Photosensitive resin composition

Abstract

To provide a photosensitive resin composition enabling the production of a cured product that enables the formation of a via hole having a small diameter and suppresses the occurrence of an undercut.SOLUTION: A photosensitive resin composition contains (A-1) a resin having an ethylenically unsaturated group and a carboxyl group having a weight average molecular weight of 6,000 or less, (A-2) a resin containing an ethylenically unsaturated group and a carboxyl group having a weight average molecular weight larger than that of the component (A-1) by 2,000 or more, and (B) a photopolymerization initiator, wherein the molecular weight of the component (B) is 400 or more.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] In printed wiring boards, solder resist is sometimes provided as a permanent protective film for preventing solder from adhering to areas where solder is not required and for preventing the circuit board from corroding. As the solder resist, a photosensitive resin composition such as that described in Patent Document 1 is generally used. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2014-115672 A Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, as printed wiring boards become smaller and thinner, there is a demand for forming small diameter via holes.

[0005] However, the smaller the diameter of the via hole to be formed, the more likely it is that an undercut will occur. Undercut is a phenomenon in which the outline of the via does not have the intended shape at the bottom of the via, but becomes enlarged in diameter. In a via hole where an undercut has occurred, the diameter of the bottom part, which corresponds to the bottom of the via hole, is larger than the diameter of the top part, which corresponds to the opening of the via hole.

[0006] An object of the present invention is to provide a photosensitive resin composition that is capable of forming a small diameter via hole and giving a cured product in which the occurrence of undercuts is suppressed; and to provide a photosensitive film with a support, a printed wiring board, and a semiconductor device obtained by using the photosensitive resin composition. [Means for solving the problem]

[0007] As a result of intensive research, the present inventors have found that by combining two or more types of resins containing an ethylenically unsaturated group and a carboxyl group, each having different weight average molecular weights, and further using a photopolymerization initiator having a molecular weight of 400 or more, it is possible to form a small diameter via hole and obtain a cured product in which the occurrence of undercuts is suppressed, and have completed the present invention.

[0008] That is, the present invention includes the following. [1] (A-1) a resin containing an ethylenically unsaturated group and a carboxyl group, having a weight average molecular weight of 6,000 or less; (A-2) a resin containing an ethylenically unsaturated group and a carboxyl group and having a weight average molecular weight 2,000 or more higher than that of the component (A-1), and (B) a photopolymerization initiator; A photosensitive resin composition, wherein the molecular weight of component (B) is 400 or more. [2] The photosensitive resin composition according to [1], further comprising (C) an inorganic filler. [3] The photosensitive resin composition according to [2], wherein the content of component (C) is 1 mass % or more, relative to 100 mass % of the non-volatile components in the photosensitive resin composition. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the component (A-1) and the component (A-2) have any one of a cresol novolac skeleton, a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, and a naphthol aralkyl skeleton. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the component (A-1) and the component (A-2) contain an acid-modified cresol novolac skeleton-containing epoxy (meth)acrylate. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the component (B) has a structural unit represented by the following formula (B-1): [ka] (In formula (B-1), R 1 represents an active light absorbing group, R 2 each independently represents a divalent hydrocarbon group; n represents an integer of 1 to 10; * represents a bond. [7] The photosensitive resin composition according to any one of [1] to [6], which is for forming a solder resist. [8] A support-attached photosensitive film comprising: a support; and a photosensitive resin composition layer provided on the support, the photosensitive resin composition layer comprising the photosensitive resin composition according to any one of [1] to [7]. [9] A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of [1] to [7].

[10] The printed wiring board according to [9], wherein the insulating layer is either an interlayer insulating material or a solder resist.

[11] A semiconductor device comprising the printed wiring board according to [9] or

[10] . Effect of the Invention

[0009] According to the present invention, it is possible to provide a photosensitive resin composition that is capable of forming a small diameter via hole and giving a cured product in which the occurrence of undercuts is suppressed; and a photosensitive film with a support, a printed wiring board, and a semiconductor device obtained using the photosensitive resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The photosensitive resin composition, the photosensitive film with a support, the printed wiring board, and the semiconductor device of the present invention will be described in detail below.

[0011] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A-1) a resin containing an ethylenically unsaturated group and a carboxyl group, and the resin has a weight average molecular weight of 6,000 or less, (A-2) a resin containing an ethylenically unsaturated group and a carboxyl group, and the resin has a weight average molecular weight that is 2,000 or more larger than that of component (A-1), and (B) a photopolymerization initiator, wherein the molecular weight of component (B) is 400 or more.

[0012] In the present invention, by using a combination of the (A-1) component and the (A-2) component having different weight average molecular weights and the (B) component having a predetermined molecular weight, it is possible to form small diameter via holes and obtain a cured product in which the occurrence of undercuts is suppressed. In addition, in the present invention, it is usually possible to obtain a cured product excellent in peel strength between the conductor layer, glass transition temperature (Tg), average coefficient of linear thermal expansion (CTE), and surface shape.

[0013] The photosensitive resin composition may further contain optional components such as (C) inorganic filler, (D) epoxy resin, (E) reactive diluent, (F) solvent, and (G) other additives, if necessary. In this specification, the (A-1) component and the (A-2) component are collectively referred to as "(A) resin containing an ethylenically unsaturated group and a carboxyl group". Each component contained in the photosensitive resin composition will be described in detail below.

[0014] <(A) Resin containing an ethylenically unsaturated group and a carboxyl group> The photosensitive resin composition contains (A-1) a resin containing an ethylenically unsaturated group and a carboxyl group, and the resin has a weight average molecular weight of 6000 or less, and (A-2) a resin containing an ethylenically unsaturated group and a carboxyl group, and the resin has a weight average molecular weight that is 2000 or more higher than that of the component (A-1). By using the components (A-1) and (A-2) in combination, it is possible to form small diameter via holes and obtain a cured product in which the occurrence of undercuts is suppressed.

[0015] From the viewpoint of forming small diameter via holes and obtaining a cured product in which the occurrence of undercuts is suppressed, the weight average molecular weight of the (A-1) component is 6000 or less, and preferably 5500 or less, with the lower limit being preferably 1000 or more, more preferably 1500 or more. The weight average molecular weight of the (A-1) component is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

[0016] The weight average molecular weight of the (A-2) component is at least 2000 larger than the weight average molecular weight of the (A-1) component, and preferably at least 2500 larger. The upper limit is preferably not more than 20000, more preferably not more than 17000, and even more preferably not more than 15000. The weight average molecular weight of the (A-2) component can be measured by the same method as that for the weight average molecular weight of the (A-1) component.

[0017] The specific weight average molecular weight of the (A-2) component will vary depending on the weight average molecular weight of the (A-1) component used in combination, but is preferably 3,000 or more, more preferably 3,500 or more, and even more preferably 4,000 or more, and is preferably 20,000 or less, more preferably 17,000 or less, and even more preferably 15,000 or less.

[0018] The ethylenically unsaturated group in the (A-1) component and the (A-2) component has a carbon-carbon double bond, and examples thereof include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadiimide group, and a (meth)acryloyl group. From the viewpoint of the reactivity of photoradical polymerization, a (meth)acryloyl group is preferable. The "(meth)acryloyl group" includes a methacryloyl group, an acryloyl group, and a combination thereof. Since the (A-1) component and the (A-2) component contain an ethylenically unsaturated group, photoradical polymerization is possible. The number of ethylenically unsaturated groups per molecule of the (A-1) component and the (A-2) component may be one or two or more. In addition, when the (A-1) component and the (A-2) component contain two or more ethylenically unsaturated groups per molecule, the ethylenically unsaturated groups may be the same or different.

[0019] In addition, since the components (A-1) and (A-2) contain a carboxyl group, the photosensitive resin composition containing the components (A-1) and (A-2) is soluble in an alkaline solution (for example, a 1 mass% aqueous sodium carbonate solution as an alkaline developer). The number of carboxyl groups per molecule of the components (A-1) and (A-2) may be one or more.

[0020] There are no particular limitations on the components (A-1) and (A-2) as long as they are compounds that have different weight-average molecular weights, have an ethylenically unsaturated group and a carboxyl group, and are capable of photoradical polymerization and alkali development; however, a resin having both a carboxyl group and two or more ethylenically unsaturated groups in one molecule is preferred.

[0021] One embodiment of the resin containing an ethylenically unsaturated group and a carboxyl group is an acid-modified unsaturated epoxy ester resin obtained by reacting an epoxy compound with an unsaturated carboxylic acid and then with an acid anhydride, etc. In detail, an unsaturated epoxy ester resin is obtained by reacting an epoxy compound with an unsaturated carboxylic acid, and an acid-modified unsaturated epoxy ester resin is obtained by reacting the unsaturated epoxy ester resin with an acid anhydride.

[0022] As the epoxy compound, any compound having an epoxy group in the molecule can be used, and examples thereof include bisphenol type epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, and modified bisphenol F type epoxy resin obtained by reacting bisphenol F type epoxy resin with epichlorohydrin to modify it to have three or more functional groups; biphenol type epoxy resin, biphenol type epoxy resin such as tetramethylbiphenol type; novolac type epoxy resins such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type novolac type epoxy resin, and alkylphenol novolac type epoxy resin; fluorine-containing epoxy resins such as bisphenol AF type epoxy resin and perfluoroalkyl type epoxy resin; naphthalene type epoxy resin, dihydroxynaphthalene type epoxy resin, polyhydroxybinaphthalene type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin, binaphthol type epoxy resin, etc. epoxy resins having a naphthalene skeleton, such as naphthylene ether type epoxy resins, naphthol novolac type epoxy resins, and naphthalene type epoxy resins obtained by a condensation reaction between polyhydroxynaphthalene and aldehydes (naphthalene skeleton-containing epoxy resins); bixylenol type epoxy resins; dicyclopentadiene type epoxy resins; trisphenol type epoxy resins; tert-butyl-catechol type epoxy resins; epoxy resins containing a condensed ring skeleton, such as anthracene type epoxy resins; glycidylamine type epoxy resins; glycidyl ester type epoxy resins; biphenyl type epoxy resins; linear aliphatic epoxy resins; epoxy resins having a butadiene structure; alicyclic epoxy resins; heterocyclic epoxy resins; spiro ring-containing epoxy resins; cyclohexane dimethanol type epoxy resins; trimethylol type epoxy resins; tetraphenylethane type epoxy resins; glycidyl group-containing acrylic resins, such as polyglycidyl (meth)acrylate and copolymers of glycidyl methacrylate and acrylic acid esters; fluorene type epoxy resins; and halogenated epoxy resins.

[0023] The epoxy compound is preferably an epoxy resin containing an aromatic skeleton from the viewpoint of reducing the average linear thermal expansion coefficient. Here, the aromatic skeleton is a concept including polycyclic aromatics and aromatic heterocycles. Among them, any of cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, and naphthol aralkyl type epoxy resin is preferred, and cresol novolac type epoxy resin, biphenyl type epoxy resin, and naphthol aralkyl type epoxy resin are more preferred, and cresol novolac type epoxy resin is even more preferred, from the viewpoint of increasing the rigidity of the molecule, suppressing the movement of the molecule, and thus further reducing the average linear thermal expansion coefficient of the cured product of the resin composition.

[0024] Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, cinnamic acid, and crotonic acid, and these may be used alone or in combination of two or more. Among them, acrylic acid and methacrylic acid are preferred from the viewpoint of improving the photocurability of the photosensitive resin composition. In this specification, the epoxy ester resin, which is a reaction product of the above-mentioned epoxy compound and (meth)acrylic acid, may be referred to as "epoxy (meth)acrylate", in which the epoxy group of the epoxy compound is substantially eliminated by the reaction with (meth)acrylic acid. "(meth)acrylate" refers to methacrylate and acrylate. Acrylic acid and methacrylic acid may be collectively referred to as "(meth)acrylic acid".

[0025] Examples of the acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride, and these may be used alone or in combination of two or more. Among these, succinic anhydride and tetrahydrophthalic anhydride are preferred from the viewpoint of improving the resolution and insulation reliability of the cured product, and tetrahydrophthalic anhydride is more preferred.

[0026] In obtaining the acid-modified unsaturated epoxy ester resin in the components (A-1) and (A-2), an unsaturated carboxylic acid and an epoxy resin may be reacted in the presence of a catalyst to obtain an unsaturated epoxy ester resin, and then the unsaturated epoxy ester resin may be reacted with an acid anhydride. If necessary, a solvent or a polymerization inhibitor may be used.

[0027] The acid-modified unsaturated epoxy ester resin in the (A-1) and (A-2) components preferably has any one of a cresol novolac skeleton, a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, and a naphthol aralkyl skeleton. The acid-modified unsaturated epoxy ester resin in the (A-1) and (A-2) components is preferably an acid-modified epoxy (meth)acrylate. The "epoxy" in the acid-modified unsaturated epoxy ester resin represents a structure derived from the above-mentioned epoxy compound. For example, "acid-modified bisphenol-type epoxy (meth)acrylate" refers to an acid-modified unsaturated epoxy ester resin obtained by using a bisphenol-type epoxy resin as an epoxy compound and (meth)acrylic acid as an unsaturated carboxylic acid. The preferred range of the acid-modified epoxy (meth)acrylate is derived from the preferred range of the epoxy compound. That is, from the viewpoint of lowering the average linear thermal expansion coefficient of the cured product of the resin composition, the acid-modified unsaturated epoxy ester resin is preferably an acid-modified cresol novolac skeleton-containing epoxy (meth)acrylate, an acid-modified bisphenol A skeleton-containing epoxy (meth)acrylate, an acid-modified bisphenol F skeleton-containing epoxy (meth)acrylate, a biphenyl skeleton-containing epoxy (meth)acrylate, or a naphthol aralkyl skeleton-containing epoxy (meth)acrylate, more preferably an acid-modified cresol novolac skeleton-containing epoxy (meth)acrylate, a biphenyl skeleton-containing epoxy (meth)acrylate, or a naphthol aralkyl skeleton-containing epoxy (meth)acrylate, and even more preferably an acid-modified cresol novolac skeleton-containing epoxy (meth)acrylate. The acid-modified cresol novolac skeleton-containing epoxy (meth)acrylate is a compound obtained by reacting a reaction product of a cresol novolac type epoxy resin and a (meth)acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. The acid-modified bisphenol A skeleton-containing epoxy (meth)acrylate is a compound obtained by reacting a reaction product of a bisphenol A type epoxy resin with a (meth)acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride.The acid-modified bisphenol F skeleton-containing epoxy (meth)acrylate is a compound obtained by reacting a reaction product of a bisphenol F type epoxy resin and a (meth)acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. The acid-modified biphenyl skeleton-containing epoxy (meth)acrylate is a compound obtained by reacting a reaction product of a biphenyl type epoxy resin and a (meth)acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. The acid-modified naphthol aralkyl skeleton-containing epoxy (meth)acrylate is a compound obtained by reacting a reaction product of a naphthol aralkyl type epoxy resin and a (meth)acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride.

[0028] The acid-modified unsaturated epoxy ester resin in component (A) can be a commercially available product. Specific examples of the acid-modified unsaturated epoxy ester resin as component (A-1) include "CCR-1373H" (cresol novolac type epoxy acrylate), "ZCR-8001H" (acid-modified biphenyl type epoxy acrylate), and "ZCR-1569H" (acid-modified biphenyl type epoxy acrylate: reaction product of biphenyl type epoxy resin, acrylic acid, and acid anhydride) manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more.

[0029] Specific examples of the acid-modified unsaturated epoxy ester resin as component (A-2) include "CCR-1171H" (cresol novolac type epoxy acrylate) and "ZCR-1797H" (acid-modified biphenyl type epoxy acrylate) manufactured by Nippon Kayaku Co., Ltd., "ZAR-2000" (reaction product of bisphenol A type epoxy resin, acrylic acid, and succinic anhydride), "ZFR-1491H", "ZFR-1533H" (reaction product of bisphenol F type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride) manufactured by Nippon Kayaku Co., Ltd., "PR-300CP" (reaction product of cresol novolac type epoxy resin, acrylic acid, and acid anhydride) manufactured by Showa Denko Co., Ltd., and "CCR-1179" (cresol novolac F type epoxy acrylate) manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more.

[0030] The acid value of the (A-1) component and the (A-2) component is preferably 0.1 mgKOH / g or more, more preferably 0.5 mgKOH / g or more, and even more preferably 1 mgKOH / g or more, 10 mgKOH / g or more, 20 mgKOH / g or more, 30 mgKOH / g or more, 40 mgKOH / g or more, and 50 mgKOH / g or more, from the viewpoint of improving the alkaline developability of the photosensitive resin composition. On the other hand, from the viewpoint of suppressing the dissolution of the fine pattern of the cured product by development and improving the insulation reliability, the acid value is preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, and even more preferably 100 mgKOH / g or less. Here, the acid value refers to the residual acid value of the carboxyl group present in the (A) component, and the acid value can be measured by the following method. First, after weighing out about 1 g of the resin solution to be measured, 30 g of acetone is added to the resin solution to dissolve the resin solution uniformly. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N aqueous ethanol solution. The acid value is then calculated using the following formula. Formula: A=10×(Vf-BL)×F×56.11 / (Wp×I)

[0031] In the above formula, A represents the acid value (mgKOH / g), Vf represents the titer of KOH (mL), BL represents the blank, F represents the factor (titer), Wp represents the mass of the resin solution to be measured (g), and I represents the proportion of non-volatile matter in the resin solution to be measured (mass%).

[0032] In producing the components (A-1) and (A-2), from the viewpoint of improving storage stability, the ratio of the number of moles of epoxy groups in the epoxy resin to the number of moles of carboxyl groups in the total of the unsaturated carboxylic acid and the acid anhydride is preferably in the range of 1:0.8 to 1.3, and more preferably in the range of 1:0.9 to 1.2.

[0033] From the viewpoint of improving alkali developability, the total content of the (A-1) component and the (A-2) component is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, when the non-volatile components of the photosensitive resin composition are taken as 100% by mass. From the viewpoint of improving heat resistance, the upper limit is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. In the present invention, the content of each component in the photosensitive resin composition is a value when the non-volatile components in the photosensitive resin composition are taken as 100% by mass, unless otherwise specified.

[0034] From the viewpoint of improving alkali developability, the content of the component (A-1) is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more, when the non-volatile components of the photosensitive resin composition are taken as 100% by mass. From the viewpoint of improving heat resistance, the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0035] From the viewpoint of improving alkaline developability, the content of the component (A-2) is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more, when the non-volatile components of the photosensitive resin composition are taken as 100% by mass. From the viewpoint of improving heat resistance, the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0036] When the content of the component (A-1) is a1 (mass %) and the content of the component (A-2) is a2 (mass %) when the non-volatile components of the photosensitive resin composition are taken as 100 mass %, from the viewpoint of improving the resolution, a1 / a2 is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more, and is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less.

[0037] <(B) Photopolymerization initiator> The photosensitive resin composition contains a photopolymerization initiator (B) as component (B). The molecular weight of component (B) is 400 or more. By containing component (B) in the photosensitive resin composition, the occurrence of undercuts is suppressed, and it is possible to obtain a cured product having excellent peel strength even if the arithmetic mean roughness (Ra) is small.

[0038] The molecular weight of component (B) is 400 or more, preferably 500 or more, more preferably 600 or more, or 700 or more, from the viewpoint of obtaining a cured product in which the occurrence of undercuts is suppressed and which has excellent peel strength even if the arithmetic mean roughness (Ra) is small. The upper limit is not particularly limited, but is preferably 3000 or less, more preferably 2500 or less, and even more preferably 2000 or less.

[0039] As the component (B), a compound having a molecular weight of 400 or more, having a group that absorbs actinic rays such as ultraviolet rays, and capable of being efficiently photocured can be used. As such a component (B), for example, a compound containing a structural unit represented by formula (B-1) can be preferably used. [ka] (In formula (B-1), R 1 represents an active light absorbing group, R 2 each independently represents a divalent hydrocarbon group; n represents an integer of 1 to 10; * represents a bond.

[0040] R 1 represents an active light absorbing group. The active light absorbing group is a group capable of absorbing active light such as ultraviolet light. The active light absorbing group may be any functional group capable of absorbing active light, and examples thereof include a group having an aminoketone skeleton, a group having an anthraquinone skeleton, a group having a thioxanthone skeleton, a group having a ketal skeleton, a group having a benzophenone skeleton, a group having a xanthone skeleton, a group having an acetophenone skeleton, a group having a benzoin skeleton, a group having a thioxanthone skeleton, and a group having a benzoate skeleton.

[0041] Specific examples of the active light absorbing group include the following groups (i) to (vii). Among them, the active light absorbing group is preferably either (i) or (ii). In the formula, * represents a bond. [ka]

[0042] R 2 each independently represents a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group, and from the viewpoint of achieving the effects of the present invention more significantly, a divalent aliphatic hydrocarbon group is preferred.

[0043] The divalent aliphatic hydrocarbon group is preferably a divalent saturated aliphatic hydrocarbon group, and examples thereof include an alkylene group and an alkenylene group, and an alkylene group is more preferred. The alkylene group may be linear, branched, or cyclic, and a linear group is preferred. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms or an alkylene group having 1 to 3 carbon atoms. Examples of such alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a cyclohexylene group, and a methylene group is preferred. The alkenylene group may be linear, branched, or cyclic, and a linear group is preferred. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and even more preferably an alkenylene group having 2 to 5 carbon atoms.

[0044] Examples of the divalent aromatic hydrocarbon group include an arylene group, a heteroarylene group, etc. As the arylene group or heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferable.

[0045] The divalent hydrocarbon group may have a substituent, for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, an oxo group, and the like.

[0046] n represents an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and even more preferably an integer of 1 to 3.

[0047] The component (B) preferably contains either a compound represented by the following general formula (B-2) or a compound represented by the following general formula (B-3). [ka] (In general formula (B-2), R 11 each independently represents an active light absorbing group; R 12 each independently represents a divalent hydrocarbon group; R 13 represents an m-valent hydrocarbon group, n1 represents an integer of 1 to 10, and m represents an integer of 1 to 4. In general formula (B-3), R 21 , R 23 each independently represents an active light absorbing group; R 22 each independently represents a divalent hydrocarbon group; and n2 represents an integer of 1 to 10.

[0048] R 11 each independently represents an active light absorbing group, and R 1 is the same as the active light absorbing group represented by

[0049] R 12 each independently represents a divalent hydrocarbon group, and R in formula (B-1) 2 is the same as the divalent hydrocarbon group represented by

[0050] R 13 R represents an m-valent hydrocarbon group. Examples of the m-valent hydrocarbon group include an m-valent aliphatic hydrocarbon group and an m-valent aromatic hydrocarbon group. An m-valent aliphatic hydrocarbon group is preferred. For example, when m is 3, an alkynylene group is preferred. 13 Specific examples of the group represented by include the following: In the formula, "*" represents a bond. [ka]

[0051] n1 represents an integer of 1 to 10 and is the same as n in formula (B-1).

[0052] m represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 3.

[0053] R 21 and R 23each independently represents an active light absorbing group, and R 1 is the same as the active light absorbing group represented by

[0054] R 22 each independently represents a divalent hydrocarbon group, and R in formula (B-1) 2 is the same as the divalent hydrocarbon group represented by

[0055] As the component (B), commercially available products can be used, such as "Omnipol 910" and "Omnipol TP" manufactured by IGM.

[0056] The content of the (B) component is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on the non-volatile components of the photosensitive resin composition being 100% by mass, from the viewpoint of suppressing the occurrence of undercuts and obtaining a cured product having excellent peel strength even with a small arithmetic mean roughness (Ra).The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, based on the viewpoint of improving heat resistance.

[0057] <(C) Inorganic filler> The photosensitive resin composition may further contain an inorganic filler (C) as an optional component. By containing the component (C), a cured product having a low average linear thermal expansion coefficient can be obtained. The component (C) may be used alone or in combination of two or more types.

[0058] The material of the (C) inorganic filler is not particularly limited, but examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica and barium sulfate are preferred, and silica is particularly preferred. As the silica, spherical silica is preferred. The (C) inorganic filler may be used alone or in combination of two or more.

[0059] From the viewpoint of obtaining a cured product having a low average linear thermal expansion coefficient, the average particle size of the (C) inorganic filler is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less, 2 μm or less, 1 μm or less, or 0.7 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more.

[0060] The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, a particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering particle size distribution measuring device, and the median diameter is taken as the average particle size. The measurement sample is preferably an inorganic filler dispersed in water using ultrasonic waves. Examples of laser diffraction / scattering particle size distribution measuring devices that can be used include the LA-500 manufactured by Horiba, Ltd. and the SALD-2200 manufactured by Shimadzu Corporation.

[0061] The specific surface area of ​​the (C) inorganic filler is preferably 1 m2 in order to obtain a cured product with a low average linear thermal expansion coefficient. 2 / g or more, more preferably 3m 2 / g or more, particularly preferably 5m 2 / g or more. There is no particular upper limit, but it is preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2 The specific surface area is determined by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method.

[0062] From the viewpoint of improving moisture resistance and dispersibility, the (C) inorganic filler is preferably treated with one or more surface treatment agents, such as a vinylsilane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane compound, an organosilazane compound, or a titanate coupling agent. Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM-1003" (vinyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE-903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM-103" (phenyltrimethoxysilane), and Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent).

[0063] (C) The inorganic filler may be a commercially available product. Examples of commercially available products include "SC2050", "SC4050", "SO-C4", "SO-C2", "SO-C1", and "ADMAFINE" manufactured by Admatechs Co., Ltd., "SFP Series" manufactured by Denki Kagaku Kogyo Co., Ltd., "SP(H) Series" manufactured by Nippon Steel & Sumikin Materials Co., Ltd., "Sciqas Series" manufactured by Sakai Chemical Industry Co., Ltd., "Sea Hoster Series" manufactured by Nippon Shokubai Co., Ltd., "AZ Series" and "AX Series" manufactured by Nippon Steel & Sumikin Materials Co., Ltd., and "B Series" and "BF Series" manufactured by Sakai Chemical Industry Co., Ltd.

[0064] The content of the (C) inorganic filler is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more, based on 100% by mass of the non-volatile components in the photosensitive resin composition, from the viewpoint of obtaining a cured product having a low average linear thermal expansion coefficient. The upper limit is, for example, preferably 65% ​​by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less, 50% by mass or less, or 40% by mass or less, based on 100% by mass of the non-volatile components in the photosensitive resin composition, from the viewpoint of obtaining excellent developability by suppressing light reflection during exposure.

[0065] <(D) Epoxy resin> The photosensitive resin composition may further contain an epoxy resin (D) as an optional component. By containing the component (D), the insulation reliability of the cured product of the photosensitive resin composition can be improved. However, the component (D) does not include the epoxy resin (A) containing an ethylenically unsaturated group and a carboxyl group. The component (D) may be used alone or in combination of two or more types.

[0066] Examples of the component (D) include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, and tetraglycidyldiaminodiphenylmethane type epoxy resins. Among these, biphenyl type epoxy resins are preferred as component (D). The epoxy resins may be used alone or in combination of two or more.

[0067] The resin composition preferably contains, as component (D), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile components of component (D) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0068] Epoxy resins include epoxy resins that are liquid at a temperature of 20° C. (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20° C. (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin as component (D), but from the viewpoint of significantly obtaining the desired effects of the present invention, it is preferable to contain only a solid epoxy resin.

[0069] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

[0070] As the solid epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferred, and biphenyl type epoxy resin is more preferred.

[0071] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", and "HP-7200H" (dicyclopentadiene epoxy resin) manufactured by DIC Corporation. ene type epoxy resins); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" (naphthylene ether type epoxy resins) manufactured by DIC; "EPPN-502H" (trisphenol type epoxy resins) manufactured by Nippon Kayaku; "NC7000L" (naphthol novolac type epoxy resins) manufactured by Nippon Kayaku; "NC3000H", "NC3000", and "NC3000L" manufactured by Nippon Kayaku ","NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; " Examples of epoxy resins include "YX8800" (anthracene type epoxy resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals, "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical, "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical, "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical, and "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical. These may be used alone or in combination of two or more.

[0072] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0073] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure are preferable. As the glycidyl amine type epoxy resin, tetraglycidyl diamino diphenyl methane type epoxy resin is preferable.

[0074] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epicoat 828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidylamine type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; and "Celloxide 2021P" (a glycidyl ester type epoxy resin having an ester skeleton) manufactured by Daicel Corporation. cyclic epoxy resin); Daicel's "PB-3600" (epoxy resin having a butadiene structure); Nippon Steel Chemical & Material's "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin); Sumitomo Chemical's "ELM-434L" (glycidylamine type epoxy resin); Sumitomo Chemical's "ELM-434VL" (tetraglycidyldiaminodiphenylmethane type epoxy resin); ADEKA's "EP-3980S" (bifunctional glycidylamine type epoxy resin); ADEKA's "EP-3950L" (trifunctional glycidylamine type epoxy resin); Nissan Chemical's "TEPIC-VL" (isocyanuric ring type epoxy resin); Sumitomo Chemical's "ELM-100H" (N-[2-methyl-4-(oxiranylmethoxy)phenyl]-N-(oxiranylmethyl)oxiranemethanamine). These may be used alone or in combination of two or more.

[0075] When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (D), the ratio thereof (liquid epoxy resin:solid epoxy resin) is preferably 1:0.01 to 1:20, more preferably 1:0.1 to 1:10, and particularly preferably 1:0.5 to 1:5, in terms of mass ratio. When the ratio of the liquid epoxy resin to the solid epoxy resin is within such a range, the desired effects of the present invention can be significantly obtained. Furthermore, when the composition is used in the form of a photosensitive film with a support, appropriate adhesion is usually obtained. Furthermore, when the composition is used in the form of a photosensitive film with a support, sufficient flexibility is usually obtained, and handling is improved. Furthermore, a cured product having sufficient breaking strength can usually be obtained.

[0076] The epoxy equivalent of the (D) component is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. When it is in this range, the crosslink density of the cured product of the resin composition layer becomes sufficient, and an insulating layer with small surface roughness can be obtained. The epoxy equivalent is the mass of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0077] From the viewpoint of significantly obtaining the desired effects of the present invention, the weight average molecular weight (Mw) of the component (D) is preferably from 100 to 5000, more preferably from 200 to 3000, and even more preferably from 250 to 1500. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0078] The content of the (D) component is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulating reliability. The upper limit of the epoxy resin content is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

[0079] <(E) Reactive Diluent> The photosensitive resin composition may further contain a reactive diluent (E) as an optional component. However, the components corresponding to the components (A), (B) and (D) are not included in the component (E). By including the component (E) in the photosensitive resin composition, the photoreactivity can be improved. As the component (E), for example, a photosensitive (meth)acrylate compound having one or more (meth)acryloyl groups in one molecule and being liquid, solid or semi-solid at room temperature can be used. Room temperature means about 25°C. The component (E) may be used alone or in combination of two or more types.

[0080] Representative photosensitive (meth)acrylate compounds include, for example, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; acrylamides such as N,N-dimethylacrylamide and N-methylolacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate; polyhydric alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol, or polyhydric acrylates of their ethylene oxide, propylene oxide, or ε-caprolactone adducts; phenols such as phenoxy acrylate and phenoxyethyl acrylate, or acrylates such as their ethylene oxide or propylene oxide adducts; epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether, modified epoxy acrylates, melamine acrylates, and / or methacrylates corresponding to the above acrylates.Among these, polyvalent acrylates or polyvalent methacrylates are preferred. For example, trivalent acrylates or methacrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane EO-added tri(meth)acrylate, glycerin PO-added tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligo(meth)acrylate, ethyl carbitol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, Examples of the photosensitive (meth)acrylate compounds include hexa(meth)acrylate and (meth)acrylic acid ester of N,N,N',N'-tetrakis(β-hydroxyethyl)ethyldiamine, and examples of the acrylates or methacrylates having a valence of three or more include phosphoric acid triester (meth)acrylates such as tri(2-(meth)acryloyloxyethyl)phosphate, tri(2-(meth)acryloyloxypropyl)phosphate, tri(3-(meth)acryloyloxypropyl)phosphate, tri(3-(meth)acryloyl-2-hydroxyloxypropyl)phosphate, di(3-(meth)acryloyl-2-hydroxyloxypropyl)(2-(meth)acryloyloxyethyl)phosphate, and (3-(meth)acryloyl-2-hydroxyloxypropyl)di(2-(meth)acryloyloxyethyl)phosphate. These photosensitive (meth)acrylate compounds may be used alone or in combination of two or more. "EO" refers to ethylene oxide.

[0081] (E) The reactive diluent may be a commercially available product, such as "DPHA" manufactured by Nippon Kayaku Co., Ltd. or "EBECRYL3708" manufactured by Daicel Allnex Corporation.

[0082] From the viewpoints of promoting photocuring and suppressing stickiness when a cured product is formed, the content of the (E) component, relative to 100 mass% of the nonvolatile components in the photosensitive resin composition, is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more, and is preferably 40 mass% or less, more preferably 35 mass% or less, even more preferably 30 mass% or less, 20 mass% or less, or 10 mass% or less.

[0083] <(F) Organic solvent> The photosensitive resin composition may further contain an organic solvent (F) as an optional component. The varnish viscosity can be adjusted by including the component (F). Examples of the organic solvent (F) include ketones such as methyl ethyl ketone (MEK) 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, carbitol acetate, and ethyl diglycol acetate, aliphatic hydrocarbons such as octane and decane, and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These may be used alone or in combination of two or more. The content of the organic solvent when used may be appropriately adjusted from the viewpoint of the coatability of the photosensitive resin composition.

[0084] <(G) Other Additives> The photosensitive resin composition may further contain (G) other additives to the extent that the object of the present invention is not hindered. Examples of (G) other additives include thermoplastic resins, organic fillers, fine particles such as melamine and organic bentonite, colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black, polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol, thickeners such as bentone and montmorillonite, silicone-based, fluorine-based, and vinyl resin-based defoamers, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus-based compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters, and thermosetting resins such as phenol-based curing agents and cyanate ester-based curing agents.

[0085] The photosensitive resin composition can be produced as a resin varnish by mixing the above-mentioned components (A) and (B) as essential components, appropriately mixing the above-mentioned components (C) to (G) as optional components, and kneading or stirring, as necessary, with kneading means such as a triple roll mill, ball mill, bead mill, or sand mill, or stirring means such as a super mixer, planetary mixer, or high-speed rotary mixer.

[0086] <Properties and applications of photosensitive resin compositions> The photosensitive resin composition contains the (A-1) component and the (A-2) component, and therefore exhibits the characteristic of excellent resolution. Specifically, when the photosensitive resin composition is exposed to light and developed to form a via hole, the minimum opening diameter (minimum via diameter) of the via hole that can be formed without causing residue or peeling can be made small. The minimum opening diameter is preferably 60 μm or less, more preferably less than 50 μm. The lower limit is not particularly limited, but may be 1 μm or more. The minimum opening diameter can be measured according to the method described in the examples below.

[0087] The photosensitive resin composition contains the (A-1) component and the (A-2) component, and therefore exhibits the characteristic of excellent resolution. Specifically, when the photosensitive resin composition is exposed to light and developed to form a via hole, it is possible to form a via hole in which the occurrence of undercut is suppressed, and more specifically, it is possible to form a via hole having a shape in which the difference between the radius of the top and the radius of the bottom is small or no difference. Specifically, the radius (μm) of the top and the radius (μm) of the cross section of a via hole with an opening diameter of 50 μm are measured by SEM. The difference between the radius of the top and the radius of the bottom (radius of the top - radius of the bottom) is obtained. As a result, it is preferably less than 3 μm, and more preferably there is no undercut (0 μm). The evaluation of the undercut can be measured according to the method described in the examples described later.

[0088] The photosensitive resin composition is photocured, and then heat-cured at 180°C for 30 minutes to obtain a cured product that can increase the peel strength (adhesion) between the cured product and a conductor layer formed by plating. Therefore, when an insulating layer and a solder resist are formed from this cured product, an insulating layer with high peel strength between the cured product and the plated conductor layer can be obtained. The peel strength is preferably 0.30 kgf / cm or more. The upper limit of the peel strength is not particularly limited, but can be, for example, 10.0 kgf / cm or less. The peel strength can be measured according to the method described in the examples below.

[0089] The photosensitive resin composition is photocured, and then heat cured at 180° C. for 30 minutes. The roughened surface of the cured product is then roughened. The roughened surface usually exhibits a low arithmetic mean roughness (Ra). Thus, the cured product provides an insulating layer with a low arithmetic mean roughness. The arithmetic mean roughness is preferably 400 nm or less, more preferably 200 nm or less, and even more preferably less than 200 nm. On the other hand, the lower limit of the arithmetic mean roughness may be 1 nm or more. The arithmetic mean roughness can be evaluated by the method described in the examples below.

[0090] The photosensitive resin composition is photocured and then thermally cured at 170°C for 1 hour, and the cured product usually exhibits the property of having a high glass transition temperature (Tg). That is, an insulating layer and a solder resist having a high glass transition temperature are obtained. The glass transition temperature is preferably higher than 150°C. The upper limit is not particularly limited, but may be 350°C or lower. The glass transition temperature (Tg) can be measured according to the method described in the examples below.

[0091] The photosensitive resin composition is photocured, and then heat-cured at 170°C for 1 hour to obtain a cured product that generally exhibits a low average linear thermal expansion coefficient (CTE). That is, an insulating layer and a solder resist having a low average linear thermal expansion coefficient are obtained. The average linear thermal expansion coefficient is preferably 70 ppm or less, more preferably 50 ppm or less, and even more preferably less than 50 ppm. The lower limit is not particularly limited, but may be 10 ppm or more. The average linear thermal expansion coefficient can be measured according to the method described in the examples below.

[0092] The use of the photosensitive resin composition of the present invention is not particularly limited, but it can be used in a wide range of applications requiring a photosensitive resin composition, such as a photosensitive film with a support, an insulating resin sheet such as a prepreg, a circuit board (for laminates, for multilayer printed wiring boards, etc.), a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, a component embedding resin, etc. In particular, it can be suitably used as a photosensitive resin composition for insulating layer of a printed wiring board (a printed wiring board in which a cured product of a photosensitive resin composition is used as an insulating layer), a photosensitive resin composition for interlayer insulating layer (a printed wiring board in which a cured product of a photosensitive resin composition is used as an interlayer insulating layer (interlayer insulating material)), a photosensitive resin composition for plating (a printed wiring board in which plating is formed on a cured product of a photosensitive resin composition), and a photosensitive resin composition for solder resist (a printed wiring board in which a cured product of a photosensitive resin composition is used as a solder resist).

[0093] [Photosensitive film with support] The photosensitive resin composition of the present invention can be suitably used in the form of a supported photosensitive film in which a photosensitive resin composition layer is formed on a support. That is, the supported photosensitive film includes a support and a photosensitive resin composition layer formed of the photosensitive resin composition of the present invention provided on the support.

[0094] Examples of the support include a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, a triacetyl acetate film, and the like, with a polyethylene terephthalate film being particularly preferred.

[0095] Examples of commercially available supports include, but are not limited to, polyethylene terephthalate films such as "Alphan MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and PS series films such as "PS-25" manufactured by Teijin Co., Ltd. These supports are preferably coated with a release agent such as a silicone coating agent on the surface in order to facilitate removal of the photosensitive resin composition layer. The thickness of the support is preferably in the range of 5 μm to 50 μm, and more preferably in the range of 10 μm to 25 μm. By making the thickness 5 μm or more, it is possible to prevent the support from being torn when peeling off the support before development, and by making the thickness 50 μm or less, it is possible to improve the resolution when exposing from above the support. In addition, a support with low fisheyes is preferable. Here, fisheyes are foreign matter, undissolved matter, oxidized deterioration products, etc. of the material that are taken into the film when the material is thermally melted and then kneaded, extruded, biaxially stretched, cast, etc. to produce a film.

[0096] In addition, in order to reduce scattering of light during exposure to actinic rays such as ultraviolet rays, the support is preferably one having excellent transparency. Specifically, the support is preferably one having a turbidity (haze standardized by JIS-K6714) as an index of transparency of 0.1 to 5. Furthermore, the photosensitive resin composition layer may be protected with a protective film.

[0097] By protecting the photosensitive resin composition layer side of the support-attached photosensitive film with a protective film, it is possible to prevent the adhesion of dirt and the like to the surface of the photosensitive resin composition layer and scratches. As the protective film, a film made of the same material as the support can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. By making the thickness 1 μm or more, the handleability of the protective film can be improved, and by making the thickness 40 μm or less, the cost tends to be improved. In addition, it is preferable that the adhesive strength between the photosensitive resin composition layer and the protective film is smaller than the adhesive strength between the photosensitive resin composition layer and the support.

[0098] The photosensitive film with a support can be produced, for example, by preparing a resin varnish by dissolving the photosensitive resin composition of the present invention in an organic solvent, applying the resin varnish on a support, and drying the organic solvent by heating or blowing hot air to form a photosensitive resin composition layer. Specifically, first, bubbles in the photosensitive resin composition are completely removed by a vacuum defoaming method or the like, and then the photosensitive resin composition is applied on a support, the solvent is removed by a hot air oven or a far-infrared oven, and the support is dried, and then a protective film is laminated on the obtained photosensitive resin composition layer as necessary to produce a photosensitive film with a support. Specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of organic solvent in the resin varnish, but in the case of a resin varnish containing 30% by mass to 60% by mass of organic solvent, drying can be performed at 80° C. to 120° C. for 3 minutes to 13 minutes. The amount of the remaining organic solvent in the photosensitive resin composition layer is preferably 5% by mass or less, more preferably 2% by mass or less, based on the total amount of the photosensitive resin composition layer, from the viewpoint of preventing the diffusion of the organic solvent in the subsequent process. Those skilled in the art can appropriately set suitable drying conditions through simple experiments. The thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm, more preferably in the range of 10 μm to 200 μm, even more preferably in the range of 15 μm to 150 μm, even more preferably in the range of 20 μm to 100 μm, and especially preferably in the range of 20 μm to 60 μm, from the viewpoint of improving the handleability and suppressing the decrease in the sensitivity and resolution inside the photosensitive resin composition layer.

[0099] Examples of the method for applying the photosensitive resin composition include a gravure coating method, a microgravure coating method, a reverse coating method, a kiss reverse coating method, a die coating method, a slot die method, a lip coating method, a comma coating method, a blade coating method, a roll coating method, a knife coating method, a curtain coating method, a chamber gravure coating method, a slot orifice method, a spray coating method, and a dip coating method.

[0100] The photosensitive resin composition may be applied in several portions, may be applied in one portion, or may be applied by combining a plurality of different methods. Among them, the die coating method is preferable because of its excellent uniformity of application. In addition, in order to avoid contamination by foreign matter, it is preferable to carry out the application process in an environment where foreign matter is unlikely to be generated, such as a clean room.

[0101] [Printed wiring board] The printed wiring board of the present invention includes an insulating layer formed from a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a solder resist.

[0102] In particular, the printed wiring board of the present invention can be produced by using the above-mentioned photosensitive film with a support. Hereinafter, the case where the insulating layer is a solder resist will be described.

[0103] <Lamination and drying process> The photosensitive resin composition layer side of the supported photosensitive film is laminated onto a circuit board and dried to form a photosensitive resin composition layer on the circuit board.

[0104] Examples of the circuit board include a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board. The circuit board here refers to a board having a patterned conductor layer (circuit) on one or both sides of the board as described above. In addition, in a multilayer printed wiring board formed by alternately laminating a conductor layer and an insulating layer, a board in which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits) is also included in the circuit board here. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

[0105] In one embodiment of the lamination process, the photosensitive resin composition layer side is laminated on one or both sides of the circuit board using a vacuum laminator. In the lamination process, if the photosensitive film with a support has a protective film, the protective film is removed, and then the photosensitive film with a support and the circuit board are preheated as necessary, and the photosensitive resin composition layer is pressure-bonded to the circuit board while being pressurized and heated. For the photosensitive film with a support, a method of laminating the film to the circuit board under reduced pressure by a vacuum lamination method is preferably used.

[0106] The conditions for the lamination step are not particularly limited, but for example, the pressure bonding temperature (lamination temperature) is preferably 70° C. to 140° C., and the pressure bonding pressure is preferably 1 kgf / cm. 2 ~11kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2 ), the pressure bonding time is preferably 5 seconds to 300 seconds, and lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The lamination process may be a batch type or a continuous type using a roll. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nikko Materials Co., Ltd., a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a roll type dry coater manufactured by Hitachi Industries Co., Ltd., and a vacuum laminator manufactured by Hitachi AIC Co., Ltd. In this way, a photosensitive film with a support is formed on the circuit board.

[0107] Instead of laminating a photosensitive film with a support, the photosensitive resin composition may be directly applied to the circuit board in a resin varnish state, and the organic solvent may be dried to form a photosensitive resin composition layer on the circuit board. As a coating method, full-surface printing by screen printing is generally used, but any other coating method that can apply uniformly may be used. For example, spray coating, hot melt coating, bar coating, applicator, blade coating, knife coating, air knife coating, curtain flow coating, roll coating, gravure coating, offset printing, dip coating, brush coating, and other normal coating methods can all be used. After coating, drying is performed in a hot air oven or far infrared oven, etc., as necessary. Drying conditions are preferably 80°C to 120°C for 3 to 13 minutes.

[0108] <Exposure process> After the photosensitive resin composition layer is provided on the circuit board by the above process, an exposure process is then performed in which a predetermined portion of the photosensitive resin composition layer is irradiated with active light through a mask pattern to photocure the photosensitive resin composition layer in the irradiated portion. Examples of active light include ultraviolet light, visible light, electron beams, and X-rays, and ultraviolet light is particularly preferred. The irradiation dose of ultraviolet light is about 10 mJ / cm. 2 ~1000mJ / cm 2 The exposure method includes a contact exposure method in which a mask pattern is closely attached to a printed wiring board, and a non-contact exposure method in which exposure is performed using parallel light without closely attaching the mask pattern to the printed wiring board, and either method may be used. In addition, when a support is present on the photosensitive resin composition layer, exposure may be performed from above the support, or after peeling off the support.

[0109] The solder resist is excellent in developability (resolution) because it uses the photosensitive resin composition of the present invention. For this reason, as the exposure pattern in the mask pattern, for example, a pattern in which the ratio (L / S) of the circuit width (line; L) to the width between circuits (space; S) is 100 μm / 100 μm or less (i.e., wiring pitch is 200 μm or less), L / S=80 μm / 80 μm or less (wiring pitch is 160 μm or less), L / S=70 μm / 70 μm or less (wiring pitch is 140 μm or less), or L / S=60 μm / 60 μm or less (wiring pitch is 120 μm or less) can be used. Note that the pitch does not need to be the same over the entire circuit board.

[0110] <Developing process> After the exposure step, if a support is present on the photosensitive resin composition layer, the support is removed, and then the non-photocured portion (unexposed portion) is removed and developed by wet development or dry development, whereby a pattern can be formed.

[0111] In the case of the wet development, a developer that is safe, stable, and easy to operate, such as an alkaline aqueous solution, a water-based developer, or an organic solvent, is used, and among them, a development process using an alkaline aqueous solution is preferred. As a development method, a known method such as spraying, rocking immersion, brushing, or scraping is appropriately adopted.

[0112] Examples of alkaline aqueous solutions used as the developer include aqueous solutions of alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; alkali metal phosphates such as sodium phosphate and potassium phosphate; and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; and aqueous solutions of organic bases that do not contain metal ions, such as tetraalkylammonium hydroxide. An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred because it does not contain metal ions and does not affect the semiconductor chip.

[0113] To improve the development effect, surfactants, antifoaming agents, etc. may be added to these alkaline aqueous solutions. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8 to 12, more preferably in the range of 9 to 11. The base concentration of the alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected according to the developability of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

[0114] Examples of organic solvents used as developers include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

[0115] The concentration of such an organic solvent is preferably 2% by mass to 90% by mass based on the total amount of the developer. The temperature of such an organic solvent can be adjusted according to the developability. Furthermore, such an organic solvent can be used alone or in combination of two or more kinds. Examples of organic solvent-based developers used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0116] In forming a pattern, two or more of the above-mentioned developing methods may be used in combination as necessary. The developing methods include a dip method, a bath method, a spray method, a high-pressure spray method, brushing, slapping, etc., and the high-pressure spray method is suitable for improving resolution. When adopting a spray method, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

[0117] <Thermal curing (post-bake) process> After the development step, a thermal curing (post-baking) step is performed to form a solder resist. Examples of the post-baking step include an ultraviolet ray irradiation step using a high-pressure mercury lamp and a heating step using a clean oven. When ultraviolet rays are irradiated, the amount of irradiation can be adjusted as necessary, for example, 0.05 J / cm. 2 ~10J / cm 2 The heating conditions may be appropriately selected depending on the type and content of the resin component in the photosensitive resin composition, but are preferably selected within the range of 150°C to 220°C for 20 minutes to 180 minutes, and more preferably 160°C to 200°C for 30 minutes to 120 minutes.

[0118] <Other processes> After the solder resist is formed, the printed wiring board may further include a drilling step and a desmearing step, which may be carried out according to various methods used in the manufacture of printed wiring boards and known to those skilled in the art.

[0119] After the solder resist is formed, via holes and through holes are formed in the solder resist formed on the circuit board by a drilling process, if desired. The drilling process can be performed by a known method such as a drill, a laser, or plasma, or by a combination of these methods if necessary, but a drilling process using a laser such as a carbon dioxide laser or a YAG laser is preferred.

[0120] The desmear process is a process of performing a desmear treatment. Generally, resin residue (smear) adheres to the inside of the opening formed in the hole drilling process. Since such smear can cause poor electrical connection, a process of removing the smear (desmear treatment) is performed in this process.

[0121] The desmear treatment may be performed by a dry desmear treatment, a wet desmear treatment, or a combination thereof.

[0122] The dry desmear treatment may be, for example, a desmear treatment using plasma. The desmear treatment using plasma may be performed using a commercially available plasma desmear treatment device. Among the commercially available plasma desmear treatment devices, examples suitable for use in the manufacture of printed wiring boards include a microwave plasma device manufactured by Nissin Co., Ltd. and an atmospheric pressure plasma etching device manufactured by Sekisui Chemical Co., Ltd.

[0123] The wet desmear treatment may be, for example, a desmear treatment using an oxidizing agent solution. When the desmear treatment is performed using an oxidizing agent solution, it is preferable to perform a swelling treatment using a swelling liquid, an oxidation treatment using an oxidizing agent solution, and a neutralization treatment using a neutralizing liquid in this order. Examples of the swelling liquid include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing a substrate on which via holes or the like are formed in a swelling liquid heated to 60°C to 80°C for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganate solution, and examples of the solution include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The oxidation treatment using an oxidizing agent solution is preferably performed by immersing a substrate after the swelling treatment in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Commercially available alkaline permanganate aqueous solutions include, for example, "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. The neutralization treatment using a neutralizing solution is preferably carried out by immersing the substrate after the oxidation treatment in the neutralizing solution at 30°C to 50°C for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and a commercially available product thereof is, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan.

[0124] When the dry desmear treatment and the wet desmear treatment are performed in combination, the dry desmear treatment may be performed first, or the wet desmear treatment may be performed first.

[0125] When the insulating layer is used as an interlayer insulating layer, it can be carried out in the same manner as in the case of a solder resist, and after the thermal curing step, a hole drilling step, a desmearing step, and a plating step may be carried out.

[0126] The plating process is a process of forming a conductor layer on an insulating layer. The conductor layer may be formed by a combination of electroless plating and electrolytic plating, or a plating resist having a reverse pattern to the conductor layer may be formed and the conductor layer may be formed only by electroless plating. Subsequent pattern formation methods may include, for example, subtractive methods and semi-additive methods known to those skilled in the art.

[0127] [Semiconductor Devices] The semiconductor device of the present invention includes a printed wiring board. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0128] Examples of the semiconductor device include various semiconductor devices used in electric appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft).

[0129] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conductive portion" refers to a portion of a printed wiring board that transmits an electric signal, and the portion may be either on the surface or embedded. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of semiconductor material.

[0130] The method of mounting the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specific examples include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), etc. Here, the "mounting method using a bumpless buildup layer (BBUL)" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess in a printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board." EXAMPLES

[0131] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. The weight average molecular weight is a weight average molecular weight calculated in terms of polystyrene measured by gel permeation chromatography.

[0132] <Synthesis Example 1: Synthesis of naphthol aralkyl type epoxy acrylate (1000)> 325 parts of an epoxy resin having a naphthol aralkyl skeleton with an epoxy equivalent of 325 g / eq. ("ESN-475V", manufactured by Nippon Steel Chemical & Material Co., Ltd.) was placed in a flask equipped with a gas inlet tube, a stirrer, a cooling tube, and a thermometer, 340 parts of carbitol acetate was added, and the mixture was dissolved by heating, and 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. This mixture was heated to 95-105°C, and 72 parts of acrylic acid were gradually added dropwise and reacted for 16 hours. This reaction product was cooled to 80-90°C, and 80 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, and cooled. The amount of solvent was adjusted to obtain a resin solution with an acid value of 60 mgKOH / g of solid matter (non-volatile content 70%, hereinafter abbreviated as "naphthol aralkyl type epoxy acrylate (1000)"). The naphthol aralkyl type epoxy acrylate (1000) had a weight average molecular weight of 1,000.

[0133] <Examples 1 to 13 and Comparative Examples 1 to 9> The components were mixed in the proportions shown in the table below, and a resin varnish was prepared using a high-speed rotating mixer.

[0134] Next, a PET film (manufactured by Toray Industries, Inc., "Lumirror T6AM", thickness 38 μm, softening point 130° C., "release PET") that had been release-treated with an alkyd resin-based release agent (manufactured by Lintec Corporation, "AL-5") was prepared as a support. The prepared resin varnish was uniformly applied to the release PET with a die coater so that the thickness of the photosensitive resin composition layer after drying was 25 μm, and the film was dried at 80° C. to 110° C. for 6 minutes to obtain a photosensitive film with a support having a photosensitive resin composition layer on the release PET.

[0135] <Measurement of glass transition temperature and average linear thermal expansion coefficient> (Preparation of Cured Material A for Evaluation) The photosensitive resin composition layer of the supported photosensitive film obtained in the Examples and Comparative Examples was subjected to 2 J / cm 2 After that, the support was peeled off to obtain a cured product A for evaluation.

[0136] (Measurement of glass transition temperature (Tg)) The cured product A for evaluation was cut into test pieces with a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by the tensile load method using a dynamic viscoelasticity measuring device (EXSTAR6000, manufactured by SII Nano Technology Co., Ltd.). After mounting the test pieces on the device, measurements were performed under the following conditions: load 200 mN, heating rate 2°C / min. The peak top of the obtained tan δ was calculated as the glass transition temperature (°C), and was evaluated according to the following criteria. Good: Glass transition temperature is 150°C or higher. ×: Glass transition temperature is less than 150°C.

[0137] (Measurement of average linear thermal expansion coefficient) The cured product A for evaluation was cut into test pieces 5 mm wide and 15 mm long, and thermomechanical analysis was performed by the tensile load method using a thermomechanical analyzer (Rigaku Corporation, Thermo Plus, TMA8310). After mounting the test pieces on the device, measurements were performed twice consecutively under the measurement conditions of a load of 1 g and a heating rate of 5°C / min. The average linear thermal expansion coefficient (ppm) from 25°C to 150°C in the second measurement was calculated and evaluated according to the following criteria. Good: Average linear thermal expansion coefficient is less than 50 ppm. △: Average linear thermal expansion coefficient is 50 ppm or more and 70 ppm or less. ×: The average linear thermal expansion coefficient exceeds 70 ppm.

[0138] <Preparation of Laminate A for Evaluation> The copper layer of a glass epoxy board (copper-clad laminate) on which a circuit patterned with a copper layer of 18 μm in thickness was formed was roughened by treatment with a surface treatment agent containing an organic acid (CZ8100, manufactured by MEC Co., Ltd.). Next, the photosensitive resin composition layer of the photosensitive film with the support obtained in the examples and comparative examples was placed so as to be in contact with the copper circuit surface, and laminated using a vacuum laminator (manufactured by Nikko Materials Co., Ltd., VP160), and the copper-clad laminate, the photosensitive resin composition layer, and the support were laminated in this order to prepare an evaluation laminate A. The pressure bonding conditions were a vacuum drawing time of 30 seconds, a pressure bonding temperature of 80° C., a pressure bonding pressure of 0.7 MPa, and a pressure application time of 30 seconds. After preparing the evaluation laminate A, it was left to stand at room temperature (25° C.) for 30 minutes or more.

[0139] <Evaluation of resolution> (1) Exposure, development, and curing steps of the photosensitive resin composition layer Using a pattern forming device and a 41-step step tablet and a round hole pattern, ultraviolet exposure was performed from above the support of the evaluation laminate A. The exposure pattern used was a quartz glass mask that drew round holes with openings of 40 μm / 50 μm / 60 μm / 70 μm / 80 μm / 90 μm / 100 μm. After leaving it to stand at room temperature for 30 minutes, the support was peeled off from the evaluation laminate A. A 1% by mass aqueous solution of sodium carbonate at 30° C. was used as a developer for the entire surface of the photosensitive resin composition layer on the evaluation laminate A, and development was performed for 1 minute by spraying at a spray pressure of 0.2 MPa. After spray development, 2 J / cm2 The photosensitive resin composition layer was then cured by performing a heat treatment at 170° C. for 1 hour.

[0140] (2) Resolution evaluation The sensitivity of the photosensitive resin composition was determined as the amount of exposure energy at which the number of remaining gloss steps in the 41-step tablet was 8. The round holes patterned on the evaluation laminate A exposed at this sensitivity were observed with an SEM (magnification 1000x) to observe the minimum via hole diameter without residue or peeling, and evaluated according to the following criteria. ◯: Minimum via hole diameter is less than 50 μm. △: The minimum via hole diameter is 50 μm or more and 60 μm or less. ×: There is no via hole with a minimum diameter of 60 μm or less.

[0141] For undercut observation, a via hole with a diameter of 50 μm was observed with an SEM (magnification 1000x). The radius (μm) of the top and bottom of the cross section of a via hole with an opening diameter of 50 μm was measured with an SEM, and the difference between the radius of the bottom and the radius of the top (radius of the bottom - radius of the top) was calculated. The calculated value was taken as the undercut and evaluated according to the following criteria. ◎: No undercut. ○: Undercut is less than 3 μm. △: Undercut is between 3 μm and 6 μm. ×: Undercut is more than 6 μm, or a via hole with a diameter of 50 μm is not opened.

[0142] <Evaluation of roughness and peel strength> (1) Exposure, development, and curing steps of the photosensitive resin composition layer Using a pattern forming device, ultraviolet light exposure was performed from above the support of evaluation laminate A at an exposure energy such that the number of gloss remaining steps of a 41-step tablet was 8. A quartz glass mask without an exposure pattern was used. After leaving it to stand at room temperature for 30 minutes, the support was peeled off from evaluation laminate A. A 1% by mass aqueous solution of sodium carbonate at 30°C was used as a developer for the entire surface of the photosensitive resin composition layer on evaluation laminate A for 1 minute for spray development at a spray pressure of 0.2 MPa. After spray development, 2 J / cm 2 The photosensitive resin composition layer was then cured by performing a heat treatment at 170° C. for 1 hour.

[0143] (2) Roughening treatment The evaluation laminate A was immersed in a swelling liquid, Swelling Dip Securigand P containing diethylene glycol monobutyl ether manufactured by Atotech Japan, for 10 minutes at 60°C, then in a roughening liquid, Concentrate Compact P (aqueous solution of KMnO4: 60g / L, NaOH: 40g / L) manufactured by Atotech Japan, for 10 minutes at 80°C, and finally in a neutralizing liquid, Reduction Showreusin Securigant P manufactured by Atotech Japan, for 5 minutes at 40°C. The evaluation laminate A after this roughening treatment was designated as Sample A.

[0144] (3) Plating using semi-additive method To form a circuit on the insulating layer surface, sample A was immersed in an electroless plating solution containing PdCl2, and then immersed in an electroless copper plating solution. After heating at 150°C for 30 minutes to perform an annealing treatment, an etching resist was formed, and after forming a pattern by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 25 μm. Next, an annealing treatment was performed at 180°C for 60 minutes. This sample A was designated as sample B.

[0145] (4) Measurement of arithmetic mean roughness (Ra) For sample A, the arithmetic mean roughness (Ra) was calculated using a non-contact surface roughness meter (WYKO NT3300 manufactured by Beco Instruments) in VSI mode with a 50x lens over a measurement range of 121μm×92μm. The average of 10 points was calculated as the measured value, and the results were evaluated according to the following criteria. ◯: Arithmetic mean roughness is less than 200 μm. △: Arithmetic mean roughness is 200 μm or more and 400 μm or less. ×: The arithmetic mean roughness is greater than 400 μm.

[0146] (5) Measurement of peel strength of plated conductor layer A 10 mm wide and 100 mm long cut was made in the conductive layer of Sample B, and one end of this cut was peeled off and held with a gripper (TSE Corporation, Autocom type testing machine, AC-50C-SL). 35 mm was peeled off vertically at a speed of 50 mm / min at room temperature, and the load (kgf / cm) was measured and evaluated according to the following criteria. 〇: Peel strength is 0.3kgf / cm or more. ×: Peel strength is less than 0.3kgf / cm.

[0147] [Table 1] [Table 2]

[0148] The abbreviations in the table are as follows: CCR-1171H: Cresol novolac epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH / g, solid content approx. 60%, weight average molecular weight 7500) CCR-1373H: Cresol novolac epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH / g, solid content approx. 60%, weight average molecular weight 2800) ZCR-1797H: Biphenyl type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mg KOH / g, solid content concentration approximately 60%, weight average molecular weight 6500) ZCR-8001H: Biphenyl type epoxy acrylate (Nippon Kayaku Co., Ltd., acid value 109 mgKOH / g, solid content approx. 60%, weight average molecular weight 3700) CCR-1224H: Cresol novolac epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH / g, solid content approx. 60%, weight average molecular weight 8700) Naphthol aralkyl type (1000): Naphthol aralkyl type epoxy acrylate (1000) synthesized in Synthesis Example 1 Omnipol 910: a compound represented by the following structure (manufactured by IGM, molecular weight is 850 or more) in which d represents an integer of 1 to 10. [ka] · OmnipolTP: a compound represented by the following structure (manufactured by IGM, molecular weight is 900 or more) In the formula, a, b, and c each represent an integer of 1 to 10. [ka] ·Omnirad379EG: (manufactured by IGM, molecular weight 380.5) [ka] OmniradTPO: (IGM, molecular weight 348) [ka] NC3000H: Biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 271g / eq.) SO-C2: Inorganic filler (spherical silica, manufactured by Admatechs, average particle size 0.5 μm, specific surface area 6 m 2 / g) DPHA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) ·EDG-Ac: Ethyl diglycol acetate MEK: Methyl ethyl ketone

[0149] In each of the examples, it has been confirmed that even when components (C) to (F) are not contained, the results are similar to those of the above examples, although to a different extent.

Claims

1. (A-1) a resin containing an ethylenically unsaturated group and a carboxyl group, the resin having a weight average molecular weight of 6,000 or less; (A-2) a resin containing an ethylenically unsaturated group and a carboxyl group and having a weight average molecular weight 2,000 or more larger than that of the component (A-1), and (B) a photopolymerization initiator; the component (A-1) and the component (A-2) each have a cresol novolak skeleton, a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, or a naphthol aralkyl skeleton; The component (B) has a structural unit represented by the following formula (B-1): A photosensitive resin composition, in which the molecular weight of component (B) is 400 or more. 【Chemistry 1】 (In formula (B-1), R １ represents an active light absorbing group, R ２ each independently represents a divalent hydrocarbon group; n represents an integer of 1 to 10; * represents a bond.

2. 2. The photosensitive resin composition according to claim 1, wherein the molecular weight of the component (B) is 700 or more.

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

4. 4. The photosensitive resin composition according to claim 3, wherein the content of the component (C) is 1% by mass or more, based on 100% by mass of nonvolatile components in the photosensitive resin composition.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the component (A-1) and the component (A-2) contain an acid-modified cresol novolac skeleton-containing epoxy (meth)acrylate.

6. The photosensitive resin composition according to any one of claims 1 to 5, which is used for forming a solder resist.

7. A supported photosensitive film comprising a support and a photosensitive resin composition layer provided on the support, the photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 6.

8. A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of claims 1 to 6.

9. 9. The printed wiring board according to claim 8, wherein the insulating layer is either an interlayer insulating material or a solder resist.

10. A semiconductor device comprising the printed wiring board according to claim 8 or 9.

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