JP6094271B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition.

  In recent years, miniaturization and high performance of electronic devices have progressed, and in printed wiring boards, wiring density has been increased by miniaturization of wiring and multilayering of buildup layers, and solder resist is used as the outermost layer. By forming the layer, the deterioration of the wiring is prevented. In general, in a printed wiring board, a thermosetting resin composition is used for a buildup layer, and a photosensitive resin composition is used for a solder resist layer. Although the photosensitive resin composition has advantages such as being inexpensive and having a simple manufacturing process, its physical performance is not sufficient and it is difficult to apply it to a buildup layer. For example, a photosensitive resin composition in which a phenol compound is blended as a thermosetting component for the purpose of improving adhesion after a PCT resistance test is known (see Patent Document 1). However, its use is limited to the protective film, and its physical performance is not sufficient.

International Publication No. 2010/026927

  The problem to be solved by the present invention is a photosensitive resin composition having sufficient physical performance for use as a material for a buildup layer, that is, heat resistance is further improved, dielectric loss tangent is low, and water resistance is low. It is to provide a photosensitive resin composition that is high in alkali development.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention provide a photosensitive resin composition comprising (A) an active ester curing agent and (B) a carboxyl group-containing radical polymerizable compound. The present invention has been completed.

That is, the present invention provides the following [1] to [20].
[1] A photosensitive resin composition comprising (A) an active ester curing agent and (B) a carboxyl group-containing radical polymerizable compound.
[2] When the total solid content of the photosensitive resin composition is 100% by mass, the content of (A) the active ester curing agent is 0.5% by mass to 20% by mass, [1] The photosensitive resin composition according to [1].
[3] When the total solid content of the photosensitive resin composition is 100% by mass, the content of the (B) carboxyl group-containing radical polymerizable compound is 10% by mass to 60% by mass, The photosensitive resin composition as described in [1] or [2].
[4] The photosensitivity according to any one of [1] to [3], wherein the acid value of the (B) carboxyl group-containing radical polymerizable compound is 0.1 mgKOH / g to 150 mgKOH / g. Resin composition.
[5] The (B) carboxyl group-containing radically polymerizable compound is a compound having both a carboxyl group and two or more radically polymerizable unsaturated groups in one molecule, [1] to [4] ] The photosensitive resin composition as described in any one of.
[6] (B) The carboxyl group-containing radical polymerizable compound is a compound obtained by reacting an epoxy resin, an unsaturated carboxylic acid and an acid anhydride,
The epoxy resin is a bisphenol F type epoxy resin, a bisphenol A type epoxy resin or a cresol novolac type epoxy resin,
The unsaturated carboxylic acid is acrylic acid or methacrylic acid,
The photosensitive resin composition according to any one of [1] to [5], wherein the acid anhydride is succinic anhydride or tetrahydrophthalic anhydride.
[7] The photosensitive resin composition according to any one of [1] to [6], further comprising (C) a photopolymerization initiator.
[8] The photosensitive resin composition according to any one of [1] to [7], further comprising (D) an epoxy resin.
[9] The photosensitive resin composition according to any one of [1] to [8], further comprising (E) a curing accelerator.
[10] The photosensitive resin composition according to any one of [1] to [9], further comprising (F) an inorganic filler.
[11] The photosensitive resin composition according to any one of [1] to [10], wherein the dielectric loss tangent of the cured product of the photosensitive resin composition is 0.005 to 0.05. object.
[12] A photosensitive film comprising the photosensitive resin composition according to any one of [1] to [11].
[13] A photosensitive film with a support, wherein the layer of the photosensitive resin composition according to any one of [1] to [11] is formed on a support.
[14] A multilayer printed wiring board in which an insulating layer is formed of a cured product of the photosensitive resin composition according to any one of [1] to [11].
[15] A multilayer printed wiring board in which an interlayer insulating layer is formed of a cured product of the photosensitive resin composition according to any one of [1] to [11].
[16] A semiconductor device comprising the multilayer printed wiring board according to [14] or [15].
[17] A method for producing a multilayer printed wiring board, comprising a step of exposing a resin composition layer formed of the photosensitive resin composition according to any one of [1] to [11] .
[18] A multi-layer characterized in that after the exposure step of the resin composition layer formed of the photosensitive resin composition according to any one of [1] to [11], a development step with an alkaline aqueous solution is performed. Manufacturing method of printed wiring board.
[19] A multilayer printed wiring board, which is formed by the method for producing a multilayer printed wiring board according to [17] or [18].
[20] A semiconductor device comprising the multilayer printed wiring board according to [19].

  The photosensitive resin composition of the present invention is further improved in heat resistance when it is used as a cured product, has a low dielectric loss tangent, has high water resistance, and can be developed with an alkali.

  The photosensitive resin composition of the present invention comprises (A) an active ester curing agent and (B) a carboxyl group-containing radical polymerizable compound.

<(A) Active ester curing agent>
The active ester-based curing agent (A) used in the photosensitive resin composition of the present invention can improve the heat resistance when made into a cured product, while reducing the dielectric loss tangent and increasing the water resistance, Moreover, alkali development is also possible. (A) Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, The compound which has two or more active ester groups in 1 molecule is preferable. (A) As an active ester type curing agent, generally two ester groups having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters are contained in one molecule. The compounds having the above are preferably used.

  From the viewpoint of improving heat resistance when a cured product is used, (A) the active ester-based curing agent is a reaction in which a carboxylic acid compound and / or a thiocarboxylic acid compound is condensed with a hydroxy compound and / or a thiol compound. An active ester compound obtained from a product is preferred, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is more preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is still more preferred. An aromatic compound having two or more active ester groups in one molecule obtained from a reaction product obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is even more preferable. (A) The active ester curing agent is an aromatic compound obtained from a reaction product obtained by reacting a compound having at least two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group. Particularly preferred are aromatic compounds having two or more active ester groups in one molecule of the aromatic compound. The active ester compound may be linear or hyperbranched. In addition, if the compound having at least two carboxylic acids in one molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be increased, and if it is a compound having an aromatic ring, it is heat resistant. Sexuality can be increased. (A) The active ester curing agent may be used alone or in combination of two or more.

  Examples of the carboxylic acid compound that can be used include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Of these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred from the viewpoint of improving heat resistance when cured. Examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid.

  Specific examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o -Cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetra Hydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, phenol novolac and the like.

  Among these, from the viewpoint of improving heat resistance and solubility when cured, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol. , Β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, Phenol novolac is preferred, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Rehydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolak are more preferable, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone , Trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolak are more preferable. 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyl di Phenol and phenol novolak are even more preferable. 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2, - dihydroxynaphthalene, dicyclopentadienyl diphenol especially preferred, dicyclopentadienyl diphenol is particularly preferred. Specific examples of the thiol compound include benzenedithiol and triazinedithiol.

  More specifically, the active ester curing agent containing a dicyclopentadienyl structure includes a compound represented by the following formula (1).

  In formula (1), two R's are each independently a phenyl group or a naphthyl group. k represents 0 or 1; n is 0.05 to 2.5 on the average of the repeating units.

  From the viewpoint of reducing the dielectric loss tangent and improving the heat resistance, R is preferably a naphthyl group. k is preferably 0. N is preferably 0.25 to 1.5.

  As the active ester curing agent, an active ester compound disclosed in JP-A-2004-277460 may be used, or a commercially available active ester curing agent may be used. Specific examples of commercially available active ester curing agents include an active ester curing agent having a dicyclopentadienyl structure, an active ester curing agent having a naphthalene structure, and an acetylated product of phenol novolac. An active ester type curing agent and an active ester type curing agent containing a phenol novolak benzoyl compound are preferable, and an active ester type curing agent containing a naphthalene structure and an active ester type curing agent containing a dicyclopentadienyl diphenol structure are more preferable. preferable. Examples of the active ester curing agent containing a dicyclopentadienyl diphenol structure include EXB9451, EXB9460, EXB9460S, and HPC8000-65T (manufactured by DIC Corporation). As an active ester curing agent containing a naphthalene structure, Examples thereof include EXB9416-70BK (manufactured by DIC Corporation), and examples of the active ester curing agent containing an acetylated product of phenol novolac include DC808 (manufactured by Mitsubishi Chemical Corporation), and phenol novolac. Examples of the active ester curing agent containing a benzoylated product of YLH1026 (manufactured by Mitsubishi Chemical Corporation).

  (A) The content of the active ester curing agent improves the heat resistance when it is used as a cured product, further reduces the dielectric loss tangent, and improves the water resistance. When the total amount is 100% by mass, it is preferable that (A) the active ester curing agent is contained in an amount of 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more. On the other hand, from the viewpoint of preventing a decrease in alkali developability, the content of the (A) active ester curing agent is 20% by mass or less when the total solid content of the photosensitive resin composition is 100% by mass. It is preferably 15% by mass or less, more preferably 10% by mass or less.

<(B) Carboxyl group-containing radical polymerizable compound>
The (B) carboxy group-containing radical polymerizable compound in the present invention is not particularly limited as long as it is a compound having a carboxyl group and capable of alkali development, but a carboxyl group and two or more radical polymerizations in one molecule. A compound having an unsaturated group is preferred. Examples thereof include unsaturated epoxy ester resins obtained by reacting an epoxy resin with an unsaturated carboxylic acid, and acid pendant unsaturated epoxy ester resins obtained by further reacting an acid anhydride.

  As the “epoxy resin”, any compound having two or more epoxy groups in the molecule can be used. Specifically, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type Epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol type epoxy resin such as bisphenol S type epoxy resin, dihydroxynaphthalene type epoxy resin, naphthalene type epoxy resin such as binaphthol type epoxy resin, biphenol type epoxy resin, tetramethylbiphenol type, etc. Biphenol type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, naphthol novolak type epoxy resin, alkylphenol novolak Novolak epoxy resins such as epoxy resins, bisphenol F type epoxy resins obtained by modifying the above trifunctional by reacting epichlorohydrin bisphenol F type epoxy resins. Any of these may be used alone or in combination of two or more. Of these, bisphenol F type epoxy resin, bisphenol A type epoxy resin, and cresol novolac type epoxy resin are preferable. Bisphenol modified with tri- or more functional groups by reacting cresol novolak type epoxy resin and bisphenol F type epoxy resin with epichlorohydrin. The F type epoxy resin is more preferable from the viewpoint of realizing a cured product of the photosensitive resin composition excellent in developability and insulation reliability.

  Here, examples of the “unsaturated carboxylic acid” include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid and the like, and these may be used alone or in combination of two or more. Good. Among these, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. Accordingly, (B) a preferred embodiment of the carboxyl group-containing radical polymerizable compound is a compound obtained by reacting an epoxy resin and an unsaturated carboxylic acid, and the epoxy resin is a bisphenol F type epoxy resin or a bisphenol A type epoxy resin. Or it is a cresol novolak-type epoxy resin, and is a compound whose unsaturated carboxylic acid is acrylic acid or methacrylic acid.

  Further, in the case of obtaining an acid pendant type unsaturated epoxy ester resin reacted with an acid anhydride, examples of the “acid anhydride” include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, and tetrahydro anhydride. Examples include phthalic acid, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, etc. These may be used alone or in combination of two or more. May be. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferable from the viewpoint of improving the developability and insulation reliability of the cured product.

  The acid-pendane cage-type unsaturated epoxy ester resin is obtained by reacting the unsaturated carboxylic acid and the epoxy resin in the presence of a catalyst, and then reacting the resulting unsaturated epoxy ester resin and acid anhydride with each other. It can be obtained by reacting.

  The amount of the catalyst used at this time is 2% by weight or less, preferably in the range of 0.0005% by weight to 1% by weight, based on the total weight of the unsaturated carboxylic acid, the epoxy resin and the acid anhydride. Particularly preferably, it is in the range of 0.001% to 0.5% by weight. Examples of the catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN). ), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3- (2-amino Ethyl) aminopropyltrimethoxysila , Various amine compounds such as 3- (2-aminoethyl) aminopropylmethyldimethoxysilane and tetramethylammonium hydroxide; phosphines such as trimethylphosphine, tributylphosphine and triphenylphosphine; tetramethylphosphonium salt, tetraethylphosphonium salt, Phosphonium salts such as tetrapropyl phosphonium salt, tetrabutyl phosphonium salt, trimethyl (2-hydroxylpropyl) phosphonium salt, triphenyl phosphonium salt, benzyl phosphonium salt, as representative counter anions such as chloride, bromide, carboxylate, Phosphonium salts having hydroxide and the like; trimethylsulfonium salt, benzyltetramethylenesulfonium salt, phenylbenzylmethylsulfoni Or sulfonium salts such as phenyldimethylsulfonium salt, which have carboxylate, hydroxide, etc. as typical counter anions; acidic compounds such as phosphoric acid, p-toluenesulfonic acid, sulfuric acid, etc. Can be mentioned. The reaction can be carried out in the range of 50 ° C to 150 ° C, preferably in the range of 80 ° C to 120 ° C.

  Accordingly, (B) a preferred embodiment of the carboxyl group-containing radical polymerizable compound is a compound obtained by reacting an epoxy resin, an unsaturated carboxylic acid and an acid anhydride, and the epoxy resin is a bisphenol F-type epoxy resin or bisphenol. A type epoxy resin or a cresol novolac type epoxy resin, an unsaturated carboxylic acid is acrylic acid or methacrylic acid, and an acid anhydride is succinic anhydride or tetrahydrophthalic anhydride.

  As commercially available acid pendant type unsaturated epoxy ester resins, ZFR-1533H (manufactured by Nippon Kayaku Co., Ltd., reaction product of bisphenol F type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride), ZAR-2000 ( Nippon Kayaku Co., Ltd., reaction product of bisphenol A type epoxy resin, acrylic acid and succinic anhydride), PR-3000 (manufactured by Showa Denko Co., Ltd., cresol novolac type epoxy resin, acrylic acid, and acid anhydride) Reaction product) and the like.

  (B) In the production of a carboxyl group-containing radical polymerizable compound, from the viewpoint of improving storage stability, the number of moles of the epoxy group of the epoxy resin and the number of moles of the total carboxyl group of unsaturated carboxylic acid and acid anhydride Is preferably in the range of 1: 0.8 to 1.3, and more preferably in the range of 1: 0.9 to 1.2.

In addition, the (B) carboxyl group-containing radical polymerizable compound preferably has an acid value of 0.1 mgKOH / g or more, from the viewpoint of improving the alkali developability of the photosensitive resin composition, and 0.5 mgKOH / g. More preferably, it is more preferably 1 mgKOH / g or more. On the other hand, the acid value is preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, from the viewpoint of preventing the fine pattern of the cured product from dissolving by development and improving the insulation reliability. Preferably, it is 90 mgKOH / g or less. Here, the acid value is a residual acid value of a carboxyl group present in the (B) carboxyl group-containing radical polymerizable compound, and the acid value can be measured by the following method. First, after precisely weighing about 1 g of the measurement resin solution, 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N aqueous KOH solution. And an acid value is computed by a following formula.
Formula: A = 10 × Vf × 56.1 / (Wp × I)

  In the above formula, A represents the acid value (mgKOH / g), Vf represents the titration amount (mL) of KOH, Wp represents the measurement resin solution mass (g), and I represents the non-volatile content of the measurement resin solution. Represents the ratio (mass%).

  (B) From the viewpoint of improving alkali developability, the carboxyl group-containing radical polymerizable compound may have a content of 10% by mass or more when the total solid content of the photosensitive resin composition is 100% by mass. It is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and particularly preferably 30% by mass or more. On the other hand, from the viewpoint of improving heat resistance, when the total solid content of the photosensitive resin composition is 100% by mass, the content is preferably 60% by mass or less, and is preferably 50% by mass or less. More preferably, it is still more preferable to set it as 40 mass% or less.

<(C) Photopolymerization initiator>
The photosensitive resin composition of the present invention can be made into a cured product by efficiently photocuring the resin composition by further containing (C) a photopolymerization initiator. (C) The photopolymerization initiator is not particularly limited. For example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4 Α-amino such as -methylphenyl) methyl]-[4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one Alkylphenone photopolymerization initiators, benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoyl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl- (2,4,6-trimethylbenzoyl) ) Phosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate, 4,4′-bis ( Ethylamino) benzophenone, 1-hydroxy-cyclohexyl-phenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- 2-methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like, and sulfonium salt photopolymerization initiators and oxime ester photopolymerization initiators Etc. can also be used. These may be used alone or in combination of two or more.

  Further, as photopolymerization initiation assistants, tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. Or photosensitizers such as pyralizones, anthracenes, coumarins, xanthones, thioxanthones, etc. may be added. These may be used alone or in combination of two or more.

  (C) The photopolymerization initiator is sufficiently contained when the entire solid content of the photosensitive resin composition is 100% by mass from the viewpoint of sufficiently photocuring the photosensitive resin composition and improving the insulation reliability. The amount is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. On the other hand, from the viewpoint of preventing a decrease in dimensional stability due to excessive sensitivity, when the total solid content of the photosensitive resin composition is 100% by mass, the content is preferably 6% by mass or less, and 4% by mass. % Or less, more preferably 2% by mass or less.

<(D) Epoxy resin>
In the photosensitive resin composition of this invention, insulation reliability can be improved by containing (D) epoxy resin further.
The (D) epoxy resin used in the present invention can be used without particular limitation. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, heterocyclic epoxy resin, phenol novolac type epoxy resin, Cresol novolac type epoxy resin Alkylphenol novolak type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, condensate of phenol and aromatic aldehyde having phenolic hydroxyl group Epoxidized products, naphthalene type epoxy resins, fluorene type epoxy resins, xanthene type epoxy resins and the like. Any one of these epoxy resins may be used, or two or more of them may be used in combination. Moreover, from the viewpoint of reactivity, the epoxy resin is preferably a resin having an epoxy equivalent of 95 to 400, and more preferably a resin having a range of 150 to 300. In addition, an epoxy equivalent (g / eq) is the gram number of resin containing the epoxy group of 1 gram equivalent prescribed | regulated to JISK7236.

  (D) Especially as an epoxy resin, a dicyclopentadiene type epoxy resin and a biphenyl type epoxy resin are preferable. Examples of the dicyclopentadiene type epoxy resin include “HP7200” (epoxy equivalent 264), “HP7200H” (epoxy equivalent 280), “HP7200HH” (epoxy equivalent 283) manufactured by DIC Corporation, Nippon Kayaku Co., Ltd. “XD-1000” (epoxy equivalent 252), “XD-1000-L” (epoxy equivalent 247), “XD-1202L” (epoxy equivalent 242) and the like, which are made of biphenyl type epoxy resin, for example, “NC3000” (epoxy equivalent of about 291), “NC3000H” (epoxy equivalent of 290), “NC3000L” (epoxy equivalent of 272) manufactured by Nippon Kayaku Co., Ltd., “GK3207” (epoxy equivalent of about 200 equivalent) manufactured by Tohto Kasei Co., Ltd. 226), “YX4000HK” (epoxy equivalent of about 19) manufactured by Mitsubishi Chemical Corporation. ), And the like.

  (D) From the viewpoint of improving heat resistance and insulation reliability, the epoxy resin is preferably 3% by weight or more when the total solid content of the photosensitive resin composition is 100% by mass. It is more preferable to set it as 6 mass% or more, and it is still more preferable to set it as 9 mass% or more. On the other hand, from the viewpoint of preventing deterioration in developability, when the total solid content of the photosensitive resin composition is 100% by mass, the content is preferably 20% by mass or less, and 18% by mass or less. More preferably, it is more preferably 16% by mass or less.

<(E) Curing accelerator>
In the photosensitive resin composition of this invention, the heat resistance of the hardened | cured material, adhesiveness, chemical-resistance, etc. can be improved by containing (E) hardening accelerator further.
(E) Although it does not specifically limit as a hardening accelerator, For example, an amine type hardening accelerator, a guanidine type hardening accelerator, an imidazole type hardening accelerator, a phosphonium type hardening accelerator, a metal type hardening accelerator etc. are mentioned. These may be used alone or in combination of two or more.

  The amine curing accelerator is not particularly limited, and examples thereof include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylamino). And amine compounds such as methyl) phenol and 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU). You may use these 1 type or in combination of 2 or more types.

  Although it does not specifically limit as a guanidine type hardening accelerator, For example, a dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, Dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-tria Zabicyclo [4.4.0] dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1- Diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide 1-phenyl biguanide, 1- (o-tolyl) biguanide, and the like. You may use these 1 type or in combination of 2 or more types.

  Although it does not specifically limit as an imidazole series hardening accelerator, For example, 2-methyl imidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1, 2- dimethyl imidazole, 2-ethyl-4-methyl Imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')] -Ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2' -Methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride Id, 2-methyl-imidazoline, adduct of 2-phenyl-imidazo imidazole compounds such as phosphorus and imidazole compound and an epoxy resin. You may use these 1 type or in combination of 2 or more types.

  Although it does not specifically limit as a phosphonium type hardening accelerator, For example, a triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, ( 4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like. You may use these 1 type or in combination of 2 or more types.

  In the photosensitive resin composition of the present invention, the content of the curing accelerator (excluding the metal curing accelerator) is 0.005% by mass to 100% by mass when the total solid content of the photosensitive resin composition is 100% by mass. The range is preferably 1% by mass, and more preferably 0.01% by mass to 0.5% by mass. If it is less than 0.005% by mass, curing tends to be slow and a long curing time is required, and if it exceeds 1% by mass, the storage stability of the resin composition tends to decrease.

  Although it does not specifically limit as a metal type hardening accelerator, For example, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, when the content of the metal-based curing accelerator is 100% by mass based on the total solid content of the photosensitive resin composition, the metal content based on the metal-based curing catalyst is 25 ppm to A range of 500 ppm is preferable, and a range of 40 ppm to 200 ppm is more preferable.

<(F) Inorganic filler>
The photosensitive resin composition of this invention can reduce a thermal expansion coefficient by containing the (F) inorganic filler further. Examples of the inorganic filler (F) include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, and titanium. Barium acid, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc., among these, amorphous silica, fused silica, hollow silica, crystalline silica, Silica such as synthetic silica is particularly suitable. As the silica, spherical silica is preferable. You may use these 1 type or in combination of 2 or more types. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs Corporation.

  (F) The average particle size of the inorganic filler is preferably 1 μm or less, more preferably 0.8 μm or less, and more preferably 0.6 μm or less from the viewpoint of improvement in insulation reliability and improvement in photocurability. More preferably, it is 0.4 μm or less. On the other hand, from the viewpoint of preventing aggregation of the inorganic filler, the average particle size of the (F) inorganic filler is preferably 0.01 μm or more, and more preferably 0.05 μm or more. Inorganic fillers include silane coupling agents (epoxysilane coupling agents, aminosilane coupling agents, mercaptosilane coupling agents, etc.) and titanate coupling agents to improve moisture resistance and dispersibility. Those that have been surface treated with a surface treating agent such as a silazane compound are preferred. You may use these 1 type or in combination of 2 or more types.

  Examples of the epoxysilane coupling agent include glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) Examples of aminosilane coupling agents include aminopropylmethoxysilane, aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-2 (aminoethyl) amino. Examples of the mercaptosilane coupling agent include mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane. You may use these 1 type or in combination of 2 or more types. Examples of commercially available epoxy silane coupling agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyl) manufactured by Shin-Etsu Chemical Co., Ltd. Trimethoxysilane), Shin-Etsu Chemical Co., Ltd. “KBE903” (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane), etc. Can be mentioned.

  Examples of titanate coupling agents include butyl titanate dimer, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene Titanate, bis (dioctylpyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) Sphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tridodecylbenzenesulfonyl titanate , Isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-amidoethyl / aminoethyl) titanate, and the like. You may use these 1 type or in combination of 2 or more types.

  Examples of the silazane compound include hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, hexa (t-butyl) disilazane, hexabutyldisilazane, hexa Octyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1, 3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, hexaphenyldisilazane, dimethyl Aminotrimethylsilazane, trisilazane, cyclotrisilazane, 1, Examples include 1,3,3,5,5-hexamethylcyclotrisilazane, and hexamethyldisilazane is particularly preferable. You may use these 1 type or in combination of 2 or more types.

  (F) It is preferable to use the inorganic filler surface-treated with the silazane compound from the viewpoint of improving the dispersibility of the photosensitive resin composition. And after surface-treating with a silazane compound, the further dispersibility improvement can be aimed at by surface-treating with a silane coupling agent. The amount of the silazane compound used for the surface treatment is preferably 0.001% by mass to 0.3% by mass, and 0.005% by mass to 0.2% by mass with respect to 100% by mass of the inorganic filler. It is more preferable. Examples of the spherical fused silica surface-treated with hexamethyldisilazane include “SC2050” manufactured by Admatechs Co., Ltd. Further, the amount of the silane coupling agent used for the surface treatment is preferably 0.1% by mass to 6% by mass, and 0.2% by mass to 4% by mass with respect to 100% by mass of the inorganic filler. Is more preferable, and it is still more preferable that it is 0.3 mass%-3 mass%.

  (F) The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-500, LA-750 manufactured by Horiba, Ltd. and the like can be used.

  (F) Content in the case of mix | blending an inorganic filler is 100 mass% of the whole solid content of the photosensitive resin composition from a viewpoint of reducing the linear thermal expansion coefficient of hardened | cured material and preventing distortion of hardened | cured material. In this case, it is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. On the other hand, the content in the case of blending (F) inorganic filler is 100% by mass based on the entire solid content of the photosensitive resin composition from the viewpoint of preventing deterioration of alkali developability and improving photocurability. In this case, it is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.

<(G) Organic filler>
The photosensitive resin composition of the present invention can further reduce the stress of the cured product by containing an organic filler (G), and can prevent the occurrence of cracks when the cured product is formed. Examples of the organic filler (G) include rubber particles, polyamide fine particles, and silicone particles.

  The rubber particles may be any rubber particles as long as they are fine particles of a resin that has been subjected to chemical cross-linking treatment to a resin exhibiting rubber elasticity and is insoluble and infusible in an organic solvent. For example, acrylonitrile butadiene rubber particles Butadiene rubber particles, acrylic rubber particles, and the like. Specific examples of the rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (above, Gantz Kasei Co., Ltd.) Paraloid EXL2655. , EXL2602 (manufactured by Kureha Chemical Co., Ltd.) and the like.

  The polyamide fine particles may be any polyamide fine particles as long as they are fine particles of 50 μm or less of a resin having an amide bond, and examples thereof include aliphatic polyamides such as nylon, aromatic polyamides such as Kevlar, and polyamideimide. Specific examples of the polyamide fine particles include VESTOSINT 2070 (manufactured by Daicel Huls Co., Ltd.) and SP500 (manufactured by Toray Industries, Inc.).

  (G) The average particle size of the organic filler is preferably in the range of 0.005 μm to 1 μm, and more preferably in the range of 0.2 μm to 0.6 μm. (G) The average particle diameter of the organic filler can be measured using a dynamic light scattering method. (G) The average particle diameter of the organic filler is, for example, by uniformly dispersing the organic filler in an appropriate organic solvent by ultrasonic waves or the like, and using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). It can be measured by creating a particle size distribution of the organic filler on a mass basis and setting its median diameter as the average particle size.

  (G) Content in the case of mix | blending an organic filler is 0.1 mass when the solid content of the photosensitive resin composition shall be 100 mass% from a viewpoint of an improvement of heat resistance and a laser workability. % To 6% by mass is preferable, and 0.5% to 4% by mass is more preferable.

<(H) Reactive diluent>
The photosensitive resin composition of this invention can improve photoreactivity by containing (H) reactive diluent further. As the (H) reactive diluent, for example, a liquid, solid or semi-solid photosensitive (meth) acrylate compound having one or more (meth) acryloyl groups in one molecule at room temperature can be used.

  Typical photosensitive (meth) acrylate compounds include, for example, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol. Mono- or diacrylates, N, N-dimethylacrylamide, acrylamides such as N-methylolacrylamide, aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, trimethylolpropane, pentaerythritol, dipentaerythritol Polyhydric acrylates of polyhydric alcohols or their adducts of ethylene oxide, propylene oxide or ε-caprolactone, Phenols such as noxyacrylate, phenoxyethyl acrylate, or acrylates such as ethylene oxide or propylene oxide adducts thereof, epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether, melamine acrylates, and / or And methacrylates corresponding to the above acrylates. Among these, polyvalent acrylates or polyvalent methacrylates are preferable. Examples of the trivalent acrylates or methacrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and trimethylolpropane. EO-added tri (meth) acrylate, glycerin PO-added tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetrafurfuryl alcohol oligo (meth) acrylate, ethyl carbitol oligo (meth) acrylate, 1,4-butanediol Oligo (meth) acrylate, 1,6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate Rate, tetramethylol methane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N, N, N ′, N′-tetrakis (β-hydroxyethyl) ethyldiamine (meth) acrylate, and the like. Examples of trivalent or higher acrylates or methacrylates include tri (2- (meth) acryloyloxyethyl) phosphate, tri (2- (meth) acryloyloxypropyl) phosphate, and tri (3- (meth) acryloyloxypropyl). Phosphate, tri (3- (meth) acryloyl-2-hydroxyloxypropyl) phosphate, di (3- (meth) acryloyl-2-hydroxyloxypropyl) (2- (meth) acryloyloxyethyl) phosphate, (3- ( Meta) Acry Yl-2-hydroxy propyl) and di (2- (meth) acryloyloxyethyl) phosphate triester (meth) acrylates such as phosphates. These photosensitive (meth) acrylate compounds may be used alone or in combination of two or more.

  (H) Content in the case of mix | blending a reactive diluent is 100 mass% of the whole solid content of the photosensitive resin composition from a viewpoint of preventing stickiness when promoting photocuring and making it hardened | cured. In this case, 0.5 mass% to 10 mass% is preferable, and 2 mass% to 8 mass% is more preferable.

<(I) Thermoplastic resin>
The photosensitive resin composition of this invention can improve the flexibility of hardened | cured material by containing (I) thermoplastic resin further. As such (I) thermoplastic resin, for example, phenoxy resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, Mention may be made of polyester resins. These thermoplastic resins may be used alone or in combination of two or more.

  The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000. If it is smaller than this range, the effect of improving the film forming ability and mechanical strength tends to be insufficient. If it is larger than this range, the compatibility with cyanate ester resin and naphthol type epoxy resin is not sufficient, and the surface after curing Concavities and convexities increase, and it tends to be difficult to form high-density fine wiring.

  In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  (I) Content in the case of mix | blending a thermoplastic resin is 100 mass% of the whole solid content of the photosensitive resin composition from a viewpoint of preventing stickiness when improving film molding ability and setting it as hardened | cured material. When it is, it is preferable that it is the range of 0.1 mass%-10 mass%, and it is more preferable that it is the range of 1 mass%-5 mass%.

<(J) Organic solvent>
The photosensitive resin composition of the present invention can adjust the varnish viscosity by further containing (J) an organic solvent. (J) Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol and propylene glycol. Glycol ethers such as monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, octane, decane, etc. Examples thereof include petroleum hydrocarbons such as aliphatic hydrocarbons, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These are used singly or in combination of two or more. Content in the case of using an organic solvent can be suitably adjusted from a viewpoint of the applicability | paintability of the photosensitive resin composition.

<(K) Other additives>
In the photosensitive resin composition of the present invention, (K) other additives can be further blended to such an extent that the object of the present invention is not impaired. (K) Other additives include, for example, fine particles such as melamine and organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and other colorants, hydroquinone Polymerization inhibitors such as phenothiazine, methyl hydroquinone, hydroquinone monomethyl ether, catechol and pyrogallol, thickeners such as benton and montmorillonite, silicone, fluorine and vinyl resin defoamers, brominated epoxy compounds, acid-modified bromine Curable epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphate esters, halogen-containing condensed phosphate esters and other flame retardants, phenolic curing agents, cyanate ester curing agents and other thermosetting resins It is possible to add various additives like.

  In the photosensitive resin composition of the present invention, the above (A) to (K) are appropriately mixed, and if necessary, kneading means such as a triple roll, ball mill, bead mill, sand mill, super mixer, planetary mixer A resin varnish can be produced by kneading or stirring with a stirring means such as the above.

  By subjecting the photosensitive resin composition of the present invention to curing treatment under the curing conditions described later, it is possible to provide a cured product capable of alkali development that has improved heat resistance, low dielectric loss tangent, and high water resistance. it can. Hereinafter, these characteristics will be described in detail.

  The dielectric loss tangent of the cured product of the photosensitive resin composition of the present invention can be measured by <Measurement of dielectric loss tangent> described later. Specifically, the dielectric loss tangent can be measured by a cavity resonance perturbation method at a frequency of 5.8 GHz and a measurement temperature of 23 ° C. From the viewpoints of preventing heat generation at high frequencies, reducing signal delay and signal noise, the dielectric loss tangent is preferably 0.05 or less, more preferably 0.04 or less, and further preferably 0.03 or less. Preferably, it is 0.02 or less, and further preferably 0.0169 or less. On the other hand, the lower limit value of the dielectric loss tangent is not particularly limited, but is preferably 0.005 or more, and more preferably 0.01 or more.

  The water resistance of the cured product of the photosensitive resin composition of the present invention can be measured by the measurement method described in <Measurement of water resistance> described later. The water resistance is preferably 3% or less, more preferably 2% or less, and more preferably 1.5% or less from the viewpoint of preventing distortion during printed wiring board production and improving insulation reliability. More preferably, it is still more preferably 1.19% or less. On the other hand, the lower limit of the water resistance is not particularly limited, but is preferably 0.01% or more, more preferably 0.1% or more, and further preferably 0.5% or more.

  The heat resistance of the cured product of the photosensitive resin composition of the present invention can be measured by the measurement method described in <Evaluation of heat resistance> described later. As an index of heat resistance, it is preferable to employ a glass transition point in terms of preventing deterioration of the cured product when a thermal history is given to the cured product. The glass transition point is preferably 160 ° C. or higher. The upper limit of the glass transition point is not particularly limited, but is preferably 300 ° C. or lower.

  The use of the photosensitive resin composition of the present invention is not particularly limited, but a photosensitive film, a photosensitive film with a support, an insulating resin sheet such as a prepreg, a circuit board (for laminated board use, multilayer printed wiring board use, etc.), It can be used in a wide range of applications where a resin composition is required, such as solder resist, underfill material, die bonding material, semiconductor sealing material, hole-filling resin, and component-filling resin. Among them, a resin composition for an insulating layer of a multilayer printed wiring board (multilayer printed wiring board using a cured product of a photosensitive resin composition as an insulating layer), a resin composition for an interlayer insulating layer (cured product of a photosensitive resin composition) Can be suitably used as a resin composition for forming a plating (a multilayer printed wiring board in which plating is formed on a cured product of a photosensitive resin composition).

<Photosensitive film>
The photosensitive resin composition of this invention can apply | coat on a support substrate in a resin varnish state, can form a resin composition layer by drying an organic solvent, and can be used as a photosensitive film. Moreover, the photosensitive film previously formed on the support body can also be laminated | stacked and used for a support substrate. The photosensitive film of the present invention can be laminated on various supporting substrates. Examples of the support substrate mainly include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate.

<Photosensitive film with support>
The photosensitive resin composition of the present invention can be suitably used in the form of a photosensitive film with a support in which a resin composition layer is formed on a support. That is, the photosensitive film with a support has a layer of the photosensitive resin composition formed on the support. Examples of the support include a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, and a triacetyl acetate film, and a polyethylene terephthalate film is particularly preferable.
Examples of commercially available supports include polypropylene films such as product names “Alphan MA-410” and “E-200C” manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and product names “PS” manufactured by Teijin Limited. Examples thereof include polyethylene terephthalate films such as PS series such as “-25”, but are not limited thereto. In order to facilitate the removal of the resin composition layer, these supports are preferably coated with a release agent such as a silicone coating agent on the surface. The thickness of the support is preferably in the range of 5 μm to 50 μm, and more preferably in the range of 10 μm to 25 μm. If the thickness is less than 5 μm, the support (support film) tends to be broken when the support is peeled off before development. On the other hand, if the thickness exceeds 50 μm, the support is exposed from above. The resolution tends to decrease. Also, a low fisheye support is preferred. Here, the fish eye means that a material is melted, kneaded, extruded, biaxially stretched, a film is produced by a casting method, etc., and foreign materials, undissolved materials, oxidized deterioration products, etc. of the material are taken into the film. It is a thing.

  Moreover, in order to reduce the scattering of the light at the time of exposure by active energy rays, such as an ultraviolet-ray, what a support body is excellent in transparency is preferable. Specifically, the support preferably has a turbidity (haze standardized by JIS-K6714) that is an index of transparency of 0.1 to 5. Furthermore, the resin composition layer may be protected with a protective film.

  By protecting the resin composition layer side of the photosensitive film with a support with a protective film, it is possible to prevent adhesion or scratches of dust or the like to the surface of the resin composition layer. As the protective film, a film made of the same material as that of the support can be used. Although the thickness of a protective film is not specifically limited, It is preferable that it is the range of 1 micrometer-40 micrometers, It is more preferable that it is the range of 5 micrometers-30 micrometers, It is still more preferable that it is the range of 10 micrometers-30 micrometers. If the thickness is less than 1 μm, the handleability of the protective film tends to be reduced, and if it exceeds 40 μm, the cost tends to be inferior. The protective film preferably has a smaller adhesive force between the resin composition layer and the protective film than the adhesive force between the resin composition layer and the support.

  The photosensitive film with a support of the present invention is prepared by, for example, preparing a resin varnish obtained by dissolving the photosensitive resin composition of the present invention in an organic solvent according to a method known to those skilled in the art, and applying this resin varnish on the support. And it can manufacture by drying an organic solvent by heating or hot air spraying, etc., and forming a resin composition layer. Specifically, first, after completely removing bubbles in the photosensitive resin composition by a vacuum defoaming method or the like, the photosensitive resin composition is applied onto a support, and a solvent is removed by a hot air furnace or a far infrared furnace. The photosensitive film with a support can be produced by removing and drying, and then laminating a protective film on the resin composition layer obtained as necessary. Specific drying conditions vary depending on the curability of the resin composition and the amount of the organic solvent in the resin varnish, but in a resin varnish containing 30% by mass to 60% by mass of the organic solvent, 80 ° C. to 120 ° C. It can be dried in minutes to 13 minutes. The amount of the remaining organic solvent in the resin composition layer is preferably 5% by mass or less with respect to the total amount of the resin composition layer from the viewpoint of preventing diffusion of the organic solvent in the subsequent step. More preferably. Those skilled in the art can appropriately set suitable drying conditions by simple experiments. The thickness of the resin composition layer is preferably in the range of 5 μm to 500 μm from the viewpoint of improving the handleability and preventing the sensitivity and resolution inside the resin composition layer from being lowered. The range of 15 μm to 150 μm is more preferable, the range of 20 μm to 100 μm is still more preferable, and the range of 20 μm to 60 μm is even more preferable.

As a coating method of the photosensitive resin composition, for example, gravure coating method, micro gravure coating method, reverse coating method, kiss reverse coating method, die coating method, slot die method, lip coating method, comma coating method, blade coating method, Examples thereof include a roll coating method, a knife coating method, a curtain coating method, a chamber gravure coating method, a slot orifice method, a spray coating method, and a dip coating method.
The photosensitive resin composition may be applied in several times, may be applied once, or may be applied by combining a plurality of different methods. Among these, the die coating method is preferable because it is excellent in uniform coatability. Further, in order to avoid contamination by foreign matters, it is preferable to carry out the coating process in an environment with little foreign matter generation such as a clean room.

<Multilayer printed wiring board>
Next, the example of the manufacturing method of a multilayer printed wiring board is demonstrated using the photosensitive resin composition.

(Coating and drying process)
A photosensitive resin composition is directly applied on a circuit board in a resin varnish state, and an organic solvent is dried to form a photosensitive film on the circuit board. Examples of the circuit board include a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, a thermosetting polyphenylene ether board, and the like. Here, the circuit board refers to a board on which a conductor layer (circuit) patterned on one or both sides of the board is formed. Further, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, a substrate having a conductor layer (circuit) in which one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned is also here. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

  As a coating method, full-screen printing by a screen printing method is generally used, but any other means may be used as long as the coating method can be applied uniformly. For example, spray coating method, hot melt coating method, bar coating method, applicator method, blade coating method, knife coating method, air knife coating method, curtain flow coating method, roll coating method, gravure coating method, offset printing method, dip coating method , Brushing and other normal application methods can be used. After coating, drying is performed in a hot air furnace or a far infrared furnace as necessary. The drying conditions are preferably 80 ° C. to 120 ° C. for 3 minutes to 13 minutes. In this way, a photosensitive film is formed on the circuit board.

(Lamination process)
Moreover, when using the photosensitive film with a support body, the resin composition layer side is laminated on the single side | surface or both surfaces of a circuit board using a vacuum laminator. In the laminating process, when the photosensitive film with a support has a protective film, the protective film is removed, and then the photosensitive film and the circuit board are preheated as necessary, and the resin composition layer is pressed. And crimping to the circuit board while heating. In the photosensitive film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used.

The conditions for the laminating step are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 ° C. to 140 ° C., and the pressure bonding pressure is preferably 1 kgf / cm ^{2 to} 11 kgf / cm ² (9. 8 × 10 ⁴ N / m ^{2 to} 107.9 × 10 ⁴ N / m ² ), the pressure bonding time is preferably 5 seconds to 300 seconds, and the air pressure is 20 mmHg (26.7 hPa) or less. Is preferred. The laminating step may be a batch type or a continuous type using a roll. The vacuum laminating method can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like. In this way, a photosensitive film is formed on the circuit board.

(Exposure process)
After a photosensitive film is provided on a circuit board by a coating and drying process or a laminating process, a predetermined part of the resin composition layer is then irradiated with actinic rays through a mask pattern, and a resin composition layer of an irradiated part An exposure process for photocuring is performed. Examples of the actinic rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. Dose of ultraviolet light is approximately ^{10mJ / cm 2 ~1000mJ / cm 2} . The exposure method includes a contact exposure method in which a mask pattern is brought into close contact with a printed wiring board, and a non-contact exposure method in which exposure is carried out using parallel light rays without being brought into close contact, either of which may be used. Moreover, when the support body exists on a resin composition layer, you may expose from a support body and may expose after a support body peels.

(Development process)
After the exposure step, if a support is present on the resin composition layer, the support is removed, and then the portion that has not been photocured (unexposed portion) is removed by wet development or dry development. By developing, a pattern can be formed.

  In the case of the wet development, as the developer, a safe and stable developer having good operability such as an alkaline aqueous solution, an aqueous developer, an organic solvent or the like is used, and a development step using an alkaline aqueous solution is particularly preferable. Further, as a developing method, a known method such as spraying, rocking dipping, brushing, scraping or the like is appropriately employed.

Examples of the alkaline aqueous solution used as a developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate, and sodium phosphate. , Alkali metal phosphates such as potassium phosphate, aqueous solutions of alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, and aqueous solutions of organic bases not containing metal ions such as tetraalkylammonium hydroxide, An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred because it does not contain metal ions and does not affect the semiconductor chip.
In these alkaline aqueous solutions, a surfactant, an antifoaming agent and the like can be added to the developer for improving the developing effect. The pH of the alkaline aqueous solution is preferably in the range of 8 to 12, for example, and more preferably in the range of 9 to 11. Moreover, it is preferable that the base concentration of the said alkaline aqueous solution shall be 0.1 mass%-10 mass%. The temperature of the alkaline aqueous solution can be appropriately selected according to the developability of the resin composition layer, but is preferably 20 ° C to 50 ° C.

  Examples of the organic solvent used as the developer include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol. Monobutyl ether.

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

  In the pattern formation of the present invention, if necessary, two or more kinds of development methods described above may be used in combination. Development methods include a dip method, a battle method, a spray method, a high-pressure spray method, brushing, and slapping, and the high-pressure spray method is suitable for improving the resolution. The spray pressure in the case of adopting the spray method is preferably 0.05 MPa to 0.3 MPa.

(Post bake process)
After the development step, a post-bake step is performed to form an insulating layer (cured product). Examples of the post-bake process include an ultraviolet irradiation process using a high-pressure mercury lamp and a heating process using a clean oven. In the case of irradiating with ultraviolet rays, the irradiation amount can be adjusted as necessary. For example, irradiation can be performed at an irradiation amount of about 0.05 J / cm ^{2 to} 10 J / cm ² . The heating conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. It is selected in the range of 30 minutes to 120 minutes at ˜200 ° C.

(Drilling process)
After the insulating layer is formed, a via hole and a through hole are formed by performing a drilling process in the insulating layer formed on the circuit board, if desired. The drilling step can be performed, for example, by a known method such as drilling, laser, or plasma, or a combination of these methods as necessary, but a drilling step using a laser such as a carbon dioxide gas laser or a YAG laser is preferable.

(Plating process)
Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as a vapor deposition method, a sputtering method, or an ion plating method can be used. In the vapor deposition method (vacuum vapor deposition method), for example, a metal film can be formed on the insulating layer by placing the support in a vacuum vessel and evaporating the metal by heating. In the sputtering method, for example, the support is placed in a vacuum vessel, an inert gas such as argon is introduced, a direct current voltage is applied, the ionized inert gas is made to collide with the target metal, and the struck metal is used. A metal film can be formed on the insulating layer.

In the case of wet plating, the surface of the formed insulating layer is subjected to a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution in this order to form an uneven anchor. The swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes. Examples of the swelling liquid include an alkaline solution, and examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securigans P (Swelling Dip Securigans SBU) and Swelling Dip Securigans SBU manufactured by Atotech Japan Co., Ltd. be able to. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C. for 10 to 30 minutes. Examples of the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by weight to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is performed by immersing in the neutralizing solution at 30 ° C. to 50 ° C. for 3 minutes to 10 minutes. As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.
Next, a conductor layer is formed by combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.

<Semiconductor device>
A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device, that is, a semiconductor device provided with the multilayer wiring board of the present invention can be manufactured by mounting a semiconductor chip on the conductive portion of the multilayer printed wiring board of the present invention. The “conduction location” is a “location where an electrical signal is transmitted in a multilayer printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

“Mounting method by buildup layer without bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a multilayer printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. Furthermore, the method is roughly divided into the following BBUL method 1) and BBUL method 2).
BBUL method 1) Mounting method for mounting semiconductor chip in recess of multilayer printed wiring board using underfill agent BBUL method 2) Mounting method for mounting semiconductor chip in recess of multilayer printed wiring board using photosensitive film

The BBUL method 1) specifically includes the following steps 1) to 6).
Process 1) A conductor layer is removed from both surfaces of a multilayer printed wiring board, and a through-hole is formed with a laser and a mechanical drill.
Step 2) Adhesive tape is attached to one side of the multilayer printed wiring board in which the through hole is formed, and the bottom surface of the semiconductor chip is arranged in the through hole so as to be fixed on the adhesive tape. The semiconductor chip at this time is preferably arranged so as to be lower than the height of the through hole.
Step 3) The semiconductor chip is fixed to the through hole by injecting and filling an underfill agent into the gap between the through hole and the semiconductor chip.
Step 4) The adhesive tape is then peeled off to expose the bottom surface of the semiconductor chip.
Step 5) The photosensitive film of the present invention is laminated on the bottom surface side of the semiconductor chip to cover the semiconductor chip.
Step 6) After the photosensitive film is cured, a hole is formed by a laser to expose the bonding pad on the bottom surface of the semiconductor chip, and the roughening treatment, electroless plating, and electrolytic plating described above are performed to connect to the wiring. If necessary, a photosensitive film may be further laminated.

The BBUL method 2) specifically includes the following steps 1) to 6).
Step 1) A photoresist film is formed on the conductor layers on both sides of the multilayer printed wiring board, and an opening is formed only on one side of the photoresist film by a photolithography method.
Step 2) The conductor layer exposed in the opening is removed with an etching solution to expose the insulating layer, and then the resist films on both sides are removed.
Step 3) Using a laser or a drill, all of the exposed insulating layer is removed and drilled to form a recess. The laser energy is preferably a laser whose energy can be adjusted so as to lower the laser absorption rate of copper and increase the laser absorption rate of the insulating layer, and more preferably a carbon dioxide laser. By using such a laser, the laser does not penetrate through the conductor layer facing the opening of the conductor layer, and it is possible to remove only the insulating layer.
Step 4) The bottom surface of the semiconductor chip is placed in the recess with the opening side facing, the photosensitive film of the present invention is laminated from the opening side, the semiconductor chip is covered, and a gap between the semiconductor chip and the recess is formed. Embed. In this case, the semiconductor chip is preferably arranged so as to be lower than the height of the recess.
Step 5) After curing the photosensitive film, holes are formed by a laser to expose the bonding pads on the bottom surface of the semiconductor chip.
Step 6) Wiring is connected by performing the roughening treatment, electroless plating, and electrolytic plating already described, and a photosensitive film is further laminated as necessary.

  Among the semiconductor chip mounting methods, the semiconductor device is miniaturized and transmission loss is reduced, and since no solder is used, the semiconductor chip does not have its thermal history, and solder and resin distortion may occur in the future. In view of the absence, a mounting method using a bumpless build-up layer (BBUL) is preferable, the BBUL method 1) and the BBUL method 2) are more preferable, and the BBUL method 2) is more preferable.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to the following Example. In the following description of the examples, “part” means “part by mass”.

  First, a measurement method and an evaluation method in the physical property evaluation in this specification will be described.

<Formation of evaluation laminate>
By treatment with a surface treatment agent (CZ8100, manufactured by MEC Co., Ltd.) containing an organic acid on the copper layer of a glass epoxy substrate (copper-clad laminate) on which a circuit is formed by patterning a copper layer having a thickness of 18 μm Roughening was performed. Next, it arrange | positions so that the resin composition layer of the photosensitive film with a support | carrier obtained by the Example mentioned later and a comparative example may contact | connect the copper circuit surface, and it laminates | stacks using a vacuum laminator (Nichigo Morton KK160). And the laminated body by which the said copper clad laminated board, the said resin composition layer, and the said support body were laminated | stacked in this order was formed. The pressure bonding conditions were a vacuum drawing time of 20 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure time of 20 seconds. The laminated body is allowed to stand at room temperature for 1 hour or longer, and a pattern forming apparatus is used to form an ultraviolet ray of 450 mJ / cm ² so that a round hole with a diameter of 80 μm can be formed on the support of the laminated body. The exposure was performed. After standing at room temperature for 30 minutes, the support was peeled off from the laminate. 1. A 1% by mass aqueous sodium carbonate solution at 30 ° C. as a developer is applied to the entire surface of the resin composition layer on the laminate at a spray pressure of 0.15 MPa for a minimum development time (minimum time for developing an unexposed portion). Spray development took 5 times longer. After spray development, 1 J / cm ² UV irradiation is performed, and further heat treatment at 165 ° C. for 60 minutes (further heat treatment at 190 ° C. for 30 minutes in Example 4), and an insulating layer having an opening with a diameter of 80 μm Was formed on the laminate. This was made into the laminated body for evaluation.

<Formation of cured product for evaluation>
The resin composition layer of the photosensitive film with a support obtained in Examples and Comparative Examples was exposed to light of 450 mJ / cm ² and photocured. Thereafter, a 1 mass% aqueous solution of sodium carbonate at 30 ° C. as a developer is applied to the entire surface of the resin composition layer at a spray pressure of 0.15 MPa, 1.5 times the minimum development time (minimum time for developing the unexposed area). Spray developed over time. After spray development, ultraviolet irradiation at 1 J / cm ² was performed, and further a heat treatment at 165 ° C. for 60 minutes (further heat treatment at 190 ° C. for 30 minutes in Example 4) was performed to form an insulating layer. Thereafter, the support was peeled off to obtain a cured product for evaluation.

<Evaluation of resolution>
As an evaluation of resolution, a round hole formed by patterning on the evaluation laminate was observed with a SEM (1000 times magnification) and evaluated according to the following criteria.
○: The shape of the round hole is good, and there is no blistering or peeling.
X: The shape of the round hole spreads due to development, and there are wrinkles and peeling.
In Comparative Example 3, it was immediately insolubilized, and it was impossible to form a round hole in the first place, so it was evaluated as “x”.

<Development evaluation>
As evaluation of developability, the residue at the bottom of the round hole formed in the evaluation laminate was observed with an SEM (magnification 1000 times), and the presence or absence of the residue at the bottom of the round hole was evaluated according to the following criteria.
○: There is no development residue on the substrate (bottom part) exposed from the round hole with a diameter of 80 μm, and the development residue removal property is excellent. X: There is a development residue on the substrate (bottom part) exposed from the round hole with a diameter of 80 μm. The development residue removability is inferior. In Comparative Example 3, it was immediately insolubilized and it was impossible to form a round hole in the first place.

<Measurement of dielectric loss tangent>
The cured product for evaluation was cut into a length of 80 mm and a width of 2 mm, and used as an evaluation sample 1. The dielectric loss tangent of this evaluation sample 1 was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using an HP 8362B apparatus manufactured by Agilent Technologies. Measurement was performed on two evaluation samples 1, and an average value was calculated.

<Measurement of water resistance>
A cured product for evaluation was cut out in 5 cm squares to obtain Evaluation Sample 2. Subsequently, the mass of the evaluation sample 2 was measured, and the evaluation sample 2 after the mass measurement was put into boiling pure water and left for 1 hour in a state where the evaluation sample 2 was completely used. Then, the evaluation sample 2 was taken out, the surface water | moisture content was wiped off sufficiently, the mass after water absorption was measured to 0.1 mg, and water resistance WA (%) was calculated | required by the following formula. Measurement was performed on four evaluation samples 2, and an average value was calculated.

Formula: WA = ((W1-W0) / W0) × 100
In the above formula, W0 represents the mass (g) of the evaluation sample before water absorption, and W1 represents the mass (g) of the evaluation sample after water absorption.

<Evaluation of heat resistance>
The evaluation cured product was cut into a test piece having a width of 5 mm and a length of 15 mm to obtain an evaluation sample 3. Subsequently, thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer TMA-SS6100 (manufactured by Seiko Instruments Inc.). After the evaluation sample 3 was mounted on the apparatus, the measurement was continuously performed twice under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. As a heat resistance index, the glass transition temperature (° C.) was calculated from the point at which the slope of the dimensional change signal in the second measurement changed.

<Examples 1-4, Comparative Examples 1-3>
Each component was mix | blended with the compounding ratio shown in Table 1, knead | mixed using 3 rolls, and the resin varnish was adjusted. Next, such a resin varnish is uniformly applied on a polyethylene terephthalate film (R310-16B, trade name, manufactured by Mitsubishi Plastics Co., Ltd.) having a thickness of 16 μm using a die coater, and dried to obtain a resin composition layer having a thickness of 20 μm. A formed photosensitive film with a support was obtained. Drying was performed at 60 ° C. for 30 minutes using a hot air convection dryer. These measurement results and evaluation results are shown in Table 1.

  Table 2 shows a photograph of the round holes after development formed on the evaluation laminate. It can be seen that Example 1 has a good shape, no curling or peeling, no development residue, and excellent resolution and developability. In Comparative Example 1, it can be seen that there are curling and peeling, there are also development residues, and the resolution and developability are poor.

The materials used are as follows.
Component (A): HPC8000-65T (manufactured by DIC Corporation): dicyclopentadienyl diphenol type active ester type hardener, solid solution 65% toluene solution EXB9416-70BK (manufactured by DIC Corporation): naphthalene Skeletal-containing active ester curing agent, methyl isobutyl ketone solution (B) component with a solid content of 70% ZFR-1533H (manufactured by Nippon Kayaku Co., Ltd.): bisphenol F type epoxy acrylate, diethylene glycol monoethyl ether with a solid content of 68% Acetate solution, acid value 70mgKOH / g
ZAR-2000 (manufactured by Nippon Kayaku Co., Ltd.): Bisphenol A type epoxy acrylate, 65% solid content diethylene glycol monoethyl ether acetate solution, acid value 99 mg KOH / g
PR-3000 (manufactured by Showa Denko KK): Cresol novolak type epoxy acrylate, a 1: 1 solution of 68% solid solvate and diethylene glycol monoethyl ether acetate, acid value 50 mgKOH / g
(C) Component / Irgacure 907 (manufactured by BASF Japan): 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (D) component / HP-7200H (manufactured by DIC Corporation): Di Cyclopentadiene type epoxy resin, epoxy equivalent 280
(E) Component / DICY7 (Mitsubishi Chemical Corporation): Dicyandiamide (F) Component / Spherical fused silica (“SC2050” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) Surface treated with 0.5 parts by mass of “KBM573” manufactured by Shin-Etsu Chemical Co., Ltd. (G) component, AC3816N (manufactured by Ganz Kasei Co., Ltd.): rubber particle (H) component, DCPA (manufactured by Kyoeisha Chemical Industry Co., Ltd.) : Tricyclodecane dimethanol diacrylate (J) component EDGac (ethyl diglycol acetate)
・ MEK (methyl ethyl ketone)
(K) Other additives, melamine (manufactured by Nissan Chemical Industries, Ltd.)
FG7351 (manufactured by Toyo Ink Manufacturing Co., Ltd.): phthalocyanine blue DETX-S (manufactured by Nippon Kayaku Co., Ltd.): 2,4-diethylthioxanthone TD2090-60M (manufactured by DIC Corporation): phenol novolac resin, MEK solution with a solid content of 60% LA7054-60M (manufactured by DIC Corporation): Triazine-containing phenol novolak resin, MEK solution with a solid content of 60% PT30-85I (manufactured by Lonza Japan Co., Ltd.): phenol novolac type polyfunctional Cyanate ester resin, 85% solid ipsol solution

  From the results of Table 1, the Examples using the photosensitive resin composition of the present invention can provide a photosensitive resin composition having resolution and developability, low dielectric loss tangent, and high water resistance. all right. On the other hand, in Comparative Examples 1 and 2, since the phenolic curing agent and the cyanate ester curing agent are used as the thermosetting component instead of the component (A), the developability and resolution are poor, and the photosensitive resin composition is used. It was not usable. Further, in Comparative Example 3, it was immediately insolubilized, and it was impossible to form a round hole in the first place, and it could not be used as a photosensitive resin composition.

  According to the present invention, it is possible to provide a photosensitive resin composition having a low dielectric loss tangent, a high water resistance, and capable of alkali development while improving heat resistance. According to the present invention, a photosensitive film, a photosensitive film with a support, a multilayer printed wiring board, and a semiconductor device using the same can be further provided. According to the present invention, it is also possible to provide electric products such as computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, airplanes, and the like equipped with these.

Claims (20)

A photosensitive resin composition comprising (A) an active ester curing agent, ( B) a carboxyl group-containing radical polymerizable compound, and (D) an epoxy resin .   The content of (A) active ester curing agent is 0.5% by mass to 20% by mass when the total solid content of the photosensitive resin composition is 100% by mass. The photosensitive resin composition as described.   The content of the (B) carboxyl group-containing radically polymerizable compound is 10% by mass to 60% by mass when the total solid content of the photosensitive resin composition is 100% by mass, 2. The photosensitive resin composition according to 2.   (B) The photosensitive resin composition according to any one of claims 1 to 3, wherein the acid value of the carboxyl group-containing radical polymerizable compound is 0.1 mgKOH / g to 150 mgKOH / g.   (B) The carboxyl group-containing radically polymerizable compound is a compound having both a carboxyl group and two or more radically polymerizable unsaturated groups in one molecule. The photosensitive resin composition according to item. (B) the carboxyl group-containing radical polymerizable compound is a compound obtained by reacting an epoxy resin, an unsaturated carboxylic acid and an acid anhydride,
The epoxy resin is a bisphenol F type epoxy resin, a bisphenol A type epoxy resin or a cresol novolac type epoxy resin,
The unsaturated carboxylic acid is acrylic acid or methacrylic acid,
The photosensitive resin composition according to claim 1, wherein the acid anhydride is succinic anhydride or tetrahydrophthalic anhydride.   Furthermore, (C) The photoinitiator is contained, The photosensitive resin composition of any one of Claims 1-6 characterized by the above-mentioned. Furthermore (E), characterized in that it contains a curing accelerator, a photosensitive resin composition according to any one of claims 1-7. Furthermore, (F) inorganic filler is contained, The photosensitive resin composition of any one of Claims 1-8 characterized by the above-mentioned. The photosensitive resin composition according to any one of claims 1 to 9 , wherein a dielectric loss tangent of a cured product of the photosensitive resin composition is 0.005 to 0.05. Characterized in that it contains a photosensitive resin composition according to any one of claims 1-10, photosensitive film. A photosensitive film with a support, wherein the layer of the photosensitive resin composition according to any one of claims 1 to 10 is formed on the support. Multilayer printed wiring board having an insulating layer formed by the cured product of the photosensitive resin composition according to any one of claims 1-10. Multilayer printed wiring board interlayer insulating layer is formed by the cured product of the photosensitive resin composition according to any one of claims 1-10. Characterized in that it comprises a multi-layer printed wiring board according to claim 13 or 14, the semiconductor device. Or characterized in that it comprises a step of exposing the resin composition layer formed by the photosensitive resin composition according to item 1, a method for manufacturing a multilayer printed wiring board according to claim 1-10. After claim 1-10 any one exposure process of the photosensitive resin composition a resin composition formed by material layer according to Section, and performing a development process by an alkaline aqueous solution, the production of a multilayer printed circuit board Method.   (A) The active ester curing agent is a reaction product obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group, and is an aromatic compound having two or more active ester groups in one molecule. The photosensitive resin composition of any one of Claims 1-10.   (A) The active ester type curing agent is an active ester type curing agent containing a dicyclopentadienyl structure, an active ester type curing agent containing a naphthalene structure, an active ester type curing agent containing an acetylated product of phenol novolak, The photosensitive resin composition of any one of Claims 1-10 chosen from the active ester type hardening | curing agent containing a benzoylation thing.   The photosensitive resin composition according to claim 19, wherein (A) the active ester curing agent is a dicyclopentadienyl diphenol type active ester curing agent or a naphthalene skeleton-containing active ester curing agent.