JP5263603B2 - Photosensitive resin composition, photosensitive film, method for forming resist pattern, and permanent resist using the same. - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for a printed wiring board excellent in cracking resistance after a repeated heat cycle test, and a photosensitive film and a permanent resist using the same. <P>SOLUTION: The photosensitive resin composition includes an acryl copolymer (a) having a repeating unit derived from maleimide or a derivative thereof, a resin (b) obtained by reacting a resin, obtained by reacting an epoxy resin with a vinyl group-containing monocarboxylic acid with a polybasic acid anhydride containing a saturated or unsaturated group, a photopolymerizable monomer (c), a photopolymerization initiator (d) and a heat curing agent (e). When the photosensitive resin composition is exposed to 1 J/cm<SP>2</SP>of ultraviolet radiation and cured at 160&deg;C, a cured film which satisfies a constant A of &ge;65 and a constant B of &le;0.06 in the expression (1): &sigma;=A&times;N<SP>-B</SP>is obtained, wherein &sigma; represents a stress amplitude value given to a photosensitive resin cured product at 25&deg;C, and N represents a number of iterations of stress amplitude until the breaking of the photosensitive resin cured product. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a photosensitive resin composition for a protective film of a printed wiring board, and more specifically, in the field of solder resist of a substrate for a semiconductor package, and a photosensitive resin composition for a protective film of a printed wiring board used as a permanent resist. , A photosensitive film using the same, a resist pattern forming method, and a permanent resist.

In the printed wiring board field, conventionally, a permanent resist (protective film, hereinafter also referred to as a permanent mask resist) is formed on a printed wiring board. This permanent mask resist has a role of preventing corrosion of the conductor layer and maintaining electrical insulation between the conductor layers when the printed wiring board is used.
Conventionally, permanent mask resist in printed wiring board production is a method of screen printing a thermosetting or photosensitive resin composition, or a method of vacuum-laminating a thermosetting or photosensitive resin composition into a B-stage film. Have been made.
For example, in a flexible wiring board using mounting methods such as FC, TAB, and COF, a thermosetting resin paste is screen-printed except for a connecting wiring pattern portion with a rigid wiring board, an IC chip, an electronic component, or an LCD panel. The permanent mask resist is formed by thermosetting (see, for example, Patent Document 1).
Further, in a semiconductor package substrate such as BGA (ball grid array) and CSP (chip size package) mounted on a personal computer, (1) a semiconductor element is flip-chip mounted on the semiconductor package substrate via solder. (2) In order to wire-bond and bond the semiconductor element and the semiconductor package substrate, (3) In order to solder-bond the semiconductor package substrate to the motherboard, it is necessary to remove the permanent mask resist at the connecting portion. Such a photosensitive resin composition that can be easily removed is used as a permanent mask resist (see, for example, Patent Document 2).

JP 2003-198105 A Japanese Patent Laid-Open No. 11-240930

In recent years, with the increase in the density of wiring patterns, permanent mask resists are required to have high resolution, and photosensitive resin compositions for pattern formation by photographic methods are actively used. Among them, the alkali development type that can be developed with a weak alkaline aqueous solution such as a sodium carbonate aqueous solution has become the mainstream from the viewpoint of the preservation of the working environment and the global environment.
For permanent mask resists, in general, in addition to characteristics such as developability, high resolution, insulation, surface hardenability, solder heat resistance and plating resistance, a temperature cycle test (TCT) of −55 ° C. to 125 ° C. Characteristics such as resistance to cracking and HAST resistance between fine wirings for a super accelerated high temperature and high humidity life test (HAST) are required. In particular, in recent semiconductor packages such as FC-BGA and CSP, the miniaturization of wiring, the enlargement of semiconductor elements, and the thinning of printed wiring boards have progressed, and the crack resistance against temperature cycle tests is greatly reduced. there were.
The present invention relates to a photosensitive resin composition for a protective film of a printed wiring board that is excellent in crack resistance even after repeated temperature cycle tests, a photosensitive film using the same, a method for forming a resist pattern, a permanent resist The purpose is to provide.

  The present invention provides [1] a resin obtained by reacting an acrylic copolymer (a) having a repeating unit derived from maleimide or a maleimide derivative in the molecule, an epoxy resin, and a vinyl group-containing monocarboxylic acid, Resin (b) obtained by reacting a saturated or unsaturated group-containing polybasic acid anhydride, a photopolymerizable monomer (c) having an ethylenically unsaturated group, a photopolymerization initiator (d), a thermosetting agent (e ), And a cured film having a constant A represented by the following formula (1) of 65 or more and a constant B of 0.06 or less is obtained. A photosensitive resin composition is provided.

（式（１）中、σは室温（２５℃）下で感光性樹脂硬化物に与える応力振幅値を示し、Ｎは感光性樹脂硬化物が破断するまでの応力振幅の繰り返し回数を示す。）
本発明の感光性樹脂組成物によれば、上記式（１）において、定数Ａを高く、及び定数Ｂを低くすることで、繰り返しの応力振幅を与えたときのクラック耐性を高く保つことが可能となり、温度サイクル試験後のクラック耐性に優れる感光性樹脂組成物を得ることができる。

(In the formula (1), σ represents a stress amplitude value applied to the cured photosensitive resin at room temperature (25 ° C.), and N represents the number of times the stress amplitude is repeated until the cured photosensitive resin is broken.)
According to the photosensitive resin composition of the present invention, in the above formula (1), by increasing the constant A and decreasing the constant B, it is possible to maintain high crack resistance when repeated stress amplitudes are applied. Thus, a photosensitive resin composition having excellent crack resistance after the temperature cycle test can be obtained.

Moreover, this invention provides the photosensitive resin composition as described in said [1] whose [2] thermosetting agent (e) is block type isocyanate. It is desirable to use a block type isocyanate because it is excellent in pot life after mixing one liquid. In particular, when it is used as a dry film type solder resist, it can be used without any problem of storage stability, which is very effective.
The present invention also provides [3] the photosensitive resin composition according to the above [1] or [2], further comprising an elastomer component (f) having a butadiene skeleton in the molecule. This makes it possible to maintain high crack resistance when a repeated stress amplitude is applied, and a photosensitive resin composition having excellent crack resistance after a temperature cycle test can be obtained.
Moreover, this invention further contains the acrylic copolymer (g) which has a repeating unit derived from [4] (meth) acrylic-acid alkylester, The photosensitive in any one of said [1]-[3]. A resin composition is provided.
It is preferable to further contain an acrylic copolymer (g) comprising a copolymer component other than maleimide or a maleimide derivative. By adding a high molecular weight acrylic copolymer, it becomes possible to maintain high crack resistance when repeated stress amplitude is applied, and to obtain a photosensitive resin composition having excellent crack resistance after a temperature cycle test. it can.
Furthermore, the present invention provides [5] the photosensitive resin composition according to any one of [1] to [4] above, which further contains an inorganic filler (h).
The inclusion of the inorganic filler (h) makes it possible to maintain high crack resistance when the coating film strength is increased and repeated stress amplitude is applied. Moreover, since the thermal expansion coefficient is also reduced, a photosensitive resin composition having excellent crack resistance after the temperature cycle test can be obtained.

Furthermore, the present invention provides a photosensitive resin comprising [6] a support and the photosensitive resin composition according to any one of the above [1] to [5] formed by coating and drying on the support. And a photosensitive layer.
Moreover, this invention provides the photosensitive resin composition layer which consists of the photosensitive resin composition in any one of said [1]-[5] on a [7] circuit formation board | substrate, The said photosensitive resin composition Provided is a method for forming a resist pattern, in which an active layer is irradiated with an actinic ray in a form of an image to photocure an exposed portion and an unexposed portion is removed by development. The actinic ray can be obtained by a direct drawing method.
The present invention also provides [8] a permanent resist formed by the method for forming a resist pattern described in [7] above.

  According to the present invention, it is possible to provide a photosensitive resin composition excellent in crack resistance even after a repeated temperature cycle test, a photosensitive film using the same, a method for forming a resist pattern, and a permanent resist. .

It is a figure which shows an example of the SN characteristic measurement result of the photosensitive permanent resist which concerns on this invention.

Hereinafter, preferred embodiments of the present invention will be described in detail.
First, the photosensitive resin composition which concerns on suitable embodiment is demonstrated. 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.
Specific examples of the acrylic copolymer having a repeating unit derived from maleimide or a maleimide derivative in the molecule as component (a) of the present invention include maleimide, ethylmaleimide, butylmaleimide, octylmaleimide, cyclohexylmaleimide, hydroxy Acrylic copolymer containing ethylmaleimide, hydroxybutylmaleimide, ethoxyethylmaleimide, butoxyethylmaleimide, cyclohexylmaleimide, phenylmaleimide, methylphenylmaleimide, hydroxyphenylmaleimide, carboxyphenylmaleimide, methoxyphenylmaleimide, benzylmaleimide, etc. as copolymerization components It is a coalescence. The repeating unit derived from this maleimide or maleimide derivative is preferably 5% or more and 60% or less, and more preferably 10% or more and 50% or less. If it is less than 5%, the heat resistance of the resin tends to be insufficient. If it exceeds 60%, the adhesion of the resin is lowered, and the resin tends to be hard and brittle.
The other copolymer components of the acrylic copolymer (a) are not particularly limited, but those containing a dicyclopentenyl or dicyclopentaniel skeleton in the molecule are desirable. Examples of such a copolymer component include dicyclopentenyl acrylate FA-511A (manufactured by Hitachi Chemical Co., Ltd.) and dicyclopentenyloxyethyl acrylate FA-512A (manufactured by Hitachi Chemical Co., Ltd.). , Dicyclopentanyl acrylate FA-513A (manufactured by Hitachi Chemical Co., Ltd.), dicyclopentanyl methacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.), dicyclopentenyloxyethyl methacrylate FA-512M (Hitachi Chemical) Kogyo Co., Ltd.).
Other examples include ethylenically unsaturated carboxylic acids such as 2-carboxyethyl (meth) acrylate and (anhydrous) maleic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth (Meth) acrylic acid alkyl esters such as n-butyl acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, ) Glycidyl acrylate, (meth) acrylonitrile, (meth) acrylamide, aminomethyl (meth) acrylate, N-methylaminomethyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, ) Aminoalkyl acrylate, styrene, vinyltoluene, α-methyls Styrene monomer Ren like, and vinyl acetate.
The acid value of the acrylic copolymer (a) is preferably 20 (KOHmg / g) or more, particularly preferably 40 to 150 (KOHmg / g). The weight average molecular weight (Mw) is 5000 to 150,000, preferably in the range of 8000 to 100,000, and more preferably in the range of 10,000 to 50,000. Furthermore, the acrylic copolymer used in the present invention preferably contains a radical polymerizable copolymer having an ethylenically unsaturated group in the side chain, and the radical copolymer having a side chain ethylenically unsaturated group is preferably used. The ethylenically unsaturated group concentration is more preferably 1.0 × 10 ^{−5 to} 6.0 × 10 ⁻³ mol / g. Moreover, it is still more desirable that it is 1.0 * 10 < ^-4 > -6.0 * 10 < ^-3 > mol / g. In addition, the side chain ethylenically unsaturated group is desirably introduced by a urethane monomer containing an ethylenically unsaturated group and an isocyanate. In addition, an ethylenically unsaturated group can be introduced by a method using a known glycidyl methacrylate, but in that case, electrical characteristics (HAST resistance) and the like tend to be reduced due to the influence of impurities derived from the raw material.

A resin obtained by reacting a saturated or unsaturated group-containing polybasic acid anhydride with a resin obtained by reacting the epoxy resin as the component (b) used in the present invention with a vinyl group-containing monocarboxylic acid; For example, an addition reaction product obtained by adding a saturated or unsaturated polybasic acid anhydride (a3) to an esterified product of an epoxy compound (a1) and a vinyl group-containing monocarboxylic acid (a2) can be used. These can be obtained by the following two-step reaction. In the first reaction (hereinafter referred to as “first reaction” for convenience), the epoxy compound (a1) reacts with the vinyl group-containing monocarboxylic acid (a2). In the next reaction (hereinafter referred to as “second reaction” for convenience), the esterified product produced in the first reaction reacts with the saturated or unsaturated polybasic acid anhydride (a3).
Although there is no restriction | limiting in particular as said epoxy compound (a1), For example, a bisphenol type epoxy compound, a novolak type epoxy compound, a biphenyl type epoxy compound, a polyfunctional epoxy compound, etc. are mentioned.
As the bisphenol type epoxy compound, those obtained by reacting bisphenol A, bisphenol F and epichlorohydrin are suitable. GY-260, GY-255, XB-2615 manufactured by Ciba Geigy Corp., Epicoat 828, 1007 manufactured by Japan Epoxy Resin Co., Ltd. 807, bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, amino group-containing, alicyclic or polybutadiene-modified epoxy compounds are preferably used.
As the novolak type epoxy compound, those obtained by reacting novolaks obtained by reacting phenol, cresol, halogenated phenol and alkylphenols with formaldehyde in the presence of an acidic catalyst and epichlorohydrin are suitable. YDCN-701, 704, YDPN-638, 602 manufactured by Dow Chemical Co., DEN-431, 439, EPN-1299 manufactured by Ciba-Geigy Co., Ltd., N-730, 770, 865, 665, 673 manufactured by Dainippon Ink & Chemicals, Inc. , VH-4150, 4240, Nippon Kayaku Co., Ltd. EOCN-120, BREN and the like.
Moreover, as an epoxy compound of another structure, for example, salicylaldehyde-phenol or cresol type epoxy compound (Nippon Kayaku Co., Ltd. EPPN502H, FAE2500, etc.), Dainippon Ink & Chemicals, Inc. Epicron 840, 860, 3050, Use DER-330, 337, 361 manufactured by Dow Chemical Company, Celoxide 2021, manufactured by Daicel Chemical Industries, Ltd., TETRAD-X, C, manufactured by Mitsubishi Gas Chemical Company, Inc., EPB-13, 27 manufactured by Nippon Soda Co., Ltd. Can do. These may be used alone or in combination of two or more, and a mixture or a block copolymer may be used.

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

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

In the first reaction, a hydroxyl group is generated by an addition reaction between the epoxy group of the epoxy compound (a1) and the carboxyl group of the 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 methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, and dipropylene. Glycol ethers such as 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, and aliphatic hydrocarbons such as octane and decane Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha can be used.

  In the first reaction, it is preferable to use a catalyst in order to accelerate the reaction. Examples of the catalyst that can be used include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, and triphenylphosphine. 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 a vinyl group containing 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, pyrogallol and the like 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 (b) can be adjusted.
As the component (b) described above, CCR-1218H, CCR-1159H, CCR-1222H, PCR-1050, TCR-1335H, ZAR-1035, ZAR-2001H, ZFR-1185 and ZCR-1569H (Nippon Kayaku) (Trade name, manufactured by Co., Ltd.) are commercially available.
Moreover, the urethane-modified epoxy resin which has a carboxyl group can also be used as (b) component of this invention. Such a modified epoxy resin is obtained by reacting an epoxy acrylate compound having two or more hydroxyl groups and an ethylenically unsaturated group in the molecule, a diisocyanate compound, and a diol compound having a carboxyl group. In the urethane-modified epoxy resin, the structure of the hard segment part of the epoxy acrylate compound having two or more hydroxyl groups and ethylenically unsaturated groups in the molecule of the raw material that becomes one of the main skeleton is preferably a bisphenol A type structure. Such a thing is available as UXE-3011, UXE-3012, UXE-3024 (made by Nippon Kayaku Co., Ltd.).

  The component (c) used in the present invention is a photopolymerizable monomer having one or more ethylenically unsaturated groups in the molecule. Examples of such photopolymerizable monomers include bisphenol A (meth) acrylate compounds, compounds obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids, and glycidyl group-containing compounds with α, β- Examples thereof include a compound obtained by reacting an unsaturated carboxylic acid, a urethane monomer such as a (meth) acrylate compound having a urethane bond in the molecule, or a urethane oligomer. Besides these, nonylphenoxy polyoxyethylene acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloyloxy Examples thereof include phthalic acid compounds such as alkyl-o-phthalate, (meth) acrylic acid alkyl esters, and EO-modified nonylphenyl (meth) acrylate. These may be used alone or in combination of two or more.

The component (c) according to this embodiment 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, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc. Is mentioned. You may use these individually or in combination of 2 or more types.
The component (c) according to the present embodiment 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) acryloxy) Hexadecaethoxy) phenyl) propane and the like. 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 FA-321M (manufactured by Hitachi Chemical Co., Ltd., trade name) or BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.). , And commercially available as trade name), and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). Are available.

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

In addition, the component (c) according to this embodiment includes 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. It is preferable. Examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups. Polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO / PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) A Chlorate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified glyceryl tri (meth) acrylate, PO-modified glyceryl tri (meth) acrylate, EO Examples thereof include PO-modified glyceryl tri (meth) acrylate. These may be used alone or in combination of two or more.
Of the above compounds, dipentaerythritol hexaacrylate is commercially available as KAYARAD-DPHA (trade name, manufactured by Toa Gosei Chemical Co., Ltd.), and trimethylolpropane triethoxytriacrylate is commercially available as SR-454 (trade name, manufactured by Nippon Kayaku Co., Ltd.). Are available.
“EO” refers to “ethylene oxide”, and “PO” refers to “propylene oxide”. Further, “EO modified” means having a block structure of ethylene oxide units (—CH ₂ —CH ₂ —O—), and “PO modified” means propylene oxide units (—CH ₂ —CH ₂ —CH _2). It means having a block structure of —O—) or isopropylene oxide unit (—CH ₂ —CH (CH ₃ ) —O—), (—CH (CH ₃ ) —CH ₂ —O—).
Examples of the compound obtained by reacting the glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4- (meta ) Acryloxy-2-hydroxy-propyloxy) phenyl and the like. These can be used alone or in combination of two or more. 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, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Examples include addition reaction products with diisocyanate compounds, 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.
Furthermore, as (meth) acrylic acid alkyl ester, for example, (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 etc. are mentioned. These can be used alone or in combination of two or more.

Examples of the photopolymerization initiator (d) used in the present invention 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 (Michler's ketone), 4,4′-bis (Diethylamino) benzophenone, aromatic ketones such as 4-methoxy-4′-dimethylaminobenzophenone, quinones such as alkylanthraquinone and phenanthrenequinone, benzoin compounds such as benzoin and alkylbenzoin, benzoin alkyl ether, and benzoin phenyl ether Benzoin ether compounds, benzyldi Benzyl derivatives such as tilketal, 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 2,4,5-triarylimidazole dimers such as phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, N-phenylglycine, N-phenylglycine Derivatives, acridine derivatives such as 9-phenylacridine, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-ben) Oxime esters), coumarin compounds such as 7-diethylamino-4-methylcoumarin, thioxanthone compounds such as 2,4-diethylthioxanthone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. A combination of acylphosphine oxide compounds can be used.
As (d) the photopolymerization initiator of this embodiment, it is desirable to use at least one phosphine oxide photoinitiator from the viewpoint of making the resist shape better. Examples of such compounds include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide as monoacylphosphine oxide, and bis (2,4,6-trimethylbenzoyl) as bisacylphosphine oxide. ) -Phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide.
Further, an acridine derivative may be included for the purpose of improving sensitivity. Examples of the acridine derivative include 9-phenylacridine, 9-aminoacridine, 9-pentylaminoacridine, 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4 -Bis (9-acridinyl) butane, 1,5-bis (9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9 -Acridinyl) dodecane and other bis (9-acridinyl) alkanes, 9-phenylacridine, 9-pyridylacridine, 9-pyrazy Luacridine, 9-monopentylaminoacridine, 1,3-bis (9-acridinyl) -2-oxapropane, 1,3-bis (9-acridinyl) -2-thiapropane, 1,5-bis (9-acridinyl) -3-thiapentane and the like, among which 1,7-bis (9-acridinyl) heptane is more preferable. 1,7-bis (9-acridinyl) heptane is commercially available as N-1717 (trade name, manufactured by Adeka Corporation).

  Further, as a sensitizer for (d) a photopolymerization initiator, a thioxanthone compound may be included from the viewpoint of further improving the resist shape. Examples of the thioxanthone compounds include 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like. Among them, it is more preferable that 2,4-diethylthioxanthone is included among them. 2,4-Diethylthioxanthone is commercially available as KAYACURE-DETX (manufactured by Nippon Kayaku Co., Ltd., product name).

As the (e) thermosetting agent used in the present invention, a compound that undergoes a thermal reaction at 130 to 200 ° C. is preferable. For example, an epoxy compound, blocked isocyanate, and the like can be used. These are used alone or in combination of two or more. It is desirable to use a block type isocyanate because it is excellent in pot life after mixing one liquid, and is particularly effective when used as a dry film type solder resist because it can be used without problems of storage stability. .
The block type isocyanate 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 used include isocyanurate type, biuret type, and adduct type, but isocyanurate type is preferable from the viewpoint of adhesion. Examples of the blocking agent include at least one compound selected from diketones, oximes, phenols, alkanols, and caprolactams. Specific examples include methyl ethyl ketone oxime and ε-caprolactam.
Block type isocyanate is commercially available, for example, Sumidur BL-3175, Desmodur TPLS-2957, TPLS-2062, TPLS-2957, TPLS-2078, BL4165, TPLS2117, BL1100, BL1265, Desmotherm 2170, Desmotherm 2265 (all manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (all trade names manufactured by Nippon Polyurethane Industry Co., Ltd.), B-830, B-815, B-846, B -870, B-874, B-882 (all are trade names, manufactured by Mitsui Takeda Chemical Co., Ltd.). These may be used alone or in combination of two or more.
In particular, when insulating properties are required for the cured resist, it is desirable to include an isocyanuric skeleton or an aromatic ring such as a benzene ring in the structure among the above-described compounds. As such a block type isocyanate, Sumijoule BL-3175, Sumijoule BL-4265 (both manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name), B-870 (made by Mitsui Takeda Chemical Co., Ltd., trade name), etc. Can be mentioned.

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. Biphenol type epoxy resins such as ether, 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 epoxies thereof Resin etc. are mentioned. These may be used alone or in combination of two or more.
Commercially available compounds can be used as these compounds. For example, examples of bisphenol A diglycidyl ether include Epicoat 828, Epicoat 1001, and Epicoat 1002 (all are trade names manufactured by Japan Epoxy Resin Co., Ltd.). Examples of bisphenol F diglycidyl ether include Epicoat 807 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), and examples of bisphenol S diglycidyl ether include EBPS-200 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and Epicron. EXA-1514 (manufactured by Dainippon Ink & Chemicals, Inc., trade name) and the like can be mentioned. Examples of biphenol diglycidyl ether include YL6121 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), and examples of bixylenol diglycidyl ether include YX4000H (trade name, manufactured by Japan Epoxy Resin Co., Ltd.). Can do. Furthermore, examples of the hydrogenated bisphenol A glycidyl ether include ST-2004 and ST-2007 (both manufactured by Tohto Kasei Co., Ltd., trade names), and the dibasic acid-modified diglycidyl ether type epoxy resin described above. ST-5100 and ST-5080 (both manufactured by Tohto Kasei Co., Ltd., trade names) and the like can be mentioned. These may be used alone or in combination of two or more.

  The content in the case where the photosensitive resin composition of the present embodiment contains (e) a thermosetting agent is 100 parts by mass of the total solid content of the components (a), (b), and (c) in the present invention. Is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and particularly preferably 5 to 20 parts by mass. When the content of the component (e) is in such a range, the sensitivity and resolution of the photosensitive resin composition can be compatible with solder heat resistance and film physical properties.

  In addition, it is effective that the photosensitive resin composition of the present invention further contains an elastomer component (f) having a butadiene skeleton in the molecule, which is not completely compatible with the components (a) and (b), if necessary. It is. By including the elastomer component in the photosensitive resin composition, it is possible to improve the adhesion with the conductor layer on the substrate, and further, heat resistance and flexibility after curing of the photosensitive resin composition. And toughness can be improved. As such an elastomer, there is no restriction | limiting in particular as a compound which has a butadiene structure, Commercially, tufprene, sorbrene T, asaprene T, tuftec (above, Asahi Kasei Kogyo Co., Ltd.), elastomer AR (Aron Kasei Co., Ltd.) ), Kraton G, Califlex (above, manufactured by Shell Japan Co., Ltd.), JSR-TR, TSR-SIS, Dynalon (above, produced by Nippon Synthetic Rubber Co., Ltd.), PB-3600 (produced by Daicel Chemical Industries, Ltd.), Denka STR (manufactured by Denki Kagaku Kogyo Co., Ltd.), Quintac (manufactured by Nippon Zeon Co., Ltd.), TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.), Lavalon (manufactured by Mitsubishi Chemical Co., Ltd.), Septon, Hibler ), Sumiflex (Sumitomo Bakelite Co., Ltd.), Rheostoma, Actima (Riken Vinyl Industrial Co., Ltd.), Mirastoma (Mitsui Petrochemical Co., Ltd.), EXACT (Exxon Chemical Co., Ltd.), ENGAGE (Dow Chemical Co., Ltd.), DYNABON HSBR which is a hydrogenated styrene-butadiene copolymer NBR series which is a butadiene-acrylonitrile copolymer, XER series (both made by Nippon Synthetic Rubber Co., Ltd.) which is a both-end carboxyl group-modified butadiene-acrylonitrile copolymer having a crosslinking point, and the like. These number average molecular weights are preferably 500 to 10,000.

  Further, as the acrylic copolymer (g), a side chain of a (meth) acrylic acid alkyl ester comprising a copolymer component other than maleimide or a maleimide derivative and a vinyl monomer copolymer capable of copolymerization with (meth) acrylic acid and / or Alternatively, a copolymer having an ethylenically unsaturated bond introduced at the terminal is also applicable. By using a high molecular weight acrylic copolymer, it becomes possible to keep the crack resistance higher when a repeated stress amplitude is applied, and a photosensitive resin composition having excellent crack resistance after a temperature cycle test can be obtained. . The acrylic copolymer (g) includes a vinyl polymerizable monomer having a carboxyl group such as acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, and itaconic acid, and methyl methacrylate, methyl acrylate, and 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 -Hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate Obtained by general solution polymerization using a vinyl polymerizable monomer such as a salt with a polymerization initiator such as azobisisobutyronitrile, azobisdimethylvaleronitrile, or benzoyl peroxide in an organic solvent. Can be used. These may be used alone or in combination of two or more.

  If necessary, the photosensitive resin composition of the present invention has increased coating strength, improved crack resistance when subjected to repeated stress amplitude, reduced thermal expansion coefficient, adhesion, hardness, plating resistance, etc. In order to improve the characteristics, an inorganic filler (h) can be used. Examples of inorganic fillers include inorganic fillers such as barium sulfate, barium titanate, powdered silicon oxide, amorphous silica, talc, clay, calcined kaolin, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. Is mentioned. These can be used alone or in combination of two or more.

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

  Furthermore, the photosensitive resin composition of the present invention can be used as an adhesion improver, for example, when adhesion between the photosensitive resin composition layer and a metal such as copper is required, such as melamine, acetoguanamine, benzoguanamine, and melamine. -Triazine derivatives such as phenol-formalin resin, dicyandiamide, triazine compound, ethyldiamino-s-triazine, 2,4-diamino-s-triazine, 2,4-diamino-6-xylyl-s-triazine, imidazole series, Additives such as thiazole, triazole, and silane coupling agents can be used. 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK (both manufactured by Shikoku Kasei Kogyo Co., Ltd.) are available as commercial products. These compounds can improve not only the adhesion between the photosensitive resin composition layer and the metal but also properties such as PCT resistance and electrolytic corrosion resistance.

  The adhesion improver according to this embodiment preferably includes dicyandiamide from the viewpoint of achieving chemical resistance and plating resistance at a higher level. When the photosensitive resin composition of this embodiment contains the said adhesive improvement agent, the content is 0.001 with respect to 100 mass parts of solid content of (a) and (b) component and (c) component. It is preferable that it is 1-10 mass parts.

  In addition, the photosensitive resin composition of the present invention is phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, malachite green, crystal violet, titanium oxide, carbon black, naphthalene black, azo organic pigment, etc. Colorants or dyes can be used. Furthermore, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol and phenothiazine, thixotropic agents such as benton, montmorillonite, aerosil and amide wax, antifoaming agents such as silicone, fluorine and polymer Further, a leveling agent or the like may be included in a range that does not affect the desired characteristics of the photosensitive resin composition.

  Moreover, you may contain a polyfunctional maleimide compound in order to improve heat resistance, solder resistance, etc. Examples of the polyfunctional maleimide are not particularly limited as long as they contain at least two maleimide groups in the molecule. For example, 1-methyl-2,4-bismaleimidebenzene, N, N′-m-phenylenebis Maleimide, N, N′-p-phenylenebismaleimide, N, N′-m-toluylene bismaleimide, N, N′-4,4′-biphenylenebismaleimide, N, N′-4,4 ′-[ 3,3′-dimethyl-biphenylene] bismaleimide, N, N′-4,4 ′-[3,3′-dimethyldiphenylmethane] bismaleimide, N, N′-4,4 ′-[3,3′- Diethyldiphenylmethane] bismaleimide, N, N′-4,4′-diphenylmethane bismaleimide, N, N′-4,4′-diphenylpropane bismaleimide, N, N′-4,4 ′ Diphenyl ether bismaleimide, N, N′-3,3′-diphenylsulfone bismaleimide, N, N′-4,4′-diphenylsulfone bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] Propane, 2,2-bis [3-tert-butyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-tert-butyl-4- (4-maleimidophenoxy) phenyl] propane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] decane, 1,1-bis [2-methyl-4- (4-maleimidophenoxy) -5-tert-butylphenyl] -2-methylpropane, 4,4′-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2- (1,1-dimethylethyl) benzene], 4,4′- Tylene-bis [1- (4-maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4′-methylene-bis [1- (4-maleimidophenoxy) -2,6 -Di-t-butylbenzene], 4,4'-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2-cyclohexylbenzene, 4,4'-methylenebis [1- (maleimidophenoxy) -2- Nonylbenzene], 4,4 ′-(1-methylethylidene) -bis [1- (maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4 ′-(2-ethyl) Hexylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4 ′-(1-methylheptylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4 '-Cyclohexylidene-bis [1- (maleimidophenoxy) -3-methylbenzene], 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4- Maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-maleimidophenoxy) phenyl ] Hexafluoropropane, 2,2-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl ] Hexafluoropropane, 2,2-bis [3-ethyl-4--4-maleimidophenoxy) phenyl] propane, 2,2-bi [3-Ethyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, bis [3-methyl- (4-maleimidophenoxy) phenyl] methane, bis [3,5-dimethyl- (4-maleimidophenoxy) phenyl ] Methane, bis [3-ethyl- (4-maleimidophenoxy) phenyl] methane, 3,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5,2,1,02.6] decane 4,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5,2,1,02.6] decane, 3,9-bis [4- (4-maleimidophenoxy) phenyl]- Tricyclo- [5,2,1,02.6] decane, 4,9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5,2,1,02.6] de 1,8-bis [4- (4-maleimidophenoxy) phenyl] menthane, 1,8-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] menthane, 1,8-bis [3,5- And dimethyl-4- (4-maleimidophenoxy) phenyl] menthane.

Next, suitable content of each component in the photosensitive resin composition which concerns on this embodiment is demonstrated.
First, the total solid content of the component (a) and the component (b) is 30 to 95 mass with respect to 100 mass parts of the total solid content of the component (a), the component (b), and the component (c). Part, preferably 40 to 85 parts by weight, particularly preferably 50 to 80 parts by weight. In addition, there is no restriction | limiting in particular in the ratio of (a) component and (b) component. Within such a range, the coating property of the photosensitive resin composition, the crack resistance of the cured film, and the HAST resistance are improved.
When the photosensitive resin composition of this embodiment contains an acrylic copolymer (g), the content of the component (g) is 100 parts by mass of the total solid content of the components (a), (b) and (c). It is preferable that it is 5-50 mass parts with respect to it, and it is more preferable that it is 10-40 mass parts. When the content of the component (g) is in such a range, the coating property and the alkali developability of the photosensitive resin composition become better.
When the photosensitive resin composition of the present embodiment contains (h) inorganic and / or organic filler, the content is 100 parts by mass of the total solid content of the component (a), the component (b), and the component (c). On the other hand, it is preferably 5 to 150 parts by mass, more preferably 15 to 120 parts by mass, and particularly preferably 30 to 100 parts by mass. When the content of the component (g) is in such a range, the hardness, thermal expansion coefficient, and plating resistance of the cured film become better.
In addition, when using the photosensitive resin composition with a liquid form, it is preferable that content of the diluent used for this invention is 5-40 mass% in the total weight.

Next, the photosensitive film of suitable embodiment is demonstrated.
The photosensitive film which concerns on this invention is equipped with a support body and the photosensitive resin composition layer which consists of the photosensitive resin composition of this invention formed on this support body. On the photosensitive resin composition layer, you may further provide the protective film which coat | covers this photosensitive resin composition layer.
As said support body, the polymer film which has heat resistance and solvent resistance, such as a polyethylene terephthalate, a polypropylene, polyethylene, polyester, can be used, for example. The thickness of the support (polymer film) is preferably 5 to 25 μm. If the thickness is less than 5 μm, the support film tends to be broken when the support film before development is peeled off. If it exceeds, the resolution tends to decrease. In addition, you may use the said polymer film by laminating | stacking on the both surfaces of the photosensitive resin composition layer by using one as a support body and another as a protective film.

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

The photosensitive resin composition layer is prepared by dissolving the photosensitive resin composition of the present invention in a solvent as described above to obtain a solution (coating solution) having a solid content of about 30 to 70% by mass. The coating liquid is preferably formed by coating on a support and drying. The application can be performed by a known method using, for example, a roll coater, comma coater, gravure coater, air knife coater, die coater, bar coater or the like. Moreover, the said drying can be performed at 70-150 degreeC and about 5 to 30 minutes. The amount of the remaining organic solvent in the photosensitive resin composition is preferably 3% by mass or less with respect to the total amount of the photosensitive resin composition from the viewpoint of preventing diffusion of the organic solvent in the subsequent step. Although the thickness of the said photosensitive resin composition layer changes with uses, it is preferable that it is 10-100 micrometers by the thickness after drying, it is more preferable that it is 15-60 micrometers, and it is especially preferable that it is 20-50 micrometers. If this thickness is less than 10 μm, it tends to be difficult to apply industrially, and if it exceeds 100 μm, the sensitivity and resolution inside the photosensitive resin composition layer tend to be reduced.
The photosensitive film may further have an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer. Moreover, the obtained photosensitive film can be stored in a sheet form or a roll around a core. In addition, it is preferable to wind up so that a support body may become the outermost part in this case. An end face separator is preferably installed on the end face of the roll-shaped photosensitive film roll from the viewpoint of end face protection, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance. Moreover, as a packing method, it is preferable to wrap and package in a black sheet with low moisture permeability. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

Next, a method for forming a resist pattern using a photosensitive film obtained from the photosensitive resin composition of the present invention will be described.
A photosensitive resin composition layer made of the above-described photosensitive resin composition is formed on a substrate on which a resist is to be formed. The protective film of the photosensitive film is peeled from the photosensitive resin composition layer, and the exposed surface is adhered by a laminate or the like so as to cover the conductor layer having a circuit pattern formed on the substrate. A method of laminating under reduced pressure is also preferable from the viewpoint of improving adhesion and followability. In addition, the photosensitive resin composition can also be apply | coated on a board | substrate by well-known methods, such as the method of apply | coating the varnish of the photosensitive resin composition with a screen printing method or a roll coater.
Next, if necessary, a removal process for removing the protective film from the photosensitive film described above is performed, and a predetermined part of the photosensitive resin composition layer is irradiated with actinic rays through the mask pattern, and the photosensitive resin composition of the irradiated part is irradiated. An exposure step for photocuring the layer is performed. At this time, although the exposure process can be performed using a batch exposure type exposure machine, it is preferable to use a direct drawing type LDI type exposure process. When the photosensitive resin composition of the present invention is used, the LDI light source may be either a 355 nm or 405 nm laser beam, and is compatible with i-line and h-line mixed type LDI apparatuses.
Further, when a support is present on the photosensitive layer, after removing the support, by removing a portion that has not been photocured by wet development or dry development (unexposed portion) and developing, A resist pattern can be formed.
In the case of the above-described wet development, as the developer, an alkaline aqueous solution, an aqueous developer, an organic solvent, or the like that is safe and stable and has good operability is used according to the type of the photosensitive resin composition. Further, as a developing method, a known method such as spraying, rocking dipping, brushing, scraping or the like is appropriately employed.
Examples of the base of the alkaline aqueous solution include alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide which are hydroxides of lithium, sodium and potassium, carbonates or bicarbonates such as alkali metals and ammonium. Alkaline carbonate or bicarbonate, alkali metal phosphate sodium phosphate, potassium phosphate, etc., alkali metal pyrophosphate sodium pyrophosphate, potassium pyrophosphate etc., safe and stable, operability The one with good is used.
Examples of the alkaline aqueous solution include a dilute solution of 0.1 to 5% by mass of sodium carbonate, a dilute solution of 0.1 to 5% by mass of potassium carbonate, and a dilute solution of 0.1 to 5% by mass of sodium hydroxide. A solution, a dilute solution of 0.1 to 5% by mass sodium tetraborate is preferred, and the pH is preferably in the range of 9 to 11. Moreover, the temperature of such alkaline aqueous solution is adjusted according to the developability of the photosensitive resin composition layer, and it is preferable to set it as 20-50 degreeC. Furthermore, a small amount of an organic solvent such as a surfactant or an antifoaming agent may be mixed in the alkaline aqueous solution in order to promote development.

As the aqueous developer, one comprising water and an alkaline aqueous solution or one or more organic solvents is used. Here, as the base of the alkaline aqueous solution, in addition to those described above, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3- Examples include propanediol, 1,3-diaminopropanol-2, and morpholine. The pH of such an aqueous developer is preferably as small as possible within a range where development processing can be sufficiently performed, preferably pH 8 to 12, and more preferably pH 9 to 10.
Examples of the organic solvent include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. . The concentration of such an organic solvent is usually preferably 2 to 90% by mass. Moreover, the temperature of such an organic solvent can be adjusted according to developability. Such organic solvents can be used alone or in combination of two or more.

  Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. Furthermore, a small amount of an organic solvent such as a surfactant or an antifoaming agent may be mixed in the alkaline aqueous solution in order to promote development.

  In the method for forming a resist pattern of the present invention, if necessary, two or more kinds of development methods described above may be used in combination. Development methods include a dip method, a battle method, a spray method, a high-pressure spray method, brushing, and slapping, and the high-pressure spray method is most suitable for improving resolution. For the etching of the metal surface performed after development, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or the like can be used.

Next, a preferred embodiment of the photosensitive permanent resist of the present invention using the photosensitive film of the present invention will be described.
After the development step, it is preferable to perform ultraviolet irradiation or heating with a high-pressure mercury lamp for the purpose of improving solder heat resistance and chemical resistance. In the case of irradiating ultraviolet rays, the irradiation amount can be adjusted as necessary, and for example, irradiation can be performed at an irradiation amount of about 0.2 to 10 J / cm ² . Moreover, when heating a resist pattern, it is preferable to carry out for about 15 to 90 minutes in the range of about 130-200 degreeC.
Both ultraviolet irradiation and heating may be performed. In this case, both may be performed at the same time, and after either one is performed, the other may be performed. When performing ultraviolet irradiation and heating simultaneously, it is preferable to heat to 60-150 degreeC from a viewpoint of providing solder heat resistance and chemical resistance more favorably.
The photosensitive permanent resist formed in this way also serves as a protective film for the wiring after soldering the substrate, and has various characteristics of a solder resist, for printed wiring boards, for semiconductor package boards, flexible wiring boards It can be used as a solder resist.
The solder resist, for example, is used as a plating resist or an etching resist when plating or etching is performed on a substrate, and is also left on the substrate as it is to protect a wiring or the like (photosensitive permanent). Resist).
Moreover, in the above-described exposure step, when exposure is performed using a mask or drawing data having a pattern in which a predetermined portion of the conductor layer is unexposed, the unexposed portion is removed by developing this, and the substrate A resist having an opening pattern in which a part of the conductor layer formed thereon is exposed is obtained. Thereafter, it is preferable to perform a treatment necessary for forming the above-described photosensitive permanent resist.
The substrate provided with the photosensitive permanent resist of the present invention is then mounted with a semiconductor element or the like (for example, wire bonding, C4 solder connection), and mounted on an electronic device such as a personal computer.
The present invention has been described in detail based on the embodiments. However, the present invention is not limited to the above embodiment, and various modifications can be made without departing from the scope of the invention.

(Examples 1-7 and Comparative Examples 1-8)
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
First, about Examples 1-7 and Comparative Examples 1-8, the photosensitive resin composition solution was obtained by mixing each component shown in Table 1 and Table 2 by the compounding quantity (mass part) shown to the same table, respectively. It was.

[Acrylic copolymer (a) having a repeating unit derived from maleimide or a maleimide derivative in the molecule]
(Synthesis of resin (1))
Resin (1) was synthesized by the following method.
A mixture of propylene glycol monomethyl ether acetate and methyl lactate is charged into a flask equipped with a stirrer, reflux condenser, thermometer, and inert gas introduction tube, heated to 80 ° C. in a nitrogen gas atmosphere, and the reaction temperature is set to 80 ° C. While maintaining ± 2 ° C., 40 parts by mass of N-cyclohexylmaleimide, 25 parts by mass of 2-hydroxyethyl methacrylate, 15 parts by mass of methacrylic acid, 10 parts by mass of benzyl methacrylate, dicyclopentadiene methacrylate (FA-513MS, Hitachi Chemical) 15 parts by mass of Kogyo Co., Ltd. was uniformly dropped over 4 hours. Thereafter, stirring was continued at 80 ° C. ± 2 ° C. for 6 hours to obtain a binder polymer solution (p-1, solid content 35% by mass) having a weight average molecular weight of about 25,000.
Furthermore, in a flask equipped with a stirrer, a reflux condenser, an inert gas inlet and a thermometer, 20 parts by mass of ethyl isocyanate, 28 parts by mass of propylene glycol monomethyl ether acetate, and 7 parts by mass of methyl lactate were charged with nitrogen gas. The temperature was raised to 70 ° C. under an atmosphere, and a mixture of 0.1 part by mass of dibutyltin dilaurate and (p-1) was uniformly added dropwise over 2 hours while maintaining the reaction temperature at 70 ° C. ± 2 ° C.
After dropping, stirring is continued at 70 ° C. ± 2 ° C. for 2 hours, and a solution of acrylic copolymer having a photopolymerizable unsaturated group having a weight average molecular weight of about 26000 (solid content 35% by mass) (resin (1)) Obtained.

  As a resin (b) obtained by reacting a resin obtained by reacting an epoxy resin and a vinyl group-containing monocarboxylic acid with a saturated or unsaturated group-containing polybasic acid anhydride, an acid-modified phenol novolac epoxy Acrylate “PCR-1050”, acid-modified cresol novolak type epoxy acrylate “CCR-1219H”, acid-modified bisphenol A type epoxy acrylate “ZAR-1626H”, bisphenol F type epoxy acrylate “ZFR-1158”, urethane modified bisphenol A type epoxy Acrylate “UXE-3024” (all manufactured by Nippon Kayaku Co., Ltd.) was used.

  As the photopolymerizable monomer (c) having an ethylenically unsaturated group, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane “FA-321M” (manufactured by Hitachi Chemical Co., Ltd.) and dipentaerythritol Hexaacrylate “KAYARAD-DPHA” (manufactured by Nippon Kayaku Co., Ltd.) was used.

  As the photopolymerization initiator (d), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (I-369, manufactured by Ciba Specialty Chemicals), and 2,4- Diethylthioxanthone “KAYACURE-DETX” (manufactured by Nippon Kayaku Co., Ltd.) was used.

  As the thermosetting agent (e), HDI isocyanurate block type isocyanate (BL-3175, manufactured by Sumika Bayer Urethane Co., Ltd.), melamine resin type curing agent Cymel 300 (made by Mitsui Toatsu Cymel Co., Ltd.), epoxy Bisphenol A type epoxy resin (Epicoat 1001, Epoxy equivalent 450, manufactured by Japan Epoxy Resin Co., Ltd.), Biphenol type epoxy resin (YX-4000, Epoxy equivalent 190, manufactured by Japan Epoxy Resin Co., Ltd.), Aron which is oxetane resin Oxetane OXT-121 (manufactured by Toa Gosei Co., Ltd.) was used.

  For the elastomer (f), Epolide PB3600 (manufactured by Daicel Chemical Industries, Ltd.), which is a butadiene-based elastomer, was used.

  Acrylic copolymer (g) (resin (2)) having a repeating unit derived from (meth) acrylic acid alkyl ester is a copolymer of methacrylic acid, methyl methacrylate and ethyl acrylate, and has a weight average molecular weight of 60,000, acid A value of 80 mg KOH / g was used.

  Barium sulfate “Variace B-30” (manufactured by Sakai Chemical Industry Co., Ltd.) was used as the inorganic filler (h).

  As another material, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide “BMI-5100” (manufactured by Daiwa Kasei Co., Ltd.) was used. Methyl ethyl ketone was used as the diluent. Melamine and phthalocyanine blue were used.

Next, a photosensitive resin composition layer is formed by uniformly coating this photosensitive resin composition solution on a 16 μm-thick polyethylene terephthalate film (G2-16, trade name, manufactured by Teijin Ltd.) as a support layer. It was dried for about 10 minutes at 100 ° C. using a hot air convection dryer. 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, a polyethylene film (NF-15, manufactured by Tamapoly Co., Ltd., trade name) is bonded as a protective film, and is photosensitive. A film was obtained.

[Evaluation of sensitivity]
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 dried. Using a press-type vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd., trade name) on this printed wiring board substrate, press hot plate temperature 70 ° C., vacuuming time 20 seconds, laminating press time 30 seconds, Under the conditions of an atmospheric pressure of 4 kPa or less and a pressure bonding pressure of 0.4 MPa, the protective film of the photosensitive film was peeled and laminated to obtain a laminate for evaluation.
Then, after standing at room temperature (25 ° C.) for 1 hour or longer, a 21-step tablet (manufactured by Eastman Kodak Co.) was brought into close contact with the obtained support for the evaluation laminate, and an ultrahigh pressure mercury lamp was used as the light source. The exposure was performed using a parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.).
After exposure, the film was allowed to stand at room temperature for 30 minutes, and then the polyethylene terephthalate on the support was removed, and the photosensitive resin composition in the unexposed area was spray-developed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 60 seconds.
After development, the exposure energy amount at which the number of remaining steps of the 21-step tablet was 8.0 was defined as the sensitivity (unit: mJ / cm ² ) of the photosensitive resin composition layer. The photosensitive resin composition layer was evaluated using the pattern exposed with this sensitivity.

[Evaluation of coating properties]
The obtained laminate for evaluation was not exposed to light, but the polyethylene terephthalate on the laminate 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. That is, the case where the sticking to the finger was not recognized or hardly recognized was evaluated as “3”, the case where the sticking was slightly recognized was evaluated as “2”, and the case where the sticking to the finger was recognized was evaluated as “1”. The evaluation results are shown in Tables 3 and 4.

[Evaluation of solder heat resistance]
The evaluation laminate obtained in the same manner as in the sensitivity evaluation described above was allowed to stand at room temperature for 1 hour or longer, and then a negative mask having a 2 mm square opening pattern was used, and the number of remaining steps of the 21-step tablet was 8.0. It exposed from the support body of this laminated body for evaluation by energy amount.
Subsequently, after leaving still at room temperature for 1 hour, the polyethylene terephthalate on this laminated body was peeled, and it was 1. Spray development took 5 times longer. After spray development, UV irradiation of 1 J / cm ² is performed using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd., and heat treatment is further performed at 160 ° C. for 60 minutes to form a solder resist having a 2 mm square opening. An evaluation board was obtained.
Next, rosin-based flux (MH-820V, manufactured by Tamura Kaken Co., Ltd., trade name) was applied to the 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.
On the evaluation substrate thus plated with solder, the state of solder resist cracking and the presence or absence of solder resist floating and peeling from the substrate were observed with a 100-fold metal microscope and evaluated according to the following criteria. In other words, "3" indicates that no cracking is observed in the solder resist and the solder resist is not lifted or peeled off, and "2" indicates that peeling is slightly observed. Was evaluated as “1”. The evaluation results are shown in Tables 3 and 4.

[Storage stability]
The produced photosensitive film is packed with a light-shielding black sheet, left at 23 ° C., and then subjected to exposure, development, UV irradiation, and heating process to form a permanent mask resist pattern under the same conditions as the evaluation of solder heat resistance. And observed with a stereomicroscope and evaluated according to the following criteria. That is, an NG determination was made when the resin residue was observed in the unexposed part. The period until it was not recognized was examined, and the results are shown in Table 2. The case where no resin residue was observed even after 60 days or more was determined as OK, and the case where the period exceeded 60 days was defined as “60 days or more”.

[Evaluation of SN characteristics]
A cured photosensitive resin for evaluating SN (Stress-Number of cycles) characteristics was prepared by the method described below. The photosensitive resin composition solution was uniformly applied on a 16 μm-thick polyethylene terephthalate film (G2-16, manufactured by Teijin Ltd., trade name) as a support layer so that the film thickness after drying was 30 μm. Was dried at 100 ° C. for about 10 minutes using a hot air convection dryer. Subsequently, on the surface of the photosensitive resin composition layer opposite to the side in contact with the support, a polyethylene film (NF-15, manufactured by Tamapoly Co., Ltd., trade name) is bonded as a protective film, and is photosensitive. A film was obtained.
The polyethylene film was peeled off from the smooth surface of the 18 μm-thick copper foil, the photosensitive resin composition layer was in contact with the copper foil, and laminate pressing was performed in the same manner as in the above sensitivity evaluation to obtain a laminate. Then, the entire surface of the photosensitive film was exposed and allowed to stand at room temperature for 1 hour, after which the polyethylene terephthalate on the laminate was peeled off and spray-developed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. After spray development, ultraviolet irradiation of 1 J / cm ² was performed using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd., followed by heat treatment at 160 ° C. for 60 minutes. And copper foil was removed by etching and the film of the photosensitive resin composition was obtained.
Subsequently, after cutting out into width 2mm and length 60mm with a cutter knife, the photosensitive resin hardened | cured material for SN characteristic evaluation was obtained.
The SN characteristic of the cured photosensitive resin was evaluated by the method shown below. An example of the measurement result of the SN characteristic is shown in FIG. A microforce precision test apparatus (Micro Tester 5548, manufactured by Instron) was used as the measurement apparatus, and a load measuring load cell having a specification of ± 10 N was used. The measurement mode was a repetitive tension / load control mode, the load upper limit was 1 N to 10 N, the load lower limit was 0.1 N, the displacement speed was 5 mm / min, the distance between chucks was 50 mm, and the measurement temperature was room temperature. The load upper limit value was arbitrarily set in the range of 1N to 10N, and the relationship between the load upper limit value and the number of repetitions until the photosensitive resin cured product was broken was plotted. At this time, the load upper limit value was converted into tensile stress. For example, when a cured photosensitive resin having a film thickness of 30 μm, a width of 2 mm, and a cross-sectional area of 0.06 mm ² is measured at a load upper limit of 3 N, the tensile stress is 3 N / 0.06 mm ² = 50 N / mm ² = 50 MPa. It becomes. The measurement results were approximated to the power, the constants A and B in the formula (1) were determined, and used as crack resistance indices. The measurement results are shown in Tables 3 and 4.

  As is apparent from Table 3, Examples 1 to 7 are generally excellent in coating properties, solder heat resistance, and storage stability, and also excellent in SN characteristics that serve as an index of crack resistance. I understand. On the other hand, as can be seen from Table 4, Comparative Examples 1 to 8 are inferior in any of the coating properties, solder heat resistance, and storage stability and inferior in the SN characteristics. Therefore, according to the photosensitive resin composition of the present invention, excellent coating properties, solder heat resistance, storage stability, and sufficient crack resistance can be obtained.

Claims (8)

A resin obtained by reacting an acrylic copolymer having a repeating unit derived from maleimide or a maleimide derivative in the molecule (a), an epoxy resin, and a vinyl group-containing monocarboxylic acid with a saturated or unsaturated group-containing polymer. Photosensitive resin containing resin (b) obtained by reacting basic acid anhydride, photopolymerizable monomer (c) having an ethylenically unsaturated group, photopolymerization initiator (d), thermosetting agent (e) When the photosensitive resin composition is irradiated with ultraviolet rays at 1 J / cm ² and cured at 160 ° C., the constant A represented by the following formula (1) is 65 or more, and the constant B is A photosensitive resin composition characterized in that a cured film of 0.06 or less is obtained.

(In the formula (1), σ represents a stress amplitude value applied to the cured photosensitive resin at room temperature (25 ° C.), and N represents the number of times the stress amplitude is repeated until the cured photosensitive resin is broken.)   The photosensitive resin composition according to claim 1, wherein the thermosetting agent (e) is a block type isocyanate.   The photosensitive resin composition of Claim 1 or Claim 2 which further contains the elastomer component (f) which has a butadiene skeleton in a molecule | numerator.   The photosensitive resin composition in any one of Claims 1-3 which further contains the acrylic copolymer (g) which has a repeating unit derived from the (meth) acrylic-acid alkylester.   Furthermore, the photosensitive resin composition in any one of Claims 1-4 containing an inorganic filler (h).   A photosensitive film provided with a support body and the photosensitive resin composition layer which consists of the photosensitive resin composition in any one of Claims 1-5 formed by apply | coating and drying on this support body.   The photosensitive resin composition layer which consists of the photosensitive resin composition in any one of Claims 1-5 is provided on the circuit formation board | substrate, Actinic rays are irradiated to the said photosensitive resin composition layer in an image form, and exposure is carried out. A method of forming a resist pattern, wherein the part is photocured and the unexposed part is removed by development.   A permanent resist formed by the method for forming a resist pattern according to claim 7.

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