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

Abstract

To provide a photosensitive resin composition which has high adhesion between a low rough copper surface and a photosensitive resin composition, prevents large reduction in adhesion after being charged to a high acceleration life testing device and making it absorb absorption and being degraded, is excellent in resolution, and enables formation of an excellent resist shape pattern, a dry film using the photosensitive resin composition, a printed wiring board, and a method for manufacturing a printed wiring board.SOLUTION: A photosensitive resin composition contains (A) an acid-modified vinyl group-containing epoxy resin, (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a photopolymerizable compound, wherein at least one kind in the component (B) has an epoxy resin having an isocyanuric acid structure. The component (A) preferably contains at least one kind of acid-modified vinyl group-containing epoxy resin (A1) using a bisphenol novolac type epoxy resin (a1), and at least one kind of acid-modified vinyl group-containing epoxy resin (A2) using an epoxy resin (a2) different from the bisphenol novolac type epoxy resin (a1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a dry film using the same, a printed wiring board, and a method for producing a printed wiring board. [Background technology]

[0002] In the field of printed wiring board manufacturing, permanent mask resists are formed on printed wiring boards. The permanent mask resists have the role of preventing corrosion of the conductor layers and maintaining electrical insulation between the conductor layers when the printed wiring board is in use. In recent years, permanent mask resists have also come to function as solder resist films that prevent solder from adhering to unnecessary portions of the conductor layers of the printed wiring board in processes such as flip-chip mounting or wire bonding mounting of semiconductor elements on the printed wiring board via solder.

[0003] Conventionally, permanent mask resists in the manufacture of printed wiring boards are prepared by screen printing using a thermosetting resin composition or by photolithography using a photosensitive resin composition. For example, in flexible wiring boards using mounting methods such as FC (Flip Chip), TAB (Tape Automated Bonding), and COF (Chip On Film), a thermosetting resin paste is screen-printed and thermally cured to form a permanent mask resist, except for IC chips, electronic components or LCD (Liquid Crystal Display) panels, and connecting wiring portions (see, for example, Patent Document 1).

[0004] Furthermore, in semiconductor package substrates such as BGA (Ball Grid Array) and CSP (Chip Size Package) mounted on electronic components, (1) to flip-chip mount a semiconductor element onto the semiconductor package substrate via solder, (2) to wire-bond the semiconductor element to the semiconductor package substrate, or (3) to solder-bond the semiconductor package substrate to a motherboard substrate, it is necessary to remove the permanent mask resist from the bonding area. Therefore, to form this permanent mask resist, a photolithography method is used, in which a photosensitive resin composition is applied and dried, and then selectively irradiated with actinic rays such as ultraviolet light to harden it, and only the unirradiated areas are removed by development to form an image. Photolithography is suitable for mass production due to its ease of operation, and is therefore widely used in the electronic materials industry for forming images of photosensitive resin compositions (see, for example, Patent Document 2).

[0005] In the production of printed wiring boards, the copper surface is roughened with a microetching agent (roughening agent) to improve adhesion between the copper surface and a photosensitive resin composition. Known microetching agents for copper or copper alloys include organic acid microetching agents and inorganic acid microetching agents.

[0006] Generally, when roughening copper wiring using a microetching agent, the greater the etching depth, the more the roughening progresses, forming deeper irregularities and tending to improve adhesion to resins and other materials. On the other hand, when copper wiring is roughened using a microetching agent, thinning occurs as etching progresses, which can lead to problems such as high resistance and wire breakage. As wiring pitches become narrower (fine wiring), the effects of thinning become more pronounced, creating a demand for microetching agents that can achieve high adhesion with a low etching depth. For example, Patent Document 3 discloses a microetching agent containing an organic acid, cupric ions, and halide ions, and describes how it is possible to form a roughened surface with excellent adhesion to resins with an etching depth of 0.4 μm or less (see, for example, Patent Document 3).

[0007] In order to improve the adhesion between metal and resin, methods of forming a roughened surface with a microetching agent and forming a coating (adhesion layer) on the roughened surface to improve adhesion with resin are known. For example, Patent Document 4 discloses that a coating that acts as an adhesion improver is formed by immersing copper in a sulfide-containing solution. Patent Document 5 discloses that a composition containing a specific aromatic compound and a thio compound has excellent film-forming properties on metal surfaces and significantly improves adhesion between metal and resin. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-198105 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-133851 [Patent Document 3] Patent No. 6338232 [Patent Document 4] Japanese Patent Application Laid-Open No. 2000-73181 [Patent Document 5] Patent No. 6387543 Summary of the Invention [Problem to be solved by the invention]

[0009] However, conventional coating compositions for improving adhesion between metal and resin on roughened surfaces may not provide sufficient adhesion between the metal and resin. For example, although initial adhesion may be maintained at a certain level, adhesion between the metal and resin may be significantly reduced after moisture absorption and degradation in a highly accelerated life test (HAST) device. Insufficient adhesion to copper may affect the insulation reliability of the photosensitive resin composition.

[0010] The object of the present disclosure is to provide a photosensitive resin composition that exhibits high adhesion between a photosensitive resin composition and an adhesive layer coating having an adhesion-improving effect formed on a low-roughening copper surface, that is resistant to significant deterioration in adhesion even after being placed in a highly accelerated life testing (HAST) device and subjected to moisture absorption degradation, that has excellent resolution, and that is capable of forming an excellent resist shape pattern, as well as a dry film, a printed wiring board, and a method for manufacturing a printed wiring board using the same. [Means for solving the problem]

[0011] The present inventors have conducted extensive research to solve the above-mentioned problems and have found that the problems can be solved by the following invention: That is, the present disclosure provides the following photosensitive resin composition, a dry film using the same, a printed wiring board, and a method for producing a printed wiring board.

[0012] [1] A photosensitive resin composition comprising (A) an acid-modified vinyl group-containing epoxy resin, (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a photopolymerizable compound, wherein at least one of the components (B) is an epoxy resin having an isocyanuric acid structure. [2] The photosensitive resin composition according to the above [1], wherein the component (A) contains at least one acid-modified vinyl group-containing epoxy resin (A1) obtained using a bisphenol novolac epoxy resin (a1), and at least one acid-modified vinyl group-containing epoxy resin (A2) obtained using an epoxy resin (a2) different from the bisphenol novolac epoxy resin (a1). [3] The photosensitive resin composition according to [2] above, wherein the epoxy resin (a2) is at least one selected from the group consisting of novolac epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, triphenolmethane epoxy resins, and biphenyl epoxy resins. [4] The photosensitive resin composition according to the above [2] or [3], wherein the acid-modified vinyl group-containing epoxy resins (A1) and (A2) are resins obtained by reacting the epoxy resins (a1) and (a2) with a vinyl group-containing monocarboxylic acid (b) to form resins (A1') and (A2'), respectively, with a saturated or unsaturated group-containing polybasic acid anhydride (c). [5] The photosensitive resin composition according to any one of the above [2] to [4], wherein the bisphenol novolac epoxy resin (a1) has a structural unit represented by the following general formula (I) or (II):

[0013] [ka] [In general formula (I), R 11 represents a hydrogen atom or a methyl group, and Y 1 and Y 2 Each of R independently represents a hydrogen atom or a glycidyl group. 11 may be the same or different, and Y 1 and Y 2 At least one of R represents a glycidyl group. 12 represents a hydrogen atom or a methyl group, and Y 3 and Y 4 each independently represents a hydrogen atom or a glycidyl group. Multiple R 12 may be the same or different, and Y 3 and Y 4 At least one of the groups represents a glycidyl group. [6] The photosensitive resin composition according to the above [5], wherein the bisphenol novolac epoxy resin (a1) has a structural unit represented by the general formula (I) and the epoxy resin (a2) is a bisphenol A epoxy resin or a bisphenol F epoxy resin containing a structural unit represented by the following general formula (IV):

[0014] [ka] [In general formula (IV), R 14 represents a hydrogen atom or a methyl group, and Y 6 represents a hydrogen atom or a glycidyl group. 14 may be the same or different. [7] The photosensitive resin composition according to the above [1], wherein the component (A) contains at least one acid-modified vinyl group-containing epoxy resin (A2) obtained by using an epoxy resin (a2) different from the bisphenol novolac epoxy resin (a1). [8] The photosensitive resin composition according to the above item [7], wherein the acid-modified vinyl group-containing epoxy resin (A2) is a resin obtained by reacting the epoxy resin (a2) with a vinyl group-containing monocarboxylic acid (b) to form a resin (A2'), and then reacting the resulting resin with a saturated or unsaturated group-containing polybasic acid anhydride (c). [9] The photosensitive resin composition according to the above [7] or [8], wherein the epoxy resin (a2) is a novolac epoxy resin having a structural unit represented by general formula (III).

[0015] [ka] [In general formula (III), R 13 represents a hydrogen atom or a methyl group, and Y 5 represents a hydrogen atom or a glycidyl group.

[10] The photosensitive resin composition according to any one of the above [1] to [9], wherein the (C) photopolymerization initiator is at least one selected from the group consisting of alkylphenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators having a thioxanthone skeleton, and acylphosphine oxide-based photopolymerization initiators.

[11] The photosensitive resin composition according to any one of the above [1] to

[10] , wherein the (D) photopolymerizable compound is a compound containing a (meth)acryloyl group.

[12] The photosensitive resin composition according to any one of the above [1] to

[11] , further comprising (E) an inorganic filler.

[13] The photosensitive resin composition according to any one of the above [1] to

[12] , further comprising (F) a pigment.

[14] The photosensitive resin composition according to any one of the above [1] to

[13] , wherein the ion scavenger (G) is at least one selected from the group consisting of inorganic ion exchangers that capture cations, inorganic ion exchangers that capture anions, and inorganic ion exchangers that capture cations and anions.

[15] The photosensitive resin composition according to the above

[14] , wherein the contents of the (A) acid-modified vinyl group-containing epoxy resin, (C) photopolymerization initiator, (D) photopolymerizable compound, and (G) ion scavenger are, based on the total amount of solids in the photosensitive resin composition, (A) 20 to 80 mass%, (C) 0.2 to 15 mass%, (D) 0.1 to 10 mass%, and (G) 0.1 to 10 mass%, respectively.

[16] A dry film comprising a carrier film and a photosensitive layer using the photosensitive resin composition according to any one of the above [1] to

[15] .

[17] A printed wiring board comprising a permanent mask resist formed from the photosensitive resin composition according to any one of the above [1] to

[15] .

[18] The printed wiring board according to

[17] above, wherein the thickness of the permanent mask resist is 5 μm or more.

[19] A method for producing a printed wiring board, comprising the steps of providing a photosensitive layer on a substrate using the photosensitive resin composition according to any one of [1] to

[15] above or the dry film according to

[16] above, forming a resist pattern using the photosensitive layer, and curing the resist pattern to form a permanent mask resist, in that order. [Effects of the Invention]

[0016] According to the present disclosure, it is possible to provide a photosensitive resin composition that has high adhesion between an adhesive layer coating formed on a low-roughening copper surface and the photosensitive resin composition, that is resistant to significant deterioration in adhesion even after being placed in a highly accelerated life testing (HAST) device and subjected to moisture absorption degradation, that has excellent resolution, and that can form an excellent resist shape pattern, as well as a dry film, a printed wiring board, and a method for manufacturing a printed wiring board using the same. [Brief explanation of the drawings]

[0017] [Figure 1] 1 is a schematic diagram showing a resist cross-sectional shape with excellent linearity of the resist pattern contour. FIG. [Figure 2] 1 is a schematic diagram showing a resist cross-sectional shape in which the resist pattern contour has poor linearity. DETAILED DESCRIPTION OF THE INVENTION

[0018] [Photosensitive resin composition] A photosensitive resin composition according to an embodiment of the present disclosure (hereinafter, may be simply referred to as the present embodiment) is a photosensitive resin composition containing (A) an acid-modified vinyl group-containing epoxy resin, (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a photopolymerizable compound, wherein at least one of the components (B) is an epoxy resin having an isocyanuric acid structure. In this specification, these components may be simply referred to as component (A), component (B), component (C), etc. In this specification, the term "solid content" refers to the non-volatile content excluding volatile substances such as water and solvent contained in the photosensitive resin composition, and indicates components that remain without volatilization when the resin composition is dried, and also includes those that are liquid, syrup-like, or waxy at room temperature around 25°C. Each component is described below. In this specification, "(meth)acrylate" means "acrylate" and the corresponding "methacrylate." Similarly, "(meth)acrylic" means "acrylic" and the corresponding "methacrylic," "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid," and "(meth)acryloyl" means "acryloyl" and the corresponding "methacryloyl." Furthermore, "(meth)acrylic acid alkyl ester" means "acrylic acid alkyl ester" and the corresponding "methacrylic acid alkyl ester."

[0019] <(A) Acid-modified vinyl group-containing epoxy resin> The photosensitive resin composition of this embodiment contains an acid-modified vinyl group-containing epoxy resin as component (A). Component (A) is a compound obtained by modifying an epoxy resin with a vinyl group-containing organic acid, such as an epoxy resin obtained by reacting a resin obtained by reacting an epoxy resin with a vinyl group-containing monocarboxylic acid with a saturated or unsaturated group-containing polybasic acid anhydride.

[0020] Examples of component (A) include an acid-modified vinyl-group-containing epoxy resin (A1) (hereinafter sometimes referred to as component (A1)) made using a bisphenol novolac epoxy resin (a1) (hereinafter sometimes referred to as component (a1)), and an epoxy resin (a2) (hereinafter sometimes referred to as component (a2)) other than the epoxy resin (a1). These can be used alone or in combination of two or more. Furthermore, from the viewpoint of improving adhesion strength in particular, component (A) may contain at least one type of component (A1) made using component (a1) and one type of component (A2) made using component (a2).

[0021] (Bisphenol novolac epoxy resin (a1)) From the viewpoints of reducing the occurrence of undercuts in the resist shape [see left in Figure 2] and improving adhesion to the copper substrate, as well as reducing warpage of the thin film substrate (warpage reduction), and improving thermal shock resistance and resolution, it is preferable for the component (A) to contain the component (A1) obtained using the component (a1). From the same viewpoints, the component (a1) is preferably a bisphenol novolac epoxy resin having a structural unit represented by the following general formula (I) or (II), and more preferably a bisphenol novolac epoxy resin having a structural unit represented by the following general formula (II).

[0022] [Epoxy resin having a structural unit represented by general formula (I)] One preferred embodiment of the component (a1) is an epoxy resin having a structural unit represented by the following general formula (I):

[0023] [ka]

[0024] In general formula (I), R 11 represents a hydrogen atom or a methyl group, and Y 1 and Y 2 Each of R independently represents a hydrogen atom or a glycidyl group. 11 may be the same or different, and Y 1 and Y 2 At least one of these groups represents a glycidyl group.

[0025] R 11 is preferably a hydrogen atom, from the viewpoint of preventing undercuts and improving the linearity and resolution of the resist pattern contour. From the same viewpoint, and also from the viewpoint of improving thermal shock resistance and warpage reduction, Y 1 and Y 2 are preferably all glycidyl groups.

[0026] The number of structural units in component (a1) having a structural unit represented by general formula (I) is 1 or more, and may be appropriately selected from 10 to 100, 15 to 80, or 15 to 70. When the number of structural units is within the above range, a resist shape with improved linearity of the resist pattern contour can be formed, and adhesion to the copper substrate, heat resistance, and electrical insulation are improved. Here, the number of structural units in a structural unit represents an integer value in a single molecule, and represents a rational number that is an average value in an aggregate of multiple types of molecules. The same applies to the number of structural units in the following structural units.

[0027] [Epoxy resin having a structural unit represented by general formula (II)] One preferred embodiment of the component (a1) is an epoxy resin having a structural unit represented by the following general formula (II):

[0028] [ka]

[0029] In general formula (II), R12 represents a hydrogen atom or a methyl group, and Y 3 and Y 4 Each of R independently represents a hydrogen atom or a glycidyl group. 12 may be the same or different, and Y 3 and Y 4 At least one of these groups represents a glycidyl group.

[0030] R 12 is preferably a hydrogen atom, from the viewpoint of preventing undercuts and improving the linearity and resolution of the resist pattern contour. From the same viewpoint, and also from the viewpoint of improving thermal shock resistance and warpage reduction, Y 3 and Y 4 are preferably all glycidyl groups.

[0031] The number of structural units in the component (a1) having the structural unit represented by general formula (II) is 1 or more, and may be appropriately selected from 10 to 100, 15 to 80, or 15 to 70. When the number of structural units is within the above range, a resist shape with improved linearity of the resist pattern contour can be formed, and adhesion to a copper substrate and heat resistance are improved.

[0032] In general formula (II), R 12 is a hydrogen atom, and Y 3 and Y 4 The glycidyl group is available as the EXA-7376 series (manufactured by DIC Corporation), and R 12 is a methyl group, and Y 3 and Y 4 Those having a glycidyl group are commercially available as the EPON SU8 series (trade name, manufactured by Mitsubishi Chemical Corporation).

[0033] (Epoxy resin (a2)) There are no particular restrictions on the component (a2), so long as it is an epoxy resin different from the bisphenol novolac epoxy resin component (a1). However, from the viewpoints of reducing undercutting and improving the linearity of the resist pattern contour, adhesion to the copper substrate, and resolution, it is preferable for the component (a2) to be at least one type selected from the group consisting of novolac epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, triphenolmethane epoxy resins, and biphenyl epoxy resins. Preferred examples of novolac-type epoxy resins include those having a structural unit represented by the following general formula (III), preferred examples of bisphenol A-type epoxy resins or bisphenol F-type epoxy resins include those having a structural unit represented by the following general formula (IV), and preferred examples of triphenolmethane-type epoxy resins include those having a structural unit represented by the following general formula (V). Preferred examples of biphenyl-type epoxy resins include those having a structural unit represented by the following general formula (VI).

[0034] The component (a2) is more preferably at least one selected from a novolac epoxy resin having a structural unit represented by general formula (III), a bisphenol A epoxy resin having a structural unit represented by general formula (IV), and a bisphenol F epoxy resin, and as for the resin having a structural unit represented by general formula (IV), a bisphenol F epoxy resin is preferred. From the viewpoint of achieving both photosensitive properties and insulating reliability, it is preferable to use no component (A1) containing component (a1) and to use a novolac epoxy resin (a2) having a structural unit represented by general formula (III). Furthermore, from the viewpoint of improving thermal shock resistance, warpage reduction, and resolution, a particularly preferred combination is one in which component (a1) is a bisphenol novolac epoxy resin containing a structural unit represented by general formula (II), and component (a2) is a bisphenol A epoxy resin or bisphenol F epoxy resin containing a structural unit represented by general formula (IV). Here, "without component (A1)" means that component (A1) is substantially absent, and indicates that the content of component (A1) is less than 5%, less than 1%, or less than 0.5% by mass of the total solids content of component (A).

[0035] [Epoxy resin having a structural unit represented by general formula (III)] The component (a2) is preferably a novolac epoxy resin having a structural unit represented by the following general formula (III). An example of a novolac epoxy resin having such a structural unit is a novolac epoxy resin represented by the following general formula (III').

[0036] [ka]

[0037] In the general formulas (III) and (III'), R 13 represents a hydrogen atom or a methyl group, and Y 5 represents a hydrogen atom or a glycidyl group. In general formula (III'), n1 is a number of 1 or more, and a plurality of R 13 and Y 5 may be the same or different, and Y 5 At least one of these groups represents a glycidyl group.

[0038] R 13 is preferably a hydrogen atom, from the viewpoint of making undercut less likely to occur and improving the linearity and resolution of the resist pattern contour. Y 5 represents a hydrogen atom in the general formula (III'). 5 and a glycidyl group, Y 5 The molar ratio of Y to Y may be appropriately selected from the range of 0 / 100 to 30 / 70 or 0 / 100 to 10 / 90 from the viewpoint of preventing undercut and improving the linearity and resolution of the resist pattern contour. 5 At least one of the groups is a glycidyl group.

[0039] n1 is a number of 1 or more, and may be appropriately selected from 10 to 200, 30 to 150, or 30 to 100. When n1 is within the above range, a resist shape with improved linearity of the resist pattern contour can be formed, and adhesion to a copper substrate and heat resistance are improved.

[0040] Examples of the novolac epoxy resin represented by general formula (III') include phenol novolac epoxy resin and cresol novolac epoxy resin. These novolac epoxy resins can be obtained, for example, by reacting a phenol novolac resin or a cresol novolac resin with epichlorohydrin using a known method.

[0041] Examples of the phenol novolac epoxy resin or cresol novolac epoxy resin represented by general formula (III') include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (all of which are trade names manufactured by Nippon Steel Chemical & Material Co., Ltd.), DEN-431, DEN-439 (all of which are trade names manufactured by The Dow Chemical Company), EOCN-120, EOCN- Commercially available examples include EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, and BREN (all of which are trade names manufactured by Nippon Kayaku Co., Ltd.), EPN-1138, EPN-1235, and EPN-1299 (all of which are trade names manufactured by BASF), and N-730, N-770, N-865, N-665, N-673, VH-4150, and VH-4240 (all of which are trade names manufactured by DIC Corporation).

[0042] [Epoxy resin having a structural unit represented by general formula (IV)] The component (a2) is preferably a bisphenol A type epoxy resin or a bisphenol F type epoxy resin having a structural unit represented by the following general formula (IV). Examples of epoxy resins having such a structural unit include a bisphenol A type epoxy resin or a bisphenol F type epoxy resin represented by the general formula (IV').

[0043] [ka]

[0044] In the general formulas (IV) and (IV'), R 14 represents a hydrogen atom or a methyl group, and Y 6 represents a hydrogen atom or a glycidyl group. 14 may be the same or different, and in the general formula (IV'), n2 represents a number of 1 or more, and when n2 is 2 or more, a plurality of Y 6 may be the same or different, and at least one Y 6 is a glycidyl group.

[0045] R 14 is preferably a hydrogen atom, from the viewpoint of making undercut less likely to occur and improving the linearity and resolution of the resist pattern contour. From the same viewpoint, and also from the viewpoint of improving thermal shock resistance and warpage reduction, Y 6 is preferably a glycidyl group.

[0046] n2 is a number of 1 or more, and may be appropriately selected from 10 to 100, 10 to 80, or 15 to 60. When n2 is within the above range, a resist shape with improved linearity of the resist pattern contour can be formed, and adhesion to a copper substrate and heat resistance are improved.

[0047] Represented by general formula (IV), Y 6The bisphenol A type epoxy resin or bisphenol F type epoxy resin in which Y is a glycidyl group is represented by, for example, the general formula (IV), 6 is a hydrogen atom of the hydroxyl group (-OY 6 ) with epichlorohydrin.

[0048] To promote the reaction between hydroxyl groups and epichlorohydrin, the reaction is preferably carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide, or dimethylsulfoxide in the presence of an alkali metal hydroxide at a reaction temperature of 50 to 120° C. When the reaction temperature is within the above range, the reaction does not slow down too much, and side reactions can be suppressed.

[0049] Commercially available examples of the bisphenol A epoxy resin or bisphenol F epoxy resin represented by general formula (IV') include jER807, jER815, jER825, jER827, jER828, jER834, jER1001, jER1004, jER1007, and jER1009 (all of which are product names manufactured by Mitsubishi Chemical Corporation), DER-330, DER-301, and DER-361 (all of which are product names manufactured by The Dow Chemical Company), YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004, and YDF-8170 (all of which are product names manufactured by Nippon Steel Chemical & Material Co., Ltd.).

[0050] [Epoxy resin having a structural unit represented by general formula (V)] Preferred examples of the component (a2) include triphenolmethane-type epoxy resins having a structural unit represented by the following general formula (V). Preferred examples of triphenolmethane-type epoxy resins having such a structural unit include triphenolmethane-type epoxy resins represented by the general formula (V').

[0051] [ka]

[0052] In the general formulas (V) and (V'), Y 7 represents a hydrogen atom or a glycidyl group, and a plurality of Y 7 may be the same or different, and at least one Y 7 is a glycidyl group. In general formula (V'), n3 is a number of 1 or more.

[0053] Y 7 is a hydrogen atom Y 7 and a glycidyl group, Y 7 The molar ratio of Y to Y may be appropriately selected from the range of 0 / 100 to 30 / 70 in order to prevent undercutting and loss of the upper part of the resist and to improve the linearity and resolution of the resist pattern contour. 7 At least one of the groups is a glycidyl group. n3 is a number of 1 or more, and may be appropriately selected from 10 to 100, 15 to 80, or 15 to 70. When n3 is within the above range, a resist shape with improved linearity of the resist pattern contour can be formed, and adhesion to a copper substrate and heat resistance are improved.

[0054] As the triphenolmethane type epoxy resin represented by the general formula (V'), for example, FAE-2500, EPPN-501H, EPPN-502H (all of which are trade names manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.

[0055] [Epoxy resin having a structural unit represented by general formula (VI)] The biphenyl-type epoxy resin is preferably at least one selected from biphenyl-type epoxy resins having a structural unit represented by the following general formula (VI), and an example of an epoxy resin having such a structural unit is a biphenyl-type epoxy resin represented by the general formula (VI').

[0056] [ka] [In the general formulas (VI) and (VI'), Y8 represents a hydrogen atom or a glycidyl group. In general formula (VI'), n4 represents a number of 1 or more, and when n4 is 2 or more, a plurality of Y 8 may be the same or different, and at least one Y 8 is a glycidyl group.

[0057] As biphenyl-type epoxy resins represented by general formula (VI'), for example, NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L (all of which are trade names manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.

[0058] From the viewpoint of improving the linearity and resolution of the resist pattern contour, the components (A1) and (A2) are preferably resins obtained by reacting the components (a1) and (a2) (hereinafter sometimes referred to as "component (a)") with a vinyl group-containing monocarboxylic acid (b) (hereinafter sometimes referred to as component (b)), to obtain resins (A1') and (A2') (hereinafter sometimes collectively referred to as "component (A')"), and then reacting these resins with a saturated or unsaturated group-containing polybasic acid anhydride (c) (hereinafter sometimes referred to as component (c)).

[0059] [Vinyl group-containing monocarboxylic acid (b)] Preferred examples of component (b) include acrylic acid, acrylic acid dimers, methacrylic acid, acrylic acid derivatives such as β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and α-cyanocinnamic acid, half-ester compounds which are reaction products of hydroxyl group-containing acrylates and dibasic acid anhydrides, and half-ester compounds which are reaction products of vinyl group-containing monoglycidyl ethers or vinyl group-containing monoglycidyl esters and dibasic acid anhydrides.

[0060] The half-ester compound can be obtained, for example, by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether, or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride in an equimolar ratio. These components (b) can be used alone or in combination.

[0061] Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the above-mentioned half-ester compound, which is an example of component (b), include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, glycidyl acrylate, and glycidyl methacrylate.

[0062] The dibasic acid anhydride used in the synthesis of the above-mentioned half ester compound may be one containing a saturated group or one containing an unsaturated group. Specific examples of the dibasic acid anhydride include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.

[0063] In the reaction of the above component (a) (component (a1) or component (a2)) with component (b), the reaction is preferably carried out in a ratio of 0.6 to 1.05 equivalents, and more preferably 0.8 to 1.0 equivalents, of component (b) per equivalent of epoxy groups in component (a). Reaction at such a ratio improves photopolymerizability, i.e., photosensitivity, and therefore improves the linearity of the resist pattern contour.

[0064] The components (a) and (b) can be reacted by dissolving them in an organic solvent. Preferred examples of the organic solvent 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 solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

[0065] Furthermore, it is preferable to use a catalyst to promote the reaction between component (a) and component (b), such as triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, or triphenylphosphine. The amount of catalyst used may be appropriately selected from 0.01 to 10 parts by mass, 0.05 to 2 parts by mass, or 0.1 to 1 part by mass relative to 100 parts by mass of the total of components (a) and (b). When used in the above amount, the reaction between components (a) and (b) is promoted.

[0066] In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor, such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, or pyrogallol. The amount of the polymerization inhibitor used may be appropriately selected from 0.01 to 1 part by mass, 0.02 to 0.8 parts by mass, or 0.04 to 0.5 parts by mass relative to 100 parts by mass of the total of the components (a) and (b) from the viewpoint of improving the storage stability of the composition.

[0067] The reaction temperature between the components (a) and (b) may be appropriately selected from 60 to 150°C, 80 to 120°C, or 90 to 110°C from the viewpoint of productivity.

[0068] In this way, it is presumed that component (A'), which is obtained by reacting component (a) with component (b), has a hydroxyl group formed by a ring-opening addition reaction between the epoxy group of component (a) and the carboxyl group of component (b). It is presumed that by further reacting the component (A') obtained above with the component (c) containing a saturated or unsaturated group, the hydroxyl groups of component (A') (including the hydroxyl groups originally present in component (a)) and the acid anhydride groups of component (c) are semi-esterified to form an acid-modified vinyl group-containing epoxy resin.

[0069] [Saturated or unsaturated group-containing polybasic acid anhydride (c)] As the component (c), those containing a saturated group or those containing an unsaturated group can be used. Specific examples of the component (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride. Among these, tetrahydrophthalic anhydride is preferred from the viewpoint of obtaining a photosensitive resin composition capable of forming a pattern with excellent resolution.

[0070] In the reaction between component (A') and component (c), for example, the acid value of the acid-modified vinyl group-containing epoxy resin can be adjusted by reacting 0.1 to 1.0 equivalents of component (c) with 1 equivalent of hydroxyl groups in component (A').

[0071] The acid value of component (A) may be 30 to 150 mgKOH / g, 40 to 120 mgKOH / g, or 50 to 100 mgKOH / g. When the acid value is 30 mgKOH / g or more, the solubility of the photosensitive resin composition in a dilute alkaline solution is excellent, and when it is 150 mgKOH / g or less, the electrical properties of the cured film are improved.

[0072] The reaction temperature between the component (A') and the component (c) may be appropriately selected from 50 to 150°C, 60 to 120°C, or 70 to 100°C from the viewpoint of productivity.

[0073] If necessary, component (a) may also contain, for example, a hydrogenated bisphenol A epoxy resin. Furthermore, component (A) may also contain, for example, a styrene-maleic acid resin such as a hydroxyethyl (meth)acrylate-modified styrene-maleic anhydride copolymer.

[0074] (Molecular weight of component (A)) The weight-average molecular weight of component (A) may be 3,000 to 30,000, 4,000 to 25,000, or 5,000 to 18,000. Within these ranges, a resist profile with improved linearity of the resist pattern contour can be formed, and adhesion to the copper substrate, heat resistance, and electrical insulation are improved. Here, the weight-average molecular weight is the weight-average molecular weight converted into polystyrene, measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. More specifically, for example, the weight-average molecular weight can be determined by measuring using the GPC measurement device and measurement conditions described below, and converting the value using a calibration curve of standard polystyrene. The calibration curve was also prepared using a five-sample set ("PStQuick MP-H" and "PStQuick B," manufactured by Tosoh Corporation) as standard polystyrene. (GPC measurement device) GPC equipment: High-speed GPC equipment "HCL-8320GPC", detector is differential refractometer or UV detector, manufactured by Tosoh Corporation Column: TSKgel SuperMultipore HZ-H column (column length: 15 cm, column inner diameter: 4.6 mm), manufactured by Tosoh Corporation (Measurement conditions) Solvent: tetrahydrofuran (THF) Measurement temperature: 40℃ Flow rate: 0.35ml / min Sample concentration: 10mg / THF5ml Injection volume: 20μl

[0075] (Content of component (A)) The content of component (A) may be appropriately selected from 20 to 80 mass%, 30 to 70 mass%, or 30 to 50 mass%, based on the total solid content of the photosensitive resin composition, from the viewpoint of improving the heat resistance, electrical properties, and chemical resistance of the coating film. In this specification, the term "solid content" refers to the non-volatile content excluding volatile substances such as water and diluents contained in the photosensitive resin composition, and indicates components that remain without evaporating or vaporizing when the resin composition is dried, and also includes liquid, starch syrup-like, and wax-like substances at room temperature around 25°C.

[0076] (Total content of components (A1) and (A2) in component (A)) When component (A) is a combination of components (A1) and (A2), the total content of components (A1) and (A2) in component (A) can be appropriately selected from 80 to 100 mass%, 90 to 100 mass%, 95 to 100 mass%, or 100 mass%, from the viewpoints of forming a resist shape with improved linearity of the resist pattern contour and improving electroless plating resistance and solder heat resistance. When component (A1) or component (A2) is used alone, the total content can also be appropriately selected from the above ranges.

[0077] (mass ratio of component (A1) to component (A2)) When the component (A1) and the component (A2) are used in combination as the component (A), the mass ratio (A1 / A2) can be appropriately selected from 20 / 80 to 90 / 10, 20 / 80 to 80 / 20, 30 / 70 to 70 / 30, 30 / 70 to 55 / 45, or 30 / 70 to 50 / 50 from the viewpoints of forming a resist shape with improved linearity of the resist pattern contour and improving electroless plating resistance and solder heat resistance.

[0078] <(B) Epoxy resin> In this embodiment, at least one of the epoxy resins used as component (B) must have an isocyanuric acid structure. However, when multiple epoxy resins are used, epoxy resins other than the epoxy resin having an isocyanuric acid structure can also be used in addition to the epoxy resin having an isocyanuric acid structure. For example, the epoxy resins listed above as component (a) can be used.

[0079] The (B) component may be used alone or in combination. The content may be appropriately selected from 2 to 40 mass%, 3 to 30 mass%, or 5 to 20 mass%, based on the total solid content of the photosensitive resin composition. Of these, the content of the epoxy resin having an isocyanuric acid structure is preferably 5 to 15 mass%, based on the total solid content of the photosensitive resin composition. By keeping the content within this range, good developability is maintained while further improving the heat resistance of the formed cured film. This enhances the adhesion between the photosensitive resin composition and the adhesion-improving adhesive layer coating formed on the low-roughening copper surface, and also makes it less likely to experience a significant decrease in adhesion after moisture absorption degradation in a highly accelerated life testing (HAST) device. As the epoxy resin having an isocyanuric acid structure, TEPIC-FL (trade name, manufactured by Nissan Chemical Industries, Ltd.), which is a trifunctional epoxy compound having an isocyanuric acid skeleton, can be used.

[0080] <(C) Photopolymerization initiator> The component (C) used in this embodiment is not particularly limited as long as it can polymerize the photopolymerizable compound of the component (D), and can be appropriately selected from commonly used photopolymerization initiators. Examples of the component (C) include benzoins 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-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-mol Acetophenones such as 1-propanone and N,N-dimethylaminoacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; thioxanthones having a thioxanthone skeleton such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone (thioxanthone-based photopolymerization initiators); ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzophenones such as benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, Michler's ketone and 4-benzoyl-4'-methyldiphenyl sulfide; acridines such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; 2,4,6-trimethylbenzoyl Examples of the component (C) include acylphosphine oxides (acylphosphine oxide photopolymerization initiators) such as diphenylphosphine oxide; and oxime esters such as 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime), and 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime]. These component (C) can be used alone or in combination of two or more.

[0081] The (C) photopolymerization initiator is preferably at least one selected from the group consisting of alkylphenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators having a thioxanthone skeleton, and acylphosphine oxide-based photopolymerization initiators. Examples of the alkylphenone photopolymerization initiator include benzil ketal, α-hydroxyalkylphenone, α-hydroxyacetophenone, and α-aminoalkylphenone. Among these, from the viewpoint of improving the curing property of the bottom portion by photobleaching, it is possible to appropriately select from the above-mentioned acylphosphine oxides, and from the viewpoint of being less likely to volatilize and to be less likely to be generated as outgassing, it is possible to appropriately select from the above-mentioned acetophenones.

[0082] ((C) Component Content) The content of component (C) may be appropriately selected from 0.2 to 15 mass%, 0.4 to 5 mass%, or 0.6 to 1 mass%, based on the total solid content of the photosensitive resin composition. If the content of component (C) is 0.2 mass% or more, the exposed area tends to be less likely to dissolve during development, and if it is 15.0 mass% or less, heat resistance is improved.

[0083] In addition to the component (C) described above, (C') photopolymerization initiation aids such as tertiary amines such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine can also be used alone or in combination.

[0084] <(D) Photopolymerizable compound> The component (D) is not particularly limited as long as it is a photopolymerizable or photocrosslinkable compound, and preferred examples thereof include compounds having a functional group that exhibits photopolymerizability, such as a vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadimide group, or (meth)acryloyl group, which has an ethylenically unsaturated bond.

[0085] From the viewpoint of photosensitivity, the component (D) is preferably a compound having a molecular weight of 1,000 or less, and examples thereof include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; glycol mono- or di(meth)acrylates such as ethylene glycol, methoxytetraethylene glycol, and polyethylene glycol; (meth)acrylamides such as N,N-dimethyl (meth)acrylamide and N-methylol (meth)acrylamide; aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate; hexanediol, trimethylolpropane, and pentaerythritol. Preferred examples of the component (D) include polyhydric alcohols such as ditrimethylolpropane, dipentaerythritol, and tris-hydroxyethyl isocyanurate, or polyhydric (meth)acrylates of these ethylene oxide or propylene oxide adducts; (meth)acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth)acrylate and polyethoxydi(meth)acrylate of bisphenol A; (meth)acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and melamine (meth)acrylate. These component (D) can be used alone or in combination of two or more. From the viewpoint of improving sensitivity, the ink may contain polyhydric (meth)acrylates of the above polyhydric alcohols or their ethylene oxide or propylene oxide adducts.

[0086] Furthermore, in order to increase the crosslink density upon photocuring and improve heat resistance and electrical reliability, a compound having three or more ethylenically unsaturated bonds in the molecule can be selected as component (D). Examples of such compounds include the polyvalent (meth)acrylates mentioned above, and dipentaerythritol tri(meth)acrylate can be selected from the viewpoint of improving sensitivity.

[0087] ((D) Component Content) The content of component (D) may be appropriately selected from 0.1 to 50 mass%, 0.1 to 20 mass%, or 0.1 to 10 mass%, based on the total solid content in the photosensitive resin composition. When the content of component (D) is 0.1 mass% or more, photosensitivity is improved and exposed areas tend to be less susceptible to elution during development, while when it is 50 mass% or less, heat resistance is improved.

[0088] <(E) Inorganic filler> The photosensitive resin composition of the present embodiment may contain component (E) mainly for the purpose of further improving various properties such as adhesive strength and coating hardness. Examples of the component (E) include silica (SiO2), alumina (Al2O3), titania (TiO2), tantalum oxide (Ta2O5), zirconia (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), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga2O3), spinel (MgO·Al2O3), magnesium hydroxide (Mg(OH)2), lead zirconate titanate (PbO·TiO2), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga2O3), spinel (MgO·Al2O3), magnesium hydroxide (Mg(OH)2), lead zirconate titanate (PbO·TiO2), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga2O3), gallium nitride (Ga2O3), gallium carbide ... Examples of inorganic fillers that can be used include zirconia (Y2O3·ZrO2), zirconia 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, and carbon (C). These inorganic fillers can be used alone or in combination.

[0089] The average particle size of component (E) may be appropriately selected from 0.01 to 5 μm, 0.1 to 3 μm, or 0.1 to 2 μm from the viewpoint of resolution. Here, the average particle size of component (E) refers to the average particle size of the inorganic filler dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows. First, the photosensitive resin composition is diluted (or dissolved) 1000 times with methyl ethyl ketone, and then particles dispersed in the solvent are measured using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., product name: N5) in accordance with the international standard ISO 13321 at a refractive index of 1.38. The particle size at 50% cumulative (volume basis) in the particle size distribution is defined as the average particle size. Furthermore, component (E) contained in the photosensitive layer or cured film of the photosensitive resin composition provided on the carrier film can also be measured using the submicron particle analyzer after diluting (or dissolving) the composition 1000 times (volume ratio) with a solvent as described above.

[0090] Among the (E) components, silica may be included from the viewpoint of improving heat resistance, barium sulfate may be included from the viewpoint of improving heat resistance and adhesive strength, or a combination of silica and barium sulfate may be included. Furthermore, the inorganic filler may be appropriately selected from those whose surface has been previously treated with alumina or an organic silane compound from the viewpoint of improving the dispersibility of the inorganic filler in the resin composition by the effect of preventing aggregation.

[0091] The elemental composition of aluminum on the surface of an inorganic filler surface-treated with alumina or an organosilane compound may be appropriately selected from 0.5 to 10 atomic %, 1 to 5 atomic %, or 1.5 to 3.5 atomic %. The elemental composition of silicon on the surface of the inorganic filler may be appropriately selected from 0.5 to 10 atomic %, 1 to 5 atomic %, or 1.5 to 3.5 atomic %. The elemental composition of carbon on the surface of the inorganic filler may be appropriately selected from 10 to 30 atomic %, 15 to 25 atomic %, or 18 to 23 atomic %. These elemental compositions can be measured using XPS (X-ray photoelectric spectroscopy).

[0092] As an inorganic filler whose surface is treated with alumina or an organic silane compound, for example, barium sulfate whose surface is treated with alumina or an organic silane compound is commercially available as NanoFine BFN40DC (trade name, manufactured by Nippon Solvay Co., Ltd.).

[0093] (Content of component (E)) The content of component (E) is 20 to 70 mass% based on the total solid content of the photosensitive resin composition. The content of component (E) may be appropriately selected from 20 to 70 mass%, 25 to 65 mass%, or 28 to 60 mass%. When the content of component (E) is within the above range, the strength, heat resistance, resolution, etc. of the cured product of the photosensitive resin composition can be improved.

[0094] When silica is used as component (E), the content of silica may be appropriately selected from 5 to 60 mass%, 10 to 55 mass%, or 15 to 50 mass%, based on the total solid content of the photosensitive resin composition. When barium sulfate is used as component (E), the content of barium sulfate may be appropriately selected from 5 to 30 mass%, 5 to 25 mass%, or 10 to 20 mass%, based on the total solid content of the photosensitive resin composition. When the contents of silica and barium sulfate are within the above ranges, a low coefficient of thermal expansion, solder heat resistance, and adhesive strength can be improved.

[0095] <(F) Pigment> The photosensitive resin composition of this embodiment may further contain component (F) depending on the desired color to improve the appearance by concealing the conductor pattern, etc. As component (F), a colorant that produces the desired color may be appropriately selected and used, and preferred examples include known colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black.

[0096] ((F) Component Content) The content of the component (F) may be appropriately selected from 0.01 to 5 mass%, 0.03 to 3 mass%, or 0.05 to 2 mass%, based on the total amount of solids in the photosensitive resin composition, from the viewpoints of making the production equipment easier to identify and further concealing the conductive pattern.

[0097] <(G) Ion scavenger> The component (G) used in this embodiment is an ion trapping agent containing at least one selected from the group consisting of Zr (zirconium), Bi (bismuth), Mg (magnesium), and Al (aluminum). The term "ion trapping agent" is not particularly limited as long as it is capable of trapping ions in the ion trapping agent and has the function of trapping at least one of cations and anions. In other words, it can also be called a compound with ion trapping function. By containing the component (G) having such a function, it is possible to form a resist pattern with an excellent resist shape. Furthermore, adhesion and flowability tend to be improved. Furthermore, by containing the component (G), it is possible to trap and inactivate ions that affect reliability, which is thought to contribute to improving reliability, etc. The ions to be trapped in this embodiment are, for example, sodium ions (Na + ), chloride ions (Cl - ), bromide ion (Br - ), copper ions (Cu + , Cu 2+ ) and other ions, and by capturing these ions, This improves electrical insulation and electrolytic corrosion resistance. Examples of such ion trapping agents include cation trapping agents that trap cations, anion trapping agents that trap anions, and ion trapping agents that trap both cations and anions.

[0098] (cation scavenger) Examples of cation scavengers that capture cations include inorganic ion exchangers such as metal oxides, such as zirconium phosphate, zirconium tungstate, zirconium molybdate, zirconium tungstate, zirconium antimonate, zirconium selenate, zirconium tellurite, zirconium silicate, zirconium phosphosilicate, and zirconium polyphosphate. Examples of these cation scavengers (which may also be referred to as "inorganic ion exchangers") that can be used include IXE-100 (Zr-containing compound) and IXE-150 (Zr-containing compound), both of which are commercially available from Toagosei Co., Ltd.

[0099] (anion scavenger) Examples of anion scavengers that capture anions include inorganic ion exchangers such as bismuth oxide hydrate and hydrotalcites. Examples of these anion scavengers (also referred to as "inorganic ion exchangers") include IXE-500 (a Bi-containing compound), IXE-530 (a Bi-containing compound), IXE-550 (a Bi-containing compound), IXE-700 (a Mg- and Al-containing compound), IXE-700F (a Mg- and Al-containing compound), IXE-770D (a Mg- and Al-containing compound), IXE-702 (an Al-containing compound), and IXE-800 (a Zr-containing compound), all of which are commercially available from Toagosei Co., Ltd.

[0100] (Ampholytic ion trapping agent) Examples of ion scavengers that capture both cations and anions include inorganic ion exchangers such as metal hydroxides, such as aluminum oxide hydrate and zirconium oxide hydrate. Examples of these ion scavengers (also referred to as "inorganic ion exchangers") include IXE-1320 (a Mg- and Al-containing compound), IXE-600 (a Bi-containing compound), IXE-633 (a Bi-containing compound), IXE-680 (a Bi-containing compound), IXE-6107 (a Zr- and Bi-containing compound), IXE-6136 (a Zr- and Bi-containing compound), IXEPLAS-A1 (a Zr-, Mg-, and Al-containing compound), IXEPLAS-A2 (a Zr-, Mg-, and Al-containing compound), and IXEPLAS-B1 (a Zr- and Bi-containing compound), all of which are commercially available from Toagosei Co., Ltd.

[0101] In this embodiment, the component (G) may be the cation scavenger, the anion scavenger, or both of the cation scavenger and the anion scavenger, either alone or in combination. + , Cl - , Br - , Cu + , Cu 2+ In consideration of simultaneously capturing cations and anions such as those mentioned above, a cation scavenger and an anion scavenger are used in combination, or both ion scavenger agents are used, It is preferable to use both ion trapping agents in combination with at least one of a cation trapping agent and an anion trapping agent.

[0102] Component (G) can be in granular form, and its average particle size may be appropriately selected from 5 μm or less, 3 μm or less, or 2 μm or less to improve insulation properties. Here, the average particle size of component (G) refers to the particle size of particles dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows. First, the photosensitive resin composition is diluted (or dissolved) 1000 times with methyl ethyl ketone, and then the particles dispersed in the solvent are measured using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., product name: N5) in accordance with the international standard ISO 13321 at a refractive index of 1.38. The particle size at 50% cumulative (volume basis) in the particle size distribution is defined as the average particle size. Furthermore, the average particle size of component (G) contained in the photosensitive layer or cured film of the photosensitive resin composition provided on the carrier film is also a value measured using the submicron particle analyzer after diluting (or dissolving) the composition 1000 times (volume ratio) with a solvent as described above.

[0103] The photosensitive resin composition of this embodiment may contain, as an ion scavenger, a compound of a metal atom other than at least one selected from the group consisting of Zr, Bi, Mg, and Al, but from the viewpoint of insulation reliability in particular, the content of the ion scavenger containing at least one selected from the group consisting of Zr, Bi, Mg, and Al may be appropriately selected from 80 mass % or more, 90 mass % or more, or 95 mass % or more based on the total solid content of the ion scavenger, with the upper limit being, for example, 100 parts by mass or less.

[0104] ((G) Component Content) The content of the (G) component may be appropriately selected from 0.1 to 10 mass%, 0.1 to 5 mass%, or 0.1 to 1 mass%, based on the total solid content of the photosensitive resin composition, from the viewpoint of improving electrical insulation properties and electrolytic corrosion resistance.

[0105] <(H) Hardener> The photosensitive resin composition of this embodiment may contain component (H). Examples of component (H) include a compound that cures by itself with heat, ultraviolet light, or the like, or a compound that cures by heat, ultraviolet light, or the like in combination with a carboxyl group or hydroxyl group in components (A) and (D), which are photocurable components in the photosensitive resin composition of this embodiment. Use of a curing agent can improve the heat resistance, adhesion, chemical resistance, and other properties of the final cured film.

[0106] Examples of component (H) include thermosetting compounds such as epoxy compounds, melamine compounds, and oxazoline compounds. Examples of epoxy compounds include bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol A epoxy resins, brominated bisphenol A epoxy resins, novolac epoxy resins, bisphenol S epoxy resins, biphenyl epoxy resins, heterocyclic epoxy resins such as triglycidyl isocyanurate, and bixylenol epoxy resins. Examples of melamine compounds include triaminotriazine, hexamethoxymelamine, hexabutoxylated melamine, etc. Among these, from the viewpoint of further improving the heat resistance of the cured film, it is preferable to contain an epoxy compound (epoxy resin), and it is more preferable to use an epoxy compound in combination with a blocked isocyanate.

[0107] The blocked isocyanate is an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent. Examples of the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, bis(isocyanatomethyl)cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate, as well as adducts, biuret compounds, and isocyanurates thereof.

[0108] The component (H) may be used alone or in combination of two or more. When the component (H) is used, its content may be appropriately selected from 2 to 40 mass%, 3 to 30 mass%, or 5 to 20 mass%, based on the total solid content of the photosensitive resin composition. By keeping the content within the above range, it is possible to further improve the heat resistance of the formed cured film while maintaining good developability.

[0109] The photosensitive resin composition of this embodiment may be used in combination with an epoxy resin curing agent for the purpose of further improving the properties of the final cured film, such as heat resistance, adhesion, and chemical resistance. Specific examples of such 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; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, and polybasic hydrazides; organic acid salts or epoxy adducts thereof; amine complexes of boron trifluoride; and triazine derivatives such as ethyldiamino-s-triazine, 2,4-diamino-s-triazine, and 2,4-diamino-6-xylyl-s-triazine.

[0110] The epoxy resin curing agent can be used alone or in combination of two or more kinds. The content of the epoxy resin curing agent in the photosensitive resin composition may be appropriately selected from 0.01 to 20 mass % or 0.1 to 10 mass % based on the total amount of solids in the photosensitive resin composition from the viewpoint of improving reliability.

[0111] <(I) Elastomer> The photosensitive resin composition of this embodiment can contain component (I). Component (I) is particularly suitable for use when the photosensitive resin composition of this embodiment is used for a semiconductor package substrate. Addition of component (I) can suppress a decrease in flexibility and adhesive strength caused by strain (internal stress) inside the resin due to cure shrinkage of component (A). In other words, the flexibility, adhesive strength, etc. of the cured film formed from the photosensitive resin composition can be improved.

[0112] Examples of component (I) include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and silicone-based elastomers. These elastomers are composed of hard segment components and soft segment components, with the former generally contributing to heat resistance and strength, and the latter contributing to flexibility and toughness.

[0113] Urethane elastomers consist of structural units of a hard segment made of a low molecular weight glycol and diisocyanate and a soft segment made of a high molecular weight (long-chain) diol and diisocyanate. Examples of high molecular weight (long-chain) diols include polypropylene glycol, polytetramethylene oxide, poly(1,4-butylene adipate), poly(ethylene-1,4-butylene adipate), polycaprolactone, poly(1,6-hexylene carbonate), and poly(1,6-hexylene-neopentylene adipate). The number-average molecular weight of the polymer (long-chain) diol is preferably 500 to 10,000. In addition to ethylene glycol, short-chain diols such as propylene glycol, 1,4-butanediol, and bisphenol A can be used, and the number-average molecular weight of the short-chain diol is preferably 48 to 500. Specific examples of commercially available urethane elastomers include PANDEX T-2185 and T-2983N (manufactured by DIC Corporation) and Miractoran E790 (manufactured by Nippon Milactone Co., Ltd.).

[0114] Examples of polyester elastomers include those obtained by polycondensation of dicarboxylic acids or their derivatives and 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 in which hydrogen atoms in the aromatic nuclei are substituted with methyl groups, ethyl groups, phenyl groups, etc., aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid, and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These compounds can be used alone or in combination.

[0115] Specific examples of the diol compound include aliphatic diols and alicyclic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol, or dihydric phenols represented by the following general formula (VII):

[0116] [ka] [In general formula (VII), Z 6 represents an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, a divalent functional group selected from -O-, -S-, and -SO2-, or represents that benzene rings are directly bonded to each other, and R 15 and R 16 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, l and m represent integers of 0 to 4, and p represents 0 or 1. The alkylene group and cycloalkylene group may be linear or branched, and may be substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amido group, an alkoxy group, or the like.

[0117] Specific examples of the dihydric phenol represented by general formula (VII) include bisphenol A, bis-(4-hydroxyphenyl)methane, bis-(4-hydroxy-3-methylphenyl)propane, resorcinol, etc. These compounds can be used alone or in combination. Multiblock copolymers can also be used, with aromatic polyesters (e.g., polybutylene terephthalate) as the hard segment components and aliphatic polyesters (e.g., polytetramethylene glycol) as the soft segment components. Various grades are available, differing in the type, ratio, and molecular weight of the hard and soft segments. Commercially available examples include Hytrel (manufactured by DuPont-Toray Co., Ltd.), Pelprene (manufactured by Toyobo Co., Ltd.), and Espel (manufactured by Hitachi Chemical Co., Ltd.).

[0118] The acrylic elastomer is mainly composed of acrylic ester, and ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, etc. are used, and as a crosslinking point monomer, glycidyl methacrylate, allyl glycidyl ether, etc. Furthermore, acrylonitrile and ethylene can also be copolymerized. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like.

[0119] In addition to the thermoplastic elastomers described above, rubber-modified epoxy resins can also be used. Rubber-modified epoxy resins can be obtained, for example, by modifying some or all of the epoxy groups in the bisphenol F epoxy resin, bisphenol A epoxy resin, salicylaldehyde epoxy resin, phenol novolac epoxy resin, or cresol novolac epoxy resin with a butadiene-acrylonitrile rubber modified at both ends with carboxylic acid, an amino-modified silicone rubber, or the like. Among these elastomers, butadiene-acrylonitrile copolymers modified at both ends with carboxyl groups and Espel (Hitachi Chemical Co., Ltd., Espel 1612, 1620), a polyester-based elastomer having hydroxyl groups, are preferred from the viewpoint of shear adhesion.

[0120] The content of component (I) may be appropriately selected from 2 to 40 parts by mass, 4 to 30 parts by mass, 10 to 25 parts by mass, or 15 to 22 parts by mass per 100 parts by mass of component (A) (solid content). By ensuring that the content is within the above range, the elastic modulus of the cured film in high temperature ranges becomes lower and the unexposed areas become more easily eluted in a developer.

[0121] <Other additives> The photosensitive resin composition of this embodiment may contain, as needed, various known and commonly used additives such as polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol, thickeners such as bentone and montmorillonite, silicone-based, fluorine-based, and vinyl resin-based antifoaming agents, and silane coupling agents.Furthermore, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, and phosphate compounds of phosphorus-based compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters may be used.

[0122] <Diluent> The photosensitive resin composition of this embodiment may contain a diluent, if necessary. Examples of the diluent include organic solvents. Examples of the organic solvent 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 solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

[0123] The amount of diluent used may be appropriately selected from amounts such that the total solid content in the photosensitive resin composition is 50 to 90 mass%, 60 to 80 mass%, or 65 to 75 mass%. In other words, when a diluent is used, the content of the diluent in the photosensitive resin composition may be appropriately selected from 10 to 50 mass%, 20 to 40 mass%, or 25 to 35 mass%. By keeping the amount within the above range, the coatability of the photosensitive resin composition is improved, and it becomes possible to form a more precise pattern.

[0124] The photosensitive resin composition of the present embodiment can be obtained by uniformly kneading and mixing the ingredients using a roll mill, a bead mill, or the like.

[0125] [Dry film] The dry film of this embodiment includes a carrier film and a photosensitive layer using the photosensitive resin composition of this embodiment. The thickness of the photosensitive layer may be appropriately selected from 5 to 50 μm, 15 to 40 μm, or 20 to 30 μm.

[0126] The dry film of the present embodiment can be produced, for example, by applying the photosensitive resin composition of the present embodiment onto a carrier film by a known method such as reverse roll coating, gravure roll coating, comma coating, or curtain coating, and drying the composition to form a photosensitive layer. Examples of the carrier film include polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyolefins such as polypropylene and polyethylene. The thickness of the carrier film may be appropriately selected from the range of 5 to 100 μm. In addition, the dry film of this embodiment may have a protective layer laminated on the surface of the photosensitive layer opposite to the surface that contacts the carrier film. For example, a polymer film such as polyethylene or polypropylene may be used as the protective layer. Furthermore, the same polymer film as the above-mentioned carrier film may be used, or a different polymer film may be used. The coating film can be dried using hot air drying or a dryer using far-infrared rays or near-infrared rays, and the drying temperature can be appropriately selected from 60 to 120° C., 70 to 110° C., or 80 to 100° C. The drying time can be appropriately selected from 1 to 60 minutes, 2 to 30 minutes, or 5 to 20 minutes.

[0127] [Printed wiring board] The printed wiring board of this embodiment is provided with a permanent mask resist formed from the photosensitive resin composition of this embodiment. The printed wiring board of this embodiment includes a permanent mask resist formed from the photosensitive resin composition of this embodiment, and therefore exhibits high adhesion between the photosensitive resin composition and the adhesion-improving adhesive layer coating formed on the low-roughening copper surface, and the adhesion is not significantly reduced even after being subjected to moisture absorption degradation in a highly accelerated life test (HAST) device, and has excellent resolution and an excellent resist shape pattern. Furthermore, this permanent mask resist exhibits excellent pattern formation stability with the miniaturized hole diameters and hole spacing pitches associated with the recent miniaturization and high performance of electronic devices.

[0128] [Printed wiring board manufacturing method] The method for producing a printed wiring board of this embodiment includes, in order, a step of providing 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 permanent mask resist. Specifically, for example, it can be produced as follows. First, a photosensitive resin composition is applied to a metal-clad laminate substrate such as a copper-clad laminate on which wiring has been formed, by a method such as screen printing, spraying, roll coating, curtain coating, electrostatic coating, or the like, to a film thickness appropriately selected from 10 to 200 μm, 15 to 150 μm, 20 to 100 μm, or 23 to 50 μm, and then the coating film is dried at 60 to 110°C, or the dry film of this embodiment from which the protective layer has been peeled off is thermally laminated onto the substrate using a laminator, thereby providing a photosensitive layer on the substrate. Next, a negative film is brought into direct contact with the photosensitive layer (or in a non-contact state via a transparent film such as a carrier film), and actinic light is irradiated at 10 to 2,000 mJ / cm 2 2 , 100-1,500mJ / cm 2 , or 300 to 1,000 mJ / cm 2 The resist pattern is then formed by dissolving and removing (developing) the unexposed areas with a dilute alkaline aqueous solution. Examples of actinic light that can be used include electron beams, ultraviolet rays, and X-rays, with ultraviolet rays being preferred. Examples of light sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and halogen lamps. Next, the exposed portion of the photosensitive layer is sufficiently cured by at least one of post-exposure (ultraviolet light exposure) and post-heating to form a permanent mask resist. The exposure dose for post-exposure is 100 to 5,000 mJ / cm 2 , 500-2,000mJ / cm 2 , or 700 to 1,500 J / cm 2 It may be selected appropriately from the above. The heating temperature for post-heating may be appropriately selected from 100 to 200°C, 120 to 180°C, or 135 to 165°C. The heating time for post-heating may be appropriately selected from 5 minutes to 12 hours, 10 minutes to 6 hours, or 30 minutes to 2 hours. [Example]

[0129] The objects and advantages of the present embodiment will be described in more detail below based on examples and comparative examples, but the present embodiment is not limited to the following examples. Note that "parts" means parts by mass.

[0130] (Synthesis Example 1) To synthesize the acid-modified vinyl group-containing epoxy resin (A1), a bisphenol F novolac epoxy resin (a1) (EXA-7376, manufactured by DIC Corporation, in which Y 3 and Y 4 is a glycidyl group, R 12 A mixture of 350 parts by weight of bisphenol F novolac epoxy resin (epoxy equivalent: 186) containing a structural unit in which (A) is a hydrogen atom, 70 parts by weight of acrylic acid as vinyl group-containing monocarboxylic acid (b), 0.5 parts by weight of methylhydroquinone, and 120 parts by weight of carbitol acetate was added and heated to 90°C with stirring to completely dissolve the mixture. The resulting solution was then cooled to 60°C, 2 parts by weight of triphenylphosphine was added, and the mixture was heated to 100°C and allowed to react until the acid value of the solution reached 1 mgKOH / g or less. To the reacted solution, 98 parts by weight of tetrahydrophthalic anhydride (THPAC) and 85 parts by weight of carbitol acetate as saturated or unsaturated group-containing polybasic acid anhydride (c) were added, heated to 80°C, and allowed to react for 6 hours. Thereafter, the mixture was cooled to room temperature (25°C) to obtain a THPAC-modified bisphenol F novolac epoxy acrylate (acid-modified vinyl group-containing epoxy resin (1)) as component (A1) with a solid content of 73 mass%.

[0131] (Synthesis Example 2) In a flask equipped with a stirrer, a reflux condenser, and a thermometer, a bisphenol F type epoxy resin (in general formula (IV), Y 6 is a hydrogen atom, R 14A mixture of 1,052 parts by weight of bisphenol F epoxy resin (a2) (epoxy equivalent: 526) containing a structural unit in which (a) is a hydrogen atom, 144 parts by weight of acrylic acid (b), 1 part by weight of methyl hydroquinone, 850 parts by weight of carbitol acetate, and 100 parts by weight of solvent naphtha was heated and stirred at 70°C to dissolve the mixture. The solution was then cooled to 50°C, and 2 parts by weight of triphenylphosphine and 75 parts by weight of solvent naphtha were added. The mixture was heated to 100°C and reacted until the solid acid value reached 1 mgKOH / g or less. The resulting solution was then cooled to 50°C, and 745 parts by weight of tetrahydrophthalic anhydride (THPAC) (c), 75 parts by weight of carbitol acetate, and 75 parts by weight of solvent naphtha were added. The mixture was heated to 80°C and reacted for 6 hours. Thereafter, the mixture was cooled to room temperature to obtain a THPAC-modified bisphenol F epoxy acrylate (acid-modified vinyl group-containing epoxy resin (2)) as component (A2) having a solid acid value of 80 mgKOH / g and a solid content of 62 mass %.

[0132] (Examples 1 to 7, Comparative Examples 1 to 6) A photosensitive resin composition was prepared by blending components according to the formulation shown in Table 1 and kneading them in a three-roll mill. Carbitol acetate was added so that the solid content concentration became 70% by mass, and a photosensitive resin composition was obtained.

[0133] [Table 1]

[0134] The details of each material in Table 1 are as follows: Component (A): Acid-modified vinyl group-containing epoxy resin Acid-modified vinyl group-containing epoxy resin (1), (2): Resin obtained in the above synthesis example Component (B): epoxy resin YDF-8170C: Tetramethylbisphenol F epoxy resin (product name, manufactured by Nippon Steel Chemical & Material Co., Ltd.) RE-306: Novolac-type multifunctional epoxy resin (product name, manufactured by Nippon Kayaku Co., Ltd.) TEPIC-FL: Isocyanuric acid structure-containing epoxy resin (Nissan Chemical Industries, Ltd., product name) Component (C): Photopolymerization initiator Irgacure 907: 2-methyl-[4-(methylthio)phenyl]morpholino-1-propanone (BASF, trade name) DETX: DETX-S, 2,4-diethylthioxanthone (trade name, manufactured by Nippon Kayaku Co., Ltd.) EAB: 4-4'-bis-(diethylamino)benzophenone (trade name, manufactured by Hodogaya Chemical Co., Ltd.) OXE02: Irgacure OXE02, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) (BASF, trade name) (D) Component; Photopolymerizable compound DPHA: Dipentaerythritol hexaacrylate (trade name, manufactured by Nippon Kayaku Co., Ltd.) (E) component; inorganic filler 180nmSV-CL1: Silica particles (manufactured by Admatechs Co., Ltd., product name, average particle size: 0.18μm) (F) Component: Pigment Phthalocyanine pigment: Phthalocyanine pigment (manufactured by Sanyo Pigment Co., Ltd.) Component (G): Ion scavenger IXEPLAS-A1: Zr, Mg, and Al-containing ion scavenger (manufactured by Toagosei Co., Ltd., trade name, average particle size: 0.5 μm, Zr compound content: 20 to 30% by mass) Component (H): hardener Melamine: Nissan Chemical Industries, Ltd. Component (I): Elastomer PB-3600: Epoxidized polybutadiene (manufactured by Daicel Corporation, product name) SP1108: Polyester resin (Espel 1108, manufactured by Hitachi Chemical Co., Ltd.)

[0135] Next, the photosensitive resin composition obtained above was used to carry out various evaluations under the conditions shown below. The evaluation results are shown in Table 2.

[0136] [Preparation of test specimens] The photosensitive resin compositions of the examples and comparative examples were applied by screen printing to a 0.6 mm thick copper-clad laminate substrate (MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) so that the dried film thickness was 25 μm, and then dried at 76° C. for 30 minutes using a hot air circulation dryer. Next, a negative mask having a predetermined pattern (opening size (diameter): 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 150, 200 μm) was attached to the substrate, and the substrate was exposed to an exposure dose using an ultraviolet exposure device to achieve 13 complete curing steps (using a step tablet manufactured by Hitachi Chemical Co., Ltd.). The resulting composition was then immersed in a 1% by mass aqueous sodium carbonate solution for 60 seconds at 1.765×10 5 The unexposed areas were then developed by spray development at a pressure of 2000 mJ / cm 2 using an ultraviolet exposure device. 2 and heated at 170° C. for 1 hour to prepare a test piece with a permanent mask resist.

[0137] [Resolution evaluation] The test piece was observed using an optical microscope, and the resolution was evaluated according to the following criteria. The evaluation results are shown in Table 2. A: The minimum diameter of the opening was 30 μm or less. B: The minimum diameter of the opening was greater than 30 μm and less than 60 μm. C: The minimum diameter of the opening exceeded 60 μm.

[0138] [Resist shape] The above test pieces were cast with epoxy resin (jER828 (trade name, manufactured by Mitsubishi Chemical Corporation) using triethylenetetramine as a curing agent) and fully cured. After that, they were polished with a polishing machine (Refine Polisher (manufactured by Refine Tech Co., Ltd.)) to remove the cross section of the pattern, and the resist shape was observed with a metallurgical microscope. The resist shape was judged and evaluated according to the following criteria. A: The resist shape was free of undercuts and missing parts at the top of the resist, and the pattern contours were linear (see Figure 1). B: The resist shape was undercut, and the upper part of the resist was missing, and the linearity of the pattern contour was poor (see Figure 2).

[0139] [Adhesion] A microetching agent (manufactured by MEC Co., Ltd.) was sprayed onto a 35 μm thick copper foil (manufactured by Nippon Denkai Co., Ltd.), and etching was performed by adjusting the etching time so that the etching depth was 0.1 μm. The foil was then washed with water, and the etched surface was sprayed with 3.5% by mass hydrochloric acid, followed by washing with water and drying. The foil was then immersed in a film-forming solution for improving adhesion (manufactured by MEC Co., Ltd.), removed, immediately washed with water, and then dried to form a film. The photosensitive resin compositions of the examples and comparative examples were applied to the treated copper foil by screen printing so that the film thickness after drying would be 20 μm, and then dried at 75° C. for 30 minutes using a hot air circulation dryer. The negative mask was then attached to the coating film, and a parallel exposure machine (manufactured by Hitec Corporation, product name: HTE-5102S) was used to expose the foil to 100 mJ / cm . 2 The photosensitive layer was then exposed to a 1% by mass aqueous solution of sodium carbonate for 60 seconds at an exposure dose of 1.765 × 10 5 The unexposed areas were then developed by spray development at a pressure of 2000 mJ / cm 2 using an ultraviolet exposure device. 2 and heated at 170°C for 1 hour to prepare a test specimen with a permanent mask resist on the copper foil. The surface of the obtained test specimen with the permanent mask resist was bonded to a copper-clad laminate (MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) using an adhesive (Bond E Set, manufactured by Konishi Co., Ltd.) and cured. After leaving for 12 hours, one end of the copper foil was peeled off by 10 mm. The laminate was then fixed, and the peeled copper foil was gripped with a gripper. The peel load (peel strength) was measured eight times at room temperature at a pulling speed of 50 mm / min in the thickness direction (perpendicular to the thickness) of the copper foil. The average value of the eight measurements was calculated and used as an index of adhesive strength. Peel strength was evaluated in accordance with JIS C 5016 (1994 - Peel Strength of Conductors), and adhesion was evaluated according to the following criteria. In this specification, room temperature refers to 25°C. A: The peel strength was high, exceeding 0.5 N / mm. B: The peel strength was in the range of 0.3 to 0.5 N / mm. C: The peel strength was less than 0.3 N / mm.

[0140] [Adhesion after moisture absorption deterioration test] As described above, copper foil was treated with a microetching agent and an adhesion-improving coating solution, and a photosensitive resin composition layer was formed on each of the examples and comparative examples. The composite was then bonded with adhesive to form a composite. The composite was subjected to moisture absorption degradation in a highly accelerated life test (HAST) device at 130°C, 85% RH, and 3.5 V for 100 hours. The peel strength of the composite after moisture absorption degradation was measured using the same procedure as described above and evaluated according to the following criteria. A: The peel strength after HAST was greater than 0.3 N / mm. B: The peel strength after HAST was in the range of 0.1 to 0.3 N / mm. C: The peel strength after HAST was less than 0.1 N / mm.

[0141] [Table 2]

[0142] As shown in Table 2, the photosensitive resin compositions of Examples 1 to 6 according to this embodiment exhibited excellent performance in terms of resolution, resist shape, adhesion, and adhesion after moisture-absorption degradation testing. In particular, with regard to adhesion after moisture-absorption degradation testing, the photosensitive resin compositions exhibited excellent performance, with a peel strength after HAST of greater than 0.3 N / mm. Thus, the photosensitive resin composition of this embodiment exhibited excellent performance in all properties, and was confirmed to be a composition that can be particularly suitably used as a permanent mask resist. In contrast, the photosensitive resin compositions of Comparative Examples 1 to 7 exhibited poor results, particularly in terms of adhesion after moisture-absorption degradation testing.

[0143] (Examples 7 to 12, Comparative Examples 8 to 14) The photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 7, prepared according to the blending ratios shown in Table 1, were diluted with methyl ethyl ketone. A 25-μm-thick polyethylene terephthalate film (G2-25, Teijin Limited, product name) was used as a carrier film. The photosensitive resin compositions of the Examples and Comparative Examples were uniformly coated onto the carrier film to a dry thickness of 25 μm. The resulting film was dried at 75°C for 30 minutes using a hot air convection dryer to form a photosensitive layer. A polyethylene film (NF-15, Tamapoly Corporation, product name) (protective layer) was then attached to the surface of the photosensitive layer opposite the side in contact with the carrier film, producing dry films of Examples 7 to 12 and Comparative Examples 8 to 14, corresponding to the respective Examples and Comparative Examples.

[0144] [Dry film evaluation] The protective layer of the dry film prepared above was peeled off and laminated onto a 0.6 mm thick copper-clad laminate (MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) using a continuous press vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd., product number) under specified lamination conditions (pressure: 0.4 MPa, press hot plate temperature: 80°C, vacuum time: 20 seconds, lamination press time: 20 seconds, air pressure: 4 kPa or less), to obtain a laminate with a photosensitive layer. Next, exposure and development were carried out in the same manner as in the above "Preparation of Test Pieces" to prepare test pieces having a permanent mask resist. The obtained test pieces were used to carry out the same evaluations as in Examples 1 to 6. The results are shown in Table 3.

[0145] [Table 3]

[0146] From the results shown in Table 3, the dry films of Examples 7 to 12 of this embodiment exhibited excellent performance in terms of resolution, resist shape, adhesion, and adhesion after moisture absorption degradation test. Thus, the dry films of this embodiment also exhibited excellent performance in all properties, and it was confirmed that they can be particularly suitable for use in the production of permanent mask resists. In contrast, the dry films of Comparative Examples 8 to 14 showed poor results, especially in terms of adhesion after moisture absorption degradation test.

Claims

1. A photosensitive resin composition for a printed wiring board and for a permanent mask resist to be formed on an adhesive layer coating having an adhesion-improving effect and formed on a low-roughening copper surface, comprising (A) an acid-modified vinyl group-containing epoxy resin, (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a photopolymerizable compound, wherein at least one of the components (B) is an epoxy resin having an isocyanuric acid structure (excluding triglycidyl isocyanurate).

2. 2. The photosensitive resin composition according to claim 1, wherein the epoxy resin having an isocyanuric acid structure is a trifunctional epoxy compound having an isocyanuric acid skeleton (excluding triglycidyl isocyanurate).

3. 3. The photosensitive resin composition according to claim 1, wherein the content of the component (B) is 2 to 40 mass% based on the total amount of solids in the photosensitive resin composition.

4. 4. The photosensitive resin composition according to claim 1, wherein the (C) photopolymerization initiator is at least one selected from the group consisting of alkylphenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators having a thioxanthone skeleton, and acylphosphine oxide-based photopolymerization initiators.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the (D) photopolymerizable compound is a compound containing a (meth)acryloyl group.

6. The photosensitive resin composition according to any one of claims 1 to 5, further comprising (E) an inorganic filler.

7. The photosensitive resin composition according to any one of claims 1 to 6, further comprising (F) a pigment.

8. The photosensitive resin composition according to any one of claims 1 to 7, further comprising an ion scavenger (G), wherein the ion scavenger (G) is at least one selected from the group consisting of inorganic ion exchangers that capture cations, inorganic ion exchangers that capture anions, and inorganic ion exchangers that capture cations and anions.

9. 9. The photosensitive resin composition according to claim 8, wherein the contents of the (A) acid-modified vinyl group-containing epoxy resin, the (C) photopolymerization initiator, the (D) photopolymerizable compound, and the (G) ion scavenger are, based on the total amount of solids in the photosensitive resin composition, respectively, 20 to 80 mass% for (A), 0.2 to 15 mass% for (C), 0.1 to 10 mass% for (D), and 0.1 to 10 mass% for (G).

10. A dry film having a carrier film and a photosensitive layer using the photosensitive resin composition according to any one of claims 1 to 9.

11. A printed wiring board comprising a permanent mask resist formed from the photosensitive resin composition according to any one of claims 1 to 9.

12. 12. The printed wiring board according to claim 11, wherein the permanent mask resist has a thickness of 5 [mu]m or more.

13. A method for producing a printed wiring board, comprising the steps of: providing a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 9 or the dry film according to claim 10; forming a resist pattern using the photosensitive layer; and curing the resist pattern to form a permanent mask resist.

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