] 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 coating the resin composition on the support and drying it. The resin layer in the resin sheet has excellent light curing and alkali developability.

[0400] The support may be a known support, 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 triacetyl acetate film. Among these, a PET film is preferred.

[0401] 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, there is a tendency that the support is easily broken when the support is peeled off before alkali development, and if the thickness exceeds 100 μm, there is a tendency that the resolution when the support is exposed is reduced.

[0402] Furthermore, in order to reduce light scattering during exposure, the resin film is preferably a film having excellent transparency.

[0403] Furthermore, in the resin sheet of the present embodiment, the resin layer may be protected by a protective film.

[0404] By protecting the resin layer side with a protective film, dust or the like can be prevented from adhering 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, 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 cheapness tends to be deteriorated. In addition, the protective film is preferably relatively small in adhesion between the resin layer and the support, and the adhesion between the resin layer and the protective film is small.

[0405] The method for producing the resin sheet of the present embodiment may be, for example, a method in which 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.

[0406] The coating method may be, for example, a known method using a roll coater, a comma coater, a gravure coater, a die coater, a rod coater, a lip coater, a knife coater, an extrusion coater, etc. Drying may be performed, for example, by heating in a dryer at 60° C. to 200° C. for 1 minute to 60 minutes.

[0407] The amount of 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 diffusion of the organic solvent in subsequent steps. The thickness of the resin layer is preferably 1 μm to 50 μm from the viewpoint of improving workability.

[0408] The resin sheet can be preferably used for producing an insulating layer of a multilayer printed wiring board.

[0409] [Multilayer printed wiring board]

[0410] The multilayer printed wiring board of the present embodiment has an insulating layer and a conductor layer formed on one side or both sides of the insulating layer, and the insulating layer comprises the resin composition of the present embodiment. For example, more than one resin sheet can be overlapped and hardened to obtain an insulating layer. The number of layers of the insulating layer and the conductor layer is not particularly limited, and the number of layers can be appropriately set according to the target application. In addition, the order of the insulating layer and the conductor layer is not particularly limited. As the conductor layer, it can be a metal foil used for various printed wiring board materials, for example, metal foils of copper and aluminum can be listed. As the metal foil of copper, copper foils such as rolled copper foil and electrolytic copper foil can be listed. The thickness of the conductor layer is generally 1 μm to 100 μm. Specifically, it can be manufactured by the following method.

[0411] (Lamination process)

[0412] In the lamination process, a vacuum laminator is used to laminate the resin layer side of the resin sheet to one or both sides of the circuit substrate. As the circuit substrate, for example, glass epoxy substrate, metal substrate, ceramic substrate, silicon substrate, semiconductor sealing resin substrate, polyester substrate, polyimide substrate, bismaleimide triazine (BT) resin substrate, and thermosetting polyphenylene ether substrate can be cited. In addition, the so-called circuit substrate refers to a substrate having a conductor layer (circuit) processed by patterning formed on one or both sides of the substrate as described above. In addition, in a multilayer printed wiring board formed by alternately stacking a conductor layer and an insulating layer, a substrate having a conductor layer (circuit) processed by patterning on one or both sides of the outermost layer of the multilayer printed wiring board is also included in the circuit substrate. In addition, the insulating layer stacked on the multilayer printed wiring board can be an insulating layer obtained by overlapping more than one piece of the resin sheet of the present embodiment and hardening, or it can be an insulating layer obtained by overlapping more than one piece of the resin sheet of the present embodiment and a known resin sheet different from the resin sheet of the present embodiment. In addition, the overlapping method of the resin sheet of the present embodiment and the known resin sheet different from the resin sheet of the present embodiment is not particularly limited. On the surface of the conductor layer, roughening treatment can also be implemented in advance by blackening treatment and / or copper etching. In the lamination process, when 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 heated while being crimped to the circuit substrate. In the present embodiment, a method in which the resin layer of the resin sheet is laminated to the circuit substrate under reduced pressure by vacuum lamination can be suitably used.

[0413] The conditions of the lamination process are preferably, for example, a pressure bonding temperature (lamination temperature) of 50° C. to 140° C. and a pressure bonding pressure of 1 kgf / cm 2 ~15kgf / cm 2 , the pressing time is set to 5 seconds to 300 seconds, and the air pressure is set to 20 mmHg or less under reduced pressure for lamination. In addition, the lamination process can be a batch type or a continuous type using a roller. The vacuum lamination method can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a two-stage build-up laminator (2stage build-up laminator) (trade name) manufactured by Nikko Materials (stock) can be cited.

[0414] (Exposure process)

[0415] In the exposure step, after the resin layer is provided on the circuit board in the lamination step, an active energy line as a light source is irradiated to a predetermined portion of the resin layer to cure the resin layer in the irradiated portion.

[0416] Irradiation can be performed through a mask pattern or by direct irradiation. Examples of active energy rays include ultraviolet rays, visible light 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 ~1000mJ / 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 line having a wavelength of 365 nm (i-ray), for example. When using an active energy line having a wavelength of 365 nm (i-ray), the irradiation amount is approximately 10 mJ / cm 2 ~10,000mJ / cm 2 When a printed wiring board having a high-density and high-precision wiring formation (pattern) is manufactured by direct drawing exposure method, it is preferable to use an active energy line having a wavelength of 405nm (h-ray), for example. When using an active energy line having a wavelength of 405nm (h-ray), the irradiation amount is approximately 10mJ / cm 2 ~10,000mJ / cm 2 .

[0417] The exposure method via the mask pattern includes a contact exposure method in which the mask pattern is brought into close contact with the multilayer printed wiring board, and a non-contact exposure method in which parallel light is used for exposure without close contact. Either method can be used. In addition, when a support is present on the resin layer, exposure can be performed from the support, or exposure can be performed after the support is peeled off.

[0418] (Alkali Development Process)

[0419] When there is no support on the resin layer, after the exposure step, the non-photocured portion (unexposed portion) is removed by alkali development and developed directly, thereby forming a pattern of the insulating layer.

[0420] When a support is present on the resin layer, after the exposure step, the support is removed and then the un-photocured portion (unexposed portion) is removed by alkali development and developed, thereby forming a pattern of the insulating layer.

[0421] Since the unexposed resin layer including the resin composition of the present embodiment has excellent alkali developability, a printed wiring board having a high-definition pattern can be obtained.

[0422] In the case of alkali development, the developer is not particularly limited as long as it is a developer that selectively dissolves the unexposed portion, and alkali 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 alkali developers can also be used alone or in combination of two or more.

[0423] In addition, as an alkali development method, for example, it can be carried out by known methods such as dipping, coating, spraying, shaking dipping, brushing, scraping, etc. In the pattern formation of this embodiment, these development methods can also be used together as needed. In addition, as a development method, it is suitable to use high-pressure spray because it will further improve the resolution. As the spray pressure when using the spray method, it is preferably 0.02MPa to 0.5MPa.

[0424] (Post-baking process)

[0425] In this embodiment, a post-baking process is performed after the alkali development process is completed to form an insulating layer (hardened material). As the post-baking process, there can be cited an ultraviolet irradiation process using a high-pressure mercury lamp, a heating process using a clean oven, etc., and these processes can also be used in combination. In the case of ultraviolet irradiation, the irradiation amount can be adjusted as needed, for example, 50mJ / cm 2 ~10,000mJ / cm 2 The heating conditions can be appropriately selected as needed, but are preferably in the range of 150°C to 220°C for 20 minutes to 180 minutes, and more preferably in the range of 160°C to 200°C for 30 minutes to 150 minutes.

[0426] (Conductor layer forming step)

[0427] 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. The evaporation method (vacuum evaporation method) is, for example, to place a multilayer printed wiring board in a vacuum container and heat and evaporate the metal, thereby forming a metal film on the insulating layer. The sputtering method is, for example, to place a multilayer printed wiring board in a vacuum container, introduce an inert gas such as argon and apply a DC voltage, so that the ionized inert gas collides with the target metal, and a metal film can be formed on the insulating layer by using the knocked-out metal.

[0428] Then, a conductor layer is formed by electroless plating or electrolytic plating, etc. As a method for subsequent pattern formation, for example, a subtractive method, a semi-additive method, etc. can be used.

[0429] [Semiconductor devices]

[0430] 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 so-called conductive part refers to the part of the multilayer printed wiring board that transmits an electrical signal, and the place can be a surface or a buried part. In addition, the semiconductor chip is not particularly limited as long as it is an electrical circuit element made of a semiconductor.

[0431] As long as the semiconductor chip functions effectively, there is no particular limitation on the method for mounting the semiconductor chip when manufacturing the semiconductor device. Specifically, there can be cited a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

[0432] In addition, a semiconductor device can also be manufactured by forming an insulating layer containing a resin composition on a semiconductor chip or a substrate on which a semiconductor chip is mounted. The shape of the substrate on which the semiconductor chip is mounted can be a wafer or a panel. After forming the insulating layer, the same method as a multilayer printed wiring board can be used for manufacturing.

[0433] Example

[0434] Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0435] The conditions for measuring the molecular weight are as follows.

[0436] Model: GPC TOSOH HLC-8220GPC

[0437] Column: Super HZM-N

[0438] Eluent: tetrahydrofuran (THF); 0.35 ml / min, 40 °C

[0439] Detector: Differential refractometer (refractive index, RI)

[0440] Molecular weight standard: polystyrene

[0441] <Synthesis of bismaleimide compound (A)>

[0442] As the bismaleimide compound (A), the following four compounds were prepared.

[0443] [Synthesis Example 1 (A-1)]

[0444] In a 1L round-bottom flask equipped with a thermometer, reflux cooler, Dean-Stark device, powder inlet, nitrogen inlet device and stirring device, 165g of toluene and 165g of N-methylpyrrolidone were added. Next, 26.6g (0.20mol) of m-xylene diamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 11.7 (0.02mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) were added, and then 20.9g (0.22mol) of methanesulfonic acid was slowly added to form a salt. Stir for about 10 minutes to mix, and then 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (48.2g, 0.11mol) 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 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 generated water. After cooling to room temperature, the organic layer was washed with water (100 ml × five times), and the salt and unreacted raw materials were removed to obtain a varnish of a bismaleimide compound. Thereafter, the varnish was added dropwise to 1,000 g of methanol, thereby implementing a reprecipitation process, removing the solvent and drying it, thereby obtaining 72 g (yield 72%, Mw = 4,000) of the target light brown solid bismaleimide compound.

[0445] [Synthesis Example 2 (A-2)]

[0446] In a 1L round-bottom flask equipped with a thermometer, a reflux cooler, a Dean-Stark device, a powder inlet, a nitrogen inlet device and a stirring device, 162g of toluene and 162g of N-methylpyrrolidone were added. Next, 32.4g (0.24mol) of m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added, and then 22.9g (0.24mol) of methanesulfonic acid was slowly added to form a salt. Stir for about 10 minutes to mix, and then 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (52.8g, 0.12mol) was slowly added to the stirred mixture. The mixture was heated to reflux for 6 hours to form an amine-terminated diimide. At this time, the theoretical amount of water generated from the condensation was obtained. The reaction mixture was cooled to below room temperature, and 28.0g (0.29mol) of maleic anhydride was added to the flask. The mixture was further refluxed for 8 hours to obtain the desired amount of generated water. After cooling to room temperature, the organic layer was washed with water (100 ml × five times), and the salt and unreacted raw materials were removed to obtain a varnish of a bismaleimide compound. Thereafter, the varnish was added dropwise to 1,000 g of methanol, thereby performing a reprecipitation process, removing the solvent and drying it, thereby obtaining 78 g (yield 78%, Mw = 3,600) of the target light brown solid bismaleimide compound.

[0447] [Synthesis Example 3 (A-3)]

[0448] In a 1L round-bottom flask equipped with a thermometer, a reflux cooler, a Dean-Stark device, a powder inlet, a nitrogen inlet device and a stirring device, 170g of toluene and 170g of N-methylpyrrolidone were added. Next, 20.2g (0.15mol) of m-xylene diamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 20.0 (0.04mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) were added, and then 17.8g (0.19mol) of methanesulfonic acid was slowly added to form a salt. Stir for about 10 minutes to mix, and then 4,4'-bisphenol A dianhydride (48.3g, 0.09mol) 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 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 generated water. After cooling to room temperature, the organic layer was washed with water (100 ml × five times), and the salt and unreacted raw materials were removed to obtain a varnish of a bismaleimide compound. Thereafter, the varnish was added dropwise to 1,000 g of methanol, thereby implementing a reprecipitation process, removing the solvent and drying it, thereby obtaining 68 g (yield 68%, Mw = 4,200) of a target white solid bismaleimide compound.

[0449] <Synthesis of Compound (B) Having One or More Carboxyl Groups>

[0450] As the compound (B) containing one or more carboxyl groups, the following four compounds were prepared.

[0451] [Synthesis Example 5 (B-1)]

[0452] 4-(N-Maleimidomethyl)cyclohexane-1-carboxylic acid (ACHA-MI)

[0453] Manufactured by Tokyo Chemical Industry Co., Ltd.

[0454] [Synthesis Example 6 (B-2)]

[0455] 6-Maleimidocaproic acid (MCA)

[0456] Manufactured by Tokyo Chemical Industry Co., Ltd.

[0457] [Compound (B-3)]

[0458] Cis-4-cyclohexene-1,2-dicarboxylic acid (TH-W)

[0459] Made by Shin Nippon Chemical Co., Ltd., product name "Rikacid TH-W"

[0460] [Compound (B-4)]

[0461] 4-Aminobenzoic acid

[0462] Manufactured by Tokyo Chemical Industry Co., Ltd.

[0463] <Photopolymerization initiator (C)>

[0464] As the photopolymerization initiator (C), the following two compounds were prepared.

[0465] Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime) (manufactured by BASF Japan, "IRGACURE OXE-02")

[0466] Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (manufactured by BASF Japan, "Omnirad 819")

[0467] (Example 1 to Example 8)

[0468] The components (A) to (C) were blended in the amounts (parts by mass) shown in Table 1 and 103 parts by mass of cyclopentanone as an organic solvent (G), to prepare photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6.

[0469] <Characteristics Evaluation>

[0470] The following properties were measured for the produced curable resin composition and cured film.

[0471] [Compatibility]

[0472] The visual compatibility refers to the state of the curable resin composition after mixing components (A) to (G) and stirring. Good compatibility means that there is no precipitate and it can be coated on the substrate, while poor compatibility means that there is precipitate and it is difficult to coat on the substrate.

[0473] (Evaluation Criteria)

[0474] ○: No precipitates

[0475] ×: There is precipitate

[0476] [Evaluation of photocurability and alkali developability]

[0477] 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 film having a thickness of 10 μm to 15 μm. Subsequently, a light source (USHIO UX-1000SM-HJ01 (trade name)) capable of irradiating active energy rays having a wavelength of 405 nm was used to irradiate the substrate at an irradiation dose of 2000 mJ / cm 2 Irradiation was performed to expose half of the coating film and leave the remaining portion unexposed. After exposure, the film was heated at 150°C for 15 minutes and shaken in a 2.38% tetramethyl ammonium hydroxide (TMAH) aqueous solution (developer, manufactured by Tokuyama Co., Ltd.) for 60 to 180 seconds. The undissolved portion of the unexposed portion was then developed using propylene glycol monomethyl ether glycol to confirm the photocurability.

[0478] The laminated body obtained after the development was visually evaluated for photocurability and alkali developability according to the following criteria.

[0479] (Alkali developability criteria)

[0480] ○: The exposed portion was insoluble, but the unexposed portion was dissolved by shaking for 60 seconds to 3 minutes.

[0481] ×: Both the exposed portion and the unexposed portion were insoluble.

[0482] In addition, the curability is also determined by whether or not a pattern remains after development.

[0483] (Light-hardening criteria)

[0484] ○: After development, the pattern remains

[0485] ×: No residue left after development

[0486] Table 1 shows the results of alkali developability and photocurability.

[0487] [Table 1]

[0488]

[0489] As is clear from Table 1, according to this embodiment, when exposure is performed using any light beam including an active energy beam having a wavelength of 405 nm (h-ray) and an active energy beam including a wavelength of 200 nm to 600 nm, the photocuring can be performed with good photosensitivity. In addition, according to this embodiment, as shown in Table 1, a cured product having excellent alkali developability can be obtained.

[0490] Industrial Applicability

[0491] The resin composition of this embodiment can be effectively used in industry due to its excellent photocuring and alkali developability. For example, it can be used for photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit substrates (for laminated boards, multilayer printed wiring boards, etc.), solder resists, bottom filling materials, adhesives, semiconductor sealing materials, hole filling resins, parts embedding resins, fiber-reinforced composite materials, etc.

Claims

1. 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); [Chemistry 1] (In formula (1), R3 independently represents a tetravalent organic group containing a cyclic structure; R2 independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms; R1 independently represents the following formula (2); 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); [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).

2. 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); [Chemistry 3] (In formula (3), R6 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 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 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 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 from 1 to 5; in formula (6), when there are more than one carboxyl group, it may be an acid anhydride formed by a carboxylmethyl 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 carboxylmethyl groups, it may be an acid anhydride formed by these groups linked to each other).

3. The resin composition according to claim 1 or 2, comprising a bismaleimide compound (A) represented by the following formula (1), wherein the organic group represented by R3 is a bismaleimide compound of any one of the tetravalent organic groups represented by the following structural formulas (7) to (15); [Chemistry 7] (In formula (1), R3 independently represents a tetravalent organic group containing a cyclic structure; R2 independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms; R1 independently represents the following formula (2); 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); [Chemistry 8] (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); [Chemistry 9] (In formula (11), Y represents C(CF3)2, SO2, CO, an oxygen atom, a direct bond or a divalent linking group represented by the following formula (16)); [Chemistry 10] The -* in the above structural formula represents a bonding bond, and in the formula (1), it is bonded to the carbonyl carbon forming the cyclic imide structure.

4. The resin composition according to claim 1 or 2, wherein The photocuring initiator (C) comprises a compound represented by the following formula (17); [Chemistry 11] (In formula (17), R9 each independently represents a substituent represented by the following formula (18) or a phenyl group); [Chemistry 12] (In formula (18), -* represents a bonding bond, R 10 each independently represents a hydrogen atom or a methyl group).

5. A resin sheet having: a support; and The resin layer is disposed on one or both sides of the support. The resin layer comprises the resin composition according to claim 1 or 2.

6. The resin sheet according to claim 5, wherein The thickness of the resin layer is 1 μm to 50 μm.

7. A multilayer printed wiring board having: Insulation layer; and A conductor layer is formed on one or both sides of the insulating layer. The insulating layer comprises the resin composition according to claim 1 or 2.

8. A semiconductor device comprising the resin composition according to claim 1 or 2.

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