JP5625721B2 - Photosensitive resin composition and photosensitive element using the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition for printed wiring boards, semiconductor package substrates, and flexible wiring boards, and a photosensitive element using the same.

  With the reduction in size and weight of various electronic devices, photosensitive solder resists capable of forming fine opening patterns are used for printed wiring boards, semiconductor package boards, flexible wiring boards, and the like.

  The solder resist generally requires characteristics such as developability, insulation reliability, solder heat resistance and gold plating resistance. In particular, in recent years, in addition to the above characteristics, high-density integration of package substrates has progressed, and high resolution, good via shape, and surface smoothness of solder resists associated with circuit miniaturization are required.

  As the photosensitive resin composition for solder resist, a liquid photosensitive resin composition is usually used particularly in the field of printed wiring boards. Then, a solder resist is formed from a two-part type photosensitive resin composition obtained by separately dividing a thermosetting epoxy resin and a photosensitive prepolymer containing a carboxylic acid group for imparting alkali developability. Is common. As the photosensitive prepolymer, an alkali developable photosensitive prepolymer which is obtained by adding acrylic acid to a cresol novolak type epoxy resin and then acid-modifying with an acid anhydride or the like is widely used (for example, see Patent Document 1). .

  Since the reaction of the carboxylic acid group of the epoxy resin and the photosensitive prepolymer proceeds at room temperature, the storage stability (pot life) after mixing the two liquids is from a few hours. The usage conditions are limited, such as being short and short and having to be mixed immediately before use. In order to avoid such problems, in recent years, a one-component type photosensitive resin composition has been proposed in which storage stability is improved by using a blocked isocyanate compound instead of an epoxy resin as a thermosetting agent (for example, Patent Document 2).

  On the other hand, in recent years, a photosensitive resin composition for a dry film type solder resist has been strongly desired from the viewpoint of improving film thickness uniformity, surface smoothness, thin film forming property, and handleability. According to such a photosensitive resin composition, in addition to the above characteristics, effects such as simplification of a process for forming a solder resist and reduction of a solvent discharge amount at the time of forming the solder resist are obtained. So far, various photosensitive resin compositions for dry film type solder resists have been developed. For example, in Patent Document 3, a photosensitive film containing a polymer having a carboxyl group, a photopolymerizable compound, a photopolymerization initiator, and a bismaleimide compound is used as an anhydride group of a maleic anhydride copolymer in Patent Document 4. On the other hand, a photosensitive film containing a copolymer obtained by reacting 0.1 to 1.2 equivalents of a primary amine compound, a polymerizable compound and a photopolymerization initiator is disclosed.

JP-A 61-243869 JP 2001-305726 A JP 2004-287267 A JP 2005-316431 A

  The dry film type photosensitive solder resist can use a vacuum press laminator at the time of lamination, and is very advantageous in terms of circuit followability, bottomed via / through hole filling property, and surface smoothness. In laminating, in order to flow the resin layer and obtain good surface smoothness and hole filling properties, it is usual to perform pressing while heating. However, when the lamination is performed at a high temperature, there is a possibility that a development residue due to hot fog is generated. On the other hand, when laminating at a low temperature, the resin layer does not flow sufficiently, and good surface smoothness and hole filling properties tend to be difficult to obtain.

  With the progress of high-density integration of package substrates, circuit miniaturization and bump diameter reduction, solder resist thinning has progressed, and further improvements in resistance to gold plating and various reliability tests are required. In particular, the floating of the solder resist around the opening via, which is said to be a whitening phenomenon, is a big problem in the gold plating process.

  An object of the present invention is to provide a photosensitive resin composition capable of forming a dry film type solder resist excellent in laminating temperature tolerance and gold plating resistance and capable of alkali development, and a photosensitive element using the same. To do. In the present specification, being excellent in the tolerance of the laminating temperature means that there is little development residue even when laminating at a high temperature of 90 ° C., for example, and there is no practical problem.

  The present invention includes (a) an acid-modified vinyl group-containing epoxy resin, (b) a photopolymerizable compound having an ethylenically unsaturated group, (c) a photopolymerization initiator, (d) a thermosetting compound, (e) 1 It contains an organic peroxide having a time half-life temperature of 100 to 200 ° C. and (f) a binder polymer, and (e) the content of the organic peroxide is (a) an acid-modified vinyl group-containing epoxy resin, (b The photosensitive resin composition which is 0.01-5 mass parts is provided with respect to a total of 100 mass parts of the photopolymerizable compound which has an ethylenically unsaturated group, and the said (f) binder polymer.

  According to the photosensitive resin composition, a dry film type solder resist excellent in laminating temperature tolerance and gold plating resistance can be formed, and a photosensitive resin composition capable of alkali development can be provided.

  When the (a) acid-modified vinyl group-containing epoxy resin is a compound having a urethane bond, a more uniform photosensitive resin composition can be easily obtained. In addition, since the photosensitive resin composition can form a cured product that is tough and excellent in elongation, the crack resistance and HAST resistance (highly accelerated stress test) of the cured product can be improved.

  Further, when the photopolymerization initiator (c) contains a compound represented by the following general formula (I), the sensitivity and the resist shape when forming a solder resist using the photosensitive resin composition of the present invention are further improved. Can be improved.

式（Ｉ）中、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に炭素数１〜６のアルキル基又は炭素数１〜４のアルコキシ基を示し、ｎ１、ｎ２及びｎ３はそれぞれ独立に０〜５の整数を示し、ｎ１、ｎ２又はｎ３が２以上のとき、複数存在するＲ^１、Ｒ^２又はＲ^３はそれぞれ同一でも異なっていてもよい。

In formula (I), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and n 1, n 2 and n 3 each independently represent 0 to 5 When n1, n2 or n3 is 2 or more, a plurality of R ¹ , R ² or R ³ may be the same or different.

  From the viewpoint of further improving the tolerance of the lamination temperature and the gold plating resistance of the photosensitive resin composition, (d) the thermosetting compound is an epoxy compound, an oxetane compound, a benzoxazine compound, an oxazoline compound, a cyclic carbonate compound, a block type. It is preferable to include at least one compound selected from the group consisting of isocyanate compounds and melamine derivatives.

  The said photosensitive resin composition can improve the adhesiveness of a hardened | cured material, hardness, surface smoothness, and hole-filling property by further containing (g) filler.

  The present invention also provides a photosensitive element comprising a support and a photosensitive resin composition layer comprising the above-described photosensitive resin composition formed on the support.

  The photosensitive element of the present invention can be used as a dry film type solder resist excellent in laminating temperature tolerance and gold plating resistance.

  According to the present invention, it is possible to form a dry film type solder resist excellent in laminating temperature tolerance and gold plating resistance, and to provide a photosensitive resin composition capable of alkali development and a photosensitive element using the same. it can.

It is a figure which shows typically the cross-sectional structure of the photosensitive element of suitable embodiment.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings as the case may be. In the description of the drawings, the same reference numerals are used for the same or equivalent elements, and duplicate descriptions are omitted. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, (meth) acryloyl group means acryloyl group and The methacryloyl group corresponding to it means a (meth) acryloxy group means an acryloxy group and a methacryloxy group corresponding to it.

[Photosensitive resin composition]
The photosensitive resin composition of the present embodiment includes (a) an acid-modified vinyl group-containing epoxy resin (hereinafter referred to as “component (a)” in some cases) and (b) a photopolymerizable compound having an ethylenically unsaturated group (hereinafter referred to as “a”). In some cases, it is referred to as component (b)), (c) a photopolymerization initiator (hereinafter, sometimes referred to as component (c)), (d) a thermosetting compound (hereinafter, sometimes referred to as component (d)). (E) an organic peroxide having a one-hour half-life temperature of 100 to 200 ° C. (hereinafter sometimes referred to as component (e)) and (f) a binder polymer (hereinafter sometimes referred to as component (f)). Containing. Hereinafter, each of these components will be described.

<(A) component: acid-modified vinyl group-containing epoxy resin>
As the component (a), for example, an addition reaction in which (a3) a saturated or unsaturated polybasic acid anhydride is added to an esterified product obtained by reacting (a1) an epoxy compound and (a2) a vinyl group-containing monocarboxylic acid. Can be used.

  Such an acid-modified vinyl group-containing epoxy resin can be obtained, for example, by the following two-stage reaction. In the first reaction (hereinafter referred to as “first reaction” for convenience), (a1) an epoxy compound and (a2) a vinyl group-containing monocarboxylic acid are reacted. In the next reaction (hereinafter referred to as “second reaction” for convenience), the esterified product produced in the first reaction is reacted with (a3) a saturated or unsaturated polybasic acid anhydride.

  (A1) Although there is no restriction | limiting in particular as an epoxy compound, For example, a bisphenol type epoxy compound, a novolak type epoxy compound, a biphenyl type epoxy compound, and a polyfunctional epoxy compound are mentioned.

  As the bisphenol type epoxy compound, for example, those obtained by reacting bisphenol A or bisphenol F with epichlorohydrin are suitable. Specifically, trade names “GY-260”, “GY-255”, “XB-2615” manufactured by Ciba-Geigy Corporation, trade names “Epicoat 828”, “Epicoat 1007”, “Epicoat” manufactured by Japan Epoxy Resin Co., Ltd. Epoxy compounds such as bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, amino group-containing, alicyclic and polybutadiene-modified such as “807” are preferably used.

  As the novolac type epoxy compound, for example, those obtained by reacting novolaks obtained by reacting phenol, cresol, halogenated phenol or alkylphenol with formaldehyde in the presence of an acidic catalyst and epichlorohydrin are suitable. Specifically, trade names “YDCN-701”, “YDCN-704”, “YDPN-638”, “YDPN-602” manufactured by Toto Kasei Co., Ltd., “DEN-431”, “DEN” manufactured by Dow Chemical Co., Ltd. -439 ", trade names" EPN-1299 "manufactured by Ciba-Geigy Corporation, trade names" N-730 "," N-770 "," N-865 "," N-665 "manufactured by Dainippon Ink & Chemicals, Inc. , “N-673”, “VH-4150”, “VH-4240”, Nippon Kayaku Co., Ltd. trade names “EOCN-120”, “BREN”, and the like.

  Moreover, a salicylaldehyde-phenol or a cresol type epoxy compound can also be used as an epoxy compound. Specifically, trade names “EPPN502H” and “FAE2500” manufactured by Nippon Kayaku Co., Ltd., trade names “Epicron 840”, “Epicron 860”, “Epicron 3050”, manufactured by Dainippon Ink & Chemicals, Inc., Dow Trade names “DER-330”, “DER-337”, “DER-361” manufactured by Chemical Corporation, “Celoxide 2021” manufactured by Daicel Chemical Industries, Ltd., and “TETRAD-” manufactured by Mitsubishi Gas Chemical Co., Ltd. X "," TETRAD-C ", Nippon Soda Co., Ltd. trade names" EPB-13 "," EPB-27 "and the like. These can be used alone or in combination of two or more.

  (A2) As the vinyl group-containing monocarboxylic acid, half-ester which is a reaction product of (meth) acrylic acid, crotonic acid, cinnamic acid, saturated or unsaturated polybasic acid anhydride and hydroxyl group-containing (meth) acrylates Examples thereof include a compound and a half-ester compound which is a reaction product of a saturated or unsaturated dibasic acid and an unsaturated monoglycidyl compound. These reactants include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, etc., hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, tris (hydroxyethyl) isocyanurate di ( Examples thereof include a reaction product obtained by reacting meth) acrylate, glycidyl (meth) acrylate and the like in an equimolar ratio by a conventional method. These vinyl group-containing monocarboxylic acids can be used alone or in combination. Among these, acrylic acid is preferable.

  Saturated or unsaturated polybasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydroanhydride Mention may be made of phthalic acid, ethylhexahydrophthalic anhydride, itaconic anhydride and trimellitic anhydride.

  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 vinyl group-containing monocarboxylic acid (a2). In the first reaction, the ratio of the epoxy compound (a1) to the vinyl group-containing monocarboxylic acid (a2) is such that the vinyl group-containing monocarboxylic acid (a2) is 1 equivalent to the epoxy group of the epoxy compound (a1). The ratio is preferably 0.7 to 1.05 equivalent, and more preferably 0.8 to 1.0 equivalent.

  The epoxy compound (a1) and the vinyl group-containing monocarboxylic acid (a2) can be dissolved and reacted 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, a catalyst can be used to accelerate the reaction. As the catalyst, for example, triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, and triphenylphosphine 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 epoxy compounds (a1) or between vinyl group-containing monocarboxylic acids (a2) or between epoxy compound (a1) and vinyl group-containing monocarboxylic acid (a2), polymerization prevention It is preferable to use an agent. As the polymerization inhibitor, for example, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol can be used. The amount of the polymerization inhibitor used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass in total of the epoxy compound (a1) and the vinyl group-containing 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, a vinyl group-containing monocarboxylic acid (a2) and polybasic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, etc. Can be used together.

  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 above-mentioned acid-modified vinyl group-containing epoxy resin include trade names “CCR-1218H”, “CCR-1159H”, “CCR-1222H”, “PCR-1050”, “TCR-” manufactured by Nippon Kayaku Co., Ltd. 1335H "," ZAR-1035 "," ZAR-2001H "," ZFR-1185 "and" ZCR-1569H "are commercially available.

  As the component (a), a compound having a urethane bond obtained by reacting an epoxy acrylate compound having two or more hydroxyl groups and an ethylenically unsaturated group, a diisocyanate compound, and a diol compound having a carboxyl group (hereinafter, “ It may also be referred to as “polyurethane compound”.

  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 diol compound having a carboxyl group. (Hereinafter referred to as “raw diol”) is a compound obtained as a raw material component. First, these raw material components will be described.

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

  As the raw material diisocyanate, any compound having two isocyanate groups can be used without particular limitation. 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 and norbornane-diisocyanate methyl. 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 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 a diol compound include dimethylolpropionic acid and dimethylolbutanoic acid.

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

  In the production process of the polyurethane compound, 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 (2). In formula (2), R ¹¹ is a residue of an epoxy acrylate compound, R ¹² is a residue of a diisocyanate compound, R ¹³ is an alkyl group having 1 to 5 carbon atoms, and R ¹⁴ is a hydrogen atom or a methyl group. 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.

Specific examples of R ¹¹ include bis (4-oxyphenyl) -methane, 2,2-bis (4-oxyphenyl) -propane, 2,2-bis (4-oxyphenyl) -1,1,1, Examples thereof include bisphenol skeletons such as 3,3,3-hexafluoropropane, novolak skeletons, and fluorene skeletons. Examples of R ¹² include phenylene, tolylene, xylylene, tetramethylxylylene, diphenylmethylene, hexamethylene, trimethylhexamethylene, dicyclohexylmethylene, isophorone and the like. Examples of R ¹³ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, and an amyl group.

Among the compounds represented by the general formula (2), the hard segment portion of the raw material epoxy acrylate that is one of the main skeletons of polyurethane, that is, the urethane compound in which R ¹¹ is a bisphenol A skeleton is manufactured by Nippon Kayaku Co., Ltd. It is commercially available as trade names “UXE-3011”, “UXE-3012”, “UXE-3024” and the like. These may be used alone or in combination of two or more.

  In the production process of the polyurethane compound described above, 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. Moreover, in each process mentioned above, you may use a catalyst etc. suitably.

  As the component (a), a compound obtained by further reacting the above-described polyurethane compound and raw material epoxy can also be used. In this reaction, a so-called epoxycarboxylation reaction occurs mainly between the carboxyl group derived from the diol compound in the polyurethane compound and the epoxy group of the raw material epoxy. Thus, the compound obtained is equipped with the principal chain formed from the polyurethane compound mentioned above, and the side chain containing the ethylenically unsaturated group originating in raw material epoxy acrylate or raw material epoxy, for example.

  The acid value of the component (a) is preferably 20 to 180 mgKOH / g, more preferably 30 to 150 mgKOH / g, and still more preferably 40 to 120 mgKOH / g. Thereby, the developability by the alkaline aqueous solution of the photosensitive resin composition becomes favorable, and excellent resolution can be obtained.

Here, the acid value of the component (a) can be measured by the following method. (1) About 1 g of the component resin is precisely weighed, and 30 g of acetone is added to the resin and uniformly dissolved to obtain a resin solution. Next, an appropriate amount of an indicator, phenolphthalein, is added to the resin solution, and titration is performed using a 0.1N aqueous KOH solution. And from the titration result, the following formula:
A = 10 × Vf × 56.1 / (Wp × I)
To calculate the acid value. In the formula, A represents the acid value (mgKOH / g), Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the mass (g) of the resin solution, and I represents the non-volatile content of the resin solution ( Mass%).

  The weight average molecular weight of the component (a) is preferably 3000 to 30000, more preferably 5000 to 20000, and particularly preferably 7000 to 15000 from the viewpoint of coating properties. In addition, a weight average molecular weight can be calculated | required from the standard polystyrene conversion value by a gel permeation chromatography (GPC).

  Since such a polyurethane compound is easily compatible with (f) a binder polymer described later, a uniform photosensitive resin composition is easily obtained by including such a polyurethane compound. Moreover, since such a polyurethane compound can form a cured product having toughness and excellent elongation, it can improve the crack resistance and HAST resistance (high acceleration stress test) of the cured product of the photosensitive resin composition.

<(B) component: Photopolymerizable compound having an ethylenically unsaturated group>
The photopolymerizable compound having an ethylenically unsaturated group as component (b) is a compound having at least one ethylenically unsaturated group in the molecule. Examples of such compounds include bisphenol A-based (meth) acrylate compounds, compounds obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids, and glycidyl group-containing compounds with α, β-unsaturated carboxylic acids. Examples thereof include a compound obtained by reacting an acid, and a urethane monomer or urethane oligomer such as a (meth) acrylate compound having a urethane bond in the molecule. 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 esters, EO-modified nonylphenyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

  The component (b) preferably contains a bisphenol A (meth) acrylate compound from the viewpoint of improving alkali developability. 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 and 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane. It is done. You may use these individually or in combination of 2 or more types.

  The component (b) more preferably contains 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane from the viewpoint of improving sensitivity and resolution. 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) acryloxyhexa) Decaethoxy) phenyl) propane. You may use these individually or in combination of 2 or more types.

  Among the above compounds, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is a trade name “FA-321M” manufactured by Hitachi Chemical Co., Ltd. or a trade name “Shin Nakamura Chemical Co., Ltd.” BPE-500 "is commercially available, and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available under the trade name" BPE-1300 "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) acrylic) Xinonapropoxy) 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. These may be used alone or in combination of two or more.

  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. These can be used alone or in combination of two or more.

  The component (b) preferably contains a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid from the viewpoint of improving the balance of adhesion, resolution and electric corrosion resistance. 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 and EO. PO-modified glyceryl tri (meth) acrylate is exemplified. These may be used alone or in combination of two or more.

  Among the above compounds, dipentaerythritol hexaacrylate is commercially available under the trade name “KAYARAD-DPHA” manufactured by Toagosei Co., Ltd., and trimethylolpropane triethoxytriacrylate is sold under the trade name “SR-454” manufactured by Nippon Kayaku Co., Ltd. Are available.

“EO” refers to “ethylene oxide”, and “PO” refers to “propylene oxide”. “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 a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4- (meth) acryloxy- 2-hydroxy-propyloxy) phenyl. These can be used alone or in combination of two or more. Examples of the α, β-unsaturated carboxylic acid for obtaining these compounds include (meth) acrylic acid.

  Examples of urethane monomers include (meth) acrylic monomers having an OH group at the β-position and diisocyanate compounds such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. And tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, and EO or PO-modified urethane di (meth) acrylate. These can be used alone or in combination of two or more.

  Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and 2-hydroxyethyl. (Meth) acrylate is mentioned. These can be used alone or in combination of two or more.

<(C) Component: Photopolymerization initiator>
Examples of the component (c) include 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 (Mihera ketone), 4,4'-bis (diethylamino) benzophenone, 4- Aromatic ketones such as methoxy-4'-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, benzyldimethyl ketal Ben etc. Derivatives, 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 2,4,5-triarylimidazole dimer such as 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, N-phenylglycine, N-phenylglycine derivative, 7 Examples include coumarin compounds such as -diethylamino-4-methylcoumarin and acylphosphine oxide compounds represented by the following general formula (I). These can be used singly or in combination of two or more.

In formula (I), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and n 1, n 2 and n 3 each independently represent 0 to 5 Indicates an integer. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a tert-butoxy group. R ¹ and R ² are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. n1 and n2 are preferably integers of 1 to 4, and more preferably 3. N3 is preferably 0. When n1, n2 or n3 is 2 or more, a plurality of R ¹ , R ² or R ³ may be the same or different.

  Since the resist shape is excellent, the component (c) contains 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 and / or 1,7-bis (9-acridinyl) heptane. It is preferable to include.

  From the viewpoint of more effectively improving sensitivity and resist shape, the component (c) preferably contains an acylphosphine oxide compound represented by the above general formula (I). Specifically, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name “DAROCURE-TPO” manufactured by Ciba Specialty Chemicals) or bis (2,4,6-trimethylbenzoyl) -phenylphosphine Oxide (trade name “IRGACURE-819” manufactured by Ciba Specialty Chemicals).

  The amount of component (c) is preferably 0.1 to 30 parts by mass, and 0.1 to 20 parts by mass with respect to 100 parts by mass in total of components (a), (b) and (f). It is more preferable that it is 0.1-10 mass parts.

<(D) component: thermosetting compound>
Examples of the component (d) include epoxy compounds, oxetane compounds, benzoxazine compounds, oxazoline compounds, cyclic carbonate compounds, block isocyanate compounds, and melamine derivatives.

  Examples of the epoxy compound include bisphenol A type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F type epoxy resins such as bisphenol F diglycidyl ether, bisphenol S type epoxy resins such as bisphenol S diglycidyl ether, and biphenol diglycidyl ether. Examples include biphenol type epoxy resins such as bixylenol type epoxy resins such as bixylenol diglycidyl ether, hydrogenated bisphenol A type epoxy resins such as hydrogenated bisphenol A glycidyl ether, and dibasic acid-modified diglycidyl ether type epoxy resins thereof. It is done. These can be used alone or in combination of two or more.

  As bisphenol A diglycidyl ether, trade names “Epicoat 828”, “Epicoat 1001” and “Epicoat 1002” manufactured by Japan Epoxy Resin Co., Ltd. and as trade names “Epicoat” manufactured by Japan Epoxy Resin Co., Ltd. 807 "is bisphenol S diglycidyl ether, and the product name" EBPS-200 "manufactured by Nippon Kayaku Co., Ltd. and the product name" Epicron EXA-1514 "manufactured by Dainippon Ink & Chemicals, Inc. are commercially available. is there. In addition, as a biphenol diglycidyl ether, a product name “YL-6121” manufactured by Japan Epoxy Resin Co., Ltd., and as a bixylenol diglycidyl ether, a product name “YX-4000” manufactured by Japan Epoxy Resin Co., Ltd. Product names “ST-2004” and “ST-2007” manufactured by Toto Kasei Co., Ltd. as A glycidyl ether, and product names “ST-5100” manufactured by Toto Kasei Co., Ltd. as dibasic acid-modified diglycidyl ether type epoxy resin “ST-5080” is available as a commercial product.

  As an oxetane compound, a compound having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, And 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like. Specific examples include the Aron Oxetane series manufactured by Toa Gosei Co., Ltd. and the Etanacol Oxetane series manufactured by Ube Industries, Ltd. Since the oxetane compound has low reactivity, it may be used together with a curing catalyst such as triphenylphosphine.

  The block-type isocyanate compound is inactive at room temperature (25 ° C.), but when heated, the blocking agent is reversibly dissociated to regenerate the isocyanate group. The dissociation temperature of the blocking agent is preferably 120 to 200 ° C.

  Examples of the isocyanate compound constituting the block type isocyanate compound include isocyanurate type, biuret type, and adduct type compounds, and isocyanurate type compounds are preferred from the standpoint of adhesion. These can be used alone or in combination of two or more.

  In the block type isocyanate compound, examples of the blocking agent bonded to the isocyanate group include at least one selected from diketones, oximes, phenols, alkanols and caprolactams. Specific examples include methyl ethyl ketone oxime and ε-caprolactam.

  The block-type isocyanate compound is easily available as a commercial product. For example, trade names “Sumidur BL-3175”, “Desmodur TPLS-2957”, “TPLS-2062”, “manufactured by Sumitomo Bayer Urethane Co., Ltd.” TPLS-2957, TPLS-2078, BL-4165, TPLS-2117, BL-1100, BL-1265, Desmotherm 2170, Desmotherm 2265, Nippon Polyurethane Industry Co., Ltd. Product names “Coronate 2512”, “Coronate 2513”, “Coronate 2520”, trade names “B-830”, “B-815”, “B-846”, “B-870” manufactured by Mitsui Takeda Chemical Co., Ltd. ”,“ B-874 ”, and“ B-882 ”.

  In the case where excellent insulating properties are required for the photosensitive resin composition, among the above-mentioned, a block type isocyanate compound is preferable, and further, an isocyanuric skeleton and a structure containing an aromatic ring such as a benzene ring are preferable. . Examples of such a block type isocyanate compound include “Sumijoule BL-3175”, “Sumijoule BL-4265”, “B-870” and the like.

  A melamine derivative is an initial condensate obtained by reacting an aldehyde with an amino group-containing compound such as melamine, urea, or benzoguanamine. For example, trimethylol melamine resin, tetramethylol melamine resin, hexamethylol melamine resin, hexamethoxymethyl Melamine resin, hexabutoxymethyl melamine resin, N, N′-dimethylol urea resin, trade names “Symel 300”, “Symel 301”, “Symel 303”, “Symel 325”, “Symel 325” manufactured by Mitsui Toatsu Cymel Co., Ltd. 350 ", melamine resins such as" Melan 523 "," Melan 623 "and" Melan 2000 "manufactured by Hitachi Chemical Co., Ltd., and" Melan 18 "manufactured by Hitachi Chemical Co., Ltd. Urea resin and Hitachi Chemical Co., Ltd. Emissions 362A "or the like of the benzoguanamine resins. Particularly preferred melamine derivatives include hexamethoxymethyl melamine resin.

  (D) The compounding quantity of a component is 0.1-40 mass parts with respect to a total of 100 mass parts of (a), (b) and (f) component from a viewpoint of photosensitivity and a solder heat resistance viewpoint. preferable. When the component (d) is a block isocyanate compound or a melamine derivative, the blending amount of the component (d) is 0.1 to 100 parts by mass in total of the components (a), (b), and (f). 20 mass parts is preferable, 0.1-15 mass parts is still more preferable, and 0.1-10 mass parts is especially preferable. When the blending amount of component (d) exceeds 40 parts by mass, outgassing tends to increase during thermosetting.

<(E) component: organic peroxide>
The organic peroxide as the component (e) functions as a crosslinking initiator, and its one-hour half-life temperature is 100 to 200 ° C. (E) It is preferable that the 1-hour half life temperature of a component is 110-180 degreeC. By using an organic peroxide having such a one-hour half-life temperature, the storage stability of the photosensitive resin composition is improved. Moreover, the tolerance of the lamination temperature and the gold plating resistance when the photosensitive resin composition is a solder resist are improved. By using such an organic peroxide, it is possible to suppress the photosensitive resin composition from being cured by heat even when lamination is performed at a relatively high temperature of 90 ° C. or higher.

  Specific examples of the component (e) include dicumyl peroxide (manufactured by NOF Corporation, trade name “PARKMILL D”), α, α′-bis (t-butylperoxy-m-isopropyl) benzene (NOF) Product name "Perbutyl P"), 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3 (manufactured by NOF Corporation, trade name "Perhexine 25b"), t-butyl per Oxybenzoate (Nippon Yushi Co., Ltd., trade name “Perbutyl Z”), t-butylcumyl peroxide (Nippon Yushi Co., Ltd., trade name “Perbutyl C”), cyclohexane peroxide, 1,1-bis (t-butyl per Oxy) cyclohexane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl 4,4-bis (t-butylperoxy) valerate, di-t-butylperoxide, benzoyl peroxide, cumylperoxyneodecanate, 2,5-dimethyl-2,5-di (benzoylperoxy) ) Hexane, t-butylperoxyisopropyl carbonate, t-butylperoxyallyl carbonate, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, di-t-butylperoxyisophthalate and t-Butylperoxymaleic acid can be used. These can be used alone or in combination of two or more.

  (E) Content of a component is 0.01-5 mass parts with respect to a total of 100 mass parts of (a), (b), and (f) component, and shall be 0.1-3 mass parts Is preferred. When the content of the component (e) is less than 0.01 parts by mass, curing is difficult to complete in a short time and the cured product tends to be non-uniform. On the other hand, when the content of the component (e) exceeds 5 parts by mass, the tolerance of the laminating temperature decreases. Moreover, there exists a tendency for the crack resistance and HAST tolerance of hardened | cured material to fall by the organic peroxide which remained without decomposing | disassembling.

<Component (f): Binder polymer>
The photosensitive resin composition of the present invention contains (f) a binder polymer from the viewpoint of improving the coating properties and alkali developability. Examples of the binder polymer include known resins such as acrylic resins, polyurethanes, epoxy resins, phenoxy resins, polyesters, polyamides, polyimides, polyamideimides, polyesterimides, polycarbonates, melamine resins, polyphenylene sulfides and polyoxybenzoyls, and acid modifications thereof. Examples of the resin include those having a carboxyl group in the molecule. Among these, those obtained by polymerizing a monomer (polymerizable monomer) having an ethylenically unsaturated group (such as radical polymerization) are preferable.

  Examples of the monomer having an ethylenically unsaturated group include acrylamide such as diacetone acrylamide, ethers of vinyl alcohol such as acrylonitrile and vinyl-n-butyl ether, (meth) acrylic acid alkyl ester, and (meth) acrylic acid. Tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid benzyl ester derivative, 2 , 2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) Acrylic acid, β- Malees such as (meth) acrylic monomers such as ril (meth) acrylic acid and β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate and monoisopropyl maleate Examples thereof include acid monomers, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. These can be used alone or in combination of two or more.

  The component (f) is preferably an acrylic resin from the viewpoints of alkali developability and resolution. The acrylic resin can be obtained by radical polymerization using, for example, (meth) acrylic acid and (meth) acrylic acid alkyl ester as a copolymerization component. In particular, a vinyl copolymer compound obtained by using methacrylic acid and (meth) acrylic acid alkyl ester as a copolymerization component is preferable.

  Examples of (meth) acrylic acid alkyl esters include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid pentyl ester. Examples include esters, (meth) acrylic acid hexyl esters, (meth) acrylic acid heptyl esters, (meth) acrylic acid octyl esters, and (meth) acrylic acid 2-ethylhexyl esters. These can be used alone or in combination of two or more. Among these, (meth) acrylic acid butyl ester is preferable.

  As a vinyl-type copolymer compound, you may use what is obtained by copolymerizing the vinyl monomer which can be copolymerized with these with (meth) acrylic-acid alkylester and (meth) acrylic acid. Examples of such vinyl monomers include (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, methacrylic acid glycidyl ester, 2,2,2- Examples include trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, acrylamide, diacetone acrylamide, styrene, and vinyltoluene. These can be used alone or in combination of two or more.

  The acid value of the component (f) is preferably 50 to 170 mgKOH / g, more preferably 70 to 150 mgKOH / g, and 90 to 130 mgKOH / g from the viewpoint of improving alkali developability. Is more preferable.

  The weight average molecular weight of the component (f) is preferably 20000 to 150,000, more preferably 40000 to 120,000, and more preferably 50000 from the viewpoint of improving the coating property and alkali developability of the photosensitive resin composition. More preferably, it is ˜100,000. In addition, a weight average molecular weight can be calculated | required from the standard polystyrene conversion value by a gel permeation chromatography (GPC).

<(G) component: filler>
The photosensitive resin composition preferably contains (g) a filler for the purpose of improving properties such as adhesion and hardness. (G) Examples of the filler include barium sulfate, barium titanate, powdered silicon oxide, amorphous silica, talc, clay, calcined kaolin, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder, aerosil, Examples include inorganic fillers such as benton and montmorillonite, and organic fillers such as diallyl phthalate, diallyl phthalate prepolymer, acrylic rubber, nitrile rubber (NBR), silicone powder, and nylon powder. (G) The usage-amount of a filler becomes like this. Preferably it is 0-60 mass% with respect to solid content of the photosensitive resin composition, Furthermore, 0-50 mass% is preferable from a viewpoint of surface smoothness and hole-filling property.

<(H) Component: Diluting solvent>
When the photosensitive resin composition is used as a varnish, (h) a diluting solvent (hereinafter sometimes referred to as component (h)) may be used. (H) Examples of the diluent solvent include aliphatic alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, n-pentanol and hexanol, hydrocarbons such as benzyl alcohol and cyclohexane, di Acetone alcohol, 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 and other aliphatic ketones, ethylene glycol, Diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate , Ethylene glycol alkyl ethers such as propylene glycol 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, toluene, petroleum ether, petroleum naphtha, water Petroleum naphtho Petroleum solvents such as solvent naphtha, carboxylic acids such as ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate Esters, amines, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dioxane, tetrahydrofuran, cyclohexanone, γ-butyrolactone, 3-hydroxy-2- Solvents such as butanone, 4-hydroxy-2-pentanone and 6-hydroxy-2-hexanone can be used alone or in combination of two or more.

  When producing a photosensitive element, the photosensitive resin composition is dissolved in (h) a diluting solvent to form a varnish, which is applied to a support. In this case, it is preferable that a varnish contains 30-70 mass% (h) dilution solvent. (H) Since the diluting solvent is volatilized in the drying process at the time of producing the photosensitive element, the final content is 3% by mass or less of the photosensitive element.

<Other ingredients>
When the photosensitive resin composition is required to be in close contact with a metal such as copper, as an adhesion improver, melamine, dicyandiamide, triazine compound and derivatives thereof, imidazole, thiazole, triazole, silane coupling agent Etc. can be contained. Specifically, for example, melamine, acetoguanamine, benzoguanamine, melamine-phenol-formalin resin, dicyandiamide, ethyldiamino-s-triazine, 2,4-diamino-s-triazine, 2,4-diamino-6-xylyl- Examples include s-triazine, trade names “2MZ-AZINE”, “2E4MZ-AZINE”, “C11Z-AZINE”, and “2MA-OK” manufactured by Shikoku Kasei Kogyo Co., Ltd. These compounds improve adhesion between the photosensitive resin composition and a metal circuit such as copper, and improve PCT resistance and electric corrosion resistance. The adhesion improver is preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the components (a), (b) and (f).

  The photosensitive resin composition may be a colorant such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, malachite green, crystal violet, titanium oxide, carbon black, naphthalene black, azo organic pigment, or the like. Dye etc. can be contained. Furthermore, it can contain thixotropic agents such as benton, montmorillonite, aerosil, amide wax, and surface modifiers such as silicone, fluorine, and polymer for improving defoaming and leveling.

  The photosensitive resin composition is 10 to 60 parts by mass of the component (a), more than 0 parts by mass and 30 parts by mass or less (100 parts by mass) of the total of the components (a), (b) and (f) It is preferable to mix | blend component b) and 5-40 mass parts (f) component, 20-50 mass parts (a) component, 20-40 mass parts (b) component, 10-30 mass parts More preferably, the component (f) is blended.

[Photosensitive element]
Next, preferred embodiments of the photosensitive element will be described. FIG. 1 is a diagram schematically showing a cross-sectional configuration of the photosensitive element of the present embodiment. As shown in FIG. 1, the photosensitive element 1 includes a support 10 and a photosensitive layer 20 made of a photosensitive resin composition formed on the support 10. Further, as shown in the figure, a protective film 30 that covers the layer may be further provided on the photosensitive layer 20.

  The photosensitive layer 20 is formed by dissolving the photosensitive resin composition in the above-described (h) dilution solvent to form a varnish having a solid content of 30 to 70% by mass, and then applying the varnish on the support 10.

  Although the thickness of the photosensitive layer 20 varies depending on the use, it is preferably 10 to 100 μm, more preferably 20 to 60 μm in thickness after drying after removing the diluted solvent by heating and / or hot air blowing (h). . If the thickness is less than 10 μm, it tends to be difficult to apply the varnish on the support 10, and if it exceeds 100 μm, the flexibility and the resolution tend to decrease.

  Examples of the support 10 include polymer films having heat resistance and solvent resistance, such as polyethylene terephthalate, polypropylene, polyethylene, and polyester.

  The thickness of the support 10 is preferably 5 to 100 μm, and more preferably 10 to 30 μm. When the thickness is less than 5 μm, the support 10 tends to be broken when the support 10 is peeled before development, and when it exceeds 100 μm, the flexibility and the resolution tend to decrease.

  The photosensitive element 1 composed of two layers of the support 10 and the photosensitive layer 20 or the photosensitive element 1 composed of three layers of the support 10, the photosensitive layer 20 and the protective film 30 may be stored as it is. The core may be wound into a roll and stored.

  Since the photosensitive element 1 includes the photosensitive layer 20 made of the above-described photosensitive resin composition, it is sufficiently flexible even when the support 10 is made thicker than before (for example, 30 to 100 μm). Can be maintained, and excellent resolution can be exhibited.

[Method of forming resist pattern]
Next, a preferred embodiment of a resist pattern forming method will be described.

  First, a photosensitive layer made of a photosensitive resin composition is formed on a substrate on which a resist is to be formed. The photosensitive layer is formed by applying a photosensitive resin composition varnish by a known method such as a screen printing method or a roll coater, or by laminating the photosensitive layer 20 using the photosensitive element 1 described above. It can be formed by an attaching method or the like. When the photosensitive element 1 is used, the protective film 30 is removed before the photosensitive layer 20 is attached to the substrate. Examples of the substrate on which the resist is to be formed include a printed wiring board, a semiconductor package substrate, and a flexible wiring board.

  Subsequently, an exposure process is performed in which the photosensitive layer 20 is irradiated with actinic rays through a mask pattern having a predetermined pattern shape, and a predetermined region of the photosensitive layer 20 is photocured. As the light source of actinic light, known light sources such as carbon arc lamps, mercury vapor arc lamps, ultra-high pressure mercury lamps, high pressure mercury lamps, xenon lamps and the like, which effectively emit ultraviolet rays, photographic flood bulbs, solar lamps, etc. What emits visible light effectively can be used. Further, direct laser exposure using a direct drawing method can also be used.

  Next, a removal step is performed in which a region (uncured portion) that has not been cured without being irradiated with actinic rays in the photosensitive layer 20 is removed by, for example, dissolving in a developer. Thereby, a resist pattern having a predetermined pattern shape is formed. As the developer, an alkali developer is used, and for example, a dilute solution of sodium carbonate (1 to 5% by mass aqueous solution) at 20 to 50 ° C. is suitable. Development can be performed by a known method such as spraying, rocking dipping, brushing, scraping or the like.

After the development process is completed, it is preferable to further irradiate the resist pattern with ultraviolet rays or heat with a high-pressure mercury lamp for the purpose of improving the solder heat resistance, chemical resistance, etc. of the resist pattern. When irradiating with ultraviolet rays, it is preferable to adjust the irradiation amount as necessary. For example, irradiation can be performed at an irradiation amount of about 0.2 to 10 J / cm ² . When heating a resist pattern, it is preferable to carry out on the conditions for about 15 to 90 minutes in the range of about 100-170 degreeC.

  Both ultraviolet irradiation and heating may be performed. In this case, ultraviolet irradiation and heating 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, chemical resistance, etc. more favorably. A resist pattern can be formed by the above operation.

The resist pattern of the present embodiment has excellent surface smoothness, crack resistance, HAST resistance, and excellent gold plating properties, so it is effective as a solder resist for printed wiring boards, semiconductor package substrates, and flexible wiring boards. It also serves as a protective film for the wiring after soldering the substrate. The substrate on which the resist pattern is formed is then mounted with a component such as an LSI (for example, wire bonding or solder connection), and further mounted on an electronic device such as a personal computer.

  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 varnish of photosensitive resin composition)
Each component shown in Table 1 was mixed in the blending amount (parts by mass) shown in the same table to obtain a photosensitive resin composition. In Table 1, the blending amount indicates solid content (parts by mass). The following were used as each component shown in Table 1.

(A) Component: Acid-modified vinyl group-containing epoxy resin Polyurethane compound: “UXE-3024” (manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight: 10,000, acid value: 60 mgKOH / g).
Bisphenol F-type acid-modified epoxy acrylate: “ZFR-1158” (trade name, weight average molecular weight: 10,000, acid value: 60 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.).

(B) Component: Photopolymerizable compound having an ethylenically unsaturated group 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane: “FA-321M” (manufactured by Hitachi Chemical Co., Ltd., trade name) ).
Dipentaerythritol hexaacrylate: “KAYARAD-DPHA” (trade name, manufactured by Nippon Kayaku Co., Ltd.).

(C) Component: Photopolymerization initiator 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide: “DAROCURE-TPO” (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.).
2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one: “IRGACURE-907” (trade name, manufactured by Ciba Specialty Chemicals).
1,7-bis (9-acridinyl) heptane: “N-1717” (trade name, manufactured by ADEKA Corporation).

(D) Component: Thermosetting compound Block type isocyanate compound: “BL-3175” (manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name).

(E) Component: Organic peroxide 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3: “Perhexin 25B” (manufactured by NOF Corporation, trade name, 1 hour half-life temperature 150) ° C).

Component (e ′): Organic peroxides other than component (e) Diisobutyroyl peroxide: “Perroyl IB” (manufactured by NOF Corporation, trade name, 1 hour half-life temperature 50 ° C.).

(F) Component: Binder polymer Acrylic resin: Copolymer of methacrylic acid / methyl methacrylate / butyl acrylate (mass ratio 17/53/30), weight average molecular weight 60000, acid value 70 mgKOH / g.

(G) Component: Filler Barium sulfate: “Variace B-30” (manufactured by Sakai Chemical Industry Co., Ltd., trade name).

Other ingredients Pigment: “Phthalocyanine blue”
Adhesion improver: Dicyandiamide “Epicure DICY7” (trade name, manufactured by Japan Epoxy Resin Co., Ltd.)

(A) 50 parts by mass (solid content) of component, (g) 40 parts by mass of component, and 50 parts by mass of methyl ethyl ketone as component (h) were introduced into Starmill LMZ (manufactured by Ashizawa Finetech Co., Ltd.) The zirconia beads were dispersed at a peripheral speed of 12 m / s for 3 hours to obtain a barium sulfate dispersion. Each component was mix | blended with this dispersion liquid so that it might become the compounding quantity of Table 1, and the varnish of the photosensitive resin composition of Examples 1-3, Reference Example 4, and Comparative Examples 1-6 was obtained. The amount of methyl ethyl ketone added was adjusted so that the solid content was 55% by mass of the varnish.

(Production of photosensitive element)
A photosensitive layer is formed by uniformly coating the varnish of the photosensitive resin composition obtained above on a polyethylene terephthalate film (trade name “G2-16”, manufactured by Teijin Limited) having a thickness of 16 μm as a support. And dried for about 10 minutes at 100 ° C. using a hot air convection dryer. The film thickness after drying of the photosensitive layer was 30 μm.

  Subsequently, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name “NF-15”) is bonded as a protective film on the surface of the photosensitive layer opposite to the side in contact with the support to obtain a photosensitive element. It was.

(Evaluation of photosensitive element)
The following tests were conducted using the photosensitive elements of Examples , Reference Examples and Comparative Examples, and the resolution, via shape, solder heat resistance, gold plating resistance, and laminating temperature tolerance when each photosensitive element was used. The degree was evaluated. The obtained results are shown in Table 2.

(Resolution evaluation)
The copper surface of a printed wiring board substrate (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. . Using a press-type vacuum laminator (trade name “MVLP-500”, manufactured by Meiki Seisakusho) on this printed wiring board substrate, press hot plate temperature (lamination temperature) 70 ° C., vacuuming time 20 seconds, laminating press time Under the conditions of 30 seconds, atmospheric pressure 4 kPa or less, and pressure bonding pressure 0.4 MPa, the polyethylene film of the photosensitive element was peeled and laminated to obtain a laminate for evaluation.

  Next, a photo tool having a via diameter of 30 to 200 μm as a negative and a photo tool having a 41-step tablet are brought into close contact with each other on the evaluation laminate, and an EXM-1201 type exposure machine manufactured by Oak Manufacturing Co., Ltd. is used. Then, the exposure was performed with an energy amount such that the number of steps remaining after development was 18.0.

  The evaluation laminate after exposure was allowed to stand at room temperature (25 ° C.) for 1 hour, and then the polyethylene terephthalate film on the laminate was peeled off, and the minimum development time (unreacted) with a 1% by mass aqueous sodium carbonate solution at 30 ° C. Spray development was performed for 1.5 times the minimum time during which the exposed area was developed. Thereby, the resist pattern formed by hardening the photosensitive resin composition layer was formed.

  The resist pattern was observed using an optical microscope, and the resolution was evaluated by measuring the smallest value (μm) of the smallest via diameter that was opened. Note that the smaller the numerical value, the better the evaluation of resolution.

(Via shape evaluation)
The via shape of the resist pattern obtained by the above-described evaluation of resolution was observed, and the shape was evaluated according to the following criteria.
“A”: Straight or tapered shape.
“B”: The occurrence of overhang and undercut was observed.

(Evaluation of solder heat resistance)
An evaluation laminate was prepared in the same manner as the evaluation of the resolution. 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 18.0. Next, after standing at room temperature (25 ° C.) for 1 hour, the polyethylene terephthalate film on the laminate was peeled off, and a minimum development time (minimum at which the unexposed area was developed) with a 1 wt% sodium carbonate aqueous solution at 30 ° C. Spray development was performed in 1.5 times the time. Thereby, the resist pattern formed by hardening the photosensitive resin composition layer was formed.

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

  Next, rosin-based flux (MH-820V, manufactured by Tamura Kaken Co., Ltd., trade name) was applied to this evaluation substrate, and then immersed in a solder bath at 260 ° C. for 10 seconds. This treatment was performed once, and the soldering treatment was performed three times in total.

Thus, the crack generation situation of the solder resist on the evaluation board | substrate which gave solder plating, the floating degree of the solder resist from the board | substrate, and the peeling degree were observed visually, and it evaluated by the following reference | standard. The results are shown in Table 2.
“A”: No cracking occurred in the solder resist, and the solder resist was not lifted or peeled off.
“B”: Solder resist floats or peels.
“C”: Cracks occurred in the solder resist, and the solder resist floated or peeled off.

(Evaluation of gold plating resistance)
In the same manner as the evaluation of solder heat resistance described above, an evaluation laminate having a resist pattern formed thereon was prepared. Subsequently, the laminate for evaluation was treated for 20 minutes using an electroless nickel plating solution (trade name “Nimden NPR-4” manufactured by Uemura Kogyo Co., Ltd.), and then plated to a thickness of 5 μm. Treatment was performed for 20 minutes using an electrolytic gold plating solution (trade name “Goblite TAM-54” manufactured by Uemura Kogyo Co., Ltd.), and gold plating was performed so that the plating thickness was 0.1 μm.

With respect to the laminate for evaluation subjected to plating, the floating and peeling of the resist from the substrate and the penetration of the plating solution into the bottom of the resist were observed with a metal microscope at a magnification of 100 times and evaluated according to the following criteria.
“A”: The solder resist does not float and peel, and the plating solution does not penetrate.
“B”: Floating or peeling of the solder resist was observed, and the penetration of the plating solution was 1 to 10 μm.
“C”: Solder resist floating and peeling were observed, and the penetration of the plating solution into the bottom of the resist exceeded 10 μm.

(Lamination temperature tolerance)
A resist pattern was formed in the same manner as in the evaluation of the resolution described above, except that an evaluation laminate was produced in which the laminating temperature was changed to 70 ° C. and 90 ° C., respectively.

The formed resist pattern was observed with a stereomicroscope, and the tolerance of the lamination temperature was determined according to the following criteria.
“A”: A development residue cannot be observed in an unexposed portion at any lamination temperature of 70 ° C. and 90 ° C.
“B”: A development residue cannot be observed in an unexposed portion when laminated at 70 ° C., but a development residue can be observed in an unexposed portion when laminated at 90 ° C.
“C”: A development residue can be observed in an unexposed portion at any lamination temperature of 70 ° C. and 90 ° C.

  According to the present invention, a dry film type solder resist excellent in laminating temperature tolerance and gold plating resistance can be formed, and a photosensitive resin composition capable of alkali development and a photosensitive element using the same can be provided.

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body, 20 ... Photosensitive layer, 30 ... Protective film

Claims (5)

(A) acid-modified vinyl group-containing epoxy resin, (b) photopolymerizable compound having an ethylenically unsaturated group, (c) photopolymerization initiator, (d) thermosetting compound, (e) 1 hour half-life temperature Containing an organic peroxide having a temperature of 100 to 200 ° C. and (f) a binder polymer,
The (a) acid-modified vinyl group-containing epoxy resin is a compound having a urethane bond,
The total content of the (e) organic peroxide is a total of 100 (a) the acid-modified vinyl group-containing epoxy resin, (b) the photopolymerizable compound having an ethylenically unsaturated group, and (f) the binder polymer. The photosensitive resin composition which is 0.01-5 mass parts with respect to a mass part. The photosensitive resin composition of Claim 1 in which the said (c) photoinitiator contains the compound represented by the following general formula (I).

[In Formula (I), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and n 1, n 2 and n 3 each independently represents 0 to 0 5 is an integer, and when n1, n2 or n3 is 2 or more, a plurality of R ¹ , R ² or R ³ may be the same or different. ] (D) The thermosetting compound contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, a benzoxazine compound, an oxazoline compound, a cyclic carbonate compound, a block-type isocyanate compound, and a melamine derivative. 3. The photosensitive resin composition according to 1 or 2 . (G) The photosensitive resin composition as described in any one of Claims 1-3 which further contains a filler. A photosensitive element provided with a support body and the photosensitive resin composition layer which consists of the photosensitive resin composition as described in any one of Claims 1-4 formed on this support body.

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