JP2010276859A - Photosensitive resin composition, and photosensitive film and photosensitive permanent resist using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that includes excellent alkali-development properties, can form a cured film having various properties required for solder resist, exhibits small tack properties and includes high luminous sensitivity compatible to an LDI system; and to provide a photosensitive film and photosensitive permanent resist using the same. <P>SOLUTION: The photosensitive resin composition includes a binder polymer (A), a photopolymerizable compound (B) having an ethylenically unsaturated group, and a photopolymerization initiator (C). The photosensitive resin composition includes, as the photopolymerizable compound (B) having an ethylenically unsaturated group, at least a polyalkylene glycol di(meth)acrylate compound (b1). The photosensitive resin composition further includes, as the photopolymerization initiator (C), at least an acridine compound having an α-aminoalkylphenone compound (c1) and an acridine group (c2). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, and a photosensitive film and a photosensitive permanent resist using the same.

  In the printed wiring board manufacturing industry, conventionally, a solder resist is formed on a printed wiring board. This solder resist has a role to prevent solder from adhering to unnecessary portions of the conductor layer of the printed wiring board in the soldering process for bonding the mounted part to the printed wiring board. When the printed wiring board is used later, it also serves as a permanent mask for preventing corrosion of the conductor layer and maintaining electrical insulation between the conductor layers.

  As a method for forming a solder resist, for example, a method of screen printing a thermosetting resin on a conductor layer of a printed wiring board is known. However, since such a method has a limit in increasing the resolution of the resist pattern, it has become difficult to cope with the recent increase in the density of printed wiring boards.

  Therefore, in order to achieve high resolution of the resist pattern, the photoresist method has been actively used. In this photoresist method, a photosensitive resin composition layer made of a photosensitive resin composition is formed on a substrate, the photosensitive resin composition layer is cured by exposure of a predetermined pattern, and unexposed portions are removed by development. Thus, a cured film having a predetermined pattern is formed.

  In addition, the photosensitive resin composition used in such a method is mainly an alkali development type that can be developed with a dilute aqueous alkali solution such as an aqueous sodium carbonate solution from the viewpoint of conservation of the working environment and global environment. . As such a photosensitive resin composition, for example, a liquid resist ink composition described in Patent Document 1 below and a photosensitive thermosetting resin composition described in Patent Document 2 below are known.

JP-A 61-243869 Japanese Patent Laid-Open No. 01-141904

  On the other hand, from the viewpoint of further increase in the density of printed wiring boards, an LDI (laser direct imaging) method, which is a method of directly drawing a pattern created by CAD (computer-aided design) without using a mask and using laser light. A compatible photosensitive curable resin composition is desired.

  The LDI method requires a highly sensitive photosensitive resin composition from the viewpoint of improving throughput. However, the conventional potential resin compositions described in Patent Document 1 and Patent Document 2 do not have sufficient photosensitivity that can correspond to the LDI system, and are difficult to apply to the LDI system. . In addition, the sensitivity can be improved by adding a large amount of a photopolymerization initiator or a sensitizer, but in that case, sufficient resist characteristics tend not to be obtained.

  Solder resists generally have developability, high resolution, solder heat resistance, plating resistance, thermal shock resistance (crack resistance) against temperature cycle test (TCT), super accelerated high temperature high humidity life test ( There is a demand for resistance (HAST resistance) between fine wirings to HAST). In addition, from the viewpoint of workability, it is also desired that the photosensitive resin composition has low tackiness (surface tack after solvent drying).

  The present invention has been made in view of the above circumstances, has an excellent alkali development product, can form a cured film having various properties required for a solder resist, has low tackiness, and It aims at providing the photosensitive resin composition which has the high photosensitivity which can respond to a LDI system, the photosensitive film using the same, and a photosensitive permanent resist.

  In order to solve the above problems, the photosensitive resin composition of the present invention comprises (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated group, and (C) a photopolymerization initiator. A photosensitive resin composition containing (B) the photopolymerizable compound having an ethylenically unsaturated group, containing at least (b1) a compound represented by the following general formula (1); ) As a photopolymerization initiator, it contains at least (c1) an α-aminoalkylphenone compound and (c2) an acridine compound having an acridin group.

In the formula, R ¹ , R ² and R ³ each independently represent H or CH ₂ , and n represents an integer of 1 to 9. When n is an integer of 2 or more, a plurality of R ² may be the same as or different from each other.

  The photosensitive resin composition of the present invention comprises (A) a binder polymer (hereinafter referred to as “(A) component”), (B) a photopolymerizable compound having an ethylenically unsaturated group (hereinafter referred to as “(B) component”. And (C) a photopolymerization initiator (hereinafter referred to as “component (C)”) as a component (B) as a compound (hereinafter referred to as (b1) general formula (1)). (C1) α-aminoalkylphenone-based compound (hereinafter referred to as “(c1) component”) and (c2) an acridine-based acridine group By containing a compound (hereinafter referred to as “component (c2)”), it is excellent in alkali developability, tackiness and photosensitivity. Moreover, according to the photosensitive resin composition of this invention, the cured film excellent in characteristics, such as developability, resolution, solder heat resistance, plating resistance, crack resistance, and HAST resistance, can be obtained. Therefore, the photosensitive resin composition of the present invention can be suitably used for the production of printed wiring boards and the like, and can be applied to the LDI system. The reason why such an effect can be obtained by the present invention is not necessarily clear, but the structure formed by the combination of the component (A), the component (b1), the component (c1), and the component (c2) has a cured film characteristic. This is considered to have a positive effect. Moreover, it is thought that the outstanding photosensitivity is acquired by the combination of (c1) component and (c2) component.

  In the photosensitive resin composition of the present invention, the component (c1) is a compound represented by the following general formula (2) from the viewpoint of further improving various properties of the cured film such as solder heat resistance and HAST resistance and photosensitivity. It is preferable that

^Wherein, R 4, ^{R 5} and ^{R 6} each independently represent an alkyl group having 1 to 10 carbon atoms, ^{R 7} and ^{R 8} are each independently a halogen atom, an alkyl group or a substituted having 1 to 10 carbon atoms The cycloalkyl group which may have a group is shown, p shows the integer of 0-5, q shows the integer of 0-4. When p is an integer of 2 or more, a plurality of R ⁷ may be the same or different from each other, and when q is an integer of 2 or more, the plurality of R ⁸ may be the same or different from each other.

  In the photosensitive resin composition of the present invention, the compound (c2) is a compound represented by the following general formula (3) from the viewpoint of further improving various properties of the cured film such as solder heat resistance and HAST resistance and photosensitivity. It is preferable that

In the formula, R ⁹ represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thiodialkylene group having 2 to 20 carbon atoms.

  In the photosensitive resin composition of the present invention, from the viewpoint of further improving the properties of the cured film such as solder heat resistance and HAST resistance and photosensitivity, as the component (A), (a1) ethylenically unsaturated group and carboxyl It is preferable to contain a urethane resin having a group (hereinafter referred to as “component (a1)”). In addition, from the viewpoint of further improving alkali developability and resolution, an acrylic resin (hereinafter referred to as (a) component) containing (a2) (meth) acrylic acid and (meth) acrylic acid alkyl ester as monomer units , “(A2) component”). In addition, from the viewpoint of further improving various properties, tackiness and photosensitivity of the cured film, the photosensitive resin composition of the present invention contains both the (a1) component and the (a2) component as the (A) component. It is more preferable.

  The photosensitive resin composition of the present invention may further contain (D) a thermosetting agent (hereinafter referred to as “component (D)”). In this case, various characteristics of the cured film formed from the photosensitive resin composition tend to be further improved.

  Moreover, this invention provides a photosensitive film provided with a support body and the photosensitive resin composition layer which consists of a photosensitive resin composition of the said this invention provided on this support body. According to such a photosensitive film, a dry film type solder resist made of the photosensitive resin composition of the present invention can be easily formed.

Furthermore, this invention provides the photosensitive permanent resist provided on the board | substrate for printed wiring boards, and formed from the photosensitive resin composition of the said invention. Such photosensitive permanent resist is
Excellent properties such as solder heat resistance, plating resistance, crack resistance and HAST resistance.

  According to the present invention, it is possible to form a cured film having various characteristics required for a solder resist, excellent alkali developability, small tackiness, and high photosensitivity capable of being compatible with the LDI method. The photosensitive resin composition, and the photosensitive film and photosensitive permanent resist using the same can be provided.

It is a figure which shows typically the cross-sectional structure of the photosensitive film which concerns on embodiment.

  Hereinafter, preferred embodiments of the present invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid and / or methacrylic acid, (meth) acrylate means acrylate and / or methacrylate, and (meth) acryloyl group means An acryloyl group and / or a methacryloyl group are meant.

(Photosensitive resin composition)
The photosensitive resin composition according to the present embodiment includes (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated group, and (C) a photopolymerization initiator. A composition comprising at least (b1) a compound represented by the following general formula (1) as the component (B) and at least (c1) an α-aminoalkylphenone compound as the component (C) And (c2) an acridine compound having an acridin group.

In the formula, R ¹ , R ² and R ³ each independently represent H or CH ₂ , and n represents an integer of 1 to 9. When n is an integer of 2 or more, a plurality of R ² may be the same as or different from each other.

  According to the photosensitive resin composition according to the present embodiment, in the combination of the component (A), the component (B) and the component (C), the component (B1) is contained as the component (B), and the component (C) Various properties (developability, resolution, insulation, solder heat resistance, plating resistance, cracks) of the cured film formed from the photosensitive resin composition by containing the component (c1) and the component (c2) Resistance and HAST resistance). Moreover, the photosensitive resin composition according to the present embodiment is excellent in alkali developability, tackiness, and photosensitivity.

  The photosensitive resin composition according to the present embodiment may further contain (D) a thermosetting agent (hereinafter referred to as “component (D)”). In this case, various characteristics of the cured film formed from the photosensitive resin composition tend to be further improved.

  Hereinafter, the (A) component, the (B) component, and the (C) component contained in the photosensitive resin composition according to the present embodiment will be described in detail.

[(A) component]
The photosensitive resin composition according to the present embodiment contains one or more binder polymers as the component (A). As the binder polymer, a polymer having a carboxyl group in the molecule is preferable. For example, acrylic resin, polyurethane, vinyl group-containing epoxy resin, epoxy resin, phenoxy resin, polyester, polyamide, polyimide, polyamideimide, polyesterimide, polycarbonate, melamine Resins, known resins such as polyphenylene sulfide and polyoxybenzoyl, and acid-modified resins thereof, including those having a carboxyl group in the molecule. These can be used alone or in combination of two or more.

  The photosensitive resin composition according to the present embodiment preferably contains the following component (a1) as the component (A). By containing the component (a1), it is excellent in various properties of the cured film such as solder heat resistance and HAST resistance, and is further excellent in photosensitivity. The reason for this is not necessarily clear, but the structure in which the (a1) component can further improve the flame retardancy, thermal shock resistance and photosensitivity by combining with the (b1) component, the (c1) component and the (c2) component. It is thought to form the body.

  The component (a1) is a urethane resin and has an ethylenically unsaturated group and a carboxyl group. As the component (a1), an epoxy acrylate compound having an ethylenically unsaturated group and two or more hydroxyl groups from the viewpoint of further improving the photosensitivity of the photosensitive resin composition and corresponding to curing with a smaller amount of active light energy A urethane resin obtained by reacting a diisocyanate compound with a diol compound having a carboxyl group is preferred.

  The epoxy acrylate compound may be an epoxy acrylate compound having an ethylenically unsaturated group and two or more hydroxyl groups. For example, a compound obtained by reacting a compound having two or more epoxy groups with an unsaturated monocarboxylic acid Etc. can be used.

  Here, as the compound having two or more epoxy groups, for example, a bisphenol type epoxy compound obtained by reaction of bisphenol A type or bisphenol F type with epichlorohydrin, hydrogenated bisphenol A type or hydrogenated bisphenol F type and epichlorohydrin. And hydrogenated bisphenol-type epoxy compounds, amino group-containing epoxy compounds, alicyclic epoxy compounds, epoxidized polybutadienes, and the like obtained by the reaction with. Moreover, the novolak-type epoxy compound obtained by reaction with novolaks and epichlorohydrin can also be used conveniently. The novolaks can be obtained, for example, by reacting phenol, cresol, rogenized phenol or alkylphenols with formaldehyde in the presence of an acidic catalyst. As the novolak type epoxy compounds, YDCN-701, YDCN-704, YDPN-638 and YDPN-602 manufactured by Toto Kasei Co., Ltd., DEN-431 and DEN-439 manufactured by Dow Chemical Company, EPN-1299 manufactured by Ciba Geigi Co., Ltd. N-730, N-770, N-865, N-665, N-673, VH-4150 and VH-4240, Nippon Kayaku Co., Ltd. EOCN-120 and BREN, etc. are commercially available It is available.

  As the compound having two or more epoxy groups, a salicylaldehyde-phenol type epoxy compound, a cresol type epoxy compound (EPPN502H, FAE2500, etc., manufactured by Nippon Kayaku Co., Ltd.) and the like are also preferably used. In addition, for example, Epicoat 828, Epicoat 1007 and Epicoat 807 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 860 and Epicron 3050 manufactured by Dainippon Ink & Chemicals, Inc. DER-330, DER-337 and DER manufactured by Dow Chemical Co., Ltd. -361, Daicel Chemical Industries, Ltd. Celoxide 2021, Mitsubishi Gas Chemical Co., Ltd. TETRAD-X and TETRAD-C, Nippon Soda Co., Ltd. EPB-13, EPB-27, etc. can be used. Furthermore, as the compound having two or more epoxy groups, a mixture or a block copolymer of the above-described compounds may be used.

  Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, cinnamic acid and the like. Among these, acrylic acid is preferable from the viewpoint of photosensitivity and solder heat resistance. Moreover, the compound obtained by reaction of a saturated or unsaturated polybasic acid anhydride and an unsaturated monoalcohol compound can also be used suitably as said unsaturated monocarboxylic acid. These can be used alone or in combination of two or more.

  Here, as the saturated or unsaturated polybasic acid anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, methylhexahexan Dibasic acid anhydrides such as hydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetra Aromatic polyvalent carboxylic anhydrides such as carboxylic dianhydrides, and other incidental examples such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride And polyvalent carboxylic anhydride derivatives such as those. Examples of the unsaturated monoalcohol compound include (meth) acrylates having one hydroxyl group, and half ester compounds of saturated or unsaturated dibasic acid. Furthermore, examples of the half ester compounds include compounds obtained by reacting a saturated or unsaturated dibasic acid with an unsaturated monoglycidyl compound. Examples of such half ester compounds include phthalic acid, tetrahydrophthalate, and the like. Acid, hexahydrophthalic acid, maleic acid or succinic acid and hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, tris (hydroxyethyl) isocyanurate di (meth) acrylate or glycidyl (meth) acrylate, It can be obtained by reacting at an equimolar ratio by a conventional method.

  Examples of the diisocyanate compound include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, o-xylene diisocyanate, o- Hydrogenated xylene diisocyanate, m-hydrogenated xylene diisocyanate, p-hydrogenated xylene diisocyanate, methylene bis (cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, Examples include 1,5-naphthalene diisocyanate. These can be used alone or in combination of two or more.

  Examples of the diol compound having a carboxyl group include dimethylolpropionic acid and dimethylolbutanoic acid.

  As urethane resins obtained by reacting an epoxy acrylate compound having an ethylenically unsaturated group and two or more hydroxyl groups, a diisocyanate compound, and a diol compound having a carboxyl group, UXE-3011, UXE-3012, UXE-3024 (Nippon Kayaku Co., Ltd., brand name) can be illustrated. Among these, UXE-3024 (trade name, manufactured by Nippon Kayaku Co., Ltd.) is most preferable from the viewpoints of flame retardancy, thermal shock resistance, and solder heat resistance.

  Moreover, as a urethane resin obtained by reacting an epoxy acrylate compound having an ethylenically unsaturated group and two or more hydroxyl groups, a diisocyanate compound, and a diol compound having a carboxyl group, for example, the following general formula (4): A urethane resin having the structure represented is preferred.

In the formula, R ¹¹ is a residue of epoxy acrylate, R ¹² is a residue of diisocyanate, 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 as or different from each other.

  In addition, as the component (a1), a polymer obtained by reacting a diol compound, a diisocyanate compound, a diol compound having a carboxyl group, and a monohydroxy compound having an ethylenically unsaturated group can also be suitably used. Here, as the diol compound, 1,6-hexanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, polycarbonate diol, polyester diol, polycaprolactone diol And polybutadienediol, and examples of the monohydroxy compound having an ethylenically unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and the like.

  The component (a1) preferably has an oxidation of 20 to 130 mgKOH / g, more preferably 40 to 110 mgKOH / g, and still more preferably 50 to 100 mgKOH / g. The photosensitive resin composition containing such a component (a1) has better developability with an alkaline aqueous solution, and more excellent resolution can be obtained.

Here, the acid value can be measured as follows. That is, first, about 1 g of a resin solution whose acid value is to be measured is precisely weighed, and then 30 g of acetone is added to this resin solution to dissolve it uniformly. 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 0.1N KOH aqueous solution, Wp represents the weight (g) of the measured resin solution, and I was measured. The ratio (mass%) of the non volatile matter in a resin solution is shown.

  In addition, the weight average molecular weight of the component (a1) is preferably 3000 to 200000 from the viewpoint of obtaining better coating properties by the photosensitive resin composition and crack resistance and HAST resistance of the cured film. More preferably, it is -100,000, and it is further more preferable that it is 7000-50000. The weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC) (in terms of standard polystyrene).

  It is preferable that the photosensitive resin composition which concerns on this embodiment contains an acrylic resin further as a binder polymer which is (A) component. As said acrylic resin, what was obtained by superposing | polymerizing (radical polymerization etc.) of the monomer (polymerizable monomer) which has an ethylenically unsaturated double bond is mentioned. Examples of such a monomer having an ethylenically unsaturated double bond include acrylamide such as diacetone acrylamide, esters of vinyl alcohol such as acrylonitrile and vinyl-n-butyl ether, alkyl (meth) acrylate, (Meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 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-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid (meth) ) Acrylic acid monomer, maleic acid, maleic anhydride, maleic acid monomer such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, Itaconic acid, crotonic acid, propiolic acid and the like can be mentioned. These can be used alone or in combination of two or more.

  As the acrylic resin, from the viewpoint of further improving the photosensitivity and the resist shape after photocuring, an acrylic resin ((a2) component) containing (meth) acrylic acid and (meth) acrylic acid alkyl ester as monomer units. Is preferred. As the component (a2), a vinyl copolymer compound obtained by using methacrylic acid and a (meth) acrylic acid alkyl ester as a copolymerization component is more 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.

  (A2) As a component, 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, vinyltoluene and the like.

  Further, as the component (a2), a copolymer having an ethylenically unsaturated bond introduced in the side chain and / or the terminal is also suitable. Such copolymers include vinyl polymerizable monomers having a carboxyl group such as acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl Acrylate, n-propyl methacrylate, n-propyl acrylate, butyl methacrylate, butyl acrylate, lauryl methacrylate, lauryl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, vinyl toluene, N-vinyl pyrrolidone, α-methyl styrene, 2-hydroxy Ethyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, etc. It is possible to use a vinyl polymerizable monomer obtained by general solution polymerization using a polymerization initiator such as azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide in an organic solvent. it can.

  As the component (A), an acid-modified polyester resin is also preferable. As an acid-modified polyester resin, for example, a chain structure including an ester bond formed by a polymerization reaction between a diglycidyl ether type epoxy compound and a dibasic acid using a tertiary amine having a pKa of 9.0 or less as a catalyst Examples thereof include resins having a carboxyl group by adding an acid anhydride to a chain structure.

  Diglycidyl ether type epoxy compounds for forming this acid-modified polyester resin include bisphenol A type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F type epoxy resins such as bisphenol F diglycidyl ether, and bisphenol S diglycidyl ether. Bisphenol S type epoxy resins such as biphenol diglycidyl ether, biphenol type epoxy resins such as bixylenol diglycidyl ether, hydrogenated bisphenol A type epoxy resins such as hydrogenated bisphenol A glycidyl ether, and the like Examples include dibasic acid-modified diglycidyl ether type epoxy resins. Of these, bisphenol A type epoxy resins are preferred because they are more excellent in heat resistance and chemical resistance and do not shrink relatively due to curing. These can be used alone or in combination of two or more.

  The acid value of the component (A) is preferably 40 to 170 mgKOH / g, and preferably 50 to 150 mgKOH / g in the case of an acrylic or acid-modified polyester binder polymer from the viewpoint of further improving alkali developability. It is more preferable that it is g, and it is still more preferable that it is 60-120 mgKOH / g. The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 to 200,000, and preferably 10,000 to 170,000 from the viewpoint of further improving the coating properties and alkali developability of the photosensitive resin composition. More preferably, it is more preferably 20000 to 150,000.

  As the component (A), it is preferable to use the component (a1) and the component (a2) in combination from the viewpoint of further improving photosensitivity, coating properties, and heat resistance.

  The content of the component (A) in the photosensitive resin composition is preferably 20 to 70 mass%, more preferably 30 to 60 mass%, based on the total amount of organic compound solids in the photosensitive resin composition.

  Moreover, 20-100 mass% is preferable in the total amount of (A) component, and, as for the content rate of the (a1) component in the case of containing (a1) component and (a2) component, 40-100 mass% is more preferable. Moreover, 5-40 mass% is preferable in the total amount of (A) component, and, as for the content rate of (a2) component, 10-30 mass% is more preferable.

[Component (B)]
The photosensitive resin composition according to the present embodiment contains a photopolymerizable compound having an ethylenically unsaturated group as the component (B), and at least one of the photopolymerizable compounds is represented by the following general formula (1). Compound (component (b1)). By containing the compound represented by the general formula (1), it is possible to obtain an ultrasensitive photosensitive resin composition compatible with the LDI method.

^Wherein, R 1, ^{R 2} and ^{R 3} each independently represent a hydrogen atom or a methyl radical, n represents an integer of 1 to 9. When n is an integer of 2 or more, a plurality of R ² may be the same as or different from each other.

  The component (b1) can be obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid. Examples of the component (b1) include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene / polypropylene glycol di (meth) acrylate, and these may be used alone or in combination of two or more. Can be used.

  In general formula (1), it is preferable that n is 1-9. When n is larger than 9, the tackiness of the photosensitive resin composition layer becomes large, and the workability tends to deteriorate.

  The compound represented by the general formula (1) (component (b1)) is also commercially available. For example, as polyethylene glycol dimethacrylate, 2G, 3G, 4G, and 9G (all of which are Shin-Nakamura Chemical Co., Ltd.) Product name).

  As the component (B), a photopolymerizable compound other than the component (b1) may be used in combination. Other photopolymerizable compounds include, for example, compounds obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids, bisphenol A (meth) acrylate compounds, and glycidyl group-containing compounds with α, β-unsaturated compounds. Examples include compounds obtained by reacting saturated carboxylic acids, urethane monomers such as (meth) acrylate compounds having a urethane bond in the molecule, or urethane oligomers. 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 can be used alone or in combination of two or more.

  Here, compounds obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, and PO-modified trimethylolpropane. Tri (meth) acrylate, EO or PO modified trimethylolpropane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate etc. are mentioned.

  Examples of the bisphenol A-based (meth) acrylate compound include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxy). Polypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane Etc.

  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) acryloxynona) Toxi) 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, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like. You may use these individually or in combination of 2 or more types. In addition, it is preferable to use a halogen-free component among the above-described component (B) from the viewpoint of impediment reduction to the environment.

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

  Examples of the compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include, for example, trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4- (meth)). (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 include (meth) acrylic monomers having an OH group at the β-position and diisocyanates such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. An addition reaction product with a compound is mentioned. Tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO or PO-modified urethane di (meth) acrylate, and the like can also be used.

  Furthermore, 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 the like. It is done. These (B) components can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (B) is preferably 5 to 45% by mass based on the total amount of organic compound solids in the photosensitive resin composition, from the viewpoints of tackiness, sensitivity, and resolution, and 10 to 35%. More preferably, it is mass%. There exists a tendency for a sensitivity and resolution to become more favorable by making content of (B) component 5 mass% or more, and there exists a tendency for tackiness to become more favorable by setting it as 45 mass% or less.

[Component (C)]
The photosensitive resin composition according to the present embodiment includes an α-aminoalkylphenone compound (component (c1)) and an acridine compound having an acridin group (component (c2)) as a photopolymerization initiator of the component (C). Containing.

  Examples of the component (c1) include 2-benzyl-2-dimethylamino-1-morpholinophenone) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [ 4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 and the like can be mentioned.

  As the component (c1), a compound represented by the following general formula (2) is more preferable.

In the formula, R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 10 carbon atoms, and R ⁷ and R ⁸ are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms or a substituent. The cycloalkyl group which may have a group is shown, p shows the integer of 0-5, q shows the integer of 0-4. When p is an integer of 2 or more, a plurality of R ⁷ may be the same or different from each other, and when q is an integer of 2 or more, the plurality of R ⁸ may be the same or different from each other.

  Examples of the compound represented by the general formula (2) include 2-benzyl-2-dimethylamino-1-morpholinophenone) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like.

  Examples of the component (c2) include 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane and the like.

  As the component (c2), a compound represented by the following general formula (3) is preferable.

In the formula, R ⁹ represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thiodialkylene group having 2 to 20 carbon atoms.

  Examples of the compound represented by the general formula (3) include 1,7-bis (9,9'-acridinyl) heptane.

  The photosensitive resin composition according to the present embodiment includes, as component (C), for example, benzophenone, 4,4′-bis (dimethylamino) benzophenone (Michler ketone), 4,4′-bis (diethylamino) benzophenone, 4- Methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-morpholinophenone) -butanone-1,2-ethylanthraquinone, aromatic ketones such as phenanthrenequinone, quinones such as alkylanthraquinone, benzoin methyl Benzoin ethers such as ether, benzoin ethyl ether and benzoin phenyl ether, benzoins such as methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, 9-phenylacridine, 1,7-bis (9,9'-acrylate) Yl) acridine derivatives such as heptane, N- phenylglycine, N- phenylglycine derivatives may contain coumarin compounds. These can be used individually by 1 type or in combination of 2 or more types.

  For example, when the photosensitive resin composition is cured by exposure to actinic rays having a wavelength range near 405 nm, 2-benzyl-2-dimethylamino-1-morpholinophenone) -butanone-1 and 1,7-bis (9 , 9′-Acridinyl) heptane is preferred because it can be cured with a smaller exposure amount. It is also preferable to use 9-phenylacridine instead of 1,7-bis (9,9'-acridinyl) heptane.

  The content of the component (C) is preferably 0.1 to 15% by mass, based on the total amount of organic compound solids in the photosensitive resin composition, from the viewpoint of further improving the photosensitivity, and is preferably 2 to 10% by mass. % Is more preferable.

[(D) component]
The photosensitive resin composition according to this embodiment preferably further contains a thermosetting agent (component (D)). (D) As a component, thermosetting compounds, such as an epoxy resin, a phenol resin, a urea resin, a melamine resin, etc. are mentioned. Examples of epoxy resins include bisphenol A type tertiary fatty acid-modified polyol epoxy resins, diglycidyl esters such as diglycidyl phthalate and diglycidyl tetrahydrophthalate, and diglycidyl amines such as diglycidyl aniline and diglycidyl toluidine. Etc. You may use these individually by 1 type or in combination of 2 or more types.

  Moreover, the block isocyanate compound which is a latent thermosetting agent can also be used as (D) component. Examples of the blocked isocyanate compound include polyisocyanate compounds blocked with a blocking agent such as an alcohol compound, a phenol compound, ε-caprolactam, an oxime compound, and an active methylene compound. Here, as a polyisocyanate compound blocked by a blocking agent, 4,4-diphenylmethane disissocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene 1,5-diisocyanate, o- Aromatic polyisocyanates such as xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene dimer, aliphatic polyisocyanates such as hexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, etc. From the viewpoint of heat resistance, aromatic polyisocyanate from the viewpoint of coloring prevention, aliphatic polyisocyanate or alicyclic polyisocyanate. It is preferred.

  (D) As a component, it is preferable to contain Sumidur BL-3175 (the Sumitomo Bayer Urethane company make, brand name) from a viewpoint which is further excellent in storage stability and HAST tolerance.

  When the photosensitive resin composition contains the component (D), the content is 5 to 40 based on the total amount of organic compound solids of the photosensitive resin composition from the viewpoint of solder heat resistance and insulation reliability. It is preferable that it is mass%, and it is more preferable that it is 10-30 mass%. When the content of the component (D) is 5% by mass or more, the soldering heat resistance and the insulation reliability of the photosensitive resin composition tend to become better, and by setting the content to 40% by mass or less, the photosensitive resin. There exists a tendency for the tackiness of a composition layer to become better.

[Other ingredients]
The photosensitive resin composition according to the present embodiment includes a dye such as malachite green, a photochromic agent such as leuco crystal violet, a thermochromic inhibitor, a plasticizer such as p-toluenesulfonamide, phthalocyanine blue, and the like as necessary. Organic pigments such as phthalocyanine or azo, inorganic pigments such as titanium dioxide, fillers made of inorganic pigments such as silica, alumina, talc, calcium carbonate or barium sulfate, the above-mentioned fillers, organic pigments, inorganic pigments, etc. Wetting and dispersing agents, flame retardants, antifoaming agents, stabilizers, adhesion-imparting agents, leveling agents, antioxidants, fragrances, imaging agents and the like can be included. When it contains these components, it is preferable that the content is about 0.01-70 mass% on the basis of the organic compound solid content whole quantity of the photosensitive resin composition. Moreover, said component can be used individually by 1 type or in combination of 2 or more types.

  In addition, the photosensitive resin composition according to the present embodiment, if necessary, is a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or the like. It can melt | dissolve in these mixed solvents and can apply | coat as a solution of solid content about 30-70 mass%.

  The photosensitive resin composition according to this embodiment is coated as a liquid resist on a metal surface such as copper, a copper-based alloy, iron, and an iron-based alloy, dried, and then coated with a protective film as necessary. It can be used in the form of a photosensitive element described later.

(Photosensitive element)
Next, the photosensitive element using the photosensitive resin composition which concerns on this embodiment is demonstrated. FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive element according to this embodiment. The photosensitive element 1 shown in FIG. 1 includes a support 10 and a photosensitive resin composition layer 20 provided on the support 10. The photosensitive resin composition layer 20 is a layer made of the photosensitive resin composition according to this embodiment. Moreover, the photosensitive element 1 which concerns on this embodiment may coat | cover the surface F1 on the opposite side to the support body 10 on the photosensitive resin composition layer 20 with the protective film 30. FIG.

  The photosensitive resin composition layer 20 is obtained by dissolving the photosensitive resin composition according to the present embodiment in the above solvent or mixed solvent to obtain a solution having a solid content of about 30 to 70% by mass, and then applying the solution on the support 10. It is preferable to form by coating.

  Although the thickness of the photosensitive resin composition layer 20 varies depending on the use, it is preferably 10 to 100 μm and more preferably 20 to 60 μm in thickness after drying after removing the solvent by heating and / or hot air blowing. preferable. When the thickness of the photosensitive resin composition layer 20 is 10 μm or more, industrial coating tends to be easier, and when the thickness is 100 μm or less, the above-described effect produced by the present invention is further increased. At the same time, the flexibility and resolution tend to be better.

  Examples of the support 10 included in the photosensitive element 1 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 5 μm or more, the support tends to be hardly broken when the support is peeled before development, and when the thickness is 100 μm or less, the resolution and flexibility tend to be better. is there.

  The photosensitive element 1 composed of two layers of the support 10 and the photosensitive resin composition layer 20 or the photosensitive element composed of three layers of the support 10, the photosensitive resin composition layer 20 and the protective film 30 is, for example, The film may be stored as it is, or may be wound around a roll core and stored after a protective film is interposed.

  The resist pattern using the photosensitive element according to the present embodiment includes a lamination process in which the photosensitive element is laminated on a circuit forming substrate, and a predetermined portion of the photosensitive resin composition layer is irradiated with actinic rays to form a photosensitive pattern. It can manufacture by the manufacturing method provided with the exposure process which forms a photocuring part in a resin composition layer, and the image development process which removes photosensitive resin composition layers other than this photocuring part.

  When the photosensitive element has a protective film, the method for producing a resist pattern may further include a removal step of removing the protective film from the photosensitive element before the laminating step. Moreover, in the said lamination process, it laminates | stacks so that the surface on the opposite side to the support body of the photosensitive resin composition layer and the circuit formation board | substrate may contact | connect. That is, the photosensitive element is laminated on the circuit board so that the photosensitive resin composition layer and the support are laminated in this order.

  The circuit forming substrate is an insulating layer and a conductor layer (copper, copper alloy, nickel, chromium, iron, stainless steel or other iron alloy, preferably copper, copper alloy, Substrate made of an iron-based alloy.

  Examples of the laminating method in the laminating step include a method of laminating by pressing the photosensitive resin composition layer on the circuit forming substrate while heating. In the case of such lamination, lamination is preferably performed under reduced pressure from the viewpoint of adhesion and followability. The surface to be laminated is usually the surface of the conductor layer of the circuit forming substrate, but may be a surface other than the conductor layer.

  Here, the heating temperature of the photosensitive resin composition layer is preferably 50 to 130 ° C., the pressure bonding pressure is preferably about 0.1 to 1.0 MPa, and the ambient pressure is more preferably 4000 Pa or less. Although preferred, these conditions are not particularly limited. Further, if the photosensitive resin composition layer is heated to 50 to 130 ° C. as described above, it is not always necessary to pre-heat the circuit forming substrate in advance, but in order to further improve the laminating property, circuit formation is performed. It is also possible to pre-heat the substrate.

  After the lamination is completed in this manner, a photocured portion is formed by irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays in the exposure step. Examples of the method for forming the photocured portion include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork. Further, exposure by a direct drawing method having no mask pattern such as an LDI method or a DLP (Digital Light Processing) exposure method is also possible. Under the present circumstances, when the support body which exists on the photosensitive resin composition layer is transparent, an actinic ray can be irradiated as it is. When the support is opaque, the photosensitive resin composition layer is irradiated with actinic rays after the support is removed.

  As the active light source, a known light source, for example, a light source that effectively emits ultraviolet rays, such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or a semiconductor laser can be used. A light source that effectively emits visible light, such as a photographic flood bulb or a solar lamp, can also be used.

  Next, when a support is present on the photosensitive resin composition layer, after removing the support, in the development process, the photosensitive resin composition layer other than the photocured portion by wet development, dry development or the like. The resist pattern is removed and developed to form a resist pattern.

  In the case of wet development, development can be performed using a developer such as an alkaline aqueous solution by a known method such as spraying, rocking immersion, brushing, or scraping. The developer is preferably safe and stable and has good operability. For example, a dilute solution (1 to 5% by mass aqueous solution) of sodium carbonate at 20 to 50 ° C. is used.

  For example, when the resist pattern obtained by the above-described forming method is used as a solder resist for a printed wiring board, a high pressure is used for the purpose of improving solder heat resistance, chemical resistance, etc. as the solder resist after completion of the development process. It is preferable to perform ultraviolet irradiation with a mercury lamp or heating with an oven.

When irradiating with ultraviolet rays, the irradiation amount can be adjusted as necessary. For example, the irradiation can be performed at an irradiation amount of about 0.2 to 10 J / cm ² . Moreover, when heating, it is preferable to carry out for about 15 to 90 minutes in the range of about 100-170 degreeC. Furthermore, both ultraviolet irradiation and heating may be performed, and after one of them is performed, the other can be performed.

  The resist pattern obtained by the above-described forming method is preferably used as a permanent mask formed on a printed wiring board. Since the cured film formed from the photosensitive resin composition according to the present embodiment has excellent flame retardancy, it also serves as a permanent mask for a printed wiring board that also serves as a protective film for wiring after soldering to the substrate. It is valid.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.
(Examples 1-3, Comparative Examples 1-3)
[Preparation of photosensitive film]
First, the solution of the photosensitive resin composition was obtained by mixing each component shown in Table 1 with the compounding ratio (weight basis) of the solid content shown in a table | surface. In the table, component (A) is an acrylic resin as component (a2), and is a copolymer of methacrylic acid, methyl methacrylate, and butyl acrylate (methacrylic acid: methyl methacrylate: butyl acrylate = 17. % By weight: 62% by weight: 21% by weight) and a weight average molecular weight of 100,000 and an acid value of 110 mgKOH / g. The component (a1) is a urethane resin (Nippon Kayaku Co., Ltd., trade name UXE-3024, weight average molecular weight: 10,000). The components (B-1) to (B-4) are polyethylene glycol dimethacrylate (all manufactured by Shin-Nakamura Chemical Co., Ltd., trade names 3G, 4G, 9G, and 23G). In addition, (B-1) component is a compound in which n is 3 in the above general formula (1), (B-2) component is a compound in which n is 4, and (B-3) component is in which n is 9 Compound (B-4) is a compound in which n is 23. The component (B-5) is bisphenol A polyoxyethylene dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name BPE-10). The component (B-6) is trimethylolpropane trimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name TMPT). Component (C-1) is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name I-369, manufactured by Ciba Specialty Chemicals), (C -2) The component is 1,7-bis (9-acridinyl) heptane (Asahi Denka Kogyo Co., Ltd., trade name N-1717). The component (D-1) is a block type isocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name Sumidur BL-3175). B30, which is another component, is barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., trade name Variace B30). In addition, methyl ethyl ketone was added to these photosensitive resin compositions as a diluent.

  Next, these photosensitive resin composition solutions were uniformly applied onto a 16 μm polyethylene terephthalate film (product name: G2-16, manufactured by Teijin Limited) as a support, and a hot air convection dryer was used. The photosensitive resin composition layer was formed on the support by using and drying at 100 ° C. for 10 minutes. The film thickness after drying of the photosensitive resin composition layer was 30 μm.

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

[Characteristic evaluation]
Using the photosensitive films prepared in Examples 1 to 3 and Comparative Examples 1 to 3, the following tests were performed, respectively, tackiness, plating resistance, solder heat resistance, cracks when each photosensitive film was used. Resistance, HAST resistance, and resolution were evaluated. The results are shown in Table 2.

(Tackiness)
First, an evaluation substrate was prepared as follows using each photosensitive film. That is, first, the copper surface of a printed wiring board substrate (trade name E-679, manufactured by Hitachi Chemical Co., Ltd.) obtained by laminating a 12 μm thick copper foil on a glass epoxy substrate was polished with an abrasive brush and washed with water. After that, it was dried. Using a press-type vacuum laminator (trade name: MVLP-500, manufactured by Meiki Seisakusho) on this printed wiring board substrate, the press hot plate temperature is 70 ° C., the evacuation time is 20 seconds, the lamination press time is 30 seconds, and the atmospheric pressure is 4 kPa or less. The polyethylene film of the photosensitive film was peeled off and laminated under the condition of the pressure bonding pressure of 0.4 MPa to obtain a laminate for evaluation. Without exposing to the laminated body for evaluation, the polyethylene terephthalate on the laminated body was peeled off, the finger was lightly pressed against the surface of the coating film, and the degree of sticking to the finger was evaluated according to the following criteria. In other words, “A” indicates that sticking to the finger is hardly or hardly recognized, “B” indicates that sticking to the finger is slightly recognized, and “C” indicates that sticking to the finger is remarkable. .

(Plating resistance)
The laminate for evaluation after lamination was allowed to stand at room temperature (25 ° C.) for 1 hour, and then a direct drawing exposure machine (product name: DE-1AH, manufactured by Hitachi Via Mechanics Co., Ltd.) using a 405 nm blue-violet laser diode as a light source. ), And using the drawing data having a grid pattern from above the evaluation laminate, exposure was performed with an energy amount that the number of remaining step stages after development of the stove 21-step step tablet was 17. . The amount of energy applied to each evaluation laminate is shown in Table 2. In addition, it means that it is a highly sensitive photosensitive resin composition, so that energy amount is small.

  After exposure, the polyethylene terephthalate film on the laminate for evaluation is peeled off and sprayed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 1.7 times the minimum development time (minimum time during which the unexposed area is developed). Developed. Thereby, the pattern formed by hardening the photosensitive resin composition layer was formed.

Subsequently, ultraviolet irradiation is performed with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd., and further heat treatment is performed at 160 ° C. for 60 minutes on the printed wiring board substrate. An evaluation substrate on which a solder resist was formed was obtained.

  The substrate for evaluation is subjected to electroless nickel plating (trade name Nimden NPR-4, manufactured by Uemura Kogyo Co., Ltd.) (treatment for 15 minutes), and further electroless gold plating (trade name, Goblite, manufactured by Uemura Kogyo Co., Ltd.). TAM-55) was applied (10 minutes treatment).

  For the evaluation substrate thus plated, the plating solution soaks into the bottom of the solder resist, and the solder resist floats and peels from the substrate is observed with a 100-fold metal microscope. evaluated. That is, the case where no penetration into the bottom of the solder resist was observed and the solder resist was not lifted or peeled off was designated as “A”, and the case where any of them was recognized as “C”. In addition, although a slight penetration into the bottom of the solder resist was recognized, there was no practical problem at all, and “B” was used in order to clarify the difference between the examples.

(Solder heat resistance)
Using the evaluation substrate having a solder resist obtained in the same manner as in the “plating resistance” test, the solder heat resistance was evaluated as follows. That is, after applying a rosin flux (trade name MH-820V, manufactured by Tamura Kaken Co., Ltd.) to the substrate for evaluation, a soldering treatment was performed in which the substrate was immersed in a solder bath at 288 ° C. for 30 seconds.

  The state of occurrence of cracks in the solder resist on the evaluation substrate subjected to solder plating in this way, and the degree to which the solder resist floated from the substrate and peeling were observed with a 100-fold metal microscope. The results were evaluated according to the following criteria. That is, “A” was given when no cracking of the solder resist was observed and no solder resist was lifted or peeled off, and “C” was given when any of them was observed.

(Crack resistance)
For the evaluation substrate having a solder resist obtained in the same manner as in the above “plating resistance” test, after being exposed to the atmosphere of −55 ° C. for 15 minutes, the temperature was increased at a temperature increase rate of 180 ° C./min. Next, after being exposed to the atmosphere at 125 ° C. for 15 minutes, a test was performed in which a thermal cycle in which the temperature was lowered at a rate of 180 ° C./min was repeated 200 times.

  After the test, cracks and peeling of the solder resist (permanent resist film) on the evaluation substrate were observed with a 100-fold metal microscope and evaluated according to the following criteria. That is, “A” indicates that the solder resist could not be observed for cracking and peeling, and “C” indicates that any of them could be confirmed.

(HAST resistance)
First, a copper surface of a printed wiring board substrate (trade name E-679, manufactured by Hitachi Chemical Co., Ltd.) in which a 12 μm thick copper foil is laminated on a glass epoxy base material is etched to have a line / space of 50 μm / 50 μm. It was processed into a comb-type electrode. This was used as an evaluation wiring board.

  A solder resist made of a cured product of a resist was formed on the comb-shaped electrode of this evaluation wiring board in the same manner as in the “plating resistance” test, and this was used as an evaluation substrate. This evaluation substrate was exposed to a super accelerated high temperature high humidity life test (HAST) bath for 100 hours under the conditions of 130 ° C./85%/5V. After the test, the degree of migration in each evaluation substrate was observed with a 100-fold metal microscope and evaluated according to the following criteria. That is, “A” indicates that no significant migration has occurred in the solder resist (permanent resist film), and “C” indicates that significant migration has occurred. Migration is a phenomenon in which discoloration of the solder resist around the electrode and a decrease in insulation resistance occur when copper is eluted and deposited from the copper electrode to the solder resist.

(Resolution)
The evaluation laminate obtained in the same manner as in the above “Plating Resistance” test was allowed to stand at room temperature for 1 hour, and then a direct drawing exposure machine using a 405 nm blue-violet laser diode as a light source (Hitachi Via Mechanics Co., Ltd.) Using product data DE-1AH), drawing data having a wiring pattern with a line width / space width of 6/6 to 47/47 (unit: μm) is used from above the evaluation laminate. The exposure was carried out with an energy amount such that the number of remaining step steps after development of the stopher 21-step step tablet was 17.

  The polyethylene terephthalate on the evaluation laminate after exposure is peeled off and spray-developed with a 1% by weight aqueous sodium carbonate solution at 30 ° C. for 1.7 times the minimum development time (minimum time for removing the unexposed area). Then, the unexposed part was removed and the resolution was evaluated. The value of the resolution is represented by the smallest value among the space widths (μm) in which the unexposed portions can be completely removed by the development processing, and the smaller the numerical value, the higher the resolution.

  As shown in Table 2, according to the photosensitive resin compositions of Examples 1 to 3, in addition to excellent tackiness, plating resistance, and solder heat resistance, sufficient crack resistance, HAST resistance, and resolution are provided. It was confirmed that it was obtained. On the other hand, in Comparative Examples 1-3, tackiness or sensitivity was insufficient.

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

Claims (8)

A photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated group, and (C) a photopolymerization initiator,
As (B) the photopolymerizable compound having an ethylenically unsaturated group, at least (b1) contains a compound represented by the following general formula (1),
A photosensitive resin composition comprising, as the photopolymerization initiator (C), at least (c1) an α-aminoalkylphenone compound and (c2) an acridine compound having an acridin group.

^[Wherein, R 1, ^{R 2} and ^{R 3} each independently represents H or CH _2, n represents an integer of 1 to 9. When n is an integer of 2 or more, a plurality of R ² may be the same as or different from each other. ] The photosensitive resin composition according to claim 1, wherein the (c1) α-aminoalkylphenone-based compound is a compound represented by the following general formula (2).

[Wherein R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 10 carbon atoms, and R ⁷ and R ⁸ each independently represent a halogen atom, an alkyl group having 1 to 10 carbon atoms or The cycloalkyl group which may have a substituent is shown, p shows the integer of 0-5, q shows the integer of 0-4. When p is an integer of 2 or more, a plurality of R ⁷ may be the same or different from each other, and when q is an integer of 2 or more, the plurality of R ⁸ may be the same or different from each other. ] The photosensitive resin composition according to claim 1 or 2, wherein the (c2) acridine compound having an acridinyl group is a compound represented by the following general formula (3).

Wherein, ^{R 9} represents an alkylene group, oxa dialkylene group or Chiojiarukiren group having 2 to 20 carbon atoms having 2 to 20 carbon atoms having 2 to 20 carbon atoms. ]   The photosensitive resin composition as described in any one of Claims 1-3 containing the urethane resin which has at least (a1) ethylenically unsaturated group and a carboxyl group as said (A) binder polymer.   The acrylic resin containing at least (a2) (meth) acrylic acid and (meth) acrylic acid alkyl ester as monomer units as the (A) binder polymer, according to any one of claims 1 to 4. The photosensitive resin composition as described.   (D) The photosensitive resin composition as described in any one of Claims 1-5 which further contains a thermosetting agent.   A photosensitive film 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 1-6 provided on this support body.   The photosensitive permanent resist provided on the board | substrate for printed wiring boards, and formed from the photosensitive resin composition as described in any one of Claims 1-6.

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