CN113946101A

CN113946101A - Photosensitive resin composition

Info

Publication number: CN113946101A
Application number: CN202110800334.7A
Authority: CN
Inventors: 唐川成弘
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2020-07-17
Filing date: 2021-07-15
Publication date: 2022-01-18
Also published as: KR20220010445A; TW202217454A; JP7306343B2; JP2022019406A

Abstract

The invention provides a photosensitive resin composition which can obtain a cured product with low dielectric constant and low dielectric loss tangent and has excellent flexibility and developability. The solution of the present invention is a photosensitive resin composition comprising: (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler, (C) a photopolymerization initiator, (D) an epoxy resin, and (E) at least one resin selected from the group consisting of an active ester resin, a maleimide resin, and a vinyl resin, wherein the component (D) comprises (D-1) an epoxy resin having a softening point of less than 30 ℃ and an epoxy equivalent of 150 g/eq.or less, and (D-2) an epoxy resin having a softening point of 30 ℃ or more and less than 59 ℃.

Description

Photosensitive resin composition

Technical Field

The present invention relates to a photosensitive resin composition. Further, the present invention relates to a photosensitive film, a printed wiring board, and a semiconductor device obtained using the photosensitive resin composition.

Background

In a printed wiring board, a solder resist is sometimes provided as a permanent protective film for suppressing adhesion of solder to a portion where solder is not required and for suppressing corrosion of a circuit board. As the solder resist, for example, a photosensitive resin composition as described in patent document 1 is generally used.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2014-115672.

Disclosure of Invention

Problems to be solved by the invention

The photosensitive resin composition is generally required to have developability during development. In recent years, photosensitive resin compositions have been tried as materials for insulating layers and sealing layers, and therefore, in addition to developability, excellent dielectric constant and dielectric loss tangent have been required. Further, from the viewpoint of improving the handling properties of a photosensitive film containing a photosensitive resin composition, it is also required to improve the flexibility of the photosensitive resin composition.

The invention provides a photosensitive resin composition which can obtain a cured product with low dielectric constant and low dielectric loss tangent and has excellent flexibility and developing property; a photosensitive film, a printed wiring board, and a semiconductor device obtained using the photosensitive resin composition.

Means for solving the problems

The present inventors have made extensive studies and, as a result, have found that: the present inventors have found that a photosensitive resin composition comprising a combination of (a) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler, (C) a photopolymerization initiator, (D) an epoxy resin, and (E) at least one resin selected from the group consisting of an active ester resin, a maleimide resin, and a vinyl resin, and containing a specific amount of a specific epoxy resin in the component (D) can be used to obtain a cured product having a low dielectric constant and a low dielectric loss tangent, and can improve flexibility and developability, thereby completing the present invention.

That is, the present invention includes the following;

[1] a photosensitive resin composition comprising:

(A) a resin containing an ethylenically unsaturated group and a carboxyl group,

(B) Inorganic filler,

(C) A photopolymerization initiator,

(D) An epoxy resin, and

(E) at least one resin selected from the group consisting of an active ester resin, a maleimide resin and a vinyl resin,

wherein the component (D) comprises:

(D-1) an epoxy resin having a softening point of less than 30 ℃ and an epoxy equivalent of 150g/eq or less, and

(D-2) an epoxy resin having a softening point of 30 ℃ or higher and less than 59 ℃;

[2] the photosensitive resin composition according to [1], wherein D2/D1 is 0.5 to 2.5, where D1 represents the content of the (D-1) component when the nonvolatile component in the photosensitive resin composition is 100% by mass and D2 represents the content of the (D-2) component when the nonvolatile component in the photosensitive resin composition is 100% by mass;

[3] the photosensitive resin composition according to [1] or [2], wherein the content of the component (D-1) is 90% by mass or less, assuming that the total amount of the component (D) is 100% by mass;

[4] the photosensitive resin composition according to any one of [1] to [3], wherein the content of the component (B) is 60% by mass or more, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass;

[5] the photosensitive resin composition according to any one of [1] to [4], wherein the component (A) comprises: (A-1) a resin having a naphthalene skeleton;

[6] the photosensitive resin composition according to any one of [1] to [5], wherein the component (D-1) has a cyclic structure;

[7] the photosensitive resin composition according to any one of [1] to [6], wherein the component (E) comprises:

an active ester resin, and

at least one resin selected from the group consisting of maleimide resins and vinyl resins;

[8] the photosensitive resin composition according to any one of [1] to [7], wherein a development point (ブレイクポイント, breakpoint) of a cured product of the photosensitive resin composition is 30 seconds or more and 150 seconds or less;

[9] a photosensitive film, comprising:

a support, and

a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of [1] to [8] provided on the support;

[10] a printed wiring board comprising an insulating layer formed by using a cured product of the photosensitive resin composition according to any one of [1] to [8 ];

[11] the printed wiring board according to [10], wherein the insulating layer is a solder resist;

[12] a semiconductor device comprising the printed wiring board according to [10] or [11 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: a photosensitive resin composition which can give a cured product having a low dielectric constant and a low dielectric loss tangent and is excellent in flexibility and developability; a photosensitive film, a printed wiring board, and a semiconductor device obtained using the photosensitive resin composition.

Detailed Description

The photosensitive resin composition, photosensitive film, printed wiring board, and semiconductor device of the present invention will be described in detail below.

[ photosensitive resin composition ]

The photosensitive resin composition of the present invention is a photosensitive resin composition containing (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler, (C) a photopolymerization initiator, (D) an epoxy resin, and (E) at least one resin selected from an active ester resin, a maleimide resin, and a vinyl resin, wherein the component (D) contains (D-1) an epoxy resin having a softening point of less than 30 ℃ and an epoxy equivalent of 150 g/eq.or less, and (D-2) an epoxy resin having a softening point of 30 ℃ or more and less than 59 ℃.

In the present invention, a cured product having low dielectric constant and low dielectric loss tangent in addition to developability can be obtained, and a photosensitive resin composition having excellent flexibility and developability can be provided. In addition, a cured product having a high glass transition temperature can be obtained.

The photosensitive resin composition may further contain optional components such as (F) a curing accelerator, (G) a solvent, and (H) other additives, if necessary. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.

< (A) resin having an ethylenically unsaturated group and a carboxyl group

The photosensitive resin composition contains as the component (a): a resin containing an ethylenically unsaturated group and a carboxyl group. By containing the component (a) in the photosensitive resin composition, the developability can be improved.

The ethylenically unsaturated group has a carbon-carbon double bond, and examples thereof include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimido (nadiimide), and a (meth) acryloyl group is preferable from the viewpoint of reactivity in photoradical polymerization. "(meth) acryloyl groups" includes methacryloyl groups, acryloyl groups, and combinations thereof. (A) Since the component (a) contains an ethylenic unsaturated group, photo radical polymerization can be performed. (A) The number of the ethylenically unsaturated groups per 1 molecule of the component (a) may be 1, or 2 or more. When the component (A) contains 2 or more ethylenically unsaturated groups per 1 molecule, the ethylenically unsaturated groups may be the same or different.

Since the component (a) contains a carboxyl group, the photosensitive resin composition containing the component (a) exhibits solubility in an alkaline solution (for example, a1 mass% aqueous solution of sodium carbonate as an alkaline developer). (A) The number of carboxyl groups per 1 molecule of the component (A) may be 1, or 2 or more.

The component (A) may be any resin containing an ethylenically unsaturated group and a carboxyl group. The component (A) is preferably at least one of (A-1) a resin having a naphthalene skeleton and (A-2) an acid-modified epoxy (meth) acrylate resin.

((A-1) resin having a naphthalene skeleton)

The resin having a naphthalene skeleton of (A-1) is a resin which is the component (A) and therefore contains an ethylenically unsaturated group and a carboxyl group. Therefore, the component (A-1) can be photo-radically polymerized, and the photosensitive resin compositions containing the component (A-1) all exhibit solubility in an alkaline solution.

The component (A-1) preferably has a plurality of ethylenically unsaturated groups in 1 molecule. This can improve the mechanical strength and the solubility resistance of the cured product of the photosensitive resin composition. The component (A-1) preferably has not more than 2 ethylenically unsaturated groups per 1 naphthalene skeleton. This makes it possible to adjust the crosslinking position (crosslinking point), and thus to control the mechanical strength and the solubility resistance of the cured product of the photosensitive resin composition. More preferably, the ethylenically unsaturated group is contained in a substituent group of the naphthalene skeleton. In order to include an ethylenically unsaturated group in a substituent of the naphthalene skeleton, for example, a compound in which an H atom of an OH group of naphthol is replaced with an epoxy group-containing substituent (for example, an epoxy group or a glycidyl group) is prepared as a first precursor, and a compound having an ethylenically unsaturated bond (for example, an unsaturated carboxylic acid, preferably (meth) acrylic acid) is added to the first precursor, whereby the naphthalene skeleton can be obtained. Thus, an ethylenic unsaturated group can be introduced into a substituent group of the naphthalene skeleton.

The component (A-1) preferably has a plurality of carboxyl groups in 1 molecule. This can improve the solubility of the photosensitive resin composition in an alkaline solution (e.g., an alkaline developer). The component (A-1) preferably has not more than 2 carboxyl groups per 1 naphthalene skeleton. This makes it possible to control the solubility. More preferably, the carboxyl group is contained in a substituent group of the naphthalene skeleton. In order to include a carboxyl group in a substituent of a naphthalene skeleton, for example, a compound in which an H atom of an OH group of naphthol is replaced with an epoxy group-containing substituent is prepared as a first precursor, a second precursor having a secondary hydroxyl group is obtained by adding a compound having an ethylenically unsaturated bond (for example, an unsaturated carboxylic acid, preferably (meth) acrylic acid) to the first precursor, and a carboxylic anhydride (for example, tetrahydrophthalic acid) is added to the second precursor. Thus, both an ethylenically unsaturated group and a carboxyl group can be introduced into the substituent group of the naphthalene skeleton.

The component (A-1) is a resin having a naphthalene skeleton. The resin having a naphthalene skeleton is a compound having 1 or more naphthalene skeletons in 1 molecule. Further, the component (A-1) can be dissolved at a dissolution rate in an appropriate range for an alkaline solution (e.g., an alkaline developer). When the photosensitive resin composition containing the component (A-1) is developed with an alkaline developer, it is possible to suppress the occurrence of a portion excessively dissolved against intention or a portion not dissolved against intention in the photosensitive resin composition. That is, BP (developing point) can be increased. Therefore, the developability of the photosensitive resin composition can be improved.

Further, when a resin containing a naphthalene skeleton is used as the component (a-1), the rigidity of the molecule is generally high, and thus the movement of the molecule in the photosensitive resin composition can be suppressed, and as a result, the glass transition temperature of the cured product of the photosensitive resin composition becomes higher. Further, the (a-1) component generally has improved resistance to internal stress caused by thermal expansion or thermal contraction, and thus can improve flexibility of the photosensitive film.

The component (A-1) may contain 1 naphthalene skeleton in 1 molecule, and may contain 2 or more naphthalene skeletons.

The component (A-1) is, for example, a resin having a structure represented by the following formula (1). The component (A-1) may have a plurality of structures represented by the following formula (1) (for example, 1 to 10, preferably 1 to 6), and when a plurality of structures represented by the following formula (1) are present, the component (A-1) may contain a plurality of structures represented by the following formula (1) as a structural unit (repeating unit). Furthermore, in the following formula (1), with R¹The bonded chemical bond may be bonded to any one of carbon atoms that can be bonded among carbon atoms that the naphthalene skeleton has. Thus, R¹The bonded chemical bond may be bonded to the same carbon atom of the benzene ring as the terminal chemical bond, or may be bonded to a carbon atom of a different benzene ring. The above-mentioned terminal chemical bond is represented by a chemical bond bonded to the naphthalene ring except for R¹The chemical bond to be bonded and the chemical bond other than the chemical bond to be bonded to OR' specifically represent the chemical bond described at the left end of formula (1). For example, a terminal chemical bond in the naphthalene skeleton, and a bond with R¹The combination of positions of the bound chemical bonds may be 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 2,3, 2,6, 2, 7.

[ chemical formula 1]

The above formula (1)In, R¹And R²Each independently represents an alkylene group optionally having a substituent. R¹The number of carbon atoms of (A) is usually 1 to 20, preferably 1 to 10, more preferably 1 to 6. The alkylene group may be linear or branched. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group.

R¹And R²Examples of the substituent which may be contained include, independently, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, and an oxo group.

In the above formula (1), X represents an arylene group which may have a substituent. The number of carbon atoms of X is usually 6 to 30, preferably 6 to 20, more preferably 6 to 10. Arylene is, for example, phenylene, anthracylene, phenanthrylene, biphenylene.

Examples of the substituent which X may have include the same as R¹And R²Examples of the substituents which may be contained are the same.

In the formula (1), a represents 0 or 1. Here, a is the number of groups X.

In the above formula (1), s represents 0 or 1. Where s and t are each independently of the other a radical R¹And a radical R²The number of (2). In the formula (1), t represents 0 or 1. However, s and t cannot be such that s + t is 0. In the case where a is 1, s and t are preferably both 1. When a is 0, one of s and t is preferably 0.

In the above formula (1), OR' is a substituent on the naphthalene skeleton. In the formula (1), R' independently represents an organic group containing an ethylenic unsaturated group and a carboxyl group.

R' preferably represents a group represented by the following formula (2):

[ chemical formula 2]

In the above formula (2), R³Represents a trivalent group, preferably optionally substitutedThe trivalent hydrocarbon group (wherein hetero atom may be present between carbon-carbon bonds (C-C bonds)), is preferably a trivalent aliphatic hydrocarbon group optionally having a substituent. The R is³May be a trivalent residue of an optionally substituted epoxy-containing substituent. R³Examples of the substituent which may be present include R¹And R²Examples of the substituents which may be contained are the same.

In the above formula (2), R⁴Represents an organic group containing ethylenic unsaturation. A preferred example of the organic group containing an ethylenically unsaturated group is a (meth) acryloyloxy group. "(meth) acryloyloxy" includes acryloyloxy, methacryloyloxy, and combinations thereof.

In the above formula (2), R⁵Is an organic group containing a carboxyl group. An example of an organic group containing a carboxyl group is-OCO-R⁶-COOH. Here, R⁶Represents a divalent group. As R⁶Preferred is a divalent hydrocarbon group optionally having a substituent. R⁶The number of carbon atoms of (A) is usually 1 to 30, preferably 1 to 20, more preferably 1 to 6. Examples of the divalent hydrocarbon group include linear or branched acyclic alkylene groups such as methylene, ethylene, propylene, and butylene; a saturated or unsaturated divalent alicyclic hydrocarbon group; arylene groups such as phenylene and naphthylene. Among them, preferred are divalent alicyclic hydrocarbon groups and arylene groups, and particularly preferred are 4-cyclohexenylene groups and phenylene groups. Furthermore, R⁶Examples of the substituent which may be present include¹And R²Examples of the substituents which may be contained are the same. -OCO-R⁶-CO-R in-COOH⁶-COOH is typically the residue of a carboxylic acid anhydride. Examples of carboxylic anhydrides are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride.

In the above formula (1), c is an integer of usually 1 to 6, preferably 1 to 3, more preferably 1 to 2. Here, c is the number of groups OR'.

The first example (a is 1) of the component (A-1)

A preferable example of the component (A-1) is a naphthol aralkyl type resin. The "naphthol aralkyl type resin" refers to a resin having a structure in which an H atom of an OH group is removed from a naphthol aralkylene group.

The naphthol aralkyl type resin is preferably a resin having a structure in which a is 1 in the above formula (1), and is preferably a resin having a structure represented by the following formula (3);

[ chemical formula 3]

In the above formula (3), R¹、R²X, s, t, R' and c are the same as described above. s and t are preferably both 1.

A more preferable resin among the naphthol aralkyl type resins is a resin containing a structure in which c is 1, s is 1 and t is 1 in the formula (3), and is, for example, a naphthol aralkyl type resin containing a divalent group having a structure represented by the following formula (4) or (5).

[ chemical formula 4]

[ chemical formula 5]

In the above formula (4) or (5), R¹、R²X, R' and c are the same as described above. The naphthol aralkyl type resin represented by the above formula (4) or (5) is a resin which can be synthesized using as a material a naphthol aralkyl type epoxy resin used in synthesis example 1 described later. The naphthol aralkyl type epoxy resin can be obtained, for example, as "ESN-475V" (epoxy equivalent 325g/eq.) manufactured by Nissan Ciki chemical Co., Ltd.

Second example (a ═ 0) of component (A-1)

Among the components (a-1), preferred examples of the (a ═ 0) other than the naphthol aralkyl type resins are resins having a structure in which c is 2, s is 1 and t is 0 in the above formula (1), and examples thereof include resins having a naphthalene skeleton which contain a divalent group having a structure represented by the following formula (6);

[ chemical formula 6]

In the above formula (6), R¹R and R' are the same as described above. The resin having a naphthalene skeleton represented by the above formula (6) is a resin which can be synthesized using 1,1' -bis (2, 7-diglycidyloxynaphthyl) methane as a material. Such an epoxy resin having a naphthalene skeleton is available as "EXA-4700" manufactured by Dainippon ink chemical industries, Ltd.

The weight average molecular weight of the component (A-1) is preferably 500 or more, more preferably 1000 or more, further preferably 1500 or more, further preferably 2000 or more, from the viewpoint of film formability. The upper limit is preferably 10000 or less, more preferably 8000 or less, and further preferably 7500 or less, from the viewpoint of developability. The weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.

Method for producing component (A-1)

The component (a-1) is not particularly limited as long as it is a compound having a resin containing a naphthalene skeleton, an ethylenically unsaturated group, and a carboxyl group, and one embodiment thereof is an acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin obtained by reacting an unsaturated carboxylic acid with a naphthalene-type epoxy compound having a naphthalene skeleton (naphthalene skeleton-containing epoxy compound) and further reacting with a carboxylic acid anhydride. A method for producing an acid-modified epoxy ester resin having an unsaturated naphthalene skeleton will be described. First, an epoxy ester resin having an unsaturated naphthalene skeleton is obtained by reacting an unsaturated carboxylic acid with an epoxy compound having a naphthalene skeleton, and then the epoxy ester resin having an unsaturated naphthalene skeleton is reacted with a carboxylic acid anhydride. Thus, an acid-modified epoxy ester resin having an unsaturated naphthalene skeleton can be obtained.

The epoxy compound having a naphthalene skeleton is applicable as long as it has 1 or more epoxy groups in the molecule, and examples thereof include naphthalene-type epoxy resins having a naphthalene skeleton in the molecule, such as monohydroxynaphthalene-type epoxy resins, dihydroxynaphthalene-type epoxy resins, polyhydroxynaphthalene-type epoxy resins, naphthalene-type epoxy resins obtained by a condensation reaction of polyhydroxynaphthalene and aldehydes, and dinaphthophenol-type epoxy resins. These compounds may be used alone or in combination of two or more.

Examples of the monohydroxynaphthalene-type epoxy resin include 1-glycidyloxynaphthalene and 2-glycidyloxynaphthalene. Examples of the dihydroxynaphthalene-type epoxy resin include 1, 3-diglycidyloxynaphthalene, 1, 4-diglycidyloxynaphthalene, 1, 5-diglycidyloxynaphthalene, 1, 6-diglycidyloxynaphthalene, 2, 3-diglycidyloxynaphthalene, 2, 6-diglycidyloxynaphthalene, and 2, 7-diglycidyloxynaphthalene.

Examples of the polyhydroxybinaphthyl-type epoxy resin include 1,1' - (2-glycidyloxy) binaphthyl (1, 1' - ビ - (2- グリシジルオキシ) ナフチル), 1- (2, 7-diglycidyloxy) -1' - (2' -glycidyloxy) binaphthyl, and 1,1' - (2, 7-diglycidyloxy) binaphthyl.

Examples of the naphthalene-type epoxy resin obtained by condensation reaction of a polyhydroxynaphthalene with an aldehyde include 1,1 '-bis (2, 7-diglycidyloxynaphthyl) methane, 1- (2, 7-diglycidyloxynaphthyl) -1' - (2 '-glycidyloxynaphthyl) methane, and 1,1' -bis (2-glycidyloxynaphthyl) methane.

Among them, preferred are polyhydroxy binaphthyl type epoxy resins having 2 or more naphthalene skeletons in 1 molecule, and naphthalene type epoxy resins obtained by condensation reaction of polyhydroxy naphthalenes with aldehydes; in addition to being excellent in the average linear thermal expansion coefficient and also being excellent in heat resistance, particularly preferred are 1,1 '-bis (2, 7-diglycidyloxynaphthyl) methane, 1- (2, 7-diglycidyloxynaphthyl) -1' - (2 '-glycidyloxynaphthyl) methane, 1- (2, 7-diglycidyloxy) -1' - (2 '-glycidyloxy) binaphthyl, and 1,1' - (2, 7-diglycidyloxy) binaphthyl, each having 3 or more epoxy groups in 1 molecule.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, and the like, and these carboxylic acids may be used singly or in combination of two or more. Among them, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. In the present specification, the naphthalene-type epoxy compound ester resin which is a reactant of the naphthalene-type epoxy compound and (meth) acrylic acid may be referred to as "naphthalene-type epoxy compound (meth) acrylate", and here, the epoxy group of the naphthalene-type epoxy compound is usually substantially eliminated by the reaction with (meth) acrylic acid. "(meth) acrylate" includes methacrylate, acrylate, and combinations thereof. Acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth) acrylic acid".

Examples of the carboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic dianhydride, and any of these carboxylic anhydrides may be used alone, or two or more thereof may be used in combination. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferred from the viewpoint of improving the developability and insulation reliability of the cured product.

In order to obtain an acid-modified epoxy ester resin having an unsaturated naphthalene skeleton, an unsaturated carboxylic acid and an epoxy compound having a naphthalene skeleton are reacted in the presence of a catalyst to obtain an epoxy ester resin having an unsaturated naphthalene skeleton, and then the epoxy ester resin having an unsaturated naphthalene skeleton is reacted with a carboxylic acid anhydride.

The amount of the catalyst used in this case is preferably 2% by mass or less, more preferably 0.0005% by mass to 1% by mass, and still more preferably 0.001% by mass to 0.5% by mass, based on the total mass of the unsaturated carboxylic acid, the naphthalene skeleton-containing epoxy compound, and the carboxylic anhydride. Examples of the catalyst include N-methylmorpholine, pyridine, 1, 8-diazabicyclo [5.4.0] undecene-7 (DBU), 1, 5-diazabicyclo [4.3.0] nonene-5 (DBN), 1, 4-diazabicyclo [2.2.2] octane (DABCO), tri-or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2, 4-dimethylimidazole, 1, 4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, Various amine compounds such as tetramethylammonium hydroxide; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium salt, tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrabutylphosphonium salt, trimethyl (2-hydroxypropyl) phosphonium salt, triphenylphosphonium salt, benzylphosphonium salt and the like, and phosphonium salts having chloride ion, bromide ion, carboxylate ion, hydroxide ion and the like as typical counter anions; sulfonium salts such as trimethylsulfonium salt, benzyltetramethylsulfonium salt, phenylbenzylmethylthiosulfonium salt, and phenyldimethylsulfonium salt, and sulfonium salts having carboxylate ions, hydroxide ions, and the like as typical counter anions; acidic compounds such as phosphoric acid, p-toluenesulfonic acid and sulfuric acid. The reaction can be carried out at a temperature of from 50 ℃ to 150 ℃ and preferably from 80 ℃ to 120 ℃.

In order to obtain an acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin, an organic solvent can be used, and as the organic solvent, the same solvent as the solvent (G) described later can be used.

In order to obtain an acid-modified epoxy ester resin having an unsaturated naphthalene skeleton, a polymerization inhibitor such as hydroquinone may be used. The amount of the polymerization inhibitor used in this case is preferably 2% by mass or less, more preferably 0.0005% by mass to 1% by mass, and still more preferably 0.001% by mass to 0.5% by mass, based on the total mass of the unsaturated carboxylic acid, the naphthalene skeleton-containing epoxy compound, and the carboxylic anhydride.

The acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin is preferably an acid-modified naphthalene skeleton-containing epoxy (meth) acrylate. The acid-modified naphthalene skeleton-containing epoxy (meth) acrylate is an acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin obtained by using a naphthalene skeleton-containing epoxy compound and (meth) acrylic acid as an unsaturated carboxylic acid.

As other modes of the component (A-1), there can be mentioned: a (meth) acrylic resin having an unsaturated modified naphthalene skeleton, in which an ethylenically unsaturated group is introduced, is obtained by reacting a (meth) acrylic resin having a structural unit obtained by polymerizing (meth) acrylic acid with an epoxy compound having an ethylenically unsaturated group and a naphthalene skeleton. Further, the carboxylic anhydride may be reacted with a hydroxyl group generated upon introduction of an unsaturated group. As the carboxylic anhydride, the same ones as the above-mentioned anhydrides can be used, and the preferable ranges are also the same.

((A-2) acid-modified epoxy (meth) acrylate resin)

The acid-modified epoxy (meth) acrylate resin as the component (a-2) is a compound having a structure in which a carboxyl group is introduced into a (meth) acrylate of an epoxy compound. However, the component (A-2) does not contain the component (A-1).

As one embodiment of the component (a-2), acid-modified Cresol Novolac epoxy (meth) acrylate obtained by reacting (meth) acrylic acid with a Cresol Novolac (Cresol Novolac) type epoxy compound such as a Cresol Novolac a type epoxy compound or a Cresol Novolac F type epoxy compound, and further reacting a carboxylic anhydride, and the like can be mentioned. Specifically, the acid-modified cresol novolac epoxy (meth) acrylate can be obtained by reacting (meth) acrylic acid with a cresol novolac epoxy compound to obtain a cresol novolac epoxy (meth) acrylate, and reacting the cresol novolac epoxy (meth) acrylate with a carboxylic anhydride.

Another embodiment of the component (a-2) includes an acid-modified epoxy (meth) acrylate obtained by reacting (meth) acrylic acid with an epoxy compound other than the cresol novolac-type epoxy compound, and further reacting a carboxylic anhydride. Examples of such epoxy compounds include biphenyl type epoxy compounds; bisphenol epoxy compounds such as bisphenol a epoxy compounds and bisphenol F epoxy compounds; phenol novolac (phenol novolac) type epoxy resins; phenol (novolac) type epoxy resins such as bisphenol a type novolac epoxy resins and alkylphenol novolac epoxy resins; fluorine-containing epoxy resins such as perfluoroalkyl epoxy resins; a biphenol-type epoxy resin; dicyclopentadiene type epoxy resins; epoxy resins having a condensed ring skeleton such as a trisphenol type epoxy resin, a t-butyl-catechol type epoxy resin, and an anthracene type epoxy resin; glycidyl amine type epoxy resins; glycidyl ester type epoxy resins; linear aliphatic epoxy resin; an epoxy resin having a butadiene structure; a cycloaliphatic epoxy resin; a heterocyclic epoxy resin; epoxy resins containing spiro rings; cyclohexane dimethanol type epoxy resins; a trimethylol type epoxy resin; tetraphenylethane type epoxy resins; glycidyl group-containing acrylic resins such as polyglycidyl (meth) acrylate and copolymers of glycidyl methacrylate and acrylic acid esters; a fluorene-type epoxy resin; halogenated epoxy resins, and the like.

Commercially available products of such acid-modified epoxy (meth) acrylates can be used, and specific examples thereof include: "CCR-1179" (cresol novolac F-type epoxy acrylate), "ZAR-2000" (acid-modified bisphenol epoxy acrylate: a reaction product of bisphenol A epoxy resin, acrylic acid, and succinic anhydride), "ZFR-1491H" (acid-modified bisphenol epoxy acrylate: a reaction product of bisphenol F epoxy resin, acrylic acid, and acid anhydride), "ZFR-1533H" (acid-modified bisphenol epoxy acrylate: a reaction product of bisphenol F epoxy resin, acrylic acid, and tetrahydrophthalic anhydride), "ZCR-1569H" (acid-modified biphenyl epoxy acrylate: a reaction product of biphenyl epoxy resin, acrylic acid, and acid anhydride), and "PR-300 CP" (a reaction product of cresol novolac epoxy resin, acrylic acid, and acid anhydride) manufactured by Showa Denko K corporation. These may be used alone or in combination of two or more.

Other forms of the component (A-2) include: an unsaturated modified (meth) acrylic resin having an ethylenically unsaturated group introduced by reacting a (meth) acrylic resin having a structural unit obtained by polymerizing (meth) acrylic acid with a (meth) acrylate of an epoxy compound. Examples of (meth) acrylates of epoxy compounds include: glycidyl methacrylate, 4-hydroxybutyl ester glycidyl ether (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, and the like. Further, a hydroxyl group generated at the time of introducing an unsaturated group may be reacted with a carboxylic acid anhydride. As the carboxylic anhydride, the same ones as those described above can be used, and the preferable ranges are also the same.

As such unsaturated modified (meth) acrylic resins, commercially available products can be used, and specific examples thereof include "SPC-1000", "SPC-3000" manufactured by Showa Denko K.K., and "Cyclic P (ACA) Z-250", "Cyclic P (ACA) Z-251", "Cyclic P (ACA) Z-254", "Cyclic P (ACA) Z-300" and "cyclic P (ACA) Z-320" manufactured by DAICEL-ALLNEX.

The weight average molecular weight of the component (A-2) is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, from the viewpoint of film formability. The upper limit is preferably 20000 or less, more preferably 15000 or less, further preferably 14000 or less, from the viewpoint of developability. The weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.

(A) Component (A-3) may be other than the above-mentioned components (A-1) and (A-2). The component (A-1) and the component (A-2) are not contained in the composition.

The weight average molecular weight and acid value of the component (A-3) are arbitrary, but are preferably in the same range as those of the component (A-2). Thereby, the same advantages as those described in the item of the (A-2) component can be obtained.

The acid value of the component (A) is preferably 0.1mgKOH/g or more, 0.5mgKOH/g or more, or 1mgKOH/g or more, from the viewpoint of improving the solubility of the photosensitive resin composition in an alkali solution. On the other hand, from the viewpoint of suppressing elution of the fine pattern of the cured product into the alkali solution, the acid value is preferably 150mgKOH/g or less, more preferably 120mgKOH/g or less, further preferably 100mgKOH/g or less. The acid value is the residual acid value of the carboxyl group present in the component (a), and can be measured by the following method. First, about 1g of a test resin solution was accurately weighed, and then 30g of acetone was added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein as an indicator was added to the solution, and titration was performed using a 0.1N alcoholic KOH solution. Then calculating an acid value by the following formula (1);

formula (II): vf × 5.611/(Wp × I) · (1).

In the above formula (1), A represents an acid value [ mgKOH/g ], Vf represents a dropping amount [ mL ] of a KOH solution, Wp represents a measured mass [ g ] of a resin solution, and I represents a ratio [ mass% ] of nonvolatile components of the measured resin solution.

The content of the component (a) is preferably 10 mass% or more, more preferably 15 mass% or more, further preferably 20 mass% or more, further preferably 40 mass% or less, further preferably 35 mass% or less, further preferably 30 mass% or less, based on 100 mass% of nonvolatile components in the photosensitive resin composition, from the viewpoint of adjusting the solubility of the photosensitive resin composition in an alkaline solution. In the present invention, the content of each component in the photosensitive resin composition is a value when the nonvolatile component in the photosensitive resin composition is 100 mass%, unless otherwise specified.

(B) inorganic filler

The photosensitive resin composition contains (B) an inorganic filler as the component (B). By containing the component (B) in the photosensitive resin composition, a photosensitive resin composition can be provided which can give a cured product having a low dielectric constant and a low dielectric loss tangent.

(B) The material of the inorganic filler is not particularly limited, and examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, and zirconium tungstate phosphate. Among them, silica is particularly preferable. Further, as the silica, spherical silica is preferable. (B) The inorganic filler may be used alone or in combination of two or more.

From the viewpoint of obtaining a cured product having a low dielectric constant and a low dielectric loss tangent, the average particle size of the inorganic filler (B) is preferably 10 μm or less, more preferably 5 μm or less, further preferably 3 μm or less, 2 μm or less, 1 μm or less, or 0.7 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more.

The average particle diameter of the inorganic filler can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size is determined as an average particle size. The measurement sample may be one obtained by dispersing the inorganic filler in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, there can be used "LA-500" manufactured by horiba, Ltd., SALD-2200 "manufactured by Shimadzu, Ltd.

From the viewpoint of obtaining a cured product having a low dielectric constant and a low dielectric loss tangent, the specific surface area of the (B) inorganic filler is preferably 1m²More than g, preferably 3m²More than g, particularly preferably 5m²More than g. The upper limit is not particularly limited, but is preferably 60m²Less than 50 m/g²Less than or equal to 40 m/g²The ratio of the carbon atoms to the carbon atoms is less than g. The specific surface area can be obtained by adsorbing nitrogen gas onto the surface of a sample by the BET method using a specific surface area measuring apparatus (Macsorb HM-1210, manufactured by Mountech corporation) and calculating the specific surface area by the BET multipoint method.

From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler (B) is preferably surface-treated with at least one surface-treating agent selected from the group consisting of an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organosilazane compound, and a titanate-based coupling agent. Examples of commercially available surface-treating agents include "KBM 403" (3-glycidoxypropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd., "KBM 803" (3-mercaptopropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd., "KBE 903" (3-aminopropyltriethoxysilane) available from shin-Etsu chemical Co., Ltd., "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) available from shin-Etsu chemical Co., Ltd., "KBM 103" (phenyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd., "KBM-4803" (long-chain epoxy-type silane coupling agent) available from shin-Etsu chemical Co., Ltd.

(B) Commercially available inorganic fillers can be used. Examples of commercially available products include: "SC 2050", "SC 4050", "Admafine", manufactured by adesmar (Admatechs), a "SFP series" manufactured by the electric chemical industry company, "sp (h) series manufactured by the new-day iron-based gold material company," Sciqas series "manufactured by the sakai chemical industry company," seashostar series "manufactured by the japan catalytic company," AZ series "," AX series ", a" B series "manufactured by the sakai chemical industry company, and" BF series "manufactured by the sakai chemical industry company.

The content of the (B) inorganic filler is preferably 50 mass% or more, more preferably 55 mass% or more, and still more preferably 60 mass% or more, based on 100 mass% of nonvolatile components in the photosensitive resin composition, from the viewpoint of obtaining a cured product having a low dielectric constant and a low dielectric loss tangent. From the viewpoint of suppressing light reflection at the time of exposure and obtaining excellent developability, the upper limit is, for example, 75 mass% or less, 70 mass% or less, or 65 mass% or less.

[ C ] photopolymerization initiator

The photosensitive resin composition contains a photopolymerization initiator as the component (C). By containing (C) a photopolymerization initiator in the photosensitive resin composition, the photosensitive resin composition can be efficiently photocured.

(C) Any compound can be used as the photopolymerization initiator, and examples thereof include: acylphosphine oxide-based photopolymerization initiators such as bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide and 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide; oxime ester type photopolymerization initiators such as 1- [4- (phenylthio) -1, 2-octanedione 2- (O-benzoyloxime) and 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyloxime); α -aminoalkylphenone-based photopolymerization initiators such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] - [4- (4-morpholino) phenyl ] -1-butanone, and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone; benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2-diethoxyacetophenone, 2, 4-diethylthioxanthone, diphenyl- (2,4, 6-trimethylbenzoyl) phosphine oxide, ethyl (2,4, 6-trimethylbenzoyl) phenylphosphonate, 4' -bis (diethylamino) benzophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-dimethoxy-1, 2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, etc., and sulfonium salt type photopolymerization initiators may also be used. These photopolymerization initiators may be used singly or in combination of two or more. Among these, from the viewpoint of more effectively photocuring the photosensitive resin composition, any of the acylphosphine oxide-based photopolymerization initiator and the oxime ester-based photopolymerization initiator is preferable, and the acylphosphine oxide-based photopolymerization initiator is more preferable. These photopolymerization initiators may be used singly or in combination of two or more.

Specific examples of the photopolymerization initiator (C) include: "Omnirad 907", "Omnirad 369", "Omnirad 379", "Omnirad 819", "Omnirad TPO", manufactured by the IGM company, "Irgacure OXE-01", "Irgacure OXE-02", "Irgacure TPO", "Irgacure 819", manufactured by the BASF company, "N-1919", and the like.

The content of the photopolymerization initiator (C) is preferably 1 mass% or more, more preferably 1.5 mass% or more, and still more preferably 2 mass% or more, based on 100 mass% of the nonvolatile component of the photosensitive resin composition, from the viewpoint of sufficiently photocuring the photosensitive resin composition and improving insulation reliability. On the other hand, from the viewpoint of suppressing the deterioration of the developability due to the excessive sensitivity, the upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and still more preferably 3% by mass or less.

The photosensitive resin composition may further contain, in combination with component (C), a tertiary amine such as ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, triethylamine or triethanolamine as a photopolymerization initiation aid, and may further contain a photosensitizer such as a pyrazoline, anthracene, coumarin, xanthenone or thioxanthone. These compounds may be used alone or in combination of two or more.

(D) epoxy resin

The photosensitive resin composition contains an epoxy resin as the component (D). By containing the component (D) in the photosensitive resin composition, insulation reliability can be improved. However, the component (D) mentioned here does not include an epoxy resin containing an ethylenic unsaturated group and a carboxyl group.

(D) The epoxy resin comprises: (D-1) an epoxy resin having a softening point of less than 30 ℃ and an epoxy equivalent of 150 g/eq.or less, and (D-2) an epoxy resin having a softening point of 30 ℃ or more and less than 59 ℃. When the component (E) described later is contained in the photosensitive resin composition, the solubility of the photosensitive resin composition tends to be lowered and the developability tends to be lowered because the component (E) is generally hydrophobic, from the viewpoint of obtaining a cured product having excellent dielectric constant and dielectric loss tangent. However, in the present invention, the combination use of the (D-1) component and the (D-2) component, which have a low softening point and a small epoxy equivalent, can suppress the decrease in solubility. As a result, a cured product having excellent developability and having excellent dielectric constant and dielectric loss tangent inherent in the component (E) is realized.

From the viewpoint of remarkably obtaining the effect of the present invention, the softening point of the component (D-1) is less than 30 ℃, preferably 25 ℃ or less, more preferably 20 ℃ or less. The lower limit is not particularly limited, but is preferably 0 ℃ or higher, more preferably 5 ℃ or higher, and still more preferably 10 ℃ or higher. The softening point can be measured according to JIS K7234.

From the viewpoint of remarkably obtaining the effect of the present invention, the epoxy equivalent of the component (D-1) is 150g/eq or less, preferably 148g/eq or less, more preferably 145g/eq or less, more preferably 10g/eq or more, still more preferably 50g/eq or more, and still more preferably 100g/eq or more. (D) The epoxy equivalent of the component (C) is the mass of the epoxy resin containing 1 equivalent of epoxy group. The epoxy equivalent can be measured according to JIS K7236.

The component (D-1) preferably has 1 or more epoxy groups in 1 molecule, more preferably 2 or more epoxy groups in 1 molecule, and still more preferably 3 or more epoxy groups in 1 molecule, from the viewpoint of remarkably obtaining the effect of the present invention. From the viewpoint of remarkably obtaining the desired effect of the present invention, the proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, relative to 100% by mass of the nonvolatile component of the (D-1) component.

The component (D-1) includes a component which is liquid at a temperature of 20 ℃ and a component which is solid at a temperature of 20 ℃. The component (D-1) is preferably a liquid from the viewpoint of improving flexibility.

As the component (D-1), an epoxy resin having a softening point of less than 59 ℃ and an epoxy equivalent of 150g/eq. or less can be used. Such an epoxy resin is preferably a cyclic structure from the viewpoint of remarkably obtaining the effect of the present invention. Examples of the cyclic structure include an aromatic ring structure and an alicyclic structure. Examples of the aromatic ring structure include a benzene ring, a naphthalene ring, and an anthracene ring. Examples of the alicyclic structure include a cyclohexane ring, a cyclopentane ring, a cycloheptane ring, and a cyclooctane ring. Among them, as the cyclic structure, an aromatic ring structure is preferable, a naphthalene ring, a benzene ring are more preferable, and a naphthalene ring is further preferable.

Further, examples of the component (D-1) include naphthalene type epoxy resins, glycidyl amine type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, glycidyl ester type epoxy resins, phenol novolac (phenol novolac) type epoxy resins, glycidyl cyclohexane type epoxy resins, isocyanurate type epoxy resins, naphthylene ether type epoxy resins, etc., preferably naphthalene type epoxy resins, glycidyl amine type epoxy resins, more preferably naphthalene type epoxy resins.

Specific examples of the component (D-1) include: "HP 4032", "HP 4032D" and "HP 4032 SS" (naphthalene epoxy resins) manufactured by DIC; "ELM-434L" (glycidylamine-type epoxy resin) manufactured by Sumitomo chemical Co., Ltd; "630" (glycidylamine type epoxy resin) manufactured by Mitsubishi chemical corporation; "ZX 1658 GS" (liquid 1, 4-glycidylcyclohexane-type epoxy resin) manufactured by Nissian iron-on-gold chemical Co., Ltd; "EP-3980S" (2-functional glycidyl amine type epoxy resin) manufactured by ADEKA corporation; "EP-3950L" (3-functional glycidyl amine type epoxy resin) by the company ADEKA; "TEPIC-VL" (isocyanuric ring type epoxy resin) manufactured by Nissan chemical Co., Ltd.; "ELM-100H" (N- [ 2-methyl-4- (oxiranylmethoxy) phenyl ] -N- (oxiranylmethyl) oxiranmethanamine, manufactured by Sumitomo chemical Co., Ltd.); and "EXA-7311-G4" (naphthylene ether type epoxy resin) manufactured by DIC corporation. These may be used alone or in combination of two or more.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of the component (D-1) is preferably 100 or more, more preferably 200 or more, further preferably 250 or more, preferably 5000 or less, more preferably 3000 or less, further preferably 1500 or less. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.

From the viewpoint of obtaining a cured product excellent in dielectric constant and dielectric loss tangent in addition to developability, the content of the (D-1) component is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, 60% by mass or less, 50% by mass or less, or 40% by mass or less, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, when the total amount of the (D) component is 100% by mass.

From the viewpoint of obtaining a cured product excellent in dielectric constant and dielectric loss tangent in addition to developability, the content of the (D-1) component is preferably 1 mass% or more, more preferably 1.5 mass% or more, further preferably 2 mass% or more, preferably 10 mass% or less, more preferably 8 mass% or less, further preferably 5 mass% or less, with respect to 100 mass% of nonvolatile components in the photosensitive resin composition.

The softening point of the component (D-2) is 30 ℃ or higher, preferably 35 ℃ or higher, more preferably 40 ℃ or higher, from the viewpoint of remarkably obtaining the effect of the present invention. From the viewpoint of remarkably obtaining the effect of the present invention, the upper limit is less than 59 ℃, preferably 55 ℃ or less, more preferably 50 ℃ or less. The softening point can be measured by the same method as that for the component (D-1).

The component (D-2) preferably has 1 or more epoxy groups in 1 molecule, more preferably 2 or more epoxy groups in 1 molecule, and still more preferably 3 or more epoxy groups in 1 molecule, from the viewpoint of remarkably obtaining the effect of the present invention. From the viewpoint of remarkably obtaining the desired effect of the present invention, the proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, relative to 100% by mass of the nonvolatile component of the (D-2) component.

The component (D-2) is preferably in a solid state at a temperature of 20 ℃.

As the component (D-2), an epoxy resin having a softening point of 30 ℃ or higher and less than 59 ℃ can be used. Such an epoxy resin is preferably a cyclic structure from the viewpoint of remarkably obtaining the effect of the present invention. Examples of the cyclic structure include an aromatic ring structure and an alicyclic structure. Examples of the aromatic ring structure include a benzene ring, a naphthalene ring, an anthracene ring, biphenyl, and the like. Examples of the alicyclic structure include a cyclohexane ring, a cyclopentane ring, a cycloheptane ring, and a cyclooctane ring. Among them, as the cyclic structure, an aromatic ring structure is preferable, a benzene ring, a biphenyl ring is more preferable, and a biphenyl ring is further preferable.

Further, as the component (D-2), for example, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthylene ether type epoxy resin and the like can be mentioned, and biphenyl type epoxy resin is more preferable.

Specific examples of the component (D-2) include: "NC 3000L" (biphenyl type epoxy resin) manufactured by japan chemical company; "HP-7200L" (dicyclopentadiene type epoxy resin) and "HP-6000L" (naphthylene ether type epoxy resin) manufactured by DIC corporation; "NC 3000" (biphenyl type epoxy resin) manufactured by Nippon chemical Co., Ltd. These may be used alone or in combination of two or more.

The epoxy equivalent of the component (D-2) is preferably 50 g/eq.about 5000g/eq, more preferably 50 g/eq.about 3000g/eq, still more preferably 80 g/eq.about 2000g/eq, and still more preferably 110 g/eq.about 1000g/eq. By setting the crosslinking density in this range, the cured product of the photosensitive resin composition layer becomes sufficient, and an insulating layer having a small surface roughness can be provided.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of the (D-2) component is preferably 100 or more, more preferably 200 or more, further preferably 250 or more, preferably 5000 or less, more preferably 3000 or less, further preferably 1500 or less.

From the viewpoint of obtaining a cured product excellent in dielectric constant and dielectric loss tangent in addition to developability, the content of the (D-2) component is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, when the total amount of the (D) component is 100% by mass.

From the viewpoint of obtaining a cured product excellent in dielectric constant and dielectric loss tangent in addition to developability, the content of the (D-2) component is preferably 1 mass% or more, more preferably 1.5 mass% or more, further preferably 2 mass% or more, preferably 15 mass% or less, more preferably 10 mass% or less, further preferably 8 mass% or less, based on 100 mass% of nonvolatile components in the photosensitive resin composition.

When the content of the (D-1) component in 100% by mass of the nonvolatile component in the photosensitive resin composition is D1 and the content of the (D-2) component in 100% by mass of the nonvolatile component in the photosensitive resin composition is D2, D2/D1 is preferably 0.5 or more, more preferably 1 or more, further preferably 1.5 or more, further preferably 2.5 or less, further preferably 2.3 or less, further preferably 2.2 or less. When the amount ratio of the (D-1) component to the (D-2) component is in the above range, the desired effects of the present invention can be remarkably obtained.

The photosensitive resin composition may contain (D-3) an epoxy resin other than the components (D-1) and (D-2). Examples of the component (D-3) include:

(1) an epoxy resin having a softening point of 59 ℃ or higher, and

(2) epoxy resin with softening point less than 30 deg.c and epoxy equivalent over 150 g/eq;

the softening point of the component (D-3) is measured in the same manner as that of the component (D-1).

Examples of the component (D-3) include: a biscresol (bixylenol) type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol novolac (naphthol novolac) type epoxy resin, a phenol novolac (phenol novolac) type epoxy resin, a tert-butyl catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac (cresol novolac) type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic type epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a bisphenol S type epoxy resin, a dicyclopentadiene type epoxy resin, a naphthol type epoxy resin, a phenol type epoxy resin, a naphthol type epoxy resin, a phenol type epoxy resin, a phenol type epoxy resin, a phenol type epoxy resin, a phenol type epoxy resin, a resin, tetraphenylethane type epoxy resins, and the like. The (D-3) epoxy resin may be used singly or in combination of two or more.

In the photosensitive resin composition, an epoxy resin having 2 or more epoxy groups in 1 molecule is preferably contained as the (D-3) component. From the viewpoint of remarkably obtaining the desired effect of the present invention, the proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, relative to 100% by mass of the nonvolatile component of the (D-3) component.

The component (D-3) contains an epoxy resin which is liquid at a temperature of 20 ℃ (hereinafter sometimes referred to as a "liquid epoxy resin") and an epoxy resin which is solid at a temperature of 20 ℃ (hereinafter sometimes referred to as a "solid epoxy resin"). The component (D-3) may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain both a liquid epoxy resin and a solid epoxy resin, and from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferable to contain only a solid epoxy resin.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.

The solid epoxy resin is preferably a biphenol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol AF-type epoxy resin, a tetraphenylethane-type epoxy resin, and more preferably a naphthalene-type epoxy resin.

Specific examples of the solid epoxy resin include: HP4032H (naphthalene epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC; "N-690" (cresol novolac epoxy resin) manufactured by DIC; "N-695" (cresol novolac epoxy resin) manufactured by DIC; "HP-7200", "HP-7200 HH" and "HP-7200H" (dicyclopentadiene type epoxy resins) manufactured by DIC; "EXA-7311" and "HP 6000" (naphthylene ether type epoxy resin) manufactured by DIC corporation; EPPN-502H (trisphenol type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "NC 7000L" (naphthol novolac type epoxy resin) manufactured by japan chemicals); "NC 3000H" and "NC 3100" (biphenyl type epoxy resin) manufactured by japan chemical company; ESN475V (naphthol type epoxy resin) manufactured by Nippon iron and gold Chemicals; ESN485 (naphthol novolac epoxy resin) manufactured by Nissian iron-on-gold chemical company; "YX 4000H", "YX 4000", "YL 6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical company; "YX 4000 HK" (bisphenol type epoxy resin) manufactured by Mitsubishi chemical corporation; YX8800 (anthracene-based epoxy resin) available from Mitsubishi chemical corporation; PG-100 and CG-500 manufactured by Osaka gas chemical company; "YL 7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL 7800" (fluorene-based epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 1010" (solid bisphenol a type epoxy resin) manufactured by mitsubishi chemical corporation; "jER 1031S" (tetrahydroxyphenylethane-type epoxy resin) manufactured by Mitsubishi chemical corporation, and the like. These may be used alone or in combination of two or more.

The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule.

The liquid epoxy resin is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a glycidyl amine type epoxy resin, or an epoxy resin having a butadiene structure, and more preferably a bisphenol a type epoxy resin or a bisphenol F type epoxy resin.

Specific examples of the liquid epoxy resin include: "828 US", "jER 828 EL", "825", "EPIKOTE 828 EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi chemical company; "jER 807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 152" (phenol novolac epoxy resin) manufactured by mitsubishi chemical corporation; "630 LSD" (glycidylamine-type epoxy resin) manufactured by Mitsubishi chemical corporation; "ZX 1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nissian Ciki Kaisha; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "CELLOXIDE 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Dailuo corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Dailuo corporation; "ZX 1658" (liquid 1, 4-glycidylcyclohexane-type epoxy resin) manufactured by Nissian iron and gold chemical Co., Ltd. These may be used alone or in combination of two or more.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (D-3), the amount ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1:1 to 1:20, more preferably 1:1.5 to 1:15, particularly preferably 1:2 to 1:10, in terms of mass ratio. By making the amount ratio of the liquid epoxy resin to the solid epoxy resin within the range, the desired effects of the present invention can be remarkably obtained.

The epoxy equivalent of the component (D-3) is preferably 50 g/eq.about 5000g/eq, more preferably 50 g/eq.about 3000g/eq, still more preferably 80 g/eq.about 2000g/eq, and still more preferably 110 g/eq.about 1000g/eq. When the content is within this range, the crosslinking density of the cured product of the photosensitive resin composition layer becomes sufficient, and an insulating layer having a small surface roughness can be provided.

The weight average molecular weight (Mw) of the component (D-3) is preferably 100 to 5000, more preferably 250 to 3000, further preferably 400 to 1500, from the viewpoint of remarkably obtaining the desired effect of the present invention.

From the viewpoint of improving the mechanical strength and the solubility resistance of a cured product of the photosensitive resin composition, the content of the (D-3) component is preferably 1 mass% or more, more preferably 1.5 mass% or more, and further preferably 2 mass% or more, when the nonvolatile component in the photosensitive resin composition is taken as 100 mass%. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit of the content of the (D-3) component is preferably 10 mass% or less, more preferably 5 mass% or less, particularly preferably 3 mass% or less.

From the viewpoint of remarkably obtaining the effect of the present invention, the content of the (D-3) component is preferably 0 mass% or more, more preferably 0.01 mass% or more, further preferably 0.1 mass% or more, preferably 1 mass% or less, further preferably 0.5 mass% or less, further preferably 0.3 mass% or less, with the total amount of the (D) component being 100 mass%.

< (E) at least one resin selected from the group consisting of an active ester resin, a maleimide resin and a vinyl resin

The photosensitive resin composition contains, as the component (E), at least one resin selected from the group consisting of an active ester resin, a maleimide resin, and a vinyl resin. When the component (E) is contained in the photosensitive resin composition, the dielectric constant, dielectric loss tangent and glass transition temperature can be improved.

Hereinafter, the active ester resin (hereinafter, sometimes referred to as "component (E1)"), the maleimide resin (hereinafter, sometimes referred to as "component (E2)") and the vinyl resin (hereinafter, sometimes referred to as "component (E3)") as the component (E) will be described.

((E1) active ester resin)

The (E1) active ester resin as the component (E) can react with the epoxy group of the component (D) to give a cured product having a low dielectric constant and a low dielectric loss tangent. The active ester resin may be used alone or in combination of two or more.

As the (E1) active ester resin, it is generally preferred to use a compound having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds. The active ester resin is preferably a compound obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac (phenol novolac) and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing 2 molecules of phenol with 1 molecule of dicyclopentadiene.

Specifically, as the (E1) active ester resin, dicyclopentadiene type active ester resin, naphthalene type active ester resin containing a naphthalene structure, active ester resin containing an acetyl compound of phenol novolac, active ester resin containing a benzoyl compound of phenol novolac are preferable, and among them, at least one selected from dicyclopentadiene type active ester resin and naphthalene type active ester resin is more preferable, and dicyclopentadiene type active ester resin is further more preferable. As the dicyclopentadiene type active ester resin, an active ester resin containing a dicyclopentadiene type diphenol structure is preferred. "Dicyclopentadiene-type diphenol structure" means a divalent structural unit formed from phenylene-dicyclopentylene (ジシクロペンチレン) -phenylene.

As commercially available products of the (E1) active ester resin, active ester resins having a dicyclopentadiene type diphenol structure include "EXB 9451", "EXB 9460S", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65 TM", "EXB-8000L-65 TM" (manufactured by DIC); examples of the active ester resin having a naphthalene structure include "EXB-8151-62T", "HPC-8150-60T", "HPC-8150-62T", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T", "EXB 9416-70 BK" (manufactured by DIC Co., Ltd.) and "PC 1300-02-65 MA" (manufactured by AIR WATER Co., Ltd.); examples of the active ester resin containing an acetylated novolak resin include "DC 808" (manufactured by Mitsubishi chemical corporation); examples of the active ester resin containing a benzoylate of a novolak resin include "YLH 1026" (manufactured by Mitsubishi chemical corporation); examples of the active ester resin of an acetylated phenol novolac resin include "DC 808" (manufactured by mitsubishi chemical corporation); examples of the active ester resin of the benzoylate of the novolak resin include "YLH 1026" (manufactured by mitsubishi chemical corporation), "YLH 1030" (manufactured by mitsubishi chemical corporation), and "YLH 1048" (manufactured by mitsubishi chemical corporation); and the like.

From the viewpoint of obtaining a cured product having a low dielectric constant and a low dielectric loss tangent, the active ester equivalent of the (E1) active ester resin is preferably from 50g/eq to 500g/eq, more preferably from 50g/eq to 400g/eq, and still more preferably from 100g/eq to 300g/eq. The active ester group equivalent is the mass of the active ester resin containing 1 equivalent of active ester groups.

(D) The amount ratio of the epoxy resin to the (E1) active ester resin, in terms of [ total number of epoxy groups of epoxy resin ]: [ total number of active groups of active ester resin ] is preferably 1: 0.01-1: 5, preferably 1: 0.3-1: 3, more preferably 1: 0.5-1: 2. here, the "number of epoxy groups of the epoxy resin" refers to a total value of all values obtained by dividing the mass of nonvolatile components of the epoxy resin present in the photosensitive resin composition by the epoxy equivalent weight. The "number of active groups of the active ester resin" refers to a total value of all the values obtained by dividing the mass of nonvolatile components of the active ester resin present in the photosensitive resin composition by the active ester group equivalent. By making the amount ratio of the (D) epoxy resin and the (E1) active ester resin within the range, the effects of the present invention can be remarkably obtained.

The content of the component (E1) is preferably 1 mass% or more, more preferably 1.5 mass% or more, further preferably 2 mass% or more, further preferably 15 mass% or less, further preferably 10 mass% or less, further preferably 8 mass% or less, based on 100 mass% of nonvolatile components in the photosensitive resin composition, from the viewpoint of obtaining a cured product excellent in dielectric constant and dielectric characteristics.

((E2) Maleimide resin)

The maleimide resin (E2) as the component (E) reacts with the ethylenically unsaturated group as the component (A) to give a cured product having a low dielectric constant and a low dielectric loss tangent. Among them, the maleimide resin (E2) does not include the above-mentioned components (A) to (D) and (E1). (E2) The maleimide resin may be used singly or in combination of two or more.

As the (E2) maleimide resin, a resin containing a maleimide group can be used. (E2) The number of maleimide groups per 1 molecule of the maleimide resin may be 1, or 2 or more, preferably 2. The maleimide group is represented by the following formula (E):

[ chemical formula 7]

(E2) The maleimide resin may be any resin containing a maleimide group. The (E2) maleimide resin is preferably at least one resin selected from the following (E2-1) to (E2-3):

(E2-1) a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of the maleimide group,

(E2-2) Maleimide Compound having an aromatic Ring directly bonded to the Nitrogen atom of the Maleimide group, and

(E2-3) a maleimide compound comprising a trimethylindan skeleton.

Here, the term "directly" means: in the component (E2-1), no other group is present between the nitrogen atom of the maleimide group and the aliphatic group having 5 or more carbon atoms; in the component (E2-2), no other group is present between the nitrogen atom of the maleimide and the aromatic ring.

Component- (E2-1) -

The component (E2-1) is a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of the maleimide. The component (E2-1) can be obtained, for example, by subjecting a component containing an aliphatic amine compound (e.g., a diamine compound having a dimer acid skeleton) and maleic anhydride, and optionally, a tetracarboxylic dianhydride to an imidization reaction.

Examples of the aliphatic group having 5 or more carbon atoms include an alkyl group, an alkylene group, and an alkenylene group.

The alkyl group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, still more preferably 50 or less carbon atoms, still more preferably 45 or less carbon atoms, and still more preferably 40 or less carbon atoms. The alkyl group may be linear, branched or cyclic, and among them, linear is preferred. Examples of such an alkyl group include pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. The alkyl group having 5 or more carbon atoms may have a substituent of an alkylene group having 5 or more carbon atoms. The alkyl group having 5 or more carbon atoms may be a part of an alkenyl group or a part of a polyene (alkapolyenyl) (the number of double bonds is preferably 2).

The alkylene group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, still more preferably 50 or less, still more preferably 45 or less, and still more preferably 40 or less. The alkylene group may be linear, branched or cyclic, and is preferably linear. Here, the cyclic alkylene group is a concept including "a case of being composed only of a cyclic alkylene group" and "a case of including both a linear alkylene group and a cyclic alkylene group". Examples of the alkylene group include a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, a hexadecylene group, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure. The alkylene group having 5 or more carbon atoms may be a part of an alkenylene group or a part of an alkenylene (alkarylene) (the number of double bonds is preferably 2).

The number of carbon atoms of the alkenylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, further preferably 50 or less, further preferably 45 or less, further preferably 40 or less. The alkenylene group may be linear, branched or cyclic, and is preferably linear. Here, the cyclic alkenylene group is a concept including "a case where the cyclic alkenylene group is composed only of" and "a case where both of the linear alkenylene group and the cyclic alkenylene group are included". Examples of such alkenylene groups include pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene, heptadecenylene, thirty-hexaenylene, a group having an octenylene-cyclohexenylene structure, a group having an octenylene-cyclohexenylene-octenylene structure, and a group having a propenylene-cyclohexenylene-octenylene structure.

As the component (E2-1), preferred are compounds represented by the following formula (E2-1-1):

[ chemical formula 8]

In the general formula (E2-1-1), M represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

M represents a divalent aliphatic group having 5 or more carbon atoms and optionally having a substituent. The divalent aliphatic group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, still more preferably 50 or less, still more preferably 45 or less, and still more preferably 40 or less carbon atoms. The aliphatic group may be linear, branched or cyclic, and among them, linear is preferred. Here, the cyclic aliphatic group is a concept including "a case where the cyclic aliphatic group is formed only" and "a case where both of the linear aliphatic group and the cyclic aliphatic group are included". Examples of the divalent aliphatic group include an alkylene group, an alkenylene group, and a polyalkenylene group (more preferably, the number of double bonds is 2). As the alkylene group and alkenylene group, those mentioned above are mentioned.

Examples of the substituent for M include a halogen atom, -OH, -O-C_1-10Alkyl, -N (C)_1-10Alkyl radical)₂、C_1-10Alkyl radical, C_2-30Alkenyl radical, C_2-30Alkynyl, C_6-10Aryl, -NH₂、-CN、-C(O)O-C_1-10Alkyl, -COOH, -C (O) H, -NO₂And the like. Here, the term "C_x-y"(x and y are positive integers, and x < y is satisfied) means that the number of carbon atoms of the organic group described immediately after the term is x to y. For example, "C_1-10The expression "alkyl" denotes an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring. The substituent is preferably an alkyl group having 5 or more carbon atoms.

L represents a single bond or a divalent linking group. As the divalent linking group, may be mentionedAlkyl, alkenylene, alkynylene, arylene, -C (═ O) -O-, -NR⁰-(R⁰Hydrogen atom, alkyl group having 1 to 3 carbon atoms), oxygen atom, sulfur atom, C (═ O) NR⁰A divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, a combination of 2 or more divalent groups of these, and the like. Alkylene groups, alkenylene groups, alkynylene groups, arylene groups, divalent groups derived from phthalimide, divalent groups derived from pyromellitic diimide, and groups in which 2 or more kinds of divalent groups are combined optionally have an alkyl group having 5 or more carbon atoms as a substituent. The divalent group derived from phthalimide means a divalent group derived from phthalimide, specifically a group represented by the general formula (E2-1-2). The divalent group derived from pyromellitic diimide means a divalent group derived from pyromellitic diimide, specifically a group represented by the general formula (E2-1-3). Wherein ". sup." represents a chemical bond;

[ chemical formula 9]

The alkylene group as the divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, particularly preferably an alkylene group having 1 to 40 carbon atoms. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylethylene group, a cyclohexylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, a hexadecylene group, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

The alkenylene group as the divalent linking group in L is preferably an alkenylene group having 2 to 50 carbon atoms, more preferably an alkenylene group having 2 to 45 carbon atoms, particularly preferably an alkenylene group having 2 to 40 carbon atoms. The alkenylene group may be linear, branched or cyclic. Examples of such alkenylene groups include methylvinylene, cyclohexenylene, pentenylene, hexenylene, heptenylene, octenylene, and the like.

The alkynylene group as the divalent linking group in L is preferably an alkynylene group having 2 to 50 carbon atoms, more preferably an alkynylene group having 2 to 45 carbon atoms, particularly preferably an alkynylene group having 2 to 40 carbon atoms. The alkynylene group may be linear, branched or cyclic. Examples of such an alkynylene group include methylacetylene, cyclohexylene, pentylene, hexylene, heptylene, octylene, and the like.

The arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, still more preferably an arylene group having 6 to 14 carbon atoms, and yet more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

The alkylene group, alkenylene group, alkynylene group, and arylene group as the divalent linking group in L may have a substituent. As the substituent, an alkyl group having 5 or more carbon atoms is preferred, as in the substituent for M in the general formula (E2-1-1).

Examples of the group consisting of a combination of 2 or more divalent groups in L include: a divalent group composed of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group composed of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a divalent group composed of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; and so on. Groups composed of a combination of 2 or more divalent groups can form a ring such as a condensed ring by the combination of the groups. The number of repeating units of a group consisting of 2 or more divalent groups may be 1 to 10.

Among these, L in the general formula (E2-1-1) is preferably an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, an alkylene group having 1 to 50 carbon atoms which may have a substituent, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, or a divalent group formed by combining 2 or more of these groups. Among them, as L, it is more preferable that: an alkylene group; a divalent group having a structure of alkylene-a divalent group derived from phthalimide-an oxygen atom-a divalent group derived from phthalimide; a divalent group having a structure of alkylene-a divalent group derived from phthalimide-oxygen atom-arylene-alkylene-arylene-oxygen atom-a divalent group derived from phthalimide; a divalent group having a structure of an alkylene-divalent group derived from pyromellitic diimide; a divalent group having a structure of alkynylene-a divalent group derived from phthalimide-an oxygen atom-a divalent group derived from phthalimide; a divalent group having the structure alkynylene-a divalent group derived from phthalimide-oxygen atom-arylene-alkynylene-arylene-oxygen atom-a divalent group derived from phthalimide; divalent radicals having the structure of alkynylene-a divalent radical derived from pyromellitic diimide.

The maleimide resin represented by the general formula (E2-1-1) is preferably a maleimide resin represented by the general formula (E2-1-4):

[ chemical formula 10]

In the general formula (E2-1-4), M¹Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and each Z independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, or a divalent group having an aromatic ring which may have a substituent. t represents an integer of 1 to 10.

M¹Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M¹The same as M in the general formula (E2-1-1).

Each Z independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, or a divalent group having an aromatic ring which may have a substituent. Examples of the divalent aliphatic group in Z include an alkylene group, an alkenylene group, and a polyalkenylene group (more preferably, the number of double bonds is 2). The divalent aliphatic group may be any of a chain, a branched chain and a cyclic group, and among them, a cyclic divalent aliphatic group having 5 or more carbon atoms, which may have a substituent, is preferable.

The number of carbon atoms of the alkylene group is preferably 6 or more, more preferably 8 or more, further preferably 50 or less, further preferably 45 or less, further preferably 40 or less. Examples of such alkylene groups include: a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like.

The number of carbon atoms of the alkenylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, further preferably 50 or less, further preferably 45 or less, further preferably 40 or less. The alkenylene group may be linear, branched or cyclic, and is preferably linear. Here, the cyclic alkenylene group is a concept including "a case where the cyclic alkenylene group is composed only of" and "a case where both of the linear alkenylene group and the cyclic alkenylene group are included". Examples of such alkenylene groups include: pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene, heptadecenylene, thirty-hexaenylene, a group having an octenylene-cyclohexenylene structure, a group having an octenylene-cyclohexenylene-octenylene structure, a group having a propenylene-cyclohexenylene-octenylene structure, and the like.

Examples of the aromatic ring in the divalent group having an aromatic ring represented by Z include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic diimide ring, an aromatic heterocycle, etc., and a benzene ring, a phthalimide ring, and a pyromellitic diimide ring are preferable. That is, as the divalent group having an aromatic ring, a divalent group having a benzene ring which may be substituted, a divalent group having a phthalimide ring which may be substituted, and a divalent group having a pyromellitic diimide ring which may be substituted are preferable. Examples of the divalent group having an aromatic ring include a group composed of a divalent group derived from phthalimide and an oxygen atom in combination; a group composed of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a group composed of an alkylene group and a divalent group derived from pyromellitic diimide; a divalent group derived from pyromellitic diimide; a group composed of a divalent group derived from phthalimide and an alkylene group; and the like. The arylene group is the same as the arylene group in the divalent linking group represented by L in the general formula (E2-1-1).

The alkylene group represented by Z and the divalent group having an aromatic ring may have a substituent. As the substituent, the same as the substituent optionally having M in the general formula (E2-1-1) can be mentioned.

Specific examples of the group represented by Z include the following groups. Wherein ". sup." represents a chemical bond;

[ chemical formula 11]

[ chemical formula 12]

The compound represented by the general formula (E2-1-1) is preferably any of the compounds represented by the general formula (E2-1-5) and the compounds represented by the general formula (E2-1-6);

[ chemical formula 13]

In the general formula (E2-1-5), M²And M³Each independently represents a divalent aliphatic group having 5 or more carbon atoms and optionally having a substituent, R⁴⁰Each independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group formed by combining 2 or more of these groups. t1 represents an integer of 1 to 10;

in the general formula (E2-1-6), M⁴、M⁶And M⁷Each independently represents an optionally substituted aliphatic group having 5 or more carbon atoms, M⁵Each independently represents a divalent group having an aromatic ring optionally having a substituent, R⁴¹And R⁴²Each independently represents an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

M²And M³Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M²And M³As the divalent aliphatic group having 5 or more carbon atoms represented by M in the general formula (E2-1-1), a triacontenylene group or a triacontenylene group is preferable.

R⁴⁰Each independently represents an oxygen atom, an arylene group, an alkylene group, or a combination of 2 or more divalent groups thereof. The arylene group and the alkylene group are the same as those in the divalent linking group represented by L in the general formula (E2-1-1). As R⁴⁰Preferably, the group is a combination of 2 or more divalent groups or an oxygen atom.

As R⁴⁰The group composed of a combination of 2 or more kinds of divalent groups in (1) includes a combination of an oxygen atom, an arylene group, and an alkylene group. Specific examples of the group consisting of 2 or more kinds of divalent groups include the following groups.

Wherein ". sup." represents a chemical bond;

[ chemical formula 14]

M⁴、M⁶And M⁷Each independently represents an aliphatic group having 5 or more carbon atoms which may have a substituent. M⁴、M⁶And M⁷As the aliphatic group having 5 or more carbon atoms which may have a substituent represented by M in the general formula (E2-1-1), a hexylene group, a heptylene group, an octylene group, a nonylene group and a decylene group are preferable, and an octylene group is more preferable.

M⁵Each independently represents a divalent group having an aromatic ring which may have a substituent. M⁵As the divalent group having an aromatic ring optionally having a substituent represented by Z in the general formula (E2-1-4), a combination of an alkylene group and a divalent group derived from pyromellitic diimide is preferable; the group comprising a combination of a divalent group derived from phthalimide and an alkylene group, more preferably a combination of an alkylene group and a divalent group derived from pyromellitic diimide. The arylene group and the alkylene group are the same as those in the divalent linking group represented by L in the general formula (E2-1-1).

As M⁵Specific examples of the group include the following groups. Wherein ". sup." represents a chemical bond;

[ chemical formula 15]

R⁴¹And R⁴²Each independently represents an alkyl group having 5 or more carbon atoms. R⁴¹And R⁴²As the alkyl group having 5 or more carbon atoms, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group are preferable, and a hexyl group and an octyl group are more preferable.

u1 and u2 each independently represent an integer of 1 to 15, preferably an integer of 1 to 10.

Specific examples of the component (E2-1) include the following compounds (E-i) to (E-iii), and are not limited to these specific examples.

Wherein v represents an integer of 1 to 10;

[ chemical formula 16]

[ chemical formula 17]

Specific examples of the component (E2-1) include "BMI 1500" (a compound of the formula (E-i) ")," BMI1700 "(a compound of the formula (E-ii)"), and "BMI 689" (a compound of the formula (E-iii)), which are manufactured by Designer polymers.

The weight average molecular weight (Mw) of the component (E2-1) is preferably 150 to 5000, more preferably 300 to 2500.

The maleimide group equivalent of the component (E2-1) is preferably 50g/eq to 2000g/eq, more preferably 100g/eq to 1000g/eq, and still more preferably 150g/eq to 500g/eq, from the viewpoint of remarkably obtaining the desired effect of the present invention. The maleimide group equivalent is the mass of the (E2-1) component containing 1 equivalent of maleimide group.

Component- (E2-2)

The component (E2-2) is a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide. The component (E2-2) can be obtained, for example, by subjecting a component containing an aromatic amine compound (such as an aromatic diamine compound) and maleic anhydride to imidization.

The aromatic ring may be carbocyclic or heterocyclic. Examples of the aromatic ring include monocyclic aromatic rings such as a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring; a fused ring formed by fusing at least 2 monocyclic aromatic rings such as a naphthalene ring, an anthracene ring, a benzofuran ring, an isobenzofuran ring, an indole ring, an isoindole ring, a benzothiophene ring, a benzimidazole ring, an indazole ring, a benzoxazole ring, a benzisoxazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring, and a phthalazine ring; and a fused ring in which 1 or more monocyclic non-aromatic rings are fused to 1 or more monocyclic aromatic rings, such as an indane ring, a fluorene ring, and a tetralin ring. Among them, as the aromatic ring, a monocyclic aromatic ring is preferable, and a benzene ring is more preferable.

As the component (E2-2), a maleimide compound represented by the following formula (E2-2-1) is preferred,

[ chemical formula 18]

In the formula, R^cEach independently represents a substituent; x^cEach independently represents a single bond, alkylene, alkenylene, -O-, -CO-, -S-, -SO-, -SO₂-, -CONH-, -NHCO-, -COO-, or-OCO- (preferably a single bond or alkylene); z^cEach independently represents a non-aromatic ring optionally having a substituent, or an aromatic ring optionally having a substituent (preferably an aromatic ring optionally having a substituent, particularly preferably a benzene ring optionally having a substituent); s represents an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, further preferably an integer of 1 to 20); t independently represents 0 or an integer of 1 or more; u independently represents an integer of 0 to 2 (preferably 0). Particularly preferred are maleimide compounds represented by the formulae (E2-2-2) to (E2-2-5).

[ chemical formula 19]

In the formula, R^c1、R^c2And R^c3Each independently represents an alkyl group; x^c1And X^c2Each independently represents a single bond or an alkylene group; s represents an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, further preferably an integer of 1 to 20); t' represents an integer of 1 to 5; u1, u2 and u3 each independently represent an integer of 0 to 2 (preferably 0). The s unit, t' unit, u1 unit, u2 unit, and u3 unit may be the same or different.

In another embodiment, the component (E2-2) is preferably a compound represented by the following formula (E2-2-6):

[ chemical formula 20]

In the formula, R³¹And R³⁶Represents a maleimido group, R³²、R³³、R³⁴And R³⁵Each independently represents a hydrogen atom, an alkyl group, or an aryl group, and each D independently represents a divalent aromatic group. m1 and m2 each independently represent an integer of 1 to 10, and a represents an integer of 1 to 100.

R in the formula (E2-2-6)³²、R³³、R³⁴And R³⁵Each independently represents a hydrogen atom, an alkyl group, or an aryl group, preferably a hydrogen atom.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an isopropyl group.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may be a single ring or a condensed ring. Examples of such aryl groups include phenyl, naphthyl and anthryl.

The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, -OH, -O-C_1-6Alkyl, -N (C)_1-10Alkyl radical)₂、C_1-10Alkyl radical, C_6-10Aryl, -NH₂、-CN、-C(O)O-C_1-10Alkyl, -COOH, -C (O) H, -NO₂And the like. Here, "C" is_p-qThe term "(p and q are positive integers, and p < q.) means that the organic group described immediately after the term has p to q carbon atoms. For example, "C_1-10The expression "alkyl" denotes an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a fused ring.

The above-mentioned substituent may further have a substituent (hereinafter, sometimes referred to as "secondary substituent"). As the secondary substituent, the same substituents as those described above may be used unless otherwise specified.

D in the formula (E2-2-6) represents a divalent aromatic group. Examples of the divalent aromatic group include phenylene, naphthylene, anthrylene, aralkyl, biphenylene, and biphenylaralkyl groups, and among them, biphenylene and biphenylaralkyl groups are preferable, and biphenylene is more preferable. The divalent aromatic group optionally has a substituent. As a substituent, with R in the formula (E2-2-6)³²The substituents which the alkyl group optionally has are the same.

m1 and m2 each independently represent an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3, further preferably 1 to 2, further preferably 1.

a represents an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 20, further preferably 1 to 5.

As the component (E2-2), a resin represented by the formula (E2-2-7):

[ chemical formula 21]

In the formula, R³⁷And R³⁸Represents a maleimide group. a1 represents an integer of 1 to 100.

a1 is the same as a in the formula (E2-2-6), and preferable ranges are the same.

Examples of commercially available products of the component (E2-2) include: "MIR-3000-70 MT" manufactured by Nippon chemical company; "BMI-50P" manufactured by KI-Chemical company; "BMI-1000", "BMI-1000H", "BMI-1100H", "BMI-4000", "BMI-5100", manufactured by Dahe chemical industry Co., Ltd; "BMI-4, 4' -BPE" manufactured by KI-Chemical company "," BMI-70 ", and" BMI-80 "manufactured by KI-Chemical company, and the like.

The weight average molecular weight (Mw) of the component (E2-2) is preferably 150 to 5000, more preferably 300 to 2500.

The equivalent of the maleimide group-containing functional group of the component (E2-2) is preferably 50 to 2000g/eq, more preferably 100 to 1000g/eq, still more preferably 150 to 500g/eq, particularly preferably 200 to 300g/eq.

Component- (E2-3) -

The component (E2-3) is a maleimide compound having a trimethylindan skeleton. The trimethylindan skeleton is represented by the following formula (E2-3-1).

[ chemical formula 22]

Substituents may be bonded to the benzene ring contained in the trimethylindane skeleton. Examples of the substituent include an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a halogen atom, a hydroxyl group, and a mercapto group;

the number of carbon atoms in the alkyl group is preferably 1 to 10. Examples of the alkyl group include methyl, ethyl, propyl, n-butyl, tert-butyl, and the like;

the number of carbon atoms of the alkyloxy group is preferably 1 to 10. Examples of the alkyloxy group include methoxy, ethoxy, propoxy, butoxy, and the like;

the number of carbon atoms of the alkylthio group is preferably 1 to 10. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, and a butylthio group;

the number of carbon atoms of the aryl group is preferably 6 to 10. Examples of the aryl group include phenyl, naphthyl, and the like;

the number of carbon atoms of the aryloxy group is preferably 6 to 10. Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, and the like;

the number of carbon atoms of the arylthio group is preferably 6 to 10. Examples of the arylthio group include phenylthio group, naphthylthio group and the like;

the number of carbon atoms of the cycloalkyl group is preferably 3 to 10. Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, and the like;

examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom and the like.

In the foregoing substituents, the hydrogen atoms of the alkyl group, the alkyloxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group, and the cycloalkyl group are optionally substituted with a halogen atom.

The number of substituents bonded to 1 benzene ring included in the trimethylindane skeleton may be 1 or 2 or more. The number of substituents bonded to the benzene ring included in the trimethylindane skeleton is usually 0 or more and 3 or less. When the number of the substituents is 2 or more, those 2 or more substituents may be the same or different. Among these, it is preferable that no substituent is bonded to the benzene ring contained in the trimethylindane skeleton.

The number of trimethylindan skeletons contained in 1 molecule of component (E2-3) may be 1, or 2 or more. The upper limit may be, for example, 10 or less, 8 or less, 7 or less, or 6 or less.

The component (E2-3) preferably contains an aromatic ring skeleton in addition to the aforementioned trimethylindan skeleton. The number of ring-forming carbon atoms of the aromatic ring skeleton is preferably 6 to 10. Examples of the aromatic ring skeleton include a benzene ring skeleton and a naphthalene ring skeleton. The number of the aromatic ring skeletons contained in 1 molecule of the component (E2-3) is preferably 1 or more, more preferably 2 or more, further preferably 6 or less, further preferably 4 or less, particularly preferably 3 or less. When the component (E2-3) contains 2 or more aromatic ring skeletons in addition to the trimethylindan skeleton, the aromatic ring skeletons may be the same or different.

The aromatic ring contained in the aforementioned aromatic ring skeleton may be bonded with a substituent. Examples of the substituent include: the substituent described above as a substituent that can be bonded to the benzene ring contained in the trimethylindane skeleton, and a nitro group. The number of substituents bonded to 1 aromatic ring may be 1 or 2 or more. The number of substituents bonded to the aromatic ring is usually 0 or more and 4 or less. When the number of the substituents is 2 or more, those 2 or more substituents may be the same or different.

The component (E2-3) preferably contains a divalent aliphatic hydrocarbon group in addition to the above-mentioned trimethylindan skeleton. In particular, when the (E2-3) component contains an aromatic ring skeleton other than the benzene ring contained in the trimethylindane skeleton, it is preferable that the (E2-3) component contains a divalent aliphatic hydrocarbon group. In this case, the divalent aliphatic hydrocarbon group is preferably a group in which a benzene ring having a trimethylindan skeleton is bonded to an aromatic ring skeleton. In addition, the divalent aliphatic hydrocarbon group is preferably formed by linking aromatic ring skeletons to each other.

The divalent aliphatic hydrocarbon group has preferably 1 or more, more preferably 12 or less, still more preferably 8 or less, particularly preferably 5 or less carbon atoms. The divalent aliphatic hydrocarbon group is more preferably an alkylene group which is a saturated aliphatic hydrocarbon group. Examples of the divalent aliphatic hydrocarbon group include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; ethylidene (-CH (CH)₃) -) propylidene (-CH (CH)₂CH₃) -) isopropylidene (-COOR-), C (-CH (CH)₃)₂-) ethylmethylmethylene (-C (CH)₃)(CH₂CH₃) -) diethyl methylene (-C (CH)₂CH₃)₂-) and the like; and the like. When (E2-3) the maleimide compound containing a trimethylindan skeleton contains 2 or more divalent aliphatic hydrocarbon groups in addition to the trimethylindan skeleton, those divalent aliphatic hydrocarbon groups may be the same or different.

The component (E2-3) preferably has a structure represented by the following formula (E2-3-2). The whole of the component (E2-3) may have a structure represented by the formula (E2-3-2), or a part of the component (E2-3) may have a structure represented by the formula (E2-3-2);

[ chemical formula 23]

(wherein Ar is^a1Represents a divalent aromatic hydrocarbon group optionally having a substituent; r^a1Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; r^a2Each independently represents a carbon atomAn alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; r^a3Each independently represents a divalent aliphatic hydrocarbon group; n is_a1Represents a positive integer; n is_a2Each independently represents an integer of 0 to 4; n is_a3Each independently represents an integer of 0 to 3. R^a1The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups of (a) are optionally replaced with halogen atoms. R^a2The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups of (a) are optionally replaced with halogen atoms. n is_a2When 2 to 4, R^a1May be the same or different within the same ring. n is_a3When 2 to 3, R^a2May be the same or different within the same ring).

In the formula (E2-3-2), Ar^a1Represents a divalent aromatic hydrocarbon group optionally having a substituent. The divalent aromatic hydrocarbon group preferably has 6 or more carbon atoms, more preferably 20 or less carbon atoms, and still more preferably 16 or less carbon atoms. Examples of the divalent aromatic hydrocarbon group include phenylene and naphthylene. Examples of the substituent which the divalent aromatic hydrocarbon group may have include an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, and a mercapto group. The hydrogen atom of each substituent is in turn optionally replaced by a halogen atom. Specific examples of these substituents include, for example, the same substituents as those that can be bonded to the benzene ring contained in the trimethylindane skeleton. When the divalent aromatic hydrocarbon group has a substituent, the number of the substituent is preferably 1 to 4. When the number of the substituents of the divalent aromatic hydrocarbon group is 2 or more, those 2 or more substituents may be the same or different. Wherein Ar is^a1Divalent aromatic hydrocarbon groups having no substituent are preferred.

In the formula (E2-3-2), R^a1Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group. The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups are optionally replaced with halogen atoms. Specific examples of these groups include, for example, the same groups as those substituents that can be bonded to the benzene ring included in the trimethylindane skeleton. Wherein R is^a1More preferably at least one group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms.

In the formula (E2-3-2), R^a2Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group. The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups are optionally replaced with halogen atoms. Specific examples of these groups include, for example, the same groups as those substituents that can be bonded to the benzene ring included in the trimethylindane skeleton. Wherein R is^a2More preferably at least one group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms.

In the formula (E2-3-2), R^a3Each independently represents a divalent aliphatic hydrocarbon group. The preferable range of the divalent aliphatic hydrocarbon group is as shown above.

In the formula (E2-3-2), n_a1Representing a positive integer. n is_a1It is preferably 1 or more, more preferably 10 or less, still more preferably 8 or less.

In the formula (E2-3-2), n_a2Each independently represents an integer of 0 to 4. n is_a2Preferably 2 or 3, more preferably 2. A plurality of n_a2May be different but is preferably the same. When n is_a2When it is 2 or more, plural R^a1May be the same or different within the same ring.

In the formula (E2-3-2), n_a3Each independently represents an integer of 0 to 3. A plurality of n_a3May be different but is preferably the same. n is_a3Preferably 0.

The component (E2-3) particularly preferably has a structure represented by the following formula (E2-3-3). The whole of the component (E2-3) may have a structure represented by the formula (E2-3-3), or a part of the component (E2-3) may have a structure represented by the formula (E2-3-3);

[ chemical formula 24]

(in the formula, R^b1Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; r^b2Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; n is_b1Represents a positive integer; n is_b2Each independently represents an integer of 0 to 4; n is_b3Each independently represents an integer of 0 to 3. R^b1The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups of (a) are optionally replaced with halogen atoms. R^b2The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups of (a) are optionally replaced with halogen atoms. When n is_b2When 2 to 4, R^b1May be the same or different within the same ring. When n is_b3When 2 to 3, R^b2May be the same or different within the same ring).

In the formula (E2-3-3), R^b1、R^b2、n_b1、n_b2And n_b3Are respectively reacted with R in the formula (E2-3-2)^a1、R^a2、n_a1、n_a2And n_a3The same is true.

The component (E2-3) may further contain a structure represented by the following formula (E2-3-4);

[ chemical formula 25]

In the formula (E2-3-4), R^c1、R^c2、n_c2And n_c3Are respectively reacted with R in the formula (E2-3-2)^a1、R^a2、n_a2And n_a3The same is true. Further, in the formula (E2-3-4), n_c1The number of the repeating units is an integer of 1 to 20. Further, in the formula (E2-3-4), it represents a chemical bond. For example, in the formula (E2-3-2), n is n for the component (E2-3)_a23 or less, and 2 or more of R are not bonded to the maleimide group in the ortho-position and para-position of the maleimide group-bonded benzene ring with respect to the maleimide group^a1In the case of (2), the structure represented by the above formula (E2-3-4) may be included in combination with the structure represented by the formula (E2-3-2). Further, for example, in the component (E2-3), n is in the formula (E2-3-3)_b23 or less, and 2 or more of the ortho-and para-positions of the maleimide group-bonded benzene ring to the maleimide group are not bonded with R^b1In the case of (2), the structure represented by the above formula (E2-3-4) may be included in combination with the structure represented by the formula (E2-3-3).

The component (E2-3) may be used alone in 1 kind, or 2 or more kinds may be used in combination in an arbitrary ratio.

The maleimide group equivalent of the component (E2-3) is preferably at least 50g/eq, more preferably at least 100g/eq, particularly preferably at least 200g/eq, still more preferably at most 2000g/eq, still more preferably at most 1000g/eq, particularly preferably at most 800g/eq. The maleimide group equivalent represents the mass of the maleimide compound per 1 equivalent of maleimide group. When the maleimide group equivalent of the component (E2-3) is in the above range, the effect of the present invention can be remarkably obtained.

The method for producing the component (E2-3) is not particularly limited. The component (E2-3) can be produced, for example, by the method described in Japanese patent publication Kokai publication Kohyo publication No. 2020 and 500211. According to the production method described in Japanese patent laid-open publication No. 2020-500211, a maleimide compound having a distribution in the number of repeating units of the trimethylindane skeleton can be obtained. The maleimide compound obtained by this method has a structure represented by the following formula (E2-3-5). Thus, the (E2-3) component may comprise: a maleimide compound having a structure represented by the formula (E2-3-5).

[ chemical formula 26]

(in the formula, R¹Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; r²Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; n is₁Represents an average number of repeating units of 0.95 to 10.0; n is₂Each independently represents an integer of 0 to 4; n is₃Each independently represents an integer of 0 to 3. R¹The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups of (a) are optionally replaced with halogen atoms. R²Alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, alkyl, alkoxy, aryloxy, or, aryloxy, or aryloxy, or aryloxy,and the hydrogen atom of the cycloalkyl group is optionally replaced by a halogen atom. When n is₂When 2 to 4, R¹May be the same or different within the same ring. When n is₃When 2 to 3, R²May be the same or different within the same ring).

In the formula (E2-3-5), R¹、R²、n₂And n₃Are respectively reacted with R in the formula (E2-3-2)^a1、R^a2、n_a2And n_a3The same is true.

In the formula (E2-3-5), n₁Represents the average number of repeating units, and is in the range of 0.95 to 10.0. According to the production method described in Japanese patent laid-open publication No. 2020-500211, a group of maleimide compounds having a structure represented by the formula (E2-3-5) can be obtained. The average number of repeating units n as represented by formula (E2-3-5)₁As can be seen from the graph showing that the content of the maleimide compound having a structure represented by the formula (E2-3-5) obtained in this way was less than 1.00, the maleimide compound having a repeating unit number of 0 of the trimethylindane skeleton was contained. Therefore, the maleimide compound having a repeating unit of 0 trimethyl indane skeleton is removed from the maleimide compound having a structure represented by the formula (E2-3-5) by purification to obtain the (E2-3) component, and only the (E2-3) component thus obtained may be contained in the photosensitive resin composition. However, the effects of the present invention can be obtained even when a maleimide compound having a repeating unit of a trimethylindane skeleton of 0 number is contained in the photosensitive resin composition. In addition, in the case of omitting purification, the cost can be controlled. Therefore, it is preferable that the photosensitive resin composition contains "a maleimide compound having a structure represented by the formula (E2-3-5)" instead of the maleimide compound having a repeating unit number of trimethylindane skeleton of 0.

In the formula (E2-3-5), the average number of repeating units n₁It is preferably at least 0.95, more preferably at least 0.98, still more preferably at least 1.0, particularly preferably at least 1.1, preferably at most 10.0, more preferably at most 8.0, still more preferably at most 7.0, particularly preferably at most 6.0. Average number of repeating units n₁In the above range, it is apparentThe effects of the present invention are obtained. In particular, the glass transition temperature of the photosensitive resin composition can be effectively increased.

Examples of the structure represented by the formula (E2-3-5) include the following structures.

[ chemical formula 27]

The maleimide compound comprising the structure represented by formula (E2-3-5) may further comprise the structure represented by the aforementioned formula (E2-3-4). For example, in the case of a maleimide compound comprising a structure represented by the formula (E2-3-5), n is in the formula (E2-3-5)₂3 or less, and 2 or more of the ortho-and para-positions of the maleimide group-bonded benzene ring to the maleimide group are not bonded with R¹In the case of (2), the structure represented by the formula (E2-3-4) may be included in combination with the structure represented by the formula (E2-3-5).

The molecular weight distribution Mw/Mn calculated by Gel Permeation Chromatography (GPC) measurement of the maleimide compound having a structure represented by the formula (E2-3-5) is preferably in a specific range. The molecular weight distribution is a value obtained by dividing the weight average molecular weight Mw by the number average molecular weight Mn, and is represented by "Mw/Mn". Specifically, the molecular weight distribution Mw/Mn of the maleimide compound having the structure represented by the formula (E2-3-5) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, further preferably 1.2 to 3.6, particularly preferably 1.3 to 3.4. When the molecular weight distribution Mw/Mn of the maleimide compound comprising the structure represented by the formula (E2-3-5) is in the aforementioned range, the effects of the present invention can be remarkably obtained.

In the maleimide compound comprising the structure represented by the formula (E2-3-5), the average number of repeating units n₁The amount of the maleimide compound of 0 is preferably in a specific range. The average number of repeating units n in the GPC measurement of the maleimide compound having a structure represented by the formula (E2-3-5)₁The amount of the maleimide compound of 0 can be expressed in area% based on the result of its GPC measurement. In detail, the foregoing is utilizedIn the chromatogram obtained by GPC measurement, the "average number of repeating units n" is used₁The ratio (% by area) of the peak area of the maleimide compound of 0 "to the total area of the peaks of the maleimide compound having the structure represented by the formula (E2-3-5)" may be represented by the average repeating unit number n₁An amount of the maleimide compound of 0. Specifically, the average number of repeating units n is calculated based on 100 area% of the total amount of the maleimide compound having a structure represented by the formula (E2-3-5)₁The amount of the maleimide compound of 0 is preferably 32 area% or less, more preferably 30 area% or less, further preferably 28 area% or less. Average number of repeating units n₁When the amount of the maleimide compound of 0 is in the foregoing range, the effect of the present invention can be remarkably obtained.

The maleimide group equivalent of the maleimide compound having a structure represented by the formula (E2-3-5) is preferably in the same range as that of the above-mentioned component (E2-3). When the maleimide equivalent of the maleimide compound having a structure represented by formula (E2-3-5) is in the above range, the effect of the present invention can be remarkably obtained.

The content of the component (E2) is preferably 0.5 mass% or more, more preferably 1 mass% or more, further preferably 1.5 mass% or more, further preferably 10 mass% or less, further preferably 5 mass% or less, further preferably 3 mass% or less, based on 100 mass% of nonvolatile components in the photosensitive resin composition, from the viewpoint of obtaining a cured product excellent in dielectric constant and dielectric characteristics.

((E3) vinyl resin)

The vinyl resin (E3) as the component (E) can react with the ethylenically unsaturated group of the component (A) to give a cured product having a low dielectric constant and a low dielectric loss tangent. However, the vinyl resin (E3) does not contain any of the resins belonging to the components (A) to (D), the component (E1) and the component (E2). (E3) The vinyl resin may be used alone or in combination of two or more.

As the (E3) vinyl resin, a resin containing a vinyl group (-CH ═ CH) can be used₂) The resin of (4). Of vinyl resinsThe number of vinyl groups per 1 molecule may be 1, or 2 or more, preferably 2.

(E3) The vinyl resin is only required to have a vinyl group (-CH ═ CH)₂) That is, the concept also includes, for example, a resin containing a vinyl group, a vinylphenyl group, an allyl group, and a maleic acyl group.

The vinyl resin may be any resin containing a vinyl group. The vinyl resin (E3) is preferably at least 1 selected from the group consisting of (E3-1) to (E3-3):

(E3-1) vinyl resin containing polyphenylene ether skeleton,

(E3-2) vinyl resin having polyethylene skeleton, and

(E3-3) an allyl group-containing resin.

Component- (E3-1) -

The component (E3-1) is a vinyl resin containing a polyphenylene ether skeleton. Examples of the component (E3-1) include compounds represented by the following formula (E3-1-1):

[ chemical formula 28]

(in the formula (E3-1-1), L¹Represents a divalent linking group; r^B11、R^B12、R^B13、R^B21、R^B22And R^B23Each independently represents a hydrogen atom or an alkyl group; r^B14、R^B15、R^B24And R^B25Each independently represents an alkyl group; r^B16And R^B26Each independently represents an alkylene group; m is_b11And m_b21Each independently represents 0 or 1; m is_b12、m_b13、m_b22And m_b23Each independently represents an integer of 0 to 4; m is_b14And m_b24Each independently represents an integer of 0 to 300; m is_b15And m_b25Each independently represents 0 or 1).

In the formula (E3-1-1), L¹Represents a divalent linking group. Examples of the divalent linking group include alkylene, alkenylene, arylene, alkylarylene and heteroaryleneRadical, -O-, -NH-, -NR^x-、-CO-、-CS-、-SO-、-SO₂-, -C (═ O) O-, -NHC (═ O) -, -NC (═ O) N-, -NHC (═ O) O-, -C (═ O) -, -S-, and a combination of a plurality of these. R^xRepresents a hydrocarbon group having 1 to 12 carbon atoms. L is¹The number of carbon atoms of (B) is usually 60 or less, preferably 48 or less, more preferably 36 or less, particularly preferably 24 or less.

In the formula (E3-1-1), R^B11、R^B12、R^B13、R^B21、R^B22And R^B23Each independently represents a hydrogen atom or an alkyl group. R^B11、R^B12、R^B13、R^B21、R^B22And R^B23Can be reacted with R in the formula (E3-1-1)^A1、R^A2And R^A3The same is true. Wherein R is^B11And R^B21Preferably a hydrogen atom or a methyl group, R^B12、R^B13、R^B22And R^B23Preferably a hydrogen atom.

In the formula (E3-1-1), R^B14、R^B15、R^B24And R^B25Each independently represents an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, further preferably 1 to 2. The alkyl group may be linear, branched or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group. Wherein R is^B14、R^B15、R^B24And R^B25Methyl is preferred.

In the formula (E3-1-1), R^B16And R^B26Each independently represents an alkylene group. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 3. The alkylene group is preferably a linear alkylene group, more preferably a methylene group.

In the formula (E3-1-1), m_b11And m_b21Each independently represents 0 or 1.

In the formula (E3-1-1), m_b12、m_b13、m_b22And m_b23Each independently represents an integer of 0 to 4. m is_b12、m_b13、m_b22And m_b23Preferably 1 to 4, more preferably 2 to 3, particularlyThe other is 2.

In the formula (E3-1-1), m_b14And m_b24Each independently represents an integer of 0 to 300. In detail, m_b14And m_b24Usually 0 or more, preferably 1 or more, usually 300 or less, preferably 100 or less, more preferably 50 or less, further preferably 20 or less, particularly preferably 10 or less.

In the formula (E3-1-1), m_b15And m_b25Each independently represents 0 or 1. m is_b11When is 0, m_b15Preferably 1, m_b11When is 1, m_b15Preferably 0. Furthermore, m_b21When is 0, m_b25Preferably 1, m_b21When is 1, m_b25Preferably 0.

As preferable examples of the compound represented by the formula (E3-1-1), compounds represented by the following formula (E3-1-2) can be mentioned.

[ chemical formula 29]

(in the formula (E3-1-2), L²Represents a divalent linking group; r^C15And R^C25Each independently represents an alkyl group; r^C16And R^C26Each independently represents an alkylene group; m is_c14And m_c24Each independently represents an integer of 0 to 300).

In the formula (E3-1-2), L²Represents a divalent linking group. L is²May be reacted with L in the formula (E3-1-1)¹The same is true. Wherein L is²A divalent group represented by the following formula (E3-1-3) is preferred.

[ chemical formula 30]

(in the formula (E3-1-3), X¹～X⁸Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. Represents a chemical bond).

In the formula (E3-1-2),R^C15and R^C25Each independently represents an alkyl group. R^C15And R^C25Can be reacted with R in the formula (E3-1-1)^B14The same is true. Wherein R is^C15And R^C25Methyl is preferred.

In the formula (E3-1-2), R^C16And R^C26Each independently represents an alkylene group. R^C16And R^C26Can be reacted with R in the formula (E3-1-1)^B16And R^B26The same is true. Wherein R is^C16And R^C26And methylene is more preferable.

In the formula (E3-1-2), m_c14And m_c24Each independently represents an integer of 0 to 300. m is_c14And m_c24Can be reacted with m in the formula (E3-1-1)_b14And m_b24The same is true. Further, in the formula (E3-1-2), m is preferred_c14And m_c24Except for the case where one of them is 0.

Examples of the compound represented by the formula (E3-1-2) include compounds represented by the following formula (E3-1-4). In the formula (E3-1-4), m_c14And m_c24Represents the same number as in the formula (E3-1-2). The compound represented by the formula (E3-1-4) is available as "OPE-2 St" manufactured by Mitsubishi gas chemical company.

[ chemical formula 31]

Further preferable examples of the compound represented by the formula (E3-1-1) include a compound represented by the following formula (E3-1-5).

[ chemical formula 32]

(in the formula (E3-1-5), L³Represents a divalent linking group; r^D11And R^D21Each independently represents a hydrogen atom or an alkyl group; r^D14、R^D15、R^D24And R^D25Each independently represents an alkyl group; m is_d14And m_d24Each independently represents an integer of 0 to 300).

In the formula (E3-1-5), L³Represents a divalent linking group. L is³Can be reacted with L in the formula (B2)¹The same is true. Wherein L is³Preferably selected from alkylene, alkenylene, -O-, -NR^x-、-CO-、-CS-、-SO-、-SO₂Any of-is preferably an alkylene group, particularly preferably isopropylidene (-C (CH)₃)₂-)。

In the formula (E3-1-5), R^D11And R^D21Each independently represents a hydrogen atom or an alkyl group. R^D11And R^D21Can be reacted with R in the formula (E3-1-1)^B11And R^B21The same is true. Wherein R is^D11And R^D21Methyl is preferred.

In the formula (E3-1-5), R^D14、R^D15、R^D24And R^D25Each independently represents an alkyl group. R^D14、R^D15、R^D24And R^D25Can be reacted with R in the formula (E3-1-1)^B14The same is true. Wherein R is^D14、R^D15、R^D24And R^D25Methyl is preferred.

In the formula (E3-1-5), m_d14And m_d24Each independently represents an integer of 0 to 300. m is_d14And m_d24Can be reacted with m in the formula (E3-1-1)_b14And m_b24The same is true. Furthermore, m_b14And m_b24The total of (2) or more is preferred.

Examples of the compound represented by the formula (E3-1-5) include compounds represented by the following formula (E3-1-6). In the formula (E3-1-6), L³、m_d14And m_d24The same as in formula (E3-1-5). The compound represented by the formula (E3-1-4) can be obtained as "NORYL SA 9000" manufactured by SABIC.

[ chemical formula 33]

Component- (E3-2)

The component (E3-2) is a vinyl resin having a polyethylene skeleton. Examples of the component (E3-2) include polymers containing a structural unit represented by the following formula (E3-2-1);

[ chemical formula 34]

(in the formula (E3-2-1), R^E1、R^E2And R^E3Each independently represents a hydrogen atom or an alkyl group; r^E4Each independently represents an alkyl group; r^E5、R^E6And R^E7Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m is_e1Represents 0 or 1; m is_e2Represents an integer of 0 to 4; represents a chemical bond).

In the formula (E3-2-1), R^E1、R^E2And R^E3Each independently represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 18, more preferably 1 to 12, further preferably 1 to 6, particularly preferably 1 to 2. The alkyl group may be linear, branched or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group. Wherein R is^E1、R^E2And R^E3Preferably a hydrogen atom.

In the formula (E3-2-1), R^E4Each independently represents an alkyl group. R^E4Can be reacted with R in the formula (E3-1-1)^B14The same is true.

In the formula (E3-2-1), R^E5、R^E6And R^E7Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Wherein R is^E5、R^E6And R^E7Preferably a hydrogen atom.

In the formula (E3-2-1), m_e1Represents 0 or 1, preferably 0.

In the formula (E3-2-1), m_e2Represents an integer of 0 to 4, preferably 0.

The molar content of the structural unit represented by the formula (E3-2-1) is preferably in a specific range with respect to 100 mol% of the total of all the structural units contained in the polymer comprising the structural unit represented by the formula (E3-2-1). Specifically, the molar content of the structural unit represented by the formula (E3-2-1) is preferably from 2 to 95 mol%, more preferably from 8 to 81 mol%. Further, the average number of the structural units represented by the formula (E3-2-1) contained in the molecule of the polymer 1 is preferably 1 to 160, more preferably 3 to 140.

The polymer comprising the structural unit represented by the formula (E3-2-1) may further comprise an arbitrary structural unit in combination with the structural unit represented by the formula (E3-2-1). Examples of the optional structural unit include a structural unit represented by the following formula (E3-2-2):

[ chemical formula 35]

(in the formula (E3-2-2), R^E8、R^E9And R^E10Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Ar (Ar)^E1Represents an optionally substituted aryl group. As Ar^E1Examples of the substituent that may be contained include an alkyl group having 1 to 6 carbon atoms. Represents a chemical bond).

Examples of the polymer containing a structural unit represented by the formula (E3-2-2) include a copolymer containing a structural unit represented by the following formula (E3-2-3), a structural unit represented by the following formula (E3-2-4), and a structural unit represented by the following formula (E3-2-5) in combination. In the formulae (E3-2-3), (E3-2-4) and (E3-2-5), the symbols represent a bond. In the copolymer, the molar contents of the structural unit represented by the formula (E3-2-3), the structural unit represented by the formula (E3-2-4), and the structural unit represented by the formula (E3-2-5) are 8 to 54 mol%, 0 to 92 mol%, and 0 to 89 mol%, respectively. In addition, the average numbers of the structural unit represented by the formula (E3-2-3), the structural unit represented by the formula (E3-2-4) and the structural unit represented by the formula (E3-2-5) contained in the molecule of the copolymer 1 are respectively 1-160, 0-350 and 0-270. The copolymer is available as "ODV-XET (X03)", "ODV-XET (X04)" and "ODV-XET (X05)" manufactured by Nikko-Tekko chemical Co., Ltd.;

[ chemical formula 36]

The component (E3-2) may be used alone in 1 kind, or 2 or more kinds may be used in combination in an arbitrary ratio.

The vinyl equivalent of the component (E3-2) is preferably 250 g/eq.1200 g/eq.more preferably 300 g/eq.1100 g/eq.. The radical polymerizable unsaturated group equivalent means the mass of the radical polymerizable aromatic resin per 1 equivalent of vinyl group. When the radical polymerizable unsaturated group equivalent of the component (E3-2) is in the above range, the effects of the present invention can be remarkably obtained.

The weight average molecular weight of the component (E3-2) is preferably 1000 to 40000, more preferably 1500 to 35000. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.

Component- (E3-3) -

(E3-3) the allyl group-containing resin means a resin having at least 1 allyl group in the molecule. The component (E3-3) preferably has 1 or more allyl groups per 1 molecule, more preferably 2 or more allyl groups. The lower limit is not particularly limited, and is preferably 10 or less, more preferably 5 or less.

In addition, from the viewpoint of remarkably obtaining the effect desired by the present invention, the component (E3-3) preferably has any of a benzoxazine ring, a phenol ring (phenol ring), an isocyanuric acid ring (イソシアヌル ring), an epoxy group, and a carboxylic acid derivative having a cyclic structure in addition to the allyl group.

The component (E3-3) having a benzoxazine ring is preferably bonded to any one of a nitrogen atom of the benzoxazine ring and a benzene ring, more preferably bonded to a nitrogen atom.

Examples of the (E3-3) component having a phenol ring include an allyl group-containing cresol resin, an allyl group-containing phenol novolac (phenol resin), and an allyl group-containing cresol novolac resin.

The component (E3-3) having an isocyanuric acid structure is preferably one in which the nitrogen atom of the isocyanuric acid structure is directly bonded to an allyl group. Examples of the (E3-4) component having an isocyanuric acid structure include allyl isocyanurate, diallyl isocyanurate, and triallyl isocyanurate.

The component (E3-3) having an epoxy group preferably contains 2 or more epoxy groups in 1 molecule. Further, the component (E3-3) having an epoxy group preferably has an aromatic structure, and when 2 or more components (E3-3) having an epoxy group are used, at least 1 is more preferably an aromatic structure. Aromatic structures are chemical structures generally defined as aromatic, and also include polycyclic aromatic and aromatic heterocycles. The component (E3-3) having an epoxy group preferably has a bisphenol structure, and examples of the bisphenol structure include bisphenol A type, bisphenol F type, and bisphenol AF type.

The component (E3-3) having the "carboxylic acid derivative having a cyclic structure" is preferably allyl carboxylate having a cyclic structure. The cyclic structure may be any of a cyclic group containing an alicyclic structure and a cyclic group containing an aromatic ring structure. In addition, the cyclic group may be a ring skeleton composed of hetero atoms in addition to carbon atoms. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom is preferable. The number of hetero atoms may be 1 or 2 or more in the above ring.

Examples of the carboxylic acid having a cyclic structure include isocyanuric acid, bibenzoic acid, phthalic acid, and cyclohexanedicarboxylic acid. Examples of the component (E3-3) having the "carboxylic acid derivative having a cyclic structure" include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl bibenzoate, allyl bibenzoate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, allyl cyclohexanedicarboxylate, and diallyl cyclohexanedicarboxylate.

As the component (E3-3), commercially available products can be used. Examples of commercially available products include: MEH-8000H and MEH-8005 (phenol ring-containing (E3-3)) manufactured by Minghe & Chemicals Inc.; "RE-810 NM" (component (E3-3) having an epoxy group) manufactured by Nippon Chemicals Co., Ltd.; ALP-d (component (E3-3) having a benzoxazine ring, manufactured by four national chemical industries, Ltd.); L-DAIC (component (E3-3) having an isocyanurate ring) manufactured by Sizhou chemical industry Co., Ltd.; "TAIC" (component (triallyl isocyanurate) (E3-3) having an isocyanurate ring) manufactured by japan chemical company; "MDAC" (component (E3-3) having a cyclohexanedicarboxylic acid derivative) manufactured by OSAKA SODA; "DAD" (diallyl bibenzoate) manufactured by Nisshoku Techno Fine Chemical); DAISO DAP MONOMER (diallyl phthalate) manufactured by OSAKA SODA.

The allyl equivalent of the (E3-3) component is preferably 20g/eq to 1000g/eq, more preferably 50g/eq to 500g/eq, and still more preferably 100g/eq to 300g/eq, from the viewpoint of remarkably obtaining the desired effect of the present invention. The allyl equivalent is the mass of the (E3-3) component containing 1 equivalent of allyl group.

The content of the component (E3) is preferably 1 mass% or more, more preferably 1.5 mass% or more, further preferably 2 mass% or more, further preferably 15 mass% or less, further preferably 10 mass% or less, further preferably 8 mass% or less, based on 100 mass% of nonvolatile components in the photosensitive resin composition, from the viewpoint of obtaining a cured product excellent in dielectric constant and dielectric characteristics.

The component (E) preferably contains at least one selected from the group consisting of an active ester resin, a maleimide resin and a vinyl resin, more preferably contains an active ester resin, and still more preferably contains an "active ester resin" and at least one selected from the group consisting of a maleimide resin and a vinyl resin, from the viewpoint of obtaining a cured product having excellent dielectric constant and dielectric loss tangent.

The total content of the component (E) is preferably 1% by mass or more, more preferably 1.5% by mass or more, further preferably 2% by mass or more, further preferably 20% by mass or less, further preferably 15% by mass or less, further preferably 10% by mass or less, based on 100% by mass of nonvolatile components in the photosensitive resin composition, from the viewpoint of obtaining a cured product excellent in dielectric constant and dielectric characteristics.

(F) curing Accelerator

The photosensitive resin composition may further contain (F) a curing accelerator as an optional component in addition to the above components. (F) One of the components may be used alone, or two or more of the components may be used in combination.

Examples of the component (F) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo (5,4,0) -undecene, and preferably 4-dimethylaminopyridine and 1, 8-diazabicyclo (5,4,0) -undecene.

Examples of the imidazole-based curing accelerator include: 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, tris (meth) acrylate ester, or a mixture thereof, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1') ] -ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based curing accelerator, commercially available products such as "P200-H50" manufactured by Mitsubishi chemical company can be used.

Examples of the guanidine-based curing accelerator include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like, and dicyandiamide and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene are preferred.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include: organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the (F) component is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, further preferably 0.01 mass% or more, further preferably 0.15 mass% or less, further preferably 0.1 mass% or less, further preferably 0.05 mass% or less, with respect to 100 mass% of the nonvolatile component in the photosensitive resin composition.

(G) solvent

The photosensitive resin composition may further contain (G) a solvent as an optional component. By containing the (G) solvent, the varnish viscosity can be adjusted. The (G) solvent may be an organic solvent.

Examples of the solvent (G) include: ketones such as ethyl methyl ketone (MEK) and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as diethylene glycol monoethyl ether acetate (EDGAc), methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl cellosolve acetate, carbitol acetate, diethylene glycol monoethyl ether acetate (ethyl diglycol acetate), and the like; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. These solvents may be used singly or in combination of two or more. The content of the solvent used may be appropriately adjusted from the viewpoint of coatability of the photosensitive resin composition.

< (H) other additives

The photosensitive resin composition may further contain (H) other additives to such an extent that the object of the present invention is not impaired. As (H) other additives, for example: fine particles of a reactive diluent, a thermoplastic resin, an organic filler, melamine, organobentonite, or the like; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black; polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc.; thickeners such as Benton and montmorillonite; silicone, fluorine, and vinyl resin defoaming agents; flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphoric esters, and halogen-containing condensed phosphoric esters; and various additives such as a phenol-based curing agent and a cyanate-based curing agent.

The photosensitive resin composition can be produced by: the above components (a) to (E) are mixed as essential components, the above components (F) to (H) are appropriately mixed as optional components, and if necessary, the mixture is kneaded or stirred by a kneading apparatus such as a three-roll mill, a ball mill, a bead mill, or a sand mill, or a stirring apparatus such as a high-speed mixer or a planetary mixer.

< Properties and applications of photosensitive resin composition >

A cured product obtained by photocuring a photosensitive resin composition exhibits such a characteristic as being excellent in developability. Therefore, the formation of residue in the unexposed portion can be suppressed. The evaluation of the residue of the unexposed portion can be carried out according to the method described in the examples below.

A cured product obtained by photocuring a photosensitive resin composition exhibits such a characteristic as being excellent in developability. Therefore, the characteristic of excellent BP (development point) is exhibited. BP means: the unexposed portion is dissolved by the developer until the dissolved resin disappears. BP is preferably 150 seconds or less, more preferably 140 seconds or less, further preferably 130 seconds or less. The lower limit is 30 seconds or more, preferably 40 seconds or more, and more preferably 50 seconds or more. The BP can be measured by the method described in examples described later.

A cured product obtained by photocuring a photosensitive resin composition exhibits such a characteristic as being excellent in developability. Therefore, a via hole free from residue and peeling, and a line width and a line pitch (L/S) free from peeling or filling can be formed. The minimum via diameter of the via hole is preferably 60 μm or less, more preferably 55 μm or less, and further preferably 50 μm or less. The lower limit is not particularly limited, and may be 1 μm or more. The minimum through hole diameter can be measured by the method described in the examples described later.

A cured product obtained by photocuring a photosensitive resin composition has such a characteristic that the cured product has an excellent dielectric constant. Therefore, an insulating layer and a solder resist layer (solder resist) having a low dielectric constant are provided. The dielectric constant is preferably 4.0 or less, more preferably 3.5 or less, and still more preferably 3.3 or less. The lower limit is not particularly limited, and may be 0.1 or more. The dielectric constant can be measured by the method described in examples described later.

A cured product obtained by photocuring a photosensitive resin composition exhibits such a characteristic that the cured product has an excellent dielectric loss tangent. Therefore, an insulating layer and a solder resist layer having a low dielectric loss tangent are provided. The dielectric loss tangent is preferably less than 0.013, more preferably 0.012 or less, and still more preferably 0.011 or less. The lower limit is not particularly limited, and may be 0.0001 or more. The dielectric loss tangent can be measured by the method described in the examples described below.

The photosensitive resin composition exhibits such a characteristic as excellent flexibility. Therefore, the photosensitive resin composition can suppress the formation of cracks even when stress is applied.

A cured product obtained by photocuring a photosensitive resin composition generally exhibits a characteristic of high glass transition temperature. Therefore, an insulating layer and a solder resist layer having a high glass transition temperature and excellent heat resistance are provided. The glass transition temperature is preferably 140 ℃ or higher, more preferably 145 ℃ or higher, and still more preferably 150 ℃ or higher. The upper limit is not particularly limited, and may be 300 ℃ or lower. The glass transition temperature can be measured by the method described in examples described later.

The application of the photosensitive resin composition of the present invention is not particularly limited, and the photosensitive resin composition can be used in a wide range of applications requiring a photosensitive resin composition, such as a photosensitive film, an insulating resin sheet such as a prepreg, a circuit board (for a laminate board, a multilayer printed wiring board, and the like), a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole filling resin, and a component embedding resin. Among them, it can be suitably used as: the photosensitive resin composition for an insulating layer of a printed wiring board (a printed wiring board having a cured product of the photosensitive resin composition as an insulating layer), the photosensitive resin composition for an interlayer insulating layer (a printed wiring board having a cured product of the photosensitive resin composition as an interlayer insulating layer), the photosensitive resin composition for plating (a printed wiring board having a plating layer formed on a cured product of the photosensitive resin composition), and the photosensitive resin composition for a solder resist (a printed wiring board having a cured product of the photosensitive resin composition as a solder resist).

[ photosensitive film ]

The photosensitive film has a support and a photosensitive resin composition layer containing the photosensitive resin composition of the present invention provided on the support.

Examples of the support include a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, and a triacetyl acetate film, and a polyethylene terephthalate film is particularly preferable.

Examples of commercially available supports include: polyethylene terephthalate films of PS series such as "ALPHAN MA-410" and "E-200C" manufactured by Wangzi paper company, polypropylene films manufactured by shin-Etsu film company, and "PS-25" manufactured by Diren company; and the like, but are not limited to these. These supports may be coated with a release agent such as a silicone coating agent for easy removal. The thickness of the support is preferably in the range of 5 to 50 μm, more preferably in the range of 10 to 25 μm. By setting the thickness to 5 μm or more, the support can be suppressed from cracking when peeling off the support before development; by setting the thickness to 50 μm or less, the resolution at the time of exposure from the support can be improved. Further, a support with a low white point (fish eye) is preferable. Here, white points refer to: when a material is thermally melted and a film is produced by kneading, extrusion, biaxial stretching, casting, or the like, foreign matter, undissolved matter, an oxidized degraded product, or the like of the material enters the film to form defects.

In addition, the support is preferably a material having excellent transparency in order to reduce light scattering when exposed to active energy rays such as ultraviolet rays. Specifically, the support is preferably a material having a haze (haze standardized in JIS K6714) of 0.1 to 5 as an index of transparency. Further, the photosensitive resin composition layer may be protected by a protective film.

By protecting the photosensitive resin composition layer side of the photosensitive film with a protective film, dust or the like can be prevented from adhering to the surface of the photosensitive resin composition layer or from being damaged. As the protective film, a film made of the same material as the support can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and still more preferably in the range of 10 μm to 30 μm. The handling property of the protective film can be improved by making the thickness of the protective film to be 1 μm or more, and the economical efficiency (low cost) tends to be improved by making the thickness of the protective film to be 40 μm or less. The protective film is preferably one having a small adhesion between the photosensitive resin composition layer and the protective film, relative to the adhesion between the photosensitive resin composition layer and the support.

From the viewpoint of improving handling properties and suppressing a decrease in sensitivity and resolution inside the photosensitive resin composition layer, the thickness of the photosensitive resin composition layer is preferably 10 μm or more, more preferably 15 μm or more, further preferably 20 μm or more, preferably 30 μm or less, further preferably 28 μm or less, further preferably 25 μm or less.

The photosensitive film can be produced, for example, by: a resin varnish in which a photosensitive resin composition is dissolved in an organic solvent is prepared, and the resin varnish is applied to a support using a die coater or the like, and then dried to form a photosensitive resin composition layer. As the organic solvent, the same solvents as those of the above-mentioned component (G) can be used.

Examples of the coating method of the resin varnish include: a gravure coating method, a micro gravure coating method, a reverse coating (reverse coating) method, a kiss reverse coating (kiss reverse coating) method, a die coating (die coating) method, a slot die (slot die) method, a lip coating (lip coating) method, a comma coating (comma coating) method, a blade coating (blade coating) method, a roll coating method, a knife coating (knife coating) method, a curtain coating (curve coating) method, a closed cavity (chamber) gravure coating method, a slot nozzle (slot orientation) method, a spray coating method, a dip coating method, and the like.

The resin varnish may be applied in several times, or may be applied in one time, or may be applied in combination of a plurality of different ways. Among them, a die coating method having excellent coating uniformity is preferred. In order to avoid the contamination of foreign substances, it is preferable to perform the coating step in an environment where foreign substances are less generated, such as a clean room.

The drying temperature varies depending on the curability of the photosensitive resin composition and the amount of the (G) component in the resin varnish, and may be 80 to 120 ℃. However, from the viewpoint of obtaining a cured product having excellent undercut (undercut) resistance, the maximum temperature of drying is preferably 105 ℃ or more, more preferably 110 ℃ or more. The lower limit of the maximum temperature is not particularly limited, but is preferably 135 ℃ or lower, more preferably 130 ℃ or lower.

The drying time varies depending on the curability of the photosensitive resin composition and the amount of the (G) component in the resin varnish, and is preferably 6 minutes or more, more preferably 30 minutes or less, and still more preferably 20 minutes or less. Here, the drying time means a time from when the drying temperature reaches 80 ℃.

The residual amount of the (G) component in the photosensitive resin composition layer is preferably 5 mass% or less, more preferably 2 mass% or less, based on the total amount of the photosensitive resin composition layer. One skilled in the art can set appropriate and suitable drying conditions by simple experiment.

The photosensitive film includes "a photosensitive resin composition layer containing the photosensitive resin composition of the present invention", and thus exhibits such a characteristic as excellent flexibility. For example, the photosensitive film is wound around a 3-inch core, and cut with a roll cutter. In this case, the occurrence of cracks in the photosensitive film can be suppressed.

[ printed Wiring Board ]

The printed wiring board of the present invention comprises an insulating layer formed using a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a solder resist layer or an interlayer insulating layer.

Specifically, the printed wiring board of the present invention can be produced using the photosensitive film described above. Hereinafter, an example of the case where the insulating layer is a solder resist layer will be described.

< coating and drying Process >

When a resin varnish containing a photosensitive resin composition is directly applied to a circuit board, the component (G) is dried and volatilized, thereby forming a photosensitive resin composition layer on the circuit board.

Examples of the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Here, the circuit board refers to a substrate in which a conductor layer (circuit) having been patterned is formed on one or both surfaces of the support substrate. In a multilayer printed wiring board in which a conductor layer and an insulating layer are alternately laminated, a substrate in which a conductor layer (circuit) having a pattern is formed on one surface or both surfaces of the outermost layer of the multilayer printed wiring board is also included in the circuit substrate described herein. The surface of the conductive layer may be subjected to a pre-roughening treatment by blackening treatment, copper etching, or the like.

As the coating method, full-page printing by a screen printing method is generally used in many cases, but any other means may be used as long as it is a coating method capable of uniform coating. For example, all of a spray coating system, a hot melt coating system, a bar coating system, a blade coating system, a knife coating system, an air knife coating system, a curtain flow coating system, a roll coating system, a gravure coating system, an offset printing system, a dip coating system, a brush coating system, and other general coating systems can be used. After coating, the coating is dried in a hot air furnace, a far infrared furnace or the like as needed. The drying conditions are preferably set to 80 to 120 ℃ for 3 to 13 minutes. Thus, a photosensitive composition layer can be formed on the circuit board.

< laminating Process >

On the other hand, when a photosensitive film is used, the photosensitive resin composition layer side is laminated on one surface or both surfaces of the circuit board by a vacuum laminator. In the laminating step, when the photosensitive film has a protective film, the protective film is removed, and then the photosensitive film and the circuit board are preheated as necessary, and the photosensitive resin composition layer is pressed and heated to be pressure-bonded to the circuit board. For the photosensitive film, a method of laminating the film on a circuit substrate under reduced pressure by a vacuum lamination method is preferably employed.

The conditions of the laminating step are not particularly limited, and for example, preferable conditions are: the pressure bonding temperature (lamination temperature) is preferably 70 to 140 ℃, and the pressure bonding pressure is preferably 1kgf/cm²～11kgf/cm²(9.8×10⁴N/m²～107.9×10⁴N/m²) The lamination is preferably performed under reduced pressure with the pressure bonding time set to 5 to 300 seconds and the air pressure set to 20mmHg (26.7hPa) or less. The laminating step may be a batch type or a continuous type using a roll. The vacuum lamination method can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include: a vacuum applicator manufactured by Nikko-Materials, a vacuum pressure type laminator manufactured by Kabushiki Kaisha, a roll type dry coater manufactured by Hitachi Industries, a vacuum laminator manufactured by Hitachi AIC, and the like.

< Exposure Process >

After the photosensitive resin composition layer is provided on the circuit board by the coating and drying step or the laminating step, an exposure step is performed in which a predetermined portion of the photosensitive resin composition layer is irradiated with active light (activation ray) through a mask pattern to photocure the photosensitive resin composition layer in the irradiation portion. Examples of the active light include ultraviolet rays, visible light rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. The dose of ultraviolet irradiation was about 10mJ/cm²～1000mJ/cm². The exposure method includes a contact exposure method in which a mask pattern is bonded to a printed wiring board, and a non-contact exposure method in which exposure is performed using parallel light rays in a state where the mask pattern is not bonded to the printed wiring board. When a support is present on the photosensitive resin composition layer, exposure may be performed from the support, or the support may be peeled off and then exposed.

Since the photosensitive resin composition of the present invention is used for a solder resist layer (solder resist), the developability is excellent. Therefore, as the exposure pattern in the mask pattern, for example, a pattern in which the ratio (L/S) of the circuit width (line width; L) to the width between circuits (line pitch; S) is 100 μm/100 μm or less (that is, 200 μm or less in wiring pitch), L/S80 μm/80 μm or less (160 μm or less in wiring pitch), L/S70 μm/70 μm or less (140 μm or less in wiring pitch), and L/S60 μm/60 μm or less (120 μm or less in wiring pitch) can be used. The pitches do not need to be the same throughout the circuit board.

Since the photosensitive resin composition of the present invention is used for a solder resist layer (solder resist), the developability is excellent. Therefore, the diameter of the through hole is preferably 100 μm or less, more preferably 90 μm or less, and still more preferably 80 μm or less. The lower limit is not particularly limited, and may be 1 μm or more and 10 μm or more.

< developing Process >

When a support is present on the photosensitive resin composition layer after the exposure step, the support is removed, and then a portion that has not been photocured (unexposed portion) is removed by wet development or dry development, followed by development, whereby a pattern can be formed.

In the case of the above wet development, a safe and stable developer having good workability, such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, can be used as the developer, and among them, a development step using an alkaline aqueous solution is preferred. As the developing method, known methods such as spraying, dipping with shaking, brushing (brushing), and knife coating (scraping) can be suitably used.

Examples of the alkaline aqueous solution used as the developer include: an aqueous solution of an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, or potassium hydroxide, a carbonate or bicarbonate such as sodium carbonate or sodium bicarbonate, an aqueous solution of an alkali metal phosphate such as sodium phosphate or potassium phosphate, an alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate, or an aqueous solution of an organic base not containing metal ions such as tetraalkylammonium hydroxide is preferably an aqueous solution of tetramethylammonium hydroxide (TMAH) from the viewpoint of not containing metal ions and not affecting the semiconductor chip.

In these alkaline aqueous solutions, a surfactant, an antifoaming agent, or the like may be added to the developer to improve the developing effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8 to 12, more preferably in the range of 9 to 11. The alkali concentration of the alkaline aqueous solution is preferably 0.1 to 10% by mass. The temperature of the alkaline aqueous solution is suitably selected in accordance with the developability of the photosensitive resin composition layer, and is preferably 20 to 50 ℃.

Examples of the organic solvent used as the developer include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

The concentration of the organic solvent is preferably 2 to 90% by mass based on the total amount of the developer. The temperature of such an organic solvent can be adjusted in accordance with the developability. Further, such organic solvents may be used alone or in combination of 2 or more. Examples of the organic solvent-based developer used alone include: 1,1, 1-trichloroethane, N-methylpyrrolidone, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone and gamma-butyrolactone.

In the pattern formation, the above-mentioned 2 or more developing methods may be used in combination as necessary. The development method includes a dipping method, a spin-coating immersion method, a spraying method, a high-pressure spraying method, a brush coating method, a blade coating method, and the like, and the high-pressure spraying method is preferable because of the improvement in resolution. The spraying pressure in the case of the spraying method is preferably 0.05MPa to 0.3 MPa.

< Heat curing (post-baking) Process

After the development step is completed, a thermosetting (post-baking) step is performed to form a solder resist layer. Examples of the post-baking step include an ultraviolet irradiation step using a high-pressure mercury lamp, and a heating step using a Clean Oven (Clean Oven). When ultraviolet rays are irradiated, the dose of the ultraviolet rays can be adjusted as needed, and the dose can be set to 0.05J/cm, for example²～10J/cm²The irradiation is performed with right and left irradiation amounts. The heating condition may be appropriately selected depending on the kind, content and the like of the resin component in the photosensitive resin composition, and is preferably in the range of from 20 minutes to 180 minutes at 150 to 220 ℃, more preferably in the range of from 30 minutes to 120 minutes at 160 to 200 ℃And selecting in the enclosure.

< other working procedures >

The printed wiring board may further include a hole opening step and a desmear (desmear) step after the solder resist layer is formed. These steps can be performed by various methods known to those skilled in the art used for manufacturing printed wiring boards.

After the solder resist layer is formed, a via hole or a through hole is formed in the solder resist layer formed on the circuit board as necessary. The hole-forming step can be performed by a known method such as a drill, a laser, or a plasma, or by a combination of these methods as necessary, and is preferably performed by a laser such as a carbon dioxide laser or a YAG laser.

The desmear process is a process for performing desmear treatment. Resin residue (contamination) is generally adhered to the inside of the opening portion formed in the hole forming step. Since the contamination causes the electrical connection failure, a process of removing the contamination (contamination removal process) is performed in this step.

The desmear treatment can be carried out by a dry desmear treatment, a wet desmear treatment or a combination of both.

Examples of the dry desmear treatment include desmear treatment using plasma. The desmear treatment using plasma can be carried out using a commercially available plasma desmear treatment apparatus. Examples of commercially available plasma desmear treatment apparatuses suitable for use in the production of printed wiring boards include: a microwave plasma apparatus manufactured by NISSIN corporation, and an atmospheric pressure plasma etching apparatus manufactured by water-accumulation chemical industry corporation.

Examples of the wet desmear treatment include desmear treatment using an oxidizing agent solution. When the desmear treatment is performed using an oxidizing agent solution, it is preferable to perform a swelling treatment using a swelling solution, an oxidation treatment using an oxidizing agent solution, and a neutralization treatment using a neutralizing solution in this order. Examples of the swelling liquid include: "spinning Dip securigant P", "spinning Dip securigant SBU", and the like, manufactured by amatt JAPAN (ato ech JAPAN) corporation. The swelling treatment is preferably carried out by immersing the substrate having the through-holes or the like formed therein in a swelling solution heated to 60 to 80 ℃ for 5 to 10 minutes. The oxidizing agent solution is preferably an aqueous alkaline permanganate solution, and examples thereof include a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous sodium hydroxide solution. The oxidation treatment with the oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in an oxidizing agent solution heated to 60 to 80 ℃ for 10 to 30 minutes. Examples of commercially available alkaline permanganic acid aqueous solutions include: "Concentrate Compact CP", "Dossing Solution securigant P", and the like, manufactured by Anmet Japan. The neutralization treatment with the neutralization solution is preferably carried out by immersing the substrate after the oxidation treatment in the neutralization solution at 30 to 50 ℃ for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and commercially available products include, for example: "Reduction Solution securigant P" manufactured by amatt japan corporation.

When the dry desmear treatment and the wet desmear treatment are carried out in combination, the dry desmear treatment may be carried out first, or the wet desmear treatment may be carried out first.

When the insulating layer is used as an interlayer insulating layer, the opening step, the desmear step, and the plating step may be performed after the thermosetting step, as in the case of the solder resist layer.

The plating step is a step of forming a conductor layer on the insulating layer. The conductor layer may be formed by combining electroless plating and electrolytic plating, or a plating resist layer having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed by only electroless plating. As a method of forming a pattern later, for example, a subtractive method, a semi-additive method, or the like known to those skilled in the art can be used.

[ semiconductor device ]

The semiconductor device of the present invention includes a printed wiring board. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Examples of the semiconductor device include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, and the like), vehicles (for example, motorcycles, automobiles, electric trains, ships, aircraft, and the like), and the like.

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conductive portion" refers to a portion of the printed wiring board that conducts an electrical signal, and may be located on the surface or embedded in the printed wiring board. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting the semiconductor chip in the production of the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip can effectively function. Specifically, a wire bonding mounting method, a flip chip mounting method, a mounting method using a build-up layer without solder (BBUL), a mounting method using an Anisotropic Conductive Film (ACF), a mounting method using a non-conductive film (NCF), and the like can be given. Here, the "mounting method using a build-up layer without solder (BBUL)" refers to a "mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip is connected to a wiring on the printed wiring board".

Examples

The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following description, "part" and "%" representing amounts are "part by mass" and "% by mass", respectively, unless otherwise stated. The epoxy equivalent of the component (D) is measured in accordance with JIS K7236, and the softening point is measured in accordance with JIS K7234.

(Synthesis example 1: Synthesis of resin (A-1))

325 parts of a naphthol aralkyl type epoxy resin (epoxy equivalent 325g/eq., ESN-475V, new york chemical) represented by the following formula (1) was charged into a flask equipped with a gas introduction tube, a stirrer, a condenser and a thermometer, 340 parts of carbitol acetate was added and dissolved by heating, and 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. Heating the mixture to 95-105 ℃, slowly and dropwise adding 72 parts of acrylic acid, and reacting for 16 hours. And cooling the reaction product to 80-90 ℃, adding 80 parts of tetrahydrophthalic anhydride, reacting for 8 hours, and cooling. Thus, a resin solution (nonvolatile matter content: 70%, hereinafter referred to simply as "resin solution (A-1)") having an acid value of 60mg KOH/g of a solid content was obtained.

[ chemical formula 37]

Wherein Z is a glycidyl group (G) or a C1-8 hydrocarbon group (R)⁶)，R⁶The ratio of/G is 0.05 to 2.0. In addition, n represents a number of 1 to 6 as an average value.

It was confirmed that the resin solution (A-1) contained at least: a resin having a structure represented by the following formula (2).

[ chemical formula 38]

Synthesis example 2 Synthesis of Maleimide Compound (E-1)

A300 mL flask equipped with a thermometer, a condenser and a Dean Stark trap (Dean Stark trap) was charged with 12.1g (0.1mol) of 2, 6-dimethylaniline, 68.0g (0.35mol) of. alpha.,. alpha.' -dihydroxy-1, 3-diisopropylbenzene, 100g of xylene and 20g of activated clay, and heated to 120 ℃ with stirring. Further, distilled water was removed by a dean-Stark tube, and the temperature was raised until 210 ℃ was reached, and the reaction was carried out for 3 hours. Then, the reaction mixture was cooled to 140 ℃ and charged with 36.4g (0.3mol) of 2, 6-dimethylaniline, and then heated to 220 ℃ to react for 3 hours. After the reaction, the reaction mixture was cooled to 100 ℃ with air, diluted with 75g of toluene, and the activated clay was removed by filtration, and low molecular weight substances such as the solvent and unreacted substances were distilled off under reduced pressure, whereby 91.0g (n is an integer of 1 to 10) of an intermediate amine compound represented by the following formula (E-1) was obtained. The amine equivalent weight is 296, and the softening point is 70 ℃;

[ chemical formula 39]

Subsequently, 32.9g (0.32mol) of maleic anhydride and 200g of toluene were charged into a 500mL flask equipped with a thermometer, a condenser, a dean-Stark trap and a stirrer, and stirred at room temperature. A mixed solution of 91g of the intermediate amine compound represented by the formula (E-1) and 40g of DMF was added dropwise over a period of 1 hour. After completion of the dropwise addition, the reaction was further carried out at room temperature for 2 hours. 9.3g of p-toluenesulfonic acid monohydrate was added, the reaction solution was heated, water azeotropic under reflux and toluene were cooled and separated, and then only toluene was returned to the system to conduct dehydration reaction for 8 hours. After air-cooling to room temperature, the mixture was concentrated under reduced pressure to dissolve a brown solution in 150g of ethyl acetate, washed 3 times with 40g of ion-exchanged water and 3 times with 40g of a 2% aqueous solution of sodium hydrogencarbonate, sodium sulfate was added thereto, and after drying, the resulting mixture was concentrated under reduced pressure, and the resulting reaction product was dried under vacuum at 80 ℃ for 4 hours to obtain 103.0g of a maleimide compound (C-1) -containing product. In the FD-MS spectrum of the maleimide compound (C-1), peaks of 560, 7, and 876 were observed, and each peak corresponds to a case where n is 0, 1, or 2. The number n of repeating units in the indane skeleton portion of the maleimide compound (C-1) was determined by GPC (based on the number average molecular weight), and as a result, n was 1.47 and the molecular weight distribution (Mw/Mn) was 1.81. Further, the maleimide group having an average repeating unit number n of 0 was 26.5 area% in 100 area% of the total amount of the maleimide E-1.

< examples 1 to 11, comparative examples 1 to 6 >

The respective components were mixed in the mixing ratios shown in the following table, and resin varnishes were prepared using a high-speed rotary mixer.

Subsequently, a PET film (manufactured by Toray corporation, "Lumiror T6 AM", thickness 38 μm, softening point 130 ℃) was prepared as a support. The PET film was uniformly coated with a resin varnish by a die coater so that the thickness of the photosensitive resin composition layer after drying became 25 μm, and dried at 80 to 110 ℃ for 6.5 minutes to obtain a photosensitive film having a photosensitive resin composition layer on the PET film.

Further, a PET film (Lumiror T6AM, manufactured by Toray corporation, "Release PET film" having a thickness of 38 μm and a softening point of 130 ℃ C.) subjected to a release treatment with an alkyd resin-based release agent ("AL-5", manufactured by Lindedoki Co., Ltd.) was prepared. The resin varnish was uniformly applied to the release PET film by a die coater so that the thickness of the photosensitive resin composition layer after drying became 25 μm, and the photosensitive film having the photosensitive resin composition layer on the release PET film was obtained by drying at 80 to 110 ℃ for 6.5 minutes.

< evaluation of flexibility >

The photosensitive film having the photosensitive resin composition layer on the PET film was wound around a core of 3 inches to confirm whether the photosensitive film had no cracks. When the photosensitive film was cut with a roll cutter (manufactured by DAHLE corporation), it was checked whether the photosensitive film had no cracks. The good quality was defined as "no crack" in these operations, and the poor quality was defined as "x" as "crack could be confirmed.

< evaluation of developability >

(formation of laminate for evaluation)

The copper layer of a glass epoxy substrate (copper-clad laminate) on which a circuit is formed by patterning the copper layer having a thickness of 18 μm was roughened by treatment with a surface treatment agent (CZ8100, manufactured by meige) containing an organic acid. Next, the photosensitive resin composition layer of the photosensitive film having the photosensitive resin composition layer on the PET film was disposed so as to be in contact with the surface of the copper circuit, and laminated using a vacuum laminator (VP 160, manufactured by Nikko-Materials), thereby forming a laminate in which the copper-clad laminate, the photosensitive resin composition layer, and the support were laminated in this order. The crimping conditions were: the vacuum-pumping time was 30 seconds, the pressure-bonding temperature was 80 ℃, the pressure-bonding pressure was 0.7MPa, and the pressing time was 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or longer, and exposed to ultraviolet light from above the support of the laminate using a pattern forming apparatus using a circular hole pattern. As for the exposure pattern, the drawing opening: 50 μm/60 μm/70 μm/80 μm/90 μm/100 μm round hole, L/S (line width/line distance): a square quartz glass mask of 50 μm/50 μm, 60 μm/60 μm, 70 μm/70 μm, 80 μm/80 μm, 90 μm/90 μm, 100 μm/100 μm in line width and line pitch, 1cm × 2 cm. After standing at room temperature for 30 minutes, the support was peeled off from the laminate.

(residue of unexposed portion)

The entire surface of the photosensitive resin composition layer on the laminate (laminated plate) from which the support was peeled off was subjected to spray development using a1 mass% sodium carbonate aqueous solution at 30 ℃ as a developer at a spray pressure of 0.2 MPa. The unexposed portions of the 1cm × 2cm portion of the laminate after the spray development were visually observed and evaluated according to the following criteria;

good: no resin remained in the unexposed portion;

x: the presence of resin was visually confirmed or a film loss occurred.

(evaluation of BP (developing Point))

While the unexposed portion of the laminate was visually observed at a 1cm × 2cm portion, a 1% by mass aqueous solution of sodium carbonate at 30 ℃ was sprayed as a developer at a spray pressure of 0.2MPa to perform spray development. The time (seconds) from the start of spraying to the time when the resin remaining on the substrate disappeared was recorded.

(evaluation of resolution (resolution), minimum through-hole diameter)

Then, the formed through-holes and L/S (magnification: 1000 times) were observed by SEM, the minimum through-hole diameter without residue and peeling was measured, and the L/S shape at any three points was measured and evaluated according to the following criteria. However, the minimum through-hole diameter was evaluated as "x" in the case of having residue and peeling. The case where the minimum L/S exceeded 60 μm/60 μm was evaluated as "X";

o: observing the L/S of three points, wherein all the L/S are not stripped and buried;

x: the L/S was observed at three points, and resin filling and peeling were observed between any two L/S points.

< measurement of dielectric constant, dielectric loss tangent, and glass transition temperature >

(formation of cured product for evaluation)

1J/cm of the photosensitive resin composition layer of the photosensitive film having the photosensitive resin composition layer on the release PET film²Is irradiated with ultraviolet rays, and thenHeat treatment was carried out at 190 ℃ for 90 minutes to form a cured product. Then, the support was peeled off to obtain a cured product A for evaluation.

(measurement of dielectric constant and dielectric loss tangent)

The cured product A for evaluation was cut into test pieces having a width of 2mm and a length of 80mm to obtain a cured product B for evaluation. For each evaluation cured product B, a dielectric constant value (Dk value) and a dielectric loss tangent value (Df value) were measured by a resonance cavity perturbation method at a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃ using "HP 8362B" manufactured by Agilent Technologies. The measurement was performed using 3 test pieces (N ═ 3), and the average value was calculated.

(measurement of glass transition temperature)

The cured product A for evaluation was cut into test pieces having a width of about 5mm and a length of about 15mm, and subjected to thermomechanical analysis by a tensile load method using a dynamic viscoelasticity measuring apparatus (EXSTAR6000, manufactured by SII nanotechnology Co.). The test piece was mounted on the above-mentioned apparatus, and then the measurement was carried out under the measurement conditions of a load of 200mN and a temperature rise rate of 2 ℃/min. The peak top of tan. delta. was calculated as the glass transition temperature (. degree. C.).

[ Table 1]

Abbreviations and the like in the tables are as follows;

(A) the components:

CCR-1179: cresol novolac F-type epoxy acrylate (manufactured by Nippon Chemicals, Ltd., acid value 99mgKOH/g, nonvolatile matter concentration 70%)

A-1: resin solution (A-1) synthesized in Synthesis example 1

(B) The components:

SC 2050: fused silica (manufactured by Yatoma, average particle diameter 0.5 μm, specific surface area 5.9 m)²Per g)100 parts by mass of a surface-treated product obtained by treating 100 parts by mass of a surface-treated product with 0.5 part by mass of aminosilane (KBM 573, manufactured by shin-Etsu chemical Co., Ltd.)

(C) The components:

irgacure TPO: bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, manufactured by BASF corporation)

Irgacure OXE-01: 1- [4- (phenylthio) -1, 2-octanedione 2- (O-benzoyloxime) (manufactured by BASF)

(D) The components:

HP 4032: naphthalene type epoxy resin (available from DIC corporation, epoxy equivalent 144g/eq., softening point less than 30 ℃ C.)

ELM-434 VL: n, N, N ', N ' -tetrakis (oxiran-2-ylmethyl) -4,4' -methylenedianiline (glycidylamine-type epoxy resin, manufactured by Sumitomo chemical Co., Ltd., epoxy equivalent 114g/eq., softening point less than 30 ℃ C.)

NC 3000L: biphenyl type epoxy resin (manufactured by Nippon chemical Co., Ltd., epoxy equivalent 271g/eq., softening point 53 ℃ C.)

NC 3000H: biphenyl type epoxy resin (manufactured by Nippon chemical Co., Ltd., epoxy equivalent of 272g/eq., softening point of 70 ℃ C.)

1031S: tetrahydroxyphenylethane-type epoxy resin (having an epoxy equivalent of 224g/eq. and a softening point of 92 ℃ C., manufactured by Mitsubishi chemical corporation)

(E) The components:

BMI-689: maleimide resin, dimer diamine type bismaleimide (manufactured by Designer Molecies Co., Ltd.)

E-1: maleimide Compound (E-1) synthesized in Synthesis example 2

BMI-5100: maleimide resin, 3,3' -dimethyl-5, 5' -diethyl-4, 4' -diphenylmethane bismaleimide manufactured by Designer Molecules Co

MIR 3000: maleimide resin, manufactured by Nippon Chemicals Ltd

EXB-8151-62T: active ester resin containing naphthalene Structure, manufactured by DIC

PC1300-02-65 MA: active ester resin having naphthalene structure, manufactured by AIR & WATER

DAD: vinyl resin: 2,2' -Biphenyldicarboxylic acid diallyl ester (manufactured by Ritacttech Fine chemical Co., Ltd.)

OPE-2 St: vinyl resin (vinylbenzyl-modified polyphenylene ether, manufactured by Mitsubishi gas chemical Co., Ltd.)

(F) Composition (I)

1B2 PZ: 2-phenyl-1-benzyl-1H-imidazole, manufactured by Siguo Kabushiki Kaisha

(G) The components:

EDGAc: diethylene glycol monoethyl ether acetate

MEK: methyl ethyl ketone

(H) The components:

DOG-a: dioxanediol Diacrylate (Dioxane Glycol Diacrylate), manufactured by Mizhou chemical Co., Ltd

TD-2090-60M: phenol novolac resin, available from DIC.

In each example, even when the components (F) to (H) were not contained, the results were similar to those in the above examples, although the differences were different in degree.

Claims

1. A photosensitive resin composition comprising the following components (A) to (E),

(A) a resin containing an ethylenically unsaturated group and a carboxyl group,

(B) Inorganic filler,

(C) A photopolymerization initiator,

(D) An epoxy resin, and

wherein the component (D) comprises:

(D-2) an epoxy resin having a softening point of 30 ℃ or higher and less than 59 ℃.

2. The photosensitive resin composition according to claim 1, wherein the component (D-1) has a softening point of 20 ℃ or lower.

3. The photosensitive resin composition according to claim 1, wherein the component (D-1) has a softening point of 0 ℃ or higher.

4. The photosensitive resin composition according to claim 1, wherein the component (D-1) has a softening point of 10 ℃ or higher.

5. The photosensitive resin composition according to claim 1, wherein the epoxy equivalent of the component (D-1) is 145g/eq.

6. The photosensitive resin composition according to claim 1, wherein the epoxy equivalent of the component (D-1) is 10g/eq.

7. The photosensitive resin composition according to claim 1, wherein the epoxy equivalent of the component (D-1) is 100g/eq.

8. The photosensitive resin composition according to claim 1, wherein the component (D-2) has a softening point of 40 ℃ or higher.

9. The photosensitive resin composition according to claim 1, wherein the component (D-2) has a softening point of 50 ℃ or lower.

10. The photosensitive resin composition according to claim 1, wherein D2/D1 is 0.5 to 2.5, where D1 represents the content of the (D-1) component at 100 mass% of nonvolatile components in the photosensitive resin composition and D2 represents the content of the (D-2) component at 100 mass% of nonvolatile components in the photosensitive resin composition.

11. The photosensitive resin composition according to claim 1, wherein D2/D1 is 1.5 or more, where D1 represents the content of the (D-1) component at 100 mass% of nonvolatile components in the photosensitive resin composition and D2 represents the content of the (D-2) component at 100 mass% of nonvolatile components in the photosensitive resin composition.

12. The photosensitive resin composition according to claim 1, wherein D2/D1 is 2.2 or less, where D1 represents the content of the (D-1) component at 100 mass% of nonvolatile components in the photosensitive resin composition and D2 represents the content of the (D-2) component at 100 mass% of nonvolatile components in the photosensitive resin composition.

13. The photosensitive resin composition according to claim 1, wherein the content of the component (D-1) is 90% by mass or less, assuming that the total amount of the component (D) is 100% by mass.

14. The photosensitive resin composition according to claim 1, wherein the content of the component (D-1) is 70% by mass or less, assuming that the total amount of the component (D) is 100% by mass.

15. The photosensitive resin composition according to claim 1, wherein the content of the component (D-1) is 40% by mass or less, assuming that the total amount of the component (D) is 100% by mass.

16. The photosensitive resin composition according to claim 1, wherein the content of the component (D-1) is 10% by mass or more, assuming that the total amount of the component (D) is 100% by mass.

17. The photosensitive resin composition according to claim 1, wherein the content of the component (D-1) is 30% by mass or more, assuming that the total amount of the component (D) is 100% by mass.

18. The photosensitive resin composition according to claim 1, wherein the content of the component (D-2) is 10% by mass or more, assuming that the total amount of the component (D) is 100% by mass.

19. The photosensitive resin composition according to claim 1, wherein the content of the component (D-2) is 60% by mass or more, assuming that the total amount of the component (D) is 100% by mass.

20. The photosensitive resin composition according to claim 1, wherein the content of the component (D-2) is 90% by mass or less, assuming that the total amount of the component (D) is 100% by mass.

21. The photosensitive resin composition according to claim 1, wherein the content of the component (D-2) is 70% by mass or less, assuming that the total amount of the component (D) is 100% by mass.

22. The photosensitive resin composition according to claim 1, wherein the content of the component (B) is 50% by mass or more, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

23. The photosensitive resin composition according to claim 1, wherein the content of the component (B) is 60% by mass or more, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

24. The photosensitive resin composition according to claim 1, wherein the content of the component (B) is 75% by mass or less, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

25. The photosensitive resin composition according to claim 1, wherein the content of the component (B) is 65% by mass or less, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

26. The photosensitive resin composition according to claim 1, wherein the component (A) comprises:

(A-1) a resin having a naphthalene skeleton.

27. The photosensitive resin composition according to claim 1, wherein the content of the component (A) is 10% by mass or more, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

28. The photosensitive resin composition according to claim 1, wherein the content of the component (A) is 20% by mass or more, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

29. The photosensitive resin composition according to claim 1, wherein the content of the component (A) is 40% by mass or less, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

30. The photosensitive resin composition according to claim 1, wherein the content of the component (A) is 30% by mass or less, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

31. The photosensitive resin composition according to claim 1, wherein the content of the component (C) is 1% by mass or more, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

32. The photosensitive resin composition according to claim 1, wherein the content of the component (C) is 2% by mass or more, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

33. The photosensitive resin composition according to claim 1, wherein the content of the component (C) is 5% by mass or less, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

34. The photosensitive resin composition according to claim 1, wherein the content of the component (C) is 3% by mass or less, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

35. The photosensitive resin composition according to claim 1, wherein the component (D-1) has a cyclic structure.

36. The photosensitive resin composition according to claim 1, wherein the component (E) comprises:

an active ester resin, and

at least one resin selected from the group consisting of maleimide resins and vinyl resins.

37. The photosensitive resin composition according to claim 1, wherein the total content of the component (E) is 1% by mass or more, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

38. The photosensitive resin composition according to claim 1, wherein the total content of the component (E) is 2% by mass or more, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

39. The photosensitive resin composition according to claim 1, wherein the total content of the component (E) is 20% by mass or less, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

40. The photosensitive resin composition according to claim 1, wherein the total content of the component (E) is 10% by mass or less, assuming that the nonvolatile component in the photosensitive resin composition is 100% by mass.

41. The photosensitive resin composition according to claim 1, wherein a development point of a cured product of the photosensitive resin composition is 30 seconds or more and 150 seconds or less.

42. The photosensitive resin composition according to claim 1, wherein a development point of a cured product of the photosensitive resin composition is 50 seconds or more.

43. The photosensitive resin composition according to claim 1, wherein a development point of a cured product of the photosensitive resin composition is 130 seconds or less.

44. A photosensitive film, comprising:

a support, and

a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 43, provided on the support.

45. A printed wiring board comprising an insulating layer formed by using a cured product of the photosensitive resin composition according to any one of claims 1 to 43.

46. The printed wiring board of claim 45, wherein the insulating layer is a solder resist layer.

47. A semiconductor device comprising the printed wiring board of claim 45 or 46.