Photosensitive resin composition, dry film, printed wiring board, and method for manufacturing printed wiring board

Abstract

The present invention provides a photosensitive resin composition, a dry film using the photosensitive resin composition, a printed wiring board, and a method for manufacturing a printed wiring board, the photosensitive resin composition containing (A) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent, (B) a curing agent, (C) a photopolymerization initiator, and (D) a photopolymerizable compound, the (D) photopolymerizable compound being a multifunctional monomer having a skeleton (X) derived from a polyol and three or more (meth)acryloyl groups, the three or more (meth)acryloyl groups being directly or indirectly bonded to the bonding group (a) having three or more groups after removal of hydrogen atoms from hydroxyl groups as bonding groups (a) to other structures, one or more of the three or more (meth)acryloyl groups being bonded to the bonding group (a) via a linking group.

Description

Technical Field

[0001] This disclosure relates to a photosensitive resin composition, a dry film, a printed wiring board, and a method for manufacturing the printed wiring board. Background Technology

[0002] In the manufacturing of printed circuit boards (PCBs), a permanent photoresist is formed on the PCB. The permanent photoresist serves several purposes: preventing corrosion of the conductor layers or maintaining electrical insulation between conductor layers during PCB use. In recent years, in the process of flip-chip mounting or wire bonding of semiconductor components on PCBs using solder, the permanent photoresist also functions as a solder resist, preventing solder from adhering to unwanted portions of the conductor layers of the PCB.

[0003] Permanent mask resists are formed by screen printing using thermosetting resin compositions or by photolithography using photosensitive resin compositions. For example, in flexible wiring boards using mounting methods such as FC (Flip Chip), TAB (Tape Automated Bonding), and COF (Chip On Film), a permanent mask resist is formed by screen printing a thermosetting resin paste and then thermally curing it, except for IC chips, electronic components or LCD (Liquid Crystal Display) panels and connecting wiring portions (see, for example, Patent Document 1).

[0004] Furthermore, for semiconductor packaging substrates such as BGA (Ball Grid Array) and CSP (Chip Size Package) mounted on electronic components, (1) in order to perform flip-chip mounting of semiconductor components on the semiconductor packaging substrate using solder, (2) in order to wire bond the semiconductor components to the semiconductor packaging substrate, or (3) in order to solder the semiconductor packaging substrate to the motherboard substrate, it is necessary to remove the permanent photoresist at the bonding portion. Therefore, the formation of this permanent photoresist uses a photolithography method as follows: after coating and drying a photosensitive resin composition, it is selectively irradiated with active light such as ultraviolet light to cure it, and imaging is performed by removing only the unirradiated portion using development. Photolithography is suitable for mass production due to its good workability, and is therefore widely used in the electronic materials industry for imaging photosensitive resin compositions (for example, see Patent Document 2).

[0005] In the manufacture of printed circuit boards (PCBs), permanent photoresists generally require high levels of insulation, copper and gold plating resistance, resistance to damp heat, thermal shock resistance (TCT resistance), HAST resistance to high-accelerated life testing (HAST) between fine wirings, and, in the case of photoresists based on photolithography, high resolution. In recent years, with the increasing density of PCBs, there has been a growing demand for higher performance permanent photoresists. In particular, requirements for fine pattern formation, heat resistance, thermal shock resistance, and insulation have been rising annually, making it crucial to achieve a high degree of balance between these requirements.

[0006] As a method to improve reliability, one could consider adding an elastomer to the photosensitive resin composition to impart softness (see, for example, Patent Document 3).

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2003-198105

[0010] Patent Document 2: Japanese Patent Application Publication No. 2011-133851

[0011] Patent Document 3: Japanese Patent Application Publication No. 2009-204805 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] However, to impart flexibility, resins with low glass transition temperatures and high weight-average molecular weights are generally required, but this may significantly reduce heat resistance and HAST resistance. On the other hand, if resins with high glass transition temperatures are used, while heat resistance and HAST resistance are excellent, the reduced flexibility may lead to decreased thermal shock resistance or a significant reduction in alkali solubility, potentially impairing developability. Based on these trade-offs, a balance between resolution, heat resistance, thermal shock resistance, and insulation is not entirely achieved.

[0014] Therefore, the objective of this invention is to provide a photosensitive resin composition capable of forming a cured material with excellent resolution, high elongation, flexibility, high tensile strength to external stress, excellent heat resistance, thermal shock resistance, and excellent insulation, as well as a dry film using the photosensitive resin composition, a printed wiring board, and a method for manufacturing the printed wiring board.

[0015] Methods for solving problems

[0016] In order to solve the above-mentioned problems, the inventors have repeatedly conducted in-depth research and found that the above-mentioned problems can be solved by the following invention, thus completing the present invention.

[0017] That is, the present invention relates to the following [1] to

[15] .

[0018] [1] A photosensitive resin composition comprising (A) a photopolymerizable compound having vinyl unsaturated groups and acidic substituents, (B) a curing agent, (C) a photopolymerization initiator, and (D) a photopolymerizable compound.

[0019] The aforementioned (D) photopolymerizable compound is a polyfunctional monomer having a backbone (X) and three or more (meth)acryloyl groups.

[0020] The skeleton (X) is derived from a polyol and has three or more groups (a) formed by removing hydrogen atoms from the hydroxyl group as binding groups with other structures.

[0021] The three or more (meth)acryloyl groups are directly or indirectly combined with the above-mentioned binding group (a).

[0022] One or more of the three or more (meth)acryloyl groups are linked to the aforementioned binding group (a) via a linking group.

[0023] [2] According to the photosensitive resin composition described above [1], the skeleton (X) is a skeleton of a polyol selected from the group consisting of glycerol, diglycerol, trimethylolpropane, di(trimethylolpropane), pentaerythritol and dipentaerythritol.

[0024] [3] According to the photosensitive resin composition described in [1] or [2] above, in the above (D) photopolymerizable compound, the number of (meth)acryloyl groups that are bonded to the above binding group (a) through the above linking group is 3 to 10.

[0025] [4] In any one of the above [1] to [3], the linking group is a divalent group containing an epoxy alkyl structural unit or a divalent group derived from a hydroxy acid.

[0026] [5] According to the photosensitive resin composition described in [4] above, the epoxy alkyl structural unit is an epoxy alkyl structural unit with 2 to 4 carbon atoms, and the hydroxy acid is an aliphatic hydroxy acid with 2 to 10 carbon atoms.

[0027] [6] According to any one of [1] to [5] above, the photopolymerizable compound having an ethylene unsaturated group and an acid substituent (A) is an acid-modified epoxy derivative containing an ethylene unsaturated group obtained by reacting (c) a polyacid anhydride containing a saturated or unsaturated group with the resin (A'), wherein the resin (A') is obtained by reacting (a) an epoxy resin with (b) an organic acid containing an ethylene unsaturated group.

[0028] [7] According to the photosensitive resin composition described in [6] above, the photopolymerizable compound (A) having an ethylene unsaturated group and an acidic substituent contains:

[0029] A photopolymerizable compound (A1) having vinyl unsaturated groups and acidic substituents is formed using bisphenol phenolic varnish-type epoxy resin (a1) as the epoxy resin described above (a); and

[0030] A photopolymerizable compound (A2) having ethylene unsaturated groups and acid substituents is formed by using an epoxy resin (a2) different from the bisphenol phenolic varnish type epoxy resin (a1) as the component of (a) above.

[0031] [8] According to the photosensitive resin composition described above [7], the epoxy resin (a2) is selected from one or more of the group consisting of phenolic varnish epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, triphenol methane type epoxy resin and biphenyl type epoxy resin, which are different from the bisphenol varnish type epoxy resin (a1).

[0032] [9] In the photosensitive resin composition according to any one of [1] to [8] above, the photopolymerization initiator of (C) is selected from one or more of the group consisting of alkyl benzophenone photopolymerization initiators, thioxanthone photopolymerization initiators having a thioxanthone skeleton, benzophenone photopolymerization initiators, oxime ester photopolymerization initiators and acylphosphine oxide photopolymerization initiators.

[0033]

[10] The photosensitive resin composition according to any one of [1] to [9] above further contains (E) inorganic filler.

[0034]

[11] According to any one of [1] to

[10] above, the contents of (A) the photopolymerizable compound having ethylene unsaturated groups and acid substituents, (B) the curing agent, (C) the photopolymerization initiator and (D) the photopolymerizable compound are 20 to 80% by mass, 2 to 40% by mass, 0.2 to 15% by mass and 1 to 15% by mass, respectively, based on the total amount of solid components in the photopolymerizable resin composition.

[0035]

[12] A dry film having a carrier film and a photosensitive layer using the photosensitive resin composition described in any one of [1] to

[11] above.

[0036]

[13] A printed wiring board having a surface protective film or interlayer insulating layer formed from the photosensitive resin composition described in any one of [1] to

[11] above.

[0037]

[14] According to the printed wiring board described in

[13] above, the thickness of the surface protective film or interlayer insulation layer is greater than or equal to 5 μm.

[0038]

[15] A method for manufacturing a printed wiring board, comprising: a step of depositing a photosensitive layer on a substrate using the photosensitive resin composition described in any one of [1] to

[11] or the dry film described in

[12] ; a step of forming a resist pattern using the photosensitive layer; and a step of curing the resist pattern to form a surface protective film or an interlayer insulating layer.

[0039] Invention Effects

[0040] According to the present invention, a photosensitive resin composition capable of forming a cured material with excellent resolution, high elongation, flexibility, high tensile strength to external stress, and excellent heat resistance, thermal shock resistance, and insulation is provided, as well as a dry film using the photosensitive resin composition, a printed circuit board, and a method for manufacturing the printed circuit board. Attached Figure Description

[0041] Figure 1 This is a schematic diagram showing the cross-sectional shape of a resist with excellent linearity in representing the resist pattern outline.

[0042] Figure 2 This is a schematic diagram showing the cross-sectional shape of a resist with poor straightness in the resist pattern outline. Detailed Implementation

[0043] The upper or lower limit of the numerical ranges described in this specification can be replaced with the values ​​shown in the examples. Furthermore, in this specification, where multiple substances equivalent to each component are present, unless otherwise specified, the content rate of each component in the photosensitive resin composition refers to the total content rate of the multiple substances present in the photosensitive resin composition.

[0044] Furthermore, any combination of the items described in this specification is also included in this invention.

[0045] In this specification, "solid components" refers to non-volatile components that do not include volatile substances such as water and solvents contained in the photosensitive resin composition. It means components that do not volatilize and remain when the resin composition is dried. It also includes components that are liquid, syrupy, or waxy at room temperature (around 25°C).

[0046] In this specification, "(meth)acrylate" means "acrylate or methacrylate", and other similar terms have the same meaning.

[0047] [Photosensitive Resin Composition]

[0048] The photosensitive resin composition of this embodiment is a photosensitive resin composition containing (A) a photopolymerizable compound having ethylene unsaturated groups and acidic substituents, (B) a curing agent, (C) a photopolymerization initiator, and (D) a photopolymerizable compound.

[0049] The aforementioned (D) photopolymerizable compound is a polyfunctional monomer having a backbone (X) and three or more (meth)acryloyl groups.

[0050] The skeleton (X) is derived from a polyol and has three or more groups (a) formed by removing hydrogen atoms from the hydroxyl group as binding groups with other structures.

[0051] The three or more (meth)acryloyl groups are directly or indirectly combined with the above-mentioned binding group (a).

[0052] One or more of the three or more (meth)acryloyl groups are linked to the aforementioned binding group (a) via a linking group.

[0053] It should be noted that in this specification, the above-mentioned ingredients are sometimes referred to as ingredient (A), ingredient (B), ingredient (C), ingredient (D), etc., and other ingredients are sometimes referred to in the same way.

[0054] <(A) Photopolymerizable compounds with ethylene unsaturated groups and acidic substituents>

[0055] The photosensitive resin composition of this embodiment contains a photopolymerizable compound having an ethylene unsaturated group and an acidic substituent as component (A).

[0056] (A) Components may be used alone or in combination with two or more.

[0057] (A) is a compound that exhibits photopolymerization properties through the presence of ethylene unsaturated groups. It should be noted that, in this specification, "ethylene unsaturated group" refers to a substituent containing an ethylene unsaturated bond, and "ethylene unsaturated bond" refers to a carbon-carbon double bond capable of undergoing addition reactions, excluding double bonds containing aromatic rings.

[0058] Examples of vinyl unsaturated groups that can be included in component (A) include vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimide, nadicimide, and (meth)acryloyl. Among these, (meth)acryloyl is preferred from the viewpoint of reactivity and resolution.

[0059] Acidic substituents in component (A) can include, for example, carboxyl groups, sulfonic acid groups, and phenolic hydroxyl groups. Among these, from the viewpoint of resolution, carboxyl groups are preferred.

[0060] (A) is preferably an acid-modified epoxy derivative containing ethylene unsaturated groups, obtained by reacting (c) a polybasic acid anhydride containing saturated or unsaturated groups with resin (A'), wherein the resin (A') is obtained by reacting (a) epoxy resin with (b) an organic acid containing ethylene unsaturated groups.

[0061] From the viewpoint of suppressing undercut, as well as the viewpoints of adhesion to the copper substrate, reducing warpage of the thin film substrate (hereinafter also referred to as "warpage reduction"), thermal shock resistance, and resolution, component (A) preferably contains a photopolymerizable compound (A1) having vinyl unsaturated groups and acidic substituents, which is made using bisphenol varnish-type epoxy resin (a1) as component (a). In particular, from the viewpoint of improving adhesion strength, it is more preferable to contain this component (A1) and a photopolymerizable compound (A2) having vinyl unsaturated groups and acidic substituents, which is made using an epoxy resin (a2) different from bisphenol varnish-type epoxy resin (a1) as component (a).

[0062] The preferred method for obtaining component (A) from (a) epoxy resin, (b) organic acid containing ethylene unsaturated groups and (c) polybasic acid anhydride containing saturated or unsaturated groups will be described below.

[0063] (Bisphenolic varnish-type epoxy resin (a1))

[0064] As component (a1), from the same viewpoint as above, a bisphenol varnish-type epoxy resin having structural units represented by the following general formula (I) or (II) is preferred, and a bisphenol varnish-type epoxy resin having structural units represented by general formula (II) is more preferred.

[0065] [Epoxy resin having structural units represented by general formula (I)]

[0066] One preferred embodiment of component (a1) is an epoxy resin having structural units represented by the following general formula (I).

[0067] [Chemistry 1]

[0068]

[0069] (where R is in the formula) 11 Each can be independently a hydrogen atom or a methyl group, Y 1 and Y 2 Each can be independently a hydrogen atom or a glycidyl group. Y 1 and Y 2 (At least one of them is glycidyl group.)

[0070] From the perspective of suppressing undercutting, and considering the straightness and resolution of the resist pattern profile, R in the above general formula (I)11 Hydrogen atoms are preferred.

[0071] Furthermore, considering the same viewpoints as above, as well as the viewpoints of thermal shock resistance and warpage reduction, Y 1 and Y 2 Preferably, all are glycidyl-based.

[0072] The number of structural units in component (a1), which has a structural unit represented by the above general formula (I), is greater than or equal to 1, preferably 10 to 100, more preferably 12 to 80, and even more preferably 15 to 70. If the number of structural units is within the above range, there is a tendency for excellent linearity of the resist pattern outline, good adhesion to the copper substrate, heat resistance, and electrical insulation.

[0073] Here, the number of structural units in a single molecule is represented as an integer value, and in an aggregate of multiple molecules, it is represented as a rational number as an average value. The same applies to the number of structural units in the following sections.

[0074] [Epoxy resin having structural units represented by general formula (II)]

[0075] One preferred form of the (a1) component is an epoxy resin having structural units represented by the following general formula (II).

[0076] [Chemistry 2]

[0077]

[0078] (where R is in the formula) 12 Each can be independently a hydrogen atom or a methyl group, Y 3 and Y 4 Each can be independently a hydrogen atom or a glycidyl group. Y 3 and Y 4 (At least one of them is glycidyl group.)

[0079] From the perspective of suppressing undercutting, and considering the straightness and resolution of the resist pattern profile, R in the above general formula (II) 12 Hydrogen atoms are preferred.

[0080] Furthermore, considering the same viewpoints as above, as well as the viewpoints of thermal shock resistance and warpage reduction, Y 3 and Y 4 Preferably, all are glycidyl-based.

[0081] The number of structural units in component (a1) having a structural unit represented by the above general formula (II) is greater than or equal to 1, preferably 10 to 100, more preferably 12 to 80, and even more preferably 15 to 70. If the number of structural units is within the above range, there is a tendency for excellent linearity of the resist pattern outline, good adhesion to the copper substrate, and excellent heat resistance.

[0082] In the above general formula (II), R 12 All are hydrogen atoms and Y 3 and Y 4 Glycidyl ether-based epoxy resins are available as the EXA-7376 series (manufactured by DIC Corporation, trade name). Additionally, R... 12 It is methyl and Y 3 and Y 4 Glycidyl-based epoxy resins are available as EPON SU8 series (manufactured by Mitsubishi Chemical Corporation, trade name).

[0083] (Epoxy resin (a2))

[0084] (a2) There are no particular restrictions on the composition of the epoxy resin as long as it is different from the bisphenol varnish type epoxy resin (a1). However, from the viewpoint of suppressing undercutting, as well as the straightness of the resist pattern outline, the adhesion to the copper substrate and the resolution, it is preferable to select one or more of the group consisting of phenolic varnish type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, triphenol methane type epoxy resin and biphenyl type epoxy resin.

[0085] As phenolic varnish-type epoxy resins, those having structural units represented by the following general formula (III) are preferably listed. As bisphenol A type epoxy resins or bisphenol F type epoxy resins, those having structural units represented by the following general formula (IV) are preferably listed. As triphenol methane type epoxy resins, those having structural units represented by the following general formula (V) are preferably listed. Furthermore, as biphenyl type epoxy resins, those having structural units represented by the following general formula (VI) are preferably listed.

[0086] [Epoxy resin having structural units represented by general formula (III)]

[0087] As a component (a2), phenolic varnish-type epoxy resins having structural units represented by the following general formula (III) are preferably listed. For example, phenolic varnish-type epoxy resins represented by the following general formula (III') are listed as phenolic varnish-type epoxy resins having such structural units.

[0088] [Chemistry 3]

[0089]

[0090] (In general formulas (III) and (III'), R 13 Each can be independently a hydrogen atom or a methyl group, Y 5 Each is independently a hydrogen atom or a glycidyl group. In the general formula (III'), n1 is a number greater than or equal to 1, Y 5 At least one of them is a glycidyl group.

[0091] From the perspective of suppressing undercutting, and considering the straightness and resolution of the resist pattern profile, R in the above general formulas (III) and (III') 13 Hydrogen atoms are preferred.

[0092] From the perspective of suppressing undercutting, and considering the linearity and resolution of the resist pattern profile, in the above general formula (III'), Y, as a hydrogen atom 5 With Y as a glycidyl group 5 The molar ratio [hydrogen atom / glycidyl group] is preferably 0 / 100 to 30 / 70, more preferably 0 / 100 to 10 / 90.

[0093] In the above general formula (III'), n1 is a number greater than or equal to 1, preferably a number from 10 to 200, more preferably a number from 20 to 150, and even more preferably a number from 30 to 100. If n1 is within the above range, there is a tendency for the resist pattern outline to have excellent linearity, adhesion to the copper substrate, and heat resistance.

[0094] Examples of phenolic varnish-type epoxy resins represented by the above general formula (III') include phenolic varnish-type epoxy resins and cresol varnish-type epoxy resins. These phenolic varnish-type epoxy resins can be obtained, for example, by reacting phenolic varnish-type epoxy resins or cresol varnish-type epoxy resins with epichlorohydrin using known methods.

[0095] As phenolic varnish-type epoxy resins or cresol varnish-type epoxy resins represented by the above general formula (III'), for example, YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (all manufactured by Nippon Steel Chemicals & Materials Co., Ltd., trade names), DEN-431, DEN-439 (all manufactured by Dow Chemical Company, trade names), EOCN-120, and EOCN-102S are available. EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, BREN (all manufactured by Nippon Kayaku Co., Ltd., trade names), EPN-1138, EPN-1235, EPN-1299 (all manufactured by BASF, trade names), N-730, N-770, N-865, N-665, N-673, VH-4150, VH-4240 (all manufactured by DIC Co., Ltd., trade names), etc.

[0096] [Epoxy resin having structural units represented by general formula (IV)]

[0097] As a component (a2), bisphenol A type epoxy resin or bisphenol F type epoxy resin having a structural unit represented by the following general formula (IV) can be preferably listed. As epoxy resin having such a structural unit, bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the following general formula (IV') can be listed, for example.

[0098] [Chemistry 4]

[0099]

[0100] (In general formulas (IV) and (IV'), R 14 Each can be independently a hydrogen atom or a methyl group, Y 6 It can be a hydrogen atom or a glycidyl group. In the general formula (IV'), n2 is a number greater than or equal to 1. When n2 is greater than or equal to 2, multiple Y 6 They can be the same or different, but at least one Y 6 It is a glycidyl group.

[0101] From the perspective of suppressing undercutting, and considering the straightness and resolution of the resist pattern profile, R in the above general formulas (IV) and (IV') 14 Hydrogen atoms are preferred.

[0102] Furthermore, considering the same viewpoints as above, as well as the viewpoints of thermal shock resistance and warpage reduction, Y 6 Glycidyl group is preferred.

[0103] In the above general formula (IV'), n2 is a number greater than or equal to 1, preferably a number from 10 to 100, more preferably a number from 12 to 80, and even more preferably a number from 15 to 60. If n2 is within the above range, there is a tendency for the resist pattern outline to have excellent linearity, adhesion to the copper substrate, and heat resistance.

[0104] Represented by the above general formula (IV') and Y 6 Bisphenol A type epoxy resin or bisphenol F type epoxy resin that is glycidyl group can be, for example, represented by the above general formula (IV') and Y 6 The hydroxyl group (-OY) of bisphenol A type epoxy resin or bisphenol F type epoxy resin containing hydrogen atoms 6 It is obtained by reacting with epichlorohydrin.

[0105] To promote the reaction between the hydroxyl group and epichlorohydrin, it is preferable to carry out the reaction in a polar organic solvent such as dimethylformamide, dimethylacetamide, or dimethyl sulfoxide at a reaction temperature of 50–120°C in the presence of an alkali metal hydroxide. If the reaction temperature is within this range, the reaction will not become too slow, and side reactions can be suppressed.

[0106] As bisphenol A type epoxy resins or bisphenol F type epoxy resins represented by the above general formula (IV'), for example, jER807, jER815, jER825, jER827, jER828, jER834, jER1001, jER1004, jER1007 and jER1009 (all manufactured by Mitsubishi Chemical Corporation, trade names), DER-330, DER-301, DER-361 (all manufactured by Dow Chemical Corporation, trade names), YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004, YDF-8170 (all manufactured by Nippon Steel Chemicals & Materials Co., Ltd., trade names), etc., are available.

[0107] [Epoxy resin having structural units represented by the general formula (V)]

[0108] As a component (a2), preferably, a pyrrolimethane-type epoxy resin having a structural unit represented by the following general formula (V) can be listed. As a pyrrolimethane-type epoxy resin having such a structural unit, for example, a pyrrolimethane-type epoxy resin represented by the following general formula (V') can be listed.

[0109] [Chemistry 5]

[0110]

[0111] (In general formulas (V) and (V'), Y 7 Each is independently a hydrogen atom or a glycidyl group, with at least one Y atom. 7It is a glycidyl group. Additionally, in the general formula (V'), n3 is a number greater than or equal to 1.

[0112] From the perspective of suppressing undercut and top defects, and considering the linearity and resolution of the resist pattern outline, in the triphenol methane-type epoxy resin represented by the above general formula (V'), Y, as a hydrogen atom... 7 With Y as a glycidyl group 7 The molar ratio [hydrogen atom / glycidyl group] is preferably 0 / 100 to 30 / 70.

[0113] In the above general formula (V'), n3 is a number greater than or equal to 1, preferably a number from 10 to 100, more preferably a number from 12 to 80, and even more preferably a number from 15 to 70. If n3 is within the above range, there is a tendency for the resist pattern outline to have excellent linearity, adhesion to the copper substrate, and heat resistance.

[0114] As a triphenol methane type epoxy resin represented by the above general formula (V'), for example, FAE-2500, EPPN-501H, EPPN-502H (the above are trade names manufactured by Nippon Kayaku Co., Ltd.) are available.

[0115] [Epoxy resin having structural units represented by general formula (VI)]

[0116] As a component (a2), a biphenyl-type epoxy resin having a structural unit represented by the following general formula (VI) can be preferably listed. For example, a biphenyl-type epoxy resin represented by the following general formula (VI') can be listed as a biphenyl-type epoxy resin having such a structural unit.

[0117] [Chemistry 6]

[0118]

[0119] (In general formulas (VI) and (VI'), Y 8 Each atom can be independently represented by a hydrogen atom or a glycidyl group, and n4 is a number greater than or equal to 1.

[0120] As biphenyl-type epoxy resins represented by the above general formula (VI'), for example, NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L (the above are trade names manufactured by Nippon Kayaku Co., Ltd.) are available.

[0121] As component (a2), it is preferably selected from one or more of the group consisting of a phenolic varnish-type epoxy resin having a structural unit represented by the above general formula (III), a bisphenol A type epoxy resin having a structural unit represented by the above general formula (IV), and a bisphenol F type epoxy resin having a structural unit represented by the above general formula (IV), and more preferably a bisphenol F type epoxy resin having a structural unit represented by the above general formula (IV).

[0122] Furthermore, from the viewpoints of thermal shock resistance, warpage reduction, and resolution, it is preferable to use component (A1), which uses bisphenol phenolic varnish-type epoxy resin having structural units represented by the above general formula (II) as component (a1), and component (A2), which uses bisphenol A type epoxy resin or bisphenol F type epoxy resin having structural units represented by the above general formula (IV) as component (a2).

[0123] (b) Organic acids containing ethylene unsaturated groups)

[0124] Examples of components (b) include acrylic acid, acrylic acid dimers, methacrylic acid, β-furfurylic acid, β-styrylic acid, cinnamic acid, crotonic acid, α-cyanocinonic acid, and other acrylic acid derivatives; half-ester compounds that are the reaction products of hydroxyl-containing acrylates and diacid anhydrides; and half-ester compounds that are the reaction products of vinyl monoglycidyl ethers or vinyl monoglycidyl esters and diacid anhydrides. Component (b) may be used alone or in combination with two or more.

[0125] Half-ester compounds can be obtained, for example, by reacting hydroxyl-containing acrylates, vinyl-containing monoglycidyl ethers, or vinyl-containing monoglycidyl esters with dicarboxylic anhydrides.

[0126] Examples of hydroxyl-containing acrylates, vinyl-containing monoglycidyl ethers, and vinyl-containing monoglycidyl esters used in the synthesis of half-ester compounds include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and glycidyl (meth)acrylate.

[0127] Dicarboxylic anhydrides used in the synthesis of half-ester compounds include, for example, dicarboxylic anhydrides containing saturated groups and dicarboxylic anhydrides containing unsaturated groups.

[0128] Specific examples of dicarboxylic anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, etc.

[0129] The reaction between component (a) and component (b) is preferably carried out at a ratio of 0.6 to 1.05 equivalents of component (b) relative to the epoxy group of component (a), more preferably 0.8 to 1.0 equivalents. By carrying out the reaction at the above ratio, there is a tendency for increased photosensitivity and excellent linearity of the resist pattern outline.

[0130] Components (a) and (b) can also react in a state where they are dissolved in an organic solvent.

[0131] Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as 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, and carbitol acetate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. They can be used individually or in combination with two or more.

[0132] The reaction between component (a) and component (b) can also be facilitated by using a catalyst to promote the reaction.

[0133] Examples of catalysts include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, and triphenylphosphine. They can be used individually or in combination with two or more.

[0134] From the viewpoint of promoting the reaction, the amount of catalyst used is preferably 0.01 to 10 parts by mass relative to the total of 100 parts by mass of component (a) and component (b), more preferably 0.05 to 2 parts by mass, and even more preferably 0.1 to 1 part by mass.

[0135] To prevent polymerization during the reaction, a polymerization inhibitor can also be used for the reaction between component (a) and component (b).

[0136] Examples of polymerization inhibitors include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol. They can be used alone or in combination of two or more.

[0137] From the viewpoint of improving stability, the amount of polymerization inhibitor used is preferably 0.01 to 1 part by mass relative to the total of 100 parts by mass of component (a) and component (b), more preferably 0.02 to 0.8 parts by mass, and even more preferably 0.04 to 0.5 parts by mass.

[0138] From a productivity point of view, the reaction temperature of component (a) and component (b) is preferably 60 to 150°C, more preferably 80 to 120°C, and even more preferably 90 to 110°C.

[0139] Component (A'), formed by reacting component (a) with component (b), has hydroxyl groups formed through a ring-opening addition reaction between the epoxy group of component (a) and the carboxyl group of component (b). By further reacting component (A') with a polybasic acid anhydride containing a saturated or unsaturated group (c), the hydroxyl groups of component (A') (including those originally present in component (a)) undergo half-esterification with the anhydride group of component (c), thereby obtaining an acid-modified epoxy derivative containing an ethylene unsaturated group.

[0140] (c) Polybasic acid anhydrides containing saturated or unsaturated groups)

[0141] As component (c), polybasic anhydrides containing saturated groups or polybasic anhydrides containing unsaturated groups can be used.

[0142] Specific examples of component (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, etc. Among these, tetrahydrophthalic anhydride is preferred from the viewpoint of resolution.

[0143] (c) Components may be used alone or in combination with two or more.

[0144] In the reaction between component (A') and component (c), for example, the acid value of the acid-modified epoxy derivative containing vinyl unsaturated groups can be adjusted by reacting 0.1 to 1.0 equivalents of component (c) relative to 1 equivalent of the hydroxyl group in component (A').

[0145] From a productivity point of view, the reaction temperature of component (A') and component (c) is preferably 50 to 150°C, more preferably 60 to 120°C, and even more preferably 70 to 100°C.

[0146] Additionally, as needed, a portion of hydrogenated bisphenol A type epoxy resin may be used in combination, for example, as component (a). Furthermore, as component (A), a portion of styrene-maleic acid resins such as hydroxyethyl methacrylate modified with styrene-maleic anhydride copolymer may also be used.

[0147] (Acid value of component A)

[0148] (A) The acid value of the component is not particularly limited, but is preferably 30 to 150 mg KOH / g, more preferably 40 to 120 mg KOH / g, and even more preferably 50 to 100 mg KOH / g. If the acid value is greater than or equal to the lower limit above, the photosensitive resin composition tends to have excellent solubility in dilute alkaline solutions, and if it is less than or equal to the upper limit above, the cured film tends to have excellent electrical properties.

[0149] ((A) Molecular weight of component)

[0150] The weight-average molecular weight of component (A) is not particularly limited, but is preferably 3,000 to 30,000, more preferably 4,000 to 25,000, and even more preferably 5,000 to 18,000. If the weight-average molecular weight of component (A) is within the above range, there is a tendency for the resist pattern profile to have excellent linearity, adhesion to the copper substrate, heat resistance, and electrical insulation.

[0151] It should be noted that the weight-average molecular weight in this specification is the weight-average molecular weight converted from that of polystyrene determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. More specifically, for example, the weight-average molecular weight can be obtained by measuring using the GPC apparatus and conditions described below and converting it using a standard curve of standard polystyrene. The standard curve was prepared using 5 sample groups (“PStQuick MP-H” and “PStQuick B”, manufactured by Tosoh Corporation) as standard polystyrene.

[0152] (GPC measuring device)

[0153] GPC Unit: High-speed GPC unit "HCL-8320GPC", detector is differential refractometer or UV detector, manufactured by Tosoh Corporation.

[0154] Chromatographic column: TSKgel SuperMultipore HZ-H column (column length: 15cm, column inner diameter: 4.6mm), manufactured by Tosoh Corporation.

[0155] (Measurement conditions)

[0156] Solvent: Tetrahydrofuran (THF)

[0157] Measurement temperature: 40℃

[0158] Flow rate: 0.35 ml / min

[0159] Sample concentration: 10 mg / THF 5 ml

[0160] Injection volume: 20 μl

[0161] (A) Content of component

[0162] The content of component (A) in the photosensitive resin composition of this embodiment is not particularly limited. From the viewpoint of improving the heat resistance, electrical properties and chemical resistance of the coating film, it is preferably 20 to 80% by mass, more preferably 25 to 70% by mass, and even more preferably 30 to 50% by mass, based on the total amount of solid components in the photosensitive resin composition.

[0163] (The total content of components (A1) and (A2) in component (A))

[0164] When components (A1) and (A2) are used together as component (A), the total content of components (A1) and (A2) in component (A) is not particularly limited, but from the viewpoint of the linearity of the resist pattern outline, chemical plating resistance and heat resistance, it is preferred to be 80 to 100% by mass, more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, and may also be 100% by mass.

[0165] When using either component (A1) or component (A2) as an acid-modified epoxy derivative containing an ethylene unsaturated group, the content of component (A1) or component (A2) in component (A) can also be appropriately selected from the above range.

[0166] (mass ratio of component (A1) to component (A2))

[0167] When components (A1) and (A2) are used together as component (A), the mass ratio [(A1) / (A2)] is not particularly limited, but from the viewpoint of the linearity of the resist pattern outline, resistance to chemical plating and heat resistance, it is preferably 20 / 80 to 90 / 10, more preferably 30 / 70 to 80 / 20, further preferably 40 / 60 to 75 / 25, and even more preferably 50 / 50 to 70 / 30.

[0168] <(B) Curing Agent>

[0169] The photosensitive resin composition of this embodiment contains (B) a curing agent.

[0170] (B) Components may include compounds that are cured by heat, ultraviolet light, etc., or compounds that are cured by heat, ultraviolet light, etc., with the carboxyl or hydroxyl groups of the photocurable components (A) and (D) in the photosensitive resin composition of this embodiment.

[0171] By using curing agent (B), the heat resistance, adhesion, and chemical resistance of the final cured film can be improved.

[0172] (B) A single curing agent may be used alone, or two or more may be used together.

[0173] Examples of components (B) include epoxy compounds, end-capped isocyanates, melamine compounds, etc. Thermosetting compounds such as zoline compounds.

[0174] As an epoxy compound, compounds listed, for example, as component (a) can be used.

[0175] As a capped isocyanate, the addition reaction product of polyisocyanate compound and isocyanate capping agent can be used.

[0176] Examples of melamine compounds include triaminotriazine, hexamethoxymelamine, and hexabutoxylated melamine.

[0177] From the viewpoint of further improving the heat resistance of the cured film, epoxy compounds (epoxy resins) are preferred.

[0178] The preferred epoxy compound is a bisphenol type epoxy resin, such as bisphenol A type epoxy resin or bisphenol F type epoxy resin, which are listed as components (a); or a phenolic varnish type epoxy resin.

[0179] Epoxy compounds can be in liquid or solid form at room temperature (25°C).

[0180] ((B) Content of component)

[0181] The content of component (B) in the photosensitive resin composition of this embodiment is not particularly limited, but is preferably 2 to 40% by mass, more preferably 3 to 30% by mass, and even more preferably 5 to 20% by mass, based on the total amount of solid components in the photosensitive resin composition. If the content of component (B) is within the above range, there is a tendency to maintain good developability and the cured film formed has excellent adhesion and heat resistance.

[0182] When using epoxy compounds as component (B), epoxy resin curing agents can also be used in conjunction with them to further improve the heat resistance, adhesion, chemical resistance, and other properties of the final cured film.

[0183] Examples of epoxy resin curing agents include imidazole derivatives such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; guanidines such as acetylguanidine and benzoguanidine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenyl sulfone, dicyandiamide, urea, urea derivatives, melamine, and polyhydrazides; their organic acid salts or epoxy adducts; amine complexes of boron trifluoride; and triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-xylene-S-triazine. These can be used alone or in combination with two or more.

[0184] When using an epoxy resin curing agent, from the viewpoint of improving reliability, its content, based on the total amount of solid components in the photosensitive resin composition, is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass.

[0185] <(C) Photopolymerization Initiator>

[0186] As for component (C) used in this embodiment, there are no particular limitations as long as it enables the photopolymerizable compound contained in the photosensitive resin composition of this embodiment to be polymerized, and it can be appropriately selected from commonly used photopolymerization initiators.

[0187] (C) Components may be used alone or in combination with two or more.

[0188] As component (C), examples include benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)] [Phenyl]-2-morpholino-1-propanone, N,N-dimethylaminoacetophenone and other alkyl phenyl ketone photopolymerization initiators; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone, 2-aminoanthraquinone and other anthraquinone-based photopolymerization initiators; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthone-based photopolymerization initiators with a thioxanthone skeleton. Photopolymerization initiators include: acetal-based photopolymerization initiators such as acetophenone dimethyl ketal and benzoyl dimethyl ketal; benzophenone-based photopolymerization initiators such as benzophenone, methyl benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, michalcone, and 4-benzoyl-4'-methyl diphenyl sulfide; acridine-based photopolymerization initiators such as 9-phenyl acridine and 1,7-bis(9,9'-acridyl)heptane; and 2,4 Acylphosphine oxide photoinitiators such as 6-trimethylbenzoyldiphenylphosphine oxide; oxime ester photoinitiators such as 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetone-1-(O-acetyl oxime), and 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl) oxime].

[0189] Preferably, it is selected from one or more of the group consisting of alkyl benzophenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators with a thioxanthone skeleton, benzophenone-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators.

[0190] (C) The component can be selected based on the desired performance. For example, from the viewpoint of improving the curability of the bottom through photobleaching, it is preferable to select an acylphosphine oxide-based photopolymerization initiator. Furthermore, from the viewpoint of being less volatile and less likely to generate as an overflow gas, it is preferable to select an alkyl phenyl ketone-based photopolymerization initiator. As an alkyl phenyl ketone-based photopolymerization initiator, acetophenone is preferred.

[0191] It should be noted that alkyl phenyl ketone photopolymerization initiators can also be classified as benzoyl ketones with a benzoyl ketal structure, α-hydroxyalkyl phenyl ketones with a hydroxyl group at the α-position of the carbonyl group, α-aminoalkyl phenyl ketones with a nitrogen atom at the α-position of the carbonyl group, etc., with α-aminoalkyl phenyl ketones being preferred.

[0192] (C) Content of component

[0193] The content of component (C) in the photosensitive resin composition of this embodiment is not particularly limited, but is preferably 0.2 to 15% by mass, more preferably 0.4 to 5% by mass, and even more preferably 0.6 to 1.5% by mass, based on the total amount of solid components in the photosensitive resin composition. If the content of component (C) is within the above range, there is a tendency for the exposed portion to be less likely to dissolve during development, and if it is less than or equal to the above upper limit, there is a tendency for excellent heat resistance.

[0194] In addition to these components (C), the photosensitive resin composition of this embodiment may also contain photopolymerization initiators such as ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, and other tertiary amines. These may be used individually or in combination with two or more.

[0195] <(D) Photopolymerizable compounds>

[0196] The (D) component used in this embodiment is a multifunctional monomer having a backbone (X) and three or more (meth)acryloyl groups.

[0197] The skeleton (X) is derived from a polyol and has three or more groups (a) formed by removing hydrogen atoms from the hydroxyl groups.

[0198] The three or more (meth)acryloyl groups are directly or indirectly combined with the above-mentioned binding group (a).

[0199] One or more of the three or more (meth)acryloyl groups are linked to the aforementioned binding group (a) via a linking group.

[0200] The photosensitive resin composition of this embodiment contains component (D), which maintains good resolution, and the elongation and tensile strength of the cured product relative to external stress are greatly improved. It also has excellent heat resistance and thermal shock resistance, and is less prone to a decrease in insulation caused by the HAST test.

[0201] Unlike component (A), component (D) does not necessarily have an acidic substituent. In addition, component (D) preferably does not have a carboxyl group, a sulfonic acid group, or a phenolic hydroxyl group, and may also not have an acidic substituent.

[0202] (D) Components can be used alone or in combination with two or more.

[0203] (D) The skeleton (X) of component (D) is derived from polyols.

[0204] The polyol providing the backbone (X) preferably has 3 to 10 hydroxyl groups per molecule, more preferably 4 to 9, and even more preferably 5 to 8.

[0205] Examples of polyols include glycerol, diglycerol, trimethylolpropane, di(trimethylolpropane), pentaerythritol, and dipentaerythritol. Among these, dipentaerythritol is preferred from the viewpoint of improving sensitivity.

[0206] The skeleton (X) has three or more groups (a) obtained by removing hydrogen atoms from the hydroxyl groups of the polyol. That is, the skeleton (X) has three or more oxygen atoms obtained by removing hydrogen atoms from the hydroxyl groups of the polyol as binding groups for bonding with other structures, which can also be described as groups with trivalent or higher oxidation states.

[0207] The hydroxyl groups in a polyol can be partially or entirely bound groups (a), but from the viewpoint of flexibility and thermal shock resistance, it is preferable that all of them are bound groups (a).

[0208] From the viewpoints of resolution, flexibility, heat resistance, thermal shock resistance and insulation, the number of binding groups (a) in the skeleton (X) is preferably 3 to 10, more preferably 4 to 9, and even more preferably 5 to 8.

[0209] The skeleton (X) is preferably represented by the following general formula (D-1).

[0210]

[0211] (where X) d This indicates an organic group, and p indicates a group related to X. d The number of -O- groups bonded is an integer from 3 to 10. * indicates bonding sites with other structures.

[0212] In the above general formula (D-1), X d The organic group represented preferably has 3 to 20 carbon atoms, more preferably 5 to 15, and even more preferably 8 to 12.

[0213] X d The -O- group is equivalent to the residue after removing the hydroxyl group from the polyol, and the -O- group is equivalent to the binding group (a) after removing the hydrogen atom from the hydroxyl group. That is, the skeleton (X) represented by the above general formula (D-1) can also be said to be a p-valent binding group. The explanation of polyols is as described above.

[0214] p is an integer from 3 to 10, and from the viewpoints of resolution, flexibility, heat resistance, thermal shock resistance and insulation, it is preferably an integer from 4 to 8, and more preferably an integer from 5 to 7.

[0215] (D) is a component in which one or more (meth)acryloyl groups are linked to a binding group (a) via a linking group.

[0216] (D) The three or more (meth)acryloyl groups of the component may be partially bonded to the binding group (a) via a linking group, preferably all of them are bonded to the binding group (a) via a linking group. Preferably, the (meth)acryloyl groups bonded to the backbone (X) are directly bonded to the binding group (a) without a linking group.

[0217] The number of (meth)acryloyl groups in component (D) that are bonded to the binding group (a) via the above-mentioned linking group is only required to be greater than or equal to 1, but from the viewpoints of resolution, softness, heat resistance, thermal shock resistance and insulation, it is preferred to be 3 to 10, more preferably 4 to 8, and even more preferably 5 to 7.

[0218] (D) The linking group of the component is preferably a divalent organic group containing one or more carbon atoms. From the viewpoints of resolution, flexibility, heat resistance, thermal shock resistance and insulation, it is more preferably a divalent organic group with 2 to 10 carbon atoms, and even more preferably a divalent organic group with 3 to 7 carbon atoms.

[0219] From the viewpoints of resolution, flexibility, heat resistance, thermal shock resistance, and insulation, the connecting group is preferably a divalent group containing an epoxide structural unit or a divalent group derived from a hydroxy acid.

[0220] From the viewpoints of resolution, flexibility, heat resistance, thermal shock resistance and insulation, the epoxide structural unit in the divalent group containing the epoxide structural unit is preferably an epoxide structural unit with 2 to 4 carbon atoms, more preferably an ethylene oxide structural unit or an propylene oxide structural unit, and even more preferably an ethylene oxide structural unit.

[0221] From the viewpoints of resolution, flexibility, heat resistance, thermal shock resistance and insulation, the number of epoxide structural units in the divalent group containing the epoxide structural unit is preferably 1 to 5, more preferably 2 to 4, and even more preferably 2 or 3.

[0222] The divalent group comprising the epoxide structural unit is preferably represented by the following general formula (D-2).

[0223] [Chemistry 7]

[0224]

[0225] (where R is in the formula) d1 It is an alkylene group with 2 to 4 carbon atoms, and q represents a number from 1 to 5. A For the site where it binds to the binding group (a) of the backbone (X), * BThis refers to the site where it binds to the (meth)acryloyl group.

[0226] As R d1 Examples of alkylene groups with 2 to 4 carbon atoms include ethylene, propyleneene, and butylene.

[0227] q is a number from 1 to 5, and from the viewpoints of resolution, flexibility, heat resistance, thermal shock resistance and insulation, it is preferably a number from 2 to 4, and more preferably a number of 2 or 3.

[0228] The divalent group derived from hydroxy acids is a group that has a binding group formed by removing hydrogen from the hydroxyl group of the hydroxy acid and a binding group formed by removing the OH group from the carboxyl group of the hydroxy acid.

[0229] The divalent group derived from the hydroxy acid is preferably a divalent group derived from an aliphatic hydroxy acid. From the viewpoints of resolution, flexibility, heat resistance, thermal shock resistance, and insulation, the number of carbon atoms in the aliphatic hydroxy acid is preferably 2 to 10, more preferably 3 to 8, and even more preferably 4 to 7.

[0230] Examples of hydroxy acids include glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxyhexanoic acid, hydroxyheptanoic acid, hydroxynonanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, hydroxydodecanoic acid, hydroxytridecanoic acid, hydroxytetradecanoic acid, hydroxypentadecanoic acid, hydroxyhexadecanoic acid, hydroxyheptadecanoic acid, hydroxyoctadecanoic acid, and hydroxynonadecanoic acid.

[0231] As a divalent group derived from the above-mentioned hydroxy acid, it is preferably represented by the following general formula (D-3).

[0232] [Chemistry 8]

[0233]

[0234] (where R is in the formula) d2 This indicates a divalent aliphatic hydrocarbon group with 1 to 9 carbon atoms. 'r' represents a number from 1 to 5. A It is the site where it binds to the binding group (a) of the backbone (X). B This is the site where it binds to the (meth)acryloyl group.

[0235] From the perspectives of resolution, flexibility, heat resistance, thermal shock resistance, and insulation, R d2 The aliphatic hydrocarbon group shown has 1 to 9 carbon atoms, preferably 2 to 7, and more preferably 3 to 6.

[0236] As R d2The aliphatic hydrocarbon groups represented may include alkylene groups such as methylene, ethylene, propylene, trimethylene, butylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and nonamethylene; alkylidene groups; alkenyl groups; and ynylene groups. Among these, alkylene groups are preferred.

[0237] r is a number from 1 to 5. From the viewpoints of resolution, flexibility, heat resistance, thermal shock resistance and insulation, a number of 1 or 2 is preferred, and a number of 1 is more preferred.

[0238] As component (D), it is preferably a compound represented by the following general formula (D-4).

[0239] [Chemistry 9]

[0240]

[0241] (where X) d X in the above general formula (D-1) d The same explanation applies. Y d This represents the linking group represented by the above general formula (D-2) or (D-3). d1 and Z d2 Each group independently represents a (meth)acryloyl group. 's' represents an integer from 0 to 9, 't' represents an integer from 1 to 10, and the sum of 's' and 't' is an integer from 3 to 10.

[0242] In the above general formula (D-4), s is an integer from 0 to 9. From the viewpoints of resolution, flexibility, heat resistance, thermal shock resistance and insulation, it is preferably an integer from 0 to 3, and more preferably 0.

[0243] t is an integer from 1 to 10. From the same point of view as above, it is preferably an integer from 4 to 8, and more preferably an integer from 5 to 7.

[0244] The sum of s and t is an integer from 3 to 10. From the same point of view as above, it is preferably an integer from 4 to 8, and more preferably an integer from 5 to 7.

[0245] (Content of component (D))

[0246] The content of component (D) in the photosensitive resin composition of this embodiment is not particularly limited, but is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, and even more preferably 3 to 7% by mass, based on the total solid content of the photosensitive resin composition. If the content of component (D) is greater than or equal to the lower limit value above, there is a tendency for increased photosensitivity and less leaching of the exposed portion during development; if it is less than or equal to the upper limit value above, there is a tendency for excellent heat resistance. Furthermore, if the content of component (D) is within the above range, there is a tendency for maintaining better resolution, significantly improved elongation and tensile strength relative to external stress of the cured product, excellent heat resistance and thermal shock resistance, and less likelihood of decreased insulation due to HAST testing.

[0247] It should be noted that the photosensitive resin composition of this embodiment may also be used in combination with photopolymerizable compounds other than components (A) and (D).

[0248] Examples of photopolymerizable compounds other than components (A) and (D) include, for example, hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; mono- or di(meth)acrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and hexanediol, or their ethylene oxide or propylene oxide adducts; (meth)acrylamides such as N,N-dimethyl(meth)acrylamide and N-hydroxymethyl(meth)acrylamide; and N,N-dimethyl(meth)acrylates. Aminoalkyl methacrylates such as aminoethyl esters; poly(meth)acrylates of polyols such as trimethylolpropane, pentaerythritol, di(trimethylolpropane), dipentaerythritol, and trihydroxyethyl isocyanurate; meth)acrylates of phenolic ethylene oxide or propylene oxide adducts such as phenoxyethyl methacrylate and polyethoxydi(meth)acrylate of bisphenol A; meth)acrylates of glycidyl ethers such as diglycidyl ether and triglycidyl isocyanurate; melamine (meth)acrylates, etc. These can be used alone or in combination with two or more. Furthermore, from the viewpoint of photosensitivity, the photopolymerizable compounds other than components (A) and (D) are preferably compounds with a molecular weight of less than or equal to 1,000.

[0249] <(E) Inorganic Packing>

[0250] From the viewpoint of further improving properties such as adhesive strength and coating hardness, the photosensitive resin composition of this embodiment may further contain component (E).

[0251] (E) Components may be used alone or in combination with two or more.

[0252] Examples of components that can be listed as (E) include silicon dioxide (SiO2), aluminum oxide (Al2O3), titanium oxide (TiO2), tantalum oxide (Ta2O5), zirconium oxide (ZrO2), silicon nitride (Si3N4), barium titanate (BaO·TiO2), barium carbonate (BaCO3), magnesium carbonate (MgCO3), aluminum hydroxide (Al(OH)3), magnesium hydroxide (Mg(OH)2), lead titanate (PbO·TiO2), lead zirconate titanate (PZT), lanthanum lead zirconate titanate (PLZT), gallium oxide (Ga2O3), and spinel (MgO·Al2O3). The following are listed: l2O3, mullite (3Al2O3·2SiO2), cordierite (2MgO·2Al2O3 / 5SiO2), talc (3MgO·4SiO2·H2O), aluminum titanate (TiO2·Al2O3), yttrium-containing zirconium oxide (Y2O3·ZrO2), barium silicate (BaO·8SiO2), boron nitride (BN), calcium carbonate (CaCO3), barium sulfate (BaSO4), calcium sulfate (CaSO4), zinc oxide (ZnO), magnesium titanate (MgO·TiO2), hydrotalcite, mica, calcined kaolin, carbon (C), etc.

[0253] (E) In terms of composition, silica may be included from the viewpoint of improving heat resistance, and barium sulfate may be included from the viewpoint of improving heat resistance and adhesive strength. A combination of silica and barium sulfate may also be included. Furthermore, from the viewpoint of improving the dispersibility of inorganic fillers in the resin composition through anti-agglomeration effects, inorganic fillers that have been pre-treated with alumina or organosilane compounds may be appropriately selected.

[0254] The elemental composition of aluminum in the surface of inorganic fillers treated with alumina or organosilane compounds can be appropriately selected from 0.5–10 atomic%, 1–5 atomic%, or 1.5–3.5 atomic%. Similarly, the elemental composition of silicon in the surface of inorganic fillers can be appropriately selected from 0.5–10 atomic%, 1–5 atomic%, or 1.5–3.5 atomic%. Furthermore, the elemental composition of carbon in the surface of inorganic fillers can be appropriately selected from 10–30 atomic%, 15–25 atomic%, or 18–23 atomic%. These elemental compositions can be determined using XPS (X-ray photoelectron spectroscopy).

[0255] As an inorganic filler that has been surface-treated with alumina or organosilane compounds, barium sulfate that has been surface-treated with alumina or organosilane compounds can be purchased as NanoFine BFN40DC (manufactured by Solvay Corporation, Japan, trade name).

[0256] From the viewpoint of resolution, the average particle size of the (E) component is preferably 0.01 to 5 μm, more preferably 0.05 to 3 μm, even more preferably 0.1 to 2 μm, and particularly preferably 0.15 to 1 μm.

[0257] Here, the average particle size of component (E) is the average particle size of the inorganic filler in the state of being dispersed in the photosensitive resin composition, and is set as the value obtained by measuring in the following manner.

[0258] First, the photosensitive resin composition was diluted 1,000 times with methyl ethyl ketone. Then, using a submicron particle analyzer (Beckman Coulter, Ltd., trade name: N5), the particles dispersed in the solvent were measured according to international standard ISO 13321 with a refractive index of 1.38. The particle size at the 50% cumulative value (volume basis) of the particle size distribution was set as the average particle size. Furthermore, the (E) component contained in the photosensitive layer disposed on the carrier film or the cured film of the photosensitive resin composition can also be diluted (or dissolved) to 1,000 times (volume ratio) with the solvent as described above and measured using the aforementioned submicron particle analyzer.

[0259] (Content of component (E))

[0260] When the photosensitive resin composition of this embodiment contains component (E), its content is not particularly limited, but is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, and even more preferably 28 to 60% by mass, based on the total amount of solid components in the photosensitive resin composition. If the content of component (E) is within the above range, the cured photosensitive resin composition tends to have excellent strength, heat resistance, resolution, etc.

[0261] When silica is used as component (E), the silica content is not particularly limited, but is preferably 5 to 60% by mass, more preferably 10 to 55% by mass, and even more preferably 15 to 50% by mass, based on the total solid content of the photosensitive resin composition.

[0262] When barium sulfate is used as component (E), the content of barium sulfate is not particularly limited, but is preferably 5 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 10 to 20% by mass, based on the total amount of solid components in the photosensitive resin composition.

[0263] If the content of silicon dioxide and barium sulfate is within the above range, there is a tendency for excellent properties such as low thermal expansion coefficient, solder heat resistance, and bonding strength.

[0264] <(F) Pigment>

[0265] From the viewpoint of improving the appearance by concealing conductor patterns, the photosensitive resin composition of this embodiment may further contain (F) pigment according to the desired color.

[0266] (F) Components can be used alone or in combination with two or more.

[0267] As for (F) pigment, any colorant that displays the desired color can be used, preferably including known colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, carbon black, and naphthalene black.

[0268] (Content of component (F))

[0269] When the photosensitive resin composition of this embodiment contains component (F), its content is not particularly limited. From the viewpoint of easily identifying the manufacturing apparatus and better concealing the conductor pattern, it is preferably 0.01 to 5% by mass, more preferably 0.03 to 3% by mass, and even more preferably 0.05 to 2% by mass, based on the total amount of solid components in the photosensitive resin composition.

[0270] <(G) Ion Scavenger>

[0271] From the viewpoint of resist shape, adhesion, flowability and reliability, the photosensitive resin composition of this embodiment may further contain (G) ion scavenger.

[0272] The term "ion scavenger" refers to a component in an ion scavenger that can capture ions; there are no particular limitations as long as it has the function of capturing at least one of cations and anions. Furthermore, in this embodiment, the captured ions are, for example, sodium ions (Na+) introduced into a composition that reacts upon irradiation by light, electron beams, etc., thereby changing its solubility in the solvent. + ), chloride ions (Cl) - ), bromide ions (Br) - ), copper ions (Cu) + Cu 2+ Plasma, by capturing these ions, improves electrical insulation, resistance to electro-erosion, and other properties.

[0273] (G) Components can be used alone or in combination with two or more.

[0274] (G) is preferably an ion scavenger having at least one selected from the group consisting of Zr (zirconium), Bi (bismuth), Mg (magnesium) and Al (aluminum).

[0275] As component (G), examples include cation trapping agents that capture cations, anion trapping agents that capture anions, and zwitterion trapping agents that capture both cations and anions.

[0276] (Cation scavenger)

[0277] Examples of inorganic ion exchangers that capture cations include zirconium phosphate, zirconium tungstate, zirconium molybdate, zirconium tungstate, zirconium antimony, zirconium selenate, zirconium tellurate, zirconium silicate, zirconium phosphosilicate, zirconium polyphosphate, and other metal oxides.

[0278] (Anion scavenger)

[0279] Examples of anion scavengers that capture anions include inorganic ion exchangers such as bismuth oxide hydrate and hydrotalcite.

[0280] (Zwitterion scavenger)

[0281] Examples of zwitterion scavengers that capture both cations and anions include inorganic ion exchangers such as alumina hydrate and zirconium oxide hydrate. Additionally, these zwitterions (also referred to as "inorganic ion exchangers") can also include IXE-1320 (containing Mg and Al), IXE-600 (containing Bi), IXE-633 (containing Bi), IXE-680 (containing Bi), IXE-6107 (containing Zr and Bi), IXE-6136 (containing Zr and Bi), IXEPLAS-A1 (containing Zr, Mg, and Al), IXEPLAS-A2 (containing Zr, Mg, and Al), and IXEPLAS-B1 (containing Zr and Bi) from Toa Synthetic Co., Ltd.

[0282] Component (G) can be a granular material. From the viewpoint of improving insulation, the average particle size of component (G) is preferably less than or equal to 5 μm, more preferably less than or equal to 3 μm, even more preferably less than or equal to 2 μm, and preferably greater than or equal to 0.1 μm. Here, the average particle size of component (G) is the particle size of the particles dispersed in the photosensitive resin composition, and can be measured by the same method as the method for measuring the average particle size of component (E).

[0283] (Content of component (G))

[0284] When the photosensitive resin composition of this embodiment contains component (G), its content is not particularly limited. From the viewpoint of improving electrical insulation and resistance to electro-erosion, it is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.2 to 1% by mass, based on the total amount of solid components in the photosensitive resin composition.

[0285] <(H) Elastomer>

[0286] The photosensitive resin composition of this embodiment may further contain component (H). Component (H) can be appropriately used, particularly when the photosensitive resin composition of this embodiment is used in a semiconductor packaging substrate. By adding component (H), the reduction in flexibility and adhesive strength caused by the curing shrinkage of component (A) due to internal deformation (internal stress) of the resin can be suppressed. That is, the flexibility and adhesive strength of the cured film formed from the photosensitive resin composition can be improved.

[0287] As a component (H), examples include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic elastomers, and silicone-based elastomers.

[0288] Among them, olefin-based elastomers and polyester-based elastomers are preferred.

[0289] As an olefin-based elastomer, epoxy-modified polybutadiene (hereinafter also referred to as "epoxide-modified polybutadiene") can be used.

[0290] The epoxy-modified polybutadiene preferably has hydroxyl groups at the ends of the molecule, more preferably has hydroxyl groups at both ends of the molecule, and even more preferably has hydroxyl groups only at both ends of the molecule. In addition, there is no particular limitation as long as the epoxy-modified polybutadiene has one or more hydroxyl groups, but it is preferred to have 1 to 5, more preferably 1 or 2, and even more preferably 2.

[0291] From the viewpoints of fit with the inner circuitry, heat resistance, coefficient of thermal expansion, and flexibility, epoxy-modified polybutadiene is preferably epoxy-modified polybutadiene represented by the following general formula (H-1).

[0292] [Chemistry 10]

[0293]

[0294] (In the formula, a, b, and c represent the ratios of the structural units within the parentheses, where a is 0.05–0.40, b is 0.02–0.30, and c is 0.30–0.80, further satisfying a+b+c=1.00 and (a+c)>b. y represents the number of structural units within the square brackets, which is an integer from 10 to 250.)

[0295] The order in which the structural units within the square brackets in the above general formula (H-1) are combined is not specific. In other words, the structural unit shown on the left, the structural unit shown in the center, and the structural unit shown on the right can be interleaved. If they are represented by (a), (b), and (c) respectively, then the following combinations are possible: -[(a)-(b)-(c)]-[(a)-(b)-(c)-]-, -[(a)-(c)-(b)]-[(a)-(c)-(b)-]-, -[(b)-(a)-(c)]-[(b)-(a)-(c)-]-, -[(a)-(b)-(c)]-[(c)-(b)-(a)-]-, -[(a)-(b)-(a)]-[(c)-(b)-(c)-]-, -[(c)-(b)-(c)]-[(b)-(a)-(a)-]-, etc.

[0296] From the viewpoints of good fit with the inner circuitry, heat resistance, coefficient of thermal expansion, and flexibility, a is preferably 0.10 to 0.30, b is preferably 0.10 to 0.30, and c is preferably 0.40 to 0.80. Furthermore, from the same viewpoint, y is preferably an integer from 30 to 180.

[0297] In the above general formula (H-1), commercially available epoxidized polybutadiene products with integers a=0.20, b=0.20, c=0.60, and y=10~250 can be listed as "Epolead (registered trademark) PB3600" (Dairu Corporation).

[0298] As polyester-based elastomers, examples include substances obtained by polycondensation of dicarboxylic acids or their derivatives with diol compounds or their derivatives. Specific examples of dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids formed by replacing the hydrogen atoms of their aromatic nuclei with methyl, ethyl, phenyl, etc.; aliphatic dicarboxylic acids with 2 to 20 carbon atoms such as adipic acid, sebacic acid, and dodecanoic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

[0299] Specific examples of diol compounds include aliphatic and alicyclic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol; and diphenols represented by the following general formula (H-2).

[0300] [Chemistry 11]

[0301]

[0302] (where Z) h1R represents alkylene groups with 1 to 10 carbon atoms, cycloalkylene groups with 4 to 8 carbon atoms, -O-, -S-, -SO2-, or benzene rings directly bonded together. h1 and R h2 Each alkyl group is independently composed of a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms; b1 and b2 are independently integers from 0 to 4; and a1 is 0 or 1. The aforementioned alkylene and cycloalkylene groups can be straight-chain or branched, and can be substituted with halogen atoms, alkyl groups, aryl groups, aralkyl groups, amino groups, amide groups, alkoxy groups, etc.

[0303] Examples of diphenols represented by the general formula (H-2) include bisphenol A, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)propane, and resorcinol. They can be used alone or in combination with two or more.

[0304] Alternatively, multi-block copolymers can be used, in which aromatic polyesters (e.g., polybutylene terephthalate) are partially configured as hard segments and aliphatic polyesters (e.g., polytetramethylene glycol) are partially configured as soft segments. Various grades of block copolymers are available depending on the type, ratio, and molecular weight of the hard and soft segments. Specifically, Hytrel (manufactured by Toray DuPont), PELPRENE (manufactured by Toyobo Co., Ltd.), and Espel (manufactured by Hitachi Chemical Co., Ltd.) are readily available.

[0305] (Content of component (H))

[0306] When the photosensitive resin composition of this embodiment contains component (H), its content is not particularly limited. It is preferably 2 to 40 parts by weight relative to 100 parts by weight of component (A) (solid component), more preferably 4 to 30 parts by weight, further preferably 6 to 20 parts by weight, and particularly preferably 10 to 15 parts by weight. If the content of component (H) is within the above range, the elastic modulus of the cured film becomes lower in the high-temperature region, and the unexposed portions are more easily dissolved in the developer.

[0307] <Diluent>

[0308] The photosensitive resin composition of this embodiment may also contain a diluent as needed.

[0309] Examples of diluents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as 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, and carbitol acetate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha.

[0310] When using a diluent, its amount can be appropriately selected from an amount that results in the total solid content of the photosensitive resin composition being preferably 50-90% by mass, more preferably 60-80% by mass, and even more preferably 65-75% by mass. That is, when the photosensitive resin composition of this embodiment contains a diluent, the content of the diluent is preferably 10-50% by mass, more preferably 20-40% by mass, and even more preferably 25-35% by mass. If the content of the diluent is within the above range, the coatability of the photosensitive resin composition is improved, and more intricate patterns can be formed. However, the photosensitive resin composition of this embodiment may also be free of diluent.

[0311] <Other Additives>

[0312] The photosensitive resin composition of this embodiment may also contain, as needed, various commonly known additives such as polymerization inhibitors such as hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; tackifiers such as bentonite and montmorillonite; defoamers such as organosilicon, fluorine-based, and vinyl resin-based agents; silane coupling agents; and flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus-based phosphate esters, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters. These additives may be used individually or in combination of two or more. However, the photosensitive resin composition of this embodiment may also be free of the aforementioned additives.

[0313] <Method for manufacturing photosensitive resin composition>

[0314] The photosensitive resin composition of this embodiment can be manufactured by mixing or kneading the above-mentioned components. Mixing can be performed using equipment such as a roller mill or a bead mill.

[0315] The photosensitive resin composition of this embodiment is suitable for pattern formation and via formation (hereinafter sometimes referred to as via formation) using photolithography. Therefore, the present invention also provides a photosensitive resin composition for forming a permanent mask resist and a photosensitive resin composition for forming vias, both composed of the photosensitive resin composition of this embodiment. Furthermore, the photosensitive resin composition of this embodiment exhibits excellent resolution, tightness with inner layer circuitry, and electrical insulation reliability, making it useful as an interlayer insulating layer for multilayer printed circuit boards. Therefore, the present invention also provides a photosensitive resin composition for an interlayer insulating layer, composed of the photosensitive resin composition of this embodiment.

[0316] [Dry film]

[0317] The dry film of this embodiment has a carrier film and a photosensitive layer using the photosensitive resin composition of this embodiment.

[0318] The thickness of the photosensitive layer in the dry film of this embodiment is preferably 5 to 50 μm, more preferably 15 to 40 μm, and even more preferably 20 to 30 μm.

[0319] Examples of suitable carrier membranes include polyesters such as polyethylene terephthalate and polybutylene terephthalate; and polyolefins such as polypropylene and polyethylene. The thickness of the carrier membrane can be appropriately selected within the range of 5–100 μm.

[0320] In this embodiment, a protective film can also be laminated on the surface of the photosensitive layer opposite to the surface in contact with the carrier film. As the protective film, polymer films such as polyethylene and polypropylene can be used. Alternatively, the same polymer film as the carrier film described above can be used, or a different polymer film can be used.

[0321] The dry film of this embodiment can be manufactured as follows: the photosensitive resin composition of this embodiment is coated onto a carrier film by known methods such as reverse roll coating, gravure roll coating, corner roller coating, and curtain coating, and then dried to form a photosensitive layer.

[0322] The coating can be dried using hot air drying, or a dryer employing far-infrared or near-infrared light. As for the drying temperature, simply select an appropriate range from 60–120°C, 70–110°C, or 80–100°C. Similarly, as for the drying time, simply select an appropriate range from 1–60 minutes, 2–30 minutes, or 5–20 minutes.

[0323] Printed wiring board

[0324] The printed wiring board of this embodiment is a printed wiring board having a surface protective film or an interlayer insulating layer formed from the photosensitive resin composition of this embodiment.

[0325] The surface protective film or interlayer insulating layer formed from the photosensitive resin composition of this embodiment has high elongation and flexibility, high tensile strength relative to external stress, excellent heat resistance, thermal shock resistance and insulation, and excellent resist shape pattern.

[0326] In addition, the surface protective film or interlayer insulating layer has a pattern with excellent formation stability, which has been miniaturized in terms of aperture size and spacing between apertures in recent years due to the miniaturization and high performance of electronic devices.

[0327] The thickness of the surface protective film or interlayer insulating layer is not particularly limited, but is preferably greater than or equal to 5 μm, more preferably 10 to 200 μm, even more preferably 15 to 150 μm, even more preferably 20 to 100 μm, and particularly preferably 23 to 50 μm.

[0328] [Manufacturing method of printed circuit boards]

[0329] The method for manufacturing the printed wiring board of this embodiment comprises the following steps in sequence: a step of forming a photosensitive layer on a substrate using the photosensitive resin composition of this embodiment or the dry film of this embodiment; a step of forming a resist pattern using the photosensitive layer; and a step of curing the resist pattern to form a surface protective film or an interlayer insulating layer.

[0330] The manufacturing method of the printed wiring board according to this embodiment will be described in more detail below.

[0331] First, a photosensitive layer is formed on a metal-clad laminate substrate by coating the photosensitive resin composition of this embodiment or by laminating a dry film of this embodiment with the protective film removed. The photosensitive layer is then deposited on the substrate.

[0332] Methods for coating photosensitive resin compositions include, for example, screen printing, spraying, roller coating, curtain coating, and electrostatic coating.

[0333] The photosensitive resin composition is preferably coated to achieve a photosensitive layer thickness of 5 μm or greater, more preferably 10–200 μm, further preferably 15–150 μm, even more preferably 20–100 μm, and particularly preferably 23–50 μm after drying. The drying conditions after coating are not particularly limited; for example, heating and drying within the range of 60–110°C is sufficient.

[0334] As a method for laminating dry films, one example is the use of a laminator for thermal lamination.

[0335] Next, the negative film is brought into direct contact with the photosensitive layer formed above (or separated by a transparent film such as a carrier film without direct contact), at a concentration of 10–2,000 mJ / cm. 2100~1,500mJ / cm 2 or 300~1,000mJ / cm 2 The active light is irradiated with an appropriate exposure level, and then the unexposed areas are dissolved and removed (developed) with a dilute alkaline aqueous solution to form a resist pattern.

[0336] Examples of active light sources include electron beams, ultraviolet rays, and X-rays, with ultraviolet rays being the preferred choice. Additionally, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and halogen lamps can be used as light sources.

[0337] Next, the exposed portion of the photosensitive layer is fully cured by at least one of post-exposure (ultraviolet exposure) and post-heating to form a surface protective film or interlayer insulating layer.

[0338] The exposure amount for post-exposure only needs to be between 100 and 5,000 mJ / cm. 2 500~2,000mJ / cm 2 Or 700~1,500J / cm 2 Choose the appropriate option from the options provided.

[0339] The heating temperature for post-heating can be appropriately selected from 100-200℃, 120-180℃, or 135-165℃.

[0340] The heating time for post-heating can be appropriately selected from 5 minutes to 12 hours, 10 minutes to 6 hours, or 30 minutes to 2 hours.

[0341] Example

[0342] The present invention will be further described in detail below through embodiments, but the present invention is not limited to these embodiments.

[0343] Synthesis of photopolymerizable compounds with ethylene unsaturated groups and acidic substituents

[0344] (Synthetic Example 1; Synthesis of acid-modified epoxy derivative (A-1) containing vinyl unsaturated groups)

[0345] Add 350 parts by weight of bisphenol F phenolic varnish-type epoxy resin (manufactured by DIC Corporation, "EXA-7376") containing Y in general formula (II) to a flask equipped with a stirrer, reflux cooler, and thermometer. 3 and Y 4 glycidyl group, R 12Bisphenol F phenolic varnish-type epoxy resin with hydrogen atom structural units, epoxy equivalent: 186) [(a1) component], 70 parts by mass of acrylic acid [(b) component], 0.5 parts by mass of methyl hydroquinone and 120 parts by mass of carbitol acetate, were reacted at 90°C while stirring to completely dissolve the mixture.

[0346] Next, the obtained solution was cooled to 60°C, and 2 parts by mass of triphenylphosphine were added. The reaction was carried out at 100°C until the acid value of the solution was less than or equal to 1 mg KOH / g.

[0347] Further, 98 parts by mass of tetrahydrophthalic anhydride (THPAC) [(c) component] and 85 parts by mass of carbitol acetate were added to the reaction solution, and the reaction was carried out at 80°C for 6 hours.

[0348] Then, the reaction solution was cooled to room temperature (25°C) to obtain THPAC-modified bisphenol F phenolic varnish epoxy acrylate (acid-modified epoxy derivative containing vinyl unsaturated groups (A-1)) as component (A1) (solid component concentration: 73% by mass).

[0349] (Synthetic Example 2; Synthesis of acid-modified epoxy derivative (A-2) containing vinyl unsaturated groups)

[0350] Add 1,052 parts by weight of bisphenol F epoxy resin (containing Y in general formula (IV)) to a flask equipped with a stirrer, reflux cooler and thermometer. 6 For hydrogen atoms, R 14 Bisphenol F type epoxy resin with hydrogen atom as the structural unit, epoxy equivalent: 526) [(a2) component], 144 parts by mass of acrylic acid [(b) component], 1 part by mass of methyl hydroquinone, 850 parts by mass of carbitol acetate and 100 parts by mass of solvent naphtha, were reacted at 70°C while stirring to completely dissolve the mixture.

[0351] Next, the obtained solution was cooled to 50°C, and 2 parts by mass of triphenylphosphine and 75 parts by mass of naphtha solvent were added. The reaction was carried out at 100°C until the acid value of the solution was less than or equal to 1 mg KOH / g.

[0352] The obtained solution was cooled to 50°C, and 745 parts by mass of tetrahydrophthalic anhydride (THPAC) [(c) component], 75 parts by mass of carbitol acetate and 75 parts by mass of solvent naphtha were added to the solution after reaction, and the reaction was carried out at 80°C for 6 hours.

[0353] Then, the reaction solution was cooled to room temperature (25°C) to obtain THPAC-modified bisphenol F epoxy acrylate (acid-modified epoxy derivative containing vinyl unsaturated groups (A-2)) as component (A2) (solid component concentration 62% by mass).

[0354] (Synthetic Example 3; Acid-modified epoxy derivative containing vinyl unsaturated groups (A-3))

[0355] In a flask equipped with a stirrer, reflux cooler and thermometer, add 220 parts by weight of cresol phenolic varnish type epoxy resin (manufactured by Toto Chemical Co., Ltd., trade name "YDCN704") [(a1) component], 72 parts by weight of acrylic acid [(b) component], 1.0 part by weight of hydroquinone and 180 parts by weight of carbitol acetate, and react at 90°C while stirring until the mixture is completely dissolved.

[0356] Next, the obtained solution was cooled to 60°C, and 1 part by mass of benzyltrimethylammonium chloride was added. The reaction was carried out at 100°C until the acid value of the solution became 1 mg KOH / g.

[0357] Further, 152 parts by mass of tetrahydrophthalic anhydride (THPAC) [(c) component] and 100 parts by mass of carbitol acetate were added to the solution after the reaction, and the reaction was carried out at 80°C for 6 hours. Then, the solution was cooled to room temperature (25°C) and diluted with carbitol acetate to obtain THPAC-modified cresol phenolic varnish-type epoxy acrylate (acid-modified epoxy derivative containing vinyl unsaturated groups (A-3)) (solid component concentration 60% by mass).

[0358] (Examples 1-6, Comparative Examples 1-4)

[0359] (1) Preparation of photosensitive resin composition

[0360] The components were compounded according to the formulation shown in Table 1 (the values ​​in the table are in parts by mass, and in the case of solution, they are converted to solids). The mixture was then kneaded using a three-roll mill. Carbitol acetate was then added at a solids concentration of 70% by mass to obtain the photosensitive resin composition.

[0361] (2) Dry film manufacturing

[0362] The substance obtained by diluting the above-obtained photosensitive resin composition with methyl ethyl ketone was coated onto a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name "G2-25", thickness 25 μm) as a carrier film to a dried thickness of 25 μm. The film was then dried at 75°C for 30 minutes using a hot air convection dryer to form a photosensitive layer on the carrier film. Next, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name "NF-15") was laminated onto the surface of the photosensitive layer opposite to the side in contact with the carrier film to form a dry film with a protective film.

[0363] [Evaluation Method]

[0364] It should be noted that the properties of the photosensitive resin compositions obtained in each example were evaluated using the methods shown below.

[0365] (1. Evaluation of resolution)

[0366] The protective film is peeled off from the dry film with protective film manufactured in each example, and the exposed photosensitive layer is laminated at 80°C onto a copper-clad laminate substrate (manufactured by Meiki Seisakusho Co., Ltd., trade name "MVLP-500") with a thickness of 0.6 mm using a pressure vacuum laminator, to obtain a laminate with a photosensitive layer with a carrier film.

[0367] Next, a negative mask with a predetermined opening pattern (opening diameter size: 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 150, 200 μm) is tightly bonded to the carrier film of the above-mentioned laminate, and exposed using an ultraviolet exposure device with an exposure level of 13, which is the number of complete curing levels in the staged exposure table (manufactured by Hitachi Chemical Co., Ltd.).

[0368] Next, the carrier film was peeled off from the photosensitive layer using a 1% sodium carbonate aqueous solution at a temperature of 1.765 × 10⁻⁶ for 60 seconds. 5 Spray development is performed at a pressure of Pa to dissolve and develop the unexposed areas. Next, an ultraviolet exposure device is used at 2000 mJ / cm². 2 After exposing the photosensitive layer to the exposure level, it is heated at 170°C for 1 hour to create a test piece with a permanent mask resist forming an opening pattern on a copper-clad laminate substrate.

[0369] The test pieces were observed using an optical microscope to confirm the minimum opening diameter and were evaluated according to the following criteria.

[0370] <Evaluation Criteria>

[0371] A: The minimum opening diameter is less than or equal to 30 μm.

[0372] B: The minimum opening diameter is greater than 30 μm and less than or equal to 50 μm.

[0373] C: The minimum opening diameter exceeds 50 μm.

[0374] (2. Evaluation of the shape of the resist pattern)

[0375] The test pieces prepared in "1. Evaluation of Resolution" above were cast using an embedding resin (using Mitsubishi Chemical Corporation's trade name "jER828" as the epoxy resin and triethylenetetramine as the curing agent). After complete curing, the pieces were ground using a polishing machine (RefineTec Corporation's trade name "Refine Polisher") to reveal the cross-section of the opening pattern of the permanent photoresist. The obtained cross-section of the opening pattern was observed using a metal microscope and evaluated according to the following criteria.

[0376] <Evaluation Criteria>

[0377] A: The absence of the bottom cut and the upper part of the resist has not been confirmed, and the straightness of the pattern outline is good (refer to...). Figure 1 ).

[0378] B: Confirm the absence of the bottom cut or the upper part of the resist, or the poor straightness of the pattern outline (refer to...). Figure 2 ).

[0379] (3. Evaluation of thermal shock resistance)

[0380] For the test pieces prepared in “1. Evaluation of resolution” above, temperature cycling tests will be carried out with each cycle set at -65°C for 30 minutes and at 150°C for 30 minutes. The test pieces will be observed visually and with an optical microscope at 1000 cycles and 2000 cycles, and evaluated according to the following criteria.

[0381] <Evaluation Criteria>

[0382] A: No cracks were detected after 2000 cycles.

[0383] B: Cracks were not detected after 1000 cycles, or cracks were detected after 2000 cycles.

[0384] C: Cracks were detected after 1000 cycles.

[0385] (4. Evaluation of heat resistance)

[0386] The test pieces prepared in “1. Evaluation of resolution” above were placed in an environment of 150°C and observed by visual inspection and optical microscope after 1000 hours and 2000 hours, and evaluated according to the following criteria.

[0387] <Evaluation Criteria>

[0388] A: No cracks were detected at 2000 hours.

[0389] B: No cracks were detected at 1000 hours, or cracks were detected at 2000 hours.

[0390] C: Cracks were detected at 1000 hours.

[0391] (5. Evaluation of insulation performance)

[0392] In the fabrication of the test piece in "1. Evaluation of Resolution" above, a bismaleimide triazine substrate with comb-shaped electrodes (line / pitch = 10 / 10 μm) was used instead of a copper-clad laminate substrate. Otherwise, the test piece was fabricated using the same method as in "1. Evaluation of Resolution" above, and exposed to conditions of 135°C, 85% RH, and 3.3V. The change in resistance value was measured using a migration testing machine (manufactured by Kusumoto Chemical Co., Ltd., trade name "SIR13"). Then, the degree of migration was observed using an optical microscope, and evaluated according to the following criteria.

[0393] <Evaluation Criteria>

[0394] A: Even after more than 200 hours, the permanent mask resist did not migrate, and the resistance did not decrease to less than or equal to 10. -6 Ω.

[0395] B: At 100 hours or more but less than 200 hours, the permanent mask resist did not migrate, and the resistance decreased to less than or equal to 10 ohms. -6 Ω.

[0396] C: In less than 100 hours, the permanent mask resist did not migrate, and the resistance value decreased to less than or equal to 10. -6 Ω.

[0397] (6. Evaluation of elongation)

[0398] A negative mask with a rectangular opening pattern of 1 cm in length and 7 cm in width was tightly fitted onto the carrier film side of the dry film prepared in each example. Using an ultraviolet exposure apparatus, exposure was performed at an exposure level of 13 (the complete curing level) on a staged exposure meter (manufactured by Hitachi Chemical Co., Ltd.). Then, the protective film was peeled off, and an aqueous solution of 1% sodium carbonate was used at an exposure time of 60 seconds and an exposure rate of 1.765 × 10⁻⁶. 5 Spray development is performed at a pressure of Pa to dissolve and develop the unexposed areas. Next, an ultraviolet exposure device is used at 2000 mJ / cm². 2 After exposure to the specified exposure level, the substrate is heated at 170°C for 1 hour to peel off the carrier film and produce a cured film of permanent mask resist monomer with a length of 1 cm and a width of 7 cm.

[0399] The cured film was used as a test piece, and the elongation was determined using a tensile testing machine according to JIS K 7127:1999, at a tensile speed of 1.0 mm / min and a temperature of 23°C. The results were evaluated according to the following criteria.

[0400] <Evaluation Criteria>

[0401] A: The elongation until the cured film breaks is greater than or equal to 8%.

[0402] B: The elongation until the cured film breaks is greater than or equal to 5% and less than 8%.

[0403] C: The elongation until the cured film breaks is less than 5%.

[0404] (7. Evaluation of tensile strength)

[0405] The cured film prepared in “6. Elongation” above was used as a test piece. The tensile strength was determined using a tensile testing machine according to JIS K7127:1999, at a tensile speed of 1.0 mm / min and a temperature of 23°C. The results were evaluated according to the following criteria.

[0406] A: The tensile strength until the cured film breaks is greater than or equal to 80 MPa.

[0407] B: The tensile strength until the cured film breaks is greater than or equal to 60 MPa and less than 80 MPa.

[0408] C: The tensile strength until the cured film breaks is less than 60 MPa.

[0409] The evaluation results are shown in Table 1.

[0410] [Table 1]

[0411]

[0412] It should be noted that the detailed contents of each material in Table 1 are as follows.

[0413] [(A) Component: Photopolymerizable compound with ethylene unsaturated groups and acidic substituents]

[0414] • A-1: ​​The acid-modified epoxy derivative containing vinyl unsaturated groups obtained in Synthesis Example 1 (A-1)

[0415] • A-2: The acid-modified epoxy derivative containing vinyl unsaturated groups obtained in Synthesis Example 2 (A-2)

[0416] • A-3: The acid-modified epoxy derivative containing vinyl unsaturated groups obtained in Synthesis Example 3 (A-3)

[0417] [(B) Component: Curing agent]

[0418] YSLV-80XY: Tetramethylbisphenol F type epoxy resin (bisphenol crystalline epoxy resin) (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name)

[0419] RE-306: Phenolic varnish-type multifunctional epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name)

[0420] • JER828: Bisphenol A type epoxy resin (liquid epoxy resin) (manufactured by Mitsubishi Chemical Corporation, trade name)

[0421] [(C) Component: Photopolymerization Initiator]

[0422] C-1: 2-Methyl-[4-(methylthio)phenyl]morpholino-1-propanone

[0423] C-2: 2,4-Diethylthioxanone

[0424] C-3: 4,4'-bis(diethylamino)benzophenone

[0425] C-4: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime)

[0426] [(D) Component: Photopolymerizable compound]

[0427] • D-1: A compound represented by the following formula (D-5)

[0428] [Chemistry 12]

[0429]

[0430]

[0431] (Z in equation (D-5)) 1 Z is the group represented by formula (D-5'). 1 In equation (D-5'), the asterisk (*) represents the part of equation (D-5') related to Z. 1 The bonding portion of the oxygen atoms.

[0432] • D-2: A compound represented by the following formula (D-6)

[0433] [Chemistry 13]

[0434]

[0435]

[0436] (Z in equation (D-6)) 2 Z is the group represented by formula (D-6'). 2 In equation (D-6'), the asterisk (*) represents the part of equation (D-6') related to Z. 2 The bonding portion of the oxygen atoms.

[0437] [(D') component: photopolymerizable compounds other than (D) component]

[0438] D'-1: Dipentaerythritol hexaacrylate

[0439] [(E) Composition: Inorganic filler]

[0440] • Silica particles: Manufactured by Denki Kagaku Kogyo Co., Ltd., trade name "SFP20M", average particle size: 0.3μm

[0441] • Barium sulfate particles: Manufactured by Sakai Chemical Industry Co., Ltd., trade name "B-34", average particle size: 0.3μm

[0442] [(F) Ingredients: Pigment]

[0443] • Phthalocyanine pigments: Manufactured by Sanyo Pigment Co., Ltd.

[0444] [(G) Component: Ion Scavenger]

[0445] ·IXEPLAS-A2: Zr, Mg, and Al zwitter (manufactured by Toa Synthetic Co., Ltd., trade name, average particle size: 0.2 μm, Zr compound content: 20-30% by mass)

[0446] [(H) Component: Elastomer]

[0447] ·PB-3600: Epoxidized polybutadiene (manufactured by Daicel Co., Ltd., trade name)

[0448] SP1108: Polyester resin (manufactured by Hitachi Chemical Co., Ltd., trade name)

[0449] Espel 1612: Polyester-based elastomer (manufactured by Hitachi Chemical Co., Ltd., trade name)

[0450] Espel 1620: Polyester-based elastomer (manufactured by Hitachi Chemical Co., Ltd., trade name)

[0451] XER-91: Crosslinked acrylonitrile butadiene rubber (manufactured by JSR Corporation, trade name)

[0452] As shown in Table 1, the photosensitive resin compositions of Examples 1-6 of this embodiment exhibit excellent resolution, high elongation, high tensile strength relative to external stress, and excellent heat resistance, thermal shock resistance, and insulation. On the other hand, the photosensitive resin compositions of Comparative Examples 1-4 are inferior in all properties.

Claims

1. A photosensitive resin composition comprising (A) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent, (B) a curing agent, (C) a photopolymerization initiator, and (D) a photopolymerizable compound, the (D) photopolymerizable compound is a multifunctional monomer having a skeleton (X) and three or more (meth)acryloyl groups, the skeleton (X) is a skeleton derived from a polyol and has three or more groups after removal of a hydrogen atom from a hydroxyl group as a binding group (a) to other structures, the three or more (meth)acryloyl groups are directly or indirectly bound to the binding group (a), one or more of the three or more (meth)acryloyl groups is bound to the binding group (a) via a linking group, the linking group is a divalent group including an alkylene oxide structural unit having 2 to 4 carbon atoms, the content of the (D) photopolymerizable compound is 2 to 15% by mass based on the total amount of solid components in the photosensitive resin composition.

2. The photosensitive resin composition according to claim 1, wherein the skeleton (X) is a skeleton derived from a polyol selected from the group consisting of glycerol, diglycerol, trimethylolpropane, di(trimethylolpropane), pentaerythritol, and dipentaerythritol.

3. The photosensitive resin composition according to claim 1 or 2, wherein the number of (meth)acryloyl groups bound to the binding group (a) via the linking group in the (D) photopolymerizable compound is 3 to 10.

4. The photosensitive resin composition according to claim 1 or 2, wherein the alkylene oxide structural unit is an ethylene oxide structural unit or a propylene oxide structural unit.

5. The photosensitive resin composition according to claim 1 or 2, wherein the (A) photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent is an acid-modified ethylenically unsaturated group-containing epoxy derivative obtained by reacting (c) a saturated group- or unsaturated group-containing polybasic acid anhydride with a resin (A') obtained by reacting (a) an epoxy resin with (b) an ethylenically unsaturated group-containing organic acid.

6. The photosensitive resin composition according to claim 5, wherein the (A) photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent contains: a photopolymerizable compound (A1) having an ethylenically unsaturated group and an acidic substituent formed using a bisphenol novolac-type epoxy resin (al) as the (a) epoxy resin; and a photopolymerizable compound (A2) having an ethylenically unsaturated group and an acidic substituent formed using an epoxy resin (a2) different from the bisphenol novolac-type epoxy resin (al) as the (a) component.

7. The photosensitive resin composition according to claim 6, wherein the epoxy resin (a2) is one or more selected from the group consisting of a novolac-type epoxy resin different from the bisphenol novolac-type epoxy resin (al), a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a triphenol methane-type epoxy resin, and a biphenyl-type epoxy resin. ​ ​ 8. The photosensitive resin composition according to claim 1 or 2, wherein the (C) photopolymerization initiator is one or more selected from the group consisting of an alkyl phenone-based photopolymerization initiator, a thioxanthone-based photopolymerization initiator having a thioxanthone skeleton, a benzophenone-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, and an acyl phosphine oxide-based photopolymerization initiator.

9. The photosensitive resin composition according to claim 1 or 2, further comprising (E) an inorganic filler.

10. The photosensitive resin composition according to claim 1 or 2, wherein the content of (A) the photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent, (B) the curing agent, (C) the photopolymerization initiator, and (D) the photopolymerizable compound is 20 to 80 mass%, 2 to 40 mass%, 0.2 to 15 mass%, and 3 to 7 mass%, respectively, based on the total amount of solid components in the photosensitive resin composition.

11. A dry film having a support film and a photosensitive layer using the photosensitive resin composition according to any one of claims 1 to 10.

12. A printed wiring board provided with a surface protective film or an interlayer insulating layer formed from the photosensitive resin composition according to any one of claims 1 to 10.

13. The printed wiring board according to claim 12, wherein the surface protective film or the interlayer insulating layer has a thickness of 5 μm or more.

14. A method for manufacturing a printed wiring board, comprising, in order, a step of providing a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 10 or the dry film according to claim 11, a step of forming a resist pattern using the photosensitive layer, and a step of curing the resist pattern to form a surface protective film or an interlayer insulating layer.

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