JP5804336B2 - Photosensitive resin composition, photosensitive film, permanent resist - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photosensitive film using the same, and a permanent resist. In particular, the present invention relates to a photosensitive resin composition suitable as a solder resist used for printed wiring boards, semiconductor package substrates, and flexible wiring boards.

  With the reduction in size and weight of various electronic devices, photosensitive solder resist is used for printed wiring boards, semiconductor package boards, and flexible wiring boards for the purpose of forming fine opening patterns. The solder resist generally requires developability, resolution, solder heat resistance, gold plating resistance, and the like.

  Since semiconductor packages have been reduced in size and increased in pin count, they are used for semiconductor packages such as BGA (Ball Grid Array) and CSP (Chip Size Package) that have been reduced in size, weight, and performance. In addition to the above characteristics, the solder resist has high crack resistance against TCT (temperature cycle test), PCT resistance (pressure cooker test resistance), and fine wiring HAST resistance (high acceleration stress test resistance) is required. Furthermore, high heat resistance (high Tg, crack resistance) is also required with the demand for lead-free due to consideration for environmental problems.

  In particular, it is also important to suppress warping to a small degree with respect to a solder resist for a flexible wiring board.

  In general solder resists currently used, the epoxy group and the carboxyl group easily react, so the epoxy resin as a curing agent and the carboxylic acid-containing photosensitive prepolymer for imparting alkali developability are separated separately. The liquid two-liquid type is the mainstream.

  As the carboxylic acid-containing photosensitive prepolymer, a photosensitive prepolymer that can be developed with an alkali that has been subjected to acid modification after adding acrylic acid to a cresol novolac-type epoxy resin because of high temperature and humidity resistance is widely used (for example, Patent Documents). 1). Recently, photosensitive prepolymers further containing an elastomer have been used for the purpose of improving the resistance to TCT (see, for example, Patent Documents 2 and 3).

  However, since the pot life when mixing two liquids is as short as several hours to one day, the usage conditions are limited, or when two liquids are mixed in advance to form a film, it is difficult to store them in a film state. I did. Furthermore, the photosensitive resin composition described in the above patent document can withstand the reflow temperature to the conventional Sn / Pb eutectic solder, but is insufficient for the resistance to the high temperature reflow temperature to the lead-free solder. It's getting on. Under these circumstances, development of a one-pack type photosensitive resin composition having high heat resistance and storage stability is desired.

  One technique for imparting high heat resistance to the photosensitive resin composition is to add a photopolymerizable monomer having a rigid structure, but it is difficult to maintain characteristics such as developability and warpage. It is.

  By the way, a negative photosensitive resin composition is cured by exposure and developed. However, in order to improve developability (high resolution), it is effective to increase the solubility of the unexposed portion in the developer. In order to increase the solubility of the unexposed area, there is a method of introducing a hydrophilic group into the photosensitive resin composition. When a carboxyl group is used as such a hydrophilic group, the high hydrophilicity has an acid value. The higher the acid value resin, the higher the solubility.

  However, in the case of a permanent resist such as a solder resist, the higher the acid value of the polymer, the higher the water absorption. Therefore, the insulation resistance (HAST resistance) and heat resistance under high temperature and high humidity conditions are likely to decrease. As described above, it is difficult to develop a photosensitive resin composition that simultaneously satisfies developability, high heat resistance, and HAST property.

JP-A 61-243869 JP 2002-162738 A JP 2004-28726 A

  The present invention has a storage stability photosensitive resin composition that is excellent in HAST resistance between fine wirings and has high heat resistance without impairing developability, and a photosensitive film using the same. An object is to provide a permanent resist.

The inventors have
(A) component: a radically reactive resin having at least one ethylenically unsaturated group and a carboxyl group in the molecule;
(B) component: a photopolymerizable monomer having at least one ethylenically unsaturated group and a tricyclodecane structure in the molecule;
(C) component: photopolymerization initiator,
(D) component: an epoxy resin, and (e) component: a photosensitive resin composition containing a silica filler, wherein the silica filler as the component (e) has an average particle diameter of 3 to 300 nm, and is photosensitive. It was found that a photosensitive resin composition having a maximum particle size of 1 μm or less dispersed in the photosensitive resin composition and having a filling amount of 20 to 70% by mass of the total mass can solve the above-mentioned problems. Was completed.

  In the present invention, the photopolymerizable monomer having at least one ethylenically unsaturated group and a tricyclodecane structure in the molecule of the component (b) is dimethylol tricyclodecane diacrylate, dimethylol. It is preferable to include one or more selected from the group consisting of tricyclodecane dimethacrylate, tricyclodecane diol diacrylate and tricyclodecane diol dimethacrylate, or the component (b) is represented by the following general formula (1) or It is preferable to include a compound having a partial structure represented by the general formula (2). These are also preferably used in combination.

[In General Formula (1) or General Formula (2), R ¹ and R ² represent a direct bond, an alkylene, or an arylene group. ]
When the photopolymerizable monomer having at least one ethylenically unsaturated group and a tricyclodecane structure in the component (b) molecule is such a compound, HAST resistance is maintained without impairing developability. And it can be set as the photosensitive resin composition excellent in heat resistance.

  The compound having the partial structure represented by the general formula (1) or the general formula (2) includes a diol compound containing a tricyclodecane structure, a diisocyanate compound, and at least one ethylenically unsaturated group in the molecule. It is preferable that it is a urethane compound obtained by making it react with the compound which has one hydroxyl group. The diisocyanate compound may be a diisocyanate having a ring structure. With such a urethane compound, heat resistance such as HAST resistance, Tg and crack resistance can be improved.

  In addition, the compound having at least one ethylenically unsaturated group and one hydroxyl group in the molecule is preferably a compound having three ethylenically unsaturated groups in the molecule. The compound shown by (3) may be sufficient.

[In General Formula (3), R ³ and R ⁴ may be the same or different, each R ³ represents an alkylene group or an arylene group having 1 to 10 carbon atoms, and R ⁴ represents a hydrogen atom or 1 carbon atom. 10 represents an alkyl group or an aryl group, and l, m, and n represent an integer of 1 to 10. ]

  By using such a compound, the heat resistance can be further improved, and the warpage can be further suppressed.

  This invention can be provided also as a photosensitive film provided with the support body and the photosensitive resin composition layer containing the said photosensitive resin composition formed on this support body. Thereby, the dry film type photosensitive film excellent in the said characteristic can be provided.

  Moreover, this invention provides the permanent resist which consists of the hardened | cured material of the said photosensitive resin composition formed on the board | substrate for printed wiring boards.

  According to the present invention, it is possible to provide a photosensitive resin composition that is excellent in developability, has sufficient HAST resistance, and has high heat resistance and is capable of alkali development, a dry film type photosensitive film, and a permanent resist. Can do. Furthermore, the photosensitive resin composition of the present invention can greatly reduce the thermal expansion coefficient of the resin due to the effect of the silica filler, and has a high crack resistance against TCT (temperature cycle test). Highly sensitive photosensitive resin composition can be obtained.

Hereinafter, preferred embodiments of the present invention will be described in detail.
[Photosensitive resin composition]
Hereinafter, each component which can be used with the photosensitive resin composition of this invention is demonstrated in detail.
In this specification, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acrylate means acrylate or methacrylate, and (meth) acryloyl group means acryloyl group or methacryloyl. Means group.

  Component (a) that can be used in the present invention: As a photo-radical reactive resin having at least one ethylenically unsaturated group and a carboxyl group in the molecule, for example, an epoxy compound (a1) and an unsaturated monovalent resin An addition reaction product obtained by adding a saturated or unsaturated polybasic acid anhydride (a3) to an esterified product of the carboxylic acid (a2) can be used. These can be obtained by the following two-step reaction. In the first reaction (hereinafter referred to as “first reaction” for convenience), the epoxy compound (a1) and the unsaturated monocarboxylic acid (a2) react. In the next reaction (hereinafter referred to as “second reaction” for convenience), the esterified product produced in the first reaction reacts with the saturated or unsaturated polybasic acid anhydride (a3).

  Although there is no restriction | limiting in particular as said epoxy compound (a1), For example, a bisphenol type epoxy compound, a novolak type epoxy compound, a biphenyl type epoxy compound, a polyfunctional epoxy compound etc. are mentioned. As the bisphenol type epoxy compound, those obtained by reacting bisphenol A type or bisphenol F type with epichlorohydrin are suitable. GY-260, GY-255, XB-2615 manufactured by Ciba Geigy Corp., Epicoat manufactured by Japan Epoxy Resin Co., Ltd. Suitable are bisphenol A type such as 828, 1007, and 807, bisphenol F type, hydrogenated bisphenol A type, amino group-containing, alicyclic or polybutadiene-modified epoxy compounds.

  As a novolak type epoxy compound, it can be obtained by reacting at least one kind selected from phenols such as phenol, cresol, halogenated phenol and alkylphenol with formaldehyde and an novolak and epichlorohydrin. Are suitable, YDCN-701, 704, YDPN-638, 602 manufactured by Tohto Kasei Co., Ltd., DEN-431, 439 manufactured by Dow Chemical Company, EPN-1299 manufactured by Ciba Geigy Co., Ltd., N manufactured by Dainippon Ink & Chemicals, Inc. -730, 770, 865, 665, 673, VH-4150, 4240, Nippon Kayaku Co., Ltd. EOCN-120, BREN, etc. are mentioned.

  Examples of epoxy compounds having other structures include salicylaldehyde-phenol or salicylaldehyde-cresol type epoxy compounds (EPPN502H, FAE2500, etc., manufactured by Nippon Kayaku Co., Ltd.), DER-330, 337, 361, manufactured by Dow Chemical Co., Ltd. Chemical Industry Co., Ltd. Celoxide 2021, Mitsubishi Gas Chemical Co., Ltd. TETRAD-X, C, Nippon Soda Co., Ltd. EPB-13, 27, etc. can also be used. These may be used alone or in combination of two or more, and a mixture or a block copolymer may be used.

  Examples of the unsaturated monocarboxylic acid (a2) include (meth) acrylic acid, crotonic acid, cinnamic acid, and saturated or unsaturated polybasic acid anhydrides and (meth) acrylates having one hydroxyl group in one molecule. Or the reaction material of the half-ester compound of a saturated or unsaturated dibasic acid and an unsaturated monoglycidyl compound is mentioned. Examples of the reactant include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and tris (hydroxyethyl) isocyanurate. Examples thereof include reactants obtained by reacting di (meth) acrylate, glycidyl (meth) acrylate and the like in an equimolar ratio by a conventional method. These unsaturated monocarboxylic acids can be used alone or in combination. Among these, acrylic acid is preferable.

  Examples of the saturated or unsaturated polybasic acid anhydride (a3) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride. Methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, trimellitic anhydride, and the like.

  In the first reaction, a hydroxyl group is generated by an addition reaction between the epoxy group of the epoxy compound (a1) and the carboxyl group of the unsaturated monocarboxylic acid (a2). In the first reaction, the ratio of the epoxy compound (a1) to the unsaturated monocarboxylic acid (a2) is such that the unsaturated monocarboxylic acid (a2) is 0.001 equivalent to 1 equivalent of the epoxy group of the epoxy compound (a1). The ratio is preferably 7 to 1.05 equivalent, and more preferably 0.8 to 1.0 equivalent.

  The epoxy compound (a1) and the unsaturated monocarboxylic acid (a2) can be reacted by dissolving in an organic solvent. 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, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic carbonization such as octane and decane Petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha can be used.

  In the first reaction, it is preferable to use a catalyst in order to accelerate the reaction. As the catalyst, for example, triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, and the like can be used. It is preferable that the usage-amount of a catalyst shall be 0.1-10 mass parts with respect to a total of 100 mass parts of an epoxy compound (a1) and unsaturated monocarboxylic acid (a2).

  In the first reaction, in order to prevent polymerization between the epoxy compounds (a1) or between the unsaturated monocarboxylic acids (a2) or between the epoxy compound (a1) and the unsaturated monocarboxylic acid (a2), a polymerization inhibitor is used. It is preferable to use it. As the polymerization inhibitor, for example, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like can be used. It is preferable that the usage-amount of a polymerization inhibitor shall be 0.01-1 mass part with respect to a total of 100 mass parts of an epoxy compound (a1) and unsaturated monocarboxylic acid (a2). 60-150 degreeC is preferable and, as for the reaction temperature of a 1st reaction, 80-120 degreeC is more preferable.

  In the first reaction, an unsaturated monocarboxylic acid (a2) and a polybasic acid anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, etc., if necessary Can be used in combination.

  In the second reaction, when the hydroxyl group formed in the first reaction and the hydroxyl group originally present in the epoxy compound (a1) undergo a half-ester reaction with the acid anhydride group of the saturated or unsaturated polybasic acid anhydride (a3). Inferred. Here, 0.1 to 1.0 equivalent of polybasic acid anhydride (a3) can be reacted with 1 equivalent of hydroxyl group in the resin obtained by the first reaction. By adjusting the amount of the polybasic acid anhydride (a3) within this range, the acid value of the component (a) can be adjusted.

  Examples of the resin include CCR-1218H, CCR-1159H, CCR-1222H, PCR-1050, TCR-1335H, ZAR-1035, ZAR-2001H, ZFR-1185, and ZCR-1569H (all manufactured by Nippon Kayaku Co., Ltd.). , Trade names) etc. are commercially available.

  When a compound having a urethane bond is used as the component (a), an epoxy acrylate compound having two or more hydroxyl groups and an ethylenically unsaturated group in the molecule, a diisocyanate compound, and a diol compound having a carboxyl group are reacted. It is preferable to use the polyurethane compound obtained by making it.

  As described above, the polyurethane compound includes an epoxy acrylate compound having two or more hydroxyl groups and an ethylenically unsaturated group (hereinafter referred to as “raw material epoxy acrylate”), a diisocyanate compound (hereinafter referred to as “raw material diisocyanate”), and a carboxyl. It is a compound obtained using a diol compound having a group (hereinafter referred to as “raw diol”) as a raw material component. These raw material components will be described.

  Examples of the raw material epoxy acrylate include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, novolac type epoxy compounds, compounds obtained by reacting (meth) acrylic acid with epoxy compounds having a fluorene skeleton, and the like.

  As said raw material diisocyanate, if it is a compound which has two isocyanate groups, it can apply without a restriction | limiting in particular. For example, phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolden diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, arylene sulfone ether diisocyanate, allyl cyanide diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, norbornane-diisocyanate methyl and the like can be mentioned. These may be used alone or in combination of two or more.

  The raw material diol is a compound having two hydroxyl groups such as an alcoholic hydroxyl group and / or a phenolic hydroxyl group in the molecule and a carboxyl group. The hydroxyl group preferably has an alcoholic hydroxyl group from the viewpoint of improving the developability of the photosensitive resin composition with an alkaline aqueous solution. Examples of such diol compounds include dimethylolpropionic acid and dimethylolbutanoic acid.

  Next, an example of a process for producing a polyurethane compound using the above raw material components will be described.

  In the production process of the polyurethane compound, first, the raw material epoxy acrylate and the raw material diol are reacted with the raw material diisocyanate. In such a reaction, a so-called urethanization reaction occurs mainly between the hydroxyl group in the raw material epoxy acrylate and the isocyanate group in the raw material diisocyanate and between the hydroxyl group in the raw material diol and the isocyanate group in the raw material diisocyanate. By this reaction, for example, a polyurethane compound in which a structural unit derived from a raw material epoxy acrylate and a structural unit derived from a raw material diol are polymerized alternately or in a block manner via a structural unit derived from a raw material diisocyanate is generated.

  An example of such a polyurethane compound is a compound represented by the following general formula (4).

Here, in the general formula (4), R ⁷ is a residue of raw material epoxy acrylate, R ⁸ is a residue of raw material diisocyanate, R ⁹ is an alkyl group having 1 to 5 carbon atoms, and R ¹⁰ is a hydrogen atom or a methyl group. Show. In addition, a residue means the structure of the part remove | excluding the functional group used for the coupling | bonding from the raw material component. In addition, a plurality of groups in the formula may be the same or different. The terminal hydroxyl group of the polyurethane compound may be treated with a saturated or unsaturated polybasic acid anhydride.

  In the production process of the polyurethane compound, a diol compound different from these may be further added in addition to the raw material epoxy acrylate, the raw material diol, and the raw material diisocyanate. Thereby, it becomes possible to change the main chain structure of the obtained polyurethane compound, and the characteristics such as the acid value described later can be adjusted to a desired range. In each of the above steps, a catalyst or the like may be used as appropriate.

  Moreover, you may make the said polyurethane compound and raw material epoxy acrylate react further. In this reaction, a so-called epoxycarboxylation reaction occurs mainly between the carboxyl group derived from the raw material diol compound in the polyurethane compound and the epoxy group of the raw material epoxy acrylate. The compound thus obtained has, for example, a main chain formed from the above polyurethane compound and a side chain containing an ethylenically unsaturated group derived from the raw material epoxy acrylate.

As the polyurethane compound of the present embodiment, among the compounds represented by the general formula (4), a hard segment part of a raw material epoxy acrylate that becomes one of the main skeletons of polyurethane, that is, R ⁷ has a bisphenol A structure. preferable. Such polyurethane compounds are commercially available as UXE-3011, UXE-3012, UXE-3024 (manufactured by Nippon Kayaku Co., Ltd.) and the like. These may be used alone or in combination of two or more. Moreover, the photosensitive resin composition containing this polyurethane compound can improve HAST tolerance more.

  The resin having a carboxyl group as the component (a) exemplified above has an acid value of preferably 20 to 180 mgKOH / g, more preferably 30 to 150 mgKOH / g, and 40 to 120 mgKOH / g. It is particularly preferred that Thereby, the developability with the alkaline aqueous solution of the photosensitive resin composition becomes good, and an excellent resolution can be obtained.

Here, 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 following Formula.
A = 10 × Vf × 56.1 / (Wp × I)
In the 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 nonvolatile content of the measurement resin solution. A ratio (mass%) is shown.

  The weight average molecular weight of the resin having a carboxyl group as component (a) is preferably 3000 to 30000, more preferably 5000 to 20000, and more preferably 7000 to 15000 from the viewpoint of coating properties. Is particularly preferred. These can also be used in combination of two or more resins having different molecular weights.

  In addition, a weight average molecular weight (Mw) can be calculated | required from the standard polystyrene conversion value by a gel permeation chromatography (GPC).

Component (b): a photopolymerizable monomer having at least one ethylenically unsaturated group and a tricyclodecane structure in the molecule. The component (b) used in the present invention contains at least one ethylene in the molecule. It is a photopolymerizable monomer having a polymerizable unsaturated group and a tricyclodecane structure.

  The component (b) is preferably at least one selected from the group consisting of dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate, tricyclodecanediol diacrylate, and tricyclodecanediol dimethacrylate. . These are commercially available as NK ester DCP and NK ester A-DCP (both manufactured by Shin-Nakamura Chemical Co., Ltd.).

  Furthermore, when using what has a urethane bond as said (b) component, it is preferable to use the compound which has the partial structure shown by the following general formula (1) or general formula (2).

“In General Formula (1) and General Formula (2), R ¹ and R ² represent a direct bond, an alkylene, or an arylene group”
The alkylene group is preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and further preferably an alkylene group having 2 to 6 carbon atoms.

  Examples of the alkylene group having 2 to 6 carbon atoms include an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, and a hexylene group. From the viewpoint of resolution and plating resistance, an ethylene group or an isopropylene group. It is preferred that it is ethylene group.

  The arylene group is preferably an arylene group having 6 to 14 carbon atoms, and more preferably an arylene group having 6 to 10 carbon atoms. Examples of such an arylene group include phenylene and naphthylene.

  When the compound having the partial structure represented by the general formula (1) or the general formula (2) is used as the component (b), (b1) a diol compound containing a tricyclodecane structure and (b2) diisocyanate A urethane compound obtained by reacting a compound with (b3) a compound having at least one ethylenically unsaturated group and one hydroxyl group in the molecule is preferable.

  Although there is no restriction | limiting in particular as said (b2) diisocyanate compound, The compound which has a ring structure is preferable. Among these, those having a rigid structure such as isophorone diisocyanate are more preferable from the viewpoint of crack resistance (heat resistance).

  In addition, the compound (b3) having at least one ethylenically unsaturated group and one hydroxyl group in the molecule has two ethylenically unsaturated groups from the viewpoint of crosslinking density. What has three is preferable.

  Among these, the diisocyanate is isophorone diisocyanate, and in addition, a compound having at least one ethylenically unsaturated group and one hydroxyl group in the molecule is represented by the general formula (3). Is more preferable. Examples of such a compound include UX-5002D-M20 (manufactured by Nippon Kayaku Co., Ltd.). These can be used alone or in combination of two or more.

  The component (b) includes at least one selected from the group consisting of dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate, tricyclodecanediol diacrylate and tricyclodecanediol dimethacrylate, and a urethane bond. It is preferable to use together the compound which has the partial structure shown by the said General formula (1) or General formula (2) which has. Thereby, HAST tolerance and high heat resistance (Tg, crack resistance) can be further improved. Moreover, CTE (thermal expansion coefficient) can be reduced more.

(C) Component: Photopolymerization initiator The (c) photopolymerization initiator used in the present invention is not particularly limited as long as it matches the light wavelength of the exposure machine to be used, and a known one can be used. it can. Specifically, for example, benzophenone, N, N′tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1 -[4- (methylthio) phenyl] -2-morpholino-propanone-1,4,4'-bis (dimethylamino) benzophenone (Michler ketone), 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4 ' -Aromatic ketones such as dimethylaminobenzophenone, quinones such as alkylanthraquinone and phenanthrenequinone, benzoin compounds such as benzoin and alkylbenzoin, benzoin ether compounds such as benzoin alkyl ether and benzoin phenyl ether, and benzyl derivatives such as benzyldimethyl ketal 2 (O-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4 , 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- 2,4,5-triarylimidazole dimer such as (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, N-phenylglycine, N-phenylglycine derivative, 9-phenylacridine and the like Oxime derivatives such as acridine derivatives, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)] , Coumarin compounds such as 7-diethylamino-4-methylcoumarin, thioxanthone compounds such as 2,4-diethylthioxanthone, acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. These may be used alone or in combination of two or more.

  From the viewpoint of making the resist shape better, it is preferable to use a phosphine oxide photopolymerization initiator having a photobleaching action. Examples of such compounds include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide as monoacylphosphine oxide, and bis (2,4,6-trimethylbenzoyl) as bisacylphosphine oxide. ) -Phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. These are commercially available as IRGACURE-TPO and IRGACURE-819 (both are trade names, manufactured by Ciba Japan).

  Moreover, it is preferable to contain further the compound which has an acridine ring and the compound which has oxime ester for the purpose of a sensitivity improvement, and these can also be used together. Examples of the compound having an acridine ring include 9-phenylacridine, 9-aminoacridine, 9-pentylaminoacridine, 1,2-bis (9-acridinyl) ethane, and 1,3-bis (9-acridinyl) propane. 1,4-bis (9-acridinyl) butane, 1,5-bis (9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, , 8-bis (9-acridinyl) octane, 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12 -Bis (9-acridinyl) alkanes such as bis (9-acridinyl) dodecane, 9-phenylacridine, 9-pyridylacridyl 9-pyrazinylacridine, 9-monopentylaminoacridine, 1,3-bis (9-acridinyl) -2-oxapropane, 1,3-bis (9-acridinyl) -2-thiapropane, 1,5- Examples include bis (9-acridinyl) -3-thiapentane, and among these, 1,7-bis (9-acridinyl) heptane is more preferable. 1,7-bis (9-acridinyl) heptane is commercially available as N-1717 (manufactured by ADEKA Corporation, trade name). Examples of the compound having the oxime ester include (2- (acetyloxyiminomethyl) thioxanthen-9-one), (1,2-octanedione, 1- [4- (phenylthio)-, 2- (o -Benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime)). Examples of commercially available products include IRGACURE-OXE01 and IRGACURE-OXE02 (both manufactured by Ciba Specialty Chemicals).

(D) Component: Epoxy Resin The (d) epoxy resin that can be used in the photosensitive resin composition of the present invention is not particularly limited, and examples thereof include bisphenol A type epoxy resins such as bisphenol A diglycidyl ether, and bisphenol. Bisphenol F epoxy resin such as F diglycidyl ether, bisphenol S epoxy resin such as bisphenol S diglycidyl ether, biphenol epoxy resin such as biphenol diglycidyl ether, bixylenol epoxy resin such as bixylenol diglycidyl ether, water Examples thereof include hydrogenated bisphenol A type epoxy resins such as hydrogenated bisphenol A glycidyl ether and dibasic acid-modified diglycidyl ether type epoxy resins thereof. These can be used alone or in combination of two or more.

  Commercial products can be used as these compounds. For example, examples of bisphenol A diglycidyl ether include Epicoat 828, Epicoat 1001, and Epicoat 1002 (all are trade names manufactured by Japan Epoxy Resin Co., Ltd.). Examples of bisphenol F diglycidyl ether include Epicoat 807 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), and examples of bisphenol S diglycidyl ether include EBPS-200 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and Epicron EXA-1514 (manufactured by Dainippon Ink & Chemicals, Inc., trade name) and the like can be mentioned. Examples of the biphenol diglycidyl ether include YL-6121 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.). Examples of the bixylenol diglycidyl ether include YX-4000 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.). Etc. Furthermore, examples of the hydrogenated bisphenol A glycidyl ether include ST-2004 and ST-2007 (both manufactured by Tohto Kasei Co., Ltd., trade names), and the above-mentioned dibasic acid-modified diglycidyl ether type epoxy resin. ST-5100 and ST-5080 (both manufactured by Tohto Kasei Co., Ltd., trade names) and the like can be mentioned.

(E) Component: Silica Filler Next, (e) silica filler will be described. The silica filler that can be used in the present invention uses a silane coupling agent in order to disperse it in the resin without agglomeration while maintaining the primary particle size. As the silane coupling agent, generally available ones can be used, for example, alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acrylic silane, methacryl silane, mercapto silane, sulfide silane, isocyanate silane, Sulfur silane, styryl silane, alkylchlorosilane, and the like can be used. Specific compound names include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxy. Silane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxy Silane, triphenylsilanol, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, n-octyldi Tylchlorosilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane , 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane Bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Lutriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3 -Mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylden) -3-aminopropyltriethoxysilane, aminosilane and the like.

  What is desirable as the silane coupling agent to be used is that (a) contained in the photosensitive resin composition reacts with a carboxyl group of a photo-radical reactive resin having at least one ethylenically unsaturated group and a carboxyl group in the molecule. For example, epoxy silane, mercapto silane, and isocyanate silane are desirable. These silane coupling agents enhance the bond between silica and resin, so that when used as a permanent mask resist, the strength of the film can be increased, and at the same time the thermal expansion coefficient can be greatly reduced. Contributes to cracking and the like.

  Acrylic silane or methacrylic silane may also be used. (B) It is thought that it reacts with the ethylenically unsaturated group of the photopolymerizable monomer having an ethylenically unsaturated group and exhibits the same effect as when the silane coupling agent is used.

  The usage-amount of a silica filler is 20-70 mass parts (20-70 mass%) with respect to 100 mass parts of total mass parts, and 30 mass parts or more from a viewpoint of a thermal expansion coefficient reduction, and a viewpoint of coating-film property. Is preferably 60 parts by mass or less.

  In addition to the above-described components (a) to (e), the photosensitive resin composition may further include other components according to desired characteristics.

  Examples of the other component include a photopolymerizable monomer having at least one ethylenically unsaturated group in the molecule, which is different from the component (b). Depending on the required properties, these photopolymerizable monomers can be appropriately selected and used in addition to the component (b).

  Specific examples of such compounds include bisphenol A (meth) acrylate compounds, compounds obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids, and glycidyl group-containing compounds with α, β- Examples thereof include a compound obtained by reacting an unsaturated carboxylic acid, a urethane monomer such as a (meth) acrylate compound having a urethane bond in the molecule, or a urethane oligomer. Besides these, nonylphenoxy polyoxyethylene acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloyloxy Examples thereof include phthalic acid compounds such as alkyl-o-phthalate, (meth) acrylic acid alkyl ester, and EO-modified nonylphenyl (meth) acrylate.

  In order to improve the alkali developability, it is preferable to use a bisphenol A-based (meth) acrylate compound in combination with the component (b). Examples of bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy). ) Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc. Is mentioned. One or more of these can be used in combination.

  In order to improve the sensitivity and resolution, among the above, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane is preferably used in combination with the component (b).

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy nonaethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ( (Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, and 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like. These can be used alone or in combination of two or more.

  Among the above compounds, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is FA-321M (manufactured by Hitachi Chemical Co., Ltd., trade name) or BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.). , And commercially available as trade name), and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). Are available.

  Examples of 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-(( (Meth) acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl ) Propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxynonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, and 2,2-bis (4-(( (Meth) acryloxyhexadecapropoxy) phenyl) propane and the like.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane, Examples include 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane. .

  In order to improve the balance of adhesion, resolution and electric corrosion resistance, it is preferable to use a compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol in combination with the component (b). .

  Examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups. Polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO / PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) A Chlorate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified glyceryl tri (meth) acrylate, PO-modified glyceryl tri (meth) acrylate, EO Examples thereof include PO-modified glyceryl tri (meth) acrylate.

“EO” refers to “ethylene oxide”, and “PO” refers to “propylene oxide”. Further, “EO modified” means having a block structure of ethylene oxide units (—CH ₂ —CH ₂ —O—), and “PO modified” means propylene oxide units (—CH ₂ —CH ₂ —CH _2). -O-) or isopropylene oxide units _{(-CH 2 -CH (CH 3)} -O -, - CH (CH 3) means having a block structure of -CH 2 -O-).

  Examples of the compound obtained by reacting the glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4- (meta ) Acryloxy-2-hydroxy-propyloxy) phenyl and the like. Examples of the α, β-unsaturated carboxylic acid for obtaining the above compound include (meth) acrylic acid.

  Examples of urethane monomers or urethane oligomers such as (meth) acrylate compounds having a urethane bond in the molecule include (meth) acrylic monomers having an OH group at the β-position, isophorone diisocyanate, and 2,6-toluene. Addition reaction products with diisocyanate compounds such as diisocyanate, 2,4-toluene diisocyanate and 1,6-hexamethylene diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meta ) Acrylate, and EO or PO-modified urethane di (meth) acrylate.

  Furthermore, when (meth) acrylic acid alkyl ester is used in combination with component (b), for example, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, ( And (meth) acrylic acid 2-ethylhexyl ester and 2-hydroxyethyl (meth) acrylate.

  Other examples of the component include a diluent. Examples of the diluent include aliphatic alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, n-pentanol and hexanol, hydrocarbons such as benzyl alcohol and cyclohexane, diacetone alcohol, Aliphatic ketones such as 3-methoxy-1-butanol, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, methyl hexyl ketone, ethyl butyl ketone, dibutyl ketone, ethylene glycol, diethylene glycol, tri Ethylene glycol, tetraethylene glycol, propylene glycol, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate, pro Ethylene glycol alkyl ethers such as lenglycol diacetate, propylene glycol monoethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate And its acetate, diethylene glycol monoalkyl ether and its acetate diethylene glycol dialkyl ether, triethylene glycol alkyl ether, propylene glycol alkyl ether and its acetate, dipropylene glycol alkyl ether, and toluene, petroleum ether, petroleum naphtha, Hydrogenated petroleum naphtha Or petroleum solvents such as solvent naphtha, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, etc. Acid esters, amines, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dioxane, tetrahydrofuran, cyclohexanone, γ-butyrolactone, 3- Solvents such as hydroxy-2-butanone, 4-hydroxy-2-pentanone and 6-hydroxy-2-hexanone can be used alone or in combination of two or more.

  Furthermore, the photosensitive resin composition of the present invention is a melamine, dicyandiamide, triazine compound and derivatives thereof, imidazole, thiazole, and triazole as adhesion improvers, particularly when adhesion with a metal such as copper is required. Additives such as systems and silane coupling agents can be used. Examples include melamine, acetoguanamine, benzoguanamine, melamine-phenol-formalin resin, dicyandiamide, manufactured by Shikoku Kasei Kogyo Co., Ltd .; 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK and the like. Alternatively, triazine derivatives such as ethyldiamino-s-triazine, 2,4-diamino-s-triazine, and 2,4-diamino-6-xylyl-s-triazine are exemplified. These compounds increase adhesion with a copper circuit and improve PCT resistance, and are also effective in HAST resistance. These are preferably used in an amount of 0.1 to 10% by mass based on 100 parts by mass of the total amount of components (a) to (c).

  If necessary, use colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, malachite green, crystal violet, titanium oxide, carbon black, naphthalene black, azo organic pigments, dyes, etc. it can. Furthermore, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol and phenothiazine, thixotropic agents such as benton, montmorillonite, aerosil and amide wax, antifoaming agents such as silicone, fluorine and polymer Leveling agents can be used.

  The content of each component in the photosensitive resin composition is preferably 30 to 80 parts by mass with respect to 100 parts by mass of the total amount of the component (a) and the component (a). It is more preferable to set it as 40-75 mass parts, and it is especially preferable to set it as 50-70 mass parts. When the content of the component (a) is within this range, the coating property of the photosensitive resin composition and the strength of the photocured product become better, and characteristics such as developability, resolution, solder heat resistance and gold plating resistance are obtained. Without impairing the resistance, the HAST resistance between fine wirings is excellent and the heat resistance is high.

  The content of the component (b) is preferably 20 to 70 parts by mass and more preferably 25 to 60 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). 30 to 50 parts by mass is particularly preferable. When the content of the component (b) is within this range, the photosensitivity and coating property of the photosensitive resin composition become better.

  The content of each component (c) and (d) in the photosensitive resin composition is 0.1 to 10 parts by mass of component (c) with respect to 100 parts by mass in total of components (a) and (b). It is preferable to mix | blend, and it is preferable that a component (d) is 3-50 mass parts, and it is more preferable in it being 5-40 mass parts.

[Photosensitive film]
Next, the photosensitive film of suitable embodiment is demonstrated. The photosensitive film which concerns on this invention consists of a photosensitive laminated body provided with the support body and the photosensitive resin composition layer which consists of the photosensitive resin composition of this invention formed on this support body. . On the photosensitive resin composition layer, you may further provide the protective film which coat | covers this photosensitive resin composition layer.

  As the support, for example, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used. The thickness of the support (polymer film) is preferably 5 to 25 μm. If the thickness is less than 5 μm, the support film tends to be broken when the support film is peeled off before development. If it exceeds, the resolution tends to decrease. In addition, you may use the said polymer film laminated | stacked on both surfaces of the photosensitive resin composition layer as a support body and a protective film.

  As the protective film, for example, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used. Examples of commercially available products include polypropylene film such as product names “Alphan MA-410” and “E-200C” manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and product name “PS-” manufactured by Teijin Limited. Polyethylene terephthalate film such as PS series such as “25” can be mentioned, but is not limited thereto. The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, further preferably 5 to 30 μm, and particularly preferably 15 to 30 μm. If this thickness is less than 1 μm, the protective film tends to be broken during lamination, and if it exceeds 100 μm, the cost tends to be inferior. The protective film preferably has a smaller adhesive strength between the photosensitive resin composition layer and the protective film than the adhesive strength between the photosensitive resin composition layer and the support, and is preferably a low fisheye film. . Fisheye is a material in which foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are incorporated into the film when the material is melted and kneaded, extruded, biaxially stretched, or casted to produce a film. It is.

  The photosensitive resin composition layer is prepared by dissolving the photosensitive resin composition of the present invention in a diluent (solvent) as described above to obtain a solution (coating liquid) having a solid content of about 30 to 70% by mass. Such a solution (coating solution) is preferably formed by coating on a support and drying. The application can be performed by a known method using, for example, a roll coater, comma coater, gravure coater, air knife coater, die coater, bar coater or the like. Moreover, the said drying can be performed at 70-150 degreeC and about 5 to 30 minutes. The amount of the remaining organic solvent in the photosensitive resin composition is preferably 3% by mass or less with respect to the total amount of the photosensitive resin composition from the viewpoint of preventing diffusion of the organic solvent in the subsequent step. Although the thickness of the said photosensitive resin layer changes with uses, it is preferable that it is 5-200 micrometers by thickness after drying, it is more preferable that it is 15-60 micrometers, and it is especially preferable that it is 20-50 micrometers. If the thickness is less than 5 μm, it tends to be difficult to apply industrially, and if it exceeds 200 μm, the sensitivity and resolution inside the photosensitive resin composition layer tend to be lowered.

  The photosensitive film may further have an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer. Moreover, the obtained photosensitive film can be wound up and stored in a sheet form or a roll around a core. In addition, it is preferable to wind up so that a support body may become the outermost part in this case. From the viewpoint of end face protection, it is preferable to install an end face separator on the end face of the roll-shaped photosensitive film roll, and it is preferable to install a moisture-proof end face separator from the viewpoint of edge fusion resistance. Moreover, as a packing method, it is preferable to wrap and package in a black sheet with low moisture permeability. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

[Method of forming resist pattern]
Next, a method for forming a resist pattern using the photosensitive film of the present invention will be described.

  A photosensitive layer made of the above-described photosensitive resin composition is formed on a substrate on which a resist is to be formed. The protective film of the photosensitive film is peeled from the photosensitive resin composition layer, and the exposed surface is adhered by a laminate or the like so as to cover the conductor layer having a circuit pattern formed on the substrate. A method of laminating under reduced pressure is also preferable from the viewpoint of improving adhesion and followability. In addition, the photosensitive resin composition can also be apply | coated on a board | substrate by well-known methods, such as the method of apply | coating the varnish of the photosensitive resin composition with a screen printing method or a roll coater.

  Next, an exposure process is performed through which a predetermined portion of the photosensitive resin composition layer is irradiated with actinic rays through the mask pattern, and the photosensitive resin composition layer in the irradiated portion is photocured.

  Further, when a support is present on the photosensitive layer, after removing the support, by removing a portion that has not been photocured by wet development or dry development (unexposed portion) and developing, A resist pattern can be formed.

  In the case of the above-described wet development, as the developer, an alkaline aqueous solution, an aqueous developer, an organic solvent or the like that is safe and stable and has good operability is used corresponding to the type of the photosensitive resin composition. Further, as a developing method, a known method such as spraying, rocking dipping, brushing, scraping or the like is appropriately employed.

  Examples of the base of the alkaline aqueous solution include alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide which are hydroxides of lithium, sodium and potassium, carbonates or bicarbonates such as alkali metals and ammonium. Alkaline carbonate or bicarbonate, alkali metal phosphate sodium phosphate, potassium phosphate, etc., alkali metal pyrophosphate sodium pyrophosphate, potassium pyrophosphate etc., safe and stable, operability The one with good is used.

  Examples of the alkaline aqueous solution include a dilute solution of 0.1 to 5% by mass of sodium carbonate, a dilute solution of 0.1 to 5% by mass of potassium carbonate, and a dilute solution of 0.1 to 5% by mass of sodium hydroxide. A solution, a dilute solution of 0.1 to 5% by mass sodium tetraborate is preferred, and the pH is preferably in the range of 9 to 11. The temperature of the alkaline aqueous solution is adjusted according to the developability of the photosensitive layer, and is preferably 20 to 50 ° C. Furthermore, a small amount of an organic solvent such as a surfactant or an antifoaming agent may be mixed in the alkaline aqueous solution in order to promote development.

  As the aqueous developer, one comprising water and an alkaline aqueous solution or one or more organic solvents is used. Here, as the base of the alkaline aqueous solution, in addition to those described above, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3- Examples include propanediol, 1,3-diaminopropanol-2, and morpholine. The pH of such an aqueous developer is preferably as small as possible within a range where development processing can be sufficiently performed, preferably pH 8 to 12, and more preferably pH 9 to 10.

  Examples of the organic solvent include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. . The concentration of such an organic solvent is usually preferably 2 to 90% by mass. 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. Furthermore, a small amount of an organic solvent such as a surfactant or an antifoaming agent may be mixed in the alkaline aqueous solution in order to promote development.

  In the method for forming a resist pattern 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 most suitable for improving resolution. For the etching of the metal surface performed after development, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or the like can be used.

[Preferred embodiment of photosensitive permanent resist]
A preferred embodiment of a photosensitive permanent resist using the photosensitive film of the present invention will be described.

After the development step, it is preferable to perform ultraviolet irradiation or heating with a high-pressure mercury lamp for the purpose of improving solder heat resistance and chemical resistance. In the case of irradiating ultraviolet rays, the irradiation amount can be adjusted as necessary, and for example, irradiation can be performed at an irradiation amount of about 0.05 to 10 J / cm ² . Moreover, when heating a resist pattern, it is preferable to carry out for about 15 to 90 minutes in the range of about 130-200 degreeC.

  Both ultraviolet irradiation and heating may be performed. In this case, both may be performed at the same time, and after either one is performed, the other may be performed. When performing ultraviolet irradiation and heating simultaneously, it is preferable to heat to 60-150 degreeC from a viewpoint of providing solder heat resistance and chemical resistance more favorably.

  The photosensitive permanent resist formed in this way also serves as a protective film for the wiring after soldering the substrate, and has various characteristics of a solder resist, for printed wiring boards, for semiconductor package boards, flexible wiring boards It can be used as a solder resist.

  The solder resist, for example, is used as a plating resist or an etching resist when plating or etching is performed on a substrate, and is also left on the substrate as it is to protect a wiring or the like (photosensitive permanent). Resist).

  Further, in the above exposure step, when exposure is performed using a mask or drawing data having a pattern in which a predetermined portion of the conductor layer is unexposed, the unexposed portion is removed by developing this, and the substrate A resist having an opening pattern in which a part of the conductor layer formed thereon is exposed is obtained. Thereafter, it is preferable to perform a treatment necessary for forming the photosensitive permanent resist.

  Thereafter, the substrate provided with the photosensitive permanent resist is mounted with a semiconductor element or the like (for example, wire bonding, C4 solder connection), and is mounted on an electronic device such as a personal computer.

  The present invention has been described in detail based on the embodiments. However, the present invention is not limited to the above embodiment, and various modifications can be made without departing from the scope of the invention.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

(Preparation of photosensitive film)
The photosensitive resin composition solutions of Examples 1 to 6 and Comparative Examples 1 to 6 were obtained by mixing the components shown in Table 1 and Table 2 at the mixing ratio (mass basis) shown therein. Note that methyl ethyl ketone was used as the diluent.

The following were used as each component shown in Table 1 and Table 2.
(A) Component EXP-2811: Acid-modified cresol novolac type epoxy acrylate (manufactured by DIC Corporation, trade name)
ZFR-1158: Bisphenol F type epoxy acrylate (Nippon Kayaku Co., Ltd., trade name)
CCR-1219H: Cresol novolac type epoxy acrylate (Nippon Kayaku Co., Ltd., trade name)
UXE-3024: Urethane-modified epoxy acrylate (trade name, manufactured by Nippon Kayaku Co., Ltd.)
Resin (1): Acrylic copolymer (methacrylic acid, methyl methacrylate, butyl acrylate copolymer, weight average molecular weight 60000, acid value 110 mg KOH / g, ZP-18, manufactured by Hitachi Chemical Co., Ltd.)
(B) Component DCP: Tricyclodecane dimethanol dimethacrylate (made by Shin-Nakamura Chemical Co., Ltd., trade name)
UX-5002D-M20: Tricyclodecane structure-containing urethane acrylate (trade name, manufactured by Nippon Kayaku Co., Ltd.)
(C) Component TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Darocur TPO, manufactured by Ciba Japan, trade name)
OXE-02: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (Irgacure OXE-02, Ciba Japan Product name)
(D) Component NC-3000H: biphenyl aralkyl type epoxy resin (epoxy equivalent 286, manufactured by Japan Epoxy Resin Co., Ltd.)
(Other ingredients)
BL-3175: Block type isocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name)
Hitaloid 9082: Urethane acrylate (trade name, manufactured by Hitachi Chemical Co., Ltd.)
DPHA: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd., trade name)
FA-321M: Bisphenol A polyoxyethylene dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., trade name)
Dicyandiamide (trade name, manufactured by Japan Epoxy Resin Co., Ltd.)
Melamine (product name, manufactured by Nissan Chemical Industries, Ltd.)
Phthalocyanine blue (manufactured by Toyo Ink Manufacturing Co., Ltd.)
(E) Component The following materials were used for the silica filler component.
Silica A: Silica filler having an average particle diameter of 50 nm and a silane coupling agent as a silane coupling agent, coupling treatment with methacrylic silane 3-methacryloxypropyltrimethoxysilane, (a) Carboxyl group and ethylenically unsaturated group in the molecule And dispersed in a resin having at least one. The dispersion state was measured using a dynamic light scattering nanotrack particle size distribution analyzer “UPA-EX150” (manufactured by Nikkiso Co., Ltd.), and it was confirmed that the maximum particle size was 1 μm or less.
Silica B: Silica filler dispersion SC2050 (manufactured by Admatechs Co., Ltd.) having an average particle diameter of 1 μm and dispersed in slurry in methyl ethyl ketone was used. The dispersion state was measured using a laser diffraction / scattering microtrack particle size distribution analyzer “MT-3100” (manufactured by Nikkiso Co., Ltd.). It was confirmed that the maximum particle size was about 3 μm.

  The barium sulfate dispersion as a filler was adjusted by the following method. The photopolymerizable monomer having at least one ethylenically unsaturated group in the molecule, which is different from the component (b) or the component (b), barium sulfate 50 parts by mass, melamine 2.0 parts by mass, methyl ethyl ketone 50 parts by mass The portion was dispersed with a star mill LMZ (manufactured by Ashizawa Finetech Co., Ltd.) using zirconia beads having a diameter of 1.0 mm for 3 hours at a peripheral speed of 12 m / s to prepare a barium sulfate dispersion.

  Next, a photosensitive resin composition layer is formed by uniformly coating the prepared photosensitive resin composition solution on a 16 μm-thick polyethylene terephthalate film (G2-16, trade name, manufactured by Teijin Ltd.) as a support layer. It was dried at 100 ° C. for about 10 minutes using a hot air convection dryer. The film thickness after drying of the photosensitive resin composition layer was 25 μm.

  Subsequently, a polyethylene film (NF-15, manufactured by Tamapoly Co., Ltd., trade name) is bonded as a protective film on the surface of the photosensitive resin composition layer opposite to the side in contact with the support layer, and the support layer / Photosensitive resin composition layer / A photosensitive film having a protective film was obtained.

(Characteristic evaluation)
[Evaluation of resolution]
The resist shape was evaluated as an index of resolution. The copper surface of a printed wiring board substrate (MCL E-679, manufactured by Hitachi Chemical Co., Ltd., trade name) obtained by laminating a 12 μm thick copper foil on a glass epoxy substrate was polished with an abrasive brush, washed with water, and then dried. . On this printed wiring board substrate, using a continuous press type vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd., trade name), press hot plate temperature 70 ° C., vacuuming time 20 seconds, laminating press time 30 seconds. The protective film of the photosensitive film was peeled off and laminated under the conditions of an atmospheric pressure of 4 kPa or less and a pressure bonding pressure of 0.4 MPa to obtain a laminate for evaluation.

Then, after standing at room temperature for 1 hour or longer, a 21-step tablet (manufactured by Eastman Kodak Co., Ltd.) was brought into close contact with the support of the obtained laminate for evaluation, and parallel light exposure using an ultrahigh pressure mercury lamp as a light source. Exposure was carried out using an exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.). After being exposed to room temperature (25 ° C.) for 30 minutes after exposure, the support was removed from the polyethylene terephthalate film, and the photosensitive resin composition in the unexposed area was spray-developed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 60 seconds. . After development, the exposure energy amount at which the number of remaining step steps of the 21-step tablet was 8.0 was determined as the optimum exposure amount (unit: mJ / cm ² ) of the photosensitive resin composition layer.

  Subsequently, the evaluation laminate obtained in the same manner at the optimum exposure amount obtained above was allowed to stand at room temperature for 1 hour or longer, and then exposed using a parallel light exposure method via a negative pattern having an opening pattern with a diameter of 60 μm. Exposure was performed using a machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.).

After exposure, it is allowed to stand at room temperature for 30 minutes, the polyethylene terephthalate film on the support is removed, and the photosensitive resin composition in the unexposed area is developed with a 1% by mass sodium carbonate aqueous solution at 30 ° C. Spray development in 1.5 times the minimum time). After spray development, UV irradiation of 1 J / cm ² is performed using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd., followed by heat treatment at 160 ° C. for 60 minutes to form a permanent mask resist pattern having an opening with a diameter of 60 μm. Formed.

Subsequently, the cross section in the opening part with a diameter of 60 micrometers of the resist pattern was observed using the S-2100A scanning electron microscope by Hitachi, Ltd. The resist shape of the opening is preferably a “forward taper” shape or a “straight” shape in terms of cross-sectional shape from the viewpoint of solder adhesion. The bottom of the resist elutes at the time of development due to underexposure, and the reverse taper shape such as “underhang” or the top of the resist remains protruding due to overexposure. Adhesion may deteriorate, which is not preferable. Evaluation of resist shape is “3” when the cross-sectional shape of the resist opening is a forward taper type or straight type, and “2” when overhang or undercut of 5 μm or less occurs. A case where a hang or undercut was generated and a complete reverse taper shape was evaluated as “1”.
[Production of evaluation substrate]
Printed wiring board substrate (MCL E) with 12μm thick copper foil laminated on glass epoxy substrate
-679, a product name of Hitachi Chemical Co., Ltd., trade name) was polished with an abrasive brush, washed with water and dried. On this printed wiring board substrate, using a continuous press type vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd., trade name), press hot plate temperature 70 ° C., vacuuming time 20 seconds, laminating press time 30 seconds. The polyethylene film of the photosensitive film was peeled off and laminated under the conditions of an atmospheric pressure of 4 kPa or less and a pressure bonding pressure of 0.4 MPa to obtain a laminate for evaluation.

  A photo tool having a 2 mm square pattern as a negative is brought into close contact with the laminate for evaluation, and the number of remaining steps after development of the stove 21-step tablet using an EXM-1201 type exposure machine manufactured by Oak Manufacturing Co., Ltd. Was exposed with an energy amount of 8.0. Subsequently, after leaving still at room temperature (25 degreeC) for 1 hour, the polyethylene terephthalate film on the said laminated body is peeled off, and the minimum image development time (minimum in which an unexposed part is developed) with 30 mass% 1 mass% sodium carbonate aqueous solution. Spray development was performed in 2.0 times the time) to form a pattern.

Subsequently, by using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd., an ultraviolet ray is irradiated with an energy amount of 1 J / cm ² , and further a heat treatment is performed at 160 ° C. for 60 minutes, whereby a solder resist having a 2 mm square opening. A laminated substrate for evaluation was formed.

[Evaluation of gold plating properties]
The evaluation laminate substrate on which the solder resist having a 2 mm square opening is formed is plated using a commercially available electroless nickel / gold plating solution so that the nickel plating thickness is 5 μm and the gold plating thickness is 0.1 μm. The appearance of the solder resist was observed with a stereomicroscope and evaluated according to the following criteria. That is, “3” indicates that the solder resist is not whitened around the opening, “2” indicates that whitening or peeling occurs at 10 μm or less, and “1” indicates that whitening or peeling greatly occurs. As evaluated. The results are shown in Tables 3 and 4.

[Evaluation of HAST resistance]
Comb type with 25μm / 25μm line / space etched by etching the copper surface of printed wiring board substrate (MCL E-679, Hitachi Chemical Co., Ltd., trade name) with 12μm thick copper foil laminated on glass epoxy substrate It processed into the electrode and made this the evaluation board | substrate.

On the comb-shaped electrode on this evaluation substrate, a solder resist made of a cured resist is formed in the same manner as in the above-mentioned “production of the evaluation substrate” (exposure is performed so that the solder resist remains on the comb-shaped electrode portion, development, and ultraviolet irradiation) Then, the film was exposed to heat treatment at 130 ° C., 85% RH, and 20 V for 100 hours. Thereafter, the resistance value was measured and the degree of migration was observed with a 100-fold metal microscope, and evaluated according to the following criteria. That is, the resistance value was maintained at 1.0 × 10 ¹⁰ Ω or more even after 100 hours of exposure, and no migration occurred in the solder resist film even after 100 hours of exposure for a total of 200 hours. 4 ”, a slight migration occurs in the solder resist film after 200 hours, but“ 100 ”indicates that no migration occurred after 100 hours, and the resistance value becomes 1.0 × 10 ¹⁰ after 100 hours. The value of Ω or higher was maintained, but a slight migration was evaluated as “2”, a resistance value of 1.0 × 10 ¹⁰ Ω or less, and a large migration was evaluated as “1”. The results are shown in Tables 3 and 4.

[Evaluation of Tg]
On the 16 μm thick polyethylene terephthalate film (G2-16, manufactured by Teijin Ltd., trade name), a cured product of the solder resist is formed as described above (the entire surface is exposed to development, ultraviolet irradiation, and heat treatment). Formation) Then, after cutting out to 3 mm in width and 30 mm in length with a cutter knife, the polyethylene terephthalate on the laminate was peeled off to obtain a cured photosensitive resin for thermal expansion coefficient evaluation. Using a TMA apparatus SS6000 (manufactured by Seiko Instruments Inc.), the coefficient of thermal expansion in the tensile mode was measured. The tensile load is 2 g, the span (distance between chucks) is 15 mm, and the heating rate is 10 ° C./min. First, the sample was attached to the apparatus, heated from room temperature (25 ° C.) to 160 ° C., and left for 15 minutes. Then, it cooled to -60 degreeC and measured on conditions with a temperature increase rate of 10 degree-C / min from -60 degreeC to 250 degreeC. The inflection point seen in the range from 25 ° C. to 200 ° C. is Tg, and the temperature at that time is “4” when the temperature is 120 ° C. or higher, “3” when the temperature is from 100 ° C. to less than 120 ° C., and from 80 ° C. to 80 ° C. The evaluation was made as “2” for the temperature lower than 80 ° C. and “1” for the temperature lower than 80 ° C. The results are shown in Tables 3 and 4.
[Evaluation of CTE]
A CTE (linear thermal expansion coefficient) equal to or less than Tg simultaneously obtained by the measurement of the Tg evaluation was compared. The CTE of less than 50 ppm was evaluated as “4”, 50 ppm or more and less than 55 ppm as “3”, 55 ppm or more and less than 60 ppm as “2”, and 60 ppm or more as “1”. The results are shown in Tables 3 and 4.

[Evaluation of crack resistance]
After the evaluation laminate substrate on which the solder resist was formed in the same manner as in the above-mentioned “production of the evaluation substrate” was exposed to the air at −65 ° C. for 15 minutes, the temperature was increased at a temperature increase rate of 180 ° C./min. After being exposed to the atmosphere at 150 ° C. for 15 minutes, a thermal cycle in which the temperature was lowered at a rate of 180 ° C./min was repeated 1000 times. After being exposed to such an environment, cracks and peeling of the permanent resist film of the evaluation laminate substrate were observed with a 100-fold metal microscope and evaluated according to the following criteria. In other words, “3” means that the cracks and peeling of the permanent resist film were not observed at all after confirming 10 places of the 2 mm square openings, and those where cracks and peeling were observed in 2 or less of the 10 places. “2” was evaluated as “1” when cracking and peeling were observed at 3 or more of 10 locations. The results are shown in Tables 3 and 4.

  From Tables 3 and 4, the photosensitive resin composition of the present invention has a HAST resistance and a high heat resistance (Tg, in particular) in addition to various properties generally required in solder resists such as resolution and gold plating resistance. It turns out that it is excellent in (crack resistance). It can also be seen that it is effective in reducing CTE.

Claims (4)

(A) component: a radically reactive resin having at least one ethylenically unsaturated group and a carboxyl group in the molecule;
(B) component: a photopolymerizable monomer having at least one ethylenically unsaturated group and a tricyclodecane structure in the molecule;
(C) component: photopolymerization initiator,
(D) component: an epoxy resin, and (e) component: a photosensitive resin composition containing a silica filler, wherein the silica filler as the component (e) has an average particle diameter of 3 to 300 nm and is photosensitive. Photosensitive resin composition in which the maximum particle size is dispersed at 1 μm or less in the photosensitive resin composition, and the filling amount is 20 to 70% by mass in the total mass.   The component (b) includes one or more selected from the group consisting of dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate, tricyclodecanediol diacrylate, and tricyclodecanediol dimethacrylate. Item 2. A photosensitive resin composition according to Item 1. The photosensitive film provided with the support body and the photosensitive resin composition layer containing the photosensitive resin composition of Claim 1 or 2 formed on this support body. The permanent resist which consists of the hardened | cured material of the photosensitive resin composition of Claim 1 or 2 formed on the board | substrate for printed wiring boards.