JP5621595B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition useful as a solder resist for a printed wiring board, and a photosensitive dry film and a printed wiring board obtained using the photosensitive resin composition.

  In recent years, a so-called photographic development type is often used as a solder resist, and an alkali development type is mainly used from the viewpoint of maintenance of work environment and pollution prevention (Patent Document 1 and the like). However, recently, with the further enhancement of performance of electronic components, the wiring pattern on the printed wiring board is further narrowed, and higher insulation reliability is required for the solder resist.

On the other hand, a polyimide resin is a resin excellent in heat resistance, electrical insulation, and mechanical strength. For example, a resist containing a polyimide resin having an isocyanurate ring, a cyclic aliphatic structure, an imide ring, and a (meth) acryloyl group. A resin composition is disclosed (Patent Document 2). However, although the composition has good insulation reliability and the like, there is a problem that it is not sufficient in terms of photocurability and developability.
JP-A 61-243869 JP 2003-221429 A

  The present invention has been made in view of the above circumstances, and the problems to be solved are excellent in photocurability, developability, and insulation reliability in a narrow-pitch wiring pattern, and also have good plating resistance. Is to provide a photosensitive resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have used a carboxyl group-containing radical polymerizable compound, a specific polyimide resin, an epoxy compound, a photopolymerization initiator, and a reactive diluent in combination. The present invention has been completed. That is, the present invention has the following characteristics.

[1] Photosensitivity comprising (a) a carboxyl group-containing radical polymerizable compound, (b) a polyimide resin, (c) an epoxy compound, (d) a photopolymerization initiator, and (e) a reactive diluent. Resin composition.
[2] The photosensitive resin composition according to [1] above, wherein the (b) polyimide resin is a polyimide resin having an isocyanurate ring, a cyclic aliphatic structure, and an imide ring.
[3] The photosensitive resin composition according to [1] above, wherein the (b) polyimide resin is a polyimide resin having a repeating unit containing an isocyanurate ring, a cyclic aliphatic structure, and an imide ring.
[4] (b) A polyimide resin was obtained by reacting an isocyanurate ring-containing polyisocyanate compound derived from a cycloaliphatic diisocyanate with an acid anhydride of a polycarboxylic acid having three or more carboxyl groups. The photosensitive resin composition according to the above [1], which is a compound.
[5] (b) A polyimide resin was obtained by reacting an isocyanurate ring-containing polyisocyanate compound derived from a cycloaliphatic diisocyanate with an acid anhydride of a polycarboxylic acid having three or more carboxyl groups. The photosensitive resin composition as described in [1] above, which is a compound obtained by reacting a compound having one epoxy group and one or more radically polymerizable unsaturated groups.
[6] (b) A polyimide resin was obtained by reacting an isocyanurate ring-containing polyisocyanate compound derived from a cycloaliphatic diisocyanate with an acid anhydride of a polycarboxylic acid having three or more carboxyl groups. The photosensitive resin composition as described in [1] above, which is a compound obtained by reacting a residual isocyanate group of a compound with a compound having one hydroxyl group and one or more radically polymerizable unsaturated groups object.
[7] Any of the above [1] to [6], wherein (b) the polyimide resin is 0.5 to 100 parts by weight with respect to 100 parts by weight of the (a) carboxyl group-containing radical polymerizable compound The photosensitive resin composition as described in 2.
[8] The photosensitive resin composition as described in any one of [1] to [7] above, further comprising (f) a curing accelerator.
[9] The photosensitive resin composition according to any one of [1] to [8] above, further comprising (g) a filler.
[10] The photosensitive resin composition according to any one of [1] to [9], which is for a solder resist.
[11] A photosensitive dry film produced from the photosensitive resin composition according to any one of [1] to [9].
[12] A printed wiring board having a cured film of the photosensitive resin composition according to any one of [1] to [9].

  According to the present invention, by using together a carboxyl group-containing radical polymerizable compound, a specific polyimide resin, an epoxy compound, a photopolymerization initiator, and a reactive diluent, photocurability, developability, and narrow pitch wiring pattern It is possible to provide a photosensitive resin composition having excellent insulation reliability and excellent plating resistance.

Hereinafter, the present invention will be described with reference to preferred embodiments thereof.
The photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as “composition”)
(A) a carboxyl group-containing radically polymerizable compound,
(B) polyimide resin,
(C) an epoxy compound,
The main feature is that it includes (d) a photopolymerization initiator and (e) a reactive diluent.

[(A) Carboxyl group-containing radical polymerizable compound]
The “carboxyl group-containing radical polymerizable compound” used in the present invention is not particularly limited as long as it has both a carboxyl group and two or more radical polymerizable unsaturated groups in one molecule. An acid pendane cage type unsaturated epoxy ester resin obtained by reacting a polyfunctional epoxy resin with an unsaturated carboxylic acid and further reacting with an acid anhydride is preferable.

  As the “polyfunctional 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 can be used. F-type epoxy resin, hydrogenated bisphenol F-type epoxy resin, bisphenol-type epoxy resin such as bisphenol S-type epoxy resin, naphthalene-type epoxy resin such as dihydroxynaphthalene-type epoxy resin, binaphthol-type epoxy resin, biphenol-type epoxy resin, tetramethylbiphenol Type biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthol novolak type epoxy resin, alkylphenol novo Novolak epoxy resins such as click type epoxy resin, bisphenol F type epoxy resin of bisphenol F type epoxy resin obtained by modifying the above trifunctional by reacting epichlorohydrin and the like. These may be used alone or in combination of two or more. Among them, a cresol novolac type epoxy resin and a bisphenol F type epoxy resin modified with trifunctional or higher functionality by reacting bisphenol F type epoxy resin with epichlorohydrin are excellent in developability, insulation reliability, and other solder resists. It is preferable from the viewpoint of realizing a composition to be a film.

  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. Of these, acrylic acid and methacrylic acid are preferred from the viewpoint of photocurability of the composition.

  The reaction between the unsaturated carboxylic acid and the polyfunctional epoxy resin has a ratio of the number of moles of the carboxyl group of the unsaturated carboxylic acid to the number of moles of the epoxy group of the polyfunctional epoxy resin (number of moles of carboxyl group / number of moles of epoxy group) It is preferable to carry out in the range of 0.8 to 1.2.

  The reaction between the unsaturated carboxylic acid and the polyfunctional epoxy resin is performed until the acid value in the system (that is, the residual acid value of the carboxylic acid of the unsaturated carboxylic acid) is 5 mgKOH / g or less, preferably 2 mgKOH / g or less. It is preferable in terms of the stability of the reaction product (unsaturated carboxylic acid-modified epoxy resin) obtained by the reaction.

  Examples of the “acid anhydride” include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid A dianhydride etc. are mentioned, These may be used individually by 1 type, or may use 2 or more types together. Among these, succinic anhydride and tetrahydrophthalic anhydride are preferable from the viewpoint of the developability of the composition and the insulation reliability of a cured coating film obtained by curing the composition.

  Acid Pendane cage type unsaturated epoxy ester resin is obtained by reacting the unsaturated carboxylic acid with a polyfunctional epoxy resin in the presence of a catalyst, and then reacting the resulting unsaturated epoxy ester resin and acid anhydride. It can obtain by making it react.

  The amount of the catalyst used in this case is 2% by weight or less, preferably 0.0005 to 1% by weight, particularly preferably 0.005% by weight based on the total weight of the unsaturated carboxylic acid, the polyfunctional epoxy resin and the acid anhydride. A range of 001 to 0.5% by weight is preferred. 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, tetramethylammonium hydroxide; phosphines such as trimethylphosphine, tributylphosphine, triphenylphosphine; tetramethylphosphonium salt, tetraethylphosphonium Salt, tetrapropyl phosphonium salt, tetrabutyl phosphonium salt, trimethyl (2-hydroxylpropyl) phosphonium salt, triphenyl phosphonium salt, benzyl phosphonium salt and the like, and representative counter anions include chloride, bromide, carboxy Phosphonium salts having rate, hydroxide, etc .; trimethylsulfonium salt, benzyltetramethylenesulfonium salt, phenylbenzylmethyls Sulfonium salts such as phonium salts or phenyldimethylsulfonium salts, and sulfonium salts having 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 at 50 to 150 ° C, preferably in the range of 80 to 120 ° C.

  As a usage rate of the acid anhydride, a range in which the solid content acid value of the product (acid-pendane cage-type unsaturated epoxy ester resin) is 30 to 150 mgKOH / g is preferable, and 50 to 120 mgKOH / g is particularly preferable. When the acid value is less than 30 mgKOH / g, the alkali developability of the composition tends to decrease, and when it exceeds 150 mgKOH / g, the fine pattern of the formed solder resist flows by development, and characteristics such as insulation reliability are exhibited. It tends to decrease.

[(B) Polyimide resin]
The polyimide resin used in the present invention can be used without particular limitation as long as it is a soluble polyimide resin that dissolves in an organic solvent, but organic solvents (for example, N, N-dimethylformamide (DMF), N, N-diethylformamide, etc.) Formamide solvents, N, N-dimethylacetamide (DMAc), acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone (NMP) and N-vinyl-2-pyrrolidone Phenolic solvents such as phenol, o-, m-, or p-cresol and xylenol, ethereal solvents such as tetrahydrofuran (THF), dioxane and dioxolane, alcoholic solvents such as methanol, ethanol and butanol, and cellosolve such as butyl cellosolve Series, ethylcarby And those having a solubility of 1 g or more at 20 ° C. with respect to 100 g of carbitol solvents such as ethyl acetate (EDGAC) and butyl carbitol acetate, or cyclohexanone, propylene glycol monomethyl ether acetate (PGMAC), butyrolactone, etc.) are preferably used. The If the solubility is too low, there is a risk of precipitation in the photosensitive resin composition, and the solubility of the polyimide resin in an organic solvent is suitable for obtaining a photosensitive resin composition excellent in desired photocurability and developability. Act on. Examples of such a soluble polyimide resin include those having an aliphatic structure in the molecular structure, those having a siloxane structure (see Japanese Patent Application Laid-Open No. 05-112760), those having a bulky branched chain structure, and asymmetric monomers as raw materials. In the present invention, from the viewpoints of compatibility with other components, insulation, etc., (i) a polyimide resin having an isocyanurate ring in the molecular structure (Ie, a polyimide resin having an isocyanurate ring and an imide ring), (ii) a polyimide resin having a cyclic aliphatic structure in the molecular structure (ie, a polyimide resin having a cyclic aliphatic structure and an imide ring) Preferably, (iii) a polyimide resin having both an isocyanurate ring and a cycloaliphatic structure in its molecular structure (that is, an isocyanurate ring and a cyclic aliphatic Polyimide resin) having a structure and an imide ring is more preferable. Particularly preferred is (iv) a polyimide resin having a repeating unit containing an isocyanurate ring, a cyclic aliphatic structure and an imide ring, as disclosed in Patent Document 2. In the following description, these polyimides (i) to (iv) may be collectively referred to as “modified polyimide”.

  As a particularly preferred embodiment of such a modified polyimide, (1) an isocyanurate ring-containing polyisocyanate compound derived from a cyclic aliphatic diisocyanate is reacted with an acid anhydride of a polycarboxylic acid having three or more carboxyl groups. Carboxylic acid group-containing branched polyimide (hereinafter referred to as “(compound b-1)”), (2) compound (b-1), and one epoxy group and at least one compound. Carboxylic acid group-containing branched polymerizable polyimide (hereinafter referred to as “compound (b-2)”), which is a compound obtained by reacting a compound having a radical polymerizable unsaturated group of (3), or (3) a compound Compound obtained by reacting a residual isocyanate group with a compound having one hydroxyl group and one or more radically polymerizable unsaturated groups in the synthesis process of (b-1) A carboxylic acid group-containing branched polymerizable polyimide (hereinafter referred to as “compound (b-3)”) can be mentioned, and among these, a compound (b-2) having photosensitivity (radical polymerization) or Compound (b-3) is preferred.

  Examples of the “isocyanurate ring-containing polyisocyanate compound derived from a cyclic aliphatic diisocyanate” for obtaining the compound (b-1) include, for example, converting a cyclic aliphatic diisocyanate compound to an isocyanurate such as a quaternary ammonium salt. Isocyanurates consisting of trimers of cycloaliphatic diisocyanate compounds, isocyanurates consisting of pentamers, isocyanurates consisting of heptamers, and the like obtained by isocyanuration in the presence or absence of a catalyst An isocyanurate mixture is mentioned. Among these polyisocyanate compounds, an isocyanurate composed of a trimer of a cyclic aliphatic diisocyanate compound, that is, a compound containing 30% by weight or more of a triisocyanate compound containing one isocyanurate ring has heat resistance and moisture resistance. It is preferable from the point of being obtained, and what contains 50 to 95 weight% of the triisocyanate compound containing one isocyanurate ring is more preferable.

  Examples of the cycloaliphatic diisocyanate compound include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and these may be used alone or in combination of two kinds. You may use the above together. Of these, isophorone diisocyanate, hydrogenated xylene diisocyanate, and norbornene diisocyanate are preferable.

  In obtaining the isocyanurate ring-containing polyisocyanate compound, a diisocyanate compound other than the cyclic aliphatic diisocyanate compound may be used together with the cyclic aliphatic diisocyanate compound. In that case, for example, an acyclic aliphatic diisocyanate compound or an aromatic diisocyanate is used. Is used in a proportion of 50% by weight or less based on the cycloaliphatic diisocyanate compound. Examples of the acyclic aliphatic diisocyanate include hexamethylene diisocyanate, lysine diisocyanate, and trimethylhexane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, p-phenylene diisocyanate, Examples include xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate, dianisidine diisocyanate, and tetramethylxylylene diisocyanate.

  The isocyanurate ring-containing polyisocyanate compound preferably contains 10 to 20% by weight of isocyanate groups from the viewpoints of curability, solvent solubility, and the like.

  The “polycarboxylic acid anhydride having three or more carboxyl groups” for obtaining the compound (b-1) may be any acid anhydride of a polycarboxylic acid having three or more carboxyl groups, and is particularly limited. In particular, tricarboxylic acid anhydrides and tetracarboxylic acid anhydrides are preferred.

  Examples of the acid anhydride of tricarboxylic acid include trimellitic anhydride and naphthalene-1,2,4-tricarboxylic acid anhydride.

  Examples of tetracarboxylic acid anhydrides include pyromellitic dianhydride, benzophenone-3,4,3 ′, 4′-tetracarboxylic dianhydride, diphenyl ether-3,4,3 ′, 4′-. Tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, biphenyl-2,3,2 ', 3'-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1, 8,4,5-tetracarboxylic dianhydride, decahydronaphthalene-1,8,4,5-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-1,2,5 6-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, berylene-3,4,9,10-tetracarboxylic dianhydride, bis (2,3-di Carboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3 4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,3-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, and the like.

  The acid anhydride of the said polycarboxylic acid can use 1 type (s) or 2 or more types. Moreover, you may use together an aromatic dicarboxylic acid compound and / or its anhydride further as needed.

  The “compound having one epoxy group and one or more radically polymerizable unsaturated groups” for obtaining the compound (b-2) is not particularly limited, but examples thereof include glycidyl (meth) acrylate and α-ethylglycidyl. Acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, β-methyl glycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7 -Epoxy heptyl (meth) acrylate, (alpha) -ethyl-6,7-epoxy- heptyl (meth) acrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. are mentioned. These may be used alone or in combination of two or more. Of these, glycidyl (meth) acrylate and α-ethylglycidyl acrylate are preferable, and glycidyl methacrylate is particularly preferable.

  The “compound having one hydroxyl group and one or more radically polymerizable unsaturated groups” for obtaining the compound (b-3) is not particularly limited, but one hydroxyl group and one or more ( A (meth) acrylate-based compound having a (meth) acryloyl group is preferable. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl ( Mono (meth) acrylates such as (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerin dimethacrylate having glycerin skeleton, glycerin diacrylate, and trimethylolpropane skeleton Having trimethylolpropane Acrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate with pentaerythritol skeleton, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate with dipentaerythritol skeleton, dipentaerythritol hexamethacrylate, epoxy ester with hydroxyl group on ethylene glycol skeleton Examples thereof include ethylene glycol diepoxy acrylate and ethylene glycol diepoxy methacrylate into which a photopolymerizable group is introduced. These may be used alone or in combination of two or more. Of these, pentaerythritol triacrylate, pentaerythritol trimethacrylate, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate are preferable from the viewpoint of photocurability, and pentaerythritol triacrylate and / or pentaerythritol trimethacrylate having a pentaerythritol skeleton is particularly preferable. Is preferred.

  As a preferable production method of the compound (b-1), for example, in an organic solvent, “an isocyanurate ring-containing polyisocyanate compound derived from a cyclic aliphatic diisocyanate”, “an acid anhydride of a polycarboxylic acid”, May be reacted at a temperature of 50 to 250 ° C. for 1 to 30 hours. Subsequently, after adjusting the temperature to 50 to 150 ° C., a “compound having one epoxy group and one or more radically polymerizable unsaturated groups” is added and reacted for about 1 to 30 hours. (B-2) is obtained. Moreover, as a preferable manufacturing method of the compound (b-3), for example, in an organic solvent, “an isocyanurate ring-containing polyisocyanate compound derived from a cyclic aliphatic diisocyanate” and “an acid anhydride of a polycarboxylic acid” Is reacted at a temperature of 50 to 250 ° C. for 1 to 30 hours. At this time, an isocyanate group is left, and a “compound having one hydroxyl group and one or more radically polymerizable unsaturated groups” is added to the remaining isocyanate group. In addition, the reaction may be performed for about 1 to 30 hours.

  When the specific example of the said (b) modified polyimide is given, as a compound (b-1), the compound (henceforth "compound (I)") represented by a following formula (I) is mentioned.

  (In the formula, n represents 0 ≦ n ≦ 15.)

  In addition, as the compound (b-2), a structure (I) in which GMA (glycidyl methacrylate) is added to an arbitrary partial carboxyl group and / or terminal carboxyl group of the repeating unit (I-1) in the above formula (I). -2) (hereinafter also referred to as “compound (II)”).

  Here, R represents a residue of compound (I).

  The proportion of GMA modification of the carboxyl group is preferably 0.3 mol% or more and 50 mol% or less, and 0.5 mol% or more and 40 mol% or less, with respect to the number of mols of the carboxyl group of the compound (b-1). More preferably, 0.7 mol% or more and 30 mol% or less is still more preferable, and 0.9 mol% or more and 20 mol% or less is still more preferable.

  In addition, as the compound (b-3), in the above formula (I), any part of the repeating unit (I-1) and / or the terminal imide group is an isocyanate residue, and these are hydroxyl groups of pentaerythritol triacrylate. And a compound having the structure (I-3) added with (hereinafter also referred to as “compound (III)”).

  Here, R 'represents a residue of compound (I).

  From the viewpoint of improving photocurability, the upper limit of the amount of addition of pentaerythritol triacrylate is preferably 40 mol%, more preferably 38 mol%, more preferably 35 mol%, based on the number of moles of isocyanate groups of the polyisocyanate at the time of preparation. Is more preferable. On the other hand, the lower limit of the amount of addition of pentaerythritol triacrylate is preferably 0.3 mol% with respect to the number of moles of the isocyanate group of the polyisocyanate at the time of charging, from the viewpoint of sufficiently obtaining the effect of addition. % Is more preferable, and 5 mol% is still more preferable.

  In the present invention, as the modified polyimide, a commercially available product can be used as it is. For example, as the compound (b-1), “Unidic V-8000” manufactured by DIC Corporation corresponding to the compound (I) can be mentioned. A compound corresponding to the compound (II) can be obtained by reacting such “Unidic V-8000” with glycidyl methacrylate.

  In the resin composition of the present invention, the upper limit of the content of the (b) polyimide resin is 100 with respect to 100 parts by weight of the (a) carboxyl group-containing radical polymerizable compound from the viewpoint of preventing the development residue from remaining. Part by weight is preferred, 75 parts by weight is more preferred, 50 parts by weight is still more preferred, and 30 parts by weight is even more preferred. On the other hand, the lower limit of the content of the (b) polyimide resin is 0.5 parts by weight with respect to 100 parts by weight of the carboxyl group-containing radical polymerizable compound from the viewpoint of preventing the insulation reliability from being lowered. Is preferred, 1 part by weight is more preferred, and 5 parts by weight is even more preferred.

[(C) Epoxy compound]
The “epoxy compound” used in the present invention is not particularly limited as long as it is suitable for an insulating material in a printed wiring board. 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 novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, phenols and phenol Epoxidized products of condensates with aromatic aldehydes having a functional hydroxyl group, naphthalene type epoxy resins, fluorene type epoxy resins, xanthene type epoxy resins, etc. Agents that blended. Any one of these epoxy resins may be used, or two or more of them may be used in combination. In addition, the epoxy resin preferably has an epoxy equivalent in the range of 95 to 400 from the viewpoint of reactivity.

  Of these, dicyclopentadiene type epoxy resins and biphenyl type epoxy resins are preferable. Examples of the dicyclopentadiene type epoxy resin include “HP-7200” (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), etc. manufactured by Nippon Kayaku ( "NC3000" (epoxy equivalent of about 291) manufactured by Co., Ltd., "GK3207" (epoxy equivalent of about 226) manufactured by Toto Kasei Co., Ltd., "YX4000HK" (epoxy equivalent of about 190) manufactured by Japan Epoxy Resin Co., Ltd. Can be mentioned.

  In the resin composition of the present invention, the (c) epoxy compound is preferably used in a ratio of 5 to 100 parts by weight, based on 100 parts by weight of the (a) carboxyl group-containing radical polymerizable compound, and 10 to 85 parts by weight. More preferred. If it is less than 5 parts by weight, the coating film will be insufficiently cured, and the heat resistance, electrical insulation and the like will tend to be reduced.

[(D) Photopolymerization initiator]
Examples of the “photopolymerization initiator” used in the present invention include 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 (di) Tilamino) 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, oxime ester photopolymerization initiators, etc. Can also be used. As the usage-amount of the said photoinitiator, it is 0.5-30 weight part with respect to 100 weight part of resin solid content in a composition, Preferably it exists in the range of 1-15 weight part. When the amount of the photopolymerization initiator used exceeds the above range, the composition tends to decrease in thermosetting, heat resistance, electrical insulation, etc., and the amount of the photopolymerization initiator used exceeds the above range. When the amount is small, the composition tends to be insufficiently cured when the composition is photocured.

[(E) Reactive diluent]
The “reactive diluent” used in the present invention is blended for the purpose of improving the photoreactivity of the composition. As the 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 examples include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol, N, Acrylamides such as N-dimethylacrylamide and N-methylolacrylamide, aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, polyhydric alcohols such as trimethylolpropane, pentaerythritol and dipentaerythritol, or ethylene oxide thereof, Polypropylene adducts of propylene oxide or ε-caprolactone adducts, phenoxy acrylate, phenoxy ethyl Corresponds to phenols such as acrylates, 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 the above acrylates And methacrylates. 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.

  In the resin composition of the present invention, the amount of the (e) reactive diluent used is 1 to 50 weights per 100 weight parts of the total amount of (a) carboxyl group-containing radical polysynthetic compound and (b) polyimide resin. It is preferably used in a proportion of 5 parts by weight, more preferably 5 to 30 parts by weight. If it is less than 1 part by weight, the photo-curing effect tends to be difficult to obtain, and if it exceeds 50 parts by weight, the stickiness of the coating film tends to be large and the workability tends to decrease.

[(F) Curing accelerator]
The resin composition of the present invention may further contain a “curing accelerator” in addition to the components (a) to (e). By using a curing accelerator, thermal curing of the coating film can be promoted, which is advantageous in improving various characteristics of the resist. Examples of such a curing accelerator include amines, polyamides, imidazoles, Lewis acids, organic phosphine compounds, and the like, and amines are preferable from the viewpoint of the balance of coating film performance. Examples include methylimidazole, triphenylphosphine, ethylguanidinoamine, diaminodiphenylmethane, melamine, and dicyandiamide (DICY). Of these, melamine and dicyandiamide (DICY) are particularly preferable. It is preferable that the compounding quantity of a hardening accelerator is used in 0.1-20 weight% with respect to the epoxy resin of (c) epoxy compound.

[(G) Filler]
The resin composition of the present invention may further contain a “filler” in addition to the components (a) to (e). An inorganic filler and / or an organic filler can be used as the filler.

  By containing an inorganic filler, the coefficient of thermal expansion can be reduced. Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Examples include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. The inorganic fillers may be used alone or in combination of two or more. Of these, silica is preferable. The average particle size of the inorganic filler is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. In addition, when the average particle diameter of the inorganic filler becomes too small, there is a tendency for secondary aggregation, so the average particle diameter is preferably 0.01 μm or more. The inorganic filler is preferably surface-treated with a surface treatment agent such as a silane coupling agent in order to improve moisture resistance.

  By containing an organic filler, the stress of the coating film can be relaxed. Examples of the organic filler include acrylic rubber particles, polyamide fine particles, and silicone particles. Specific examples of the acrylic rubber particles are fine particles of a resin that has been subjected to a chemical crosslinking treatment on a resin exhibiting rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber, and is insoluble and infusible in an organic solvent. Any of them may be used, for example, XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (above, manufactured by Ganz Kasei Co., Ltd.) EXL2655, EXL2602 (above, manufactured by Kureha Chemical Industry Co., Ltd.) and the like. Specific examples of the polyamide fine particles include aliphatic polyamides such as nylon, aromatic polyamides such as Kevlar, and polyamide imide and other resins having an amide bond of 50 microns or less. For example, VESTOSINT 2070 (manufactured by Daicel Huls Co., Ltd.) or SP500 (manufactured by Toray Industries, Inc.) can be used. The organic filler also preferably has an average particle size of 20 μm or less.

  The average particle size of the inorganic filler and the organic 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 or an organic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd. can be used.

  In the present invention, the amount of the filler (g) used is preferably 1 to 50% by weight, more preferably 2 to 40% by weight when the nonvolatile content in the composition of the present invention is 100% by weight. preferable.

[(H) Other additives]
In the resin composition of the present invention, in addition to the components (a) to (g), (h) other additives can be blended. For example, for preventing dark reaction and improving storage stability. Examples include, but are not limited to, polymerization inhibitors, antifoaming agents, thixotropic agents, and pigments. Examples of the polymerization inhibitor include hydroquinone and phenothiazine. Examples of the antifoaming agent include silicone-based and hydrocarbon-based compounds.

  The photosensitive resin composition of the present invention is mixed from the above (a) to (e), or selected from the above (f), (g) and (h) together with the above (a) to (e). It can be produced by mixing at least one and, if necessary, kneading or mixing with a kneading means such as a three-roll, ball mill, or sand mill, or a stirring means such as a super mixer or a planetary mixer.

[Photosensitive dry film]
Next, the photosensitive dry film of this invention and its manufacturing method are demonstrated. The photosensitive dry film of the present invention is a photosensitive film in which a layer made of the photosensitive resin composition is laminated on a support. As the support, a general thermoplastic resin film is used, but a film made of a material that makes it impossible to remove the layer made of the photosensitive resin composition, or a surface that makes removal impossible. Films that have been treated are unsuitable. Examples of the thermoplastic resin film include films made of polyethylene terephthalate, polypropylene, polyethylene, polyvinyl alcohol, triacetyl acetate, and the like, and polyethylene terephthalate film is particularly preferable. These thermoplastic resin films may have a surface coated with a release agent such as a silicone coating agent in order to facilitate removal of the layer made of the photosensitive resin composition. 5-50 micrometers is preferable and, as for the thickness of a support body, 10-25 micrometers is more preferable.

  Moreover, in order to reduce the scattering of the light at the time of exposure by active energy rays, such as an ultraviolet-ray, it is preferable that the thermoplastic resin film is excellent in transparency. Specifically, it is preferable that the turbidity (haze, JIS-K6714) serving as an index of transparency is 0.1 to 5. The thermoplastic resin film is used as a support for the layer made of the photosensitive resin composition, but may be laminated on both sides of the layer made of the photosensitive resin composition as a protective film for the layer made of the photosensitive resin composition. . In that case, the side which peels more easily becomes a protective film. However, the protective film may not be provided in the case where the layer made of the photosensitive resin composition is laminated on the support and then used immediately in the same process or when there is almost no tackiness at room temperature.

  The photosensitive dry film of this invention can be manufactured by apply | coating the said photosensitive resin composition on a support body, drying, and forming the layer which consists of a photosensitive resin composition. 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. A photosensitive dry film can be produced by removing and drying, and then laminating a protective film on the dried film obtained as necessary.

  Photosensitive resin composition coating methods include 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, roll coating. Examples include a method, knife coating method, curtain coating method, chamber gravure coating method, slot orifice method, spray coating method, and 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. Moreover, in order to avoid foreign matter mixing etc., it is preferable to apply in an environment with little foreign matter generation such as a clean room.

  Further, when the thickness of the support is thin, the support may shrink or the support may be broken by heating. In this case, the photosensitive resin composition is once applied to a film having a silicone release treatment of about 100 μm, dried and then laminated with a desired support, and the layer made of the photosensitive resin composition is transferred to the support. After that, the film which has been subjected to the silicone peeling treatment may be removed and the protective film may be laminated again. Although the thickness in particular of the layer which consists of photosensitive resin compositions is not restrict | limited, 5-100 micrometers is preferable and 10-45 micrometers is more preferable.

[Printed wiring board]
Furthermore, the manufacturing method of the printed wiring board using the photosensitive resin composition and photosensitive dry film of this invention as a soldering resist is demonstrated. When the photosensitive resin composition is applied directly on a printed wiring board on which a copper circuit is formed, it is applied on the printed wiring board in a thickness of 5 to 100 μm, preferably 15 to 45 μm after drying. Currently, full screen printing by screen printing is generally used as a coating means, but any means may be used as long as it can be applied uniformly including this. 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 methods can be used.

After the application, if necessary, a prebaking process, that is, temporary drying is performed in a hot air furnace or a far infrared furnace. The prebaking temperature is preferably about 50 to 100 ° C. Next, the exposure process is started. In the exposure step, exposure with active energy rays is performed using a negative mask in which only the portions to be plated with solder do not pass active energy rays. Alternatively, direct writing may be performed with a beam of active energy rays without using a negative mask. As the negative mask, a negative film is used when the active energy ray is ultraviolet light or visible light, a metal mask is used when it is an electron beam, and a lead mask is used when it is an X-ray. Therefore, ultraviolet rays are often used as active energy rays in the production of printed wiring boards. The exposure method includes a contact exposure method in which a negative mask 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. The irradiation amount of ultraviolet rays is about 10 to 1000 mJ / cm ² .

  After the exposure process, the developing process is started. The development step is performed by using an alkaline solution such as an aqueous sodium carbonate solution or an aqueous sodium hydroxide solution by means of spraying, dipping or the like, and the unexposed portions are removed by the action of dissolution, swelling, peeling and the like. Finally, the post-bake process is entered. Post-baking may be performed in a hot air furnace or a far-infrared furnace at a temperature and time sufficient for the epoxy component to react. The solder resist is applied on the printed wiring board through the above steps.

  When using a photosensitive dry film to provide a layer made of a photosensitive resin composition on a printed wiring board, if there is a protective film, remove the protective film and then heat the photosensitive dry film and / or printed wiring board. On the other hand, it laminates | stacks by crimping in the direction which the layer which consists of a photosensitive resin composition, and a printed wiring board contact. The heating and pressure bonding methods are not particularly limited, but it is preferably performed by a vacuum laminating method that heats to 50 to 120 ° C. and hardly contains air or the like. After crimping, with the support remaining, place the negative mask on the support, and after exposing as in the case of direct printing described above, remove the support, and then perform development and post-baking as in direct printing. By carrying out to the above, a solder resist by a photosensitive dry film is applied on the substrate.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

Synthesis Example 1 (Synthesis of carboxyl group-containing radical polymerizable compound solution)
In a 1 liter separable flask, 210.0 g of EPICLON N-680 (o-cresol novolac type epoxy, epoxy equivalent 210 g / eq) manufactured by DIC Corporation was dissolved in 201.0 g of ethyl carbitol acetate to obtain acrylic acid. 72.0 g was charged. Hydroquinone (0.3 g) as a polymerization inhibitor and triphenylphosphine (1.0 g) as a catalyst were added, heated to 120 ° C. with stirring, and the reaction was continued for 10 hours while maintaining the temperature at 120 ° C. The reaction product was once cooled to room temperature, added with 91.2 g of tetrahydrophthalic anhydride, heated to 100 ° C. and reacted for 4 hours to obtain a carboxyl group-containing radical polymerizable compound solution having a solid content concentration of 65%. This solid content is equivalent to (a) a carboxyl group-containing radical polymerizable compound. When the acid value was measured, it was 58.5 mgKOH / g (solid content acid value 90.0 mgKOH / g). Hereinafter, this varnish is referred to as A varnish.

Synthesis Example 2 (Synthesis of carboxyl group-containing radical polymerizable compound solution)
In a 20-liter separable flask, 201.6 g of ethyl carbitol acetate was added to Epoxy resin varnish KAYARAD R-7509 manufactured by Nippon Kayaku Co., Ltd. (bisphenol F type modified epoxy, epoxy equivalent 395 g / eq, solid content 75%). 526.7 g was dissolved and 72.0 g of acrylic acid was charged. Hydroquinone (0.5 g) was added as a polymerization inhibitor and triphenylphosphine (2.0 g) was added as a catalyst. The mixture was heated to 120 ° C. with stirring, and the reaction was continued for 10 hours while maintaining at 120 ° C. Once the reaction product was cooled to room temperature, 152.0 g of tetrahydrophthalic anhydride was added, heated to 100 ° C. and reacted for 6 hours to obtain a carboxyl group-containing radical polymerizable compound solution having a solid content concentration of 65%. This solid content is equivalent to (a) a carboxyl group-containing radical polymerizable compound. When the acid value was measured, it was 58.9 mgKOH / g (solid content acid value 90.6 mgKOH / g). Hereinafter, this varnish is referred to as B varnish.

Synthesis Example 3 (Synthesis of modified polyimide A)
Into a 1 liter separable flask, 500 g (carboxyl group 0.35 mol) of Unidic V-8000 (soluble polyimide, solid content 40%, acid value 98 mgKOH / g) manufactured by DIC Corporation was charged and heated to 120 ° C. Hydroquinone (0.1 g) was added as a polymerization inhibitor, triphenylphosphine (2 g) and glycidyl methacrylate (0.5 g) (epoxy group 0.0035 mol) were added as a polymerization inhibitor, and the reaction was continued for 1 hour while maintaining at 120 ° C. When the epoxy equivalent of the reaction product was confirmed, it was confirmed that it was 10000 g / eq or more. Hereinafter, this varnish is referred to as modified polyimide A.

Synthesis Example 4 (Synthesis of modified polyimide B)
Into a 1 liter separable flask, 500 g (carboxyl group 0.35 mol) of Unidic V-8000 (soluble polyimide, solid content 40%, acid value 98 mgKOH / g) manufactured by DIC Corporation was charged and heated to 120 ° C. Hydroquinone (0.1 g) was added as a polymerization inhibitor, triphenylphosphine (2 g) and glycidyl methacrylate (5 g) (epoxy group 0.035 mol) were added as a polymerization inhibitor, and the reaction was continued for 3 hours while maintaining at 120 ° C. When the epoxy equivalent of the reaction product was confirmed, it was confirmed that it was 10000 g / eq or more. Hereinafter, this varnish is referred to as modified polyimide B.

Synthesis Example 5 (Synthesis of modified polyimide D)
In a 2 liter separable flask, 300 g of ethyl carbitol acetate and Desmodur Z 4470SN manufactured by Sumika Bayer Urethane Co., Ltd. (polyisocyanate of isophorone diisocyanate, NCO equivalent 360, average functional group number 3.3, solid content 70%) 432.0 g (1.2 mol of isocyanate groups) was dissolved and 170.9 g of trimellitic anhydride was charged. The temperature was raised to 160 ° C. while stirring in an N ₂ atmosphere. The reaction was carried out at 160 ° C. for 4 hours, and it was confirmed that the isocyanate content was 0.03%, and then cooled to 80 ° C. To confirm the isocyanate content, after dissolving the sample in dehydrated toluene according to JIS 1556, an excess di-normal butylamine solution was added and reacted, and the remaining di-normal butylamine was back titrated with hydrochloric acid and titrated to the end point. Calculated with Next, 307.2 g of ethyl carbitol acetate and 0.6 g of hydroquinone were added, and further 17.9 g of pentaerythritol triacrylate (0.06 mol of hydroxyl group) was added and reacted at 80 ° C. for 2 hours. It was confirmed by FT-IR that the absorption of isocyanate at 2270 cm ⁻¹ disappeared. Hereinafter, this varnish is referred to as modified polyimide D.

Synthesis Example 6 (Synthesis of modified polyimide E)
In a 2 liter separable flask, 300 g of ethyl carbitol acetate and Desmodur Z 4470 SN (manufactured by Sumika Bayer Urethane Co., Ltd.) (polyisocyanate of isophorone diisocyanate, NCO equivalent 360, average functional group number 3.3, solid content 70% ) 432.0 g (1.2 mol of isocyanate groups) was dissolved and 103.6 g of trimellitic anhydride was charged. The temperature was raised to 160 ° C. while stirring in an N ₂ atmosphere. The reaction was performed at 160 ° C. for 2 hours, and it was confirmed that the isocyanate content was 1.81%, and the mixture was cooled to 80 ° C. To confirm the isocyanate content, after dissolving the sample in dehydrated toluene according to JIS 1556, an excess di-normal butylamine solution was added and reacted, and the remaining di-normal butylamine was back titrated with hydrochloric acid and titrated to the end point. Calculated with Next, 363.4 g of ethyl carbitol acetate and 0.7 g of hydroquinone were added, 122.5 g of pentaerythritol triacrylate (0.41 mol of hydroxyl group) was further added, and the mixture was reacted at 80 ° C. for 4 hours. It was confirmed by FT-IR that the absorption of isocyanate at 2270 cm ⁻¹ disappeared. Hereinafter, this varnish is referred to as modified polyimide E.

Examples 1-10, Comparative Examples 1-6
Using the varnishes obtained in Synthesis Examples 1 to 6, each component was blended in the blending ratio shown in Table 1 below, and 30 parts by weight of methyl ethyl ketone was further added, and kneaded using three rolls. Prepared. The numerical values in Table 1 are all “parts by weight”.

^* 1: Soluble polyimide “V-8000” manufactured by DIC
^* 2: α-aminoalkylphenone photopolymerization initiator, manufactured by Ciba Specialty Chemicals
^* 3: 2,4-diethylthioxanthone manufactured by Nippon Kayaku
^* 4: Nippon Kayaku dipentaerythritol hexaacrylate
^* 5: Dicyclopentadiene type epoxy resin manufactured by DIC (epoxy equivalent 264)
^* 6: Japan epoxy resin, biphenyl type epoxy resin (epoxy equivalent 190)
^* 7: Nippon Aerosil Co., Ltd., A200 (thixotropic agent)

(Manufacture of printed wiring boards)
The resin composition obtained in each example and each comparative example was applied to a PET film having a thickness of 16 μm so as to have a dry film thickness of 20 μm using an applicator, and then dried in a hot air drying oven at 80 ° C. for photosensitivity. Dry film was prepared. Then, it thermocompression-bonded at 80 degreeC using the vacuum laminator to the copper clad laminated board by which pattern formation was carried out. Next, the negative film of the resist pattern was brought into contact with the coating film and exposed using an ultraviolet exposure apparatus (exposure amount: 300 mJ / cm ² ). Thereafter, the PET film having a thickness of 16 μm was peeled off, and then developed with a sodium carbonate aqueous solution adjusted to 30 ° C. at a concentration of 1% at a spray pressure of 0.2 MPa for 1 minute to dissolve and remove the unexposed portion. A cured coating film was obtained by thermosetting at 60 ° C. for 60 minutes.

(Evaluation test)
1. Evaluation of photocurability Photosensitive dry film (resin composition layer having a dry film thickness of 20 μm on a 16 μm thick PET film) using a vacuum laminator on a substrate (a copper foil 18 μm, FR4 double-sided copper clad laminate having a thickness of 0.8 mm). A test substrate on which a coating film is formed) is exposed to 300 mJ / cm ² using a step tablet for sensitivity measurement (21 steps of Stouffer), peeled off the PET film, and developed (1%) Perform development for 1 minute at a spray pressure of 0.2 MPa using a sodium carbonate aqueous solution (30 ° C.) at a concentration. Number of steps (number of steps) where the resin composition layer (coating film) of the substrate after development is not removed ) The larger the number of steps, the better the photocurability. The case where the number of steps was 5 or more was evaluated as “◎”, the case where the number of steps was 4, “◯”, and the case where the number of steps was 3, as “Δ”. Further, “−” indicates that the number of steps cannot be determined due to development failure.

2. Evaluation of developability A photosensitive dry film was laminated on a copper-clad laminate using a vacuum laminator, the PET film was peeled off, developed in the same manner as described above, and evaluated according to the following criteria.
○: Unexposed part is completely removed and no residue ×: Unexposed part is not completely removed and there is a residue

3. Evaluation of adhesion After producing a test substrate similar to the above, a peeling test using a cellophane tape was performed on a test piece cross-cut to 100 mm in accordance with JIS D0202 on the coating film surface of the test substrate. The number was visually observed and evaluated according to the following criteria.
○: 100/100
Δ: 50/100 to 99/100
X: 0/100 to 49/100

4). Evaluation of Electroless Gold Plating Resistance A photosensitive dry film was laminated on a copper-clad laminate, and a negative mask was adhered thereto, and exposed to 300 mJ / cm ² using an ultraviolet irradiation device. After peeling off the 16 μm PET film, it was developed with a sodium carbonate aqueous solution adjusted to 30 ° C. at a concentration of 1% at a spray pressure of 0.2 MPa for 1 minute to form an opening pattern with a diameter of 200 μm. Heated for minutes to form a cured coating. And after performing the electroless nickel / gold plating process, the peeling test by a cellophane tape was done. The cured coating film peeling due to the gold plating submerged under the coating film and the discoloration caused by the plating solution were visually observed and evaluated according to the following criteria.
◎: No change is observed at all ○: Slightly changed △: Remarkably changed ×: The coating film was peeled off

5. Insulation reliability test (HAST)
A photosensitive dry film was laminated on a comb wiring pattern of L (wiring width) / S (interval) = 20 μm / 20 μm, and exposed to 300 mJ / cm ² using an ultraviolet irradiation device. After peeling off the 16 μm PET film, it was developed with a sodium carbonate aqueous solution adjusted to 30 ° C. at a concentration of 1% at a spray pressure of 0.2 MPa for 1 minute, and further heated at 165 ° C. for 60 minutes to give a 20 μm thick cured coating. A film was formed.
A copper wire was soldered as an electrode on both sides of the comb-shaped wiring pattern, a voltage of 5.5 V was applied at 130 ° C. and 85% RH, and a resistance value (Ω) was measured after 200 hours. Moreover, the presence or absence of ion migration was investigated.

  About the resin composition obtained by each Example and each comparative example, the above 1-5 evaluation tests were done. The results are shown in Table 2 below.

From Table 2, the photosensitive resin composition of the present invention can be a photosensitive resin composition having good photocurability, developability, adhesion and gold plating resistance, and extremely good insulation reliability. It turns out that it is the photosensitive resin composition which can make the outstanding gold-plating tolerance and insulation reliability as a resist compatible.
This application is based on Japanese Patent Application No. 2008-330867 for which it applied in Japan, The content is altogether included in this specification.

Claims (13)

(A) a carboxyl group-containing radically polymerizable compound,
(B) polyimide resin,
(C) an epoxy compound,
(D) a photopolymerization initiator, and (e) a reactive diluent seen including,
The photosensitive resin composition, wherein the (b) polyimide resin is a polyimide resin having a repeating unit containing an isocyanurate ring, a cyclic aliphatic structure, and an imide ring . (B) The polyimide resin is a compound obtained by reacting an isocyanurate ring-containing polyisocyanate compound derived from a cycloaliphatic diisocyanate with an acid anhydride of a polycarboxylic acid having three or more carboxyl groups. The photosensitive resin composition according to claim 1, wherein: (B) 1 is a compound obtained by reacting an isocyanurate ring-containing polyisocyanate compound derived from a cycloaliphatic diisocyanate with an acid anhydride of a polycarboxylic acid having three or more carboxyl groups. The photosensitive resin composition according to claim 1, which is a compound obtained by reacting a compound having one epoxy group and one or more radically polymerizable unsaturated groups. (B) Residue of a compound obtained by reacting an isocyanurate ring-containing polyisocyanate compound derived from a cycloaliphatic diisocyanate with an acid anhydride of a polycarboxylic acid having three or more carboxyl groups. The photosensitive resin composition according to claim 1, which is a compound obtained by reacting an isocyanate group with a compound having one hydroxyl group and one or more radically polymerizable unsaturated groups. (A ) The photosensitive resin composition of any one of Claims 1-4 which contains 0.5-100 weight part of (b) polyimide resins with respect to 100 weight part of carboxyl group-containing radically polymerizable compounds. . Furthermore, (f) hardening accelerator is contained, The photosensitive resin composition of any one of Claims 1-5 characterized by the above-mentioned. Furthermore, (g) a filler is contained, The photosensitive resin composition of any one of Claims 1-6 characterized by the above-mentioned. (A) The carboxyl group-containing radical polymerizable compound is an acid-pendane cage type unsaturated epoxy ester resin obtained by reacting an unsaturated carboxylic acid with a polyfunctional epoxy resin and further reacting with an acid anhydride. The photosensitive resin composition of any one of these. The polyfunctional epoxy resin is a bisphenol F-type epoxy resin and / or a cresol novolac-type epoxy resin modified to have at least three functions by reacting bisphenol F-type epoxy resin with epichlorohydrin. Photosensitive resin composition. (C) The photosensitive resin composition of any one of Claims 1-9 whose epoxy compound is a dicyclopentadiene type epoxy resin and / or a biphenyl type epoxy resin. The photosensitive resin composition according to any one of claims 1 to 10, which is a solder resist. Photosensitive dry films prepared from the photosensitive resin composition according to any one of claims 1-10. Printed wiring board having a cured film of the photosensitive resin composition according to any one of claims 1-10.