Photosensitive resin composition

Abstract

The objective of this invention is to provide a photosensitive resin composition with excellent flexibility that can suppress the formation of depressions from aggregates on the surface of a cured material after roughening treatment and has high peel strength. The solution of this invention is a photosensitive resin composition containing the following components (A) to (E): (A) a resin containing olefinic unsaturated groups and carboxyl groups, (B) an inorganic filler, (C) a photopolymerization initiator, (D) an epoxy resin, and (E) a high molecular weight component, wherein the glass transition temperature of component (E) is 65°C or less, and the weight-average molecular weight is 1000 or more and less than 10000.

Description

Technical Field

[0001] This invention relates to photosensitive resin compositions. Further, it relates to photosensitive films, printed wiring boards, and semiconductor devices obtained using the photosensitive resin compositions. Background Technology

[0002] In printed wiring boards, a solder resist layer (solder resist) is sometimes provided as a permanent protective film to prevent solder from adhering to areas where solder is not needed and to inhibit corrosion of the circuit board. As a solder resist layer, a photosensitive resin composition, such as that described in Patent Document 1, is generally used.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent document 1: Japanese Patent Application Publication No. 2014-115672. Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] Photosensitive resin compositions are generally required to have high resolution during development. Furthermore, in recent years, photosensitive resin compositions have been explored as materials for insulating or sealing layers; therefore, in addition to resolution, excellent peel strength to the conductor layer is also required. Moreover, from the viewpoint of improving the operability of photosensitive films containing photosensitive resin compositions, there is also a need to improve the flexibility of the photosensitive resin composition.

[0008] The inventors have discovered that when a photosensitive resin composition is photocured, the components of the photosensitive resin composition undergo phase separation, and the peel strength is improved due to the phase separation.

[0009] However, when the degree of phase separation is significant, aggregates of specific components may sometimes form. When the surface of the cured photosensitive resin composition is roughened, these aggregates detach, creating depressions on the roughened surface. These depressions can sometimes reduce the uniformity and insulation properties of surfaces that are essential for solder resists, sealants, or insulating layers. Furthermore, from the viewpoint of improving the processability of photosensitive films containing photosensitive resin compositions, there is a need to increase the flexibility of the photosensitive resin composition.

[0010] The present invention was made in view of the above-mentioned problems. The object of the present invention is to provide: a photosensitive resin composition with excellent flexibility, which can produce a cured material with high peel strength and the ability to suppress the formation of depressions from aggregates on the surface of the cured material after roughening treatment; and photosensitive films, printed wiring boards, and semiconductor devices obtained using the photosensitive resin composition.

[0011] Methods for solving problems

[0012] Through diligent research, the inventors discovered that by using a photosensitive resin composition containing a high molecular weight component with a glass transition temperature of 65°C or lower and a weight-average molecular weight of 1000 or more but less than 10000, and further combining a photosensitive resin composition containing (A) a resin with olefinic unsaturated groups and carboxyl groups, (B) an inorganic filler, (C) a photopolymerization initiator, and (D) an epoxy resin, a cured product that can suppress the formation of depressions from aggregates on the surface of the cured product after roughening treatment, has high peel strength, and exhibits excellent flexibility, thus completing the present invention.

[0013] That is, the present invention includes the following:

[0014] [1] A photosensitive resin composition comprising the following components (A) to (E),

[0015] (A) Resins containing olefinic unsaturated groups and carboxyl groups,

[0016] (B) Inorganic filler materials,

[0017] (C) Photopolymerization initiator,

[0018] (D) Epoxy resin, and

[0019] (E) High molecular weight components

[0020] Among them, the glass transition temperature of component (E) is below 65°C, and the weight-average molecular weight is above 1000 and below 10000.

[0021] [2] According to the photosensitive resin composition of [1], wherein when the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (B) is 50% by mass or more and 85% by mass or less.

[0022] [3] The photosensitive resin composition according to [1] or [2], wherein the (E) component has one or more groups selected from carboxyl, hydroxyl, epoxy and (meth)acryloyl;

[0023] [4] The photosensitive resin composition according to any one of [1] to [3], wherein component (A) has a naphthalene skeleton;

[0024] [5] The photosensitive resin composition according to any one of [1] to [4], wherein component (A) is an acid-modified epoxy (meth)acrylate containing a naphthalene skeleton;

[0025] [6] The photosensitive resin composition according to any one of [1] to [5], wherein component (D) contains at least one of biphenyl epoxy resin and glycidylamine epoxy resin;

[0026] [7] The photosensitive resin composition according to any one of [1] to [6], wherein component (B) comprises silicon dioxide;

[0027] [8] A photosensitive film comprising any one of the photosensitive resin compositions described in [1] to [7];

[0028] [9] A photosensitive film with a support, comprising:

[0029] Support body, and

[0030] A photosensitive resin composition layer comprising any one of [1] to [7] is disposed on the support;

[0031]

[10] A printed wiring board comprising an insulating layer formed by curing a photosensitive resin composition according to any one of [1] to [7];

[0032]

[11] The printed wiring board according to

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

[0033]

[12] A semiconductor device comprising the printed wiring board described in

[10] or

[11] .

[0034] The effects of the invention

[0035] According to the present invention, a photosensitive resin composition with excellent flexibility that can suppress the formation of depressions from aggregates on the surface of a cured material after roughening treatment and has high peel strength can be provided; a photosensitive film, a printed wiring board, and a semiconductor device obtained using the photosensitive resin composition can be provided. Detailed Implementation

[0036] The photosensitive resin composition, photosensitive film, printed wiring board, and semiconductor device of the present invention will now be described in detail.

[0037] [Photosensitive Resin Composition]

[0038] The photosensitive resin composition of the present invention comprises (A) a resin containing olefinic unsaturated groups and carboxyl groups, (B) an inorganic filler, (C) a photopolymerization initiator, (D) an epoxy resin, and (E) a high molecular weight component, wherein the glass transition temperature of component (E) is below 65°C, and the weight-average molecular weight is above 1000 and below 10000. Using this photosensitive resin composition, cured products with excellent flexibility, the ability to suppress depressions originating from aggregates on the surface of the cured product after roughening treatment, and high peel strength can be obtained. Furthermore, this photosensitive resin composition generally exhibits excellent developability.

[0039] The photosensitive resin composition may further include, as needed, any components such as (F) reactive diluent, (G) solvent, and (H) other additives. The components contained in the photosensitive resin composition are described in detail below.

[0040] <(A) Resins containing olefinic unsaturated groups and carboxyl groups>

[0041] The photosensitive resin composition contains, as component (A), a resin containing olefinic unsaturated groups and carboxyl groups. By including component (A) in the photosensitive resin composition, resolution can be improved.

[0042] The olefinic unsaturated group has a carbon-carbon double bond, and examples include vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimide, nadiimide, and (meth)acryloyl. From the viewpoint of photoradical polymerization reactivity, (meth)acryloyl is preferred. "(meth)acryloyl" includes methacryloyl, acryloyl, and combinations thereof. Component (A) can undergo photoradical polymerization because it contains an olefinic unsaturated group. Each molecule of component (A) may contain one or more olefinic unsaturated groups. Furthermore, when each molecule of component (A) contains two or more olefinic unsaturated groups, those olefinic unsaturated groups may be the same or different.

[0043] 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 solution of sodium carbonate as an alkaline developer). Each molecule of component (A) may contain one or more carboxyl groups.

[0044] As component (A), any resin containing an olefinic unsaturated group and a carboxyl group is acceptable. As component (A), it is preferably at least one of (A-1) a resin containing a naphthalene skeleton and (A-2) an acid-modified epoxy (meth)acrylate resin.

[0045] ((A-1) Resins containing a naphthalene skeleton)

[0046] Resins containing a naphthalene skeleton (A-1) belong to component (A) and therefore contain olefinic unsaturated groups and carboxyl groups. Therefore, component (A-1) can undergo photoradical polymerization, and photosensitive resin compositions containing component (A-1) all exhibit solubility in alkaline solutions.

[0047] The (A-1) component preferably has multiple olefinic unsaturated groups in one molecule. This improves the mechanical strength and solvent resistance of the cured photosensitive resin composition. Furthermore, the (A-1) component preferably has two or fewer olefinic unsaturated groups per naphthalene skeleton. This allows adjustment of the crosslinking position (crosslinking point), thus controlling the mechanical strength and solvent resistance of the cured photosensitive resin composition. More preferably, the olefinic unsaturated groups are included in the substituents of the naphthalene skeleton. To include the olefinic unsaturated groups in the substituents of the naphthalene skeleton, as a first precursor, a compound in which the H atom of the OH group of naphthol is replaced by a substituent containing an epoxy group (e.g., epoxy group, glycidyl group) is prepared. For the first precursor, an addition reaction is performed with a compound having an olefinic unsaturated bond (e.g., an unsaturated carboxylic acid, preferably (meth)acrylic acid), thereby obtaining the desired product. This allows the introduction of olefinic unsaturated groups into the substituents of the naphthalene skeleton.

[0048] (A-1) The component preferably has multiple carboxyl groups in one molecule. This improves the solubility of the photosensitive resin composition in alkaline solutions (e.g., alkaline developers). (A-1) The component preferably has two or fewer carboxyl groups per naphthalene skeleton. This allows for controllability of solubility. More preferably, the carboxyl groups are included in the substituents of the naphthalene skeleton. To include the carboxyl groups in the substituents of the naphthalene skeleton, as a first precursor, for example, a compound in which the H atom of the OH group of naphthol is replaced by a substituent containing an epoxy group is prepared. For the first precursor, a compound having an alkene-like unsaturated bond (e.g., an unsaturated carboxylic acid, preferably (meth)acrylic acid) is added, thereby obtaining a second precursor having a secondary hydroxyl group. For the second precursor, a carboxylic anhydride (e.g., tetrahydrophthalic acid) is added, thereby obtaining the desired product. Thus, both alkene-like unsaturated groups and carboxyl groups can be introduced into the substituents of the naphthalene skeleton.

[0049] Furthermore, 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 per molecule. Furthermore, component (A-1) can dissolve in alkaline solutions (e.g., alkaline developers) at a suitable dissolution rate. Moreover, when the photosensitive resin composition containing component (A-1) is developed with an alkaline developer, the formation of unintended over-dissolved portions and unintended non-dissolved portions in the photosensitive resin composition can be suppressed. That is, the breakpoint (BP) can be increased. Therefore, the developability of the photosensitive resin composition can be improved.

[0050] Furthermore, when a resin containing a naphthalene skeleton is used as component (A-1), the rigidity of the molecules is generally increased, thus suppressing molecular movement in the photosensitive resin composition. As a result, the glass transition temperature of the cured photosensitive resin composition is further increased. Moreover, through the action of component (A-1), resistance to internal stresses caused by thermal expansion or contraction is generally improved, thereby enhancing the flexibility of the photosensitive film.

[0051] The (A-1) component may contain one naphthalene skeleton or more than two naphthalene skeletons in one molecule.

[0052] Component (A-1) is, for example, a resin containing the structure shown in formula (1) below. Component (A-1) may have multiple (e.g., 1 to 10, preferably 1 to 6) structures shown in formula (1) below. When multiple structures shown in formula (1) are present, component (A-1) may include those multiple structures shown in formula (1) below as structural units (repeating units). Furthermore, in formula (1) below, with R... 1 The chemical bond formed can bond with any carbon atom that can bond to any carbon atom in the naphthalene skeleton. Therefore, R 1 The chemical bonds formed can be attached to the same carbon atom of the benzene ring as the terminal bonds, or they can be attached to carbon atoms of different benzene rings. The terminal bonds mentioned above refer to those attached to the naphthalene ring, excluding those with R... 1 The chemical bonds that are bonded to OR' and other chemical bonds, specifically, those depicted on the left-hand side of equation (1). For example, the terminal chemical bonds in the naphthalene skeleton and the bonds with R'. 1 The combination of positions of the chemical bonds can be 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 2,3, 2,6, or 2,7.

[0053] [Chemical Formula 1]

[0054]

[0055] In equation (1) above, R1 and R 2 Each alkylene group can be independently represented by a substituent. R 1 The number of carbon atoms is typically 1 to 20, preferably 1 to 10, and even more preferably 1 to 6. Furthermore, the alkylene group can be linear or branched. Examples of alkylene groups include methylene, ethylene, propylene, and butylene.

[0056] R 1 and R 2 The substituents that can be present can be listed independently, such as halogen atoms, alkyl, alkoxy, aryl, arylalkyl, silyl, acyl, acyloxy, carboxyl, sulfonyl, cyano, nitro, hydroxyl, mercapto, oxo, etc.

[0057] In formula (1) above, X represents an arylene group optionally having substituents. The number of carbon atoms in X is usually 6 to 30, preferably 6 to 20, and more preferably 6 to 10. Examples of arylene groups are phenylene, anthracene, phenanthrene, and biphenylene.

[0058] Examples of substituents that X can have include, for example, those with R. 1 and R 2 Examples of substituents that can be the same.

[0059] In equation (1) above, a represents 0 or 1. Here, a is the number of groups X.

[0060] In equation (1) above, s represents 0 or 1. Here, s and t are the groups R and T, respectively. 1 and group R 2 The number of. Furthermore, in equation (1) above, t represents 0 or 1. However, s and t cannot be s+t = 0. Wherein, when a = 1, it is preferable that both s and t are 1. When a = 0, it is preferable that one of s and t is 0.

[0061] In formula (1) above, OR' is a substituent on the naphthalene skeleton. In formula (1) above, R' independently represents an organic group containing an alkene-type unsaturated group and a carboxyl group, respectively.

[0062] R' preferably represents the group shown in formula (2) below:

[0063] [Chemical Formula 2]

[0064]

[0065] In equation (2) above, R 3 The symbol represents a trivalent group, preferably a trivalent hydrocarbon group optionally having substituents (wherein the heteroatom may be present between carbon-carbon bonds (C-C bonds)), and preferably a trivalent aliphatic hydrocarbon group optionally having substituents. The R... 3It can be a trivalent residue containing an epoxy group that is optionally substituent. R 3 The substituents that can be present can be listed, for example, with R. 1 and R 2 Examples of substituents that can be the same.

[0066] In equation (2) above, R 4 This refers to an organic group that contains an olefinically unsaturated group. A good example of an organic group containing an olefinically unsaturated group is (meth)acryloyloxy. "(meth)acryloyloxy" includes acryloyloxy, methacryloyloxy, and combinations thereof.

[0067] In equation (2) above, R 5 It is an organic group containing a carboxyl group. An example of an organic group containing a carboxyl group is -OCO-R. 6 -COOH. Here, R 6 This indicates a divalent group. As R... 6 Preferably, it is a divalent hydrocarbon group with a substituent. R 6 The number of carbon atoms is typically 1 to 30, preferably 1 to 20, and even more preferably 1 to 6. Examples of divalent hydrocarbon groups include straight-chain or branched acyclic 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 these, divalent alicyclic hydrocarbon groups and arylene groups are preferred, and 4-cyclohexenylene and phenylene groups are particularly preferred. Furthermore, R... 6 Possible substituents include, for example, those with R. 1 and R 2 Examples of substituents that can be the same. -OCO-R 6 -CO-R in -COOH 6 -COOH is usually a residue of a carboxylic anhydride. Examples of carboxylic anhydrides are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic dianhydride.

[0068] In equation (1) above, c usually represents 1 to 6, preferably 1 to 3, and even more preferably an integer from 1 to 2. Here, c is the number of groups OR'.

[0069] The first example of component (A-1) (a=1)-

[0070] A good example of component (A-1) is naphthol aralkyl resin. “Naphthol aralkyl resin” refers to a resin containing a group with a structure consisting of a group after removing the H atom of the OH group from the naphthol aralkylene group.

[0071] A better naphthol aralkyl type resin is a resin containing a structure in the above formula (1) where a = 1, for example, a resin containing the structure shown in the following formula (3);

[0072] [Chemical Formula 3]

[0073]

[0074] In equation (3) above, R 1 R 2 X, s, t, R', and c are the same as described above. It is preferable that s and t are both 1.

[0075] A better resin among naphthol aralkyl resins is a resin containing a structure of c=1, s=1 and t=1 in the above formula (3), for example, a naphthol aralkyl resin containing a divalent group of the structure shown in the following formula (4) or (5).

[0076] [Chemical Formula 4]

[0077]

[0078] [Chemical Formula 5]

[0079]

[0080] In equation (4) or (5) above, R 1 R 2 X, R', and c are the same as described above. The naphthol aralkyl type resin shown in formula (4) or (5) above is a resin that can be synthesized using the naphthol aralkyl type epoxy resin used in the synthesis example 1 described later. For example, the naphthol aralkyl type epoxy resin can be obtained as "ESN-475V" (epoxy equivalent 325 g / eq.) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.

[0081] The second example of component -(A-1) (a=0)-

[0082] In component (A-1), a better example other than naphthol aralkyl type resin (a=0) is a resin containing a structure of c=2, s=1 and t=0 in the above formula (1), for example, a resin containing a naphthalene skeleton containing a divalent group with the structure shown in the following formula (6).

[0083] [Chemical Formula 6]

[0084]

[0085] In equation (6) above, R 1R and R' are the same as described above. The resin containing a naphthalene skeleton shown in formula (6) above is a resin that can be synthesized using 1,1'-bis(2,7-diglycidyloxynaphthyl)methane as a material. Such an epoxy resin containing a naphthalene skeleton can be obtained, for example, as "EXA-4700" manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.

[0086] From the viewpoint of film-forming properties, the weight-average molecular weight of component (A-1) is preferably 500 or higher, more preferably 1000 or higher, further preferably 1500 or higher, and even more preferably 2000 or higher. From the viewpoint of reproducibility, the upper limit is preferably 10000 or lower, more preferably 8000 or lower, and even more preferably 7500 or lower. The weight-average molecular weight is the weight-average molecular weight converted from that of polystyrene determined by gel permeation chromatography (GPC).

[0087] -(A-1) Manufacturing method of component-

[0088] (A-1) Any compound containing a naphthalene skeleton, an olefinic unsaturated group, and a carboxyl group is acceptable, and is not limited to the examples mentioned above. One possible method is to react an unsaturated carboxylic acid with a naphthalene-type epoxy compound (an epoxy compound containing a naphthalene skeleton), and then react it with a carboxylic anhydride to obtain an acid-modified unsaturated epoxy ester resin containing a naphthalene skeleton. The method for manufacturing an acid-modified unsaturated epoxy ester resin containing a naphthalene skeleton will be described. First, an unsaturated carboxylic acid is reacted with an epoxy compound containing a naphthalene skeleton to obtain an unsaturated epoxy ester resin containing a naphthalene skeleton. Then, the unsaturated epoxy ester resin containing a naphthalene skeleton is reacted with a carboxylic anhydride. This yields an acid-modified unsaturated epoxy ester resin containing a naphthalene skeleton.

[0089] As epoxy compounds containing a naphthalene skeleton, any compound having one or more epoxy groups in its molecule can be used. Examples include: monohydroxynaphthalene-type epoxy resins, dihydroxynaphthalene-type epoxy resins, polyhydroxynaphthalene-type epoxy resins, naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene with aldehydes, bis(naphthol)-type epoxy resins, and naphthalene-type epoxy resins having a naphthalene skeleton in their molecule. Any one of these compounds can be used alone, or two or more can be used in combination.

[0090] Examples of monohydroxynaphthalene-type epoxy resins include 1-glycidyloxynaphthalene and 2-glycidyloxynaphthalene. Examples of dihydroxynaphthalene-type epoxy resins include 1,3-dicylatedryloxynaphthalene, 1,4-dicylatedryloxynaphthalene, 1,5-dicylatedryloxynaphthalene, 1,6-dicylatedryloxynaphthalene, 2,3-dicylatedryloxynaphthalene, 2,6-dicylatedryloxynaphthalene, and 2,7-dicylatedryloxynaphthalene.

[0091] Examples of polyhydroxybenzylene epoxy resins include 1,1'-(2-glycidyloxy)benzylene (1,1'-bi-(2-glycidyloxy)nafylene), 1-(2,7-diglycidyloxy)-1'-(2'-glycidyloxy)benzylene, and 1,1'-(2,7-diglycidyloxy)benzylene.

[0092] Examples of naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene with aldehydes include 1,1'-bis(2,7-diglycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxynaphthyl)-1'-(2'-glycidyloxynaphthyl)methane, and 1,1'-bis(2-glycidyloxynaphthyl)methane.

[0093] Among these, the preferred are polyhydroxy naphthyl-type epoxy resins having two or more naphthalene skeletons in one molecule, and naphthyl-type epoxy resins obtained by the condensation reaction of polyhydroxy naphthalene with aldehydes; in addition to having excellent average linear thermal expansion coefficients, they also have excellent heat resistance, and are particularly preferred are 1,1'-bis(2,7-diglycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxynaphthyl)-1'-(2'-glycidyloxynaphthyl)naphthyl, and 1,1'-(2,7-diglycidyloxy)naphthyl.

[0094] Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, cinnamic acid, and crotonic acid. These carboxylic acids can be used alone or in combination of two or more. 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 ester resin, which is a product of the reaction between a naphthalene-type epoxy compound and (meth)acrylic acid, is sometimes described as "naphthalene-type epoxy (meth)acrylate." Here, the epoxy groups of the naphthalene-type epoxy compound are usually substantially eliminated through the reaction with (meth)acrylic acid. "(meth)acrylate" includes methacrylates, acrylates, and combinations thereof. Sometimes acrylic acid and methacrylic acid are collectively referred to as "(meth)acrylic acid."

[0095] Examples of carboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic tetracarboxylic anhydride, and benzophenone tetracarboxylic dianhydride. Any one of these carboxylic anhydrides can be used alone, or two or more can be used in combination. From the perspective of improving the developability and insulation reliability of the cured product, succinic anhydride and tetrahydrophthalic anhydride are preferred.

[0096] In obtaining an acid-modified unsaturated epoxy ester resin containing a 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 an unsaturated epoxy ester resin containing a naphthalene skeleton, and then the unsaturated epoxy ester resin containing a naphthalene skeleton can be reacted with a carboxylic anhydride.

[0097] The amount of catalyst used at this time, relative to the total mass of the unsaturated carboxylic acid, the epoxide containing the naphthalene skeleton, and the carboxylic anhydride, is preferably less than 2% by mass, more preferably in the range of 0.0005% to 1% by mass, and even more preferably in the range of 0.001% to 0.5% by mass. Examples of catalysts 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-methylimidazolium, 2,4-dimethylimidazolium, 1,4-diethylimidazolium, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-amino)aminopropyltrimethoxysilane, 3-(2-amino)aminopropyltrimethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(N-amino)aminopropyltrimethoxysilane, 3-(N-phenyl ... Various amine compounds such as ethyl(aminopropylmethyldimethoxysilane) and tetramethylammonium hydroxide; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphine salts such as tetramethylphosphine, tetraethylphosphine, tetrapropylphosphine, tetrabutylphosphine, trimethyl(2-hydroxypropyl)phosphine, triphenylphosphine, and benzylphosphine, especially those with chloride, bromide, carboxylate, and hydroxide ions as typical equilibrium anions; sulfonium salts such as trimethylsulfonium, benzyltetramethylenesulfonium, phenylbenzylmethylsulfonium, or phenyldimethylsulfonium, especially those with carboxylate and hydroxide ions as typical equilibrium anions; and acidic compounds such as phosphoric acid, p-toluenesulfonic acid, and sulfuric acid. The reaction can be carried out in the range of 50℃ to 150℃, preferably in the range of 80℃ to 120℃.

[0098] When obtaining an acid-modified unsaturated epoxy ester resin containing a naphthalene skeleton, an organic solvent may be used. The same solvent as (G) solvent described later may be used as the organic solvent.

[0099] When obtaining an acid-modified unsaturated epoxy ester resin containing a naphthalene skeleton, a polymerization inhibitor such as hydroquinone can be used. The amount of polymerization inhibitor used, relative to the total mass of the unsaturated carboxylic acid, the epoxy compound containing the naphthalene skeleton, and the carboxylic anhydride, is preferably less than 2% by mass, more preferably in the range of 0.0005% to 1% by mass, and even more preferably in the range of 0.001% to 0.5% by mass.

[0100] As an acid-modified unsaturated epoxy ester resin containing a naphthalene skeleton, an acid-modified epoxy (meth)acrylate containing a naphthalene skeleton is preferred. An acid-modified epoxy (meth)acrylate containing a naphthalene skeleton refers to an acid-modified unsaturated epoxy ester resin containing a naphthalene skeleton obtained by using an epoxy compound containing a naphthalene skeleton and (meth)acrylate, which is an unsaturated carboxylic acid.

[0101] Other possible embodiments of component (A-1) include: reacting a (meth)acrylic resin having structural units obtained by polymerizing (meth)acrylic acid with an epoxy compound containing an olefinic unsaturated group and a naphthalene skeleton to introduce an unsaturated (meth)acrylic resin with an olefinic unsaturated group. Furthermore, a carboxylic anhydride may be reacted with a hydroxyl group generated during the introduction of the unsaturated group. The same substance as the aforementioned anhydride can be used as the carboxylic anhydride, and the preferred range is also the same.

[0102] ((A-2) Acid-modified epoxy (meth)acrylate resin)

[0103] The acid-modified epoxy (meth)acrylate resin, which is component (A-2), is a compound having a structure in which a carboxyl group is introduced into the (meth)acrylate of the epoxy compound. However, component (A-2) does not contain the aforementioned component (A-1).

[0104] As one method of obtaining component (A-2), examples include reacting (meth)acrylic acid with cresol-formaldehyde type A epoxy compounds, cresol-formaldehyde type F epoxy compounds, etc., to obtain cresol-formaldehyde type epoxy (meth)acrylates, and further reacting them with carboxylic anhydrides. Specifically, cresol-formaldehyde type epoxy (meth)acrylates can be obtained by reacting (meth)acrylic acid with cresol-formaldehyde type epoxy compounds, and acid-modified cresol-formaldehyde type epoxy (meth)acrylates can be obtained by reacting cresol-formaldehyde type epoxy (meth)acrylates with carboxylic anhydrides.

[0105] Other forms of the (A-2) component include acid-modified epoxy (meth)acrylates obtained by reacting (meth)acrylic acid with an epoxy compound other than the aforementioned cresol-phenolic aldehyde type epoxy compounds, and further reacting the reaction with a carboxylic anhydride. Examples of such epoxy compounds include: biphenyl-type epoxy compounds; bisphenol-type epoxy compounds such as bisphenol A-type epoxy compounds and bisphenol F-type epoxy compounds; and phenolic aldehydes. Novolac type epoxy resins; phenolic (novolac) type epoxy resins such as bisphenol A type phenolic epoxy resins and alkylphenol phenolic epoxy resins; fluorinated epoxy resins such as perfluoroalkyl type epoxy resins; bixylenol type epoxy resins; dicyclopentadiene type epoxy resins; triphenol type epoxy resins, tert-butyl-catechol type epoxy resins, anthracene type epoxy resins, and other epoxy resins containing fused ring skeletons; glycidylamine type epoxy resins; glycidyl ester type epoxy resins; linear aliphatic epoxy resins; epoxy resins with butadiene structure; alicyclic epoxy resins; heterocyclic epoxy resins; spirocyclic epoxy resins; cyclohexanediol type epoxy resins; trihydroxymethyl type epoxy resins; tetraphenylethane type epoxy resins; acrylic resins containing glycidyl groups such as (meth)acrylate polyglycidyl esters and copolymers of glycidyl methacrylate and acrylates; fluorene type epoxy resins; halogenated epoxy resins, etc.

[0106] Such acid-modified epoxy (meth)acrylates can be commercially available products. Specific examples include: "CCR-1179" (cresol phenolic formaldehyde 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" (cresol phenolic formaldehyde type epoxy resin, acrylic acid, and acid anhydride) manufactured by Showa Denko Co., Ltd., etc. These can be used individually or in combination of two or more.

[0107] Other forms of component (A-2) include unsaturated modified (meth)acrylate resins, which are obtained by reacting (meth)acrylate resins (having structural units obtained by polymerizing (meth)acrylate) with (meth)acrylates of epoxy compounds to introduce olefinic unsaturated groups. Examples of (meth)acrylates of epoxy compounds include glycidyl methacrylate, 4-hydroxybutyl methacrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl methacrylate. Furthermore, the hydroxyl groups generated during the introduction of unsaturated groups can be reacted with carboxylic anhydrides. The same substances as those described above can be used as carboxylic anhydrides, and the preferred range is also the same.

[0108] Such unsaturated modified (meth)acrylic resins can be commercially available. Specific examples include: "SPC-1000" and "SPC-3000" manufactured by Showa Denko Corporation, 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 DAICL-ALLNEX Corporation.

[0109] From the viewpoint of film-forming properties, the weight-average molecular weight of component (A-2) is preferably 1000 or higher, more preferably 1500 or higher, and even more preferably 2000 or higher. From the viewpoint of reproducibility, the upper limit is preferably 20000 or lower, more preferably 15000 or lower, and even more preferably 14000 or lower. The weight-average molecular weight is the weight-average molecular weight converted from that of polystyrene determined by gel permeation chromatography (GPC).

[0110] Component (A) can also be component (A-3) other than components (A-1) and (A-2) mentioned above. This component does not contain components (A-1) and (A-2).

[0111] The weight-average molecular weight and acid value of component (A-3) are arbitrary, but preferably within the same range as those of component (A-2) above. Therefore, the same advantages as those described in the section on component (A-2) can be obtained.

[0112] From the viewpoint of improving the solubility of the photosensitive resin composition in alkaline solution, the acid value of component (A) is preferably 0.1 mg KOH / g or more, 0.5 mg KOH / g or more, or 1 mg KOH / g or more. On the other hand, from the viewpoint of inhibiting the dissolution of fine patterns of the cured product into the alkaline solution, the acid value is preferably 150 mg KOH / g or less, more preferably 120 mg KOH / g or less, and even more preferably 100 mg KOH / g or less. Here, the acid value is the residual acid value of the carboxyl groups present in component (A), and the acid value can be determined by the following method. First, accurately weigh about 1 g of the resin solution to be tested, and then add 30 g of acetone to the resin solution to dissolve the resin solution uniformly. Next, add an appropriate amount of phenolphthalein as an indicator to the solution, and titrate with 0.1 N ethanolic KOH solution. Then calculate the acid value using the following formula (1);

[0113] Formula: A=Vf×5.611 / (Wp×I)···(1).

[0114] It should be noted that in the above formula (1), A represents the acid value [mgKOH / g], Vf represents the titration amount of KOH solution [mL], Wp represents the mass of the resin solution to be determined [g], and I represents the proportion of non-volatile components in the resin solution to be determined [mass %].

[0115] Regarding the content of component (A), from the viewpoint of adjusting the solubility of the photosensitive resin composition in an alkaline solution, when the non-volatile component in the photosensitive resin composition is set to 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less. It should be noted that, in this invention, the content of each component in the photosensitive resin composition, unless otherwise specified, refers to the value when the non-volatile component in the photosensitive resin composition is set to 100% by mass.

[0116] <(B) Inorganic filler materials>

[0117] The photosensitive resin composition contains (B) inorganic filler material as component (B). By containing component (B), a photosensitive resin composition in which a cured product with excellent insulating properties can be obtained can be provided.

[0118] (B) The inorganic filler material is not particularly limited, and examples include silicon dioxide, alumina, 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 titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silicon dioxide is particularly preferred. Furthermore, spherical silicon dioxide is preferred as the silicon dioxide. (B) One inorganic filler material may be used alone, or two or more may be used in combination.

[0119] From the viewpoint of obtaining a cured material with low dielectric constant and low dielectric loss tangent, the average particle size of (B) the inorganic filler material is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less, 2 μm or less, 1 μm or less, or 0.7 μm or less. There is no particular limitation on the lower limit of this average particle size, but it is preferably 0.01 μm or more, more preferably 0.05 μm or more, and even more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more.

[0120] The average particle size of inorganic filler materials can be determined using laser diffraction-scattering based on the Mie scattering theory. Specifically, a laser diffraction-scattering particle size distribution measuring device can be used to prepare the particle size distribution of the inorganic filler material based on volume, and the median particle size can be used as the average particle size for measurement. Samples prepared by dispersing the inorganic filler material in water using ultrasound are preferred for testing. Suitable laser diffraction-scattering particle size distribution measuring devices include the "LA-500" manufactured by Horiba Corporation and the "SALD-2200" manufactured by Shimadzu Corporation.

[0121] From the perspective of obtaining a cured material with low dielectric constant and low dielectric loss tangent, (B) the inorganic filler material has a better specific surface area of ​​1m². 2 / g or higher, preferably 3m 2 / g or higher, especially 5m 2 / g or above. There is no particular limit to the upper limit, but 60m is preferred. 2 / g or less, 50m 2 / g or less or 40m 2 / g or less. The specific surface area can be obtained by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen gas onto the sample surface and then calculating the specific surface area using the BET multi-point method.

[0122] From the perspective of improving moisture resistance and dispersibility, (B) inorganic filler materials are preferably treated with one or more surface treatment agents such as aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. Commercially available surface treatment agents include, for example: KBM403 (3-epoxypropoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM803 (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBE903 (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM573 (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., SZ-31 (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM103 (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and KBM-4803 (long-chain epoxy silane coupling agent) manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0123] (B) Commercially available inorganic filler materials may be used. Examples of commercially available products include: Admatechs' "SC2050", "SC4050", and "Admafine"; Denki Kagaku Kogyo's "SFP series"; Nippon Steel & Sumitomo Metal Materials' "SP(H) series"; Sakai Chemical Industries' "Sciqas series"; Nippon Shokubai's "SEAHOSTAR series"; Nippon Steel & Sumitomo Metal Materials' "AZ series" and "AX series"; and Sakai Chemical Industries' "B series" and "BF series".

[0124] From the viewpoint of obtaining a cured product with low dielectric constant and low dielectric loss tangent, when the non-volatile component in the photosensitive resin composition is set to 100% by mass, the content of (B) inorganic filler material is preferably 50% by mass or more, more preferably 55% by mass or more, and even more 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, 85% by mass or less, 70% by mass or less, and 65% by mass or less.

[0125] <(C) Photopolymerization Initiator>

[0126] In the photosensitive resin composition, a photopolymerization initiator is contained as component (C). By containing the photopolymerization initiator (C) in the photosensitive resin composition, the photosensitive resin composition can be effectively photocured.

[0127] (C) The photopolymerization initiator can be any compound, such as: acylphosphine oxide photoinitiators like bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; oxime ester photoinitiators like 1-[4-(phenylthio)-1,2-octanedione 2-(O-benzoyl oxime) and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone 1-(O-acetyl oxime); 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-[4-(4-morpholino)phenyl]-1-butanone, 2-methyl- α-aminoalkylphenyl ketone photoinitiators such as 1-[4-(methylthio)phenyl]-2-morpholino-1-propanone; benzophenone, methyl benzophenone, o-benzoylbenzoic acid, benzoyl ethyl 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-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, etc.; sulfonium salt photoinitiators can also be used. These photoinitiators can be used alone or in combination of two or more. From the viewpoint of enabling more effective photocuring of the photosensitive resin composition, it is preferable to use any one of acylphosphine oxide-based photopolymerization initiators and oxime ester-based photopolymerization initiators, and more preferably an acylphosphine oxide-based photopolymerization initiator. These photopolymerization initiators can be used alone or in combination of two or more.

[0128] Specific examples of photopolymerization initiators (C) include: "Omnirad 907", "Omnirad 369", "Omnirad 379", "Omnirad 819", and "Omnirad TPO" manufactured by IGM Resins; "Irgacure OXE-01", "Irgacure OXE-02", "Irgacure TPO", and "Irgacure 819" manufactured by BASF; and "N-1919" manufactured by ADEKA.

[0129] Regarding the content of the photopolymerization initiator (C), from the viewpoint of ensuring sufficient photocuring of the photosensitive resin composition and improving insulation reliability, when the non-volatile component of the photosensitive resin composition is set to 100% by mass, it is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more. On the other hand, from the viewpoint of suppressing the decrease in developability caused by excessive sensitivity, the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.

[0130] Furthermore, the photosensitive resin composition may include, 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 initiators, and may also include photosensitizers such as pyrazolines, anthracene derivatives, coumarins, xanthones, and thioxanthones. Any one of these compounds may be used alone, or two or more may be used in combination.

[0131] <(D) Epoxy Resin>

[0132] The photosensitive resin composition contains epoxy resin as component (D). The presence of component (D) improves insulation reliability. However, component (D) as described here does not include epoxy resins containing olefinic unsaturated groups and carboxyl groups. Furthermore, component (D) does not contain substances belonging to component (E).

[0133] Examples of components (D) include: bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butylcatechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin. Novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins with butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexane type epoxy resins, cyclohexanediethanol type epoxy resins, naphthyl ether type epoxy resins, tris(hydroxymethyl) type epoxy resins, tetraphenylethane type epoxy resins, tetraglycidyldiaminodiphenylmethane type epoxy resins, etc. Among these, as component (D), it is preferable to be either a biphenyl type epoxy resin or a glycidylamine type epoxy resin. Epoxy resins can be used alone or in combination of two or more.

[0134] For the resin composition, as component (D), it is preferable to include an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the proportion of epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the non-volatile components of component (D).

[0135] The epoxy resin includes an epoxy resin that is liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at 20°C (hereinafter sometimes referred to as "solid epoxy resin"). As component (D), the resin composition layer may contain only liquid epoxy resin or only solid epoxy resin; from the viewpoint of significantly achieving the desired effects of the present invention, it is preferable to combine both liquid and solid epoxy resins.

[0136] As a solid epoxy resin, it is preferable to be a solid epoxy resin having three or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

[0137] As solid epoxy resins, the preferred types are xylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol-phenolic epoxy resins, dicyclopentadiene-type epoxy resins, triphenol-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, with biphenyl-type epoxy resins being more preferred.

[0138] Specific examples of solid epoxy resins include: DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC's "N-690" (cresol-phenolic epoxy resin); DIC's "N-695" (cresol-phenolic epoxy resin); and DIC's "HP-7200," "HP-7200HH," and "HP-7200..." H (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (triphenol type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC7000L" (naphthol phenolic resin type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC3000H" "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.; "ESN485" (naphthol phenolic type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. These include: epoxy resins such as: Mitsubishi Chemical's "YX8800" (anthracene-type epoxy resin); Osaka Gas Chemical's "PG-100" and "CG-500"; Mitsubishi Chemical's "YL7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical's "YL7800" (fluorene type epoxy resin); Mitsubishi Chemical's "jER1010" (solid bisphenol A type epoxy resin); and Mitsubishi Chemical's "jER1031S" (tetraphenylethane type epoxy resin). These can be used individually or in combination of two or more.

[0139] As a liquid epoxy resin, it is preferable to be a liquid epoxy resin having two or more epoxy groups in one molecule.

[0140] As liquid epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenolic aldehyde type epoxy resin, alicyclic epoxy resin with an ester skeleton, cyclohexane type epoxy resin, cyclohexanediethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin with a butadiene structure are preferred, with glycidylamine type epoxy resin being more preferred. As a glycidylamine type epoxy resin, tetraglycidyldiaminodiphenylmethane type epoxy resin is more preferred.

[0141] Specific examples of liquid epoxy resins include: DIC's "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US", "jER828EL", "825", and "EPIKOTE828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER807" and "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "jER152" (phenolic resin); Mitsubishi Chemical's "630" and "630LSD" (glycidylamine type epoxy resin); Nippon Steel Chemical Materials Co., Ltd.'s "ZX1059" (a mixture of bisphenol A and bisphenol F type epoxy resin); Nagase ChemteX's "EX-721" (glycidyl ester type epoxy resin); and Daicel's "CELLOXIDE". 2021P (alicyclic epoxy resin with an ester skeleton); Daicel's "PB-3600" (an epoxy resin with a butadiene structure); Nippon Steel Chemical Materials Co., Ltd.'s "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin); Sumitomo Chemical Co., Ltd.'s "ELM-434L" (glycidylamine type epoxy resin); Sumitomo Chemical Co., Ltd.'s "ELM-434VL" (tetraglycidyldiaminodiphenylmethyl... Alkane-type epoxy resins; ADEKA's "EP-3980S" (difunctional glycidylamine type epoxy resin); ADEKA's "EP-3950L" (trifunctional glycidylamine type epoxy resin); Nissan Chemical's "TEPIC-VL" (isocyanuric acid cyclic epoxy resin); Sumitomo Chemical's "ELM-100H" (N-[2-methyl-4-(epoxyethylene methoxy)phenyl]-N-(epoxyethylene methyl)epoxymethylamine), etc. These can be used individually or in combination.

[0142] As component (D), when liquid epoxy resin and solid epoxy resin are used in combination, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.01 to 1:20, more preferably 1:0.1 to 1:10, and particularly preferably 1:0.5 to 1:5. By keeping the mass ratio of liquid epoxy resin to solid epoxy resin within the aforementioned range, the desired effects of the present invention can be significantly obtained. Furthermore, suitable adhesion can be obtained when it is typically used in the form of resin sheets. In addition, sufficient flexibility and improved processability can be obtained when it is typically used in the form of resin sheets. Furthermore, a cured product with sufficient tensile strength can typically be obtained.

[0143] The epoxy equivalent of component (D) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. By setting the epoxy equivalent of component (D) within this range, the crosslinking density of the cured resin composition layer becomes sufficient, resulting in an insulating layer with low surface roughness. Epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be determined according to JIS K7236.

[0144] From the viewpoint of achieving the desired effects of the present invention, the weight-average molecular weight (Mw) of component (D) is preferably 100–5000, more preferably 200–3000, and even more preferably 250–1500. The weight-average molecular weight of the resin can be determined by gel permeation chromatography (GPC) as a polystyrene equivalent.

[0145] From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, when the non-volatile component in the resin composition is set to 100% by mass, the content of component (D) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. From the viewpoint of significantly obtaining the desired effects of the present invention, the upper limit of the epoxy resin content is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less.

[0146] <(E) High molecular weight components>

[0147] The photosensitive resin composition includes a high molecular weight component (E) as component (E). Component (E) has a glass transition temperature of 65°C or lower and a weight-average molecular weight of 1000 or more but less than 10000. However, substances belonging to component (A) are excluded from component (E). By including component (E) in the photosensitive resin composition, high peel strength can be obtained when a conductive layer is formed on the surface of a roughened cured material using a plating process. Furthermore, component (E) suppresses the formation of depressions originating from aggregates on the surface of the roughened cured material, thus enabling the formation of fine wiring on the surface of the cured material. Furthermore, component (E) generally improves flexibility and resolution. Component (E) can be used alone or in combination of two or more.

[0148] From the viewpoint of suppressing the formation of depressions on the surface of the cured material after roughening treatment originating from aggregates, the weight-average molecular weight of the (E) high molecular weight component is 1000 or more, preferably 1500 or more, more preferably 2000 or more, or 3000 or more. The upper limit is less than 10000, preferably less than 8000, and more preferably less than 5000. The weight-average molecular weight of the (E) component is the weight-average molecular weight converted from polystyrene determined by gel permeation chromatography (GPC).

[0149] From the viewpoint of exhibiting an island structure after roughening treatment and obtaining high peel strength when forming a conductor layer, the glass transition temperature (Tg) of the (E) composition is below 65°C, preferably below 60°C, more preferably below 50°C, below 40°C, below 30°C, below 20°C, below 10°C, below 0°C, below -10°C, below -20°C, below -30°C, below -35°C, and below -40°C. The lower limit is preferably above -100°C, more preferably above -80°C, and even more preferably above -75°C.

[0150] The glass transition temperature (Tg) can be determined by differential scanning calorimetry based on JIS K 7121, with a heating rate of 5 °C / min.

[0151] By using the (E) component comprising the combination of the aforementioned weight-average molecular weight and glass transition temperature, the inventors hypothesize that the aforementioned excellent effects can be obtained through the following configuration (mechanism). However, the technical scope of the present invention is not limited to the following configuration (mechanism). Regarding the resin component contained in the photosensitive resin composition, an island structure can generally be formed, with the (E) component as islands and the resin components other than the (E) component as seas. Here, "resin component" refers to the component after removing inorganic fillers from the non-volatile components contained in the photosensitive resin composition. Then, when a roughening treatment is performed on the cured photosensitive resin composition, the treatment liquid easily penetrates the interface between the sea and the islands, and therefore, after the roughening treatment, pits of a size related to the size of the sea can be formed. Here, the (E) component comprising the combination of the aforementioned weight-average molecular weight and glass transition temperature can be well dispersed in the photosensitive resin composition because each molecule is small in size and the molecules have high flexibility. Therefore, the islands of the (E) component contained in the island structure can be relatively small. Therefore, the surface of the cured material after roughening treatment can have a large number of small pits, thus significantly increasing its surface area and achieving a high anchoring effect. Furthermore, component (E) has high flexibility, which improves the toughness of the cured photosensitive resin composition, resulting in high mechanical strength and suppressing peeling that accompanies the destruction of the cured material. Therefore, improved peel strength can be achieved. In addition, component (E) is well dispersed in the photosensitive resin composition, making it difficult for aggregates of component (E) to form in the cured material. This suppresses the formation of large depressions caused by the detachment of these aggregates, thus inhibiting the formation of depressions on the surface of the cured material. Furthermore, component (E) generally has excellent flexibility, resulting in high flexibility of the cured material.

[0152] As component (E), substances with glass transition temperature and weight-average molecular weight within the aforementioned ranges can be used. Examples of such components include resins such as (meth)acrylic resins, polyester resins, polyurethane resins, polyether resins, and polyolefin resins. "(Meth)acrylic resins" include acrylic acid and methacrylic acid, as well as combinations thereof.

[0153] Furthermore, as component (E), from the viewpoint of enabling component (E) to disperse well in the resin composition, making the island structure more compact, and thus significantly obtaining the effects of the present invention, it is preferable to have a functional group that can react with component (D). Examples of functional groups include carboxyl, hydroxyl, epoxy, and (meth)acryloyl groups. Among these, it is preferable to have one or more functional groups selected from carboxyl, hydroxyl, epoxy, and (meth)acryloyl groups, more preferably to have any functional group selected from carboxyl and hydroxyl groups, and even more preferably to have a hydroxyl group.

[0154] Functional groups may be present at the ends of components (E) or in repeating units. Preferably, functional groups are present in repeating units. Each molecule of component (E) may contain one or more functional groups. Furthermore, when each molecule of component (E) contains two or more functional groups, these functional groups may be the same or different.

[0155] A preferred embodiment of component (E) is a (meth)acrylic resin. Examples of (meth)acrylic resins include: carboxyl-containing (meth)acrylic resins, hydroxyl-containing (meth)acrylic resins, epoxy-containing (meth)acrylic resins, and (meth)acryloyl-containing (meth)acrylic resins, among which carboxyl-containing (meth)acrylic resins and hydroxyl-containing (meth)acrylic resins are preferred.

[0156] Examples of repeating units that form the main framework of (meth)acrylic resins include: structural units derived from methyl acrylate (MA), structural units derived from ethyl acrylate (EA), structural units derived from butyl acrylate (BA), structural units derived from 2-ethylhexyl acrylate (2EHA), and structural units derived from methyl methacrylate (MMA). Among these, structural units derived from butyl methacrylate and structural units derived from 2-ethylhexyl methacrylate are preferred as the main framework of (meth)acrylic resins; structural units derived from 2-ethylhexyl methacrylate are even more preferred.

[0157] Commercially available (meth)acrylic resins are acceptable. Examples of commercially available (meth)acrylic resins include: "CB-3060", "CB-3098", "CBB-3098", and "UT-1001" manufactured by Soken Chemical Co., Ltd.; and "BPX-003" manufactured by Negami Kogyo Co., Ltd.

[0158] Another preferred embodiment of component (E) is a polyester resin. Examples of polyester resins include: carboxyl-containing polyester resins, hydroxyl-containing polyester resins, epoxy-containing polyester resins, and (meth)acryloyl-containing polyester resins.

[0159] Examples of polyester resins include: self-condensates of fatty acids, and condensates of alcohols such as polyglycerol with fatty acids, i.e., fatty acid esters. Among these, self-condensates of fatty acids are preferred as polyester resins. Self-condensates of fatty acids can be synthesized by heating fatty acids.

[0160] The fatty acid may optionally have substituents such as hydroxyl groups, halogen atoms, or alkyl groups having 1 to 3 carbon atoms. Examples of fatty acids include 12-hydroxystearic acid, stearic acid, myristic acid, linalic acid, and palmitic acid. From the viewpoint of significantly obtaining the effects of the present invention, 12-hydroxystearic acid is preferred.

[0161] Commercially available polyester resins can be used. Examples of commercially available polyester resins include: "UE-3980" manufactured by UNITIKA, "XA-0653" manufactured by UNITIKA, and "PA-111" manufactured by Ajinomoto Fine-TechnoCo., Inc.

[0162] Another preferred embodiment of component (E) is a polyurethane resin. Examples of polyurethane resins include: carboxyl-containing polyurethane resins, hydroxyl-containing polyurethane resins, epoxy-containing polyurethane resins, and (meth)acryloyl-containing polyurethane resins.

[0163] Commercially available polyurethane resins can be used. Examples of commercially available polyurethane resins include "AGKN-026" manufactured by Negami Kogyo Co., Ltd.

[0164] When component (E) contains a carboxyl group, from the viewpoint of improving resolution, the acid value of component (E) is preferably 10 mg KOH / g or higher, more preferably 20 mg KOH / g or higher, further preferably 30 mg KOH / g or higher, preferably 150 mg KOH / g or lower, more preferably 120 mg KOH / g or lower, and further preferably 100 mg KOH / g or lower. The acid value can be calculated using the same method as for component (A).

[0165] When component (E) contains a hydroxyl group, from the viewpoint of improving resolution, the hydroxyl value of component (E) is preferably 20 mg KOH / g or more, more preferably 30 mg KOH / g or more, further preferably 40 mg KOH / g or more, preferably 450 mg KOH / g or less, more preferably 200 mg KOH / g or less, further preferably 150 mg KOH / g or less, 120 mg KOH / g or less, or 100 mg KOH / g or less. The hydroxyl value can be calculated by the following method;

[0166] First, accurately weigh 2g of resin, add 5ml of acetylation reagent (add pyridine to 25g of acetic anhydride to make a 100mL solution), and heat in an oil bath at 95-100℃ for 1 hour. Then, add 1mL of water, and heat at 95-100℃ for 10 minutes, then add 5mL of ethanol. Add a few drops of phenolphthalein solution as an indicator, and titrate with 0.5mol / L potassium hydroxide ethanol solution. Set the endpoint when the indicator remains pale red for about 30 seconds. Perform a blank test using the same method, and calculate the hydroxyl value using the following formula (2).

[0167] Formula: B={(ab)×28.05 / (Wp×I)}+acid value A···(2)

[0168] It should be noted that in the above formula (2), B represents the hydroxyl value [mgKOH / g], a represents the titration volume of KOH solution in the blank test [mL], b represents the titration volume of KOH solution when using the sample [mL], Wp represents the mass of the resin solution to be determined [g], and I represents the proportion of non-volatile components in the resin solution to be determined [mass %]. The acid value A is the acid value of component (E) calculated using the same method as the acid value of component (A).

[0169] From the viewpoint of suppressing the formation of depressions originating from aggregates on the surface of the cured material after roughening treatment, and improving peel strength, flexibility, and resolution, when the non-volatile component in the resin composition is set to 100% by mass, the content of component (E) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and particularly preferably 5% by mass or less.

[0170] When the content of component (A) is 100% by mass in the resin composition and the content of component (E) is e, the ratio a / e is preferably 1 or more, more preferably 1.5 or more, further preferably 2 or more, more preferably 30 or less, more preferably 25 or less, and further preferably 10 or less.

[0171] When the content of component (D) is 100% by mass in the resin composition, and the content of component (E) is e, the ratio of d / e is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 1 or more, preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.

[0172] <(F) Reactive Diluent>

[0173] The photosensitive resin composition may further contain (F) an active diluent as an optional component. Components belonging to (A) through (E) are not included in component (F). The presence of component (F) improves photoreactivity. Component (F) may be, for example, a photosensitive (meth)acrylate compound having one or more (meth)acryloyl groups in one molecule and being liquid, solid, or semi-solid at room temperature. Room temperature refers to approximately 25°C.

[0174] Representative photosensitive (meth)acrylate compounds include, for example: hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; monoacrylates or diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; acrylamides such as N,N-dimethylacrylamide and N-hydroxymethylacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate; polyacrylates of polyols such as trimethylolpropane, pentaerythritol, and dipentaerythritol, or their adducts of ethylene oxide, propylene oxide, or ε-caprolactone; acrylates of phenols such as phenoxy acrylate and phenoxyethyl acrylate, or their adducts of ethylene oxide or propylene oxide; epoxy acrylates, melamine acrylates, and / or methacrylates corresponding to the above acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether. Among these, polypropylene acrylates or polypropylene methacrylates are preferred. Examples of ternary acrylates or methacrylates include: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane EO addition tri(meth)acrylate, glycerol PO addition tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligo(meth)acrylate, ethyl carbitol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. (Meth)acrylates, (meth)acrylates of N,N,N',N'-tetra(β-hydroxyethyl)ethyldiamine, etc., as ternary or higher-order acrylates or methacrylates, include: tri(2-(meth)acryloyloxyethyl) phosphate, tri(2-(meth)acryloyloxypropyl) phosphate, tri(3-(meth)acryloyloxypropyl) phosphate, tri(3-(meth)acryloyl-2-hydroxyoxypropyl) phosphate, di(3-(meth)acryloyl-2-hydroxyoxypropyl)(2-(meth)acryloyloxyethyl) phosphate, (3-(meth)acryloyl-2-hydroxyoxypropyl)di(2-(meth)acryloyloxyethyl) phosphate, etc., as phosphate triacrylates (meth)acrylates. These photosensitive (meth)acrylate compounds can be used alone or in combination of two or more.

[0175] From the viewpoint of promoting photocuring and suppressing stickiness when forming a cured product, when the solid content of the photosensitive resin composition is set to 100% by mass, the content of component (F) is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less.

[0176] <(G)solvent>

[0177] The photosensitive resin composition may further contain (G) solvent as an optional component. By containing (G) solvent, the viscosity of the varnish can be adjusted. Organic solvents can be cited as examples of (G) solvent.

[0178] Examples of solvents used as (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, 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-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. These solvents can be used alone or in combination of two or more. The solvent content can be appropriately adjusted from the viewpoint of the coatability of the photosensitive resin composition.

[0179] <(H) Other Additives>

[0180] The photosensitive resin composition may further contain (H) other additives to a degree that does not impede the purpose of the present invention. As (H) other additives, for example: microparticles of organic fillers, melamine, organobentonite, etc.; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, carbon black, and naphthalene black; polymerization inhibitors such as hydroquinone, phenothiazine, methyl hydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; thickeners such as bentonite and montmorillonite; defoamers based on organosilicon, fluorine, and vinyl resins; flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphates, and halogen-containing condensed phosphates; and various additives such as phenolic curing agents and cyanate ester curing agents for thermosetting resins.

[0181] The photosensitive resin composition can be manufactured by mixing the above-mentioned components (A) to (E) as essential components and appropriately mixing the above-mentioned components (F) to (H) as optional components. Furthermore, it can be mixed or stirred as needed using a mixing device such as a three-roll mill, ball mill, bead mill, sand mill, or a stirring device such as a high-speed mixer or planetary mixer.

[0182] <Properties and Uses of Photosensitive Resin Compositions>

[0183] Cured products obtained by photocuring photosensitive resin compositions typically exhibit excellent resolution (developability). Therefore, the formation of residue in unexposed areas can be suppressed. Furthermore, the through-holes are not formed into an inverted cone shape (reverse taper), and there are no cracks, etc. The evaluation of residue in unexposed areas and the evaluation of the shape of the through-holes can be performed according to the methods described in the examples below.

[0184] Cured products obtained by photocuring photosensitive resin compositions typically exhibit excellent resolution. Therefore, it is possible to form a minimum through-hole diameter free of residue. Preferably, the minimum through-hole diameter is 60 μm or less, more preferably 45 μm or less, and even more preferably 40 μm or less. The lower limit is not particularly limited and can be set to 1 μm or more, etc. The minimum through-hole diameter can be determined according to the method described in the examples below.

[0185] The cured product formed by photocuring the photosensitive resin composition can improve the peel strength between the cured product and the conductor layer formed by plating. Therefore, when an insulating layer is formed using this cured product, an insulating layer with high peel strength to the conductor layer can be obtained. The peel strength is preferably 0.15 kgf / cm or more, more preferably 0.20 kgf / cm or more, and particularly preferably 0.3 kgf / cm or more. There is no particular limitation on the upper limit of the peel strength; for example, it can be 10.0 kgf / cm or less. The peel strength can be measured according to the method described in the examples below.

[0186] The cured product formed by photocuring the photosensitive resin composition can suppress depressions originating from aggregates on the surface of the cured product after roughening treatment (excluding contamination treatment). Thus, an insulating layer or solder resist layer in which the formation of depressions originating from aggregates on the surface is suppressed can be obtained. Specifically, for the aforementioned depressions, the formation of depressions with a width of 2 μm or more and a depth of 1 μm or more can be suppressed. The evaluation of the aforementioned depressions can be performed according to the method described in the examples below.

[0187] Photosensitive resin compositions typically exhibit excellent flexibility. Therefore, even under stress, resin scattering and crack formation can be suppressed in photosensitive resin compositions.

[0188] The applications of the photosensitive resin composition of the present invention are not particularly limited, and can be used in a wide range of applications requiring photosensitive resin compositions, such as insulating resin sheets for photosensitive films and prepregs, circuit boards (for laminates, multilayer printed wiring boards, etc.), solder resists, underfill materials, chip bonding materials, semiconductor sealing materials, through-hole filling resins, component embedding resins, etc. Suitable applications include: photosensitive resin compositions for insulating layers of printed wiring boards (printed wiring boards where the cured product of the photosensitive resin composition serves as the insulating layer), photosensitive resin compositions for interlayer insulating layers (printed wiring boards where the cured product of the photosensitive resin composition serves as the interlayer insulating layer), photosensitive resin compositions for plating formation (printed wiring boards where a plating layer is formed on the cured product of the photosensitive resin composition), and photosensitive resin compositions for solder resist layers (printed wiring boards where the cured product of the photosensitive resin composition serves as the solder resist layer).

[0189] [Photosensitive film]

[0190] The photosensitive film has: a support, and a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention disposed on the support.

[0191] Examples of supports include polyethylene terephthalate films, polyethylene naphthalate films, polypropylene films, polyethylene films, polyvinyl alcohol films, triacetyl acetate films, etc., with polyethylene terephthalate films being particularly preferred.

[0192] Commercially available supports include, but are not limited to, products such as "ALPHAN MA-410" and "E-200C" manufactured by Oji Paper, polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and polyethylene terephthalate films such as "PS-25" manufactured by Teijin Co., Ltd. For these supports, a release agent such as a silicone coating can be applied to the surface for easy removal. The thickness of the support is preferably in the range of 5μm to 50μm, and more preferably in the range of 10μm to 25μm. By setting the thickness to 5μm or more, support breakage can be suppressed during support peeling before development; by setting the thickness to 50μm or less, the resolution during exposure from the support can be improved. Furthermore, a support with low white point (fish eye) is preferred. Here, white point refers to defects formed when foreign matter, undissolved substances, oxidized deterioration products, etc., enter the film during the manufacturing process of a film by hot melting of the material and mixing, extrusion, biaxial stretching, casting, etc.

[0193] Furthermore, to reduce light scattering during exposure using active energy rays such as ultraviolet light, the support is preferably made of a material with excellent transparency. Specifically, for the support, it is preferable to use a material with a turbidity (haze standardized in JIS K6714) of 0.1 to 5, which is an indicator of transparency. Furthermore, the photosensitive resin composition layer can also be protected with a protective film.

[0194] By protecting the photosensitive resin composition layer of the photosensitive film with a protective film, dust or other contaminants can be prevented from adhering to the surface of the photosensitive resin composition layer, or damage can occur. The protective film can be made of the same material as the support described above. The thickness of the protective film is not particularly limited, but it is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. A thickness of 1 μm or more improves the processability of the protective film, while a thickness of 40 μm or less tends to improve economic efficiency (low cost). It should be noted that, for the protective film, a protective film with lower adhesion between the photosensitive resin composition layer and the support is preferable.

[0195] From the viewpoint of improving processability and suppressing the reduction of 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, even more preferably 20 μm or more, preferably 30 μm or less, more preferably 28 μm or less, and even more preferably 25 μm or less.

[0196] Photosensitive films can be manufactured, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish onto a support using a die coater or similar device, and then drying it to form a resin composition layer. The same solvent as the component described in (G) above can be used as the organic solvent.

[0197] Examples of coating methods for resin varnishes include: gravure coating, micro-gravure coating, reverse coating, kiss reverse coating, die coating, slot die coating, lip coating, comma coating, blade coating, roller coating, knife coating, curtain coating, chamber gravure coating, slot orifice coating, spraying, and dip coating.

[0198] Resin varnish can be applied in multiple coats, in a single coat, or in a combination of different methods. Among these, the top-coating method, which provides excellent uniformity, is preferred. Furthermore, to avoid contamination by foreign matter, it is best to perform the coating process in an environment with minimal foreign matter generation, such as a cleanroom.

[0199] The drying temperature varies depending on the curability of the photosensitive resin composition and the amount of component (G) in the resin varnish, and can be carried out at 80°C to 120°C. However, from the viewpoint of obtaining a cured product with excellent undercut resistance, the maximum drying temperature is preferably 105°C or higher, and more preferably 110°C or higher. There is no particular limitation on the lower limit of the maximum temperature, but it is preferably 135°C or lower, and more preferably 130°C or lower.

[0200] The drying time varies depending on the curability of the photosensitive resin composition and the amount of component (G) in the resin varnish, and is preferably 6 minutes or more, preferably 30 minutes or less, and more preferably 20 minutes or less. Here, drying time refers to the time starting from when the drying temperature reaches 80°C.

[0201] The residual amount of component (G) in the photosensitive resin composition layer, relative to the total amount of the photosensitive resin composition layer, is preferably set to 5% by mass or less, more preferably 2% by mass or less. Those skilled in the art can establish appropriate drying conditions through simple experiments.

[0202] The photosensitive film comprises a "photosensitive resin composition layer containing the photosensitive resin composition of the present invention," thus exhibiting excellent flexibility. For example, the photosensitive film is wound onto a 3-inch core and cut using a roller cutter. In this case, the formation of cracks can be suppressed on the photosensitive film.

[0203] Printed wiring board

[0204] The printed wiring board of the present invention comprises an insulating layer formed by curing the photosensitive resin composition of the present invention. This insulating layer is preferably used as a solder resist layer or an interlayer insulating layer.

[0205] In detail, the printed wiring board of the present invention can be manufactured using the photosensitive film described above. Hereinafter, an example is described where the insulating layer is a solder resist layer.

[0206] <Coating and Drying Process>

[0207] When a resin varnish containing a photosensitive resin composition is directly coated onto a circuit board, a photosensitive resin composition layer is formed on the circuit board by drying and evaporating component (G).

[0208] Examples of circuit boards include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. It should be noted that, here, "circuit board" refers to a substrate on which a patterned conductor layer (circuit) is formed on one or both sides of such a supporting substrate. Furthermore, in multilayer printed wiring boards (PCBs) formed by alternating layers of conductors and insulating layers, the substrate on which a patterned conductor layer (circuit) is formed on one or both sides of the outermost layer of the PCB is also included within the scope of the circuit board discussed here. It should be noted that the surface of the conductor layer can be pre-roughened through blackening treatment, copper etching, or similar processes.

[0209] As for coating methods, screen printing is generally the most common method, but any other means that can achieve uniform coating can also be used. For example, spray coating, hot melt coating, rod coating, application coating, blade coating, knife coating, air knife coating, curtain flow coating, roller coating, gravure coating, offset printing, dip coating, brush coating, and all other common coating methods can be used. After coating, drying is performed as needed using a hot air oven or far-infrared oven. The drying conditions are preferably set at 80°C to 120°C for 3 to 13 minutes. This forms a photosensitive composite layer on the circuit board.

[0210] <Lamination Process>

[0211] On the other hand, when using a photosensitive film, a 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, the protective film is removed, and the photosensitive film and circuit board are preheated as needed. The photosensitive resin composition layer is then pressed onto the circuit board while being pressurized and heated. For the photosensitive film, a method of laminating it onto the circuit board under reduced pressure using vacuum lamination is preferred.

[0212] There are no particular limitations on the conditions for the lamination process. For example, preferred conditions are: a pressing temperature (lamination temperature) of 70℃ to 140℃ and a pressing pressure of 1 kgf / cm². 2 ~11kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2The lamination time is preferably set to 5 to 300 seconds, and lamination is performed under reduced pressure of 20 mmHg (26.7 hPa) or less. Furthermore, the lamination process can be batch-type or continuous using rollers. Vacuum lamination can be performed using commercially available vacuum laminators. Examples of commercially available vacuum laminators include: vacuum dressing machines manufactured by Nikko Materials Co., Ltd., vacuum pressure laminators manufactured by Meiki Seisakusho Co., Ltd., roller dry coating machines manufactured by Hitachi Industries Co., Ltd., and vacuum laminators manufactured by Hitachi AIC Co., Ltd.

[0213] <Exposure Process>

[0214] After a photosensitive resin composition layer is deposited on a circuit board through a coating and drying process or a lamination process, an exposure process is performed in which a predetermined portion of the photosensitive resin composition layer is irradiated with active light (activation rays) through a mask pattern, thereby photocuring the irradiated portion of the photosensitive resin composition layer. Examples of active light include ultraviolet light, visible light, electron beams, and X-rays, with ultraviolet light being particularly preferred. The irradiation dose of ultraviolet light is approximately 10 mJ / cm². 2 ~1000mJ / cm 2 Exposure methods include contact exposure, where the mask pattern is tightly adhered to the printed wiring board, and non-contact exposure, where parallel light is used for exposure in a loosely adhered state; either method can be used. Furthermore, if a support is present on the photosensitive resin composition layer, exposure can be performed from the support, or the support can be peeled off before exposure.

[0215] Because the solder resist layer (solder resist) uses the photosensitive resin composition of the present invention, it exhibits excellent developability. Therefore, as the exposure pattern in the mask pattern, for example, patterns with a circuit width (line width; L) to circuit spacing (line pitch; S) ratio (L / S) of 100μm / 100μm or less (i.e., wiring spacing 200μm or less), L / S = 80μm / 80μm ​​or less (wiring spacing 160μm or less), L / S = 70μm / 70μm or less (wiring spacing 140μm or less), and L / S = 60μm / 60μm or less (wiring spacing 120μm or less) can be used. It should be noted that the spacing does not need to be uniform throughout the circuit board.

[0216] Because the solder resist layer (solder resist) uses the photosensitive resin composition of the present invention, it exhibits excellent developability. Therefore, the via diameter can preferably be set to 100 μm or less, more preferably 90 μm or less, and even more preferably 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.

[0217] <Developing Process>

[0218] After the exposure process, if a support is present on the photosensitive resin composition layer, the support is removed, and the uncured portion (unexposed portion) is removed by wet development or dry development, thereby forming a pattern.

[0219] In the case of wet development described above, the developer can be a safe, stable, and easy-to-handle developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, with the development step preferably using an alkaline aqueous solution. Furthermore, as the development method, known methods such as spraying, shaking immersion, brushing, or scraping can be appropriately employed.

[0220] Examples of alkaline aqueous solutions used as developers include: aqueous solutions of 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; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; or aqueous solutions of organic bases that do not contain metal ions, such as tetraalkylammonium hydroxide. From the viewpoint that it does not contain metal ions and will not affect the semiconductor chip, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred.

[0221] To improve the developing effect, surfactants, defoamers, etc., can be added to these alkaline aqueous solutions. The pH value of the alkaline aqueous solution is preferably in the range of 8 to 12, and more preferably in the range of 9 to 11. Furthermore, the alkali concentration of the alkaline aqueous solution is preferably set to 0.1% 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.

[0222] Organic solvents used as developing solutions include, for example, acetone, ethyl acetate, alkoxyethanol having alkoxy groups having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

[0223] The concentration of this organic solvent relative to the total amount of developer is preferably 2% to 90% by mass. Furthermore, the temperature of this organic solvent can be adjusted according to the developer's properties. Moreover, this organic solvent can be used alone or in combination of two or more. Examples of organic solvent-based developers that can be used alone include: 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0224] During pattern formation, two or more of the above-mentioned developing methods can be used simultaneously as needed. Developing methods include immersion, spin-dip, spraying, high-pressure spraying, brushing, and scraping, with high-pressure spraying being preferred due to its improved resolution. When using the spraying method, a spray pressure of 0.05 MPa to 0.3 MPa is preferred.

[0225] <Thermosetting (Post-baking) Process>

[0226] After the above developing process, a heat curing (post-baking) process is performed to form the solder resist layer. Examples of post-baking processes include ultraviolet irradiation using a high-pressure mercury lamp or heating using a clean oven. When irradiating with ultraviolet light, the irradiation dose can be adjusted as needed, for example, to 0.05 J / cm². 2 ~10J / cm 2 Irradiation is performed at approximately the same irradiation level. Furthermore, the heating conditions can be appropriately selected based on the type and content of the resin components in the photosensitive resin composition, preferably within the range of 150°C to 220°C for 20 to 180 minutes, and more preferably within the range of 160°C to 200°C for 30 to 120 minutes.

[0227] <Other Processes>

[0228] For printed circuit boards, after the solder mask layer is formed, the process may include opening vias and desmearing. These processes can be carried out according to various methods known to those skilled in the art in the manufacture of printed circuit boards.

[0229] After the solder mask layer is formed, a hole-opening process is performed on the solder mask layer formed on the circuit board to form through holes or vias, as needed. The hole-opening process can be performed by known methods such as drilling, laser, and plasma, and combinations of these methods as needed. It is preferable to use lasers such as carbon dioxide lasers or YAG lasers for the hole-opening process.

[0230] The decontamination process is a step to remove contaminants. Resin residue (contamination) often adheres to the inside of the openings formed during the drilling process. This contamination can cause poor electrical connections, therefore, a decontamination removal process is performed in this step.

[0231] Decontamination treatment can be carried out using dry decontamination treatment, wet decontamination treatment, or a combination of the two.

[0232] As a dry decontamination process, plasma decontamination can be used as an example. Plasma decontamination can be performed using commercially available plasma decontamination equipment. Examples of commercially available plasma decontamination equipment suitable for printed circuit board manufacturing include: microwave plasma equipment manufactured by NISSIN Corporation and atmospheric pressure plasma etching equipment manufactured by Sekisui Chemicals Co., Ltd.

[0233] For example, wet decontamination treatment can be performed using an oxidizing solution. When using an oxidizing solution for decontamination, it is preferable to sequentially perform swelling treatment using a swelling solution, oxidation treatment using an oxidizing solution, and neutralization treatment using a neutralizing solution. Examples of swelling solutions include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN. Swelling treatment is preferably performed by immersing the substrate with through-holes or the like in a swelling solution heated to 60°C–80°C for 5–10 minutes. An alkaline permanganate aqueous solution is preferable, for example, a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous sodium hydroxide solution. Oxidation treatment using an oxidizing solution is preferably performed by immersing the swollen substrate in an oxidizing solution heated to 60°C–80°C for 10–30 minutes. Commercially available alkaline permanganate solutions include, for example, "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Ammet Japan. Neutralization treatment using a neutralizing solution is preferably performed by immersing the oxidized substrate in a neutralizing solution at 30°C to 50°C for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution; commercially available examples include "Reduction Solution Securiganth P" manufactured by Ammet Japan.

[0234] When combining dry and wet decontamination treatments, either the dry or wet decontamination treatment can be performed first.

[0235] When the insulating layer is used as an interlayer insulating layer, it can be processed in the same way as the solder resist layer. After the heat curing process, the hole opening process, the decontamination process, and the plating process can be performed.

[0236] The plating process is the process of forming a conductor layer on an insulating layer. The conductor layer can be formed by combining electroless plating and electrolytic plating. Alternatively, a resist layer with a pattern opposite to the conductor layer can be formed, and the conductor layer can be formed using only electroless plating. As for the subsequent patterning method, subtractive or semi-additive methods known to those skilled in the art can be used, for example.

[0237] [Semiconductor Devices]

[0238] 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.

[0239] As semiconductor devices, examples include various semiconductor devices that can be used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trams, ships, and airplanes).

[0240] 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. A "conductive portion" refers to a portion of the printed wiring board that conducts electrical signals; its location can be on the surface or embedded. Furthermore, the semiconductor chip is not particularly limited to any electrical circuit element made of semiconductor material.

[0241] There are no particular limitations on the method of mounting the semiconductor chip when manufacturing the semiconductor device of the present invention, as long as the semiconductor chip can effectively perform its function. Specifically, examples include wire bonding mounting methods, flip chip mounting methods, mounting methods based on built-in bumpless layer (BBUL), mounting methods based on anisotropic conductive film (ACF), mounting methods based on non-conductive film (NCF), and so on. Here, "mounting method based on built-in bumpless layer (BBUL)" refers to "a mounting method in which the semiconductor chip is directly embedded in a recess of a printed wiring board, thereby connecting the semiconductor chip to the wiring on the printed wiring board."

[0242] Example

[0243] The present invention will now be specifically described by way of examples, but the present invention is not limited to these examples. It should be noted that, unless otherwise expressly stated, in the following description, “parts” and “%” refer to “parts by mass” and “% by mass”, respectively.

[0244] - (E) Determination of the weight-average molecular weight of component -

[0245] For the weight-average molecular weight of each (E) component, the weight-average molecular weight of polystyrene determined by gel permeation chromatography (GPC) will be used as the weight-average molecular weight of the (E) component.

[0246] -Determination of the glass transition temperature (Tg) of the (E) composition-

[0247] The glass transition temperatures of each (E) component were determined as follows: differential scanning calorimetry was performed based on JIS K 7121 at a heating rate of 5 °C / min.

[0248] (Synthesis Example 1: Synthesis of Resin (A-1))

[0249] 162 parts of 1,1'-bis(2,7-diglycidyloxynaphthyl)methane ("EXA-4700", manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.) with an epoxy equivalent of 162 g / eq. were added to a flask equipped with a gas inlet tube, a stirrer, a condenser, and a thermometer. 340 parts of carbitol acetate were added, and the mixture was heated to dissolve. 0.46 parts of hydroquinone and 1 part of triphenylphosphine were then added. The mixture was heated to 95–105°C, and 72 parts of acrylic acid were slowly added dropwise, allowing the reaction to proceed for 16 hours. The reaction product was cooled to 80–90°C, and 80 parts of tetrahydrophthalic anhydride were added, allowing the reaction to proceed for 8 hours, followed by cooling. This yielded a resin solution with a solid acid value of 90 mg KOH / g (70% non-volatile components).

[0250] (Synthesis Example 2: Synthesis of Resin (E-1))

[0251] In a reaction flask equipped with a thermometer, stirrer, nitrogen inlet, reflux tube, water separator, and pressure reducing port, 100 parts of 12-hydroxystearic acid (trade name: 12-hydroxy acid (12-hidrolic acid) (manufactured by Kokura Synthetic Industries Co., Ltd.)) were added. The mixture was reacted at 150°C for 3 hours under a nitrogen atmosphere, followed by heating at 200°C for 6 hours under reduced pressure. The mixture was then cooled to room temperature. This yielded a resin (E-1) with an acid value of 32 mg KOH / g, a weight-average molecular weight of 6000, and a Tg of -58°C.

[0252] <Examples 1-14, Comparative Examples 1-4>

[0253] The components are mixed in the proportions shown in the table below, and a resin varnish is prepared using a high-speed rotary mixer.

[0254] Next, as a support, a PET film (Toray Industries, Inc., “Lumirror T6AM”, 38 μm thick, softening point 130°C, “release PET”) that had been released using an alkyd resin-based release agent (Lintec Corporation, “AL-5”) was prepared. The prepared resin varnish was uniformly coated onto the release PET using a die coater to achieve a dried photosensitive resin composition layer thickness of 20 μm. After drying at 80°C to 110°C for 5 minutes, a photosensitive film with a photosensitive resin composition layer on the release PET film was obtained.

[0255] <Flexible Evaluation>

[0256] The resin scattering and crack formation were visually evaluated when the photosensitive resin composition layer of the photosensitive film prepared in the examples and comparative examples was cut 5 cm in a straight line at three locations using a cutting knife. Furthermore, the crack formation was visually confirmed when the film was bent 180° at three locations.

[0257] 〇: No scattering or cracking of the photosensitive resin composition was observed in any of the three locations;

[0258] △: Any one of the following three locations is observed: scattering of the photosensitive resin composition or cracking.

[0259] ×: Scattering or cracking of the photosensitive resin composition was observed in all three locations.

[0260] <Evaluation of Discrimination>

[0261] (Evaluation of the formation of layer A)

[0262] The copper layer of the glass epoxy board (copper-clad laminate) on which a circuit patterned with a copper layer of 18 μm thickness is formed is roughened by treatment with a surface treatment agent containing organic acid (CZ8100, manufactured by Magnesium Corporation). Next, a configuration is made to bring the photosensitive resin composition layer of the photosensitive film obtained in the examples and comparative examples into contact with the copper circuit surface. Lamination is performed using a vacuum laminator (manufactured by Nichigo Materials Corporation, VP160) to form a laminate in which the aforementioned copper-clad laminate, the aforementioned photosensitive resin composition layer, and the aforementioned support are sequentially stacked. The lamination conditions are set as follows: vacuum time 30 seconds, lamination temperature 80°C, lamination pressure 0.7 MPa, and lamination time 30 seconds. The laminate is left to stand at room temperature for at least 30 minutes. A circular hole pattern is then formed on the support of the laminate using a patterning apparatus and exposed to ultraviolet light. The exposure pattern used was a quartz glass mask with circular holes of 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm, and 100μm, and a 1cm × 2cm quadrilateral shape. After standing at room temperature for 30 minutes, the support was peeled off from the aforementioned laminate. The entire surface of the photosensitive resin composition layer on the laminate was sprayed with a 1% by mass sodium carbonate aqueous solution at 30°C as the developer at a spray pressure of 0.2MPa for 2 minutes. After spray development, it was subjected to a 1J / cm² exposure. 2 The laminate is subjected to ultraviolet irradiation and then heat treatment at 180°C for 30 minutes to form an insulating layer with openings. This is used as laminate A for evaluation.

[0263] (Evaluation of discrimination ability)

[0264] The unexposed portion of a 1cm × 2cm section of laminate A was evaluated by visual inspection. A condition where no resin residue remained in the unexposed portion was rated as 0, and a condition where resin was visually confirmed was rated as ×. Next, the formed through-holes were observed using SEM (1000x magnification), and the minimum diameter of the through-hole without residue was measured. Furthermore, the shape of the through-holes was evaluated according to the following criteria;

[0265] ○: The through hole is not formed into an inverted cone shape, nor does it have cracks, etc.;

[0266] ×: The through hole is formed into an inverted cone shape, or there are cracks on the wall surface of the through hole.

[0267] <Evaluation of dents after contamination treatment and determination of peel strength>

[0268] (Evaluate the formation of laminates C and D)

[0269] For the copper layer of the glass epoxy board (copper-clad laminate) with a copper layer thickness of 18 μm, roughening was performed by treatment with a surface treatment agent containing organic acid (CZ8100, manufactured by Magnesium Corporation). Next, a configuration was made to bring the photosensitive resin composition layer of the photosensitive film obtained using the examples and comparative examples into contact with the copper circuit surface, and lamination was performed using a vacuum laminator (manufactured by Nichigo Materials Corporation, VP160) to form a laminate in which the aforementioned copper-clad laminate, the aforementioned photosensitive resin composition layer, and the aforementioned support are sequentially stacked. The lamination conditions were set as follows: vacuum time 30 seconds, lamination temperature 80°C, lamination pressure 0.7 MPa, and lamination time 30 seconds.

[0270] The laminate was left to stand at room temperature for at least 30 minutes, and then subjected to a 100 mJ / cm test from its support. 2 After being irradiated with ultraviolet light and left to stand at room temperature for 30 minutes, the support was peeled off from the aforementioned laminate. The entire surface of the photosensitive resin composition layer on the laminate was sprayed with a 1% by mass sodium carbonate aqueous solution at 30°C using a spray pressure of 0.2 MPa as the developing solution for 2 minutes. After spray development, a 1 J / cm² solution was applied. 2 The laminate is subjected to ultraviolet irradiation and then heat treatment at 180°C for 30 minutes to form an insulating layer. This is used as laminate B for evaluation.

[0271] As a roughening treatment of the insulating layer of the evaluation laminate B, a decontamination treatment was performed as follows: The substrate was immersed in a swelling solution ("Swelling Dip Securiganth P" manufactured by Amtec Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 2 minutes, followed by immersion in an oxidizing agent solution ("Concentrate Compact CP" manufactured by Amtec Japan, an aqueous solution of approximately 6% potassium permanganate and approximately 4% sodium hydroxide) at 80°C for 3 minutes, and finally immersed in a neutralizing solution ("Reduction Solution Securiganth P" manufactured by Amtec Japan, an aqueous solution of sulfuric acid) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. The resulting substrate was referred to as the evaluation laminate C.

[0272] A conductor layer is formed on the roughened surface of the insulating layer using a semi-additive method for conductor layer formation. Specifically, the roughened substrate is immersed in an electroless plating solution containing PdCl2 at 40°C for 5 minutes, followed by immersion in an electroless copper plating solution at 25°C for 20 minutes. Next, it is annealed at 150°C for 30 minutes, then electrolyzed with copper sulfate to form a 30 μm thick conductor layer, followed by annealing at 200°C for 60 minutes. The resulting substrate is designated as evaluation laminate D.

[0273] (Evaluation of dents after stain treatment)

[0274] The roughened surface of the insulating layer of the evaluation substrate laminate C after decontamination treatment was observed using SEM (1000x magnification) and evaluated according to the following criteria:

[0275] ○: No depressions with a width greater than 2μm and a depth greater than 1μm were observed;

[0276] ×: More than one depression with a width of more than 2μm and a depth of more than 1μm was observed.

[0277] (Determination of peel strength)

[0278] The peel strength of the plated conductor layer and the insulation layer was determined according to Japanese Industrial Standard (JIS C6481) for the evaluation laminate D. Specifically, a 10 mm wide and 100 mm long cut was made in the conductor layer of the evaluation laminate C, one end of which was peeled off and clamped. The load (kgf / cm) at which 35 mm was peeled off vertically at a speed of 50 mm / min at room temperature was measured, and the peel strength was determined. A tensile testing machine (TSE Corporation "AC-50C-SL") was used for the test. Furthermore, the peel strength was evaluated according to the following criteria:

[0279] ◎: Peel strength is above 0.30 kgf / cm

[0280] 〇: Peel strength is ≥0.20 kgf / cm and <0.30 kgf / cm

[0281] △: Peel strength is ≥0.15 kgf / cm and <0.20 kgf / cm

[0282] ×: Peel strength is less than 0.15 kgf / cm.

[0283] [Table 1]

[0284]

[0285] The abbreviations in the table are as follows:

[0286] (A)Ingredients

[0287] • Synthesis Example 1: The resin synthesized in Synthesis Example 1 (A-1)

[0288] ZFR-1491H: Bisphenol F type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mg KOH / g, solid content concentration approximately 70%)

[0289] ZAR-2000: Bisphenol A type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mg KOH / g, solid content concentration approximately 70%)

[0290] (B) Ingredients

[0291] SC2050: A material for which 100 parts by weight of fused silica (Admatechs, average particle size 0.5 μm) has been surface-treated with 0.5 parts by weight of aminosilane (Shin-Etsu Chemical, "KBM573").

[0292] (C) Components

[0293] • Omnirad TPO: Diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by IGM Resins)

[0294] (D) Components

[0295] NC3000L: Biphenyl-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent approximately 271 g / eq.)

[0296] • ELM-434VL: Tetraglycidyl diaminodiphenylmethane type epoxy resin (manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent approximately 115 g / eq.)

[0297] (E) Components

[0298] ·CB-3060: A multifunctional acrylic polymer containing carboxyl groups (manufactured by Zongyan Chemical Co., Ltd., 2EHA backbone, weight-average molecular weight 3000, acid value 60mgKOH / g, Tg: -70℃)

[0299] ·CB-3098: A multifunctional acrylic polymer containing carboxyl groups (manufactured by Zongyan Chemical Co., Ltd., 2EHA backbone, weight average molecular weight 3000, acid value 98mgKOH / g, Tg: -70℃)

[0300] •CBB-3098: A multifunctional acrylic polymer containing carboxyl groups (manufactured by Zongyan Chemical Co., Ltd., BA backbone, weight-average molecular weight 3000, acid value 98 mg KOH / g, Tg: -54℃)

[0301] UT-1001: Hydroxyl-containing acrylic polymer (manufactured by Zongyan Chemical Co., Ltd., 2EHA backbone, weight average molecular weight 3000, hydroxyl value 57mgKOH / g, Tg: -70℃)

[0302] UE-3980: Polyester (manufactured by UNITIKA, weight average molecular weight 8000, Tg: 58℃)

[0303] XA-0653: Polyester (manufactured by UNITIKA, weight average molecular weight 5000, acid value 20mgKOH / g, Tg: 56℃)

[0304] • Synthesis Example 2: The (E-1) component synthesized in Synthesis Example 2

[0305] ·AGKN-026: Polyurethane (manufactured by Nekami Kogyo Co., Ltd., weight average molecular weight 3000, Tg: -40℃)

[0306] ·BPX-003: Hydroxyl-containing acrylic polymer (manufactured by Nekami Kogyo Co., Ltd., weight average molecular weight 3000, hydroxyl value 48mgKOH / g, Tg: -63℃)

[0307] (F)Ingredients

[0308] •DPHA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., acrylic acid equivalent approximately 96 g / eq.)

[0309] (G) component

[0310] ·EDGAc: Diethylene glycol monoethyl ether acetate

[0311] MEK: Methyl Ethyl Ketone

[0312] (H) component

[0313] AB-6: Polybutyl acrylate containing a single terminal methacrylamide group (manufactured by Toa Synthetic Co., Ltd., weight average molecular weight 13,000, Tg: -55℃)

[0314] UN-7600: Polyurethane (manufactured by Nekami Kogyo Co., Ltd., weight average molecular weight 11500, Tg: -41℃)

[0315] US-1071: Carboxyl-containing acrylic polymer (manufactured by Starlight PMC, weight average molecular weight 9500, acid value 75mgKOH / g, Tg: 104℃)

[0316] (B) Content of component: When the total solid content of the photosensitive resin composition is set to 100% by mass, the content of component (B) is...

[0317] (E) Content: The content of (E) component when the solid component of the photosensitive resin composition is set to 100% by mass.

[0318] As can be seen from the results in the table above, in Examples 1 to 14, the coating is flexible, has high resolution, and thus has high adhesion, while there are no aggregates or depressions after decontamination.

[0319] On the other hand, it can be seen that Comparative Example 1, which does not contain component (E), has a lower coating peel strength compared to Examples 1-14. Furthermore, it can be seen that Comparative Examples 2 and 3, which use polymers with a weight-average molecular weight of 10,000 or higher, have high coating peel strength, but aggregates and pits are formed after decontamination. Furthermore, it can be seen that Comparative Example 4, which uses polymer components with a Tg higher than 65°C, has low coating peel strength, and aggregates and pits are formed after decontamination.

[0320] It was confirmed that in each embodiment, even without the (F) to (G) components, although the degree of difference was different, the result was the same as that in the above embodiments.

Claims

1. A photosensitive resin composition comprising the following components (A) to (E), (A) A resin containing olefinic unsaturated groups and carboxyl groups, and which contains a naphthalene skeleton. (B) Inorganic filler materials (C) Photopolymerization initiator, (D) Epoxy resin, and (E) A high molecular weight component, wherein the high molecular weight component is one or more resins selected from (meth)acrylic resins, polyester resins, polyurethane resins, polyether resins, and polyolefin resins. in, (E) The glass transition temperature of the component is below 65°C, and the weight-average molecular weight is above 1000 and below 10000.

2. The photosensitive resin composition according to claim 1, wherein When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (A) is 5% by mass or more.

3. The photosensitive resin composition according to claim 1, wherein, When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (A) is 15% by mass or more.

4. The photosensitive resin composition according to claim 1, wherein When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (A) is 30% by mass or less.

5. The photosensitive resin composition according to claim 1, wherein, When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (A) is 20% by mass or less.

6. The photosensitive resin composition according to claim 1, wherein When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (B) is 50% by mass or more and 85% by mass or less.

7. The photosensitive resin composition according to claim 1, wherein When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (B) is 60% by mass or more.

8. The photosensitive resin composition according to claim 1, wherein, When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (B) is 65% by mass or less.

9. The photosensitive resin composition according to claim 1, wherein, When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (C) is 1% by mass or more.

10. The photosensitive resin composition according to claim 1, wherein When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (C) is 2% by mass or more.

11. The photosensitive resin composition according to claim 1, wherein When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (C) is less than 10% by mass.

12. The photosensitive resin composition according to claim 1, wherein, When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (C) is less than 5% by mass.

13. The photosensitive resin composition according to claim 1, wherein, When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (D) is 1% by mass or more.

14. The photosensitive resin composition according to claim 1, wherein When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (D) is 5% by mass or more.

15. The photosensitive resin composition according to claim 1, wherein When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (D) is 25% by mass or less.

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

17. The photosensitive resin composition according to claim 1, wherein When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (E) is 0.1% by mass or more.

18. The photosensitive resin composition according to claim 1, wherein When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (E) is 1.5% by mass or more.

19. The photosensitive resin composition according to claim 1, wherein When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (E) is 10% by mass or less.

20. The photosensitive resin composition according to claim 1, wherein When the non-volatile component of the photosensitive resin composition is set to 100% by mass, the content of component (E) is 5% by mass or less.

21. The photosensitive resin composition according to claim 1, wherein (E) Components have one or more groups selected from carboxyl, hydroxyl, epoxy and (meth)acryloyl.

22. The photosensitive resin composition according to claim 1, wherein, (E) The glass transition temperature is below -40°C.

23. The photosensitive resin composition according to claim 1, wherein (E) The glass transition temperature is above -100℃.

24. The photosensitive resin composition according to claim 1, wherein, (E) The glass transition temperature is above -75°C.

25. The photosensitive resin composition according to claim 1, wherein, (E) The weight-average molecular weight of the component is above 3000.

26. The photosensitive resin composition according to claim 1, wherein, (E) The weight-average molecular weight of the component is below 5000.

27. The photosensitive resin composition according to claim 1, wherein (A) is an acid-modified epoxy (meth)acrylate containing a naphthalene skeleton.

28. The photosensitive resin composition according to claim 1, wherein (D) Components contain at least one of biphenyl-type epoxy resin and glycidylamine-type epoxy resin.

29. The photosensitive resin composition according to claim 1, wherein (B) Components include silicon dioxide.

30. A photosensitive film comprising the photosensitive resin composition according to any one of claims 1 to 29.

31. A photosensitive film with a support, comprising: Support body, and A photosensitive resin composition layer comprising any one of claims 1 to 29 is disposed on the support.

32. A printed wiring board comprising an insulating layer formed using a cured product of the photosensitive resin composition according to any one of claims 1 to 29.

33. The printed wiring board of claim 32 wherein, The insulating layer is a solder resist layer.

34. A semiconductor device comprising the printed wiring board of claim 32 or 33.