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 enables formation of a resist shape that is excellent in not only basic performance such as electric insulation properties, solder heat resistance, thermal shock resistance, solvent resistance, acid resistance and alkali resistance required for a photosensitive resin composition used in printed wiring board manufacture but also linearity of a resist pattern contour while preventing an undercut with a hollowed bottom part and missing of an upper part of a resist, is excellent in adhesion to a copper substrate and flowability; a dry film and a printed wiring board using the same; and a method for manufacturing a printed wiring board.SOLUTION: There are provided a photosensitive resin composition containing (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerization initiator, (C) an ion scavenger having at least one selected from the group consisting of Zr, Bi, Mg and Al, and (D) a photopolymerizable compound; a dry film and a printed wiring board using the same; and a method for manufacturing a printed wiring board.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure 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 a photographic method 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, it is necessary to remove the permanent mask resist from the bonding area in order to (1) flip-chip mount a semiconductor element onto the semiconductor package substrate via solder, (2) wire-bond the semiconductor element to the semiconductor package substrate, or (3) solder-bond the semiconductor package substrate to a motherboard. Therefore, to form this permanent mask resist, a photographic method is used, in which a photosensitive resin composition is applied and dried, 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. Because of its ease of operation and its suitability for mass production, the photographic method is widely used in the electronic materials industry for forming images of photosensitive resin compositions (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-198105 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-133851 Summary of the Invention [Problem to be solved by the invention]

[0006] However, when using a photosensitive resin composition containing a pigment or filler as described in Patent Document 2, the pigment or filler may prevent transmission of ultraviolet light or absorb ultraviolet light, and therefore, when attempting to form a thick permanent mask resist of 10 μm or more, the photocuring of the photosensitive resin composition at the bottom may not be sufficient, which may result in undercutting of the bottom after development (see Figure 2, left). Increasing the UV exposure dose to improve bottom photocuring results in increased optical diffraction and footing (halation), resulting in larger line widths at the middle (center) and deepest (bottom) portions of the resist pattern cross section compared to the line width at the surface (top). This can lead to poor resist shape and reduced resolution. Oxygen inhibition can also cause insufficient photocuring in the resist depth direction, extending to approximately 3 μm from the surface, resulting in footing (halation), where the top of the resist pattern is missing and the bottom remains. Oxygen inhibition can also cause thickening (diffraction), where both the top and bottom of the resist pattern are missing, resulting in poor resist shape (see center and right of Figure 2).

[0007] Furthermore, in recent years, with the miniaturization and high performance of electronic devices, the hole diameter and the distance between the centers of the holes in permanent mask resists have tended to become finer, and for example, fine patterns with hole diameters of 100 μm and distances between the centers of the holes of 100 μm, or hole diameters of 80 μm and distances between the centers of the holes of 80 μm, are being used. Furthermore, in flip-chip mounting, in addition to improved resolution, photosensitive resin compositions are recently required to have improved adhesion to copper substrates and improved fluidity. When a permanent mask resist is formed using a photosensitive resin composition, if the adhesion to the copper substrate is insufficient, plating solution may seep in through that area, affecting insulation reliability. Furthermore, when forming even finer wiring (also referred to as a "conductor pattern"), it is effective to carry out coating or lamination under high temperature conditions in order to allow the photosensitive resin composition to flow uniformly. However, when coating or laminating under high temperature conditions, the risk of generating residue increases. Therefore, there is a demand for fluidity that allows the composition to flow uniformly without requiring high temperature conditions.

[0008] The object of the present disclosure is to provide a photosensitive resin composition that can form a resist pattern with an excellent resist shape, in which undercuts (where the bottom of the resist pattern is gouged out) and chipping of the upper part of the resist pattern are unlikely to occur, and in which the line widths of the middle part (center) and deepest part (bottom) of the cross section of the resist pattern are unlikely to become larger than the line width of the surface part (i.e., the linearity of the resist pattern contour is good), and that further has excellent adhesion and flowability to copper substrates, as well as a dry film, a printed wiring board, and a method for producing a printed wiring board using the same. [Means for solving the problem]

[0009] 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.

[0010] [1] A photosensitive resin composition comprising: (A) an acid-modified vinyl group-containing epoxy resin; (B) a photopolymerization initiator; (C) an ion scavenger having at least one element selected from the group consisting of Zr, Bi, Mg, and Al; and (D) a photopolymerizable compound. [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 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, and triphenolmethane 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): [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 the groups represents a glycidyl group. [ka] [In general formula (II), R 12 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 the groups represents a glycidyl group. [6] The photosensitive resin composition according to any one of the above [2] to [5], wherein the bisphenol novolac epoxy resin (a1) has a structural unit represented by the above 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): [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). [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 (B) photopolymerization initiator is at least one selected from the group consisting of alkylphenone-based photopolymerization initiators, compounds having a thioxanthone skeleton (thioxanthone-based photopolymerization initiators), and acylphosphine oxide-based photopolymerization initiators.

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

[10] , wherein the (C) ion scavenger 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.

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

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

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

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

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

[13] , further comprising (F) an inorganic filler.

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

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

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

[15] above.

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

[15] above.

[18] The printed wiring board according to

[17] above, wherein the thickness of the permanent mask resist is 10 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]

[0011] According to the present disclosure, it is possible to provide a photosensitive resin composition that can form a resist pattern with excellent linearity of the resist pattern contour (i.e., an excellent resist shape) and is less likely to cause undercuts, in which the bottom of the resist pattern is gouged out, or chipping of the upper part of the resist pattern, and that further has excellent adhesion and flowability to copper substrates, as well as a dry film, a printed wiring board, and a method for producing a printed wiring board using the same. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a schematic diagram showing a resist cross-sectional shape with excellent linearity of the resist pattern contour. [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

[0013] [Photosensitive resin composition] The photosensitive resin composition according to an embodiment of the present disclosure (hereinafter sometimes simply referred to as this embodiment) contains (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerization initiator, (C) an ion scavenger containing at least one selected from the group consisting of Zr, Bi, Mg, and Al, and (D) a photopolymerizable compound. In this specification, these components may be simply referred to as component (A), component (B), component (C), etc. By having the above-described configuration, the photosensitive resin composition of this embodiment can improve the photocurability of the bottom, thereby reducing the occurrence of undercuts in which the bottom of the resist pattern is scooped out and chipping of the upper part of the resist pattern. Since the exposure dose of ultraviolet radiation is not increased, it is believed that a thick resist pattern with excellent linearity of the resist pattern contour can be formed. Furthermore, by having the above-described specific configuration, the photosensitive resin composition of this embodiment has excellent adhesion to copper substrates and excellent flowability. It is also believed that the composition will have excellent basic properties, such as electrical insulation, soldering heat resistance, thermal shock resistance, solvent resistance, acid resistance, and alkali resistance, which are required of photosensitive resin compositions used in the manufacture of printed wiring boards. Each component will be explained below.

[0014] <(A) Acid-modified vinyl group-containing epoxy resin> The photosensitive resin composition of this embodiment contains component (A). Component (A) is an epoxy resin modified with a vinyl group-containing organic acid, such as an epoxy resin obtained by reacting an epoxy resin with a vinyl group-containing monocarboxylic acid to obtain a resin, and then reacting the resin with a saturated or unsaturated group-containing polybasic acid anhydride.

[0015] Examples of component (A) include an acid-modified vinyl group-containing epoxy resin (A1) (hereinafter sometimes referred to as component (A1)) obtained using a bisphenol novolac epoxy resin (a1) (hereinafter sometimes referred to as component (a1)), and an acid-modified vinyl group-containing epoxy resin (A2) (hereinafter sometimes referred to as component (A2)) obtained using an epoxy resin (a2) (hereinafter sometimes referred to as component (a2)) other than the epoxy resin (a1). Component (A) can be used alone or in combination of two or more types. Furthermore, from the standpoint of reducing the occurrence of undercuts and chipping of the upper part of the resist, and improving the linearity of the resist pattern contour, adhesion to the copper substrate, and flowability, the component (A) may contain at least one type of component (A1) and at least one type of component (A2), or may contain one type of component (A1) and one type of component (A2), or may contain one type of component (A1) or one type of component (A2), or may contain one type of component (A2).

[0016] (Epoxy resin (a1)) From the viewpoints of reducing undercut and chipping of the upper part of the resist, improving the linearity of the resist pattern contour, adhesion to the copper substrate, and flowability, 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 a 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).

[0017] [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):

[0018] [ka]

[0019] 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.

[0020] R 11 is preferably a hydrogen atom, from the viewpoint of preventing undercut and loss of the upper part of the resist and improving the linearity and resolution of the resist pattern contour. 1 and Y 2 are preferably all glycidyl groups.

[0021] 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.

[0022] [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):

[0023] [ka]

[0024] In general formula (II), R 12 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.

[0025] R 12 is preferably a hydrogen atom, from the viewpoint of making it difficult for undercuts and chipping of the upper part of the resist 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 3 and Y 4 are preferably all glycidyl groups.

[0026] 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, heat resistance, and electrical insulation properties are improved.

[0027] 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 4Those having a glycidyl group are commercially available as the EPON SU8 series (trade name, manufactured by Mitsubishi Chemical Corporation).

[0028] (Epoxy resin (a2)) There are no particular restrictions on the component (a2), so long as it is an epoxy resin different from the component (a1). However, from the standpoint of reducing undercut and chipping of the upper part of the resist, improving the linearity of the resist pattern contour, adhesion to the copper substrate, and flowability, as well as improving 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, and triphenolmethane 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).

[0029] 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).

[0030] [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').

[0031] [ka]

[0032] 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.

[0033] R 13is preferably a hydrogen atom, from the viewpoint of making it difficult for undercuts and chipping of the upper part of the resist 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 undercutting and loss of the upper part of the resist and improving the linearity and resolution of the resist pattern contour. 5 At least one of the groups is a glycidyl group.

[0034] 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, heat resistance, and electrical insulation properties are improved.

[0035] 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.

[0036] 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 Co., Ltd.), DEN-431, DEN-439 (all of which are trade names manufactured by The Dow Chemical Company), EOCN-120, and EOCN-102. Commercially available examples include EOCN-S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, and BREN (all trade names manufactured by Nippon Kayaku Co., Ltd.), EPN-1138, EPN-1235, and EPN-1299 (all trade names manufactured by BASF), N-730, N-770, N-865, N-665, N-673, VH-4150, and VH-4240 (all trade names manufactured by DIC Corporation).

[0037] [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').

[0038] [ka]

[0039] 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.

[0040] R14 is preferably a hydrogen atom, from the viewpoint of making it difficult for undercuts and chipping of the upper part of the resist 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.

[0041] 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, heat resistance, and electrical insulation properties are improved.

[0042] Represented by general formula (IV), Y 6 The 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, the hydroxyl group (-OY 6 ) with epichlorohydrin.

[0043] 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.

[0044] 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 of Mitsubishi Chemical Corporation), DER-330, DER-301, and DER-361 (all of which are product names of The Dow Chemical Company), YD-8125, YDF-170, YDF-170, YDF-175S, YDF-2001, YDF-2004, and YDF-8170 (all of which are product names of Nippon Steel Chemical Co., Ltd.).

[0045] [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').

[0046] [ka]

[0047] In 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.

[0048] 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, heat resistance, and electrical insulation properties are improved.

[0049] 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.

[0050] 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')"), with a saturated or unsaturated group-containing polybasic acid anhydride (c) (hereinafter sometimes referred to as component (c)).

[0051] [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.

[0052] 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.

[0053] 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, pentaerythritol pentamethacrylate, glycidyl acrylate, and glycidyl methacrylate.

[0054] 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.

[0055] In the reaction of the above components (a) and (b), the ratio of component (b) is preferably 0.6 to 1.05 equivalents, more preferably 0.8 to 1.0 equivalents, of component (b) per equivalent of epoxy group in component (a). Reaction at such a ratio improves photopolymerization, i.e., photosensitivity, and therefore improves the linearity of the resist pattern contour.

[0056] 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-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] [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.

[0062] 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').

[0063] 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.

[0064] 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.

[0065] 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.

[0066] (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 polyethylene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. More specifically, 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 of standard polystyrenes ("PStQuick MP-H" and "PStQuick B," manufactured by Tosoh Corporation). (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

[0067] (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.

[0068] (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.

[0069] (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.

[0070] <(B) Photopolymerization initiator> The component (B) used in this embodiment is not particularly limited as long as it can polymerize the component (E), which will be described later, and can be appropriately selected from commonly used photopolymerization initiators. Examples include conventionally known photopolymerization initiators such as alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, compounds having a thioxanthone skeleton, and titanocene-based photopolymerization initiators. Among these, 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, at least one selected from the group consisting of alkylphenone-based photopolymerization initiators, compounds having a thioxanthone skeleton (thioxanthone-based photopolymerization initiators), and acylphosphine oxide-based photopolymerization initiators may be used. An alkylphenone-based photopolymerization initiator and a compound having a thioxanthone skeleton may be used in combination, or a compound having a thioxanthone skeleton and an acylphosphine oxide-based photopolymerization initiator may be used in combination.

[0071] The alkylphenone-based photopolymerization initiator is not particularly limited as long as it is a compound having an alkylphenone skeleton, and examples thereof include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, phenyl glyoxylic acid methyl ester, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and the like. The alkylphenone photopolymerization initiators can be used alone or in combination. As the alkylphenone photopolymerization initiator, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one may be selected. Examples of compounds having a thioxanthone skeleton include 2,4-diethylthioxanthone and 2-chlorothioxanthone. Compounds having a thioxanthone skeleton can be used alone or in combination. 2,4-diethylthioxanthone may be selected as the compound having a thioxanthone skeleton. The acylphosphine oxide photopolymerization initiator is not particularly limited as long as it is a compound having an acylphosphine oxide group (=P(=O)-C(=O)- group), and examples thereof include (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2,5-dihydroxyphenyl)diphenylphosphine oxide, (p-hydroxyphenyl)diphenylphosphine oxide, bis(p-hydroxyphenyl)phenylphosphine oxide, tris(p-hydroxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. The acylphosphine oxide photopolymerization initiators can be used alone or in combination of two or more. As the acylphosphine oxide-based photopolymerization initiator, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide may be selected.

[0072] ((B) Component Content) The content of component (B) may be appropriately selected from 0.2 to 15 mass%, 0.2 to 10 mass%, 0.4 to 5 mass%, or 0.6 to 1 mass%, based on the total solid content of the photosensitive resin composition, from the viewpoint of obtaining a photosensitive resin composition capable of forming a resist shape with improved linearity of the resist pattern contour. Furthermore, if the content of component (B) is 0.2 mass% or more, the exposed area is less likely to dissolve during development, and if it is 15 mass% or less, a decrease in heat resistance is suppressed.

[0073] <(C) Ion scavenger> The component (C) 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 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 (C) 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 (C), 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 do not react when irradiated with light, electron beams, etc. 、 The solubility of the compound in the solvent is changed. For example, sodium ions (Na + ), chloride ions (Cl - ), bromide ion (Br - ), copper ions (Cu + , Cu 2+ ) and the like, and by capturing these ions, electrical insulation and resistance to electrolytic corrosion are improved. 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.

[0074] (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 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 available from Toagosei Co., Ltd.

[0075] (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") that can be used 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.

[0076] (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. 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.

[0077] In this embodiment, the component (C) may be the cation scavenger, the anion scavenger, or both of these ion scavengers, either alone or in combination. + , Cl - , Br - , Cu + , Cu 2+In consideration of simultaneously capturing cations and anions such as those mentioned above, it is preferable to use a combination of a cation scavenger and an anion scavenger, to use both ion scavenger and anion scavenger, or to use both ion scavenger and at least one of a cation scavenger and an anion scavenger.

[0078] Component (C) 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 (C) 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 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 (C) contained in the photosensitive layer or cured film of the photosensitive resin composition provided on the carrier film is also measured using the submicron particle analyzer after diluting (or dissolving) the composition 1000 times (volume ratio) with a solvent as described above.

[0079] The photosensitive resin composition of this embodiment may contain, as an ion scavenger, a compound of at least one metal atom selected from the group consisting of Zr, Bi, Mg, and Al. From the viewpoint of insulation reliability, the content of the ion scavenger containing at least one metal atom 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. The upper limit of the content of the ion scavenger containing at least one metal atom selected from the group consisting of Zr, Bi, Mg, and Al is, for example, 100 mass % or less, based on the total solid content of the ion scavenger.

[0080] ((C) Component Content) The content of component (C) 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.

[0081] <(D) Photopolymerizable compound> The component (D) is not particularly limited as long as it is a compound having an ethylenically unsaturated group such as a functional group exhibiting photopolymerization, for example, a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, or a (meth)acryloyl group, and from the viewpoint of reactivity, it is preferably a compound having a (meth)acryloyl group.

[0082] Examples of component (D) 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, pentaerythritol, ditrimethylolpropane, di Preferred examples of the component (D) include polyhydric (meth)acrylates of polyhydric alcohols such as pentaerythritol and tris-hydroxyethyl isocyanurate, or their 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 components (D) can be used alone or in combination. In particular, component (D) may contain polyhydric (meth)acrylates of the above polyhydric alcohols or their ethylene oxide or propylene oxide adducts, or may be polyhydric (meth)acrylates of the above polyhydric alcohols or their ethylene oxide or propylene oxide adducts. Dipentaerythritol hexaacrylate may be selected as component (D).

[0083] ((D) Component Content) The content of component (D) may be appropriately selected from 0.1 to 10 mass%, 0.1 to 5 mass%, or 0.3 to 3 mass%, based on the total solid content in the photosensitive resin composition. If it is 0.1 mass% or more, the photosensitivity is low, which can suppress the tendency of the exposed area to dissolve during development, and if it is 10 mass% or less, the decrease in heat resistance can be suppressed.

[0084] <(E) Pigment> Component (E) is preferably used depending on the desired color when concealing wiring, etc. As component (E), a colorant that develops 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.

[0085] (Content of component (E)) The content of component (E) may be appropriately selected from 0.1 to 20 mass%, 0.1 to 10 mass%, or 1 to 10 mass%, based on the total solid content in the photosensitive resin composition, from the viewpoint of further concealing the wiring, and may also be 0.1 to 5 mass%.

[0086] <(F) Inorganic filler> The photosensitive resin composition of this embodiment may further contain component (F) for the purpose of further improving various properties such as adhesion and coating hardness. Examples of the (F) component that can be used include silica (SiO2), alumina (Al2O3), zirconia (ZrO2), talc (3MgO·4SiO2·H2O), aluminum hydroxide (Al(OH)3), calcium carbonate (CaCO3), barium sulfate (BaSO4), calcium sulfate (CaSO4), zinc oxide (ZnO), magnesium titanate (MgO·TiO2), and carbon (C). These inorganic fillers can be used alone or in combination.

[0087] The average particle size of component (F) may be appropriately selected from 0.1 to 20 μm, 0.1 to 10 μm, 0.1 to 5 μm, or 0.1 to 1 μm. When the average particle size is 20 μm or less, deterioration of insulation reliability can be further suppressed. Here, the average particle size of component (F) is measured in the same manner as the average particle size of component (C) described above.

[0088] Among the (F) components, silica may be included from the viewpoint of improving heat resistance, and barium sulfate may be included or a combination of silica and barium sulfate may be included from the viewpoint of improving solder heat resistance, crack resistance (thermal shock resistance), and adhesive strength between the underfill material and the cured film after a PCT resistance test. Furthermore, the inorganic filler may be appropriately selected from those whose surface has been treated with alumina or an organosilane compound from the viewpoint of improving the aggregation prevention effect.

[0089] The aluminum elemental composition on the surface of an inorganic filler that has been 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 silicon elemental composition on the surface of an inorganic filler that has been surface-treated with 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 carbon elemental composition on the surface of an inorganic filler that has been surface-treated with an organosilane compound 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 photoelectron spectroscopy).

[0090] 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.).

[0091] ((F) Component Content) The content of component (F) may be appropriately selected from 10 to 80 mass%, 15 to 70 mass%, 20 to 50 mass%, or 25 to 40 mass%, based on the total solid content of the photosensitive resin composition. Within the above range, the cured product strength, heat resistance, insulation reliability, thermal shock resistance, resolution, etc. of the photosensitive resin composition can be further improved.

[0092] When silica is used as component (F), the content of silica may be appropriately selected from 5 to 60 mass%, 15 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 (F), the content of barium sulfate may be appropriately selected from 5 to 30 mass%, 5 to 25 mass%, or 5 to 20 mass%, based on the total solid content of the photosensitive resin composition. Within the above ranges, solder heat resistance and adhesive strength between the underfill material and the cured film after PCT resistance testing can be further improved.

[0093] <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.

[0094] 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.

[0095] <(G) Hardener> The photosensitive resin composition of this embodiment may contain component (G). Examples of component (G) 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 the carboxyl group and / or hydroxyl group of component (A), the photocurable component 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.

[0096] Examples of the (G) component include thermosetting compounds such as epoxy compounds, melamine compounds, and oxazoline compounds. Examples of the 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. However, the epoxy compounds do not include the (A) component. Examples of the melamine compounds include triaminotriazine, hexamethoxymelamine, and hexabutoxylated melamine. Among these, from the viewpoint of further improving the heat resistance of the cured film, it is preferable to include an epoxy compound (epoxy resin), and it is more preferable to use an epoxy compound in combination with a blocked isocyanate.

[0097] 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.

[0098] The component (G) may be used alone or in combination of two or more. When the component (G) 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.

[0099] 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.

[0100] 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.

[0101] <(H) Elastomer> The photosensitive resin composition of this embodiment may contain component (H). Component (H) is particularly suitable when the photosensitive resin composition of this embodiment is used for a semiconductor package substrate. Addition of component (H) 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.

[0102] Examples of component (H) 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.

[0103] 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 polymeric (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 also 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 Silactran E790.

[0104] 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 the hydrogen atoms of 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.

[0105] 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 (VI):

[0106] [ka]

[0107] In general formula (VI), Y 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 a direct bond between benzene rings; R 1 and R 2 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.

[0108] Specific examples of the dihydric phenol represented by general formula (VI) include bisphenol A, bis-(4-hydroxyphenyl)methane, bis-(4-hydroxy-3-methylphenyl)propane, resorcinol, etc. These compounds can be used alone or in combination. Alternatively, a multiblock copolymer can be used in which an aromatic polyester (e.g., polybutylene terephthalate) portion serves as the hard segment component and an aliphatic polyester (e.g., polytetramethylene glycol) portion serves as the soft segment component. Various grades are available, depending on the type, ratio, and molecular weight of the hard and soft segments. Specifically, commercially available products include Hytrel (manufactured by DuPont-Toray Industries, Inc., "Hytrel" is a registered trademark), Pelprene (manufactured by Toyobo Co., Ltd., "Pelprene" is a registered trademark), and Espel (manufactured by Hitachi Chemical Co., Ltd., "Espel" is a registered trademark).

[0109] Acrylic elastomers are primarily made of acrylic esters, and include ethyl acrylate, butyl acrylate, methoxyethyl acrylate, and ethoxyethyl acrylate. Crosslinking monomers include glycidyl methacrylate and allyl glycidyl ether. Furthermore, acrylonitrile and ethylene can also be copolymerized. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, and acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer.

[0110] 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 of 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.

[0111] The content of component (H) 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 the high temperature range becomes lower and the unexposed areas become more easily eluted in a developer.

[0112] <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 phosphorus-based compounds such as phosphate compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters may also be used. Furthermore, the photosensitive resin composition of the present embodiment may further contain (I) a triazine compound such as melamine, if necessary.

[0113] 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.

[0114] [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 10 to 50 μm, 15 to 40 μm, or 20 to 30 μm.

[0115] 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.

[0116] [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 does not suffer from undercutting of the bottom or chipping of the upper part of the resist, and the line widths of the middle (center) and deepest (bottom) parts of the pattern cross section are not larger than the line widths of the surface parts, resulting in a pattern with good linearity of the pattern contour, excellent resist shape, and excellent resolution. Furthermore, this permanent mask resist has a pattern with excellent formation stability for the miniaturized hole diameters and hole spacing pitches that have become increasingly smaller due to the miniaturization and high performance of electronic devices in recent years.

[0117] [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 by a method such as screen printing, spraying, roll coating, curtain coating, or electrostatic coating 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 a dose of 10 to 2,000 mJ / cm. 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. Thereafter, wiring is formed by etching to produce a printed wiring board. [Example]

[0118] The objects and advantages of the present embodiment will be explained in more detail below based on examples and comparative examples, but the present embodiment is not limited to the following examples.

[0119] (Synthesis Example 1) Bisphenol F novolac epoxy resin (a) (EXA-7376, manufactured by DIC Corporation, in the general formula (II), Y 3 and Y 4 is a glycidyl group, R 12 A mixture of 350 parts by weight of a bisphenol F novolac epoxy resin (epoxy equivalent: 186) containing a structural unit in which ⁻ is a hydrogen atom, 70 parts by weight of acrylic acid (b), 0.5 parts by weight of methylhydroquinone, and 120 parts by weight of carbitol acetate was heated to 90°C and stirred to react until the mixture was completely dissolved. 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 reacted 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) (c) and 85 parts by weight of carbitol acetate were added, heated to 80°C, and reacted for 6 hours. The mixture was then cooled to room temperature to obtain a THPAC-modified bisphenol F novolac epoxy acrylate (epoxy resin (1)) as component (A1) with a solids concentration of 73% by weight.

[0120] (Synthesis Example 2) A flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with bisphenol F epoxy resin (Y 6 is a hydrogen atom, R 14A mixture of 1,052 parts by weight of bisphenol F epoxy resin (a) (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 (epoxy resin (2)) as component (A2) having a solid acid value of 80 mgKOH / g and a solid content of 62 mass %.

[0121] (Synthesis Example 3) Cresol novolac epoxy resin (a) (manufactured by Tohto Kasei Co., Ltd., trade name "YDCN704"), in the general formula (III), Y 5 is a glycidyl group, R 13 220 parts by weight of a novolac epoxy resin (epoxy equivalent: 206) containing a structural unit in which (A) is a methyl group, 72 parts by weight of acrylic acid (b), 1.0 part by weight of hydroquinone, and 180 parts by weight of carbitol acetate were charged and heated and stirred at 90°C to dissolve the reaction mixture. The resulting solution was then cooled to 60°C, and 1 part by weight of benzyltrimethylammonium chloride was added. The mixture was heated to 100°C and reacted until the solid acid value reached 1 mgKOH / g or less. 152 parts by weight of tetrahydrophthalic anhydride (THPAC) (c) and 100 parts by weight of carbitol acetate were then added, heated to 80°C, and reacted for 6 hours. The mixture was then cooled to room temperature and diluted with carbitol acetate to a solid concentration of 60% by weight to obtain a THPAC-modified cresol novolac epoxy acrylate (epoxy resin (3)) as component (A2).

[0122] (Examples 1 to 5, Comparative Examples 1 to 6) A photosensitive resin composition was prepared by mixing the 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.

[0123] [Table 1]

[0124] The details of each material in Table 1 are as follows: Epoxy resins (1) to (3) are the acid-modified vinyl group-containing epoxy resins (1) to (3) obtained in Synthesis Examples 1 to 3, respectively. Irgacure 907: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (BASF, trade name), alkylphenone photopolymerization initiator DETX: KAYACURE DETX-S, 2,4-diethylthioxanthone (trade name, manufactured by Nippon Kayaku Co., Ltd.), compounds with a thioxanthone skeleton (thioxanthone-based photopolymerization initiator) Irgacure 819: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BASF, trade name), acylphosphine oxide photopolymerization initiator ·IXE500: Bi-containing anion scavenger (manufactured by Toagosei Co., Ltd., trade name, average particle size: 1.5 μm, Bi compound content: 100% by mass) ·IXE800: Zr-containing anion scavenger (manufactured by Toagosei Co., Ltd., trade name, average particle size: 2.0 μm, Zr compound content: 100% by mass) ·IXEPLAS-A2: Zr, Mg, Al-containing ion scavenger (manufactured by Toagosei Co., Ltd., trade name, average particle size: 0.2 μm, Zr compound content: 20~30% by mass) IXE300: Cation scavenger (manufactured by Toagosei Co., Ltd., does not contain Zr, Bi, Mg, or Al) DPHA: Dipentaerythritol hexaacrylate (trade name, manufactured by Nippon Kayaku Co., Ltd.) Phthalocyanine pigments: Phthalocyanine pigments (manufactured by Sanyo Dye Co., Ltd.) B34: Barium sulfate particles (manufactured by Sakai Chemical Industry Co., Ltd., trade name, average particle size: 0.3 μm) SFP20M: Silica particles (Denki Kagaku Kogyo Co., Ltd., product name, average particle size: 0.3 μm) SG-95: Talc (Nippon Talc Co., Ltd., trade name, average particle size: 2.5 μm, compound without ion-trapping function) ZR-30AL: Zirconia particles (Nissan Chemical Industries, Ltd., product name, average particle size: 50 μm, compound with no ion-trapping function) BL103: Aluminum hydroxide particles (Nippon Light Metal Co., Ltd., product name, average particle size: 10 μm) Curing agent: YX4000X (Mitsubishi Chemical Corporation, trade name, biphenyl-type epoxy resin) Melamine: Nissan Chemical Industries, Ltd.

[0125] 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.

[0126] [Preparation of test specimens] The photosensitive resin compositions of the Examples and Comparative Examples were applied to a 0.6 mm thick copper-clad laminate substrate (MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) by screen printing so that the dried film thickness would be 35 μm, and then dried at 80° C. for 20 minutes using a hot air circulation dryer. Next, a negative mask having a predetermined pattern (a pattern with a hole diameter of 50 μm and a center-to-center distance of 50 μm) was attached to the coating film, and the coating film was exposed to 600 mJ / cm 2 using an ultraviolet exposure device. 2 After that, the film was 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 1000 mJ / cm 2 using an ultraviolet exposure device. 2 and heated at 150° C. for 1 hour to prepare a test piece with a permanent mask resist.

[0127] [Resist shape] The above test pieces were cast in epoxy resin (jER828, product 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. Evaluation was made 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).

[0128] [Adhesion] The photosensitive resin compositions of the Examples and Comparative Examples were applied to a copper foil (manufactured by Nippon Denkai Co., Ltd.) having a thickness of 35 μm by screen printing so that the film thickness after drying would be 35 μm, and then dried at 80° C. for 20 minutes using a hot air circulation dryer. Next, the negative mask was attached to the coating film, and the film was exposed to 200 mJ / cm 2 using a parallel exposure machine (manufactured by HITECH Corporation, product name: HTE-5102S). 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 1000 mJ / cm 2 using an ultraviolet exposure device. 2 The specimens were then exposed to an exposure dose of 1000 ppm and heated at 150°C for 1 hour to prepare test specimens with a permanent mask resist on the copper foil. The surface of the resulting 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 (manufactured by Nichiban Co., Ltd., trade name: Araldite) and cured. After leaving the specimen 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 in the thickness direction (perpendicular to the thickness direction) of the copper foil at room temperature at a pulling rate of 50 mm / min. 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 evaluated according to the following criteria. In this specification, room temperature refers to 25°C. A: The peel strength was greater than 0.5 kN / mm. B: The peel strength was in the range of 0.3 to 0.5 kN / mm. C: The peel strength was less than 0.3 kN / mm.

[0129] [Melt viscosity (fluidity)] A photosensitive resin composition was applied to a polyethylene terephthalate (PET) film in a circular shape with a diameter of 2.5 cm and a thickness of 100 to 1000 μm, and the solvent in the composition was evaporated to prepare a test piece that would not flow even when left standing. The melt viscosity of the test piece was then measured using a rheometer (manufactured by Thermo Scientific, Inc., product name: Rheostress 6000). A: The viscosity at 100°C is less than 100 Pa / s. B: The viscosity at 100°C is 100 Pa / s or more.

[0130] [Insulation (electrical insulation)] A test piece was prepared in the same manner as described in the above [Test Piece Preparation], except that a bismaleimide triazine substrate with interdigital electrodes (line / space = 10 μm / 10 μm) was used instead of a copper-clad laminate substrate, and this was exposed to conditions of 135°C, 85%, and 5 V. The extent of migration was then observed using a metallurgical microscope at 100x magnification and evaluated according to the following criteria. A: Even after 200 hours, no migration occurred in the permanent mask resist and the resistance value was 10 -6 It never dropped below Ω. B: 100 hours or more but less than 200 hours, no migration occurs in the permanent mask resist, and the resistance value is 10 -6 It never dropped below Ω. C: Migration occurs in the permanent mask resist within 100 hours, and the resistance value is 10 -6 It dropped below Ω.

[0131] [Solder heat resistance] A water-soluble flux was applied to a test piece prepared in the same manner as in the above [Preparation of test piece], and the test piece was immersed in a solder bath at 265°C for 10 seconds. This constitutes one cycle, and after six cycles were repeated, the appearance of the permanent mask resist was visually observed and evaluated according to the following criteria. 3: There was no change in appearance within a 30cm x 30cm area of ​​the permanent mask resist. 2: Within a 30cm x 30cm area of ​​permanent mask resist, 1 to 5 lifts or blisters of the coating occurred. 1: Six or more lifts or blisters of the coating occurred within a 30cm x 30cm area of ​​the permanent mask resist.

[0132] [Crack resistance] Test pieces were prepared in the same manner as in the above [Preparation of Test Pieces], and the test pieces were subjected to 1000 cycles of -65°C for 30 minutes / (room temperature: 25°C) / 150°C for 30 minutes. The appearance of the permanent mask resist was then visually observed and evaluated according to the following criteria. 3: There was no change in appearance within a 30cm x 30cm area of ​​the permanent mask resist. 2: Within a 30cm x 30cm area of ​​permanent mask resist, 1 to 5 lifts or blisters of the coating occurred. 1: Six or more lifts or blisters of the coating occurred within a 30cm x 30cm area of ​​the permanent mask resist.

[0133] [Solvent resistance] Test pieces prepared in the same manner as described in [Preparation of test pieces] above were immersed in isopropyl alcohol at room temperature (25°C, same below) for 30 minutes, and after checking whether there were any abnormalities in the appearance of the permanent mask resist, a peeling test was performed using cellophane tape. 3: There was no abnormality in the appearance of the permanent mask resist, and no peeling occurred. 2: Only a slight change occurred in the appearance of the permanent mask resist. 1: The appearance of the permanent mask resist is abnormal or peeling has occurred.

[0134] [Acid resistance] A test piece prepared in the same manner as described in [Preparation of test piece] above was immersed in a 10% by mass aqueous solution of hydrochloric acid at room temperature for 30 minutes, and after checking whether there were any abnormalities in the appearance of the permanent mask resist, a peeling test was performed using cellophane tape. 3: There was no abnormality in the appearance of the permanent mask resist, and no peeling occurred. 2: Only a slight change occurred in the appearance of the permanent mask resist. 1: The appearance of the permanent mask resist is abnormal or peeling has occurred.

[0135] [Alkali resistance] A test piece prepared in the same manner as described in [Preparation of test piece] above was immersed in a 5% by mass aqueous solution of sodium hydroxide at room temperature for 30 minutes, and after checking whether there were any abnormalities in the appearance of the permanent mask resist, a peeling test was performed using cellophane tape. 3: There was no abnormality in the appearance of the permanent mask resist, and no peeling occurred. 2: Only a slight change occurred in the appearance of the permanent mask resist. 1: The appearance of the permanent mask resist is abnormal or peeling has occurred.

[0136] [Table 2]

[0137] As can be seen from Table 2, the photosensitive resin compositions of Examples 1 to 5 according to this embodiment exhibited excellent performance in terms of resist shape, adhesion, melt viscosity (fluidity), and insulating properties, and were also rated "3" in the evaluations of solder heat resistance, crack resistance, solvent resistance, acid resistance, and alkali resistance. 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 resin compositions of Comparative Examples 1 to 6 did not exhibit excellent effects, particularly in terms of adhesion and insulating properties.

[0138] (Examples 6 to 10, Comparative Examples 7 to 12) The photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 6, prepared according to the blending ratios shown in Table 1, were diluted with methyl ethyl ketone, applied to a polyethylene terephthalate (PET) film, and dried at 90°C for 10 minutes to form a 25µm-thick photosensitive layer made of the photosensitive resin composition. A cover film was then laminated on top of the photosensitive layer to produce dry films of Examples 6 to 10 and Comparative Examples 7 to 12, respectively.

[0139] [Dry film evaluation] The cover film was peeled off from the dry film obtained above, and the dry film was thermally laminated onto a solid copper foil substrate. Then, the dry film was exposed in the same manner as described above in [Preparation of test pieces] to prepare test pieces having a permanent mask resist. The obtained test piece was used to carry out the same evaluation as in Example 1. The results are shown in Table 3.

[0140] [Table 3]

[0141] From the results shown in Table 3, the dry films of Examples 6 to 10 of this embodiment exhibited excellent performance in terms of resist shape, adhesion, melt viscosity (fluidity), and insulating properties, and were also rated "3" in the evaluations of solder heat resistance, crack resistance, solvent resistance, acid resistance, and alkali resistance. Thus, the dry films of this embodiment also exhibited excellent performance in all properties, and it was confirmed that they can be particularly suitably used for producing permanent mask resists. In contrast, the dry films of Comparative Examples 7 to 12 did not exhibit excellent effects, especially in terms of adhesion and insulating properties.

Claims

1. (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerization initiator, (C) an ion scavenger having Zr, Mg, and Al, (D) a photopolymerizable compound, and (F) an inorganic filler, The component (F) contains at least one of silica and barium sulfate, 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), A photosensitive resin composition, wherein the content of the inorganic filler (F) is 15 mass% or more based on the total amount of solids in the photosensitive resin composition.

2. 2. The photosensitive resin composition according to claim 1, wherein the component (A) further contains at least one acid-modified vinyl group-containing epoxy resin (A1) obtained using a bisphenol novolac epoxy resin (a1).

3. 2. The photosensitive resin composition according to claim 1, 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, and triphenolmethane epoxy resins.

4. 3. The photosensitive resin composition according to claim 2, wherein the acid-modified vinyl group-containing epoxy resin (A1) is a resin obtained by reacting the epoxy resin (a1) with a vinyl group-containing monocarboxylic acid (b) to form a resin (A1′), and then reacting the resulting resin with a saturated or unsaturated group-containing polybasic acid anhydride (c).

5. 5. The photosensitive resin composition according to claim 2, wherein the bisphenol novolac epoxy resin (a1) has a structural unit represented by the following general formula (I) or (II): 【Chemistry 1】 [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 the groups represents a glycidyl group. 【Chemistry 2】 [In general formula (II), R １２ 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 the groups represents a glycidyl group.

6. 6. The photosensitive resin composition according to claim 5, wherein the bisphenol novolac epoxy resin (a1) has a structural unit represented by 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): 【Transformation 3】 [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. 2. The photosensitive resin composition according to claim 1, 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).

8. 8. The photosensitive resin composition according to claim 1, wherein the epoxy resin (a2) is a novolac epoxy resin having a structural unit represented by general formula (III). 【Chemistry 4】 [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.

9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the (B) photopolymerization initiator is at least one selected from the group consisting of alkylphenone-based photopolymerization initiators, compounds having a thioxanthone skeleton (thioxanthone-based photopolymerization initiators), and acylphosphine oxide-based photopolymerization initiators.

10. 10. The photosensitive resin composition according to claim 1, wherein the ion scavenger (C) 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.

11. The photosensitive resin composition according to any one of claims 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 claims 1 to 11, further comprising (E) a pigment.

13. The photosensitive resin composition according to any one of claims 1 to 12, wherein the content of the acid-modified vinyl group-containing epoxy resin (A) is 50 mass% or less based on the total amount of solids in the photosensitive resin composition.

14. The photosensitive resin composition according to any one of claims 1 to 12, wherein the contents of the (A) acid-modified vinyl group-containing epoxy resin, the (B) photopolymerization initiator, the (C) ion scavenger, and the (D) photopolymerizable compound are 20 to 80 mass%, 0.2 to 15 mass%, 0.1 to 10 mass%, and 0.1 to 10 mass%, respectively, based on the total amount of solids in the photosensitive resin composition.

15. A dry film having a carrier film and a photosensitive layer using the photosensitive resin composition according to any one of claims 1 to 14.

16. A printed wiring board comprising a permanent mask resist formed from the photosensitive resin composition according to any one of claims 1 to 14.

17. 17. The printed wiring board according to claim 16, wherein the permanent mask resist has a thickness of 10 [mu]m or more.

18. 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 14 or the dry film according to claim 15; forming a resist pattern using the photosensitive layer; and curing the resist pattern to form a permanent mask resist.

Images