JP2005141084A - Photosensitive resin composition, photosensitive element using the same, resist pattern forming method and method for manufacturing printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in all of such properties as sensitivity, resolution and adhesion to a substrate. <P>SOLUTION: The photosensitive resin composition contains (A) an alkali-soluble binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond, (C) a photopolymerization initiator and (D) a maleic acid derivative. The photosensitive resin composition contains both the photopolymerization initiator and the maleic acid derivative. Even if a content of the photopolymerization initiator is made small, therefore, the photosensitive resin composition attains high sensitivity, and resolution and adhesion of the photosensitive resin composition are made also good. The photosensitive resin composition is also suitably applicable to manufacture of a high density resist pattern and a printed wiring board. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a resist pattern forming method, and a printed wiring board manufacturing method.

  As a resist material for forming a wiring pattern of a printed wiring board, a photosensitive resin composition or a photosensitive element using the same is widely used. When forming a wiring pattern using a photosensitive element, first, this photosensitive element is laminated on a circuit forming substrate to form a photosensitive resin composition layer on a metal foil. Next, this layer is subjected to pattern exposure to cure the exposed portion, and then the uncured portion is removed by development to form a resist pattern. And this board | substrate is etched or plated, a pattern is formed in metal foil, and the board | substrate (printed wiring board) which has a wiring pattern is obtained by removing a resist from the obtained board | substrate.

  In recent years, with the increase in the density of wiring patterns in printed wiring boards, the resist material used has high sensitivity and high resolution, and further has good adhesion to the substrate (or metal foil on the substrate). Is also required to have excellent characteristics. For this reason, various photosensitive resin compositions have been studied for the purpose of improving these characteristics.

  The above sensitivity and resolution characteristics greatly depend on the type or amount of the photopolymerization initiator contained in the photosensitive resin composition. For this reason, photopolymerization initiators that can improve these properties have been widely searched. For example, initiators described in the following Patent Documents 1, 2, 3, 4, 5, etc. can be used to achieve high sensitivity. Found as an agent. However, these photopolymerization initiators have the disadvantage that they contaminate the plating bath in the plating step performed when forming the wiring pattern.

  Therefore, using 2,4,5-triphenylimidazole dimer, which is a photopolymerization initiator with low plating bath contamination, and combining this initiator with a hydrogen donating compound provides high sensitivity and low plating bath contamination. An realized photosensitive resin composition has been proposed (see, for example, Patent Document 6). However, when this photosensitive resin composition is used, it is necessary to use a large amount of a photopolymerization initiator or a hydrogen donating compound in order to obtain sufficient sensitivity. When the content of the photopolymerization initiator becomes excessive in this way, the line width of the resist pattern obtained by reducing the resolution of the photosensitive resin composition tends to increase. On the other hand, when the content of the hydrogen-donating compound is excessive, the adhesion to the metal foil is lowered and the storage stability of the photosensitive resin composition tends to be lowered.

  Further, when the above-described photopolymerization initiator is used, the following disadvantages may occur. For example, the photopolymerization initiator or a decomposition product thereof may remain in the photosensitive resin composition after exposure, and this residue may decrease the curing rate of the photosensitive resin composition, or may cause fading or oxidative decomposition. In some cases, a decrease in resistance to aging was caused. Further, as a photopolymerization initiator, a compound having an aromatic ring is often used in order to improve light absorption efficiency. For this reason, the cured product often turns yellow due to the influence of heat or the like. .

  As a photosensitive resin composition that eliminates the drawbacks caused when these photopolymerization initiators are used, those containing a maleimide compound are known. For example, a photosensitive resin composition containing a maleimide compound that is an electron acceptor and an electron donor in combination and performing photopolymerization via a charge transfer complex generated by the combination (for example, Patent Document 7, Non-Patent Document) 1), a photosensitive resin composition for photopolymerizing a maleimide derivative (see, for example, Non-Patent Document 2), or a photosensitive resin composition containing a maleimide derivative (for example, Patent Documents 8, 9, 10). Etc.) are known.

In addition, among maleimide compounds, it is also known that pendant maleimide undergoes photocrosslinking (photocyclization dimerization reaction of [2 + 2]). As such a pendant maleimide, a photocrosslinkable polymer having an α-arylmaleimide group in the side chain (for example, see Patent Documents 11, 12, and 13), and a side chain maleimide group having an alkyl substituent. (For example, refer to Patent Documents 14 and 15).
German patent invention 2027467 specification European Patent Application No. 11786 European Patent Application No. 220 European Patent Application Publication No. 589 JP-A-6-69631 US Pat. No. 3,479,185 JP-A-6-298817 JP 61-250064 A JP-A-62-64813 JP-A-62-79243 JP-A-49-58196 JP 50-123138 A JP 51-47940 A JP-A-52-988 Japanese Patent Laid-Open No. 55-160010 “Polymer Preprints”, 1996, Vol. 37, p. 348-349 “Polymer Letters”, 1996, Vol. 6, p. 883-888

  However, the photosensitive resin composition containing these maleimide compounds has a slower curing rate with respect to light irradiation than those containing the photopolymerization initiator described above, and has sufficient sensitivity in a short time. There was a tendency not to be obtained. In addition, when the above-described pendant maleimide is used, the degree of curing of the exposed portion and insolubilization to the solvent due to light irradiation at the time of forming the resist pattern is small. In this case, the photocrosslinking is several tens of seconds to several minutes. Therefore, it was necessary to irradiate light with an excessive amount of light for a long time, so that the practicality as a resist material was poor. As described above, the photosensitive resin composition containing the conventional maleimide-based compound is superior in adhesion and storage stability of the photosensitive resin composition as compared with the case where the photopolymerization initiator is used. The resolution characteristics are often inferior, and the characteristics are still insufficient for producing a high-density printed wiring board.

  The present invention has been made in view of the above circumstances, and provides a photosensitive resin composition that is excellent in all characteristics of sensitivity, resolution, and adhesion to a substrate, and also excellent in storage stability. For the purpose. Another object of the present invention is to provide a photosensitive element, a resist pattern forming method and a printed wiring board manufacturing method using the photosensitive resin composition.

  In order to achieve the above object, the present invention provides a photopolymerization having (A) an alkali-soluble binder polymer (hereinafter simply referred to as “binder polymer”) and (B) at least one polymerizable ethylenically unsaturated bond. An organic compound (hereinafter simply referred to as “photopolymerizable compound”), (C) a photopolymerization initiator (hereinafter simply referred to as “initiator”), and (D) a maleic acid derivative. A photosensitive resin composition is provided.

  The photosensitive resin composition of the present invention contains a basic composition comprising a binder polymer and a photopolymerizable compound in combination with a photopolymerization initiator and a maleic acid derivative typified by a maleimide compound. For this reason, a high photosensitivity is exhibited compared with the case where a maleic acid derivative is contained independently by the synergistic effect with a photoinitiator. As a result, the photosensitive resin composition is exposed with good sensitivity even when the content of the initiator is suppressed to such an extent that the problems caused by the initiator as described above do not occur. In addition, since the content of the initiator can be reduced in this way, a decrease in adhesion with the substrate due to an excessive amount of the initiator is suppressed, and the mechanical strength of the cured film is also improved. The storage stability will be greatly improved.

  Here, as the maleic acid derivative, at least one selected from the group consisting of a substituted maleimide compound in which a hydrogen atom of an imide group is substituted with a substituent, polymaleimide having two or more maleimide groups, maleimide, and maleic anhydride. A maleic acid derivative is mentioned.

  Among these, as the maleic acid derivative, a substituted maleimide compound is preferable, and as such a substituted maleimide compound, an alkylmaleimide in which a hydrogen atom of an imide group is substituted with an alkyl group, and a hydrogen atom of an imide group in an alkyl group having a substituent. A substituted substituted alkylmaleimide, an arylmaleimide in which a hydrogen atom of an imide group is substituted with an aryl group, and a non-carbon atom-containing maleimide in which a hydrogen atom of an imide group is replaced by a non-carbon atom of a non-carbon atom-containing group At least one maleimide compound selected from the group is preferred.

［式中、Ｒ^１は、炭素数１〜１０のアルキル基又は炭素数３〜１０のシクロアルキル基を示し、Ｒ^９１及びＲ^９２はそれぞれ独立に、水素原子、炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基、アリール基、アルコキシ基又はハロゲン原子を示す。なお、Ｒ^９１とＲ^９２とは一緒になってイミド基の３位及び４位の炭素と共に５員環又は６員環構造を構成する２価の基を形成してもよい。］ Specifically, examples of the alkylmaleimide include maleimide represented by the following general formula (1).

[Wherein, R ¹ represents an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, and R ⁹¹ and R ⁹² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. , A cycloalkyl group having 3 to 10 carbon atoms, an aryl group, an alkoxy group or a halogen atom. R ⁹¹ and R ⁹² may be combined together to form a divalent group constituting a 5-membered or 6-membered ring structure with the 3rd and 4th carbons of the imide group. ]

  The alkylmaleimide represented by the above formula (1) is preferably at least one maleimide selected from the group consisting of methylmaleimide, t-butylmaleimide, hexylmaleimide and cyclohexylmaleimide.

［式中、Ｒ^２１は炭素数１〜１０のアルキレン基又は炭素数３〜１０のシクロアルキレン基を示し、Ｒ^２２はハロゲン原子、ニトリル基、イソシアネート基、スルホン酸基、第４級アンモニウム基若しくは第４級アンモニウムの塩からなる基、又は、−ＯＲ^２３、−ＳＲ^２３、−ＳｉＨ_２Ｒ^２３、−ＯＣ（Ｏ）Ｎ（Ｒ^２３）_２、−ＯＣ（Ｏ）Ｃ（Ｒ^２３）＝ＣＨＲ^２３、−ＯＣ（Ｏ）Ｒ^２３、−Ｃ（Ｏ）Ｒ^２３、−Ｎ（Ｒ^２３）_２、−Ｃ（Ｏ）ＯＲ^２３、−Ｃ（Ｏ）Ｎ（Ｒ^２３）_２、−ＯＣ（Ｏ）ＯＲ^２３、−Ｎ−Ｒ^２４−Ｒ^２５若しくは−Ｎ−Ｒ^２４−Ｒ^２６−Ｒ^２５で表される基を示し、Ｒ^２３は、水素原子、アルキル基、シクロアルキル基、アリール基、アリールアルキル基又はアルキルアリール基を示し、Ｒ^２４はアリーレン基を示し、Ｒ^２５はハロゲン原子、炭素数１〜４のアルキル基、ニトリル基、イソシアネート基、スルホン酸基、第４級アンモニウム基若しくは第４級アンモニウムの塩からなる基、又は、−ＯＲ^２３、−ＳＲ^２３、−ＳｉＨ_２Ｒ^２３、−ＯＣ（Ｏ）Ｎ（Ｒ^２３）_２、−ＯＣ（Ｏ）Ｃ（Ｒ^２３）＝ＣＨＲ^２３、−ＯＣ（Ｏ）Ｒ^２３、−Ｃ（Ｏ）Ｒ^２３、−Ｎ（Ｒ^２３）_２、−Ｃ（Ｏ）ＯＲ^２３、−Ｃ（Ｏ）Ｎ（Ｒ^２３）_２若しくは−ＯＣ（Ｏ）ＯＲ^２３で表される基を示し、Ｒ^２６はアルキレン基、アリーレン基及びシクロアルキレン基からなる群より選ばれる少なくとも１つの基からなる２価の基を示し、Ｒ^９１及びＲ^９２はそれぞれ独立に水素原子、炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基、アリール基、アルコキシ基又はハロゲン原子を示す。なお、Ｒ^９１とＲ^９２とは一緒になってイミド基の３位及び４位の炭素と共に５員環又は６員環構造を構成する２価の基を形成してもよい。］ Moreover, as a substituted alkyl maleimide, the maleimide represented by following General formula (2) can be illustrated.

[Wherein R ²¹ represents an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms, and R ²² represents a halogen atom, a nitrile group, an isocyanate group, a sulfonic acid group, a quaternary ammonium group or group consisting of salts of quaternary ammonium, _{^{or, -OR 23, -SR 23, -SiH}} 2 R 23, -OC (O) N (R 23) 2, -OC (O) C (R 23) = CHR ^{23, -OC (O) R 23} , -C (O) R 23, -N (R 23) 2, -C (O) OR 23, -C (O) N (R 23) 2, -OC (O ) OR ²³ , —N—R ²⁴ —R ²⁵ or —N—R ²⁴ —R ²⁶ —R ²⁵ represents a group represented by R ²³ , wherein R ²³ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aryl Indicates an alkyl group or an alkylaryl group R ²⁴ represents an arylene group, and R ²⁵ represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, a nitrile group, an isocyanate group, a sulfonic acid group, a quaternary ammonium group or a quaternary ammonium salt. _{^{or, -OR 23, -SR 23, -SiH}} 2 R 23, -OC (O) N (R 23) 2, -OC (O) C (R 23) = CHR 23, -OC (O) R 23 , -C (O) R ²³ , -N (R ²³ ) ₂ , -C (O) OR ²³ , -C (O) N (R ²³ ) ₂ or -OC (O) OR ²³ R ²⁶ represents a divalent group consisting of at least one group selected from the group consisting of an alkylene group, an arylene group and a cycloalkylene group, and R ⁹¹ and R ⁹² each independently represent a hydrogen atom, a carbon number of 1 to 10 Alkyl group, carbon 3-10 cycloalkyl group, an aryl group, an alkoxy group or a halogen atom. R ⁹¹ and R ⁹² may be combined together to form a divalent group constituting a 5-membered or 6-membered ring structure with the 3rd and 4th carbons of the imide group. ]

  Such substituted alkylmaleimides include hydroxymethylmaleimide, hydroxyethylmaleimide, triethylene glycol biscarbonate bisethylmaleimide, 2-ethylcarbonate ethylmaleimide, 2-isopropylurethaneethylmaleimide, 2-acryloylethylmaleimide, acetoxyethylmaleimide, Preferred is at least one maleimide selected from the group consisting of isophorone urethane bisethylmaleimide, bisethylmaleimide carbonate, 4,9-dioxa-1,12-dodecane bismaleimide, bispropylmaleimide, and dodecane-N, N′-bismaleimide. .

［式中、Ｒ^３１は、水素原子、ハロゲン原子、アルキル基、ハロゲン化アルキル基、シクロアルキル基、ニトリル基若しくはアリール基、又は−ＣＯＯＲ^３２、−ＣＯＲ^３２、−ＯＲ^３２、−ＳＲ^３２若しくは−Ｎ（Ｒ^３２）_２で表される基を示し、Ｒ^３２は、アルキル基、シクロアルキル基又はアリール基を示し、Ｒ^９１及びＲ^９２はそれぞれ独立に、水素原子、炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基、アリール基、アルコキシ基又はハロゲン原子を示し、ｐは１〜５の整数を示す。なお、Ｒ^３１が複数存在する場合、それぞれは同一でも異なっていてもよく、また、Ｒ^９１とＲ^９２とは一緒になってイミド基の３位及び４位の炭素と共に５員環又は６員環構造を構成する２価の基を形成してもよい。］ Furthermore, examples of the arylmaleimide include maleimide represented by the following general formula (3).

[Wherein R ³¹ represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, a cycloalkyl group, a nitrile group or an aryl group, or —COOR ³² , —COR ³² , —OR ³² , —SR ³² or — N (R ³² ) ₂ represents a group, R ³² represents an alkyl group, a cycloalkyl group or an aryl group, and R ⁹¹ and R ⁹² each independently represent a hydrogen atom, an alkyl having 1 to 10 carbon atoms. Group, a C3-C10 cycloalkyl group, an aryl group, an alkoxy group, or a halogen atom, p shows the integer of 1-5. When a plurality of R ³¹ are present, each may be the same or different, and R ⁹¹ and R ⁹² together form a 5- or 6-membered ring with the 3rd and 4th carbons of the imide group. You may form the bivalent group which comprises a ring structure. ]

  Such arylmaleimides include phenylmaleimide, N- (2-trifluoromethylphenyl) maleimide, N- (2-t-butylphenyl) maleimide, N- (2-trifluoromethylphenyl) methylmaleimide, N- (2,4,6-Isopropyl-3-malimidophenyl) maleimide, N- (2-iodophenyl) maleimide, N- (2-bromo-3,5-trifluoromethylphenyl) maleimide, di (4-maleimide) Selected from the group consisting of phenyl) methane, N- (2-chlorophenyl) maleimide, N- (2-bromophenyl) maleimide, N- (2-fluorophenyl) maleimide and N- (4-trifluoromethylphenyl) methane. At least one maleimide is preferred.

［式中、Ｒ^４１は非炭素原子を有する２価の基を示し、Ｒ^４２は、水素原子、アルキル基、シクロアルキル基、アリール基、アルキルアリール基又はアリールアルキル基を示し、Ｒ^４３は、前記Ｒ^４２で表される基（但し、水素原子を除く。）から水素原子１つが除かれてなる２価の基を示し、ｔは０又は１を示し、Ｒ^９１及びＲ^９２はそれぞれ独立に、水素原子、炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基、アリール基、アルコキシ基又はハロゲン原子を示す。なお、Ｒ^９１とＲ^９２とは一緒になってイミド基の３位及び４位の炭素と共に５員環又は６員環構造を構成する２価の基を形成してもよい。］ Moreover, as a non-carbon atom containing maleimide, the maleimide represented by following General formula (4) can be illustrated.

[Wherein, R ⁴¹ represents a divalent group having a non-carbon atom, R ⁴² represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and R ⁴³ represents the groups represented by R ⁴² (excluding the hydrogen atom.) from which one hydrogen atom is a divalent group formed by removed, t represents 0 or 1, R ⁹¹ and R ⁹² are each independently , A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, an alkoxy group, or a halogen atom. R ⁹¹ and R ⁹² may be combined together to form a divalent group constituting a 5-membered or 6-membered ring structure with the 3rd and 4th carbons of the imide group. ]

［式中、Ｒ^５１は単結合、アルキレン基、アリーレン基、オキシ基、カルボニル基、エステル基、カ−ボネート基及びウレタン基からなる群より選ばれる少なくとも１つの基から構成される２価の有機基を示し、Ｒ^５２は、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、ハロゲン化アルキル基、アリール基若しくはニトリル基、又は、−ＣＯＯＲ^５３、−ＣＯＲ^５３、−ＯＲ^５３、−ＳＲ^５３若しくは−Ｎ（Ｒ^５３）_２で表される基を示し、Ｒ^５３はアルキル基、シクロアルキル基又はアリール基を示し、Ｒ^９１及びＲ^９２はそれぞれ独立に、水素原子、炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基、アリール基、アルコキシ基又はハロゲン原子を示し、ｑは１〜（Ｒ^５１の結合可能な結合手の数）の整数、ｍは１〜５の整数、ｒは５−ｍで表される数以下の整数を示す。なお、Ｒ^５２が複数存在する場合、それぞれは同一でも異なっていてもよく、また、Ｒ^９１とＲ^９２とは一緒になってイミド基の３位及び４位の炭素と共に５員環又は６員環構造を構成する２価の基を形成してもよい。］ Furthermore, examples of the polymaleimide include maleimides represented by the following general formula (5a) or (5b).

[Wherein R ⁵¹ is a divalent organic compound composed of at least one group selected from the group consisting of a single bond, an alkylene group, an arylene group, an oxy group, a carbonyl group, an ester group, a carbonate group and a urethane group. R ⁵² represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an aryl group or a nitrile group, or —COOR ⁵³ , —COR ⁵³ , —OR ⁵³ , —SR ⁵³ or -N (R ⁵³ ) ₂ represents a group, R ⁵³ represents an alkyl group, a cycloalkyl group or an aryl group, R ⁹¹ and R ⁹² each independently represents a hydrogen atom, an alkyl having 1 to 10 carbon atoms. group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, an alkoxy group or a halogen atom, q is 1 (matable bonds of R ⁵¹ Integer), m is an integer of 1 to 5, and r is an integer equal to or less than the number represented by 5-m. When a plurality of R ⁵² are present, each may be the same or different, and R ⁹¹ and R ⁹² together form a 5- or 6-membered ring with the 3rd and 4th carbons of the imide group. You may form the bivalent group which comprises a ring structure. ]

  Furthermore, the photopolymerizable compound is preferably a bisphenol A (meth) acrylate compound. Furthermore, as the photoinitiator, a benzophenone photopolymerization initiator is preferable.

  The photosensitive element according to the present invention is preferably provided with a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention, and a support and the book formed on the support. And a photosensitive resin composition layer comprising the photosensitive resin composition of the invention.

  Furthermore, the method for forming a resist pattern according to the present invention is an effective method using the photosensitive resin composition or photosensitive element of the present invention, wherein the photosensitive resin composition of the present invention is formed on a circuit forming substrate. A photosensitive resin composition layer composed of a product is laminated, and an exposed portion is formed by irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to be photocured, and then a portion other than the exposed portion is removed. It is characterized by doing.

  A printed wiring board can be easily manufactured by forming a circuit (wiring pattern) on a circuit forming substrate on which a resist pattern is formed. That is, the method for producing a printed wiring board according to the present invention is characterized by etching or plating a circuit forming substrate on which a resist pattern is formed by the resist pattern forming method of the present invention.

  Since the photosensitive resin composition of the present invention contains a combination of a photoinitiator and a maleic acid derivative, the content of the photoinitiator is an amount that does not cause inconvenience due to the photoinitiator. Even in this case, high sensitivity can be achieved. Moreover, since it consists of the basic composition of a binder polymer and a photopolymerizable compound, it is excellent in resolution and also in adhesion to the substrate. By using such a photosensitive resin composition of the present invention or a photosensitive element of the present invention using the same, a resist pattern having excellent resolution and adhesion can be formed. And the printed wiring board which has a high-density wiring pattern can be manufactured with the circuit formation board | substrate with which the resist pattern was formed in this way.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  The photosensitive resin composition of the present invention is characterized by containing the above (A) binder polymer, (B) a photopolymerizable compound, (C) a photoinitiator, and (D) a maleic acid derivative. Hereinafter, each component will be described first.

(Binder polymer)
Examples of the binder polymer include polyester resins, acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, urethane resins, and the like. These may be used alone or in combination of two or more.

  As such a binder polymer, a polymer obtained by radical polymerization of a monomer having an ethylenically unsaturated double bond is preferable. Examples of the monomer having an ethylenically unsaturated double bond include styrene, vinyl toluene, α-methyl styrene, p-methyl styrene, p-ethyl styrene, p-methoxy styrene, p-ethoxy styrene, p- Polymerizable styrene derivatives such as chlorostyrene and p-bromostyrene, acrylamides such as diacetone acrylamide, ethers of vinyl alcohol such as vinyl-n-butyl ether, (meth) acrylic acid alkyl esters, (meth) acrylic acid tetrahydrofur Furyl 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-tetrafluoropropi (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, etc. ) Acrylic acid monomers, maleic acid, maleic anhydride, maleic acid monomers such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate, acrylonitrile, fumaric acid, cinnamic acid, α-cyanosilicic acid Cinnamic acid, itaconic acid, crotonic acid, and propiolic acid can be exemplified. These can be used alone or in combination of two or more. (Meth) acrylic acid refers to acrylic acid or methacrylic acid. Similarly, (meth) acrylate refers to acrylate or methacrylate, and (meth) acryloyl refers to acryloyl or methacryloyl.

  The binder polymer in the present invention is preferably composed of one or more kinds of polymers having a carboxyl group from the viewpoint of obtaining good developability when alkali development is performed using an alkaline solution. Such a polymer having a carboxyl group can be produced by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer.

  Furthermore, from the viewpoint of improving the flexibility after curing of the photosensitive resin composition, the polymer having a carboxyl group is composed of (meth) acrylic acid and a monomer that can be copolymerized with the (meth) acrylic acid. A copolymer is preferred. Examples of monomers that can be copolymerized with (meth) acrylic acid include (meth) acrylic acid alkyl esters and styrene compounds (styrene and / or styrene derivatives), and one or more of these can be used. . The styrene derivative means one in which a hydrogen atom in styrene is substituted with a substituent (an organic group such as an alkyl group or a halogen atom).

  As the polymer having a carboxyl group, a copolymer of (meth) acrylic acid, a (meth) acrylic acid alkyl ester, and a monomer copolymerizable therewith is preferable. As the copolymerizable monomer, a styrene compound is used. preferable.

  Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth) Examples include hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and structural isomers thereof. These can be used alone or in combination of two or more.

  When styrene and / or a styrene derivative are contained, the content thereof is preferably 0.1 to 30% by weight, more preferably 1 to 28% by weight, based on the total weight of the binder polymer. More preferably, it is 5-27 weight%. By containing styrene and / or a styrene derivative in the above range, the adhesiveness, release characteristics and flexibility of the cured product can be improved. If the content of styrene and / or styrene derivative is less than 0.1% by weight, the adhesion tends to be inferior, and if it exceeds 30% by weight, the peel piece tends to be large and the peel time tends to be long.

  Moreover, it is preferable that it is 30-200 mgKOH / g, and, as for the acid value of a binder polymer, it is more preferable that it is 45-150 mgKOH / g. When the acid value is less than 30 mgKOH / g, the development time tends to be long, and when it exceeds 200 mgKOH / g, the developer resistance of the photocured photosensitive resin composition tends to be lowered. Moreover, when developing with a solvent as a development process, it is preferable to prepare the monomer which has the ethylenically unsaturated double bond which has a carboxyl group in a small quantity.

  The weight average molecular weight (Mw) of the binder polymer can be measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene). According to this measuring method, the Mw of the binder polymer is preferably 20,000 to 300,000, more preferably 25,000 to 150,000. When Mw is less than 20,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be longer.

  The above binder polymer can optionally have a photosensitive group. Moreover, these binder polymers can be used individually or in combination of 2 or more types. Examples of the binder polymer used in combination of two or more types include, for example, two or more types of binder polymers composed of different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binders having different degrees of dispersion. Examples thereof include polymers. A polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used.

(Photopolymerizable compound)
As a photopolymerizable compound, for example, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxypolyethoxypolypropoxy) phenyl) A compound obtained by reacting an α, β-unsaturated carboxylic acid with a bisphenol A-based (meth) acrylate compound such as propane, a glycidyl group-containing compound, and a urethane bond Urethane monomers such as (meth) acrylate compounds, nonylphenoxypolyethyleneoxy (meth) acrylate, γ-chloro-β-hydride Phthalic acid compounds such as xylpropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloyloxyalkyl-o-phthalate, (meth) acrylic acid alkyl esters, etc. Can be mentioned. Of these, bisphenol A-based (meth) acrylate compounds, (meth) acrylate compounds having a urethane bond, alkylene glycol di (meth) acrylate compounds, or polyalkylene glycol di (meth) acrylate compounds are preferred. These can be used alone or in combination of two or more.

  Examples of the compound obtained by reacting the 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 2 propylene groups. Polypropylene glycol di (meth) acrylate which is 14, polyethylene polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO, PO modified trimethylolpropane tri (meth) acrylate, tetramethylol methanetri ( Me ) Acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. These can be used alone or in combination of two or more.

  Examples of the 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-((meta ) 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) acryloxynononaethoxy) phenyl) propa 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) acrylic) Loxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl ) Propane and the like. 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). 4- (Methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). These can be used alone or in combination of two or more.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl. ) Propane, 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane, etc. Can be mentioned. These can be used alone or in combination of two or more.

  Examples of the urethane monomer include a (meth) acryl monomer having an OH group at the β-position and a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition reaction product, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. Examples of the EO-modified urethane di (meth) acrylate include Shin-Nakamura Chemical Co., Ltd., product name UA-11, and the like. Examples of EO and PO-modified urethane di (meth) acrylates include product name UA-13 manufactured by Shin-Nakamura Chemical Co., Ltd.

  Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups.

  Examples of the nonylphenoxypolyethyleneoxy (meth) acrylate include nonylphenoxytetraethyleneoxy (meth) acrylate, nonylphenoxypentaethyleneoxy (meth) acrylate, nonylphenoxyhexaethyleneoxy (meth) acrylate, nonylphenoxyheptaethyleneoxy ( Examples include (meth) acrylate, nonylphenoxyoctaethyleneoxy (meth) acrylate, nonylphenoxynonaethyleneoxy (meth) acrylate, nonylphenoxydecaethyleneoxy (meth) acrylate, and nonylphenoxyundecaethyleneoxy (meth) acrylate. These can be used alone or in combination of two or more.

  In addition, reactive vinyl monomers such as acrylic acid and methacrylic acid, and (meth) acrylic monomers such as amides, esters, salts, or corresponding nitriles, and vinyl compounds can also be used. Such reactive vinyl monomers include methyl acrylate, ethyl acrylate, n- or t-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, butyl acrylate, isobutyl methacrylate. (Meth) acrylic acid alkyl esters such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl hexyl methacrylate and other hydroxy (meth) acrylates, ethylene glycol dimethyl methacrylate, hexamethylene glycol dimethacrylate and other glycol (meth) acrylates, aryl methacrylate, Aryl (meth) acrylates such as diallyl methacrylate and epoxy (meth) acrylates such as glycidyl methacrylate , Aminoplast acrylates such as melamine acrylate, vinyl or vinylidene halides, (meth) acrylamides such as methacrylamide, acrylamide, diacetone acrylamide, vinyl aromatics such as styrene, alkylstyrene, halostyrene, alkoxystyrene, divinylbenzene, vinyltoluene, Examples thereof include vinyl or vinylidene ester, vinyl or vinylidene ether, vinyl or vinylidene ketone, vinyl acetate, butadiene and the like. These can be used alone or in combination of two or more.

(Photoinitiator)
As a photoinitiator, 1 or more types of the compound conventionally used as a photoinitiator or a sensitizer can be especially used without a restriction | limiting. Examples of such photoinitiator include benzophenone, 3-methylbenzophenone, 4-benzoylbiphenyl, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), 4-morpholinobenzophenone, 4,4′- Benzophenone compounds such as diphenoxybenzophenone, 4,4′-di- (4-isopropylphenoxy) benzophenone, 4,4′-diphenylbenzophenone, 4-phenylbenzophenone, thioxanthone, isopropylthioxanthone, fluorothioxanthone, 1-methyl-2- (2-Ethylhexyloxy) thioxanthone, methyl-o-benzoylbenzoate, acrylic acid-4-benzoylphenyl ester, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone Aromatic ketones such as 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, quinones such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin, alkylbenzoin Benzoin compounds such as benzyl dimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole 2-mer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl)- 2,4,5-triaryl, such as 4,5-diphenylimidazole dimer Examples include midazole dimer, 9-phenylacridine, acridine derivatives such as 1,7-bis (9,9'-acridinyl) heptane, N-phenylglycine, N-phenylglycine derivatives, and coumarin compounds. In addition, the substituents of the two aryl groups in the 2,4,5-triarylimidazole dimer may give the same and symmetric compounds, or differently give asymmetric compounds. As the photopolymerization initiator, a benzophenone photopolymerization initiator containing a benzophenone compound is preferable. By using a benzophenone-based photopolymerization initiator as the photopolymerization initiator, it becomes possible to improve the adhesion and sensitivity of the photosensitive resin composition.

(Maleic acid derivative)
The maleic acid derivative contained in the photosensitive resin composition of the present invention comprises a substituted maleimide compound in which a hydrogen atom of an imide group is substituted with a substituent, a polymaleimide having two or more maleimide groups, maleimide and maleic anhydride. And at least one maleic acid derivative selected from the group. As such a maleic acid derivative, a maleimide compound having a maleimide group is preferable.

  Examples of such maleimide compounds include substituted maleimide compounds in which a hydrogen atom of an imide group is substituted with a substituent, polymaleimides having two or more maleimide groups, maleimides, etc. Among them, substituted maleimide compounds or polymaleimides are preferable. is there.

  Examples of the substituted maleimide compounds include alkyl maleimides in which the hydrogen atom of the imide group is substituted with an alkyl group, substituted alkyl maleimides in which the hydrogen atom of the imide group is substituted with an alkyl group having a substituent, and the hydrogen atom of the imide group is converted into an aryl group. Examples include substituted arylmaleimides or non-carbon atom-containing maleimides in which a hydrogen atom of an imide group is substituted by a non-carbon atom of a non-carbon atom-containing group, and using at least one maleimide compound selected from these groups Can do. Of these, alkylmaleimide, substituted alkylmaleimide, and arylmaleimide are preferable because they are easily available and have excellent practicality. Hereinafter, these substituted maleimide compounds will be described.

The alkylmaleimide is a compound in which a nitrogen atom in maleimide is substituted with an alkyl group, and a compound represented by the above general formula (1) is preferable. The alkylmaleimide represented by the general formula (1) is a compound in which R ¹ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, and R ⁹¹ and R ⁹² are hydrogen atoms. Is more preferable. As such an alkylmaleimide, at least one alkylmaleimide selected from the group consisting of methylmaleimide, t-butylmaleimide, hexylmaleimide and cyclohexylmaleimide is more preferable, and methylmaleimide, t-butylmaleimide or cyclohexyl is more preferable. Maleimide is particularly preferred.

The substituted alkylmaleimide is a compound in which the nitrogen atom of maleimide is substituted with an alkyl group having a substituent other than the alkyl group, and examples thereof include compounds represented by the general formula (2). In the substituted alkylmaleimide represented by the general formula (2), R ²¹ is preferably an alkylene group having 1 to 3 carbon atoms, R ²² is a hydroxyl group, an alkyl carbonate group having 1 to 6 carbon atoms, or 1 to carbon atoms. It is preferably at least one group selected from the group consisting of 6 alkylcarbamoyloxy groups, (meth) acryloyl groups and 1 to 3 carbon acyloxy groups.

  Specific examples of such a substituted alkylmaleimide include hydroxymethylmaleimide (a compound represented by the following chemical formula (6a)), hydroxyethylmaleimide (a compound represented by the following chemical formula (6b)), 2-ethyl carbonate. Ethyl maleimide (compound represented by the following chemical formula (6c)), 2-isopropyl urethane ethyl maleimide (compound represented by the following chemical formula (6d)), 2-acryloylethyl maleimide (compound represented by the following chemical formula (6e)) ), Acetoxyethylmaleimide (a compound represented by the following chemical formula (6f)), and the like. Of these, 2-ethyl carbonate ethyl maleimide is particularly preferable.

これらの置換アルキルマレイミドは、公知の製造方法により製造することができる。具体的には、例えば、Z .Y . Wang, Synth. Commn. , 20(11)1607-1610(1990)、P .O. Tawneyら,J .Org .Chem .,26 ,15(1961) 、米国特許第２，５４２，１４５号明細書等に記載された方法により製造可能である。

These substituted alkylmaleimides can be produced by a known production method. Specifically, for example, Z.Y.Wang, Synth. Commn., 20 (11) 1607-1610 (1990), P.O.Tawney et al., J.Org.Chem., 26, 15 (1961), It can be produced by the method described in US Pat. No. 2,542,145.

  The arylmaleimide is a compound in which the hydrogen atom of the imide group in the maleimide is substituted with an aryl group. In this case, the aryl group may further have a substituent. Examples of such arylmaleimides include compounds represented by the above general formula (3).

In the arylmaleimide represented by the general formula (3), R ³¹ is a group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and a trifluoromethyl group. At least one group selected from the above is preferred. R ⁹¹ and R ⁹² are preferably hydrogen atoms.

  Specific examples of such arylmaleimides include N-phenylmaleimide (a compound represented by the following chemical formula (7a)) and N- (2-trifluoromethylphenyl) maleimide (the following chemical formula (7b)). Compound), N- (2-t-butylphenyl) maleimide (compound represented by the following chemical formula (7c)), α-methyl-N- (2-trifluoromethylphenyl) maleimide (the following chemical formula (7d)) Compound), N- (2-iodophenyl) maleimide (compound represented by the following chemical formula (7e)), N- (2-bromo-3,5-trifluoromethylphenyl) maleimide (the following chemical formula (7f) ), N- (2-chlorophenyl) maleimide (compound represented by the following chemical formula (7 g)), N- (2-bromophenyl) male Mido (compound represented by the following chemical formula (7h)), N- (2-fluorophenyl) maleimide (compound represented by the following chemical formula (7i)), N- (4-trifluoromethylphenyl) maleimide (the following chemical formula Examples thereof include a compound represented by (7j).

  Among these, from N- (2-trifluoromethylphenyl) maleimide, N- (2-t-butylphenyl) maleimide, α-methyl-N- (2-trifluoromethylphenyl) maleimide, N-phenylmaleimide More preferred is at least one maleimide selected from the group consisting of N- (2-trifluoromethylphenyl) maleimide or N- (2-t-butylphenyl) maleimide.

  Furthermore, the non-carbon atom-containing maleimide is a compound in which the hydrogen atom of the imide group in the maleimide is substituted with a non-carbon atom of the non-carbon atom-containing group, and examples thereof include the compound represented by the general formula (4). .

In the general formula (4), the group represented by R ⁴¹ is a divalent group having a non-carbon atom, and examples of the non-carbon atom include Si, O, and N. As such a divalent group, groups represented by —SiH ₂ —, —O—, and —NH— are preferable. Further, the group represented by R ⁴² is an alkyl group, a cycloalkyl group, an aryl group, at least one group selected from the group consisting of alkyl aryl and aryl alkyl groups.

  As the maleic acid derivative to be contained in the photosensitive resin composition of the present invention, it is also preferable to use polymaleimide in addition to the substituted maleimide compound described above. Such polymaleimide is a compound having two or more maleimide groups, and examples thereof include compounds represented by the above general formula (5a) or (5b).

In the above formula (5a) or ^(5b), as the ^{R 51,} the number of carbon atoms, which may have an alkyl group or an oxyalkyl group having 1 to 10 carbon atoms having 1 to 4 carbon atoms in the side chain 1 12 alkylene group, C1-C4 alkyl group, or C1-C10 oxyalkyl group which may have in a side chain a C3-C12 cycloalkylene group, C1-C12 oxy Examples thereof include an alkylene group, an arylene group which may have a substituent, and a divalent group represented by the following general formulas (8a) to (8e). These divalent groups are preferably divalent groups containing one or more oxygen atoms derived from compounds such as ethylene glycol, carbonate, aryl, alkylaryl, arylalkyl and the like.

In the formula, each of R ⁸¹ and R ⁸² is independently at least one selected from the group consisting of an alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an oxy group, a carbonyl group, and an imino group. And a divalent group derived from an alkylene group, an oxyalkylene group, or isophorone diisocyanate is preferable, v is an integer of 1 to 10, and w is an integer of 0 to 10. preferable.

  Examples of such polymaleimides include triethylene glycol biscarbonate bisethylmaleimide (compound represented by the following chemical formula (9a)), isophorone bisurethane bisethylmaleimide (compound represented by the following chemical formula (9b)), bisethyl. Maleimide carbonate (compound represented by the following chemical formula (9c)), 4,9-dioxa-1,12-decanbismaleimide (compound represented by the following chemical formula (9d)), 4,9-dioxa-1,12 -Dodecane bismaleimide, bispropylmaleimide (compound represented by the following chemical formula (9e)), dodecane-N, N'-bismaleimide (compound represented by the following chemical formula (9f)), N- (2, 4, 6-isopropyl-3-malimidophenyl) maleimide (compound represented by the following chemical formula (9 g)) Di (4-maleimidophenyl) methane (compound represented by the following chemical formula (9h)), di (3,5-diethyl-4-maleimidophenyl) methane (compound represented by the following general formula (9i)) and the like As an example, di (4-maleimidophenyl) methane is particularly preferable.

Furthermore, as the maleic acid derivative to be contained in the photosensitive resin composition of the present invention, maleimide represented by the following general formula (10a) or maleic anhydride represented by the following general formula (10b) should be used. Even when these compounds are used, the effect of improving the sensitivity is sufficiently exhibited. In the formula, R ⁹¹ and R ⁹² have the same meaning as described above, and a hydrogen atom is particularly preferable.

  As mentioned above, although the maleic acid derivative which can be used for the photosensitive resin composition of this invention has been demonstrated, it selects from the group which consists of N-methylmaleimide, N-phenylmaleimide, and di (4-maleimidophenyl) methane among these. Particularly preferred is at least one maleimide.

  The four components of the binder polymer, photopolymerizable compound, photoinitiator and maleic acid derivative described above are preferably mixed in the following amounts in the photosensitive resin composition of the present invention.

  First, the blending amount of the binder polymer is preferably 20 to 90 parts by weight, more preferably 30 to 85 parts by weight, with respect to 100 parts by weight of the total amount of the binder polymer and the photopolymerizable compound. More preferably, it is 80 parts by weight. If this blending amount is less than 20 parts by weight, the photocured product tends to be brittle and tends to be inferior in coating properties when used as a photosensitive element, and if it exceeds 90 parts by weight, the sensitivity tends to be insufficient. is there.

  The blending amount of the photopolymerizable compound is preferably 10 to 80 parts by weight, more preferably 15 to 70 parts by weight with respect to 100 parts by weight of the total amount of the binder polymer and the photopolymerizable compound. More preferably, it is 20-60 weight part. If the amount is less than 10 parts by weight, the sensitivity tends to be insufficient, and if it exceeds 80 parts by weight, the photocured product tends to be brittle.

  Furthermore, the blending amount of the photoinitiator is preferably 0.01 to 20 parts by weight and preferably 0.02 to 15 parts by weight with respect to 100 parts by weight of the total amount of the binder polymer and the photopolymerizable compound. More preferred is 0.03 to 10 parts by weight. If the blending amount is less than 0.01 parts by weight, sufficient photosensitivity tends not to be obtained, and if it exceeds 20 parts by weight, light absorption on the surface of the composition increases during exposure, and the internal Tends to be insufficiently photocured.

  Furthermore, the blending amount of the maleic acid compound is preferably about 0.001 to 100 parts by weight, and about 0.005 to 20 parts by weight with respect to 100 parts by weight of the total amount of the binder polymer and the photopolymerization initiator. More preferably, it is more preferably about 0.01 to 10 parts by weight.

(Other ingredients)
In addition to the essential components described above, one or more other components can be added to the photosensitive resin composition of the present invention.

  As other components, for example, a hydrogen atom donor that functions as a coinitiator or a synergist and has a function of donating electrons or electrons can be contained. As such a hydrogen atom donor, a compound having an active hydrogen atom can be used, and examples thereof include an alcohol having a hydrogen atom at a carbon adjacent to a hetero atom, a tertiary amine or an ether. Examples of such a hydrogen atom donor include triethanolamine, methyl-diethanolamine, ethyldiethanolamine, dimethylaminobenzoic acid and the like. Also, for example, when the photopolymerizable compound itself has an active hydrogen atom as described above in the molecule, such as polyethylene glycol diacrylate, the same effect as when the above hydrogen atom donor is contained. Can be obtained.

  When a hydrogen atom donor is contained as the other component, the content of the hydrogen atom donor can be about 0.1 to 5% by weight based on the total weight of the composition. In addition, when the photopolymerizable compound itself has an active hydrogen atom, the total light contained in the photosensitive resin composition can be obtained in order to obtain the same effect as that of separately including a coinitiator or a synergist. The weight of the photopolymerizable compound having an active hydrogen atom in the polymerizable compound is preferably 85% by weight or more.

  Furthermore, in the photosensitive resin composition, if necessary, a photopolymerizable compound (for example, oxetane compound) having at least one cationically polymerizable cyclic ether group, a cationic polymerization initiator, a dye such as malachite green, Photochromic agents such as tribromomethylphenylsulfone and leucocrystal violet, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, A leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent, and the like may be contained in an amount of about 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of binder polymer and photopolymerizable compound. it can.

  Such a photosensitive resin composition of the present invention may contain, as necessary, an organic 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 be dissolved or dispersed in these mixed solvents and used as a varnish having a solid content of about 30 to 60% by weight.

  Next, the photosensitive element according to the present invention will be described.

  The photosensitive element of the present invention comprises a support and a photosensitive resin composition layer comprising the above-described photosensitive resin composition of the present invention formed on the support, and the photosensitive resin composition layer. Above, you may further provide the protective film which coat | covers this photosensitive resin composition layer. In this case, the thickness after drying of the photosensitive resin composition layer can be about 1 to 100 μm. The photosensitive element according to the present invention further includes an intermediate layer and a protective layer such as a cushion layer, an adhesive layer, a light absorbing layer, and a gas barrier layer in addition to the photosensitive resin composition layer, the support and the protective film. Also included.

  The photosensitive element uses a polymer film having a thickness of about 1 to 100 μm made of polyethylene terephthalate, polypropylene, polyethylene, polyester or the like as a support, and after applying the photosensitive resin composition on the support, It can be obtained by drying. Such coating can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater. Moreover, drying can be implemented by heating to such an extent that the solvent which remains in the photosensitive resin composition volatilizes, and it is normally heated at about 70-150 degreeC for about 5 to 30 minutes. The amount of the remaining organic solvent in the photosensitive resin composition layer after drying is preferably 2% by weight or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.

  As the protective film for covering the photosensitive resin composition layer in this photosensitive element, the same film as that used for the support can be applied, but the adhesive strength with the photosensitive resin composition layer is used for the support. A film smaller than the conventional film is preferable, and a film having a low fisheye is more preferable.

  Such a photosensitive element can be stored, for example, in the form of a flat plate as it is or in the form of a roll wound around a cylindrical core. In the latter case, for example, a plastic such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer) can be used as the winding core. Moreover, when storing with the form of a roll, it is desirable to provide the protective film on the photosensitive resin composition layer, and it is more preferable to wind up so that a support body may become the outermost part at the time of winding. More preferably, an end face separator is installed on the end face of the roll-shaped photosensitive element from the viewpoint of end face protection, and in addition, a moisture-proof end face separator is installed from the viewpoint of edge fusion resistance. When these photosensitive elements are packaged and stored, the packaging method is preferably wrapped in a black sheet with low moisture permeability.

  Next, a resist pattern forming method according to the present invention will be described.

  In the method for forming a resist pattern according to the present invention, a photosensitive resin composition layer comprising the above-described photosensitive resin composition of the present invention is laminated on a circuit forming substrate, and an active portion is applied to a predetermined portion of the photosensitive resin composition layer. An exposed portion is formed by irradiating light rays, and then portions other than the exposed portion are removed.

  Here, as the circuit forming substrate, a laminated substrate in which a conductive layer such as a metal foil is formed on an insulating substrate, or an insulating substrate having no such conductive layer can be used. A laminated substrate having a conductive layer is applied to, for example, a subtractive method in which a wiring pattern is formed by etching a conductive layer in manufacturing a printed wiring board. On the other hand, an insulating substrate having no conductive layer is applied to an additive method in which a wiring pattern is formed on an insulating substrate by plating.

The lamination of the photosensitive resin composition layer on the circuit forming substrate is performed by applying the photosensitive resin composition on the substrate, preferably in a varnish state, or by the method using the photosensitive element according to the present invention. Can be implemented. When laminating by coating, a known method such as a roll coater, comma coater, gravure coater, air knife coater, die coater, bar coater, etc. can be applied to such coating. Moreover, when using a photosensitive element, after removing the protective film in a photosensitive element as needed, the photosensitive resin composition by the method (laminate) which press-bonds on a board | substrate, heating the photosensitive resin composition layer. Stacking of physical layers is possible. In the case of laminating using the latter photosensitive element, it is preferable to perform pressure bonding under reduced pressure from the viewpoint of adhesion and followability. Moreover, it is preferable that the heating temperature of the photosensitive resin composition layer at the time of pressure bonding is 70 to 130 ° C., and the pressure is preferably about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). In addition, it is not always necessary if the photosensitive resin composition layer is heated to 70 to 130 ° C. as described above, but from the viewpoint of further improving the laminating property, pre-heat treatment of the circuit forming substrate may be performed. It is valid.

  After the lamination of the photosensitive resin composition layer is completed in this way, an exposed portion is formed by irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays. Examples of the method for forming the exposed portion include a method of irradiating actinic rays in an image form through a negative or positive mask pattern called an artwork. At this time, when the support existing on the photosensitive resin composition layer is transparent to the active light, the active light can be irradiated through the support, and the support is opaque to the active light. For this, the photosensitive resin composition layer is irradiated with actinic rays after the support is removed.

  As the actinic ray light source, a known light source can be used. 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, or a xenon lamp is used. Further, those that effectively emit visible light, such as a photographic flood bulb, a solar lamp, etc., are used, and a laser direct drawing exposure method can also be applied.

  After the exposure, when a support is present on the photosensitive resin composition layer, the support is removed with an auto peeler or the like, and then a portion other than the exposed portion is removed by wet development, dry development or the like ( Development) to form a resist pattern. When the photosensitive resin composition of the present invention is used, development is preferably performed by wet development. In this case, a developer such as an alkaline aqueous solution, an aqueous developer, an organic solvent developer is appropriately selected and used. Development is performed by a known method such as dipping, spraying, brushing, or scraping.

  As the developer, an alkaline aqueous solution is particularly preferable because it is safe and stable, and has good operability. Examples of the base in the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium or ammonium carbonate or bicarbonate, potassium phosphate, sodium phosphate And alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate. Among them, 0.1-5 wt% dilute sodium carbonate solution, 0.1-5 wt% dilute potassium carbonate solution, 0.1-5 wt% dilute sodium hydroxide solution, 0.1-5 wt% A dilute solution of sodium tetraborate is preferred. The pH of these alkaline aqueous solutions is preferably 9 to 11, and the temperature can be adjusted according to the developability of the photosensitive resin composition layer. Furthermore, a surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.

After the development, heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm ² can be performed as necessary (post-curing step). By such heating or exposure, the formed resist pattern is further cured, the adhesion to the substrate and the mechanical strength are further improved, and peeling or the like in the etching or plating process described later is further less likely to occur.

  Next, the manufacturing method of the printed wiring board by this invention is demonstrated.

  The method for producing a printed wiring board according to the present invention comprises removing the resist pattern after etching (subtractive method) or plating (additive method) the substrate on which the resist pattern is formed by the resist pattern forming method of the present invention. It is a method characterized by performing.

  Etching and plating of the laminated substrate or the insulating substrate is performed on the conductor layer of the substrate using the formed resist pattern as a mask. Etching is performed using a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, or the like as an etching solution, and a circuit forming substrate (conductive layer) in which a resist pattern is formed in these solutions. For example, by dipping the insulating substrate). For the photosensitive resin composition of the present invention, a ferric chloride solution is preferable as an etchant because it has a good etch factor.

  In addition, for example, copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, nickel plating such as watt bath (nickel sulfate-nickel chloride) plating, nickel sulfamate plating, and hard gold Examples thereof include gold plating such as plating and soft gold plating. The circuit forming substrate (insulating substrate not having a conductive layer) on which a resist pattern is formed is immersed in these plating solutions. When a wiring pattern made of copper is formed by copper sulfate plating or the like, solder plating may be further performed on the copper pattern for the purpose of protecting the copper pattern. The circuit formation by plating can also be applied when an insulating substrate with a conductive layer is used as the circuit forming substrate. In this case, plating is performed on the conductive layer, the resist pattern is removed by a method described later, and then the conductive layer at a portion protected by the resist and not plated is removed by soft etching or the like to form a wiring pattern. .

  After the etching or plating is finished, the resist pattern on the circuit forming substrate is removed from the substrate by peeling off the resist pattern with a stronger alkaline aqueous solution than the alkaline aqueous solution used for the development, for example, so that a predetermined wiring pattern is formed on the insulating substrate. A printed wiring board having the following is obtained. Examples of the strong alkaline aqueous solution used for removing the resist pattern include a 1 to 10% by weight sodium hydroxide aqueous solution and a 1 to 10% by weight potassium hydroxide aqueous solution. And a resist pattern is removed by implementing well-known methods, such as an immersion system and a spray system, individually or in combination using these strong alkali solutions.

  Although the printed wiring board is obtained as described above, in the printed wiring board manufacturing method of the present invention, the above-described photosensitive resin composition or photosensitive element of the present invention is used, and therefore, the pattern interval is narrowed. However, exposure / development can be carried out with high sensitivity and high resolution, thereby enabling good etching or plating. As a result, high density of the wiring pattern on the printed wiring board is realized. In addition, the manufacturing method of the printed wiring board of the said invention is not limited to manufacture of a single layer printed wiring board, It can apply suitably also to manufacture of a multilayer printed wiring board.

  Hereinafter, the present invention will be described in more detail with reference to preferred examples, but the present invention is not limited thereto.

[Synthesis of binder polymer]
(Synthesis Example 1)
To a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube, 700 g of a mixed solvent in which methyl cellosolve: toluene was mixed at a weight ratio of 3: 2 was added, and 85 ° C. while blowing nitrogen gas. And stirred. A solution obtained by previously mixing 110 g of methacrylic acid, 225 g of methyl methacrylate, 135 g of ethyl acrylate, 30 g of styrene and 3 g of azobisisobutyronitrile was dropped into this mixed solvent over 4 hours, and then stirred at 85 ° C. The mixture was kept warm for 2 hours. Next, a solution prepared by dissolving 0.3 g of azobisisobutyronitrile in 60 g of the same mixed solvent as described above was dropped into the flask over 10 minutes. Then, after stirring the obtained solution at 85 degreeC for 5 hours, stirring, it cooled and the polymer which is a binder polymer was obtained. The obtained polymer had a nonvolatile content of 41.8% by weight and a weight average molecular weight of 84,000. The weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

[Preparation of photosensitive resin composition]
(Examples 1-3, Comparative Example 1)
First, a binder polymer (component A), a photopolymerizable compound (component B), a photoinitiator (component C) and other components shown in Table 1 were blended to obtain a first solution.

  In the table, HDDA is 1,6-hexanediol diacrylate, UA-13 is EO, PO-modified urethane dimethacrylate, MECHPP is γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate, BP represents benzophenone, Cl-HABI represents 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylimidazole dimer, and EAB represents diethylaminobenzophenone.

  Subsequently, the maleic acid derivative (component D) shown in Table 2 was dissolved in the obtained first solution to obtain solutions of the photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1.

  In the formula, MMI represents N-methylmaleimide, PMI represents N-phenylmaleimide, and BMI represents di (4-maleimidophenyl) methane.

[Manufacture of photosensitive elements]
(Examples 4 to 6, Comparative Example 2)
The solutions of the photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 were each dried on a polyethylene terephthalate film (PET film, support) having a width of 380 mm and a thickness of 20 μm so that the film thickness after drying was 40 μm. The photosensitive resin composition layer was formed by coating. Next, after drying the applied photosensitive resin composition layer at 100 ° C. with a hot air convection dryer, a 35 μm thick polyethylene film (protective film) is placed on the photosensitive resin composition layer, and a roll The photosensitive elements of Examples 4 to 6 and Comparative Example 2 were obtained. In addition, the case where the photosensitive resin composition of Examples 1-3 is used corresponds to Examples 4-6, and the case where the photosensitive resin of Comparative Example 1 is used corresponds to Comparative Example 2, respectively.

[Evaluation of photosensitivity, adhesion and resolution]
The copper surface of a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., MCL-E-67), which is a glass epoxy material in which copper foil (thickness 35 μm) is laminated on both sides, is scotch bright buffol (manufactured by Sumitomo 3M Ltd.) After being polished and washed with water, it was dried with a stream of air. This copper clad laminate was heated to 60 ° C., and the photosensitive elements of Examples 4 to 6 and Comparative Example 2 were placed on the copper surface at 110 ° C. with the photosensitive resin composition layer facing the copper surface. A photosensitive resin composition layer was laminated while heating to obtain a sample for characteristic evaluation.

  About each obtained sample for characteristic evaluation, the photosensitivity, adhesiveness, and the resolution were evaluated by the method shown below. The results are summarized in Table 3.

(Light sensitivity)
On a photosensitive resin composition layer of a sample for characteristic evaluation, a stove 41 step tablet is placed as a negative, and using an exposure machine (HMW201GX, manufactured by Oak Co., Ltd.) having a high-pressure mercury lamp lamp, exposure amounts 30, 60, The exposure was performed at 120 mJ / cm ² . After exposure, after standing at room temperature for 30 minutes, the PET film was peeled off, and a 1 wt% sodium carbonate aqueous solution at 30 ° C. was sprayed to remove unexposed portions. Thereafter, the number of steps of the step tablet of the formed cured film was measured, and the photosensitivity was evaluated by calculating the exposure amount at which the step tablet remained at 23 steps / 41 steps. The photosensitivity is indicated by the exposure amount, and the smaller the exposure amount that the step tablet gives 23/41 steps, the higher the photosensitivity.

(Adhesion and resolution)
A phototool having a wiring pattern having a line width / space width of 30/400 to 200/400 (for adhesion evaluation, unit: μm) on the photosensitive resin composition layer of the sample for property evaluation, or 30/30 to A photo tool having a wiring pattern of 200/200 (for resolution evaluation, unit: μm) is brought into close contact, and using the same means as the photosensitivity evaluation, the exposure amount that the step tablet of each test piece gives 23/41 steps After exposure, the unexposed part was removed. Adhesion and resolution were determined by measuring the minimum line width (μm) remaining without peeling after development in samples for physical property evaluation that were exposed and developed using the respective photo tools for evaluation. The smaller these widths, the better the adhesion or resolution.

Claims (16)

  (A) an alkali-soluble binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a maleic acid derivative. The photosensitive resin composition characterized by the above-mentioned.   The maleic acid derivative (D) is at least one maleate selected from the group consisting of a substituted maleimide compound in which a hydrogen atom of an imide group is substituted with a substituent, a polymaleimide having two or more maleimide groups, maleimide and maleic anhydride The photosensitive resin composition according to claim 1, which is an acid derivative.   The substituted maleimide compound is an alkyl maleimide in which the hydrogen atom of the imide group is substituted with an alkyl group, a substituted alkyl maleimide in which the hydrogen atom of the imide group is substituted with an alkyl group having a substituent, and the hydrogen atom of the imide group is converted into an aryl group. It is a substituted arylmaleimide and at least one maleimide compound selected from the group consisting of a non-carbon atom-containing maleimide in which a hydrogen atom of an imide group is substituted by a non-carbon atom of a non-carbon atom-containing group The photosensitive resin composition of Claim 2. The photosensitive resin composition according to claim 3, wherein the alkylmaleimide is a maleimide represented by the following general formula (1).

[Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms,
R ⁹¹ and R ⁹² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, an alkoxy group or a halogen atom.
R ⁹¹ and R ⁹² may be combined together to form a divalent group constituting a 5-membered or 6-membered ring structure with the 3rd and 4th carbons of the imide group. ]   The photosensitive resin composition according to claim 4, wherein the alkylmaleimide is at least one maleimide selected from the group consisting of methylmaleimide, t-butylmaleimide, hexylmaleimide, and cyclohexylmaleimide. The photosensitive resin composition according to claim 3, wherein the substituted alkylmaleimide is a maleimide represented by the following general formula (2).

[Wherein R ²¹ represents an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms,
R ²² is a halogen atom, a nitrile group, an isocyanate group, a sulfonic acid group, a quaternary ammonium group or a group consisting of a quaternary ammonium salt, or —OR ²³ , —SR ²³ , —SiH ₂ R ²³ , —OC. (O) N (R ²³ ) ₂ , —OC (O) C (R ²³ ) ═CHR ²³ , —OC (O) R ²³ , —C (O) R ²³ , —N (R ²³ ) ₂ , —C ^{(O) oR} _23, represented by -C (O) N (R 23 ) 2, -OC (O) oR 23, -N-R 24 -R 25 or ^{-N-R 24 -R} 26 -R ²⁵ Group,
R ²³ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkylaryl group;
R ²⁴ represents an arylene group,
R ²⁵ is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a nitrile group, an isocyanate group, a sulfonic acid group, a quaternary ammonium group or a quaternary ammonium salt, or —OR ²³ , —SR. _{^{23, -SiH 2 R 23, -OC}} (O) N (R 23) 2, -OC (O) C (R 23) = CHR 23, -OC (O) R 23, -C (O) R 23, -N ^(R ₂₃₎ ^2, shows the -C (O) oR 23, -C (O) N group represented by ^(R _{23) 2} or -OC (O) ^{oR 23,}
R ²⁶ represents a divalent group composed of at least one group selected from the group consisting of an alkylene group, an arylene group and a cycloalkylene group;
R ⁹¹ and R ⁹² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, an alkoxy group, or a halogen atom.
R ⁹¹ and R ⁹² may be combined together to form a divalent group constituting a 5-membered or 6-membered ring structure with the 3rd and 4th carbons of the imide group. ]   The substituted alkyl maleimide is hydroxymethyl maleimide, hydroxyethyl maleimide, triethylene glycol biscarbonate bisethyl maleimide, 2-ethyl carbonate ethyl maleimide, 2-isopropyl urethane ethyl maleimide, 2-acryloyl ethyl maleimide, acetoxyethyl maleimide, isophorone urethane bis. It is at least one maleimide selected from the group consisting of ethyl maleimide, bisethyl maleimide carbonate, 4,9-dioxa-1,12-dodecane bismaleimide, bispropyl maleimide and dodecane-N, N′-bismaleimide. The photosensitive resin composition according to claim 6. The photosensitive resin composition according to claim 3, wherein the arylmaleimide is a maleimide represented by the following general formula (3).

[Wherein R ³¹ represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, a cycloalkyl group, a nitrile group or an aryl group, or —COOR ³² , —COR ³² , —OR ³² , —SR ³² or — A group represented by N (R ³² ) ₂ ;
R ³² represents an alkyl group, a cycloalkyl group or an aryl group,
R ⁹¹ and R ⁹² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, an alkoxy group or a halogen atom,
p shows the integer of 1-5.
When a plurality of R ³¹ are present, each may be the same or different, and R ⁹¹ and R ⁹² together form a 5- or 6-membered ring with the 3rd and 4th carbons of the imide group. You may form the bivalent group which comprises a ring structure. ]   The arylmaleimide is phenylmaleimide, N- (2-trifluoromethylphenyl) maleimide, N- (2-tert-butylphenyl) maleimide, N- (2-trifluoromethylphenyl) methylmaleimide, N- (2, 4,6-isopropyl-3-maleimidophenyl) maleimide, N- (2-iodophenyl) maleimide, N- (2-bromo-3,5-trifluoromethylphenyl) maleimide, di (4-maleimidophenyl) methane, At least one maleimide selected from the group consisting of N- (2-chlorophenyl) maleimide, N- (2-bromophenyl) maleimide, N- (2-fluorophenyl) maleimide and N- (4-trifluoromethylphenyl) methane The photosensitive resin composition according to claim 8, wherein: The photosensitive resin composition according to claim 3, wherein the non-carbon atom-containing maleimide is a maleimide represented by the following general formula (4).

[Wherein R ⁴¹ represents a divalent group having a non-carbon atom,
R ⁴² represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group,
R ⁴³ represents a divalent group formed by removing one hydrogen atom from the group represented by R ⁴² (excluding a hydrogen atom),
t represents 0 or 1,
R ⁹¹ and R ⁹² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, an alkoxy group or a halogen atom.
R ⁹¹ and R ⁹² may be combined together to form a divalent group constituting a 5-membered or 6-membered ring structure with the 3rd and 4th carbons of the imide group. ] 3. The photosensitive resin composition according to claim 2, wherein the polymaleimide is a maleimide represented by the following general formula (5a) or (5b).

[Wherein R ⁵¹ is a divalent organic compound composed of at least one group selected from the group consisting of a single bond, an alkylene group, an arylene group, an oxy group, a carbonyl group, an ester group, a carbonate group and a urethane group. Group,
R ⁵² represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an aryl group or a nitrile group, or —COOR ⁵³ , —COR ⁵³ , —OR ⁵³ , —SR ⁵³ or —N (R ⁵³ ) represents a group represented by ₂ ,
R ⁵³ represents an alkyl group, a cycloalkyl group or an aryl group,
R ⁹¹ and R ⁹² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, an alkoxy group or a halogen atom,
q is an integer of 1 to 1 (the number of bonds that R ⁵¹ can bond to), m is an integer of 1 to 5, and r is an integer equal to or less than the number represented by 5-m.
When a plurality of R ⁵² are present, each may be the same or different, and R ⁹¹ and R ⁹² together form a 5- or 6-membered ring with the 3rd and 4th carbons of the imide group. You may form the bivalent group which comprises a ring structure. ]   The said (B) photopolymerizable compound is a bisphenol A type (meth) acrylate compound, The photosensitive resin composition as described in any one of Claims 1-11 characterized by the above-mentioned.   The said (C) photoinitiator is a benzophenone series photoinitiator, The photosensitive resin composition as described in any one of Claims 1-12 characterized by the above-mentioned.   A photosensitive element comprising: a support; and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 13 formed on the support. .   A photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 13 is laminated on a circuit forming substrate, and an active portion is formed on a predetermined portion of the photosensitive resin composition layer. A method for forming a resist pattern, comprising: exposing an exposed portion of light to form a light-cured exposed portion; and then removing a portion other than the exposed portion.   A method for manufacturing a printed wiring board, comprising etching or plating a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern according to claim 15.