Photosensitive resin composition, photosensitive resin film, printed wiring board, and semiconductor package

Abstract

The present invention relates to: a photosensitive resin composition containing (A) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent and (B) a blocked isocyanate compound having a molecular weight of 3,000 or less; a photosensitive resin film using the photosensitive resin composition; a printed wiring board; and a semiconductor package.

Description

Technical Field

[0001] The present embodiment relates to a photosensitive resin composition, a photosensitive resin film, a printed wiring board, and a semiconductor package. Background Art

[0002] In recent years, electronic devices have been miniaturized and improved in performance, and printed wiring boards have been increasingly densified due to the increase in the number of circuit layers and the miniaturization of wiring. In particular, semiconductor package substrates such as BGA (ball grid array) and CSP (chip size package) equipped with semiconductor chips have become more dense, requiring not only miniaturization of wiring, but also thinner insulation layers and smaller diameters of through holes for interlayer connections.

[0003] As a conventional method for manufacturing a printed wiring board, there is a method for manufacturing a printed wiring board using a build-up method in which an interlayer insulating layer and a conductor circuit layer are sequentially stacked (for example, see Patent Document 1). In printed wiring boards, as wiring becomes finer, a semi-additive method in which circuits are formed by plating has become the mainstream.

[0004] In the conventional semi-additive method, for example, (1) a thermosetting resin film is laminated on a conductor circuit and then cured by heating to form an "interlayer insulating layer". (2) Then, after forming through holes for interlayer connection by laser processing, desmearing and roughening are performed by alkaline permanganate treatment or the like. (3) Then, after chemical copper plating is performed on the substrate, a pattern is formed using a resist, and then copper is electroplated to form a copper circuit layer. (4) Then, after the resist is stripped off, the chemically plated layer is flash-etched to form a copper circuit.

[0005] As described above, laser processing has become the mainstream method for forming through holes in an interlayer insulating layer formed by curing a thermosetting resin film, but the reduction in diameter of through holes by laser irradiation using a laser processing machine is reaching its limit. Furthermore, in the formation of through holes using a laser processing machine, each through hole needs to be formed one by one. In the case where a plurality of through holes need to be provided due to high density, the formation of the through holes requires a lot of time, resulting in a problem of poor manufacturing efficiency.

[0006] Under such circumstances, as a method capable of forming multiple through holes at a time, the following method has been proposed: using a photosensitive resin composition containing an acid-modified vinyl epoxy resin, a photopolymerizable compound, a photopolymerization initiator, an inorganic filler and a silane compound, and wherein the content of the inorganic filler is 10 to 80% by weight, a plurality of small-diameter through holes are formed at a time by photolithography (for example, refer to Patent Document 2).

[0007] Prior art literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 7-304931

[0009] Patent Document 2: Japanese Patent Application Publication No. 2017-116652 Summary of the invention

[0010] Problems to be solved by the invention

[0011] In addition, as signals become faster and larger in capacity, printed wiring board substrate materials are required to have dielectric properties (hereinafter sometimes referred to as "high-frequency properties") that can reduce transmission losses of high-frequency signals, that is, low relative dielectric constant and low dielectric loss tangent.

[0012] In photosensitive resin compositions, from the viewpoint of photosensitivity, photosensitive resins having acidic substituents such as carboxyl groups are sometimes used as photosensitive resins. However, according to studies by the present inventors, it has been found that photosensitive resin compositions containing such photosensitive resins have difficulty in achieving both dielectric properties and developability.

[0013] In view of such a current situation, the present embodiment aims to provide a photosensitive resin composition capable of achieving both dielectric properties and developability, and a photosensitive resin film, a printed wiring board, and a semiconductor package using the photosensitive resin composition.

[0014] Means for solving problems

[0015] The present inventors have studied to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by the present embodiment described below.

[0016] That is, this embodiment relates to the following [1] to

[15] .

[0017] [1] A photosensitive resin composition comprising: (A) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent, and (B) a blocked isocyanate compound having a molecular weight of 3,000 or less.

[0018] [2] The photosensitive resin composition according to [1] above, wherein the dissociation temperature of the component (B) is 80 to 250°C.

[0019] [3] The photosensitive resin composition according to [1] or [2], wherein the component (B) is a compound containing an isocyanurate ring.

[0020] [4] The photosensitive resin composition according to [3], wherein the component (B) is a compound in which a trifunctional isocyanate compound containing an isocyanurate ring is blocked with a blocking agent.

[0021] [5] The photosensitive resin composition according to any one of [1] to [4] above, wherein the content of the component (B) is 1 to 40% by mass based on the total amount of the resin components.

[0022] [6] The photosensitive resin composition according to any one of [1] to [5], wherein the component (A) comprises an alicyclic skeleton represented by the following general formula (A-1).

[0023] [Chemistry 1]

[0024]

[0025] (Where R A1 represents an alkyl group having 1 to 12 carbon atoms, which may be substituted at any position of the above-mentioned alicyclic skeleton. 1 is an integer from 0 to 6. * is a bonding site with other structures. )

[0026] [7] The photosensitive resin composition according to any one of [1] to [6] above, further comprising (C) a thermosetting resin.

[0027] [8] The photosensitive resin composition according to any one of [1] to [7] above, further comprising (D) a photopolymerization initiator.

[0028] [9] The photosensitive resin composition according to any one of [1] to [8] above, further comprising (E) a crosslinking agent.

[0029]

[10] The photosensitive resin composition according to any one of [1] to [9], further comprising (F) an elastomer.

[0030]

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

[10] , further comprising (G) an inorganic filler.

[0031]

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

[11] above, which is used for forming an optical through hole.

[0032]

[13] A photosensitive resin film comprising the photosensitive resin composition according to any one of [1] to

[12] above.

[0033]

[14] A printed wiring board comprising a cured product of the photosensitive resin composition according to any one of [1] to

[12] above.

[0034]

[15] A semiconductor package comprising the printed wiring board described in

[14] above, and a semiconductor element.

[0035] Effects of the Invention

[0036] According to the present embodiment, it is possible to provide a photosensitive resin composition capable of achieving both dielectric properties and developability, and a photosensitive resin film, a printed wiring board, and a semiconductor package using the photosensitive resin composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] [ Figure 1 ] is a schematic diagram showing one method of manufacturing a printed wiring board using the photosensitive resin film of the present embodiment as a material for an interlayer insulating layer. DETAILED DESCRIPTION

[0038] In the numerical range described in this specification, the lower limit and upper limit of the numerical range can be replaced by the values ​​shown in the embodiments. In addition, the lower limit and upper limit of the numerical range can be arbitrarily combined with the lower limit or upper limit of other numerical ranges. In the expression of the numerical range "AA to BB", the numerical values ​​AA and BB at both ends are included in the numerical range as the lower limit and upper limit, respectively.

[0039] In this specification, for example, a statement such as "greater than or equal to 10" refers to 10 and a value greater than 10, and this is also used as a reference when the values ​​are different. In addition, for example, a statement such as "less than or equal to 10" refers to 10 and a value less than 10, and this is also used as a reference when the values ​​are different.

[0040] In the present specification, when there are plural substances corresponding to each component, the content of each component refers to the total content of the plural substances unless otherwise specified.

[0041] In this specification, "solid content" refers to non-volatile components other than volatile substances such as solvents. That is, "solid content" refers to components that do not volatilize and remain when the resin composition is dried, and also includes components that are liquid at room temperature. Here, in this specification, room temperature refers to 25°C.

[0042] In this specification, the "ring carbon number" refers to the number of carbon elements required to form a ring, and does not include the number of carbon atoms of substituents possessed by the ring. For example, the number of ring carbon atoms of a cyclohexane skeleton and a methylcyclohexane skeleton are both 6.

[0043] The expression "(meth)acrylic acid XX" means one or both of acrylic acid XX and the corresponding methacrylic acid XX. In addition, "(meth)acryloyl" means one or both of acryloyl and methacryloyl.

[0044] In this specification, when a "layer" such as an interlayer insulating layer is expressed as a "layer", in addition to a solid layer, a layer in which a part is not a solid layer but is island-shaped, a layer with holes, and a layer in which the interface with the adjacent layer is unclear are also included in the "layer".

[0045] The weight average molecular weight (Mw) and number average molecular weight (Mn) in this specification refer to values ​​measured by gel permeation chromatography (GPC) in terms of polystyrene. Specifically, the weight average molecular weight (Mw) in this specification can be measured by the method described in Examples.

[0046] The action mechanism described in this specification is a guess, and does not limit the mechanism by which the effects of the present embodiment are achieved.

[0047] Any combination of the matters described in this specification is also included in this embodiment.

[0048] [Photosensitive resin composition]

[0049] The photosensitive resin composition of the present embodiment is a photosensitive resin composition containing (A) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent and (B) a blocked isocyanate compound having a molecular weight of 3,000 or less.

[0050] The photosensitive resin composition of this embodiment is suitable for forming a through hole (also referred to as optical via hole formation) by photolithography, and is therefore suitable for forming one or more selected from the group consisting of an optical via hole and an interlayer insulating layer. That is, the photosensitive resin composition of this embodiment is suitable for forming an optical via hole.

[0051] Moreover, the photosensitive resin composition of this embodiment is suitable for a negative photosensitive resin composition.

[0052] <(A) Photopolymerizable Compound Having an Ethylenically Unsaturated Group and an Acidic Substituent>

[0053] (A) Component is a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent.

[0054] (A) The component may be used alone or in combination of two or more.

[0055] (A) The component is a compound that exhibits photopolymerization, particularly radical polymerization, due to having an ethylenically unsaturated group.

[0056] Examples of the ethylenically unsaturated group possessed by the component (A) include photopolymerizable functional groups such as vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimide, nadicimide, and (meth)acryloyl. Among them, (meth)acryloyl is preferred from the viewpoint of reactivity and resolution of through-holes.

[0057] (A) Component has an acidic substituent from the viewpoint of enabling alkali development.

[0058] Examples of the acidic substituent possessed by the component (A) include a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl group, etc. Among them, a carboxyl group is preferred from the viewpoint of the resolution of the through-hole.

[0059] The acid value of component (A) is preferably 20 to 200 mgKOH / g, more preferably 40 to 180 mgKOH / g, further preferably 70 to 150 mgKOH / g, and particularly preferably 90 to 120 mgKOH / g. When the acid value of component (A) is greater than or equal to the above lower limit, the solubility of the photosensitive resin film in a dilute alkaline solution tends to be excellent, and when it is less than or equal to the above upper limit, the dielectric properties tend to be excellent. The acid value of component (A) can be measured by the method described in the Examples.

[0060] In addition, two or more (A) components having different acid values ​​may be used in combination. In this case, the weighted average acid value of the acid values ​​of the two or more (A) components is preferably within any of the above ranges.

[0061] The weight average molecular weight (Mw) of the component (A) is preferably 600 to 30,000, more preferably 800 to 25,000, further preferably 1,000 to 18,000, further preferably 1,100 to 8,000, particularly preferably 1,200 to 5,000, and most preferably 1,200 to 3,500. When the weight average molecular weight (Mw) of the component (A) is within the above range, there is a tendency for the bonding strength with the copper plating layer, heat resistance, and insulation reliability to be excellent.

[0062] From the viewpoint of dielectric properties, the component (A) preferably includes an alicyclic skeleton.

[0063] The alicyclic skeleton possessed by the component (A) is preferably an alicyclic skeleton having 5 to 20 ring carbon atoms, more preferably an alicyclic skeleton having 5 to 18 ring carbon atoms, further preferably an alicyclic skeleton having 6 to 18 ring carbon atoms, particularly preferably an alicyclic skeleton having 8 to 14 ring carbon atoms, and most preferably an alicyclic skeleton having 8 to 12 ring carbon atoms, from the viewpoints of through-hole resolution, adhesion strength to the copper plating layer, and electrical insulation reliability.

[0064] In addition, from the viewpoint of the resolution of the through-hole, the bonding strength with the copper plating layer and the reliability of electrical insulation, the above-mentioned alicyclic skeleton preferably contains more than 2 rings, more preferably contains 2 to 4 rings, and further preferably contains 3 rings. As alicyclic skeletons with more than 2 rings, there can be cited a norbornane skeleton, a decalin skeleton, a bicycloundecane skeleton, a saturated dicyclopentadiene skeleton, etc. It should be noted that in this specification, a saturated dicyclopentadiene skeleton refers to a skeleton of a ring structure containing saturated unsaturated bonds contained in a dicyclopentadiene ring. Among them, from the viewpoint of the resolution of the through-hole, the bonding strength with the copper plating layer and the reliability of electrical insulation, a saturated dicyclopentadiene skeleton is preferred.

[0065] From the same viewpoint, the component (A) preferably includes an alicyclic skeleton represented by the following general formula (A-1).

[0066] [Chemistry 2]

[0067]

[0068] (Where R A1 represents an alkyl group having 1 to 12 carbon atoms, which may be substituted at any position of the above-mentioned alicyclic skeleton. 1 is an integer from 0 to 6. * is a bonding site with other structures. )

[0069] In the above general formula (A-1), R A1 The alkyl group having 1 to 12 carbon atoms represented by , includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is further preferred.

[0070] m 1 It is an integer of 0 to 6, preferably an integer of 0 to 2, and more preferably 0.

[0071] m 1 When it is an integer from 2 to 6, multiple R A1 They may be the same or different. A1 Substitution may be on the same carbon atom or on different carbon atoms to the extent possible.

[0072] * is a bonding site to other structures, and may be bonded to any carbon atom on the alicyclic skeleton, and preferably is bonded to a carbon atom at the site represented by 1 or 2 and a carbon atom at the site represented by 3 or 4 in the following general formula (A-1').

[0073] [Chemistry 3]

[0074]

[0075] (Where R A1 、m 1 and * are the same as in the general formula (A-1). )

[0076] From the viewpoint of the resolution of the through hole and the bonding strength with the copper plating layer, the component (A) is preferably an acid-modified vinyl-containing epoxy resin, which is obtained by reacting a compound (a1) obtained by modifying an epoxy resin with an organic acid (a2) containing an ethylenically unsaturated group [hereinafter, sometimes referred to as the component (A')]. ] with a polyacid anhydride (a3) ​​containing a saturated group or an unsaturated group. Here, the "acid-modified" of the acid-modified vinyl-containing epoxy resin means having an acidic substituent, "vinyl" means an ethylenically unsaturated group, and "epoxy resin" means using an epoxy resin as a raw material. The acid-modified vinyl-containing epoxy resin does not necessarily need to have an epoxy group and may not have an epoxy group.

[0077] Hereinafter, preferred embodiments of the component (A) obtained from (a1) an epoxy resin, (a2) an organic acid containing an ethylenically unsaturated group, and (a3) ​​a polybasic acid anhydride containing a saturated group or an unsaturated group will be described.

[0078] ((a1) Epoxy resin)

[0079] As the (a1) epoxy resin, an epoxy resin having two or more epoxy groups is preferred.

[0080] (a1) The epoxy resin may be used alone or in combination of two or more.

[0081] (a1) Epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among them, glycidyl ether type epoxy resins are preferred.

[0082] (a1) Epoxy resins can also be classified into various epoxy resins according to the difference in the main skeleton, and can be classified into epoxy resins having an alicyclic skeleton, novolac epoxy resins, bisphenol epoxy resins, aralkyl epoxy resins, other epoxy resins, etc. Among them, epoxy resins having an alicyclic skeleton and novolac epoxy resins are preferred.

[0083] -Epoxy resin having an alicyclic skeleton-

[0084] The alicyclic skeleton of the epoxy resin having an alicyclic skeleton is described in the same manner as the alicyclic skeleton of the above-mentioned component (A), and the preferred aspects are also the same.

[0085] As the epoxy resin having an alicyclic skeleton, an epoxy resin represented by the following general formula (A-2) is preferred.

[0086] [Chemistry 4]

[0087]

[0088] (Where R A1 represents an alkyl group having 1 to 12 carbon atoms, which may be substituted at any position of the above-mentioned alicyclic skeleton. A2 represents an alkyl group having 1 to 12 carbon atoms. 1 is an integer from 0 to 6, m 2 is an integer from 0 to 3, and n is a number from 0 to 50. )

[0089] In the general formula (A-2), R A1 and R in the general formula (A-1) A1 The same, the preferred method is also the same.

[0090] As R in the general formula (A-2) A2 Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group.

[0091] m in the general formula (A-2) 1 and m in the general formula (A-1) 1 The same, the preferred method is also the same.

[0092] m in the general formula (A-2) 2 It is an integer of 0 to 3, preferably 0 or 1, and more preferably 0.

[0093] n in the general formula (A-2) represents the number of repetitions of the structural unit in parentheses, and is a number from 0 to 50. Usually, the epoxy resin is a mixture of substances having different numbers of repetitions of the structural unit in parentheses, so in this case, n is represented by the average value of the mixture. As n, a number of 0 to 30 is preferred.

[0094] As the epoxy resin having an alicyclic skeleton, a commercially available item may be used, and examples of the commercially available item include XD-1000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and EPICLON (registered trademark) HP-7200 (trade name, manufactured by DIC Corporation).

[0095] -Novolac type epoxy resin-

[0096] Examples of the novolac epoxy resin include bisphenol novolac epoxy resins such as bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, and bisphenol S novolac epoxy resin; phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, and naphthol novolac epoxy resin.

[0097] As the novolac-type epoxy resin, an epoxy resin having a structural unit represented by the following general formula (A-3) is preferred.

[0098] [Chemistry 5]

[0099]

[0100] (Where R A3 represents a hydrogen atom or a methyl group, Y A1 Each independently represents a hydrogen atom or a glycidyl group. A3 They can be the same or different. A1 At least one of them represents a glycidyl group. )

[0101] From the perspective of through-hole resolution and bonding strength with copper plating, R A3 Preferably, all of them are hydrogen atoms. A1 Preferably, both are glycidyl groups.

[0102] The number of structural units of the structural unit in the epoxy resin (a1) having the structural unit represented by the general formula (A-3) is 1 or more, preferably 10 to 100, more preferably 13 to 80, and still more preferably 15 to 70. When the number of structural units is within the above range, there is a tendency for the bonding strength with the copper plating layer, heat resistance, and insulation reliability to be improved.

[0103] In the general formula (A-3), R A3 are hydrogen atoms, Y A1 The compounds containing all glycidyl groups are commercially available as EXA-7376 series (manufactured by DIC Corporation, trade name). A3 All are methyl, Y A1 Those having all glycidyl groups are commercially available as EPON SU8 series (trade name, manufactured by Mitsubishi Chemical Corporation).

[0104] Examples of the bisphenol epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and 3,3′,5,5′-tetramethyl-4,4′-diglycidyloxydiphenylmethane.

[0105] Examples of the aralkyl epoxy resin include phenol aralkyl epoxy resin, biphenyl aralkyl epoxy resin, and naphthol aralkyl epoxy resin.

[0106] Other epoxy resins include stilbene-type epoxy resins, naphthalene-skeletal-containing epoxy resins, biphenyl-type epoxy resins, dihydroanthracene-type epoxy resins, cyclohexanedimethanol-type epoxy resins, trimethylol-type epoxy resins, alicyclic epoxy resins, aliphatic chain epoxy resins, heterocyclic epoxy resins, spiro-ring-containing epoxy resins, and rubber-modified epoxy resins.

[0107] ((a2) Organic acid containing ethylenically unsaturated group)

[0108] As the (a2) ethylenically unsaturated group-containing organic acid, an ethylenically unsaturated group-containing monocarboxylic acid is preferred.

[0109] As the ethylenically unsaturated group which the component (a2) has, there may be mentioned the same groups as those exemplified as the ethylenically unsaturated group which the component (A) has.

[0110] Component (a2) includes acrylic acid derivatives such as acrylic acid, acrylic acid dimer, methacrylic acid, β-furfuryl acrylate, β-styryl acrylate, cinnamic acid, crotonic acid, and α-cyanocinnamic acid; half-ester compounds of reaction products of hydroxyl-containing acrylic acid esters and dibasic acid anhydrides; and half-ester compounds of reaction products of vinyl-containing monoglycidyl ethers or vinyl-containing monoglycidyl esters and dibasic acid anhydrides.

[0111] The component (a2) may be used alone or in combination of two or more.

[0112] The half ester compound is obtained by reacting one or more ethylenically unsaturated group-containing compounds selected from the group consisting of hydroxyl-containing acrylates, vinyl-containing monoglycidyl ethers and vinyl-containing monoglycidyl esters with a dibasic acid anhydride. The reaction is preferably carried out by reacting the ethylenically unsaturated group-containing compound and the dibasic acid anhydride in equimolar amounts.

[0113] Examples of the hydroxyl-containing acrylate used in the synthesis of the half ester compound include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0114] Examples of the vinyl group-containing monoglycidyl ether include glycidyl (meth)acrylate and the like.

[0115] The dibasic acid anhydride used in the synthesis of the above-mentioned half ester compound may contain a saturated group or an unsaturated group. Examples of the dibasic acid anhydride include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.

[0116] In the reaction of component (a1) and component (a2), the amount of component (a2) used is preferably 0.6 to 1.05 equivalents, more preferably 0.7 to 1.02 equivalents, and even more preferably 0.8 to 1.0 equivalents relative to 1 equivalent of the epoxy group of component (a1). By reacting component (a1) and component (a2) at the above ratio, there is a tendency that the photopolymerizability of component (A) is improved and the resolution of the through-holes of the obtained photosensitive resin composition is improved.

[0117] The components (a1) and (a2) are preferably dissolved in an organic solvent for reaction.

[0118] Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ether compounds such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, and carbitol acetate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha, etc. The organic solvent may be used alone or in combination of two or more.

[0119] In the reaction of component (a1) and component (a2), a catalyst for promoting the reaction is preferably used. Examples of the catalyst include amine catalysts such as triethylamine and benzylmethylamine; quaternary ammonium salt catalysts such as methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide; and phosphine catalysts such as triphenylphosphine. Among them, phosphine catalysts are preferred, and triphenylphosphine is more preferred. The catalyst may be used alone or in combination of two or more.

[0120] When a catalyst is used, the amount used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 2 parts by mass based on 100 parts by mass of the total of the components (a1) and (a2), from the viewpoint of obtaining an appropriate reaction rate.

[0121] In the reaction of component (a1) and component (a2), a polymerization inhibitor is preferably used for the purpose of preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc. The polymerization inhibitor may be used alone or in combination of two or more.

[0122] When a polymerization inhibitor is used, the amount used is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.8 part by mass, and even more preferably 0.1 to 0.5 part by mass, based on 100 parts by mass of the total of the components (a1) and (a2).

[0123] The reaction temperature of the components (a1) and (a2) is preferably 60 to 150°C, more preferably 80 to 120°C, and even more preferably 90 to 110°C from the viewpoint of obtaining sufficient reactivity and homogeneously reacting.

[0124] As described above, when a monocarboxylic acid containing an ethylenically unsaturated group is used as the component (a2), the component (A') obtained by reacting the components (a1) and (a2) has a hydroxyl group formed by a ring-opening addition reaction between the epoxy group of the component (a1) and the carboxyl group of the component (a2). Then, by reacting the component (A') with the component (a3), an acid-modified vinyl-containing epoxy resin can be obtained in which the hydroxyl group of the component (A') (including the hydroxyl group originally present in the component (a1)) and the acid anhydride group of the component (a3) ​​are half-esterified.

[0125] ((a3) polybasic acid anhydride containing saturated or unsaturated groups)

[0126] As (a3) ​​component, it is possible to contain a saturated group or an unsaturated group. As (a3) ​​component, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride etc. can be listed. Among them, from the viewpoint of the resolution of through hole, tetrahydrophthalic anhydride is preferred. (a3) ​​component can be used alone or in combination of two or more.

[0127] In the reaction between the components (A') and (a3), for example, 0.1 to 1.0 equivalent of the component (a3) ​​is reacted per 1 equivalent of the hydroxyl group in the component (A'), whereby the acid value of the acid-modified vinyl-containing epoxy resin can be adjusted.

[0128] The reaction temperature of the component (A') and the component (a3) ​​is preferably 50 to 150°C, more preferably 60 to 120°C, and even more preferably 70 to 100°C from the viewpoint of obtaining sufficient reactivity and allowing the reaction to proceed homogeneously.

[0129] The content of the component (A) in the photosensitive resin composition of the present embodiment is not particularly limited, but is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, further preferably 12 to 50% by mass, particularly preferably 15 to 45% by mass, and most preferably 20 to 40% by mass based on the total amount of the resin components in the photosensitive resin composition from the viewpoints of heat resistance, dielectric properties, and chemical resistance.

[0130] <(B) Blocked Isocyanate Compound Having a Molecular Weight of 3,000 or Less>

[0131] The component (B) is a blocked isocyanate compound having a molecular weight of 3,000 or less.

[0132] Here, the "molecular weight" of a compound in this specification refers to a molecular weight that can be calculated from the structural formula when the compound is not a polymer but the structural formula of the compound can be determined, and refers to a number average molecular weight (Mn) when the compound is a polymer.

[0133] (B) The component may be used alone or in combination of two or more.

[0134] The photosensitive resin composition of the present embodiment can achieve both dielectric properties and developability by containing the component (B). The reason for this is not clear in detail, but is presumed as follows.

[0135] In the cured product of the photosensitive resin composition, hydroxyl groups or unreacted acidic substituents generated during the curing process may remain, and these functional groups become the main cause of the deterioration of the dielectric loss tangent (Df). On the other hand, in the component (B) contained in the photosensitive resin composition of the present embodiment, the end-capping agent is dissociated by heating, and the generated isocyanate group reacts with the functional group that deteriorates the dielectric loss tangent (Df), so that good dielectric properties can be obtained. Furthermore, the molecular weight of the component (B) contained in the photosensitive resin composition of the present embodiment is less than or equal to 3,000, so it is estimated that the developability is also maintained well.

[0136] The molecular weight of the component (B) is 3,000 or less, preferably 200 to 2,700, more preferably 350 to 2,500, further preferably 400 to 2,300, particularly preferably 600 to 2,000.

[0137] If the molecular weight of component (B) is less than or equal to the above upper limit, the developability of the photosensitive resin composition of the present embodiment tends to be better. On the other hand, if the molecular weight of component (B) is greater than or equal to the above lower limit, the smear resistance of the photosensitive resin composition of the present embodiment tends to be better.

[0138] From the above viewpoints, the molecular weight of the component (B) may be 1,500 or less, 1,200 or less, 700 or more, or 800 or more.

[0139] The dissociation temperature of the component (B) is not particularly limited, but is preferably 80 to 250°C, more preferably 90 to 200°C, further preferably 100 to 180°C, and particularly preferably 110 to 150°C.

[0140] When the dissociation temperature of the component (B) is greater than or equal to the above lower limit, the circuit embedding property of the photosensitive resin film formed by the photosensitive resin composition of the present embodiment tends to be better. In addition, when the dissociation temperature of the component (B) is less than or equal to the above upper limit, the effect of reducing the dielectric loss tangent tends to be more easily exhibited.

[0141] In addition, the dissociation temperature of (B) component refers to the endothermic peak temperature accompanying the deprotection reaction of the blocked isocyanate compound in differential scanning calorimetry analysis.

[0142] The isocyanate compound (also referred to as "isocyanate compound (b1)") serving as a precursor of the blocked isocyanate compound may be a monoisocyanate compound, a diisocyanate compound, or a trifunctional or higher polyisocyanate compound, preferably a trifunctional or higher polyisocyanate compound, and more preferably a trifunctional isocyanate compound from the viewpoint of achieving better dielectric properties.

[0143] The trifunctional or higher polyisocyanate compound is preferably a polymer of a diisocyanate compound. As a polymer of a diisocyanate compound, a trimer or a tetramer or more is preferred, and a trimer is more preferred from the viewpoint of making the dielectric properties better. It should be noted that the trimer of the diisocyanate compound has three isocyanate groups.

[0144] As the trimer of the diisocyanate compound, from the viewpoint of making the dielectric properties better, a trifunctional isocyanate compound having a biuret structure obtained by trimerizing a diisocyanate compound, a trifunctional isocyanate compound obtained by trimerizing a diisocyanate compound to form an isocyanurate ring, and a trifunctional isocyanate compound obtained by trimerizing a diisocyanate compound to form an isocyanurate ring are preferred, and a trifunctional isocyanate compound obtained by trimerizing a diisocyanate compound to form an isocyanurate ring is more preferred.

[0145] That is, from the viewpoint of improving dielectric properties, the component (B) is preferably a compound containing an isocyanurate ring, and more preferably a compound in which a trifunctional isocyanate compound containing an isocyanurate ring is blocked with a blocking agent.

[0146] As isocyanate compound (b1), aliphatic isocyanate compound, aromatic isocyanate compound, etc. are mentioned, for example.

[0147] It should be noted that, in this specification, an aliphatic isocyanate compound refers to an isocyanate compound having an isocyanate group directly bonded to an aliphatic group, and an aromatic isocyanate compound refers to an isocyanate compound having an isocyanate group directly bonded to an aromatic group. Compounds having both an isocyanate group directly bonded to an aliphatic group and an isocyanate group directly bonded to an aromatic group belong to both aliphatic isocyanate compounds and aromatic isocyanate compounds.

[0148] It should be noted that the aliphatic isocyanate compound also includes an alicyclic isocyanate compound.

[0149] Examples of the aliphatic isocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanate methylhexanoate, xylylene diisocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, methylenebis(cyclohexyl isocyanate), methylcyclohexane diisocyanate, norbornane diisocyanate, bis(isocyanatomethyl)cyclohexane, and isophorone diisocyanate; and polymers of the above aliphatic diisocyanate compounds.

[0150] Among them, polymers of aliphatic diisocyanate compounds are preferred, trimers of aliphatic diisocyanate compounds are more preferred, and trifunctional isocyanate compounds in which hexamethylene diisocyanate is trimerized to form an isocyanurate ring, trifunctional isocyanate compounds in which isophorone diisocyanate is trimerized to form an isocyanurate ring, and trifunctional isocyanate compounds having a biuret structure formed by trimerization of hexamethylene diisocyanate are further preferred.

[0151] Examples of the aromatic isocyanate compound include tolylene diisocyanate, phenylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-toluidine diisocyanate, and 4,4′-diphenyl ether diisocyanate.

[0152] Examples of the terminal blocking agent include oxime compounds, alcohol compounds, amide compounds, imide compounds, phenol compounds, amine compounds, active methylene compounds, imidazole compounds, and pyrazole compounds.

[0153] Examples of the oxime compound include formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, 2-butanone oxime, and cyclohexanone oxime.

[0154] Examples of the alcohol compound include methanol, ethanol, 2-heptanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol.

[0155] Examples of the amide compound include acetanilide, acetamide, ε-caprolactam, δ-valerolactam, and γ-butyrolactam.

[0156] Examples of the imide compound include succinimide and maleimide.

[0157] Examples of the phenolic compound include phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, and hydroxybenzoic acid esters.

[0158] Examples of the amine compound include diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, and isopropylethylamine.

[0159] Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone.

[0160] Examples of the imidazole compound include imidazole and 2-methylimidazole.

[0161] Examples of the pyrazole compound include pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole.

[0162] The content of the component (B) in the photosensitive resin composition of the present embodiment is not particularly limited, but is preferably 1 to 40% by mass, more preferably 3 to 35% by mass, further preferably 5 to 30% by mass, and particularly preferably 6 to 25% by mass based on the total amount of the resin components in the photosensitive resin composition.

[0163] If the content of the component (B) in the photosensitive resin composition of the present embodiment is greater than or equal to the above lower limit, there is a tendency for the dielectric properties to become better. In addition, when the content of the component (B) in the photosensitive resin composition of the present embodiment is less than or equal to the above upper limit, there is a tendency for the bonding strength with the copper plating layer to become better.

[0164] <(C) Thermosetting resin>

[0165] The photosensitive resin composition of the present embodiment preferably further contains a thermosetting resin as the component (C). The component (C) does not contain the component (A).

[0166] The photosensitive resin composition of the present embodiment tends to have improved heat resistance in addition to improved bonding strength with the copper plating layer and improved insulation reliability by containing the (C) thermosetting resin.

[0167] (C) The component may be used alone or in combination of two or more.

[0168] Examples of the thermosetting resin (C) include epoxy resins, phenolic resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoic acid resins, Oxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, melamine resin, etc. In addition, it is not particularly limited to the above resins, and known thermosetting resins can be used. Among them, epoxy resin is preferred from the viewpoint of bonding strength with copper plating, insulation reliability and heat resistance.

[0169] As the epoxy resin, an epoxy resin having two or more epoxy groups is preferred. Epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among them, glycidyl ether type epoxy resins are preferred.

[0170] In addition, epoxy resins are also classified into various epoxy resins according to the difference of the main skeleton. Among the above-mentioned various types of epoxy resins, they can be further classified as follows. Specifically, they can be classified into bisphenol-based epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin; bisphenol-based novolac epoxy resins such as bisphenol A novolac epoxy resin and bisphenol F novolac epoxy resin; novolac epoxy resins other than the above-mentioned bisphenol-based novolac epoxy resins such as phenol novolac epoxy resin, cresol novolac epoxy resin, and biphenyl novolac epoxy resin; phenol aralkyl epoxy resin; stilbene epoxy resin; naphthol phenol Epoxy resins containing naphthalene skeletons such as aldehyde varnish type epoxy resins, naphthol type epoxy resins, naphthol aralkyl type epoxy resins, and naphthylene ether type epoxy resins; biphenyl type epoxy resins; biphenyl aralkyl type epoxy resins; diphenyl dimethyl type epoxy resins; dihydroanthracene type epoxy resins; alicyclic epoxy resins such as saturated dicyclopentadiene type epoxy resins; heterocyclic epoxy resins; epoxy resins containing spiro rings; cyclohexanedimethanol type epoxy resins; trimethylol type epoxy resins; aliphatic chain epoxy resins; rubber modified epoxy resins, etc.

[0171] Among them, in particular, from the viewpoints of heat resistance, electrical insulation reliability, developability and bonding strength with the copper plating layer, the epoxy resin preferably contains at least one selected from the group consisting of bisphenol epoxy resins, naphthalene skeleton-containing epoxy resins and biphenyl aralkyl type epoxy resins, and more preferably contains at least one selected from the group consisting of naphthalene skeleton-containing epoxy resins and biphenyl aralkyl type epoxy resins.

[0172] The equivalent ratio [epoxy group / acidic substituent] of the acidic substituent of the component (A) and the epoxy group of the component (C) in the photosensitive resin composition of the present embodiment is not particularly limited, but is preferably 0.5 to 6.0, more preferably 0.7 to 4.0, further preferably 0.8 to 2.0, and particularly preferably 0.9 to 1.8 from the viewpoint of insulation reliability, dielectric properties, heat resistance, and adhesion strength to the copper plating layer.

[0173] When the photosensitive resin composition of the present embodiment contains (C) a thermosetting resin, the content of the (C) thermosetting resin is not particularly limited, but is preferably 1 to 50% by mass, more preferably 5 to 45% by mass, further preferably 15 to 40% by mass, and particularly preferably 20 to 35% by mass, based on the total amount of the resin components in the photosensitive resin composition, from the viewpoints of insulation reliability, dielectric properties, heat resistance, and adhesion strength to the copper plating layer.

[0174] <(D) Photopolymerization Initiator>

[0175] The photosensitive resin composition of the present embodiment preferably further contains a photopolymerization initiator as the component (D). The photosensitive resin composition of the present embodiment tends to improve the resolution of the through-hole by containing the photopolymerization initiator (D).

[0176] (D) The photopolymerization initiator may be used alone or in combination of two or more. From the viewpoint of the resolution of the through-hole, the photosensitive resin composition of the present embodiment preferably contains two or more (D) photopolymerization initiators.

[0177] (D) The photopolymerization initiator is not particularly limited as long as it can photopolymerize an ethylenically unsaturated group, and can be appropriately selected from commonly used photopolymerization initiators.

[0178] (D) The photopolymerization initiator includes benzoin compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-[4-(methylthio)benzoyl]-2-(4-morpholino)propane, and N,N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, Anthraquinone compounds such as 2-aminoanthraquinone; ketal compounds such as acetophenone dimethyl ketal and benzil dimethyl ketal; acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; oxime ester compounds such as 1,2-octanedione-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetyl oxime), and 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime], etc.

[0179] Among them, oxime ester compounds and acylphosphine oxide compounds are preferred, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetoxime) and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide are more preferred. Oxime ester compounds have the advantage of improving photocurability, and acylphosphine oxide compounds have the advantages of improving the curing degree of the bottom of the cured product obtained by curing the photosensitive resin film and inhibiting undercutting. By using oxime ester compounds and acylphosphine oxide compounds in combination, there is a tendency for the resolution of the through-hole to be further improved.

[0180] When the photosensitive resin composition of the present embodiment contains (D) a photopolymerization initiator, the content of the (D) photopolymerization initiator is not particularly limited, but is preferably 0.01 to 20% by mass, more preferably 0.02 to 10% by mass, further preferably 0.03 to 3% by mass, and particularly preferably 0.05 to 1% by mass, based on the total amount of the resin components of the photosensitive resin composition, from the viewpoint of easily obtaining a moderate effect of promoting the polymerization reaction.

[0181] <(E) Cross-linking agent>

[0182] The photosensitive resin composition of the present embodiment preferably further contains a crosslinking agent as component (E). As a crosslinking agent, a crosslinking agent having two or more ethylenically unsaturated groups and having no acidic substituent is preferred. The crosslinking agent reacts with the ethylenically unsaturated groups possessed by component (A) to increase the crosslinking density of the photosensitive resin film after curing. Therefore, the photosensitive resin composition of the present embodiment has a tendency to improve heat resistance and dielectric properties by containing a crosslinking agent.

[0183] (E) The cross-linking agent may be used alone or in combination of two or more.

[0184] Examples of the crosslinking agent (E) include a bifunctional monomer having two ethylenically unsaturated groups and a polyfunctional monomer having three or more ethylenically unsaturated groups. The crosslinking agent (E) preferably contains the above-mentioned polyfunctional monomer.

[0185] (E) As the ethylenically unsaturated group which the crosslinking agent has, the same groups as the ethylenically unsaturated group which the component (A) has are mentioned, and preferred aspects are also the same.

[0186] Examples of the difunctional monomer include aliphatic di(meth)acrylates such as trimethylolpropane di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate; di(meth)acrylates having an alicyclic skeleton such as dicyclopentadiene di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate; and aromatic di(meth)acrylates such as 2,2-bis(4-(meth)acryloyloxypolyethoxypolypropoxyphenyl)propane and bisphenol A diglycidyl ether di(meth)acrylate.

[0187] Among them, from the viewpoint of obtaining more excellent dielectric properties, di(meth)acrylates having an alicyclic skeleton are preferred, and tricyclodecane dimethanol diacrylate is more preferred.

[0188] Examples of the polyfunctional monomer include (meth)acrylate compounds having a skeleton derived from trimethylolpropane such as trimethylolpropane tri(meth)acrylate; (meth)acrylate compounds having a skeleton derived from tetramethylolmethane such as tetramethylolmethane tri(meth)acrylate and tetramethylolmethane tetra(meth)acrylate; (meth)acrylate compounds having a skeleton derived from pentaerythritol such as pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate; (meth)acrylate compounds having a skeleton derived from dipentaerythritol such as dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate; (meth)acrylate compounds having a skeleton derived from di(trimethylolpropane) such as di(trimethylolpropane) tetra(meth)acrylate; (meth)acrylate compounds having a skeleton derived from diglycerol, and the like. Among them, from the viewpoint of the resolution of the through hole and the bonding strength with the copper plating layer, a (meth)acrylate compound having a skeleton derived from dipentaerythritol is preferred, and dipentaerythritol hexa(meth)acrylate is more preferred.

[0189] Here, the above-mentioned “(meth)acrylate compound having a skeleton derived from XXX” (wherein XXX is a compound name) refers to an esterification product of XXX and (meth)acrylic acid, and the esterification product also includes compounds modified with an alkenyloxy group.

[0190] When the photosensitive resin composition of the present embodiment contains the crosslinking agent (E), the content of the crosslinking agent (E) is not particularly limited, but is preferably 10 to 85 parts by mass, more preferably 25 to 80 parts by mass, further preferably 35 to 75 parts by mass, and particularly preferably 45 to 70 parts by mass, relative to 100 parts by mass of the component (A), from the viewpoint of heat resistance and dielectric properties.

[0191] <(F) Elastomer>

[0192] The photosensitive resin composition of the present embodiment preferably further contains an elastic elastomer as the (F) component. The photosensitive resin composition of the present embodiment tends to improve the bonding strength with the copper plating layer by containing the (F) elastomer.

[0193] (F) The elastomer may be used alone or in combination of two or more.

[0194] (F) The elastomer may have a reactive functional group at a molecular terminal or in a molecular chain.

[0195] As the reactive functional group, anhydride groups, epoxy groups, hydroxyl groups, carboxyl groups, amino groups, amide groups, isocyanate groups, acryloyl groups, methacryloyl groups, vinyl groups, etc. can be cited. Among them, from the viewpoint of the resolution of the through hole and the bonding strength with the copper plating layer, anhydride groups are preferred. As the anhydride group, anhydride groups derived from maleic anhydride are preferred.

[0196] (F) When the elastomer has an acid anhydride group, the number of the acid anhydride groups in one molecule is preferably 1 to 10, more preferably 3 to 10, and even more preferably 6 to 10, from the viewpoint of through-hole resolution and dielectric properties.

[0197] (F) Elastomers include polybutadiene elastomers, polyester elastomers, styrene elastomers, olefin elastomers, urethane elastomers, polyamide elastomers, acrylic elastomers, silicone elastomers, and derivatives of these elastomers. Among them, polybutadiene elastomers are preferred from the viewpoints of improving the bonding strength with the copper plating layer and improving the compatibility and solubility with the resin component. From the viewpoint of the resolution of the through hole, the polybutadiene elastomer is preferably a polybutadiene elastomer having an anhydride group modified with an acid anhydride, and more preferably a polybutadiene elastomer having an anhydride group derived from maleic anhydride.

[0198] From the viewpoint of the bonding strength with the copper plating layer, the polybutadiene-based elastomer may be polybutadiene having an epoxy group [hereinafter, sometimes referred to as epoxidized polybutadiene].

[0199] From the viewpoint of the bonding strength with the copper plating layer and the flexibility, the epoxidized polybutadiene is preferably an epoxidized polybutadiene represented by the following general formula (F-1).

[0200] [Chemistry 6]

[0201]

[0202] (In the formula, a, b and c represent the ratio of the structural units in the parentheses, respectively, a is 0.05 to 0.40, b is 0.02 to 0.30, and c is 0.30 to 0.80, and further, a+b+c=1.00 is satisfied, and (a+c)>b. y represents the number of structural units in the square brackets, which is an integer of 10 to 250.)

[0203] In the above general formula (F-1), the bonding order of each structural unit within the square brackets is different. That is, the structural units shown on the left, the structural units shown in the center, and the structural units shown on the right can be interchanged. If they are represented by (a), (b), and (c), respectively, there can be various combination orders such as -[(a)-(b)-(c)]-[(a)-(b)-(c)-]-, -[(a)-(c)-(b)]-[(a)-(c)-(b)-]-, -[(b)-(a)-(c)]-[(b)-(a)-(c)-]-, -[(a)-(b)-(c)]-[(c)-(b)-(a)-]-, -[(a)-(b)-(c)]-[(c)-(b)-(a)-]-, -[(a)-(b)-(a)]-[(c)-(b)-(c)-]-, -[(c)-(b)-(c)]-[(b)-(a)-(a)-]-

[0204] From the viewpoint of the bonding strength with the copper plating layer and the flexibility, a is preferably 0.10 to 0.30, b is preferably 0.10 to 0.30, and c is preferably 0.40 to 0.80. From the same viewpoint, y is preferably an integer of 30 to 180.

[0205] The number average molecular weight (Mn) of the (F) elastomer is not particularly limited, but is preferably 10,000 to 80,000, may be 20,000 to 70,000, may be 30,000 to 65,000, or may be 40,000 to 60,000.

[0206] When the photosensitive resin composition of the present embodiment contains the elastomer (F), the content of the elastomer (F) is not particularly limited, but is preferably 0.5 to 15% by mass, more preferably 1 to 14% by mass, further preferably 3 to 13% by mass, and particularly preferably 5 to 12% by mass, based on the total amount of the resin components of the photosensitive resin composition, from the viewpoint of heat resistance and adhesion strength to the copper plating layer.

[0207] <(G) Inorganic filler>

[0208] The photosensitive resin composition of the present embodiment preferably further contains an inorganic filler as the component (G).

[0209] The photosensitive resin composition of the present embodiment tends to have better low thermal expansion, heat resistance, and flame retardancy by containing the (G) inorganic filler.

[0210] (G) The inorganic filler may be used alone or in combination of two or more.

[0211] (G) Inorganic fillers include silica, alumina, titanium oxide, mica, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, molybdate compounds, talc, aluminum borate, silicon carbide, etc. Among them, as inorganic fillers, from the viewpoint of thermal expansion coefficient, heat resistance and flame retardancy, silica and alumina are preferred, and silica is more preferred. As silica, crushed silica, fumed silica, fused silica, etc. are listed.

[0212] (G) Volume average particle size of the inorganic filler (D 50 ) is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, further preferably 0.2 to 1 μm, and particularly preferably 0.3 to 0.8 μm.

[0213] It should be noted that in this specification, the volume average particle size (D 50 ) can be determined as follows: using a submicron particle analyzer (manufactured by Beckman Coulter, Ltd., trade name: N5), in accordance with international standard ISO13321, particles dispersed in a solvent are measured with a refractive index of 1.38, and the particle size is determined as the particle size equivalent to the cumulative value of 50% (volume basis) in the particle size distribution.

[0214] When the photosensitive resin composition of the present embodiment contains (G) an inorganic filler, the content of the (G) inorganic filler is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, further preferably 15 to 55% by mass, and particularly preferably 25 to 50% by mass based on the total solid content of the photosensitive resin composition, from the viewpoint of forming an interlayer insulating layer having low thermal expansion, heat resistance, flame retardancy, and conductor adhesion.

[0215] <(H) Curing Accelerator>

[0216] The photosensitive resin composition of the present embodiment preferably further contains a curing accelerator as the component (H).

[0217] The photosensitive resin composition of the present embodiment tends to have better heat resistance, dielectric properties, and the like by containing the (H) curing accelerator.

[0218] (H) The curing accelerator may be used alone or in combination of two or more.

[0219] Examples of the (H) curing accelerator include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-1-benzyl-1H-imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and isocyanate-blocked imidazole (addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole); tertiary amines such as trimethylamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl)melamine, 2,4,6-tris(dimethylaminophenol), tetramethylguanidine, and m-aminophenol; organic phosphines such as tributylphosphine, triphenylphosphine, and tri-2-cyanoethylphosphine; tri-n-butyl(2,5-dihydroxyphenyl)bromide; Hexadecyl tributyl chloride wait Salts; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the above-mentioned polyacid anhydrides; diphenyl iodide Tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyran Hexafluorophosphate, etc.

[0220] Among them, imidazole compounds are preferred from the viewpoint of obtaining an excellent curing effect.

[0221] When the photosensitive resin composition of the present embodiment contains (H) a curing accelerator, the content of the (H) curing accelerator is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and even more preferably 0.1 to 2% by mass, based on the total amount of the resin components of the photosensitive resin composition, from the viewpoint of improving heat resistance and dielectric properties.

[0222] <(I) Other ingredients>

[0223] The photosensitive resin composition of the present embodiment may contain (I) other components as necessary.

[0224] (I) Other components include, for example, resins other than the above-mentioned components; curing agents, organic fillers; photosensitizers; polymerization inhibitors; foam stabilizers; pigments; adhesion aids such as melamine; foam stabilizers such as silicone compounds; thickeners; flame retardants; organic solvents, etc.

[0225] These may be used alone or in combination of two or more.

[0226] The content of (I) other components in the photosensitive resin composition of the present embodiment may be appropriately adjusted depending on the purpose, and each may be 0.01 to 10 mass %, 0.05 to 5 mass %, or 0.1 to 1 mass % based on the total solid content of the photosensitive resin composition.

[0227] <Method for producing photosensitive resin composition>

[0228] The photosensitive resin composition of the present embodiment can be obtained by kneading and mixing the components using a roll mill, a bead mill, or the like.

[0229] [Photosensitive resin film]

[0230] The photosensitive resin film of this embodiment contains the photosensitive resin composition of this embodiment. This photosensitive resin film is useful as a photosensitive layer for forming an interlayer insulating layer.

[0231] The components and contents thereof in the photosensitive resin film of the present embodiment are as described in the description of the components and contents thereof in the photosensitive resin composition of the present embodiment.

[0232] The photosensitive resin film of this embodiment may be provided on a carrier film.

[0233] Examples of the carrier film include polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyolefins such as polypropylene and polyethylene. The thickness of the carrier film is preferably 5 to 100 μm, more preferably 10 to 60 μm, and even more preferably 15 to 45 μm.

[0234] Moreover, the photosensitive resin film of this embodiment may have a protective film on the surface opposite to the surface in contact with the carrier film.

[0235] The photosensitive resin film of the present embodiment can be formed by coating the photosensitive resin composition of the present embodiment on a carrier film using a known coating apparatus such as a notch wheel coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater, and drying the coating.

[0236] The coating formed by applying the photosensitive resin composition can be dried using a hot air drying, far infrared or near infrared drying machine. As the drying temperature, it is preferably 60 to 150 ° C, more preferably 70 to 120 ° C, and further preferably 80 to 110 ° C. In addition, as the drying time, it is preferably 1 to 60 minutes, more preferably 2 to 30 minutes, and further preferably 5 to 20 minutes. From the viewpoint of avoiding the diffusion of the diluent in the manufacturing process of the printed wiring board, the content of the residual diluent in the dried photosensitive resin film is preferably less than or equal to 3% by mass, more preferably less than or equal to 2% by mass, and further preferably less than or equal to 1% by mass.

[0237] The thickness of the photosensitive resin film of the present embodiment is not particularly limited, but is preferably 1 to 100 μm, more preferably 3 to 60 μm, and even more preferably 5 to 40 μm from the viewpoint of reducing the thickness of a printed wiring board.

[0238] [Printed wiring board]

[0239] The printed wiring board of the present embodiment is a printed wiring board including a cured product of the photosensitive resin composition of the present embodiment.

[0240] The printed wiring board of the present embodiment is preferably a printed wiring board having an interlayer insulating layer which is a cured product of the photosensitive resin film of the present embodiment.

[0241] It should be noted that the “interlayer insulating layer” included in the printed wiring board of the present embodiment also includes a state after various processing or treatments such as formation of through holes and wirings and roughening are performed.

[0242] The method for producing a printed wiring board according to the present embodiment is not particularly limited as long as it is a method using the photosensitive resin film according to the present embodiment, but a method for producing a printed wiring board including the following (1) to (4) is preferred.

[0243] (1): The photosensitive resin film of the present embodiment is laminated on one surface or both surfaces of a circuit board (hereinafter also referred to as "lamination step (1)").

[0244] (2): The photosensitive resin film laminated in the above (1) is exposed and developed to form an interlayer insulating layer having a through hole (hereinafter also referred to as "through hole forming step (2)").

[0245] (3): The interlayer insulating layer having the through-hole is heated and cured (hereinafter also referred to as "heat-curing step (3)").

[0246] (4): A circuit pattern is formed on the interlayer insulating layer (hereinafter also referred to as "circuit pattern forming step (4)").

[0247] Below, refer to Figure 1 A method for manufacturing a printed wiring board according to the present embodiment will be described.

[0248] It should be noted that, in this specification, for convenience, a predetermined operation may be referred to as "XX step" in some cases, but this "XX step" is not limited to the method specifically described in this specification.

[0249] (Lamination process (1))

[0250] In the lamination step (1), the photosensitive resin film of the present embodiment is laminated on one surface or both surfaces of a circuit board.

[0251] Figure 1 (a) shows a process of forming a photosensitive layer 103 on both surfaces of a substrate 101 having a circuit pattern 102 .

[0252] The photosensitive layer 103 can be formed by laminating the photosensitive resin film of this embodiment on both surfaces of the substrate 101 such that the second surface serves as an attachment surface.

[0253] The lamination may be performed by pressure bonding while applying pressure and heat using, for example, a vacuum laminator or the like.

[0254] When a carrier film is attached to the photosensitive layer 103 after lamination, the carrier film may be peeled off before exposure described later or after exposure.

[0255] (Through-hole forming step (2))

[0256] In the through-hole forming step (2), the photosensitive layer formed in the lamination step (1) is exposed and developed to form an interlayer insulating layer having a through-hole.

[0257] Figure 1 (b) shows a process of forming the interlayer insulating layer 104 having the through hole 105 by exposing and developing the photosensitive layer 103 .

[0258] By exposing the photosensitive layer 103, a photoradical polymerization reaction is initiated, and the photosensitive resin film is cured.

[0259] The exposure method of the photosensitive layer 103 can be, for example, a mask exposure method in which active light is irradiated in an image form through a negative or positive mask pattern of a workpiece called an artwork, or a method in which active light is irradiated in an image form through a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Processing) exposure method.

[0260] Examples of the light source of active light include gas lasers such as carbon arc lamps, mercury vapor arc lamps, high pressure mercury lamps, xenon lamps, and argon lasers; solid lasers such as YAG lasers; and known light sources that efficiently radiate ultraviolet light or visible light such as semiconductor lasers.

[0261] The exposure amount can be appropriately adjusted according to the light source used and the thickness of the photosensitive layer. For example, when a photosensitive layer having a thickness of 1 to 100 μm is exposed using ultraviolet radiation from a high-pressure mercury lamp, the exposure amount is not particularly limited, but is preferably 10 to 1,000 mJ / cm 2 , more preferably 50 to 700 mJ / cm 2 , and more preferably 150 to 400 mJ / cm 2 .

[0262] Next, if a carrier film exists on the photosensitive layer 103, the carrier film is removed and then development is performed. In the development, the uncured portion of the photosensitive layer 103 is removed, so that the photocured portion is formed as the interlayer insulating layer 104 on the substrate.

[0263] The developing method may be wet developing or dry developing, but wet developing is preferred. As a method based on wet developing, a spray method is preferred from the viewpoint of improving resolution.

[0264] Examples of the developer include alkaline aqueous solutions, water-based developers, and organic solvent-based developers. Among these, alkaline aqueous solutions are preferred.

[0265] After exposure and development, post-exposure may be performed from the viewpoint of improving the curing degree of the interlayer insulating layer. The exposure amount in the post-exposure is not particularly limited, but is preferably 0.2 to 10 J / cm 2 , more preferably 0.5 to 5 J / cm 2 .

[0266] The shape of the through hole is not particularly limited, and if described in terms of cross-sectional shape, for example, a quadrilateral, an inverted trapezoid, etc. may be listed. In addition, an inverted trapezoid is a shape in which the upper side is longer than the lower side. In addition, if described in terms of a top view, a circle, a quadrilateral, etc. may be listed.

[0267] In the formation of the through hole by photolithography in this embodiment, a through hole having an inverted trapezoidal cross-sectional shape can be formed. A through hole having such a shape is preferred because the copper plating layer has high coverage (recovery) on the through hole wall surface.

[0268] In the formation of the through hole based on the photolithography method of this embodiment, the diameter of the through hole can be made smaller than the diameter of the through hole made by laser processing. The diameter of the through hole formed by the manufacturing method of this embodiment can be, for example, less than or equal to 40 μm, less than or equal to 35 μm, or less than or equal to 30 μm. The lower limit of the diameter of the through hole is not particularly limited, for example, it can be greater than or equal to 15 μm, or greater than or equal to 20 μm.

[0269] (Heating and curing step (3))

[0270] In the heat curing step (3), the interlayer insulating layer having the through hole is heat cured.

[0271] That is, in the heat curing step (3), the curing reaction of the thermosetting component contained in the photosensitive resin film of the present embodiment is advanced by heating.

[0272] The heating temperature is not particularly limited, but is preferably 100 to 300° C., more preferably 120 to 200° C., and further preferably 150 to 180° C. The heating time is not particularly limited, but is preferably 0.3 to 3 hours, more preferably 0.5 to 2 hours, and further preferably 0.75 to 1.5 hours.

[0273] (Circuit pattern forming step (4))

[0274] Next, a circuit pattern is formed on the interlayer insulating layer formed above.

[0275] From the viewpoint of forming fine wiring, the circuit pattern is preferably formed by a semi-additive process of sequentially performing roughening treatment, formation of a seed layer, formation of a resist pattern, formation of a copper circuit layer, and removal of the resist pattern.

[0276] Roughening treatment is a treatment for roughening the surface of the interlayer insulating layer to form a concave and convex anchor point. In the case where smear is generated in the through-hole forming step (2), a roughening liquid can be used to simultaneously perform the roughening treatment and remove the smear. Examples of the roughening liquid include alkaline permanganate roughening liquids such as sodium permanganate roughening liquid, chromium / sulfuric acid roughening liquid, sodium fluoride / chromium / sulfuric acid roughening liquid, and the like.

[0277] Figure 1 (c) shows the step of forming the seed layer 106 .

[0278] The seed layer 106 is used to form a power supply layer for performing copper electroplating.

[0279] The seed layer 106 can be formed by performing chemical copper plating on the entire surface of the through-hole bottom, the through-hole wall surface, and the interlayer insulating layer using a palladium catalyst or the like.

[0280] Figure 1 (d) shows a step of forming a resist pattern 107 on the seed layer 106 .

[0281] The resist pattern 107 can be formed, for example, by thermally pressing a dry film resist onto the seed layer 106 using a roll laminator or the like, and then exposing and developing the resist. As the dry film resist, a commercially available product can be used.

[0282] The exposure of the dry film resist can be performed through a mask having a desired wiring pattern drawn thereon. After exposure, the dry film resist is developed using an alkaline aqueous solution to remove the unexposed portion to form a resist pattern 107. Then, a plasma treatment can be performed to remove the development residue of the dry film resist as needed.

[0283] Figure 1 (e) shows the step of forming the copper circuit layer 108.

[0284] The copper circuit layer 108 is preferably formed by copper electroplating.

[0285] As the copper electroplating solution used for copper electroplating, for example, a commercially available copper electroplating solution such as a copper electroplating solution containing copper sulfate can be used.

[0286] After copper electroplating, the resist pattern 107 is removed using an alkaline aqueous solution or an amine stripper, and then, flash etching to remove the seed layer 106 between wirings, removal of the palladium catalyst, etc. are appropriately performed by a known method. Furthermore, a post-baking treatment for sufficiently thermally curing the unreacted thermal curing component may be performed as needed.

[0287] Figure 1 (f) shows a multilayer printed wiring board 100A which is multilayered by repeating the above-mentioned steps and has a solder resist layer 109 on the outermost surface.

[0288] The solder resist layer 109 can be formed using a known photosensitive resin film for solder resist.

[0289] In the above, the method for manufacturing a printed wiring board in which a through hole is formed using the photosensitive resin film of the present embodiment is described, but the photosensitive resin film of the present embodiment is also suitable for forming a cavity for a built-in chip or a passive element, for example, because of its excellent pattern resolution. Regarding the cavity, for example, in the above description of the printed wiring board, the cavity can be appropriately formed by setting the drawing pattern when the photosensitive resin film is exposed to form a pattern to form a desired cavity.

[0290] [Semiconductor packaging]

[0291] The semiconductor package of the present embodiment is a semiconductor package including the printed wiring board of the present embodiment and a semiconductor element.

[0292] The semiconductor package of the present embodiment can be manufactured by, for example, mounting a semiconductor element such as a semiconductor chip or a memory on a predetermined position of a printed wiring board of the present embodiment and sealing the semiconductor element with a sealing resin or the like.

[0293] Example

[0294] Hereinafter, the present embodiment will be described in more detail with reference to Examples, but the present embodiment is not limited to these Examples.

[0295] [Measurement method of acid value]

[0296] The acid value is calculated from the amount of potassium hydroxide aqueous solution required to neutralize the measurement object.

[0297] [Method for measuring weight average molecular weight (Mw)]

[0298] The weight average molecular weight (Mw) was measured using the following GPC measuring apparatus and measuring conditions and converted using a calibration curve of standard polystyrene. In preparing the calibration curve, five sample sets ("PStQuick MP-H" and "PStQuick B", manufactured by Tosoh Corporation) were used as standard polystyrene.

[0299] (GPC measurement device)

[0300] GPC device: High-speed GPC device "HCL-8320GPC", detector is differential refractometer or UV, manufactured by Tosoh Corporation

[0301] Column: Column TSKgel SuperMultipore HZ-H (column length: 15cm, column inner diameter: 4.6mm), manufactured by Tosoh Corporation

[0302] (Measurement conditions)

[0303] Solvent: Tetrahydrofuran (THF)

[0304] Measurement temperature: 40℃

[0305] Flow rate: 0.35ml / min

[0306] Sample concentration: 10mg / THF 5ml

[0307] Injection volume: 20μl

[0308] [Production of Photosensitive Resin Composition and Photosensitive Resin Film]

[0309] Examples 1 to 8, Comparative Examples 1 to 5

[0310] (1) Production of photosensitive resin composition

[0311] The components were mixed according to the composition shown in Table 1 (the units of the values ​​in the table are parts by mass, and in the case of a solution, the solid content conversion amount), and kneaded using a three-roll mill and a rotation and revolution mixer. Thereafter, methyl ethyl ketone was added so that the solid content concentration became 65% by mass to obtain a photosensitive resin composition.

[0312] (2) Production of photosensitive resin film

[0313] A polyethylene terephthalate film (manufactured by Teijin Co., Ltd., trade name "G2-16") with a thickness of 16 μm was used as a carrier film. The photosensitive resin composition prepared in each example was coated on the carrier film so that the film thickness after drying was 25 μm, and dried at 100° C. for 10 minutes using a hot air convection dryer to form a photosensitive resin film. Next, a polyethylene film (manufactured by TAMAPOLY Co., Ltd., trade name "NF-15") was laminated as a protective film on the surface of the photosensitive resin film on the opposite side of the side in contact with the carrier film, thereby preparing a photosensitive resin film laminated with a carrier film and a protective film.

[0314] [Determination of relative dielectric constant (Dk) and dielectric loss tangent (Df)]

[0315] Two photosensitive resin films with the protective films peeled off were laminated together and irradiated with 400 mJ / cm2 using a flat exposure machine with carrier films on both sides. 2 (wavelength 365nm), irradiated with 2J / cm using UV conveyor exposure machine 2 (wavelength 365nm). Then, the sample was heated at 170°C for 1 hour using a hot air circulation dryer and cut into 7cm×10cm size to serve as an evaluation sample. A desiccant was sealed in the obtained evaluation sample and dried for more than 10 hours, and the relative dielectric constant (Dk) and dielectric loss tangent (Df) in the 10GHz band were measured using the separated column dielectric resonator method (SPDR method).

[0316] [Determination of minimum development time]

[0317] The copper foil surface of a printed wiring board substrate (manufactured by Resonac Co., Ltd., trade name "MCL-E-679") having copper foil (thickness 12 μm) laminated on a glass epoxy substrate was roughened using a roughening pretreatment liquid (manufactured by MEC Co., Ltd., trade name "CZ-8101"), and then washed and dried. Next, the photosensitive resin film from which the protective film was peeled off was laminated on the copper foil of the printed wiring board substrate after the roughening pretreatment in such a way that the photosensitive resin film became the adhesive surface. It should be noted that a pressing vacuum laminator (manufactured by Meiki Manufacturing Co., Ltd., trade name "MVLP-500") was used for lamination, and the lamination conditions were set to a pressing hot plate temperature of 75°C, a vacuuming time of 20 seconds, a lamination pressing time of 30 seconds, an air pressure of less than or equal to 4 kPa, and a crimping pressure of 0.4 MPa. After the lamination treatment, the film was left to stand at room temperature for 1 hour or more, thereby obtaining a laminate for evaluation in which a photosensitive resin film and a carrier film were laminated in this order on the copper foil surface of the printed wiring board substrate.

[0318] The carrier film of the evaluation laminate obtained above was removed, and the photosensitive resin film was spray-developed using a 1 mass % sodium carbonate aqueous solution at 30° C. At this time, the minimum time that could be developed was defined as the minimum development time.

[0319] [Measurement of bonding strength with copper plating]

[0320] (1) Preparation of evaluation laminate and measurement of sensitivity of photosensitive resin film

[0321] An evaluation laminate was prepared in the same manner as in the above-mentioned [Measurement of Minimum Development Time], and a 41-step step exposure meter was placed on the carrier film of the evaluation laminate. Next, exposure was performed using a parallel light exposure machine (manufactured by ORC Manufacturing Co., Ltd., trade name "EXM-1201") using an ultra-high pressure mercury lamp as a light source.

[0322] After exposure, the film was left at room temperature for 30 minutes, the carrier film of the evaluation laminate was removed, and the photosensitive resin film was spray developed using a 1 mass % sodium carbonate aqueous solution at 30°C. The exposure energy when the gloss residual stage number became 8.0 was calculated and used as the sensitivity of the photosensitive resin film (unit: mJ / cm 2 ).

[0323] (2) Exposure and Development Process

[0324] The entire surface of the evaluation laminate was exposed at the sensitivity obtained above, i.e., the exposure energy, to cure the photosensitive resin film. After exposure, the laminate was left at room temperature for 30 minutes, the carrier film of the evaluation laminate was peeled off, and the photosensitive resin film was spray-developed using a 1 mass % sodium carbonate aqueous solution at 30° C. for a development time twice the minimum development time.

[0325] (3) Post-curing treatment

[0326] Next, a high-pressure mercury lamp irradiation type UV conveyor device (manufactured by ORC Manufacturing Co., Ltd.) was used to expose the film at an exposure dose of 2 J / cm 2 Then, the film was heated at 170° C. for 1 hour using a hot air circulation dryer to obtain a laminate for evaluation having an interlayer insulating layer formed by curing the photosensitive resin film.

[0327] (4) Roughening treatment

[0328] The heated evaluation laminate was treated with a swelling liquid "Swelling Dip Securiganth P" at 70°C for 5 minutes, and then roughened with a roughening liquid "Dosing Securiganth P500J" at 70°C for 10 minutes. Next, a neutralization treatment was performed at 50°C for 5 minutes using a neutralizing liquid "Reduction Conditioner Securiganth P500". Then, a hydrofluoric acid treatment was performed at room temperature for 10 minutes using a buffered hydrofluoric acid "LAL1800 SA High Purity Buffered Hydrofluoric Acid". It should be noted that the swelling liquid, the roughening liquid, and the neutralizing liquid were all made by ATOTECH JAPAN Co., Ltd., and the buffered hydrofluoric acid was made by Stella Chemifa Co., Ltd.

[0329] (5) Plating treatment

[0330] The roughened laminate was subjected to chemical plating at 30°C for 15 minutes using a chemical plating solution "Priganth MSK-DK" (manufactured by ATOTECH JAPAN Co., Ltd.). Then, the roughened laminate was subjected to chemical plating at 24°C, 2 A / dm 2 The electroplating treatment was performed for 1.5 hours to form a copper plating layer on the interlayer insulating layer. The thickness of the copper plating layer was set to 25 μm.

[0331] (6) Determination of bonding strength with copper plating

[0332] Regarding the bonding strength to the copper plating layer, vertical peel strength was measured at 23° C. in accordance with JIS C6481:1996, and the strength was defined as the bonding strength to the copper plating layer.

[0333] It should be noted that "lifting" in the table refers to peeling between the copper plating layer and the interlayer insulating layer, or peeling between the interlayer insulating layer and the copper substrate interface.

[0334] [Determination of weight reduction of desmear]

[0335] A laminate for evaluation having an interlayer insulating layer was prepared in the same manner as in the above [Measurement of Adhesion Strength to Copper Plating], and the laminate for evaluation was immersed in a swelling liquid "Swelling Dip Securiganth P" (aqueous solution of glycol ethers and sodium hydroxide, manufactured by ATOTECH JAPAN Co., Ltd.) at 70°C for 10 minutes, and then washed with water at 25°C for 3 minutes. Next, a roughening liquid "Concentrate Compact P" (KMnO 4: 60g / L, NaOH: 40g / L aqueous solution, manufactured by ATOTECH JAPAN Co., Ltd.) at 80°C for 15 minutes, and then rinsed with water at 50°C for 1 minute. Finally, it was immersed in "Reduction Solution Securiganth P" (an aqueous solution of sulfuric acid, manufactured by ATOTECH JAPAN Co., Ltd.) as a neutralizing solution at 40°C for 5 minutes, and then rinsed with water at 25°C for 3 minutes. Then, it was dried at 105°C for 10 minutes to obtain an evaluation laminate after desmear treatment. The difference between the weight of the evaluation laminate before desmear treatment and the weight of the evaluation laminate after the above-mentioned desmear treatment [before desmear treatment - after desmear treatment] was taken as the desmear weight reduction.

[0336] [Table 1]

[0337] Table 1

[0338]

[0339] The components used in Table 1 are as follows.

[0340] [(A) Photopolymerizable Compound Having Ethylenically Unsaturated Group and Acidic Substituent]

[0341] A1: "ZXR-1935H" (manufactured by Nippon Kayaku Co., Ltd., acid value: 110 mg KOH / g, weight average molecular weight (Mw): 2,000), a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent and comprising an alicyclic skeleton represented by the above general formula (A-1)

[0342] [(B) Blocked isocyanate compound having a molecular weight of 3,000 or less]

[0343] B1: "BI7951" (manufactured by LANXESS), molecular weight: 955, dissociation temperature 120°C, a blocked isocyanate compound obtained by blocking the isocyanate group of the trimer of isophorone diisocyanate represented by the following formula with 3,5-dimethylpyrazole (DMP)

[0344] [Chemistry 7]

[0345]

[0346] B2: "TPA-B80E" (manufactured by Asahi Kasei Corporation), molecular weight: 766, dissociation temperature 130°C, a blocked isocyanate compound obtained by blocking the isocyanate group of a trimer of 1,6-hexamethylene diisocyanate represented by the following formula with 2-butanone oxime

[0347] [Chemistry 8]

[0348]

[0349] B3: "CORONATE 2554" (manufactured by Tosoh Corporation), molecular weight: 844, dissociation temperature 160°C, a blocked isocyanate compound obtained by blocking the isocyanate group of the trimer of 1,6-hexamethylene diisocyanate represented by the following formula with ε-caprolactam

[0350] [Chemistry 9]

[0351]

[0352] B4: "MOI-MP" (manufactured by Resonac Co., Ltd.), molecular weight: 250, dissociation temperature 170°C, blocked isocyanate compound obtained by blocking 2-isocyanatoethyl methacrylate with 1-methoxy-2-propanol

[0353] [(B') Blocked isocyanate compound having a molecular weight greater than 3,000]

[0354] · B'5: "Blonate 1950" (manufactured by Daiei Sangyo Co., Ltd.), molecular weight: greater than 3,000, dissociation temperature 140°C, phenol-terminated polyisocyanate

[0355] B'6: "Blonate 1901" (manufactured by Daiei Sangyo Co., Ltd.), molecular weight: greater than 3,000, dissociation temperature 140°C, phenol-terminated polyisocyanate

[0356] · B'7: "Blonate 1631V01" (manufactured by Daiei Sangyo Co., Ltd.), molecular weight: greater than 3,000, dissociation temperature 150°C, oxime-terminated polyisocyanate

[0357] · B'8: "Blonate 1227EV" (manufactured by Daiei Sangyo Co., Ltd.), molecular weight: greater than 3,000, dissociation temperature 80-100°C, active methylene polyisocyanate

[0358] [(C) Thermosetting resin]

[0359] C1: "EPOTOHTO (registered trademark) ESN-475V" (manufactured by Nippon Steel Chemical Materials Co., Ltd.), α-naphthol aralkyl type epoxy resin, acid value: 110 mgKOH / g, weight average molecular weight (Mw): 2,000

[0360] C2: "NC-3000L" (manufactured by Nippon Kayaku Co., Ltd.), biphenyl aralkyl type epoxy resin, epoxy equivalent: 272 g / eq

[0361] [(D) Photopolymerization initiator]

[0362] ·D1: "Irgacure OXE02" (manufactured by BASF Japan Co., Ltd.), oxime ester compound

[0363] D2: "Omnirad 819" (manufactured by IGM Resins BV), acylphosphine oxide compounds

[0364] [(E) Cross-linking agent]

[0365] ·E1: “DPHA” (dipentaerythritol hexaacrylate)

[0366] [(F) Elastomer]

[0367] F1: "Ricon (registered trademark) 131MA17" (manufactured by Cray Valley Corporation), maleic acid-modified polybutadiene, number average molecular weight (Mn) 54,000 (catalog value)

[0368] [(G) Inorganic filler]

[0369] G1: Spherical fused silica (volume average particle size (D 50 ): 0.5μm)

[0370] [(H) Curing accelerator]

[0371] ·H1: 1-Benzyl-2-phenylimidazole

[0372] [(I) Other ingredients]

[0373] ·I1: 4,4'-Bis-(diethylamino)benzophenone (sensitizer)

[0374] I2: tert-butylcatechol (inhibitor)

[0375] According to Table 1, the photosensitive resin compositions of Examples 1 to 8 of the present embodiment all have both good dielectric properties and developability. On the other hand, the photosensitive resin compositions of Comparative Examples 1 to 5 that do not satisfy the configuration of the photosensitive resin composition of the present embodiment have poor dielectric properties or developability.

[0376] Description of Reference Numerals

[0377] 100A Multilayer Printed Wiring Board

[0378] 101 substrate

[0379] 102 Circuit Pattern

[0380] 103 Photosensitive layer

[0381] 104 interlayer insulation layer

[0382] 105 Through hole

[0383] 106 Seed Layer

[0384] 107 Resist pattern

[0385] 108 Copper circuit layer

[0386] 109 Solder mask.

Claims

1. A photosensitive resin composition comprising (A) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent and (B) a blocked isocyanate compound having a molecular weight of 3,000 or less. 2 . The photosensitive resin composition according to claim 1 , wherein the dissociation temperature of the component (B) is 80 to 250° C. 3 . The photosensitive resin composition according to claim 1 , wherein the component (B) is a compound containing an isocyanurate ring. 4 . The photosensitive resin composition according to claim 3 , wherein the component (B) is a compound obtained by blocking a trifunctional isocyanate compound including an isocyanurate ring with a blocking agent. 5 . The photosensitive resin composition according to claim 1 , wherein the content of the component (B) is 1 to 40% by mass based on the total amount of the resin components.

6. The photosensitive resin composition according to claim 1 or 2, wherein the component (A) comprises an alicyclic skeleton represented by the following general formula (A-1): [Chemistry 1] In the formula, R A1 represents an alkyl group having 1 to 12 carbon atoms, which may be substituted at any position of the alicyclic skeleton, and m 1 is an integer of 0 to 6, and * is a bonding site with other structures. 7 . The photosensitive resin composition according to claim 1 , further comprising (C) a thermosetting resin. 8 . The photosensitive resin composition according to claim 1 , further comprising (D) a photopolymerization initiator. 9 . The photosensitive resin composition according to claim 1 , further comprising (E) a crosslinking agent. 10 . The photosensitive resin composition according to claim 1 , further comprising (F) an elastomer. 11 . The photosensitive resin composition according to claim 1 , further comprising (G) an inorganic filler. 12 . The photosensitive resin composition according to claim 1 , which is used for forming an optical through hole. 13 . A photosensitive resin film comprising the photosensitive resin composition according to claim 1 or 2 . 14 . A printed wiring board comprising a cured product of the photosensitive resin composition according to claim 1 . 15 . A semiconductor package comprising the printed wiring board according to claim 14 and a semiconductor element.

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