Photosensitive resin composition

Abstract

The present invention aims to provide a photosensitive resin composition that can produce a cured product with a low dielectric constant and dielectric loss tangent, and exhibits excellent flexibility and developability. The present invention provides 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 an active ester resin, a maleimide resin, and a vinyl resin, wherein component (D) comprises (D-1) an epoxy resin having a softening point of less than 30°C and an epoxy equivalent of 150 g / eq. or less, and (D-2) an epoxy resin having a softening point of 30°C or higher and less than 59°C.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition and further to a photosensitive film, a printed wiring board, and a semiconductor device obtained using the photosensitive resin composition. Background Art

[0002] In printed wiring boards, a solder resist is sometimes provided as a permanent protective film to prevent solder from adhering to unnecessary portions and to prevent corrosion of the circuit board. As the solder resist, a photosensitive resin composition such as that described in Patent Document 1 is generally used.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2014-115672. Summary of the Invention

[0006] Problems to be solved by the invention

[0007] Photosensitive resin compositions are generally required to have excellent developability during development. Furthermore, in recent years, photosensitive resin compositions have been used as materials for insulating layers or sealing layers. Therefore, in addition to developability, they are also required to have excellent dielectric constant and dielectric loss tangent. Furthermore, from the perspective of improving the handleability of a photosensitive film containing the photosensitive resin composition, the flexibility of the photosensitive resin composition is also required to be improved.

[0008] The present invention aims to provide a photosensitive resin composition that can produce a cured product having low dielectric constant and dielectric loss tangent and excellent flexibility and developability; and a photosensitive film, a printed wiring board, and a semiconductor device obtained using the photosensitive resin composition.

[0009] Solutions to Problems

[0010] The present inventors have conducted intensive research and have discovered that by using 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) one or more resins selected from an active ester resin, a maleimide resin, and a vinyl resin, wherein component (D) contains a specified amount of a specific epoxy resin, a cured product having a low dielectric constant and dielectric loss tangent and improved flexibility and developability can be obtained, thereby completing the present invention.

[0011] That is, the present invention includes the following contents;

[0012] [1] A photosensitive resin composition comprising:

[0013] (A) a resin containing an ethylenically unsaturated group and a carboxyl group,

[0014] (B) Inorganic filling materials,

[0015] (C) photopolymerization initiator,

[0016] (D) Epoxy resin, and

[0017] (E) one or more resins selected from active ester resins, maleimide resins, and vinyl resins,

[0018] Wherein, component (D) comprises:

[0019] (D-1) an epoxy resin having a softening point of less than 30°C and an epoxy equivalent of 150 g / eq. or less, and

[0020] (D-2) an epoxy resin having a softening point of 30°C or higher and less than 59°C;

[0021] [2] The photosensitive resin composition according to [1], wherein, when the content of the component (D-1) is D1 and the content of the component (D-2) is D2, the ratio D2 / D1 is 0.5 or more and 2.5 or less, based on the non-volatile content in the photosensitive resin composition being 100% by mass;

[0022] [3] The photosensitive resin composition according to [1] or [2], wherein the content of the component (D-1) is 90% by mass or less when the total amount of the component (D) is 100% by mass;

[0023] [4] The photosensitive resin composition according to any one of [1] to [3], wherein the content of component (B) is 60% by mass or more when the non-volatile component in the photosensitive resin composition is 100% by mass;

[0024] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the component (A) comprises: (A-1) a resin containing a naphthalene skeleton;

[0025] [6] The photosensitive resin composition according to any one of [1] to [5], wherein the component (D-1) has a cyclic structure;

[0026] [7] The photosensitive resin composition according to any one of [1] to [6], wherein the component (E) comprises:

[0027] Active ester resin, and

[0028] One or more resins selected from maleimide resins and vinyl resins;

[0029] [8] The photosensitive resin composition according to any one of [1] to [7], wherein a cured product of the photosensitive resin composition has a breakpoint of 30 seconds to 150 seconds.

[0030] [9] A photosensitive film comprising:

[0031] Support, and

[0032] A photosensitive resin composition layer comprising the photosensitive resin composition according to any one of [1] to [8], provided on the support;

[0033]

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

[0034]

[11] The printed wiring board according to

[10] , wherein the insulating layer is a solder resist;

[0035]

[12] A semiconductor device comprising the printed wiring board according to

[10] or

[11] .

[0036] Effects of the Invention

[0037] The present invention can provide a photosensitive resin composition that can produce a cured product having low dielectric constant and dielectric loss tangent and excellent flexibility and developability; and a photosensitive film, a printed wiring board, and a semiconductor device obtained using the photosensitive resin composition. DETAILED DESCRIPTION

[0038] Hereinafter, the photosensitive resin composition, photosensitive film, printed wiring board, and semiconductor device of the present invention will be described in detail.

[0039] [Photosensitive resin composition]

[0040] The photosensitive resin composition of the present invention comprises (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. Component (D) comprises (D-1) an epoxy resin having a softening point of less than 30°C and an epoxy equivalent of 150 g / eq. or less, and (D-2) an epoxy resin having a softening point of 30°C or higher and less than 59°C.

[0041] The present invention can provide a cured product having not only good developability but also low dielectric constant and dielectric loss tangent, thereby providing a photosensitive resin composition having excellent flexibility and developability. Furthermore, a cured product having a high glass transition temperature can generally be obtained.

[0042] The photosensitive resin composition may further contain optional components such as (F) a curing accelerator, (G) a solvent, and (H) other additives as needed. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.

[0043] <(A) Resin containing an ethylenically unsaturated group and a carboxyl group>

[0044] The photosensitive resin composition contains a resin containing an ethylenically unsaturated group and a carboxyl group as the component (A). By containing the component (A) in the photosensitive resin composition, the developability can be improved.

[0045] The ethylenically unsaturated group has a carbon-carbon double bond, and examples thereof include vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimide, nadiimide, and (meth)acryloyl. From the viewpoint of reactivity in photoradical polymerization, (meth)acryloyl is preferred. "(Meth)acryloyl" includes methacryloyl, acryloyl, and combinations thereof. Component (A) contains ethylenically unsaturated groups and can be photoradical polymerized. The number of ethylenically unsaturated groups per molecule of component (A) may be 1 or more than 2. Furthermore, when component (A) contains two or more ethylenically unsaturated groups per molecule, those ethylenically unsaturated groups may be the same or different.

[0046] Furthermore, since component (A) contains carboxyl groups, the photosensitive resin composition containing component (A) exhibits solubility in alkaline solutions (e.g., a 1% by mass aqueous sodium carbonate solution as an alkaline developer). The number of carboxyl groups per molecule of component (A) may be one or two or more.

[0047] Component (A) may be any resin containing an ethylenically unsaturated group and a carboxyl group. Component (A) is preferably at least one of (A-1) a naphthalene skeleton-containing resin and (A-2) an acid-modified epoxy (meth)acrylate resin.

[0048] ((A-1) Naphthalene skeleton-containing resin)

[0049] Since the naphthalene skeleton-containing resin (A-1) is a resin included in component (A), it contains ethylenically unsaturated groups and carboxyl groups. Therefore, component (A-1) is capable of photoradical polymerization, and photosensitive resin compositions containing component (A-1) are soluble in alkaline solutions.

[0050] The component (A-1) preferably has a plurality of ethylenically unsaturated groups in one molecule. Thus, the mechanical strength and solubility resistance of the cured product of the photosensitive resin composition can be improved. In addition, the component (A-1) preferably has two or less ethylenically unsaturated groups per one naphthalene skeleton. Thus, the crosslinking position (crosslinking point) can be adjusted, and thus the mechanical strength and solubility resistance of the cured product of the photosensitive resin composition can be controlled. It is better that the ethylenically unsaturated group is contained in the substituent possessed by the naphthalene skeleton. In order to include the ethylenically unsaturated group in the substituent possessed by the naphthalene skeleton, a compound in which the H atom of the OH group of naphthol is replaced by a substituent containing an epoxy group (e.g., an epoxy group, a glycidyl group) is prepared as a first precursor, and a compound having an ethylenically unsaturated bond (e.g., an unsaturated carboxylic acid, preferably (meth) acrylic acid) is added to the first precursor to obtain a photosensitive resin composition. Thus, an ethylenically unsaturated group can be introduced into the substituent possessed by the naphthalene skeleton.

[0051] The component (A-1) preferably has a plurality of carboxyl groups in one 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 two or fewer carboxyl groups per one naphthalene skeleton. This can control the solubility. It is more preferable that the carboxyl group is contained in the substituent possessed by the naphthalene skeleton. In order to include the carboxyl group in the substituent possessed by the naphthalene skeleton, a compound in which the H atom of the OH group of naphthol is replaced by a substituent containing an epoxy group is prepared as a first precursor, for example, and a compound having an ethylenically unsaturated bond (e.g., an unsaturated carboxylic acid, preferably (meth) acrylic acid) is added to the first precursor to obtain a second precursor having a secondary hydroxyl group. This can be obtained by adding a carboxylic anhydride (e.g., tetrahydrophthalic acid). This can introduce both ethylenically unsaturated groups and carboxyl groups into the substituent possessed by the naphthalene skeleton.

[0052] In addition, component (A-1) is a resin containing a naphthalene skeleton. A resin containing a naphthalene skeleton refers to a compound containing one or more naphthalene skeletons in one molecule. In addition, component (A-1) can dissolve at a dissolution rate within an appropriate range in an alkaline solution (e.g., an alkaline developer). In addition, when the photosensitive resin composition containing component (A-1) is developed with an alkaline developer, the local generation of portions that dissolve excessively and involuntarily in the photosensitive resin composition can be suppressed. That is, the BP (development point) can be increased. Therefore, the developability of the photosensitive resin composition can be improved.

[0053] Furthermore, when a resin containing a naphthalene skeleton is used as component (A-1), the molecular rigidity is generally increased, thereby suppressing the movement of molecules in the photosensitive resin composition. As a result, the glass transition temperature of the cured product of the photosensitive resin composition is further increased. Furthermore, the action of component (A-1) generally improves the resistance to internal stress caused by thermal expansion and thermal contraction, thereby improving the flexibility of the photosensitive film.

[0054] The component (A-1) may contain one naphthalene skeleton in one molecule, or may contain two or more naphthalene skeletons.

[0055] The component (A-1) is, for example, a resin containing a structure represented by the following formula (1). The component (A-1) may have a plurality of (e.g., 1 to 10, preferably 1 to 6) structures represented by the following formula (1). When the component (A-1) has a plurality of structures represented by the following formula (1), the component (A-1) may contain the plurality of structures represented by the following formula (1) as structural units (repeating units). In addition, in the following formula (1), 1 The chemical bond can be bonded to any carbon atom that can be bonded among the carbon atoms in the naphthalene skeleton. 1 The chemical bond can be bonded to the same carbon atom of the benzene ring as the terminal chemical bond, or it can be bonded to a carbon atom of a different benzene ring. 1 The chemical bonds other than the chemical bonds that bind to OR' specifically refer to the chemical bonds described on the left side of formula (1). For example, the terminal chemical bonds in the naphthalene skeleton and the chemical bonds that bind to R 1 The combination of positions of the combined chemical bonds may be 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 2,3, 2,6, 2,7.

[0056] [Chemical Formula 1]

[0057]

[0058] In the above formula (1), R 1 and R 2 R each independently represents an alkylene group which may have a substituent. 1 The number of carbon atoms 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 methylene, ethylene, propylene, and butylene.

[0059] R 1 and R 2Examples of the substituents that may be possessed include 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.

[0060] In the above formula (1), X represents an arylene group which may have a substituent. The number of carbon atoms in X is usually 6 to 30, preferably 6 to 20, more preferably 6 to 10. Examples of the arylene group include phenylene, anthracene, phenanthrenylene, and biphenylene.

[0061] The substituents that X may have include, for example, 1 and R 2 The substituents which may be possessed are the same as those exemplified above.

[0062] In the above formula (1), a represents 0 or 1. Here, a is the number of groups X.

[0063] In the above formula (1), s represents 0 or 1. Here, s and t are respectively 1 and group R 2 In the above formula (1), t represents 0 or 1. However, s and t cannot be such that s+t is 0. When a=1, it is preferred that both s and t are 1. When a=0, it is preferred that either s or t is 0.

[0064] In the above formula (1), OR' is a substituent on the naphthalene skeleton. In the above formula (1), R' each independently represents an organic group containing an ethylenically unsaturated group and a carboxyl group.

[0065] R' preferably represents a group represented by the following formula (2):

[0066] [Chemical Formula 2]

[0067]

[0068] In the above formula (2), R 3 represents a trivalent group, preferably a trivalent hydrocarbon group optionally having a substituent (wherein a heteroatom may be interposed between carbon-carbon bonds (CC bonds)), preferably a trivalent aliphatic hydrocarbon group optionally having a substituent. 3 It may be a trivalent residue of an epoxy-containing substituent which may have a substituent. 3 The substituents that may be present include, for example, 1 and R 2 The substituents which may be possessed are the same as those exemplified above.

[0069] In the above formula (2), R 4"(Meth)acryloyloxy" refers to an organic group containing an ethylenically unsaturated group. A preferred example of an organic group containing an ethylenically unsaturated group is a (meth)acryloyloxy group. "(Meth)acryloyloxy" includes acryloyloxy, methacryloyloxy, and combinations thereof.

[0070] In the above formula (2), R 5 An example of an organic group containing a carboxyl group is -OCO-R 6 -COOH. Here, R 6 represents a divalent group. 6 , preferably a divalent hydrocarbon group which may have a substituent. 6 The number of carbon atoms is usually 1 to 30, preferably 1 to 20, and more preferably 1 to 6. Examples of the divalent hydrocarbon group include linear or branched non-cyclic alkylene groups such as methylene, ethylene, propylene, and butylene; saturated or unsaturated divalent alicyclic hydrocarbon groups; and arylene groups such as phenylene and naphthylene. Among them, divalent alicyclic hydrocarbon groups and arylene groups are preferred, and 4-cyclohexenylene and phenylene are particularly preferred. In addition, R 6 The substituents that may be present include, for example, 1 and R 2 The substituents that may be possessed are the same as those in the examples. 6 -CO-R in -COOH 6 -COOH is generally a residue of a carboxylic anhydride. Examples of carboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride.

[0071] In the above formula (1), c is generally an integer of 1 to 6, preferably 1 to 3, and more preferably 1 to 2. Here, c is the number of groups OR'.

[0072] -(A-1) First Example of Component (a=1)-

[0073] A preferred example of the component (A-1) is a naphthol aralkyl type resin. "Naphthol aralkyl type resin" refers to a resin containing a group having a structure obtained by removing the H atom of the OH group from a naphthol aralkylene group.

[0074] A preferred naphthol aralkyl type resin is a resin containing a structure in which a=1 in the above formula (1), for example, a resin containing a structure represented by the following formula (3);

[0075] [Chemical Formula 3]

[0076]

[0077] In the above formula (3), R1 、R 2 , X, s, t, R' and c are the same as those described above. Preferably, both s and t are 1.

[0078] A more preferable resin among the naphthol aralkyl type resins is a resin containing a structure in which c=1, s=1 and t=1 in the above formula (3), for example, a naphthol aralkyl type resin containing a divalent group having a structure represented by the following formula (4) or (5).

[0079] [Chemical Formula 4]

[0080]

[0081] [Chemical Formula 5]

[0082]

[0083] In the above formula (4) or (5), R 1 、R 2 , X, R', and c are the same as those described above. The naphthol aralkyl type resin represented by the above formula (4) or (5) is a resin that can be synthesized using the naphthol aralkyl type epoxy resin used in Synthesis Example 1 described later as a material. The naphthol aralkyl type epoxy resin is available, for example, as "ESN-475V" (epoxy equivalent 325 g / eq.) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

[0084] -(A-1) Second Example of Component (a=0)-

[0085] In the component (A-1), preferred examples of resins other than the naphthol aralkyl type resin (a=0) are resins containing a structure in which c=2, s=1, and t=0 in the above formula (1), for example, resins containing a naphthalene skeleton and a divalent group having a structure represented by the following formula (6);

[0086] [Chemical Formula 6]

[0087]

[0088] In the above formula (6), R 1 , R, and R' are the same as those described above. The resin containing a naphthalene skeleton represented by the above formula (6) is a resin that can be synthesized using 1,1'-bis(2,7-diglycidyloxynaphthyl)methane as a raw material. Such a naphthalene skeleton-containing epoxy resin is available, for example, as "EXA-4700" manufactured by Dainippon Ink and Chemicals Co., Ltd.

[0089] The weight average molecular weight of component (A-1) is preferably 500 or more, more preferably 1000 or more, further preferably 1500 or more, and further preferably 2000 or more from the viewpoint of film-forming properties. As the upper limit, from the viewpoint of developability, it is preferably 10000 or less, more preferably 8000 or less, and further preferably 7500 or less. The weight average molecular weight is a weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC).

[0090] -Method for producing component (A-1)-

[0091] (A-1) component is as long as it is the compound with the resin containing naphthalene skeleton, olefinic unsaturated group and carboxyl, is not limited to the above-mentioned example, is not particularly limited, as its one mode, can enumerate and make unsaturated carboxylic acid react with naphthalene-type epoxy compound (epoxy compound containing naphthalene skeleton) with naphthalene skeleton, and then the acid-modified epoxy ester resin containing unsaturated naphthalene skeleton obtained by reacting with carboxylic anhydride etc. for acid-modified epoxy ester resin.For the manufacture method of the epoxy ester resin containing unsaturated naphthalene skeleton, describe.First, make unsaturated carboxylic acid react with the epoxy compound containing naphthalene skeleton and obtain the epoxy ester resin containing unsaturated naphthalene skeleton, then make the epoxy ester resin containing unsaturated naphthalene skeleton and carboxylic anhydride reaction.So can obtain the epoxy ester resin containing unsaturated naphthalene skeleton of acid-modified.

[0092] As the epoxy compound containing a naphthalene skeleton, any compound having one or more epoxy groups in the molecule can be used, and examples thereof include monohydroxynaphthalene-type epoxy resins, dihydroxynaphthalene-type epoxy resins, polyhydroxybinaphthyl-type epoxy resins, naphthalene-type epoxy resins obtained by a condensation reaction of polyhydroxynaphthalene with aldehydes, bis-naphthol-type epoxy resins, and naphthalene-type epoxy resins having a naphthalene skeleton in the molecule. These compounds can be used alone or in combination of two or more.

[0093] Examples of monohydroxynaphthalene epoxy resins include 1-glycidyloxynaphthalene and 2-glycidyloxynaphthalene. Examples of dihydroxynaphthalene epoxy resins include 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene, 2,3-diglycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, and 2,7-diglycidyloxynaphthalene.

[0094] Examples of the polyhydroxybinaphthyl epoxy resin include 1,1'-(2-glycidyloxy)binaphthyl, 1-(2,7-diglycidyloxy)-1'-(2'-glycidyloxy)binaphthyl, and 1,1'-(2,7-diglycidyloxy)binaphthyl.

[0095] Examples of naphthalene-type epoxy resins obtained by a condensation reaction of polyhydroxynaphthalene and aldehydes include 1,1'-bis(2,7-diglycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxynaphthyl)-1'-(2'-glycidyloxynaphthyl)methane, and 1,1'-bis(2-glycidyloxynaphthyl)methane.

[0096] Among them, polyhydroxybinaphthyl epoxy resins having two or more naphthalene skeletons in one molecule and naphthalene epoxy resins obtained by a condensation reaction of polyhydroxynaphthalene and aldehydes are preferred. In terms of excellent average linear thermal expansion coefficient and excellent heat resistance, 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 three or more epoxy groups in one molecule, are particularly preferred.

[0097] As unsaturated carboxylic acids, for example, acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, etc. can be mentioned. These carboxylic acids can be used alone or in combination of two or more. Among them, from the viewpoint of improving the photocurability of the photosensitive resin composition, acrylic acid and methacrylic acid are preferred. It should be noted that in this specification, the above-mentioned naphthalene-type epoxy compound ester resin as a reactant of a naphthalene-type epoxy compound and (meth) acrylic acid is sometimes described as "naphthalene-type epoxy compound (meth) acrylate", where the epoxy group of the naphthalene-type epoxy compound is generally substantially eliminated by reaction with (meth) acrylic acid. "(Meth) acrylate" includes methacrylate, acrylate and a combination thereof. Acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth) acrylic acid".

[0098] Examples of the carboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. Any one of these carboxylic anhydrides may be used alone, or two or more may be used in combination. Among these, succinic anhydride and tetrahydrophthalic anhydride are preferred from the perspective of improving the developability and insulation reliability of the cured product.

[0099] When obtaining the acid-modified epoxy ester resin containing an unsaturated naphthalene skeleton, an unsaturated carboxylic acid can be reacted with an epoxy compound containing a naphthalene skeleton in the presence of a catalyst to obtain the epoxy ester resin containing an unsaturated naphthalene skeleton, and then the epoxy ester resin containing an unsaturated naphthalene skeleton can be reacted with carboxylic anhydride.

[0100] The amount of the catalyst used is preferably at most 2 mass%, more preferably 0.0005 to 1 mass%, further preferably 0.001 to 0.5 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-n-butylamine 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)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, and 2,4-dimethylimidazole. Various amine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium salts, tetraethylphosphonium salts, tetrapropylphosphonium salts, tetrabutylphosphonium salts, trimethyl(2-hydroxypropyl)phosphonium salts, triphenylphosphonium salts, and benzylphosphonium salts, typically having a chloride ion, bromide ion, carboxylate ion, or hydroxide ion as a counter anion; sulfonium salts such as trimethylsulfonium salts, benzyltetramethylenesulfonium salts, phenylbenzylmethylsulfonium salts, and phenyldimethylsulfonium salts, typically having a carboxylate ion, hydroxide ion, or the like as a counter anion; and acidic compounds such as phosphoric acid, p-toluenesulfonic acid, and sulfuric acid. The reaction can be carried out at a temperature between 50°C and 150°C, preferably between 80°C and 120°C.

[0101] When obtaining the acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin, an organic solvent may be used. As the organic solvent, the same solvent as the solvent (G) described later may be used.

[0102] When obtaining an acid-modified epoxy ester resin containing 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 in the range of 0.0005% by mass to 1% by mass, and even more preferably in the range of 0.001% by mass to 0.5% by mass, relative to the total mass of the unsaturated carboxylic acid, the epoxy compound containing a naphthalene skeleton, and the carboxylic anhydride.

[0103] The acid-modified epoxy ester resin containing an unsaturated naphthalene skeleton is preferably an acid-modified epoxy (meth)acrylate containing a naphthalene skeleton. The acid-modified epoxy (meth)acrylate containing a naphthalene skeleton is an acid-modified epoxy ester resin containing an unsaturated naphthalene skeleton obtained by using an epoxy compound containing a naphthalene skeleton and (meth)acrylic acid as an unsaturated carboxylic acid.

[0104] Another embodiment of component (A-1) includes a (meth)acrylic resin containing an unsaturated modified naphthalene skeleton, wherein an ethylenically unsaturated group is introduced by reacting a "(meth)acrylic resin having a structural unit obtained by polymerizing (meth)acrylic acid" with an "epoxy compound containing an ethylenically unsaturated group and a naphthalene skeleton." Furthermore, a carboxylic anhydride can be reacted with the hydroxyl group generated by the introduction of the unsaturated group. The carboxylic anhydride can be the same as that of the acid anhydride described above, and the preferred range is the same.

[0105] ((A-2) Acid-modified epoxy (meth)acrylate resin)

[0106] The acid-modified epoxy (meth)acrylate resin as 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, component (A-2) does not contain component (A-1).

[0107] One embodiment of the component (A-2) includes acid-modified cresol novolac epoxy (meth)acrylates obtained by reacting (meth)acrylic acid with a cresol novolac epoxy compound such as a cresol novolac epoxy compound such as a cresol novolac epoxy compound A or a cresol novolac epoxy compound F, and then reacting the mixture with a carboxylic anhydride. 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, or by reacting the cresol novolac epoxy (meth)acrylate with a carboxylic anhydride.

[0108] Other embodiments of the component (A-2) include acid-modified epoxy (meth)acrylates obtained by reacting (meth)acrylic acid with an epoxy compound other than the above-mentioned cresol novolac epoxy compound and further reacting with a carboxylic anhydride. Examples of such epoxy compounds include biphenyl epoxy compounds; bisphenol-type epoxy compounds such as bisphenol A epoxy compounds and bisphenol F epoxy compounds; and phenol novolac epoxy compounds. novolac epoxy resins; novolac epoxy resins such as bisphenol A novolac epoxy resins and alkylphenol novolac epoxy resins; fluorinated epoxy resins such as perfluoroalkyl epoxy resins; biphenylol epoxy resins; dicyclopentadiene epoxy resins; epoxy resins containing condensed ring skeletons such as trisphenol epoxy resins, tert-butyl-catechol epoxy resins, and anthracene epoxy resins; glycidylamine epoxy resins; glycidyl ester epoxy resins; linear aliphatic epoxy resins; epoxy resins having a butadiene structure; alicyclic epoxy resins; heterocyclic epoxy resins; epoxy resins containing spiro rings; cyclohexanedimethanol epoxy resins; trimethylol epoxy resins; tetraphenylethane epoxy resins; glycidyl group-containing acrylic resins such as polyglycidyl (meth)acrylate and copolymers of glycidyl methacrylate and acrylate; fluorene epoxy resins; halogenated epoxy resins, etc.

[0109] Such acid-modified epoxy (meth)acrylates can be commercially available products. Specific examples include: "CCR-1179" (cresol novolac F-type epoxy acrylate) manufactured by Nippon Kayaku Co., Ltd.), "ZAR-2000" (acid-modified bisphenol-type epoxy acrylate: a reaction product of bisphenol A-type epoxy resin, acrylic acid, and succinic anhydride), "ZFR-1491H" (acid-modified bisphenol-type epoxy acrylate: a reaction product of bisphenol F-type epoxy resin, acrylic acid, and acid anhydride), "ZFR-1533H" (acid-modified bisphenol-type epoxy acrylate: a reaction product of bisphenol F-type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride), "ZCR-1569H" (acid-modified biphenyl-type epoxy acrylate: a reaction product of biphenyl-type epoxy resin, acrylic acid, and acid anhydride), and "PR-300CP" (a reaction product of cresol novolac-type epoxy resin, acrylic acid, and acid anhydride) manufactured by Showa Denko K.K. These may be used alone or in combination of two or more.

[0110] As another form of component (A-2), there can be mentioned an unsaturated modified (meth) acrylic resin into which an ethylenically unsaturated group is introduced by reacting a (meth) acrylic resin (which has a structural unit obtained by polymerizing (meth) acrylic acid) with a (meth) acrylic acid ester of an epoxy compound. Examples of the (meth) acrylic acid ester of an epoxy compound include glycidyl methacrylate, 4-hydroxybutyl (meth) acrylic acid glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth) acrylic acid. Furthermore, the hydroxyl group generated when the unsaturated group is introduced can also be reacted with a carboxylic anhydride. As the carboxylic anhydride, the same substances as those described above can be used, and the preferred range is also the same.

[0111] Commercially available products can be used for such unsaturated modified (meth) acrylic resins. Specific examples include "SPC-1000" and "SPC-3000" manufactured by Showa Denko K.K., and "CYCLOMER P(ACA)Z-250," "CYCLOMER P(ACA)Z-251," "CYCLOMER P(ACA)Z-254," "CYCLOMER P(ACA)Z-300," and "CYCLOMER P(ACA)Z-320" manufactured by Daicel-Allnex.

[0112] The weight average molecular weight of component (A-2) is preferably 1000 or more, more preferably 1500 or more, and further preferably 2000 or more from the viewpoint of film-forming properties. As the upper limit, from the viewpoint of developability, it is preferably 20000 or less, more preferably 15000 or less, and further preferably 14000 or less. The weight average molecular weight is a weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC).

[0113] The component (A) may be a component (A-3) other than the components (A-1) and (A-2). This component does not include the components (A-1) and (A-2).

[0114] The weight average molecular weight and acid value of component (A-3) are arbitrary, but are preferably in the same range as those of component (A-2). Thus, the same advantages as those described in the section on component (A-2) can be obtained.

[0115] The acid value of component (A) is preferably 0.1 mgKOH / g or more, 0.5 mgKOH / g or more, or 1 mgKOH / g or more, from the viewpoint of improving the solubility of the photosensitive resin composition in an alkaline solution. On the other hand, from the viewpoint of suppressing the dissolution of the fine pattern of the cured product into the alkaline solution, the acid value is preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, and further preferably 100 mgKOH / g or less. Here, the acid value is the residual acid value of the carboxyl group present in component (A), and the acid value can be measured by the following method. First, accurately weigh about 1 g of the resin solution to be measured, and then add 30 g of acetone to the resin solution to uniformly dissolve the resin solution. Next, add an appropriate amount of phenolphthalein as an indicator to the solution, and titrate using a 0.1 N ethanolic KOH solution. The acid value is then calculated by the following formula (1);

[0116] Formula: A = Vf × 5.611 / (Wp × I) ···(1).

[0117] In the above formula (1), A represents the acid value [mgKOH / g], Vf represents the titration amount of the KOH solution [mL], Wp represents the mass of the measured resin solution [g], and I represents the ratio of the nonvolatile component of the measured resin solution [mass %].

[0118] From the viewpoint of adjusting the solubility of the photosensitive resin composition in an alkaline solution, the content of component (A) is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, based on 100% by mass of the non-volatile component in the photosensitive resin composition. It should be noted that, in the present invention, the content of each component in the photosensitive resin composition is a value based on 100% by mass of the non-volatile component in the photosensitive resin composition, unless otherwise specified.

[0119] <(B) Inorganic fillers>

[0120] The photosensitive resin composition contains an inorganic filler (B) as the component (B). By containing the component (B) in the photosensitive resin composition, a photosensitive resin composition capable of producing a cured product having a low dielectric constant and dielectric loss tangent can be provided.

[0121] (B) The material of the inorganic filler is not particularly limited, and examples thereof include silica, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium 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, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate. Among them, silica is particularly preferred. In addition, spherical silica is preferably used as silica. (B) The inorganic filler can be used alone or in combination of two or more.

[0122] From the viewpoint of obtaining a cured product with low dielectric constant and dielectric loss tangent, the average particle size of the (B) inorganic filler is preferably less than 10 μm, more preferably less than 5 μm, further preferably less than 3 μm, less than 2 μm, less than 1 μm or less than 0.7 μm. The lower limit of the average particle size is not particularly limited, but is preferably more than 0.01 μm, more preferably more than 0.05 μm, further preferably more than 0.07 μm, more than 0.1 μm or more than 0.2 μm.

[0123] The average particle size 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 made on a volume basis by using a laser diffraction scattering particle size distribution measuring device, and its median particle size is measured as the average particle size. The measurement sample can preferably use a sample in which the inorganic filler is dispersed in water using ultrasound. As a laser diffraction scattering particle size distribution measuring device, "LA-500" manufactured by Horiba, Ltd., "SALD-2200" manufactured by Shimadzu Corporation, etc. can be used.

[0124] From the viewpoint of obtaining a cured product having low dielectric constant and dielectric loss tangent, the specific surface area of the inorganic filler (B) is preferably 1 m 2 / g or more, preferably 3m 2 / g or more, particularly preferably 5m 2 There is no particular upper limit, but it is preferably 60 m 2 / g or less, 50m 2 / g or less or 40m 2 The specific surface area can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring apparatus (Macsorb HM-1210 manufactured by Mountech) according to the BET method and calculating the specific surface area by the BET multipoint method.

[0125] From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler (B) is preferably surface-treated with one or more surface treatment agents such as an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane compound, an organosilazane compound, or a titanate coupling agent. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM-4803” (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.

[0126] (B) Inorganic fillers can be commercially available. Examples of commercially available products include "SC2050," "SC4050," and "Admafine" manufactured by Admatechs, "SFP Series" manufactured by Denki Kagaku Kogyo Co., Ltd., "SP(H) Series" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd., "Sciqas Series" manufactured by Sakai Chemical Industries, Ltd., "SEAHOSTAR Series" manufactured by Nippon Shokubai Co., Ltd., "AZ Series" and "AX Series" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd., and "B Series" and "BF Series" manufactured by Sakai Chemical Industries, Ltd.

[0127] From the viewpoint of obtaining a cured product with a low dielectric constant and dielectric loss tangent, when the non-volatile component in the photosensitive resin composition is set to 100% by mass, the content of the (B) inorganic filler is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more. From the viewpoint of suppressing light reflection during exposure and obtaining excellent developability, the upper limit is, for example, 75% by mass or less, 70% by mass or less, or 65% by mass or less.

[0128] <(C) Photopolymerization initiator>

[0129] The photosensitive resin composition contains a photopolymerization initiator as the component (C). By containing the photopolymerization initiator (C) in the photosensitive resin composition, the photosensitive resin composition can be efficiently photocured.

[0130] (C) As the photopolymerization initiator, any compound may be used, 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-based 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-acetoxime); 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-[4-(4-morpholinophenyl)phenyl]-1-butanone, 2-methyl- α-Aminoalkylphenone-based photopolymerization initiators such as 1-[4-(methylthio)phenyl]-2-morpholino-1-propanone; benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl (2,4,6-trimethylbenzoyl)phenylphosphonate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxycyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, and sulfonium salt-based photopolymerization initiators can also be used. These photopolymerization initiators can be used alone or in combination of two or more. Among them, from the viewpoint of making the photosensitive resin composition more effectively photocurable, preferably any of acylphosphine oxide-based photopolymerization initiators and oxime ester-based photopolymerization initiators, more preferably acylphosphine oxide-based photopolymerization initiators. These photopolymerization initiators can be used alone or in combination of two or more.

[0131] Specific examples of the (C) photopolymerization initiator include "Omnirad 907", "Omnirad 369", "Omnirad 379", "Omnirad 819", and "Omnirad TPO" manufactured by IGM, "Irgacure OXE-01", "Irgacure OXE-02", "Irgacure TPO", and "Irgacure 819" manufactured by BASF, and "N-1919" manufactured by ADEKA.

[0132] As for the content of the photopolymerization initiator (C), from the viewpoint of sufficiently photocuring the photosensitive resin composition and improving insulation reliability, when the non-volatile component of the photosensitive resin composition is set to 100 mass %, it is preferably 1 mass % or more, more preferably 1.5 mass % or more, and further preferably 2 mass % or more. On the other hand, from the viewpoint of suppressing the reduction in developability caused by excessive sensitivity, the upper limit is preferably 5 mass % or less, more preferably 4 mass % or less, and further preferably 3 mass % or less.

[0133] Furthermore, the photosensitive resin composition may contain, in combination with component (C), tertiary amines such as ethyl N,N-dimethylaminobenzoate, isopentyl N,N-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, triethylamine, and triethanolamine as photopolymerization initiation aids, and may also contain photosensitizers such as pyrazolines, anthracenes, coumarins, xanthones, and thioxanthones. These compounds may be used alone or in combination of two or more.

[0134] <(D) Epoxy resin>

[0135] The photosensitive resin composition contains an epoxy resin as component (D). Inclusion of component (D) in the photosensitive resin composition can improve insulation reliability. However, component (D) herein does not include epoxy resins containing ethylenically unsaturated groups and carboxyl groups.

[0136] (D) The epoxy resin includes: (D-1) an epoxy resin having a softening point of less than 30°C and an epoxy equivalent of 150 g / eq. or less, and (D-2) an epoxy resin having a softening point of 30°C or higher and less than 59°C. From the viewpoint of obtaining a cured product having excellent dielectric constant and dielectric loss tangent, when the photosensitive resin composition contains the component (E) described later, the solubility of the photosensitive resin composition decreases due to its generally hydrophobic nature, and there is a tendency for the developability to decrease. However, in the present invention, by using the component (D-1) and the component (D-2) having a low softening point and a small epoxy equivalent in combination, the decrease in solubility can be suppressed. As a result, a cured product having the advantages of excellent developability and excellent dielectric constant and dielectric loss tangent inherent to the component (E) is achieved.

[0137] From the viewpoint of significantly achieving the effects of the present invention, the softening point of component (D-1) is less than 30°C, preferably 25°C or less, and more preferably 20°C or less. The lower limit is not particularly limited, but is preferably 0°C or more, more preferably 5°C or more, and further preferably 10°C or more. The softening point can be measured in accordance with JIS K7234.

[0138] From the perspective of significantly achieving the effects of the present invention, the epoxy equivalent of component (D-1) is 150 g / eq. or less, preferably 148 g / eq. or less, more preferably 145 g / eq. or less, preferably 10 g / eq. or more, more preferably 50 g / eq. or more, and even more preferably 100 g / eq. or more. The epoxy equivalent of component (D) is the mass of the epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured in accordance with JIS K7236.

[0139] From the viewpoint of significantly obtaining the effects of the present invention, component (D-1) preferably has one or more epoxy groups in one molecule, more preferably has two or more epoxy groups in one molecule, and further preferably has three or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile component of component (D-1) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0140] The component (D-1) includes a component that is liquid at 20° C. and a component that is solid at 20° C. The component (D-1) is preferably liquid from the viewpoint of improving flexibility.

[0141] As component (D-1), an epoxy resin having a softening point of less than 59°C and an epoxy equivalent of 150 g / eq. or less can be used. From the viewpoint of significantly obtaining the effects of the present invention, such an epoxy resin preferably has a cyclic structure. Examples of the cyclic structure include aromatic ring structures and alicyclic structures. Examples of the aromatic ring structure include benzene rings, naphthalene rings, and anthracene rings. Examples of the alicyclic structure include cyclohexane rings, cyclopentane rings, cycloheptane rings, and cyclooctane rings. Among these, the cyclic structure is preferably an aromatic ring structure, more preferably a naphthalene ring or a benzene ring, and still more preferably a naphthalene ring.

[0142] In addition, examples of the component (D-1) include naphthalene-type epoxy resins, glycidylamine-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-type epoxy resins, glycidylcyclohexane-type epoxy resins, isocyanurate-type epoxy resins, and naphthylene ether-type epoxy resins. Preferred are naphthalene-type epoxy resins and glycidylamine-type epoxy resins, and more preferred are naphthalene-type epoxy resins.

[0143] Specific examples of the component (D-1) include: "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "ELM-434L" (glycidylamine-type epoxy resin) manufactured by Sumitomo Chemical Co., Ltd.; "630" (glycidylamine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by Nippon Steel & Sumikin Chemicals Co., Ltd.; and "EP-398" (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by ADEKA Corporation. 0S" (2-functional glycidylamine type epoxy resin); "EP-3950L" (3-functional glycidylamine type epoxy resin) manufactured by ADEKA; "TEPIC-VL" (isocyanuric acid ring type epoxy resin) manufactured by Nissan Chemical Co., Ltd.; "ELM-100H" (N-[2-methyl-4-(oxiranylmethoxy)phenyl]-N-(oxiranylmethyl)oxiranemethaneamine) manufactured by Sumitomo Chemical Co., Ltd.; "EXA-7311-G4" (naphthylene ether type epoxy resin) manufactured by DIC Corporation, etc. These can be used alone or in combination of two or more.

[0144] From the viewpoint of significantly obtaining the desired effects of the present invention, the weight average molecular weight (Mw) of the component (D-1) is preferably at least 100, more preferably at least 200, further preferably at least 250, and is preferably at most 5000, more preferably at most 3000, further preferably at most 1500. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0145] From the viewpoint of obtaining a cured product having excellent developability as well as dielectric constant and dielectric loss tangent, when the total amount of component (D) is 100 mass%, the content of component (D-1) is preferably 90 mass% or less, more preferably 80 mass% or less, further preferably 70 mass% or less, 60 mass% or less, 50 mass% or less, or 40 mass% or less, preferably 10 mass% or more, more preferably 20 mass% or more, further preferably 30 mass% or more.

[0146] From the viewpoint of obtaining a cured product having excellent developability and excellent dielectric constant and dielectric loss tangent, when the non-volatile component in the photosensitive resin composition is set to 100 mass%, the content of the component (D-1) 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.

[0147] From the viewpoint of significantly achieving the effects of the present invention, the softening point of component (D-2) is 30°C or higher, preferably 35°C or higher, and more preferably 40°C or higher. From the viewpoint of significantly achieving the effects of the present invention, the upper limit is less than 59°C, preferably 55°C or lower, and more preferably 50°C or lower. The softening point can be measured by the same method as for component (D-1).

[0148] As component (D-2), from the viewpoint of significantly obtaining the effect of the present invention, it is preferred that one or more epoxy groups be present in one molecule, more preferably two or more epoxy groups be present in one molecule, and further preferably three or more epoxy groups be present in one molecule. From the viewpoint of significantly obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile component of component (D-2) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0149] The component (D-2) is preferably in a solid state at a temperature of 20°C.

[0150] As component (D-2), an epoxy resin having a softening point of 30°C or higher and less than 59°C can be used. From the viewpoint of significantly obtaining the effects of the present invention, such an epoxy resin preferably has a cyclic structure. Examples of the cyclic structure include aromatic ring structures and alicyclic structures. Examples of the aromatic ring structure include benzene rings, naphthalene rings, anthracene rings, and biphenyl rings. Examples of the alicyclic structure include cyclohexane rings, cyclopentane rings, cycloheptane rings, and cyclooctane rings. Among these, the cyclic structure is preferably an aromatic ring structure, more preferably a benzene ring or a biphenyl ring, and further preferably a biphenyl ring.

[0151] Moreover, as (D-2) component, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthylene ether type epoxy resin etc. are mentioned, for example, Biphenyl type epoxy resin is more preferable.

[0152] Specific examples of the component (D-2) include "NC3000L" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "HP-7200L" (dicyclopentadiene-type epoxy resin) and "HP-6000L" (naphthylene ether-type epoxy resin) manufactured by DIC Corporation; and "NC3000" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more.

[0153] The epoxy equivalent of component (D-2) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., further preferably 80 g / eq. to 2000 g / eq., and further preferably 110 g / eq. to 1000 g / eq. Within this range, the crosslinking density of the cured product of the photosensitive resin composition layer is sufficient, and an insulating layer with reduced surface roughness can be obtained.

[0154] From the viewpoint of significantly obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of the component (D-2) 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.

[0155] From the viewpoint of obtaining a cured product having excellent developability as well as dielectric constant and dielectric loss tangent, when the total amount of component (D) is 100% by mass, the content of component (D-2) 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, or 60% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.

[0156] From the viewpoint of obtaining a cured product having excellent developability and excellent dielectric constant and dielectric loss tangent, when the non-volatile component in the photosensitive resin composition is set to 100 mass%, the content of the component (D-2) 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.

[0157] When the content of component (D-1) when the non-volatile components in the photosensitive resin composition are 100% by mass is D1, and the content of component (D-2) when the non-volatile components in the photosensitive resin composition are 100% by mass is D2, D2 / D1 is preferably at least 0.5, more preferably at least 1, further preferably at least 1.5, and preferably at most 2.5, more preferably at most 2.3, further preferably at most 2.2. By setting the ratio of the amount of component (D-1) to the amount of component (D-2) within the above range, the desired effect of the present invention can be significantly achieved.

[0158] 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:

[0159] (1) Epoxy resins with a softening point of 59°C or above, and

[0160] (2) Epoxy resins with a softening point less than 30°C and an epoxy equivalent weight exceeding 150 g / eq.;

[0161] The softening point of the component (D-3) is measured in the same manner as that of the component (D-1).

[0162] Examples of the component (D-3) include bixylenol epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AF epoxy resins, dicyclopentadiene epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, phenol novolac epoxy resins, tert-butylcatechol epoxy resins, naphthalene epoxy resins, naphthol epoxy resins, anthracene epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, cresol novolac epoxy resins, and the like. Novolac-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro-ring-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, and the like. The epoxy resins (D-3) may be used alone or in combination of two or more.

[0163] In the photosensitive resin composition, it is preferred that an epoxy resin having two or more epoxy groups per molecule be included as component (D-3). From the viewpoint of significantly achieving the desired effect of the present invention, the proportion of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the non-volatile component of component (D-3) is preferably at least 50% by mass, more preferably at least 60% by mass, and particularly preferably at least 70% by mass.

[0164] The component (D-3) contains an epoxy resin that is liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resin"). The component (D-3) may contain only the liquid epoxy resin, only the solid epoxy resin, or a combination of the liquid epoxy resin and the solid epoxy resin. However, from the viewpoint of significantly achieving the desired effects of the present invention, it is preferred that only the solid epoxy resin be contained.

[0165] The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

[0166] As solid epoxy resins, preferred are biphenylol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins, and more preferred are naphthalene-type epoxy resins.

[0167] Specific examples of solid epoxy resins include: "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "HP-7200" and "HP-7100" (naphthalene-type tetrafunctional epoxy resins) manufactured by DIC Corporation. "200HH", "HP-7200H" (dicyclopentadiene type epoxy resin); "EXA-7311" and "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol phenol formaldehyde type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H" and "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Epoxy resin); ESN475V (naphthol epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; ESN485 (naphthol novolac epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; YX4000H, YX4000, and YL6121 (biphenyl epoxy resin) manufactured by Mitsubishi Chemical Corporation; YX4000HK (biphenyl epoxy resin) manufactured by Mitsubishi Chemical Corporation; YX880 0" (anthracene type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetrahydroxyphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These can be used alone or in combination of two or more.

[0168] The liquid epoxy resin is preferably one having two or more epoxy groups in one molecule.

[0169] As liquid epoxy resins, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure, and more preferred are bisphenol A type epoxy resin and bisphenol F type epoxy resin.

[0170] Specific examples of liquid epoxy resins include: "828US", "jER828EL", "825", and "EPIKOTE 828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemicals; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; and "CELLOXIDE 2021P" (alicyclic epoxy resin with an ester skeleton); "PB-3600" manufactured by Daicel Corporation (epoxy resin with a butadiene structure); "ZX1658" manufactured by Nippon Steel & Sumikin Chemical Corporation (liquid 1,4-glycidylcyclohexane type epoxy resin), etc. These may be used alone or in combination of two or more.

[0171] When a liquid epoxy resin and a solid epoxy resin are used in combination as component (D-3), the mass ratio of these components (liquid epoxy resin:solid epoxy resin) is preferably from 1:1 to 1:20, more preferably from 1:1.5 to 1:15, and particularly preferably from 1:2 to 1:10. By adjusting the mass ratio of the liquid epoxy resin to the solid epoxy resin within this range, the desired effects of the present invention can be significantly achieved.

[0172] The epoxy equivalent of component (D-3) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., further preferably 80 g / eq. to 2000 g / eq., and further preferably 110 g / eq. to 1000 g / eq. Within this range, the crosslinking density of the cured product of the photosensitive resin composition layer is sufficient, resulting in an insulating layer with reduced surface roughness.

[0173] From the viewpoint of remarkably obtaining the desired effects of the present invention, the weight average molecular weight (Mw) of the component (D-3) is preferably from 100 to 5,000, more preferably from 250 to 3,000, further preferably from 400 to 1,500.

[0174] From the viewpoint of improving the mechanical strength and solubility resistance of the cured product of the photosensitive resin composition, when the non-volatile component in the photosensitive resin composition is set to 100% by mass, the content of component (D-3) is preferably 1% by mass or more, more preferably 1.5% by mass or more, and further preferably 2% by mass or more. From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit of the content of component (D-3) is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less.

[0175] From the viewpoint of significantly obtaining the effects of the present invention, when the total amount of the component (D) is 100% by mass, the content of the component (D-3) is preferably 0% by mass or more, more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.3% by mass or less.

[0176] <(E) One or more resins selected from active ester resins, maleimide resins, and vinyl resins>

[0177] The photosensitive resin composition comprises, as component (E), one or more resins selected from active ester resins, maleimide resins, and vinyl resins. The inclusion of component (E) in the photosensitive resin composition can improve the dielectric constant, dielectric loss tangent, and glass transition temperature.

[0178] 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.

[0179] ((E1) Active ester resin)

[0180] The active ester resin (E1) as the component (E) can react with the epoxy group of the component (D) to obtain a cured product with low dielectric constant and dielectric loss tangent. The active ester resins may be used alone or in combination of two or more.

[0181] As (E1) active ester resin, it is generally preferred to use phenolic esters, thiophenolic esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc., which have two or more reactive ester groups in one molecule. The active ester resin is preferably a compound obtained by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferably an active ester resin obtained from a carboxylic acid compound and a hydroxy compound, and more preferably an active ester resin obtained from a carboxylic acid compound and a phenolic compound and / or a naphthol compound. As the carboxylic acid compound, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. can be listed. Examples of the phenolic compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, 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, pyrogallol, dicyclopentadiene-type diphenolic compounds, and phenol novolac. Here, the term "dicyclopentadiene-type diphenolic compound" refers to a diphenolic compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0182] Specifically, the active ester resin (E1) is preferably a dicyclopentadiene-type active ester resin, a naphthalene-type active ester resin containing a naphthalene structure, an active ester resin containing an acetylated product of a novolac resin, or an active ester resin containing a benzoylated product of a novolac resin. More preferably, at least one selected from the group consisting of a dicyclopentadiene-type active ester resin and a naphthalene-type active ester resin is used, and even more preferably, a dicyclopentadiene-type active ester resin. The dicyclopentadiene-type active ester resin is preferably an active ester resin containing a dicyclopentadiene-type diphenol structure. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit composed of a phenylene-dicyclopentylene-phenylene group.

[0183] Examples of commercially available active ester resins (E1) include active ester resins containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", and "EXB-8000L-65TM" (manufactured by DIC Corporation); and active ester resins containing a naphthalene structure include "EXB-8151-62T", "HPC-8150-60T", "HPC-8150-62T", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T", and "EXB9416-70BK" (manufactured by DIC Corporation), and "PC1300-02-65MA" (manufactured by WATER Co., Ltd.); active ester resins comprising acetylated products of novolac resins include "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester resins comprising benzoylated products of novolac resins include "YLH1026" (manufactured by Mitsubishi Chemical Corporation); active ester resins comprising acetylated products of novolac resins include "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester resins comprising benzoylated products of novolac resins include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); etc.

[0184] From the perspective of obtaining a cured product with low dielectric constant and dielectric loss tangent, the active ester group equivalent of the active ester resin (E1) is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., and further preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester resin containing one equivalent of active ester groups.

[0185] The amount ratio of the epoxy resin (D) to the active ester resin (E1) is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.3 to 1:3, and even more preferably 1:0.5 to 1:2, as measured by the ratio of [the total number of epoxy groups of the epoxy resin]:[the total number of active groups of the active ester resin]. Here, the "number of epoxy groups of the epoxy resin" refers to the total value obtained by dividing the mass of the non-volatile components of the epoxy resin present in the photosensitive resin composition by the epoxy equivalent. Furthermore, the "number of active groups of the active ester resin" refers to the total value obtained by dividing the mass of the non-volatile components of the active ester resin present in the photosensitive resin composition by the active ester group equivalent. By setting the amount ratio of the epoxy resin (D) to the active ester resin (E1) within the above range, the effects of the present invention can be significantly achieved.

[0186] From the viewpoint of obtaining a cured product having excellent dielectric constant and dielectric properties, the content of the component (E1) is preferably 1% by mass or more, more preferably 1.5% by mass or more, further preferably 2% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, based on 100% by mass of the non-volatile component in the photosensitive resin composition.

[0187] ((E2)Maleimide resin)

[0188] The maleimide resin (E2) as component (E) reacts with the ethylenically unsaturated groups of component (A) to produce a cured product with a low dielectric constant and dielectric loss tangent. However, the maleimide resin (E2) does not include components (A) to (D) and component (E1). The maleimide resins (E2) may be used alone or in combination of two or more.

[0189] As the maleimide resin (E2), a resin containing a maleimide group can be used. The number of maleimide groups per molecule of the maleimide resin (E2) can be 1 or 2 or more, preferably 2. The maleimide group is represented by the following formula (E):

[0190] [Chemical Formula 7]

[0191]

[0192] The maleimide resin (E2) may be any resin containing a maleimide group. The maleimide resin (E2) is preferably one or more selected from the following (E2-1) to (E2-3):

[0193] (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,

[0194] (E2-2) a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group, and

[0195] (E2-3) A maleimide compound containing a trimethylindane skeleton.

[0196] Here, the term "directly" means that in component (E2-1), no other group exists between the nitrogen atom of the maleimide group and the aliphatic group having 5 or more carbon atoms; and in component (E2-2), no other group exists between the nitrogen atom of the maleimide group and the aromatic ring.

[0197] -(E2-1) Component-

[0198] 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. Component (E2-1) can be obtained, for example, by an imidization reaction of a component containing an aliphatic amine compound (such as a diamine compound having a dimer acid skeleton), maleic anhydride, and, if necessary, tetracarboxylic dianhydride.

[0199] Examples of the aliphatic group having 5 or more carbon atoms include an alkyl group, an alkylene group, and an alkenylene group.

[0200] The number of carbon atoms of the alkyl group with more than 5 carbon atoms is preferably more than 6, more preferably more than 8, preferably less than 50, more preferably less than 45, and further preferably less than 40. The alkyl group can be any one of straight-chain, branched, and cyclic, wherein straight-chain is preferred. Examples of such alkyl groups include pentyl, hexyl, heptyl, octyl, nonyl, and decyl. The alkyl group with more than 5 carbon atoms can be a substituent of an alkylene group with more than 5 carbon atoms. The alkyl group with more than 5 carbon atoms can be a part of an alkenyl group or a part of an alkapolyenyl group (the number of double bonds is preferably 2).

[0201] The number of carbon atoms of the alkylene group with more than 5 carbon atoms is preferably more than 6, more preferably more than 8, preferably less than 50, more preferably less than 45, and further preferably less than 40. The alkylene group can be any of straight-chain, branched, and cyclic, wherein straight-chain is preferred. Here, the cyclic alkylene group is a concept including "a case consisting only of a cyclic alkylene group" and "a case comprising both a straight-chain alkylene group and a cyclic alkylene group". As such alkylene groups, for example, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecylene, heptahedylene, hexadecylene, a group with an octylene-cyclohexylene structure, a group with an octylene-cyclohexylene-octylene structure, a group with a propylene-cyclohexylene-octylene structure, etc. The alkylene group with more than 5 carbon atoms can be a part of an alkenylene group or a part of an alkapolyenylene group (the number of double bonds is preferably 2).

[0202] 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, preferably 50 or less, more preferably 45 or less, and further preferably 40 or less. The alkenylene group may be any of straight-chain, branched, and cyclic, wherein straight-chain is preferred. Here, the cyclic alkenylene group is a concept that also includes "a case consisting only of a cyclic alkenylene group" and "a case comprising both a straight-chain alkenylene group and a cyclic alkenylene group". Examples of such alkenylene groups include pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene, heptadecenylene, triheptenylene, trihexadecen ...

[0203] As the component (E2-1), a compound represented by the following formula (E2-1-1) is preferred:

[0204] [Chemical Formula 8]

[0205]

[0206] 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.

[0207] M represents a divalent aliphatic group having 5 or more carbon atoms which may optionally have a substituent. The carbon number of the divalent aliphatic group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and further preferably 40 or less. The aliphatic group may be any one of a straight chain, a branched chain, and a cyclic shape, wherein a straight chain shape is preferred. Here, a cyclic aliphatic group is a concept that also includes "a case formed only by a cyclic aliphatic group" and "a case containing both a straight chain aliphatic group and a cyclic aliphatic group". As divalent aliphatic groups, alkylene groups, alkenylene groups, polyalkenylene groups (preferably having 2 double bonds) and the like can be cited. For alkylene groups and alkenylene groups, as shown above.

[0208] Examples of the substituent of M include a halogen atom, -OH, -OC 1-10 Alkyl, -N(C 1-10 Alkyl)2, C 1-10 Alkyl, C 2-30 Alkenyl, C 2-30 Alkynyl, C 6-10 Aryl, -NH2, -CN, -C(O)OC 1-10 Alkyl, -COOH, -C(O)H, -NO2, etc. Here, the term "C x-y"" (x and y are positive integers, satisfying x < y) means that the number of carbon atoms in the organic group immediately following the term is x to y. For example, "C 1-10 The expression "alkyl" means an alkyl group having 1 to 10 carbon atoms. These substituents may be combined with each other to form a ring, and the ring structure may include a spiro ring or a condensed ring. The substituent is preferably an alkyl group having 5 or more carbon atoms.

[0209] L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C(=O)-, -C(=O)-O-, and -NR 0 -(R 0 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms), an oxygen atom, a sulfur atom, C(=O)NR 0 -, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and a group composed of two or more divalent groups thereof. Alkylene, alkenylene, alkynylene, arylene, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and a group composed of two or more divalent groups may 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 acid diimide means a divalent group derived from pyromellitic acid diimide, specifically a group represented by the general formula (E2-1-3). In the formula, "*" represents a chemical bond;

[0210] [Chemical Formula 9]

[0211]

[0212] 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, and particularly preferably an alkylene group having 1 to 40 carbon atoms. The alkylene group may be any of linear, branched, and cyclic. Examples of such alkylene groups include methylethylene, cyclohexylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecylene, hexatriadecylene, groups having an octylene-cyclohexylene structure, groups having an octylene-cyclohexylene-octylene structure, and groups having a propylene-cyclohexylene-octylene structure.

[0213] 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, and 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, and octenylene.

[0214] 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, and particularly preferably an alkynylene group having 2 to 40 carbon atoms. The alkynylene group may be linear, branched, or cyclic. Examples of such alkynylene groups include methylethynylene, cyclohexynylene, pentynylene, hexynylene, heptynylene, and octynylene.

[0215] 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, further preferably an arylene group having 6 to 14 carbon atoms, and further more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include phenylene, naphthylene, and anthracene.

[0216] The divalent linking group in L, alkylene, alkenylene, alkynylene, and arylene, may have a substituent. The substituent is the same as the substituent of M in the general formula (E2-1-1), and is preferably an alkyl group having 5 or more carbon atoms.

[0217] Examples of the group composed of two 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 an alkylene group and a divalent group derived from pyromellitic acid imide; and the like. A group composed of two or more divalent groups can form a ring such as a fused ring by combining the groups. Furthermore, the number of repeating units of the group composed of two or more divalent groups can be 1 to 10.

[0218] Among them, 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 acid diimide, or a divalent group composed of a combination of two or more of these groups. Among them, L is more preferably: an alkylene group; a divalent group having a structure of an alkylene group-divalent group derived from phthalimide-oxygen atom-divalent group derived from phthalimide; a divalent group having a structure of an alkylene group-divalent group derived from phthalimide-oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-divalent group derived from phthalimide; a divalent group having a structure of an alkylene group-divalent group derived from pyromellitic acid imide; a divalent group having a structure of an alkynylene group-divalent group derived from phthalimide-oxygen atom-divalent group derived from phthalimide; a divalent group having a structure of an alkynylene group-divalent group derived from phthalimide-oxygen atom-arylene group-alkynylene group-arylene group-oxygen atom-divalent group derived from phthalimide; a divalent group having a structure of an alkynylene group-divalent group derived from phthalimide-oxygen atom-arylene group-alkynylene group-arylene group-oxygen atom-divalent group derived from phthalimide; a divalent group having a structure of an alkynylene group-divalent group derived from pyromellitic acid imide.

[0219] The maleimide resin represented by the general formula (E2-1-1) is preferably a maleimide resin represented by the general formula (E2-1-4):

[0220] [Chemical Formula 10]

[0221]

[0222] In the general formula (E2-1-4), M 1 Each 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.

[0223] M 1 Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. 1 The same as M in the general formula (E2-1-1).

[0224] Z each independently represents a divalent aliphatic group having 5 or more carbon atoms and optionally having a substituent or a divalent group having an aromatic ring and optionally having a substituent. Examples of the divalent aliphatic group in Z include an alkylene group, an alkenylene group, and a polyalkenylene group (more preferably having 2 double bonds). The divalent aliphatic group may be any of chain, branched, and cyclic, and preferably is a cyclic, i.e., a cyclic, divalent aliphatic group having 5 or more carbon atoms and optionally having a substituent.

[0225] The number of carbon atoms of the alkylene group is preferably at least 6, more preferably at least 8, preferably at most 50, more preferably at most 45, further preferably at most 40. Examples of such an alkylene group include a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

[0226] 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, preferably 50 or less, more preferably 45 or less, and further preferably 40 or less. The alkenylene group may be any of straight-chain, branched, and cyclic, wherein straight-chain is preferred. Here, the cyclic alkenylene group is a concept that also includes "a case consisting only of a cyclic alkenylene group" and "a case comprising both a straight-chain alkenylene group and a cyclic alkenylene group". Examples of such alkenylene groups include pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene, heptadecenylene, trihexadecen ...

[0227] 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 acid diimide ring, and an aromatic heterocyclic ring. A benzene ring, a phthalimide ring, and a pyromellitic acid diimide ring are preferred. Specifically, the divalent group having an aromatic ring is preferably a divalent group having a benzene ring optionally having a substituent, a divalent group having a phthalimide ring optionally having a substituent, or a divalent group having a pyromellitic acid diimide ring optionally having a substituent. Examples of the divalent group having an aromatic ring include a group composed of a divalent group derived from phthalimide and an oxygen atom; 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 acid imide; a divalent group derived from pyromellitic acid imide; a group composed of a divalent group derived from phthalimide and an alkylene group; and the like. These arylene groups are the same as the arylene groups in the divalent linking group represented by L in general formula (E2-1-1).

[0228] The alkylene group and the divalent group having an aromatic ring represented by Z may have a substituent. The substituent is the same as the substituent that M in the general formula (E2-1-1) may have.

[0229] Specific examples of the group represented by Z include the following groups: Wherein, "*" represents a chemical bond;

[0230] [Chemical Formula 11]

[0231]

[0232] [Chemical Formula 12]

[0233]

[0234] 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);

[0235] [Chemical Formula 13]

[0236]

[0237] In the general formula (E2-1-5), M 2 and M 3 Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, R 40 Each independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group composed of two or more of these groups. t1 represents an integer from 1 to 10;

[0238] In the general formula (E2-1-6), M 4 、M 6 and M 7 Each independently represents an aliphatic group having 5 or more carbon atoms which may have a substituent, M 5 Each independently represents a divalent group having an aromatic ring which may have a substituent, R 41 and R 42 Each independently represents an alkyl group having at least 5 carbon atoms. t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

[0239] M 2 and M 3 Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. 2 and M 3The divalent aliphatic group having 5 or more carbon atoms represented by M in the general formula (E2-1-1) is the same as that of the divalent aliphatic group, and preferably is a hexatriacenylene group or a hexatriadecylene group.

[0240] R 40 Each independently represents an oxygen atom, an arylene group, an alkylene group, or a group composed of two or more divalent groups thereof. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (E2-1-1). 40 , preferably a group composed of two or more divalent groups or an oxygen atom.

[0241] As R 40 The group consisting of two or more divalent groups in the combination thereof includes a combination of an oxygen atom, an arylene group, and an alkylene group. Specific examples of the group consisting of two or more divalent groups include the following groups.

[0242] In the formula, “*” represents a chemical bond;

[0243] [Chemical Formula 14]

[0244]

[0245] M 4 、M 6 and M 7 Each independently represents an aliphatic group having 5 or more carbon atoms which may have a substituent. 4 、M 6 and M 7 The aliphatic group having 5 or more carbon atoms and optionally having a substituent represented by M in the general formula (E2-1-1) is the same as that represented by M, preferably a hexylene group, a heptylene group, an octylene group, a nonylene group or a decylene group, and more preferably an octylene group.

[0246] M 5 Each independently represents a divalent group having an aromatic ring which may have a substituent. 5 The same as the divalent group having an aromatic ring and optionally having a substituent represented by Z in the general formula (E2-1-4), preferably a group composed of a combination of an alkylene group and a divalent group derived from pyromellitic acid imide; a group composed of a combination of a divalent group derived from phthalimide and an alkylene group, more preferably a group composed of a combination of an alkylene group and a divalent group derived from pyromellitic acid imide. The above-mentioned arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in the general formula (E2-1-1).

[0247] As M 5 Specific examples of the group represented by include the following groups. In the formula, “*” represents a chemical bond;

[0248] [Chemical Formula 15]

[0249]

[0250] R 41 and R 42 Each independently represents an alkyl group having 5 or more carbon atoms. 41 and R 42 As with the above-mentioned alkyl group having 5 or more carbon atoms, preferred are hexyl, heptyl, octyl, nonyl and decyl, and more preferred are hexyl and octyl.

[0251] u1 and u2 each independently represent an integer of 1-15, preferably an integer of 1-10.

[0252] Specific examples of the component (E2-1) include the following compounds (Ei) to (E-iii), but the present invention is not limited to these specific examples.

[0253] Wherein, v represents an integer from 1 to 10;

[0254] [Chemical Formula 16]

[0255]

[0256] [Chemical Formula 17]

[0257]

[0258] Specific examples of the component (E2-1) include "BMI1500" (compound of formula (Ei)), "BMI1700" (compound of formula (E-ii)), and "BMI689" (compound of formula (E-iii)) manufactured by Designer Molecules.

[0259] The weight average molecular weight (Mw) of the component (E2-1) is preferably from 150 to 5,000, more preferably from 300 to 2,500.

[0260] From the viewpoint of significantly achieving the desired effects of the present invention, the maleimide group equivalent of component (E2-1) is preferably from 50 g / eq. to 2000 g / eq., more preferably from 100 g / eq. to 1000 g / eq., and further preferably from 150 g / eq. to 500 g / eq. The maleimide group equivalent is the mass of component (E2-1) containing one equivalent of maleimide groups.

[0261] -(E2-2) ingredient-

[0262] Component (E2-2) is a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of maleimide. Component (E2-2) can be obtained, for example, by subjecting an aromatic amine compound (such as an aromatic diamine compound) and maleic anhydride to an imidization reaction.

[0263] The aromatic ring may be a carbocyclic ring or a heterocyclic ring. 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; condensed rings formed by condensing two or more 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 condensed rings formed by condensing one or more monocyclic non-aromatic rings to one or more monocyclic aromatic rings such as an indane ring, a fluorene ring, and a tetralin ring. Among them, the aromatic ring is preferably a monocyclic aromatic ring, and more preferably a benzene ring.

[0264] As the component (E2-2), a maleimide compound represented by the following formula (E2-2-1) is preferred.

[0265] [Chemical Formula 18]

[0266]

[0267] Where R c Each independently represents a substituent; X c Each independently represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO- (preferably a single bond or an alkylene group); Z c Each 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 greater (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and further preferably an integer of 1 to 20); t each independently represents an integer of 0 or greater; and u each independently represents an integer of 0 to 2 (preferably 0). Particularly preferred are maleimide compounds represented by formulas (E2-2-2) to (E2-2-5).

[0268] [Chemical Formula 19]

[0269]

[0270] Where R c1 、R c2 and Rc3 Each independently represents an alkyl group; X c1 and X c2 Each independently represents a single bond or an alkylene group; s represents an integer greater than 1 (preferably an integer from 1 to 100, more preferably an integer from 1 to 50, and even more preferably an integer from 1 to 20); t' represents an integer from 1 to 5; u1, u2, and u3 each independently represent an integer from 0 to 2 (preferably 0). It should be noted that the s unit, t unit, t' unit, u unit, u1 unit, u2 unit, and u3 unit may be the same or different.

[0271] Furthermore, as another embodiment, the component (E2-2) is preferably a structure represented by the following formula (E2-2-6):

[0272] [Chemical Formula 20]

[0273]

[0274] Where R 31 and R 36 Represents a maleimide group, R 32 、R 33 、R 34 and R 35 Each of m1 and m2 independently represents a hydrogen atom, an alkyl group, or an aryl group, and each of D independently represents a divalent aromatic group. m1 and m2 independently represent an integer of 1 to 10, and a represents an integer of 1 to 100.

[0275] R in formula (E2-2-6) 32 、R 33 、R 34 and R 35 Each independently represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom.

[0276] 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 even more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear, branched, or cyclic. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, and isopropyl.

[0277] 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 even more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may be a monocyclic ring or a condensed ring. Examples of such aryl groups include phenyl, naphthyl, and anthracenyl.

[0278] The alkyl group and the aryl group may have a substituent. There are no particular restrictions on the substituent, and examples thereof include a halogen atom, -OH, -OC 1-6 Alkyl, -N(C 1-10Alkyl)2, C 1-10 Alkyl, C 6-10 Aryl, -NH2, -CN, -C(O)OC 1-10 Alkyl, -COOH, -C(O)H, -NO2, etc. Here, "C p-q "(p and q are positive integers, satisfying p<q.) Such a term means that the number of carbon atoms of the organic group described immediately after the term is p to q. For example, "C 1-10 The expression "alkyl" refers to an alkyl group having 1 to 10 carbon atoms. These substituents may be combined with each other to form a ring, and the ring structure may include a spiro ring or a condensed ring.

[0279] The above-mentioned substituents may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). As the secondary substituent, unless otherwise specified, the same substituents as those mentioned above can be used.

[0280] D in formula (E2-2-6) represents a divalent aromatic group. Examples of the divalent aromatic group include phenylene, naphthylene, anthrylene, aralkyl, biphenylene, and biphenylaralkyl. Among them, biphenylene and biphenylaralkyl are preferred, and biphenylene is more preferred. The divalent aromatic group may optionally have a substituent. As a substituent, R in formula (E2-2-6) 32 The substituents that the alkyl groups represented may have are the same.

[0281] m1 and m2 each independently represent an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3, further preferably 1 or 2, further more preferably 1.

[0282] a represents an integer of 1-100, preferably 1-50, more preferably 1-20, further preferably 1-5.

[0283] As the component (E2-2), a resin represented by the formula (E2-2-7) is preferred:

[0284] [Chemical Formula 21]

[0285]

[0286] Where R 37 and R 38 represents a maleimide group. a1 represents an integer of 1 to 100.

[0287] a1 is the same as a in formula (E2-2-6), and the preferred range is also the same.

[0288] Commercially available products of the component (E2-2) include, for example, “MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd.; “BMI-50P” manufactured by KI-Chemical Co., Ltd.; “BMI-1000”, “BMI-1000H”, “BMI-1100”, “BMI-1100H”, “BMI-4000”, and “BMI-5100” manufactured by Yamato Chemical Industry Co., Ltd.; “BMI-4,4′-BPE” and “BMI-70” manufactured by KI-Chemical Co., Ltd.; and “BMI-80” manufactured by KI-Chemical Co., Ltd.

[0289] The weight average molecular weight (Mw) of the component (E2-2) is preferably from 150 to 5,000, more preferably from 300 to 2,500.

[0290] The functional group equivalent of the maleimide group of the component (E2-2) is preferably from 50 g / eq. to 2000 g / eq., more preferably from 100 g / eq. to 1000 g / eq., further preferably from 150 g / eq. to 500 g / eq., particularly preferably from 200 g / eq. to 300 g / eq.

[0291] -(E2-3) Component-

[0292] The component (E2-3) is a maleimide compound containing a trimethylindane skeleton. The trimethylindane skeleton is a skeleton represented by the following formula (E2-3-1).

[0293] [Chemical Formula 22]

[0294]

[0295] A substituent 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.

[0296] 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, and tert-butyl groups;

[0297] The number of carbon atoms in the alkyloxy group is preferably 1 to 10. Examples of the alkyloxy group include methoxy, ethoxy, propoxy, and butoxy groups;

[0298] The number of carbon atoms in the alkylthio group is preferably from 1 to 10. Examples of the alkylthio group include methylthio, ethylthio, propylthio, and butylthio.

[0299] The number of carbon atoms of the aryl group is preferably 6 to 10. Examples of the aryl group include phenyl and naphthyl;

[0300] The number of carbon atoms in the aryloxy group is preferably from 6 to 10. Examples of the aryloxy group include phenyloxy and naphthyloxy;

[0301] The number of carbon atoms of the arylthio group is preferably from 6 to 10. Examples of the arylthio group include phenylthio and naphthylthio.

[0302] The number of carbon atoms in the cycloalkyl group is preferably 3 to 10. Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and cycloheptyl;

[0303] Examples of the halogen atom include a fluorine atom, a chlorine atom, and an iodine atom.

[0304] In the aforementioned substituents, the hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with a halogen atom.

[0305] The number of substituents bonded to one benzene ring contained in the trimethylindane skeleton may be 1 or 2 or more. The number of substituents bonded to the benzene ring contained in the trimethylindane skeleton is usually 0 or more and 3 or less. When the number of substituents is 2 or more, the 2 or more substituents may be the same or different. However, it is preferred that no substituents be bonded to the benzene ring contained in the trimethylindane skeleton.

[0306] The number of trimethylindane skeletons contained in one molecule of the 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.

[0307] The component (E2-3) preferably contains an aromatic ring skeleton in addition to the above-mentioned trimethylindane 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 aforementioned aromatic ring skeletons contained in one molecule of the component (E2-3) is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 4 or less, and particularly preferably 3 or less. When the component (E2-3) contains two or more aromatic ring skeletons in addition to the trimethylindane skeleton, those aromatic ring skeletons may be the same or different.

[0308] Substituents may be bonded to the aromatic ring contained in the aforementioned aromatic ring skeleton. Examples of substituents include the substituents described above as substituents that may be bonded to the benzene ring contained in the trimethylindane skeleton, and a nitro group. The number of substituents bonded to one aromatic ring may be one or two or more. The number of substituents bonded to an aromatic ring is generally from zero to four. When the number of substituents is two or more, the two or more substituents may be the same or different.

[0309] (E2-3) component preferably includes a divalent aliphatic hydrocarbon group in addition to the above-mentioned trimethyl indane skeleton. In particular, when (E2-3) component includes an aromatic ring skeleton other than the benzene ring included in the trimethyl indane skeleton, it is preferred that (E2-3) component includes a divalent aliphatic hydrocarbon group. At this time, the divalent aliphatic hydrocarbon group is preferably connected between the benzene ring and the aromatic ring skeleton that include the trimethyl indane skeleton. In addition, the divalent aliphatic hydrocarbon group is preferably connected between the aromatic ring skeleton.

[0310] The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 or more, preferably 12 or less, more preferably 8 or less, and particularly preferably 5 or less. 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 straight-chain alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; and branched-chain alkylene groups such as ethylidene (-CH(CH3)-), propylidene (-CH(CH2CH3)-), isopropylidene (-C(CH3)2-), ethylmethylmethylene (-C(CH3)(CH2CH3)-), and diethylmethylene (-C(CH2CH3)2-). When the maleimide compound (E2-3) containing a trimethylindane skeleton contains two or more divalent aliphatic hydrocarbon groups in addition to the trimethylindane skeleton, those divalent aliphatic hydrocarbon groups may be the same or different.

[0311] The component (E2-3) preferably comprises a structure represented by the following formula (E2-3-2). The entire component (E2-3) may have the structure represented by the formula (E2-3-2), or a portion of the component (E2-3) may have the structure represented by the formula (E2-3-2);

[0312] [Chemical Formula 23]

[0313]

[0314] (where Ar a1 represents a divalent aromatic hydrocarbon group optionally having a substituent; R a1 R each 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; a2 R each 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; a3Each independently represents a divalent aliphatic hydrocarbon group; n a1 Represents a positive integer; n a2 Each independently represents an integer from 0 to 4; n a3 Each independently represents an integer from 0 to 3. a1 The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups may be replaced by halogen atoms. a2 The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups may be replaced by halogen atoms. a2 When R is 2 to 4, a1 They can be the same or different within the same ring. a3 When R is 2 to 3, a2 can be the same or different within the same ring).

[0315] In formula (E2-3-2), Ar a1 Represents a divalent aromatic hydrocarbon group optionally having a substituent. The number of carbon atoms of the divalent aromatic hydrocarbon group is preferably 6 or more, preferably 20 or less, and more preferably 16 or less. Examples of the divalent aromatic hydrocarbon group include phenylene and naphthylene. Examples of substituents that the divalent aromatic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms, alkyloxy groups having 1 to 10 carbon atoms, alkylthio groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, arylthio groups having 6 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, halogen atoms, hydroxyl groups, and mercapto groups. The hydrogen atoms of each substituent may further be optionally replaced by a halogen atom. Specific examples of these substituents include the same examples as those that may be bonded to the benzene ring contained in the trimethylindane skeleton. When the divalent aromatic hydrocarbon group has a substituent, the number of the substituents is preferably 1 to 4. When the number of substituents possessed by the divalent aromatic hydrocarbon group is 2 or more, the 2 or more substituents may be the same or different. a1 It is preferably a divalent aromatic hydrocarbon group having no substituent.

[0316] In formula (E2-3-2), R a1 Each 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 group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be replaced by halogen atoms. Specific examples of these groups include the same substituents as those that can be bound to the benzene ring contained in the trimethylindane skeleton. Among them, R a1More preferably, it is one or more groups selected from 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, and particularly preferably, it is an alkyl group having 1 to 4 carbon atoms.

[0317] In formula (E2-3-2), R a2 Each 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 group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with a halogen atom. Specific examples of these groups include the same substituents as those that can be bonded to the benzene ring contained in the trimethylindane skeleton. Among them, R a2 More preferably, it is at least one group selected from 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.

[0318] In formula (E2-3-2), R a3 Each independently represents a divalent aliphatic hydrocarbon group. The preferred range of the divalent aliphatic hydrocarbon group is as shown above.

[0319] In formula (E2-3-2), n a1 Represents a positive integer. n a1 It is preferably at least 1, more preferably at most 10, more preferably at most 8.

[0320] In formula (E2-3-2), n a2 Each independently represents an integer from 0 to 4. a2 Preferably it is 2 or 3, more preferably it is 2. a2 Can be different, but preferably the same. a2 When it is 2 or more, multiple R a1 They can be the same or different within the same ring.

[0321] In formula (E2-3-2), n a3 Each independently represents an integer from 0 to 3. a3 Can be different, but preferably the same. a3 Preferably it is 0.

[0322] The component (E2-3) particularly preferably comprises a structure represented by the following formula (E2-3-3). The entire component (E2-3) may have the structure represented by the formula (E2-3-3), or a portion of the component (E2-3) may have the structure represented by the formula (E2-3-3);

[0323] [Chemical Formula 24]

[0324]

[0325] (Where R b1 R each 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; b2 each 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 b1 Represents a positive integer; n b2 Each independently represents an integer from 0 to 4; n b3 Each independently represents an integer from 0 to 3. b1 The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups may be replaced by halogen atoms. b2 The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups may be replaced by halogen atoms. b2 When R is 2 to 4, b1 They can be the same or different in the same ring. b3 When R is 2 to 3, b2 They can be the same or different within the same ring).

[0326] In formula (E2-3-3), R b1 、R b2 、n b1 、n b2 and n b3 Respectively with R in formula (E2-3-2) a1 、R a2 、n a1 、n a2 and n a3 same.

[0327] Component (E2-3) may further include a structure represented by the following formula (E2-3-4);

[0328] [Chemical Formula 25]

[0329]

[0330] In formula (E2-3-4), R c1、R c2 、n c2 and n c3 Respectively with R in formula (E2-3-2) a1 、R a2 、n a2 and n a3 In addition, in formula (E2-3-4), n c1 is the number of repeating units, and represents an integer from 1 to 20. Furthermore, in formula (E2-3-4), * represents a chemical bond. For example, for component (E2-3), in formula (E2-3-2), n a2 is 3 or less, and at least two R groups are not bonded at the ortho and para positions relative to the maleimide group of the benzene ring to which the maleimide group is bonded. a1 In the case of, it can be combined with the structure represented by formula (E2-3-2) to include the structure represented by the above formula (E2-3-4). In addition, for example, in the formula (E2-3-3), n b2 The number of the maleimide group-bonded benzene ring is 3 or less, and at least two R groups are not bonded at the ortho and para positions relative to the maleimide group. b1 In the case of, it can be combined with the structure represented by formula (E2-3-3) to include the structure represented by the above formula (E2-3-4).

[0331] The component (E2-3) may be used alone or in combination of two or more at any ratio.

[0332] The maleimide group equivalent weight of the component (E2-3) is preferably at least 50 g / eq., more preferably at least 100 g / eq., particularly preferably at least 200 g / eq., and preferably at most 2000 g / eq., more preferably at most 1000 g / eq., particularly preferably at most 800 g / eq. The maleimide group equivalent weight represents the mass of the maleimide compound per equivalent of maleimide groups. When the maleimide group equivalent weight of the component (E2-3) is within the aforementioned range, the effects of the present invention can be significantly achieved.

[0333] There is no particular limitation on the manufacturing method of component (E2-3). Component (E2-3) can be manufactured, for example, by the method described in Public Technical Bulletin of the Japan Invention Association No. 2020-500211. According to the manufacturing method described in Public Technical Bulletin of the Japan Invention Association No. 2020-500211, a maleimide compound having a distribution of the number of repeating units of the trimethylindane skeleton can be obtained. The maleimide compound obtained by this method includes a structure shown in the following formula (E2-3-5). Therefore, component (E2-3) may include: a maleimide compound including a structure shown in formula (E2-3-5).

[0334] [Chemical Formula 26]

[0335]

[0336] (Where R 1 R each 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; 2 Each 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; n1 represents the average number of repeating units of 0.95 to 10.0; n2 each independently represents an integer of 0 to 4; and n3 each independently represents an integer of 0 to 3. 1 The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups are optionally replaced by halogen atoms. 2 The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups are optionally replaced by halogen atoms. 1 They can be the same or different in the same ring. When n3 is 2 to 3, R 2 They can be the same or different within the same ring).

[0337] In formula (E2-3-5), R 1 、R 2 , n2 and n3 are respectively the same as R in formula (E2-3-2) a1 、R a2 、n a2 and n a3 same.

[0338] In formula (E2-3-5), n1 represents the average number of repeating units, and its range is 0.95~10.0. According to the manufacturing method described in the public technical report of Japan Invention Association No. 2020-500211, a group of maleimide compounds containing the structure shown in formula (E2-3-5) can be obtained. As can be seen from the fact that the average number of repeating units n1 in formula (E2-3-5) can be less than 1.00, the maleimide compound containing the structure shown in formula (E2-3-5) thus obtained may contain a maleimide compound having a repeating unit number of 0 of the trimethylindane skeleton. Therefore, by purification, the maleimide compound having a repeating unit number of 0 of the trimethylindane skeleton is removed from the maleimide compound containing the structure shown in formula (E2-3-5) to obtain component (E2-3), and only the obtained component (E2-3) may be contained in the photosensitive resin composition. However, the effects of the present invention can be achieved even when the photosensitive resin composition contains a maleimide compound having a trimethylindane skeleton with zero repeating units. Furthermore, costs can be reduced by omitting purification. Therefore, it is preferred that the photosensitive resin composition contain a "maleimide compound having a structure represented by formula (E2-3-5)" without removing the maleimide compound having a trimethylindane skeleton with zero repeating units.

[0339] In formula (E2-3-5), the average number of repeating units n1 is preferably 0.95 or more, more preferably 0.98 or more, further preferably 1.0 or more, particularly preferably 1.1 or more, preferably 10.0 or less, more preferably 8.0 or less, further preferably 7.0 or less, particularly preferably 6.0 or less. When the average number of repeating units n1 is within the aforementioned range, the effects of the present invention can be significantly achieved. In particular, the glass transition temperature of the photosensitive resin composition can be effectively increased.

[0340] Examples of the structure represented by formula (E2-3-5) include the following structures.

[0341] [Chemical Formula 27]

[0342]

[0343] The maleimide compound comprising the structure represented by formula (E2-3-5) may further comprise the structure represented by formula (E2-3-4). For example, in the case of the maleimide compound comprising the structure represented by formula (E2-3-5), in formula (E2-3-5), n2 is 3 or less, and in the ortho and para positions of the benzene ring to which the maleimide group is bonded relative to the maleimide group, there are no R bonded to two or more of the following: 1 In the case of, it can be combined with the structure represented by formula (E2-3-5) to include the structure represented by formula (E2-3-4).

[0344] For the maleimide compound comprising the structure shown in formula (E2-3-5), the molecular weight distribution Mw / Mn calculated by gel permeation chromatography (GPC) is preferably in a specific range. Molecular weight distribution is the 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 comprising the structure shown in 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, and particularly preferably 1.3 to 3.4. When the molecular weight distribution Mw / Mn of the maleimide compound comprising the structure shown in formula (E2-3-5) is in the aforementioned range, the effect of the present invention can be significantly obtained.

[0345] In the maleimide compound comprising the structure shown in formula (E2-3-5), the amount of the maleimide compound having an average number of repeating units n1 of 0 is preferably within a specific range. When the aforementioned GPC measurement of the maleimide compound comprising the structure shown in formula (E2-3-5) is performed, the amount of the maleimide compound having an average number of repeating units n1 of 0 can be expressed as area % based on the result of its GPC measurement. In detail, in the chromatogram obtained by the aforementioned GPC measurement, the ratio (area %) of "peak area of maleimide compound having an average number of repeating units n1 of 0" relative to "total area of peak of maleimide compound having a structure shown in formula (E2-3-5)" can be used to represent the amount of maleimide compound having an average number of repeating units n1 of 0. Specifically, relative to the total amount 100 area % of the maleimide compound comprising the structure shown in formula (E2-3-5), the amount of the maleimide compound having an average repeating unit number n1 of 0 is preferably 32 area % or less, more preferably 30 area % or less, and further preferably 28 area % or less. When the amount of the maleimide compound having an average repeating unit number n1 of 0 is within the aforementioned range, the effects of the present invention can be significantly obtained.

[0346] The maleimide group equivalent of the maleimide compound comprising the structure represented by formula (E2-3-5) is preferably in the same range as the maleimide group equivalent of the above-mentioned component (E2-3). When the maleimide group equivalent of the maleimide compound comprising the structure represented by formula (E2-3-5) is in the aforementioned range, the effects of the present invention can be significantly obtained.

[0347] From the viewpoint of obtaining a cured product having excellent dielectric constant and dielectric properties, the content of component (E2) is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 1.5% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, based on 100% by mass of the non-volatile component in the photosensitive resin composition.

[0348] ((E3) Vinyl resin)

[0349] The vinyl resin (E3) as component (E) reacts with the ethylenically unsaturated groups of component (A) to produce a cured product with a low dielectric constant and dielectric loss tangent. However, the vinyl resin (E3) does not include the resins belonging to components (A) to (D), component (E1), and component (E2). The vinyl resins (E3) may be used alone or in combination of two or more.

[0350] As the vinyl resin (E3), a resin containing a vinyl group (-CH=CH2) can be used. The number of vinyl groups per molecule of the vinyl resin may be one or two or more, and is preferably two.

[0351] (E3) The vinyl resin only needs to have a vinyl group (—CH═CH 2 ), and is a concept that also includes resins containing, for example, a vinyl group, a vinylphenyl group, an allyl group, and a maleoyl group.

[0352] The vinyl resin may be any resin containing a vinyl group. As the vinyl resin (E3), at least one selected from (E3-1) to (E3-3) is preferred:

[0353] (E3-1) vinyl resin containing a polyphenylene ether skeleton,

[0354] (E3-2) vinyl resin containing a polyethylene skeleton, and

[0355] (E3-3) Allyl group-containing resin.

[0356] -(E3-1) Components-

[0357] Component (E3-1) is a vinyl resin containing a polyphenylene ether skeleton. Component (E3-1) includes compounds represented by the following formula (E3-1-1):

[0358] [Chemical Formula 28]

[0359]

[0360] (In formula (E3-1-1), L 1 Represents a divalent linking group; R B11 、RB12 、R B13 、R B21 、R B22 and R B23 Each independently represents a hydrogen atom or an alkyl group; R B14 、R B15 、R B24 and R B25 Each independently represents an alkyl group; R B16 and R B26 Each independently represents an alkylene group; m b11 and m b21 Each independently represents 0 or 1; m b12 、m b13 、m b22 and m b23 Each independently represents an integer from 0 to 4; m b14 and m b24 Each independently represents an integer from 0 to 300; m b15 and m b25 represent 0 or 1 respectively).

[0361] In formula (E3-1-1), L 1 represents a divalent linking group. Examples of the divalent linking group include alkylene, alkenylene, arylene, alkylarylene, heteroarylene, -O-, -NH-, -NR x -, -CO-, -CS-, -SO-, -SO2-, -C(=O)O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, and a group formed by combining a plurality of these. x represents a hydrocarbon group having 1 to 12 carbon atoms. 1 The number of carbon atoms in the polyol is usually 60 or less, more preferably 48 or less, further preferably 36 or less, particularly preferably 24 or less.

[0362] In formula (E3-1-1), R B11 、R B12 、R B13 、R B21 、R B22 and R B23 R each independently represents a hydrogen atom or an alkyl group. B11 、R B12 、R B13 、R B21 、R B22 and R B23 Can be combined with R in formula (E3-1-1) A1 、R A2 and R A3 The same. Among them, R B11 and RB21 Preferably, it is a hydrogen atom or a methyl group, R B12 、R B13 、R B22 and R B23 A hydrogen atom is preferred.

[0363] In formula (E3-1-1), R B14 、R B15 、R B24 and R B25 Each independently represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 2. The alkyl group may be any of a linear, branched, or cyclic type. Examples of alkyl groups include methyl, ethyl, propyl, n-butyl, and tert-butyl groups. B14 、R B15 、R B24 and R B25 Preferred is methyl.

[0364] In formula (E3-1-1), R B16 and R B26 Each independently represents an alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 3. The alkylene group is preferably a straight-chain alkylene group, more preferably a methylene group.

[0365] In formula (E3-1-1), m b11 and m b21 Each independently represents 0 or 1.

[0366] In formula (E3-1-1), m b12 、m b13 、m b22 and m b23 Each independently represents an integer from 0 to 4. m b12 、m b13 、m b22 and m b23 1 to 4 are preferred, 2 to 3 are more preferred, and 2 is particularly preferred.

[0367] In formula (E3-1-1), m b14 and m b24 Each independently represents an integer from 0 to 300. Specifically, m b14 and m b24 It is usually 0 or more, preferably 1 or more, and usually 300 or less, preferably 100 or less, more preferably 50 or less, further preferably 20 or less, particularly preferably 10 or less.

[0368] In formula (E3-1-1), m b15 and m b25 Each independently represents 0 or 1.b11 When it is 0, m b15 Preferably 1, m b11 When it is 1, m b15 Preferably, it is 0. In addition, m b21 When it is 0, m b25 Preferably 1, m b21 When it is 1, m b25 Preferably it is 0.

[0369] When listing preferred examples of the compound represented by formula (E3-1-1), the compound represented by the following formula (E3-1-2) can be mentioned.

[0370] [Chemical Formula 29]

[0371]

[0372] (In formula (E3-1-2), L 2 Represents a divalent linking group; R C15 and R C25 Each independently represents an alkyl group; R C16 and R C26 Each independently represents an alkylene group; m c14 and m c24 Each independently represents an integer from 0 to 300).

[0373] In formula (E3-1-2), L 2 Represents a divalent linking group. 2 Can be combined with L in formula (E3-1-1) 1 The same. Among them, L 2 A divalent group represented by the following formula (E3-1-3) is preferred.

[0374] [Chemical formula 30]

[0375]

[0376] (In formula (E3-1-3), X 1 ~X 8 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. (* represents a chemical bond).

[0377] In formula (E3-1-2), R C15 and R C25 Each independently represents an alkyl group. C15 and R C25 Can be combined with R in formula (E3-1-1) B14 The same. Among them, R C15 and R C25 Preferred is methyl.

[0378] In formula (E3-1-2), R C16 and R C26 R are independently an alkylene group. C16 and R C26 Can be combined with R in formula (E3-1-1) B16 and R B26 The same. Among them, R C16 and R C26 More preferably, it is a methylene group.

[0379] In formula (E3-1-2), m c14 and m c24 Each independently represents an integer from 0 to 300. c14 and m c24 Can be combined with m in formula (E3-1-1) b14 and m b24 In addition, in formula (E3-1-2), preferably m c14 and m c24 Except for the scenario where one of them is 0.

[0380] Examples of the compound represented by formula (E3-1-2) include compounds represented by the following formula (E3-1-4). In formula (E3-1-4), m c14 and m c24 The compound represented by formula (E3-1-4) is available as "OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0381] [Chemical Formula 31]

[0382]

[0383] If other preferable examples of the compound represented by formula (E3-1-1) are listed, the compound represented by the following formula (E3-1-5) can be mentioned.

[0384] [Chemical Formula 32]

[0385]

[0386] (In formula (E3-1-5), L 3 Represents a divalent linking group; R D11 and R D21 Each independently represents a hydrogen atom or an alkyl group; R D14 、R D15 、R D24 and R D25 Each independently represents an alkyl group; m d14 and m d24 Each independently represents an integer from 0 to 300).

[0387] In formula (E3-1-5), L 3 Represents a divalent linking group. 3 Can be combined with L in formula (B2) 1 The same. Among them, L 3 It is preferably selected from alkylene, alkenylene, -O-, -NR x -, -CO-, -CS-, -SO-, and -SO2-, and is preferably an alkylene group, particularly preferably an isopropylidene group (-C(CH3)2-).

[0388] In formula (E3-1-5), R D11 and R D21 R each independently represents a hydrogen atom or an alkyl group. D11 and R D21 Can be combined with R in formula (E3-1-1) B11 and R B21 The same. Among them, R D11 and R D21 Preferred is methyl.

[0389] In formula (E3-1-5), R D14 、R D15 、R D24 and R D25 Each independently represents an alkyl group. D14 、R D15 、R D24 and R D25 Can be combined with R in formula (E3-1-1) B14 The same. Among them, R D14 、R D15 、R D24 and R D25 Preferred is methyl.

[0390] In formula (E3-1-5), m d14 and m d24 Each independently represents an integer from 0 to 300. d14 and m d24 Can be combined with m in formula (E3-1-1) b14 and m b24 In addition, m b14 and m b24 The total of is preferably 2 or more.

[0391] Examples of the compound represented by formula (E3-1-5) include compounds represented by the following formula (E3-1-6). 3 、m d14 and m d24The same as formula (E3-1-5). The compound represented by formula (E3-1-4) can be obtained as "NORYL SA9000" manufactured by SABIC.

[0392] [Chemical Formula 33]

[0393]

[0394] -(E3-2) Component-

[0395] Component (E3-2) is a vinyl resin containing a polyethylene skeleton. Component (E3-2) includes a polymer containing a structural unit represented by the following formula (E3-2-1);

[0396] [Chemical Formula 34]

[0397]

[0398] (In formula (E3-2-1), R E1 、R E2 and R E3 Each independently represents a hydrogen atom or an alkyl group; R E4 Each independently represents an alkyl group; R E5 、R E6 and R E7 Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m e1 Indicates 0 or 1; m e2 represents an integer from 0 to 4; * represents a chemical bond).

[0399] In formula (E3-2-1), R E1 、R E2 and R E3 Each independently represents a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 12, further preferably 1 to 6, and particularly preferably 1 to 2. The alkyl group may be any of linear, branched, or cyclic. Examples of the alkyl group include methyl, ethyl, propyl, n-butyl, and tert-butyl. E1 、R E2 and R E3 A hydrogen atom is preferred.

[0400] In formula (E3-2-1), R E4 Each independently represents an alkyl group. E4 Can be combined with R in formula (E3-1-1) B14 same.

[0401] In formula (E3-2-1), R E5 、R E6 and R E7Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. E5 、R E6 and R E7 A hydrogen atom is preferred.

[0402] In formula (E3-2-1), m e1 It represents 0 or 1, preferably 0.

[0403] In formula (E3-2-1), m e2 It represents an integer of 0 to 4, preferably 0.

[0404] The molar content of the structural unit represented by formula (E3-2-1) is preferably within a specific range relative to 100 mol% of the total of all structural units contained in the polymer containing the structural unit represented by formula (E3-2-1). Specifically, the molar content of the structural unit represented by formula (E3-2-1) is preferably 2 mol% to 95 mol%, more preferably 8 mol% to 81 mol%. In addition, the average number of structural units represented by formula (E3-2-1) contained in one molecule of the aforementioned polymer is preferably 1 to 160, more preferably 3 to 140.

[0405] The polymer containing the structural unit represented by formula (E3-2-1) may further contain an arbitrary structural unit in combination with the structural unit represented by formula (E3-2-1). Examples of the arbitrary structural unit include the structural unit represented by the following formula (E3-2-2):

[0406] [Chemical Formula 35]

[0407]

[0408] (In formula (E3-2-2), R E8 、R E9 and R E10 Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. E1 represents an aryl group which may have a substituent. E1 The substituent group that may be present includes an alkyl group having 1 to 6 carbon atoms. (* represents a chemical bond).

[0409] Examples of polymers containing the structural unit represented by formula (E3-2-2) include copolymers containing a combination of the structural unit represented by the following formula (E3-2-3), the structural unit represented by the following formula (E3-2-4), and the structural unit represented by the following formula (E3-2-5). In formulas (E3-2-3), (E3-2-4), and (E3-2-5), * represents a chemical bond. In this copolymer, the molar contents of the structural unit represented by formula (E3-2-3), the structural unit represented by formula (E3-2-4), and the structural unit represented by formula (E3-2-5) are 8 mol% to 54 mol%, 0 mol% to 92 mol%, and 0 mol% to 89 mol%, respectively. Furthermore, the average numbers of the structural unit represented by formula (E3-2-3), the structural unit represented by formula (E3-2-4), and the structural unit represented by formula (E3-2-5) contained in one molecule of the copolymer are 1 to 160, 0 to 350, and 0 to 270, respectively. The copolymer is available as "ODV-XET (X03)", "ODV-XET (X04)", and "ODV-XET (X05)" manufactured by Nippon Steel Chemicals Co., Ltd.

[0410] [Chemical Formula 36]

[0411]

[0412] The component (E3-2) may be used alone or in combination of two or more at any ratio.

[0413] The vinyl equivalent weight of component (E3-2) is preferably 250 g / eq. to 1200 g / eq., more preferably 300 g / eq. to 1100 g / eq. The radically polymerizable unsaturated group equivalent weight represents the mass of the radically polymerizable aromatic resin per 1 equivalent of vinyl group. When the radically polymerizable unsaturated group equivalent weight of component (E3-2) is within the aforementioned range, the effects of the present invention can be significantly achieved.

[0414] The weight average molecular weight of the component (E3-2) is preferably from 1000 to 40000, more preferably from 1500 to 35000. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

[0415] -(E3-3) Component-

[0416] The allyl group-containing resin (E3-3) refers to a resin having at least one allyl group in the molecule. Component (E3-3) preferably has one or more allyl groups per molecule, more preferably two or more allyl groups. The lower limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less.

[0417] Furthermore, from the viewpoint of significantly achieving the desired effects of the present invention, the component (E3-3) is preferably a compound having, in addition to an allyl group, a benzoxazine ring, a phenol ring, an isocyanuric acid ring, an epoxy group, and a carboxylic acid derivative having a cyclic structure.

[0418] The component (E3-3) having a benzoxazine ring is preferably bonded to any one of the nitrogen atom of the benzoxazine ring and the benzene ring, more preferably bonded to the nitrogen atom.

[0419] Examples of the component (E3-3) having a phenol ring include cresol resins containing an allyl group, novolac-type phenol resins containing an allyl group, and cresol novolac resins containing an allyl group.

[0420] The component (E3-3) having an isocyanuric acid structure preferably has a nitrogen atom of the isocyanuric acid structure directly bonded to an allyl group. Examples of the component (E3-4) having an isocyanuric acid structure include allyl isocyanurate, diallyl isocyanurate, and triallyl isocyanurate.

[0421] The (E3-3) component having an epoxy group preferably contains two or more epoxy groups in one molecule. In addition, the (E3-3) component having an epoxy group preferably has an aromatic structure. When using two or more (E3-3) components having an epoxy group, it is more preferable that at least one has an aromatic structure. An aromatic structure is a chemical structure generally defined as an aromatic structure, and also includes polycyclic aromatics and aromatic heterocycles. As the (E3-3) component having an epoxy group, it is preferably a bisphenol structure. As the bisphenol structure, for example, bisphenol A type, bisphenol F type, bisphenol AF type, etc. can be cited.

[0422] As the component (E3-3) having a "carboxylic acid derivative having a cyclic structure", it is preferably a carboxylic acid allyl ester having a cyclic structure. As the cyclic structure, it can be any group among the cyclic groups comprising an alicyclic structure and the cyclic groups comprising an aromatic ring structure. In addition, for the cyclic group, in addition to utilizing carbon atoms, heteroatoms can also be utilized to constitute the skeleton of the ring. As heteroatoms, for example, oxygen atoms, sulfur atoms, nitrogen atoms, etc. can be listed, preferably nitrogen atoms. The number of heteroatoms in the above-mentioned ring can be 1, or it can be 2 or more.

[0423] 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 a "carboxylic acid derivative having a cyclic structure" include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl bibenzoate, allyl dibenzoate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, allyl cyclohexanedicarboxylate, and diallyl cyclohexanedicarboxylate.

[0424] As the component (E3-3), a commercially available product can be used. Examples of commercially available products include "MEH-8000H" and "MEH-8005" manufactured by Meiwa Chemicals (component (E3-3) having a phenol ring); "RE-810NM" manufactured by Nippon Kayaku Co., Ltd. (component (E3-3) having an epoxy group); "ALP-d" manufactured by Shikoku Chemicals (component (E3-3) having a benzoxazine ring); "L-DAIC" manufactured by Shikoku Chemicals (component (E3-3) having an isocyanuric acid ring); "TAIC" manufactured by Nippon Chemicals (component (E3-3) having an isocyanuric acid ring (triallyl isocyanurate)); "MDAC" manufactured by Osaka Soda Co., Ltd. (component (E3-3) having a cyclohexanedicarboxylic acid derivative); "DAD" manufactured by Nisshoku Techno Fine Chemical Co., Ltd. (diallyl bibenzoate); and "DAISO DAP" manufactured by Osaka Soda Co., Ltd. MONOMER" (diallyl phthalate), etc.

[0425] From the viewpoint of significantly achieving the desired effects of the present invention, the allyl equivalent of component (E3-3) is preferably 20 g / eq. to 1000 g / eq., more preferably 50 g / eq. to 500 g / eq., and even more preferably 100 g / eq. to 300 g / eq. The allyl equivalent is the mass of component (E3-3) containing one equivalent of allyl groups.

[0426] From the viewpoint of obtaining a cured product having excellent dielectric constant and dielectric properties, the content of component (E3) is preferably 1% by mass or more, more preferably 1.5% by mass or more, further preferably 2% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, based on 100% by mass of the non-volatile component in the photosensitive resin composition.

[0427] From the viewpoint of obtaining a cured product having excellent dielectric constant and dielectric loss tangent, component (E) preferably comprises one or more resins selected from active ester resins, maleimide resins, and vinyl resins, more preferably comprises an active ester resin, and further preferably comprises "active ester resin" and "one or more resins selected from maleimide resins and vinyl resins."

[0428] The total content of the component (E) is preferably at least 1% by mass, more preferably at least 1.5% by mass, further preferably at least 2% by mass, and is preferably at most 20% by mass, more preferably at most 15% by mass, further preferably at most 10% by mass, based on 100% by mass of the non-volatile component in the photosensitive resin composition, from the viewpoint of obtaining a cured product having excellent dielectric constant and dielectric properties.

[0429] <(F) Curing accelerator>

[0430] The photosensitive resin composition may further contain (F) a curing accelerator as an optional component in addition to the above components. The (F) component may be used alone or in combination of two or more.

[0431] 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.

[0432] Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. Triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

[0433] 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, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

[0434] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-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-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Imidazole compounds such as 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, 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 adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

[0435] As the imidazole-based curing accelerator, a commercially available item can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0436] 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-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine. Preferred are dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0437] Examples of metallic curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, organozinc complexes such as zinc (II) acetylacetonate, organoferric complexes such as iron (III) acetylacetonate, organonickel complexes such as nickel (II) acetylacetonate, and organomanganese complexes such as manganese (II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0438] From the viewpoint of significantly obtaining the desired effect of the present invention, the content of the component (F) is preferably at least 0.001 mass%, more preferably at least 0.005 mass%, further preferably at least 0.01 mass%, and is preferably at most 0.15 mass%, more preferably at most 0.1 mass%, further preferably at most 0.05 mass%, based on 100 mass% of the non-volatile component in the photosensitive resin composition.

[0439] (G) Solvent

[0440] The photosensitive resin composition may further contain (G) a solvent as an optional component. By containing (G) a solvent, the varnish viscosity can be adjusted. Examples of (G) the solvent include organic solvents.

[0441] 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 acetate, butyl cellosolve acetate, carbitol acetate, and diethylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as octane and decane; and petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. These solvents may be used alone or in combination of two or more. The content of the solvent when used may be appropriately adjusted from the perspective of the coating properties of the photosensitive resin composition.

[0442] <(H) Other additives>

[0443] The photosensitive resin composition may further contain (H) other additives to the extent that the purpose of the present invention is not impaired. Examples of (H) other additives include: reactive diluents, thermoplastic resins, organic fillers, melamine, organic bentonite, and other fine particles; 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, and pyrogallol; thickeners such as Benton and montmorillonite; silicone-based, fluorine-based, and vinyl resin-based defoamers; flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters; and thermosetting resins such as phenolic curing agents and cyanate ester curing agents.

[0444] The photosensitive resin composition can be produced by mixing the essential components (A) to (E) and the optional components (F) to (H), and kneading or stirring them as needed using a kneading device such as a three-roll mill, a ball mill, a bead mill, or a sand mill, or a stirring device such as a high-speed mixer or a planetary mixer.

[0445] <Physical Properties and Applications of Photosensitive Resin Compositions>

[0446] The cured product obtained by photocuring the photosensitive resin composition exhibits excellent developability. Therefore, the formation of residues in the unexposed area can be suppressed. The residues in the unexposed area can be evaluated according to the method described in the Examples below.

[0447] The cured product obtained by photocuring the photosensitive resin composition exhibits excellent developability. Therefore, it exhibits excellent BP (development point) characteristics. BP refers to the time from when 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, and further preferably 130 seconds or less. The lower limit is 30 seconds or more, more preferably 40 seconds or more, and further preferably 50 seconds or more. BP can be measured according to the method described in the examples described below.

[0448] The cured product obtained by photocuring the photosensitive resin composition shows excellent developability. Therefore, a through hole without residue or peeling, and a line width and line spacing (L / S) without peeling or embedding can be formed. As the minimum through hole diameter of the above-mentioned through hole, it is preferably less than 60 μm, more preferably less than 55 μm, and further preferably less than 50 μm. The lower limit is not particularly limited and can be set to more than 1 μm. The determination of the minimum through hole diameter can be measured according to the method described in the embodiments described below.

[0449] The cured product formed by photosensitive resin composition light curing shows the characteristic of excellent dielectric constant. Therefore, an insulating layer and a solder mask (solder resist) with low dielectric constant are brought. As dielectric constant, it is preferably less than 4.0, more preferably less than 3.5, and further preferably less than 3.3. The lower limit is not particularly limited and can be set to more than 0.1. The determination of dielectric constant can be measured according to the method described in the embodiment described later.

[0450] The cured product obtained by photocuring the photosensitive resin composition shows excellent properties such as dielectric loss tangent. Therefore, an insulating layer and a solder mask with low dielectric loss tangent are provided. As dielectric loss tangent, it is preferably less than 0.013, more preferably less than 0.012, and further preferably less than 0.011. The lower limit is not particularly limited and can be set to more than 0.0001. The determination of dielectric loss tangent can be determined according to the method described in the embodiments described later.

[0451] The photosensitive resin composition exhibits excellent flexibility. Therefore, even when stress is applied, the photosensitive resin composition can suppress the formation of cracks.

[0452] A cured product obtained by photocuring a photosensitive resin composition generally exhibits a high glass transition temperature. This results in an insulating layer and solder resist layer having a high glass transition temperature and excellent heat resistance. The glass transition temperature is preferably 140°C or higher, more preferably 145°C or higher, and even more preferably 150°C or higher. The upper limit is not particularly limited and can be 300°C or lower. The glass transition temperature can be measured according to the method described in the Examples below.

[0453] The use of the photosensitive resin composition of the present invention is not particularly limited, and can be used in a wide range of applications requiring a photosensitive resin composition, such as insulating resin sheets such as photosensitive films and prepregs, circuit substrates (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, chip bonding materials, semiconductor sealing materials, hole-filling resins, and component embedding resins. Among them, it can be suitably used as a photosensitive resin composition for an insulating layer of a printed wiring board (a printed wiring board using a cured product of the photosensitive resin composition as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a printed wiring board using a cured product of the photosensitive resin composition as an interlayer insulating layer), a photosensitive resin composition for forming a plating layer (a printed wiring board having a plating layer formed on a cured product of the photosensitive resin composition), and a photosensitive resin composition for a solder mask layer (a printed wiring board using a cured product of the photosensitive resin composition as a solder mask layer).

[0454] [Photosensitive film]

[0455] The photosensitive film has a support and a photosensitive resin composition layer formed on the support and containing the photosensitive resin composition of the present invention.

[0456] Examples of the support include polyethylene terephthalate films, polyethylene naphthalate films, polypropylene films, polyethylene films, polyvinyl alcohol films, and triacetyl acetate films, and polyethylene terephthalate films are particularly preferred.

[0457] As commercially available supports, there can be mentioned, for example, polyethylene terephthalate films such as "ALPHAN MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., PS series such as "PS-25" manufactured by Teijin Co., Ltd., etc., but are not limited to these. For these supports, a release agent such as a silicone coating agent can be coated on the surface for easy removal. The thickness of the support is preferably in the range of 5 μm to 50 μm, more preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, cracking of the support can be suppressed when the support is peeled off before development; by setting the thickness to 50 μm or less, the resolution when exposing from the support can be improved. In addition, a support with low white spots (fish eyes) is preferred. Here, white spots refer to defects formed when foreign matter, undissolved matter, oxidative degradation products, etc. of the material enter the film when the material is hot-melted and the film is manufactured by kneading, extrusion, biaxial stretching, casting, etc.

[0458] Furthermore, to reduce light scattering during exposure to active energy rays such as ultraviolet rays, the support is preferably a material with excellent transparency. Specifically, the support preferably has a turbidity (haze standardized according to JIS K6714), which serves as an indicator of transparency, of 0.1 to 5. Furthermore, the photosensitive resin composition layer may be protected by a protective film.

[0459] By protecting the photosensitive resin composition layer side of the photosensitive film with a protective film, it is possible to prevent dust from adhering to the surface of the photosensitive resin composition layer or causing damage. As the protective film, a film made of the same material as the above-mentioned support can be used. The thickness of the protective film is not particularly limited, and is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and further preferably in the range of 10 μm to 30 μm. By making the thickness more than 1 μm, the handleability of the protective film can be improved, and by making the thickness less than 40 μm, there is a tendency for the economy (cheapness) to become better. It should be noted that, for the protective film, relative to the adhesive force between the photosensitive resin composition layer and the support, it is preferably a protective film having a smaller adhesive force between the photosensitive resin composition layer and the protective film.

[0460] From the viewpoint of improving handleability and suppressing a decrease in sensitivity and resolution within 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, more preferably 28 μm or less, further preferably 25 μm or less.

[0461] The photosensitive film can be produced, for example, by preparing a resin varnish in which a photosensitive resin composition is dissolved in an organic solvent, applying the resin varnish onto a support using a die coater or the like, and drying the varnish to form a photosensitive resin composition layer. As the organic solvent, the same solvents as those described for component (G) can be used.

[0462] Examples of the coating method for the resin varnish include gravure coating, micro gravure coating, reverse coating, kiss reverse coating, die coating, slot die coating, lip coating, comma coating, blade coating, roll coating, knife coating, curtain coating, closed chamber gravure coating, slot orifice coating, spray coating, and dip coating.

[0463] The resin varnish can be applied in several times or in one application, or in a combination of different methods. Preferably, a die coating method is used, which provides excellent coating uniformity. In addition, in order to prevent foreign matter from being mixed in, the coating process is preferably carried out in an environment where there is little foreign matter, such as a clean room.

[0464] The drying temperature varies depending on the curability of the photosensitive resin composition and the amount of component (G) in the resin varnish, but can be 80°C to 120°C. However, from the perspective of obtaining a cured product with excellent undercut resistance, the maximum drying temperature is preferably 105°C or higher, more preferably 110°C or higher. The lower limit of the maximum temperature is not particularly limited, but is preferably 135°C or lower, more preferably 130°C or lower.

[0465] The drying time varies depending on the curability of the photosensitive resin composition and the amount of component (G) in the resin varnish, but is preferably 6 minutes or longer, preferably 30 minutes or shorter, and more preferably 20 minutes or shorter. Here, the drying time refers to the time from when the drying temperature reaches 80°C.

[0466] The residual amount of the component (G) in the photosensitive resin composition layer is preferably 5% by mass or less, more preferably 2% by mass or less, based on the total amount of the photosensitive resin composition layer.

[0467] Because the photosensitive film includes a "photosensitive resin composition layer comprising the photosensitive resin composition of the present invention," it exhibits excellent flexibility. For example, the photosensitive film can be wound around a 3-inch core and cut using a roll cutter. This method can suppress the occurrence of cracks in the photosensitive film.

[0468] [Printed wiring board]

[0469] The printed wiring board of the present invention includes an insulating layer formed from 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.

[0470] Specifically, the printed wiring board of the present invention can be produced using the above-mentioned photosensitive film. Hereinafter, an example in which the insulating layer is a solder resist layer will be described.

[0471] <Coating and Drying Process>

[0472] When a resin varnish composed of a photosensitive resin composition is directly applied on a circuit board, the component (G) is dried and volatilized to form a photosensitive resin composition layer on the circuit board.

[0473] Examples of the circuit substrate include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. It should be noted that the circuit substrate herein refers to a substrate having a patterned conductor layer (circuit) formed on one or both sides of the above-mentioned supporting substrate. Furthermore, in a multilayer printed wiring board formed by alternately stacking conductor layers and insulating layers, a substrate having a patterned conductor layer (circuit) formed on one or both sides of the outermost layer of the multilayer printed wiring board is also included in the circuit substrate herein. It should be noted that the surface of the conductor layer may be pre-roughened by blackening, copper etching, or the like.

[0474] As a coating method, generally, full-plate printing based on screen printing is mostly adopted, but any other means can also be used, as long as it is a coating method that can be evenly coated. For example, spray coating method, hot melt coating method, rod coating method, coating method, blade coating method, knife coating method, air knife coating method, curtain flow coating method, roller coating method, gravure coating method, offset printing method, dip coating method, brush coating, other common coating methods can all be used. After coating, dry with a hot air furnace or a far infrared furnace as needed. Drying conditions are preferably set to 3 minutes to 13 minutes at 80 ° C ~ 120 ° C. In this way, a photosensitive composition layer can be formed on a circuit substrate.

[0475] Lamination process

[0476] On the other hand, when using a photosensitive film, the photosensitive resin composition layer is laminated onto one or both sides of the circuit board using a vacuum laminator. During the lamination process, if the photosensitive film has a protective film, this protective film is removed. The photosensitive film and circuit board are then preheated as needed, and the photosensitive resin composition layer is pressurized and heated while being bonded to the circuit board. The photosensitive film is preferably laminated onto the circuit board using a vacuum lamination method under reduced pressure.

[0477] The conditions of the lamination process are not particularly limited. For example, the preferable conditions are: the pressing temperature (lamination temperature) is preferably set to 70° C. to 140° C., and the pressing pressure is preferably set to 1 kgf / cm 2 ~11kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2 ), the pressing time is preferably set to 5 seconds to 300 seconds, and the lamination is carried out under reduced pressure with the air pressure being set to 20 mmHg (26.7 hPa) or less. In addition, the lamination process may be a batch process or a continuous process using a roller. The vacuum lamination method may be carried out using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nikko-Materials, a vacuum pressurized laminator manufactured by Meiki Manufacturing Co., Ltd., a roller dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC.

[0478] Exposure process

[0479] After a photosensitive resin composition layer is formed on a circuit board through a coating and drying process or a lamination process, an exposure process is performed to irradiate a predetermined portion of the photosensitive resin composition layer with active light (activating radiation) through a mask pattern to photocure the photosensitive resin composition layer in the irradiated portion. Examples of active light include ultraviolet rays, visible rays, electron beams, and X-rays, with ultraviolet rays being particularly preferred. The irradiation dose of ultraviolet rays is approximately 10 mJ / cm 2 ~1000mJ / cm 2 Exposure methods include contact exposure methods in which a mask pattern is brought into close contact with a printed wiring board, and non-contact exposure methods in which exposure is performed using parallel light without close contact. Either method can be used. Furthermore, when a support is present on the photosensitive resin composition layer, exposure can be performed from above the support, or after the support is peeled off.

[0480] Since the solder resist layer (solder resist) uses the photosensitive resin composition of the present invention, it has excellent developability. Therefore, as the exposure pattern in the mask pattern, for example, a ratio (L / S) of the circuit width (line width; L) to the width between the circuits (line spacing; S) of 100 μm / 100 μm or less (i.e., wiring spacing 200 μm or less), L / S = 80 μm / 80 μm or less (wiring spacing 160 μm or less), L / S = 70 μm / 70 μm or less (wiring spacing 140 μm or less), L / S = 60 μm / 60 μm or less (wiring spacing 120 μm or less) can be used. It should be noted that the spacing does not need to be the same in the entire circuit board.

[0481] Since the solder mask (solder resist) uses the photosensitive resin composition of the present invention, it has excellent developability. Therefore, as the through-hole diameter, it can be preferably set to 100 μm or less, more preferably to 90 μm or less, and further preferably to 80 μm or less. The lower limit is not particularly limited and can be set to 1 μm or more, 10 μm or more, etc.

[0482] <Development Process>

[0483] After the exposure step, if a support is present on the photosensitive resin composition layer, the support is removed and then the uncured portion (unexposed portion) is removed by wet development or dry development and then developed to form a pattern.

[0484] In the case of the wet development, as the developer, a safe, stable and easy-to-use developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent can be used. Among them, the development process using an alkaline aqueous solution is preferred. In addition, as the development method, known methods such as spraying, shaking immersion, brushing, and scraping can be appropriately adopted.

[0485] The alkaline aqueous solution used as the developer includes, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate, alkali metal phosphates such as sodium phosphate and potassium phosphate, aqueous solutions of alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, or aqueous solutions of organic bases such as tetraalkylammonium hydroxide that do not contain metal ions. From the viewpoint of not containing metal ions and not affecting the semiconductor chip, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred.

[0486] To improve the development effect, surfactants, defoaming agents, etc. may be added to the developer. The pH value of the alkaline aqueous solution is 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 set to 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected according to the developability of the photosensitive resin composition layer, and is preferably set to 20°C to 50°C.

[0487] 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, isopropyl alcohol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

[0488] The concentration of such an organic solvent is preferably 2% to 90% by mass relative to the total amount of the developer. In addition, the temperature of such an organic solvent can be adjusted according to the developability. Furthermore, such an organic solvent can be used alone or in combination of two or more. Examples of organic solvent-based developers used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0489] In pattern formation, two or more of the above-mentioned development methods may be used in combination as needed. Development methods include immersion, immersion, spraying, high-pressure spraying, brushing, and blade coating. High-pressure spraying is preferred due to its improved resolution. When using a spray method, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

[0490] Thermal Curing (Post-baking) Process

[0491] After the above-mentioned development process is completed, a thermal curing (post-baking) process is performed to form a solder resist layer. As the post-baking process, an ultraviolet irradiation process using a high-pressure mercury lamp or a heating process using a clean oven can be listed. In the case of ultraviolet irradiation, the irradiation amount can be adjusted as needed, for example, 0.05 J / cm 2 ~10J / cm2 The heating conditions can be appropriately selected depending on the type and content of the resin component in the photosensitive resin composition, and are preferably within the range of 20 to 180 minutes at 150 to 220°C, and more preferably within the range of 30 to 120 minutes at 160 to 200°C.

[0492] <Other Process>

[0493] For printed wiring boards, after forming the solder resist layer, a hole-forming step and a desmearing step may be further included. These steps can be carried out according to various methods known to those skilled in the art used in the production of printed wiring boards.

[0494] After forming solder mask, the solder mask formed on the circuit substrate is subjected to a perforation process to form through holes and through holes as required. The perforation process can be carried out by known methods such as a drill, a laser, and plasma, and these methods are combined as required to carry out the perforation process, preferably the perforation process carried out by lasers such as carbon dioxide laser and YAG laser.

[0495] The desmearing process is a process for performing a desmearing treatment. Resin residue (smearing) is often found inside the openings formed during the drilling process. This staining can cause poor electrical connections, so this process involves removing the stain (desmearing).

[0496] The desmear treatment can be performed by dry desmear treatment, wet desmear treatment, or a combination of the two.

[0497] Examples of dry desmear treatments include desmear treatments using plasma. Desmear treatments using plasma can be performed using commercially available plasma desmear treatment equipment. Examples of commercially available plasma desmear treatment equipment suitable for printed wiring board production include microwave plasma equipment manufactured by NISSIN and atmospheric pressure plasma etching equipment manufactured by SEKISUI CHEMICAL CO., LTD.

[0498] As wet decontamination treatment, for example, decontamination treatment using an oxidizing solution can be mentioned. When using an oxidizing solution for decontamination treatment, it is preferred to carry out swelling treatment using a swelling solution, oxidation treatment using an oxidizing solution, and neutralization treatment using a neutralizing solution in sequence. As swelling liquid, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan can be mentioned. The swelling treatment is preferably carried out by immersing the substrate having through holes formed thereon in a swelling solution heated to 60°C to 80°C for 5 to 10 minutes. As the oxidizing solution, an alkaline permanganate aqueous solution is preferred, and for example, a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous sodium hydroxide solution can be mentioned. The oxidation treatment using an oxidizing solution is preferably carried out by immersing the substrate after the swelling treatment in an oxidizing solution heated to 60°C to 80°C for 10 to 30 minutes. Commercially available alkaline permanganate aqueous solutions include, for example, "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. Neutralization with a neutralizing solution is preferably performed by immersing the substrate after oxidation treatment in the neutralizing solution at 30°C to 50°C for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution. Commercially available products include, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan.

[0499] When the dry desmear treatment and the wet desmear treatment are performed in combination, the dry desmear treatment may be performed first, or the wet desmear treatment may be performed first.

[0500] When the insulating layer is used as an interlayer insulating layer, the same process as the solder resist layer can be performed, and a hole forming process, a desmear process, and a plating process can be performed after the thermal curing process.

[0501] The plating step is the process of forming a conductive layer on the insulating layer. The conductive layer can be formed by combining electroless and electrolytic plating. Alternatively, a plating resist with a pattern opposite to that of the conductive layer can be formed, and the conductive layer can be formed solely by electroless plating. Subsequent patterning methods known to those skilled in the art, such as subtractive and semi-additive methods, can be used.

[0502] [Semiconductor devices]

[0503] 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.

[0504] Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and aircraft).

[0505] 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. "Conductive portion" refers to a portion of the printed wiring board that conducts electrical signals and can be located on the surface or embedded. Furthermore, the semiconductor chip is not particularly limited as long as it is an electrical circuit element made of semiconductor material.

[0506] The method for mounting the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip can function effectively. Specifically, there can be mentioned a wire bonding mounting method, a flip chip mounting method, a mounting method using a solderless build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), etc. Here, "a mounting method using a solderless build-up layer (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and connected to the wiring on the printed wiring board."

[0507] Example

[0508] The present invention will be described in detail below using examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing quantities refer to "parts by mass" and "mass %," respectively, unless otherwise specified. The epoxy equivalent of component (D) was measured in accordance with JIS K7236, and the softening point was measured in accordance with JIS K7234.

[0509] (Synthesis Example 1: Synthesis of Resin (A-1))

[0510] In a flask equipped with a gas inlet tube, a stirrer, a condenser, and a thermometer, 325 parts of a naphthol aralkyl epoxy resin represented by the following formula (1) (epoxy equivalent 325 g / eq., "ESN-475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) were added, followed by heating and dissolving 340 parts of carbitol acetate. 0.46 parts of hydroquinone and 1 part of triphenylphosphine were then added. The mixture was heated to 95-105°C, 72 parts of acrylic acid were slowly added dropwise, and the mixture was allowed to react for 16 hours. The reaction product was cooled to 80-90°C, 80 parts of tetrahydrophthalic anhydride were added, the mixture was allowed to react for 8 hours, and the mixture was then cooled. Thus, a resin solution having an acid value of 60 mg KOH / g of solids (non-volatile content 70%, hereinafter referred to as "resin solution (A-1)") was obtained.

[0511] [Chemical Formula 37]

[0512]

[0513] Wherein, Z is a glycidyl group (G) or a hydrocarbon group having 1 to 8 carbon atoms (R 6 ), R 6 The ratio of G is 0.05 to 2.0. In addition, n represents a number of 1 to 6 as an average value.

[0514] It was confirmed that the resin solution (A-1) contains at least a resin having a structure represented by the following formula (2).

[0515] [Chemical Formula 38]

[0516]

[0517] (Synthesis Example 2: Synthesis of Maleimide Compound (E-1))

[0518] A 300 mL flask equipped with a thermometer, condenser, and Dean-Stark trap was charged with 12.1 g (0.1 mol) of 2,6-dimethylaniline, 68.0 g (0.35 mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 100 g of xylene, and 20 g of activated clay. The mixture was heated to 120°C while stirring. The distilled water was removed using a Dean-Stark trap while the temperature was raised to 210°C and allowed to react for 3 hours. The mixture was then cooled to 140°C, 36.4 g (0.3 mol) of 2,6-dimethylaniline was added, and the temperature was raised to 220°C for 3 hours. After the reaction, the mixture was air-cooled to 100°C and diluted with 75 g of toluene. The activated clay was removed by filtration, and low-molecular-weight substances such as the solvent and unreacted products were distilled off under reduced pressure to obtain 91.0 g of an intermediate amine compound represented by the following formula (E-1) (n is an integer of 1 to 10). The amine equivalent weight was 296, and the softening point was 70°C.

[0519] [Chemical Formula 39]

[0520]

[0521] Next, a 500 mL flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 32.9 g (0.32 mol) of maleic anhydride and 200 g of toluene, and stirred at room temperature. A mixed solution of 91 g of the intermediate amine compound represented by formula (E-1) and 40 g of DMF was added dropwise over 1 hour. After the addition was completed, the reaction was allowed to proceed for a further 2 hours at room temperature. 9.3 g of p-toluenesulfonic acid monohydrate was added, and the reaction solution was heated. The azeotropic water and toluene, which were refluxed, were cooled and separated, and only the toluene was returned to the system for an 8-hour dehydration reaction. After air cooling to room temperature, the solution was concentrated under reduced pressure, and the brown solution was dissolved in 150 g of ethyl acetate. The solution was washed three times with 40 g of ion-exchanged water and three times with 40 g of a 2% aqueous sodium bicarbonate solution. Sodium sulfate was added, dried, and then concentrated under reduced pressure. The resulting reaction mixture was vacuum-dried at 80°C for 4 hours to obtain 103.0 g of a product containing the maleimide compound (C-1). In the FD-MS spectrum of the maleimide compound (C-1), peaks of M+=560, 7, and 876 were confirmed, corresponding to the cases where n is 0, 1, and 2, respectively. The number of repeating units n in the indane skeleton portion of the maleimide compound (C-1) was determined by GPC (based on the number average molecular weight) and found to be 1.47, with a molecular weight distribution (Mw / Mn) of 1.81. Furthermore, out of the total amount (100 area %) of the maleimide E-1, the maleimide compound having an average repeating unit number n of 0 accounted for 26.5 area %.

[0522] <Examples 1 to 11, Comparative Examples 1 to 6>

[0523] The components were blended in the proportions shown in the following table, and a resin varnish was prepared using a high-speed rotary mixer.

[0524] Next, a PET film ("Lumirror T6AM" manufactured by Toray Industries, Ltd., thickness 38 μm, softening point 130°C) was prepared as a support. A resin varnish was uniformly applied to the PET film using a die coater so that the thickness of the photosensitive resin composition layer after drying would be 25 μm. The film was then dried at 80°C to 110°C for 6.5 minutes to obtain a photosensitive film having a photosensitive resin composition layer on the PET film.

[0525] Separately, a PET film ("Lumirror T6AM" manufactured by Toray Industries, Ltd., 38 μm thick, softening point 130°C, "release PET film") was prepared, which had been release-treated with an alkyd resin release agent ("AL-5" manufactured by Lintec). A resin varnish was uniformly applied to the release PET using a die coater so that the thickness of the photosensitive resin composition layer after drying would be 25 μm. The film was then dried at 80°C to 110°C for 6.5 minutes to obtain a photosensitive film having a photosensitive resin composition layer on the release PET film.

[0526] <Flexibility Evaluation>

[0527] A photosensitive film having a photosensitive resin composition layer on a PET film was wound onto a 3-inch core and the film was checked for cracks. Furthermore, the film was cut using a roll cutter (manufactured by DAHLE) to confirm the film's crack-free condition. In these operations, the absence of cracks was scored as "◯," while the presence of cracks was scored as "×."

[0528] <Evaluation of Development Properties>

[0529] (Formation of Evaluation Laminate)

[0530] For the copper layer of the glass epoxy substrate (copper-clad laminate) having a circuit patterned with a copper layer having a thickness of 18 μm, roughening was performed by treating with a surface treatment agent (CZ8100, manufactured by Meige Co., Ltd.) comprising an organic acid. Next, a photosensitive resin composition layer having a photosensitive resin composition layer on a PET film was arranged in contact with the surface of the copper circuit, and a vacuum laminator (Nikko-Materials, VP160) was used to laminate to form a laminate having the copper-clad laminate, the photosensitive resin composition layer, and the support laminated therein. The pressing conditions were as follows: 30 seconds for vacuuming, 80°C for pressing, 0.7 MPa for pressing, and 30 seconds for pressing. The laminate was left to stand at room temperature for more than 30 minutes, and was exposed to ultraviolet light from above the support of the laminate using a circular hole pattern and a pattern forming device. The exposure pattern used was a quartz glass mask with a 1 cm x 2 cm square pattern, with circular openings of 50 μm / 60 μm / 70 μm / 80 μm / 90 μm / 100 μm, and line / space (L / S) ratios of 50 μm / 50 μm, 60 μm / 60 μm, 70 μm / 70 μm, 80 μm / 80 μm, 90 μm / 90 μm, and 100 μm / 100 μm. After standing at room temperature for 30 minutes, the support was peeled off from the laminate.

[0531] (Residue in unexposed area)

[0532] After the support was removed, the entire surface of the photosensitive resin composition layer on the laminate (laminated plate) was spray-developed using a 1% by mass sodium carbonate aqueous solution at 30°C as a developer at a spray pressure of 0.2 MPa. The unexposed area of a 1 cm x 2 cm portion of the laminate after spray development was visually observed and evaluated according to the following criteria:

[0533] ○: No resin remains in the unexposed area;

[0534] ×: The presence of resin was visually confirmed, or film weight loss occurred.

[0535] (Evaluation of BP (Development Point))

[0536] While visually observing the unexposed area of 1 cm x 2 cm of the laminate, spray development was performed while spraying a 1 mass % sodium carbonate aqueous solution at 30°C as a developer at a spray pressure of 0.2 MPa. The time (seconds) from the start of spraying to the disappearance of the resin remaining on the substrate was recorded.

[0537] (Resolution (clarity) and minimum through-hole diameter evaluation)

[0538] Next, the formed through-holes and L / S ratios were observed using an SEM (1000x magnification) to measure the minimum through-hole diameter without residue or peeling. Furthermore, the L / S ratios at any three points were measured and evaluated according to the following criteria. However, for the minimum through-hole diameter, cases with residue or peeling were evaluated as "×." Cases with a minimum L / S ratio exceeding 60 μm / 60 μm were evaluated as "×."

[0539] ○: Observe the L / S at three points. There is no peeling or filling between all L / S points.

[0540] ×: When L / S at three points were observed, resin embedment or peeling was observed between any of the L / S.

[0541] <Measurement of dielectric constant, dielectric loss tangent, and glass transition temperature>

[0542] (Formation of Cured Material for Evaluation)

[0543] The photosensitive resin composition layer of the photosensitive film having the photosensitive resin composition layer on the release PET film was subjected to a 1 J / cm 2 The support was then peeled off to obtain a cured product A for evaluation.

[0544] (Determination of dielectric constant and dielectric loss tangent)

[0545] Cured Material A for evaluation was cut into test pieces with a width of 2 mm and a length of 80 mm to obtain Cured Material B for evaluation. For each Cured Material B for evaluation, the dielectric constant (Dk value) and dielectric loss tangent (Df value) were measured using an HP8362B manufactured by Agilent Technologies using the cavity perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. The measurements were performed on three test pieces (N=3), and the average values were calculated.

[0546] (Determination of glass transition temperature)

[0547] Cured Material A for evaluation was cut into test pieces approximately 5 mm wide and 15 mm long. Thermomechanical analysis was performed using a dynamic viscoelasticity measuring instrument (EXSTAR6000, manufactured by SII Nanotech Co., Ltd.) using the tensile loading method. The test pieces were mounted in the instrument and measured under the conditions of a load of 200 mN and a heating rate of 2°C / minute. The resulting tan δ peak was calculated as the glass transition temperature (°C).

[0548] [Table 1]

[0549]

[0550] The abbreviations in the table are as follows;

[0551] (A)Ingredients:

[0552] CCR-1179: Cresol novolac F-type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH / g, non-volatile content 70%)

[0553] A-1: Resin solution (A-1) synthesized in Synthesis Example 1

[0554] (B) Ingredients:

[0555] SC2050: Fused silica (manufactured by Yaduma Co., Ltd., average particle size 0.5 μm, specific surface area 5.9 m 2 / g) 100 parts by mass, and surface-treated with 0.5 parts by mass of aminosilane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0556] (C) Ingredients:

[0557] Irgacure TPO: bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, manufactured by BASF

[0558] Irgacure OXE-01: 1-[4-(phenylthio)-1,2-octanedione 2-(O-benzoyl oxime)] (manufactured by BASF)

[0559] (D) Ingredients:

[0560] HP4032: Naphthalene-based epoxy resin (manufactured by DIC Corporation, epoxy equivalent weight 144 g / eq., softening point less than 30°C)

[0561] ELM-434VL: N,N,N',N'-tetrakis(oxiran-2-ylmethyl)-4,4'-methylenedianiline (glycidylamine-type epoxy resin, manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent weight 114 g / eq., softening point less than 30°C)

[0562] NC3000L: Biphenyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight 271 g / eq., softening point 53°C)

[0563] NC3000H: Biphenyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight 272 g / eq., softening point 70°C)

[0564] 1031S: Tetrahydroxyphenylethane epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 224 g / eq., softening point 92°C)

[0565] (E) Ingredients:

[0566] BMI-689: Maleimide resin, dimer diamine type bismaleimide (manufactured by Designer Molecules)

[0567] E-1: Maleimide compound (E-1) synthesized in Synthesis Example 2

[0568] BMI-5100: Maleimide resin, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, manufactured by Designer Molecules

[0569] MIR3000: Maleimide resin, manufactured by Nippon Kayaku Co., Ltd.

[0570] EXB-8151-62T: Active ester resin containing a naphthalene structure, manufactured by DIC Corporation

[0571] PC1300-02-65MA: Active ester resin containing a naphthalene structure, manufactured by Air & Water

[0572] DAD: Vinyl resin: Diallyl 2,2'-biphenyldicarboxylate (manufactured by Nichihaku Techno Fine Chemicals Co., Ltd.)

[0573] OPE-2St: Vinyl resin (vinyl benzyl-modified polyphenylene ether, manufactured by Mitsubishi Gas Chemical Co., Ltd.)

[0574] (F)Ingredients

[0575] 1B2PZ: 2-phenyl-1-benzyl-1H-imidazole, manufactured by Shikoku Chemical Co., Ltd.

[0576] (G) Ingredients:

[0577] EDGAc: diethylene glycol monoethyl ether acetate

[0578] MEK: Methyl Ethyl Ketone

[0579] (H) Ingredients:

[0580] DOG-A: Dioxane Glycol Diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0581] TD-2090-60M: Novolac-type phenolic resin, manufactured by DIC Corporation.

[0582] It was confirmed that in each example, even when the components (F) to (H) were not contained, the same results as those of the above-mentioned examples were achieved, although the degree of difference was different.

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 filling materials, (C) photopolymerization initiator, (D) Epoxy resin, and (E) one or more resins selected from active ester resins, maleimide resins, and vinyl resins, in, (D) Ingredients include: (D-1) an epoxy resin having a softening point of less than 30°C and an epoxy equivalent of 150 g / eq. or less, and (D-2) An epoxy resin having a softening point of 30°C or higher and lower than 59°C.

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

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

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

5. The photosensitive resin composition according to claim 1, wherein The epoxy equivalent of the component (D-1) is 145 g / eq. or less. The photosensitive resin composition according to claim 1 , wherein The epoxy equivalent of the component (D-1) is 10 g / eq. or more.

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

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

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

10. The photosensitive resin composition according to claim 1, wherein When the content of the component (D-1) when the nonvolatile component in the photosensitive resin composition is 100 mass % is D1 and the content of the component (D-2) when the nonvolatile component in the photosensitive resin composition is 100 mass % is D2, D2 / D1 is 0.5 or more and 2.5 or less.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

26. The photosensitive resin composition according to claim 1, wherein (A) Ingredients include: (A-1) Resin containing a naphthalene skeleton.

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

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

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

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

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

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

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

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

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 (E) Ingredients include: Active ester resin, and One or more resins selected from maleimide resins and vinyl resins.

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

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

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

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

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

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

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

44. A photosensitive film comprising: Support, and A photosensitive resin composition layer provided on the support and comprising the photosensitive resin composition according to any one of claims 1 to 43. 45 . A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to claim 1 .

46. The printed wiring board according to claim 45, wherein The insulating layer is a solder resist layer. A semiconductor device comprising the printed wiring board according to claim 45 or 46.

Images