JP2010151946A - Photosensitive resin composition and photosensitive element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having satisfactorily low water absorption and excellent alkali developing properties and capable of forming an image with a thick film. <P>SOLUTION: The photosensitive resin composition includes a polyamic acid having constituent units represented by general formulae (1), (2) and (3), a photopolymerizable compound and a photopolymerization initiator. In the formulae, Ar<SP>1</SP>denotes a tetravalent group having a 5-20C alkylene group, Ar<SP>2</SP>denotes a bivalent group having a 5-20C alkylene group and Ar<SP>3</SP>denotes a bivalent group having an aromatic hydrocarbon group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition and a photosensitive element.

  Conventionally, a photosensitive resin composition containing a polyimide resin or a polybenzoxazole resin, which has excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like, is used for a surface protective film and an interlayer insulating film of a semiconductor element. It is used.

  As the photosensitive resin composition, there are a solvent developing type and an alkali developing type, and the alkali developing type is mainly used from the viewpoint of working environment preservation and global environment preservation. As such a photosensitive resin composition, for example, a liquid resist ink composition described in Patent Document 1, a photosensitive thermosetting resin composition described in Patent Document 2, and the like are known.

  However, since the conventional alkali development type photosensitive resin composition is mainly composed of a hydrophilic group in order to enable alkali development, the developer, water, etc. penetrate into the exposed area. This tends to reduce the practical moisture resistance of the resist film to be formed.

On the other hand, Patent Document 3 discloses a resin composition in which moisture absorption is improved by blending an inorganic filler with a polyamide-imide resin or the like to improve moisture resistance. Patent Document 4 discloses a photosensitive resin composition containing an alicyclic polyimide, and Patent Document 5 discloses a polymer compound synthesized from a fluorine-containing diamine, which is reported to have low water absorption. .
JP-A 61-243869 JP-A-1-141904 JP 2006-348178 A JP 2007-314583 A JP 2008-150534 A

  However, a resin composition containing an inorganic filler may have a high viscosity and low fluidity, or the inorganic filler may settle during long-term storage and storage stability may decrease. For this reason, the resin composition which can achieve a low water absorption rate without mix | blending an inorganic filler is calculated | required.

  On the other hand, the resin compositions described in Patent Documents 4 and 5 have low water absorption, but are not sufficiently soluble in an alkali developer, and thus it is difficult to form an image with a thick film.

  The present invention has been made in view of the above problems, and provides a photosensitive resin composition having sufficiently low water absorption, excellent alkali developability, and capable of forming an image with a thick film. Objective.

ここで、式（１）、（２）及び（３）中、Ａｒ^１は炭素数５〜２０のアルキレン基を有する４価の基を示し、Ａｒ^２は炭素数５〜２０のアルキレン基を有する２価の基を示し、Ａｒ^３は芳香族炭化水素基を有する２価の基を示す。
The present invention provides (A) a polyamic acid having structural units represented by the following general formulas (1), (2) and (3), (B) a photopolymerizable compound, (C) a photopolymerization initiator, The photosensitive resin composition containing is provided.

Here, in the formulas (1), (2) and (3), Ar ¹ represents a tetravalent group having an alkylene group having 5 to 20 carbon atoms, and Ar ² has an alkylene group having 5 to 20 carbon atoms. Ar ³ represents a divalent group, and Ar ³ represents a divalent group having an aromatic hydrocarbon group.

  According to such a photosensitive resin composition, by containing a polyamic acid having a specific structure, a photopolymerizable compound and a photopolymerization initiator, sufficient alkali developability can be obtained, and an unexposed portion can be obtained. Therefore, it is possible to achieve both good solubility and a residual film property of the exposed portion, to form a good image even with a thick film, and to form a cured film with sufficiently low water absorption.

ここで、式（４）中、Ｘは炭素数５〜２０のアルキレン基を示し、Ｒ^１及びＲ^２はそれぞれ独立に水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｍ及びｎはそれぞれ独立に１〜３の整数を示し、ｍが２以上の場合、複数存在するＲ^１は同一でも異なっていてもよく、ｎが２以上の場合、複数存在するＲ^２は同一でも異なっていてもよい。 From the viewpoint of improving developability and resolution, in the general formula (1), Ar ¹ is preferably a tetravalent group represented by the following general formula (4).

Here, in formula (4), X represents an alkylene group having 5 to 20 carbon atoms, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. M and n each independently represents an integer of 1 to 3, and when m is 2 or more, a plurality of R ¹ may be the same or different, and when n is 2 or more, a plurality of R ¹ are present. R ² may be the same or different.

ここで、式（５）中、Ｚは単結合又は２価の有機基を示し、Ｙ^１及びＹ^２はそれぞれ独立に炭素数５〜２０のアルキレン基を示す。 In the general formula (2), when Ar ² is a divalent group represented by the following general formula (5), imidization at a relatively low temperature is likely to proceed, and the flexibility is excellent. Warpage can be reduced.

Here, in Formula (5), Z represents a single bond or a divalent organic group, and Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms.

ここで、式（６）、（７）及び（８）中、Ｒ^３、Ｒ^４及びＲ^５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１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｑ、ｒ及びｓは、それぞれ独立に１〜４の整数を示し、ｑが２以上の場合、複数存在するＲ^３は同一でも異なっていてもよく、ｒが２以上の場合、複数存在するＲ^４は同一でも異なっていてもよく、ｓが２以上の場合、複数存在するＲ^５は同一でも異なっていてもよい。 In the above general formula (5), Z is preferably at least one group selected from the group consisting of divalent groups represented by the following general formulas (6), (7) and (8). . Thereby, not only is the developability excellent, but the curing temperature after pattern formation can be lowered.

Here, in formula (6), (7) and (8), R < ³ >, R < ⁴ > and R < ⁵ > are respectively independently a hydrogen atom, a C1-C10 alkyl group, and a C1-C10 alkenyl group. Or an alkoxy group having 1 to 3 carbon atoms, q, r and s each independently represent an integer of 1 to 4, and when q is 2 or more, a plurality of R ³ may be the same or different. , When r is 2 or more, a plurality of R ⁴ may be the same or different, and when s is 2 or more, a plurality of R ⁵ may be the same or different.

ここで、式（８）中、Ｄは単結合、エーテル結合、チオエーテル結合、カルボニル基、スルホニル基、メチレン基、エチレン基、イソプロピリデン基、ヘキサフルオロイソプロピリデン基、下記式（ｉ）で表される基又は下記式（ｉｉ）で表される基を示し、Ｒ^６及びＲ^７は、それぞれ独立に水素原子、水酸基、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｔ１及びｔ２は、それぞれ独立に１〜４の整数を示す。ｔ１が２以上の場合、複数存在するＲ^６は同一でも異なっていてもよく、ｔ２が２以上の場合、複数存在するＲ^７は同一でも異なっていてもよい。

From the viewpoint of improving the transparency of the cured film, the remaining film ratio during photocuring, alkali solubility, and heat resistance, the Ar ³ may be an arylene group which may have a substituent or the following general formula (8). It is preferred that

Here, in the formula (8), D is a single bond, an ether bond, a thioether bond, a carbonyl group, a sulfonyl group, a methylene group, an ethylene group, an isopropylidene group, a hexafluoroisopropylidene group, and represented by the following formula (i). Or a group represented by the following formula (ii), wherein R ⁶ and R ⁷ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. , T1 and t2 each independently represents an integer of 1 to 4. When t1 is 2 or more, a plurality of R ⁶ may be the same or different, and when t2 is 2 or more, a plurality of R ⁷ may be the same or different.

  In the above formula (8), when D is a sulfonyl group, it is possible to form an image with a thick film by improving the remaining film ratio at the time of photocuring, and the swelling at the time of development is reduced. The developability with the liquid is improved. For this reason, in the thick film, the effect of the present invention that enables image formation with excellent resolution can be exhibited more effectively and reliably.

  The present invention also provides a photosensitive element comprising a support and a layer made of the photosensitive resin composition formed on the support (hereinafter referred to as “photosensitive layer”). Thus, a non-photosensitive resin composition is applied to form a non-photosensitive layer, and then a photosensitive resin composition is applied onto the non-photosensitive layer to form a photosensitive layer, which is exposed and developed to form a pattern. Thus, it is not necessary to go through such complicated steps, and the process can be shortened. Moreover, since the photosensitive layer is a film, handling becomes easy.

  According to the present invention, it is possible to provide a photosensitive resin composition having sufficiently low water absorption, excellent alkali developability, and capable of forming an image with a thick film.

  Hereinafter, preferred embodiments of the present invention will be described in detail. In the present specification, “(meth) acrylate” means “acrylate” and “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” and “methacryl” corresponding thereto.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises (A) polyamic acid (hereinafter sometimes referred to as “component (A)”) and (B) a photopolymerizable compound (hereinafter sometimes referred to as “component (B)”). And (C) a photopolymerization initiator (hereinafter sometimes referred to as “component (C)”). Hereinafter, each component will be described in detail.

<(A) component>
The polyamic acid in the present invention has structural units represented by the above general formulas (1), (2) and (3) (hereinafter referred to as “general formulas (1) to (3)”). . Moreover, (A) component may consist only of the structural unit represented by the said general formula (1)-(3), and further comprises structural units other than the said general formula (1)-(3). You may have. Furthermore, as the component (A), a polyamic acid having the structural units represented by the general formulas (1) to (3) may be used alone, or may be used in combination with other polyamic acids.

  These (A) polyamic acids can be produced, for example, by reacting a tetracarboxylic dianhydride component and a diamine component in a solvent.

  In this case, the general formula (1) is a tetracarboxylic dianhydride component residue having an alkylene group having 5 to 20 carbon atoms, and the general formula (2) is a diamine component having an alkylene group having 5 to 20 carbon atoms. As a residue, the general formula (3) is incorporated into a polyamic acid as a diamine component residue having an aromatic hydrocarbon group. A C5-C20 alkylene group and an aromatic hydrocarbon group can comprise the principal chain of a polyamic acid. Thereby, it is possible to provide a photosensitive resin composition capable of obtaining sufficient developability and capable of forming an image with a thick film with high resolution. Moreover, low temperature curability, flexibility, low water absorption and low warpage of the photosensitive resin composition can be achieved by containing an alkylene group having 5 to 20 carbon atoms in the main chain. In the present specification, the term “thick film” refers to a case where the thickness of the coating film formed from the photosensitive resin composition is 20 μm or more.

A tetracarboxylic acid dianhydride component with Ar ^1, and a diamine component having Ar ^2, it is possible to form a repeating unit represented by the following general formula (I).

A repeating unit represented by the following general formula (II) can be formed from a tetracarboxylic dianhydride component having Ar ¹ and a diamine component having Ar ³ .

ここで、式（９）中、Ｘは炭素数５〜２０アルキレン基であり、炭素数８〜１５のアルキレン基であることが好ましい。 (Tetracarboxylic dianhydride component)
The tetracarboxylic dianhydride component may be any component that can form the structural unit represented by the general formula (1). In General Formula (1), Ar ¹ preferably has an alkylene group having 5 to 20 carbon atoms in the main chain, and more preferably a tetravalent organic group represented by General Formula (4). Examples of such a tetracarboxylic dianhydride component include a compound represented by the following general formula (9).

Here, in Formula (9), X is a C5-C20 alkylene group, and it is preferable that it is a C8-C15 alkylene group.

  Examples of the compound represented by the general formula (9) include pentamethylene bis trimellitate dianhydride, hexamethylene bis trimellitate dianhydride, heptamethylene bis trimellitate dianhydride, octamethylene bis trimellitate dianhydride. Nonamethylene bis trimellitate dianhydride, decamethylene bis trimellitate dianhydride, dodecamethylene bis trimellitate dianhydride. Among these, decamethylene bistrimellitate dianhydride is preferable because the resulting film has low water absorption and low elasticity. These can be used alone or in combination of two or more.

  In synthesizing the polyamic acid (A), a tetracarboxylic dianhydride other than the tetracarboxylic dianhydride component having an alkylene group having 5 to 20 carbon atoms in the main chain may be used in combination. Examples of such tetracarboxylic dianhydrides include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic anhydride. 1,2,4,5-cyclopentanetetracarboxylic anhydride, 1,2,4,5-cyclohexanetetracarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,3 ′ , 4,4′-bicyclohexyltetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid dianhydride, 3 , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, 3,3 ′, 4,4′-benzophenonetetracar Acid dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic acid anhydride (4,4′-oxydiphthalic acid dianhydride), 2,3 ′, 4,4′-diphenyl ether tetracarboxylic acid Dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic anhydride, 2,3,6,7-naphthalene Tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic Acid dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis [4- (3 4-dicarboxybe Zoyloxy) phenyl] nonane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] decane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyl) Oxy) phenyl] tridecane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] tetradecane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyl) Oxy) phenyl] pentadecane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] -2-methyldecane dianhydride, 1,1-bis [4- (3,4- Dicarboxybenzoyloxy) phenyl] -2-methyloctane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] -2-ethyl Pentadecane dianhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] dodecane dianhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] decane dianhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] tridecane dianhydride, 2, 2-bis [3,5-diethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] pentadecane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] cyclohexane Dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] propylcyclohexane dianhydride, 1,1-bis [4- (3,4-dica Boxybenzoyloxy) phenyl] heptylcyclohexane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) tetrafluoropropane dianhydride, 4,4-bis (2,3-dicarboxyphenoxy) diphenylmethane Anhydrides are mentioned. These are used singly or in combination of two or more.

(Diamine component)
The diamine component should just be what can form the structural unit represented by the said General formula (2) or (3). In the general formula (2), Ar ² is one having an alkylene group having 5 to 20 carbon atoms, and more preferably a divalent organic group represented by the above general formula (5). In the general formula (5), when Z is a divalent organic group, it is selected from the group consisting of divalent organic groups represented by the general formulas (6), (7) and (8), respectively. It is preferably at least one group.

  Examples of the diamine component having an alkylene group having 5 to 20 carbon atoms in the main chain include hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 1,12-dodecane diamine, and 2,11. -Diaminododecane, 1,12-diaminooctadecane, 2,5-dimethylhexamethylenediamine, 3-methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methylnonamethylene Examples thereof include aliphatic diamines such as diamine and 3-methoxyhexamethylenediamine, and compounds represented by the following general formulas (10), (11) and (12). These are used individually by 1 type or in combination of 2 or more types.

ここで、式（１０）中、Ｙ^１及びＹ^２は、それぞれ独立に炭素数５〜２０のアルキレン基を示し、Ｒ^８は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｑは１〜４の整数を示す。なお、ｑが２以上の場合、複数存在するＲ^８は同一でも異なっていてもよい。

Here, in Formula (10), Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. An alkenyl group or an alkoxy group having 1 to 3 carbon atoms, and q represents an integer of 1 to 4. When q is 2 or more, a plurality of R ⁸ may be the same or different.

ここで、式（１１）中、Ｙ^１及びＹ^２は、それぞれ独立に炭素数５〜２０のアルキレン基を示し、Ｒ^９は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｒは１〜４の整数を示す。なお、ｒが２以上の場合、複数存在するＲ^９は同一でも異なっていてもよい。

Here, in Formula (11), Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Alkenyl group or an alkoxy group having 1 to 3 carbon atoms, and r represents an integer of 1 to 4. When r is 2 or more, a plurality of R ⁹ may be the same or different.

ここで、式（１２）中、Ｙ^１及びＹ^２は、それぞれ独立に炭素数５〜２０のアルキレン基を示し、Ｒ^１０は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｓは１〜４の整数を示す。なお、ｓが２以上の場合、複数存在するＲ^１０は同一でも異なっていてもよい。

Here, in the formula (12), ^{Y 1} and ^{Y 2} each independently represent an alkylene group having 5 to 20 carbon ^{atoms, R 10} is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, carbon atoms 1 to 10 An alkenyl group or an alkoxy group having 1 to 3 carbon atoms, and s represents an integer of 1 to 4. When s is 2 or more, a plurality of R ¹⁰ may be the same or different.

  Examples of the diamine component containing the compound represented by the general formula (10) include 1,4-bis (1,1-dimethyl-5-aminopentyl) benzene and 1,4-bis (2-methoxy-4). -Aminopentyl) benzene.

As a diamine component containing the compound represented by the general formula (11) and / or (12), [3,4-bis (1-aminoheptyl) -6-hexylu-5- (1-octenyl)] cyclohexene ( A product name “Versamine 551” manufactured by Cognis Japan Co., Ltd. is commercially available. Here, “Versamine 551” is a diamine compound including a compound represented by the following formula (13) and / or a compound in which an unsaturated portion of the compound represented by the following (13) is hydrogenated.

  (A) It is preferable that content of the diamine component which can form the structural unit represented by General formula (2) used in the synthesis | combination of a polyamic acid is 50-99 mol% with respect to the diamine component whole quantity, and 60- More preferably, it is 98 mol%, and it is further more preferable that it is 70-97 mol%. Compared to the case where the content of the diamine component capable of forming the structural unit represented by the general formula (2) is out of the above range, the developability and the resolution tend to be improved.

In the general formula (3), Ar ³ has an aromatic hydrocarbon group in the main chain, and may be an arylene group which may have a substituent or the general formula (8). It is preferable to have a group.

ここで、式（１４）中、Ｄは単結合、エーテル結合、チオエーテル結合、カルボニル基、スルホニル基、メチレン基、エチレン基、イソプロピリデン基、ヘキサフルオロイソプロピリデン基、下記式（ｉ）で表される基又は下記式（ｉｉ）で表される基を示す。Ｒ^６及びＲ^７はそれぞれ独立に水素原子、水酸基、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｔ１及びｔ２はそれぞれ独立に１〜４の整数を示す。ｔ１が２以上の場合、複数存在するＲ^６は同一でも異なっていてもよく、ｔ２が２以上の場合、複数存在するＲ^７は同一でも異なっていてもよい。

Examples of the diamine compound having a group represented by the general formula (8) include a diamine compound represented by the following general formula (14).

Here, in the formula (14), D is a single bond, an ether bond, a thioether bond, a carbonyl group, a sulfonyl group, a methylene group, an ethylene group, an isopropylidene group, a hexafluoroisopropylidene group, and represented by the following formula (i). Or a group represented by the following formula (ii). R ⁶ and R ⁷ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and t1 and t2 each independently represent an integer of 1 to 4. When t1 is 2 or more, a plurality of R ⁶ may be the same or different, and when t2 is 2 or more, a plurality of R ⁷ may be the same or different.

  Examples of the diamine compound having an aromatic hydrocarbon group include 4,4′-diaminodibenzyl sulfoxide, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) diphenylsilane, and bis (4-amino). Phenyl) ethylphosphine oxide, bis (4-aminophenyl) phenylphosphine oxide, bis (4-aminophenyl) -N-phenylamine, bis (4-aminophenyl) -N-methylamine, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminonaphthalene, 1 , 4-Diamino-2-methylnaphthalene, 1,5-diamy 2-methylnaphthalene, 1,3-diamino-2-phenylnaphthalene, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 2,4 -Diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminotoluene, 1-methoxy-2,4-diaminobenzene, 1,3-diamino-4,6-dimethylbenzene, 1 , 4-diamino-2,5-dimethylbenzene, 1,4-diamino-2-methoxy-5-methylbenzene, 1,4-diamino-2,3,5,6-tetramethylbenzene, o-xylenediamine, m-xylenediamine, p-xylenediamine, 9,10-bis (4-aminophenyl) anthracene, 4-aminophenyl-3-aminobenzoe 1,1-bis (4-aminophenyl) -1-phenyl-2,2,2-trifluoroethane, 1,1-bis [4- (4-aminophenoxy) phenyl] -1-phenyl-2 , 2,2-trifluoroethane, 1,3-bis (3-aminophenyl) decafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,4-bis (3 -Aminophenyl) but-1-ene-3-yne 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4 , 4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodi Phenylmethane, 3,3′-dimethoxy-4,4′-diaminodiphenylmethane, 3,3′diethoxy-4,4′-diaminodiphenylmethane, bis (3-aminophenyl) ether, bis (4-aminophenyl) ether, 3,4′-diaminodiphenyl ether, 3,3′-diethyl-4,4′-diaminodiphenyl ether, 3,3′-dimethoxy-4,4′-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] Ether, 3,3′-dimethyl-4,4′-diaminodiphenyl sulfone, 3,3′-diethyl-4,4′-diaminodiphenyl sulfone, 3,3′-dimethoxy-4,4′-diaminodiphenyl sulfone, 3,3′-diethoxy-4,4′-diaminodiphenylsulfone, 3,3′-dimethyl 4,4′-diaminodiphenylpropane, 3,3′-diethyl-4,4′-diaminodiphenylpropane, 3,3′-dimethoxy-4,4′-diaminodiphenylpropane, 3,3′-diethoxy-4, 4'-diaminodiphenylpropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane 4,4′-diaminodiphenyl sulfide, 3,3′-dimethyl-4,4′-diaminodiphenyl sulfide, 3,3′-diethyl-4,4′-diaminodiphenyl sulfide, 3,3′-dimethoxy-4 , 4′-diaminodiphenyl sulfide, 3,3′-diethoxy-4,4′-diaminodiphenyl sulfide, 2,4′-dia Nodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (4-aminophenyl) ) Ethane, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, bis (4-toluidine) sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3- Aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene, 4,4′-diaminobiphenyl, 9,9-bis [4- (4-aminophenoxy) phenyl] fluorene, 9,9- Bis [4- (3-aminophenoxy) phenyl] fluorene, 3,3′-diaminobiphenyl, 3,3′-dimethyl -4,4'-diaminobiphenyl, 3,4'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy ) Biphenyl, 1,4-bis (4-aminophenoxy) benzene, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2 -Bis (3-aminophenyl) hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexa Fluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (3-aminophenyl) Sa fluoro propane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (5-amino-4-methylphenyl) hexafluoropropane and the like. Among these, 4,4′-diaminodiphenyl sulfone is preferably used because alkali solubility is improved and developability is improved. These diamine components may be used alone or in combination of two or more.

  (A) It is preferable that content of the diamine component which can form the structural unit represented by General formula (3) used in the synthesis | combination of a polyamic acid is 1-50 mol% with respect to the diamine component whole quantity, More preferably, it is 45 mol%, and further more preferably 10-40 mol%. If the content of the diamine component capable of forming the structural unit represented by the general formula (3) is less than 1 mol%, the film loss during development tends to be large, and the reliability at high temperature and high humidity tends to decrease. If it exceeds%, the solubility in the developer tends to be low, and the developability with an alkaline aqueous solution tends to be low.

  In the present invention, the tetracarboxylic dianhydride represented by the general formula (9) from the viewpoint of further reducing the water absorption rate, making it possible to improve the remaining film ratio during development, and achieving both alkali developability, Containing a polyamic acid synthesized from the diamine compound represented by the general formula (10), (11), (12) and / or (13) and the diamine compound represented by the general formula (14). Is preferred.

  Moreover, in this invention, diamine compounds other than the diamine compound represented by the said General formula (10)-(14) can be used together. Examples of such diamine compounds include 4,4′-methylenebis (cyclohexylamine), 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 2,2′-diaminodiethylsulfide, adipic acid dihydrazide, Aliphatic dicarboxylic acid dihydrazide such as dodecanedioic acid dihydrazide. Furthermore, silicon-containing diamines such as dimethylsiloxane-based diamines (for example, trade name: “LP-7100” manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as part of the diamine component. Since the resolution can be further improved, it is also preferable to use an aliphatic dicarboxylic acid dihydrazide such as adipic acid dihydrazide or dodecanedioic acid dihydrazide. These diamine components may be used alone or in combination of two or more.

  In addition, as a diamine component, diamine compounds other than the diamine compound mentioned above can be used together in the range which does not deviate from the range of the effect which this invention has.

(Method for synthesizing polyamic acid)
(A) The polyamic acid is synthesized from the diamine component and the tetracarboxylic dianhydride component by a known method. That is, it is synthesized by selectively combining a tetracarboxylic dianhydride component and a diamine component and causing a polymerization reaction in an organic solvent. Specifically, (A) polyamic acid is an addition of approximately equimolar amounts of tetracarboxylic dianhydride component and diamine component in an organic solvent at a reaction temperature of 80 ° C. or lower, preferably 70 ° C. or lower for 1 to 12 hours. It can be obtained by a polymerization reaction.

  Examples of the solvent include nitrogen-containing solvents (N, N′-dimethylsulfoxide, N, N′-dimethylformamide, N, N′-diethylformamide, N, N′-dimethylacetamide, N, N′- Diethylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphoamide, N-methylpyrrolidone, etc.), lactones (γ-butyrolactone, γ-valerolactone, γ-caprolactone, ε-caprolactone, α-acetyl-γ-butyrolactone Etc.), alicyclic ketones (cyclohexanone, 4-methylcyclohexanone, etc.), ethers (3-methyl-3-methoxybutyl acetate, diethylene glycol dimethyl ether acetate, etc.). Among these, from the viewpoints of solubility and water absorption, nitrogen-containing solvents and alicyclic ketones are preferable, and N-methyl-2-pyrrolidone and cyclohexanone are particularly preferable. These can be used individually by 1 type or in mixture of 2 or more types.

  The combination of the tetracarboxylic dianhydride component and the diamine component is selected from the above-mentioned components in consideration of the heat resistance, mechanical properties, electrical properties, etc. of the cured film made of the polyimide resin to be finally formed. You can choose.

  Moreover, in order to improve the adhesiveness and developability of (A) polyamic acid, it is preferable to introduce aminobenzimidazole or a derivative thereof into (A) polyamic acid. Examples of aminobenzimidazole and derivatives thereof include 2-aminobenzimidazole, 2-amino-6-methyl-benzimidazole, 2-amino-6-ethyl-benzimidazole, 2-amino-6-butyl-benzimidazole, 2-amino-6-nitro-benzimidazole is mentioned. Among these, 2-amino-benzimidazole is preferable from the viewpoint of adhesiveness.

  The amount introduced when aminobenzimidazole or a derivative thereof is introduced is preferably 0.1 to 10 mol, more preferably 1 to 5 mol, and more preferably 2 to 3 mol with respect to 100 mol of (A) polyamic acid. It is particularly preferred. If the amount of aminobenzimidazole or its derivative introduced is less than 0.1 mol, the effect of improving adhesiveness tends to be insufficient, and if it exceeds 10 mol, developability and storage stability tend to be lowered.

  From the viewpoint of improving the solubility in an alkali developer and the properties of the cured film, the weight average molecular weight of the polyamic acid as the component (A) is preferably 10,000 to 50,000, more preferably 20,000 to 45,000. It is preferably 25,000 to 40,000. If the weight average molecular weight of the polyamic acid is less than 10,000, the polyamic acid tends to swell easily during development, and if it exceeds 50,000, the solubility in the developer tends to be lowered and insolubilized.

  In the photosensitive resin composition, the content of the (A) polyamic acid is preferably 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the (A) component and the (B) component, and is preferably 30 to 70 parts. It is more preferable that it is a mass part, and it is especially preferable that it is 40-60 mass parts. When this content is less than 20 parts by mass, the developability tends to decrease, and when the content exceeds 80 parts by mass, the resolution tends to decrease or the imidization rate at low temperatures tends to decrease. is there.

<(B) component>
Next, the component (B) will be described.

  The component (B) is not particularly limited as long as it is a photopolymerizable compound having an ethylenically unsaturated group. For example, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, bisphenol A Urethane monomers such as system (meth) acrylate compounds, compounds obtained by reacting glycidyl group-containing compounds with α, β-unsaturated carboxylic acids, photopolymerizable compounds having urethane bonds and ethylenically unsaturated groups in the molecule, Nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, and (meth) acrylic acid alkyl esters are exemplified. These are used singly or in combination of two or more. In addition, (B) a photopolymerizable compound may be synthesize | combined by a conventional method, and a commercially available thing may be obtained.

  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. 14 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, Trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meta) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol diacrylate, and nonanediol diacrylate. These are used singly or in combination of two or more. Here, “EO” represents ethylene oxide, and an EO-modified compound represents one having a block structure of an ethylene oxide group. “PO” represents propylene oxide, and a PO-modified compound has a propylene oxide group block structure.

  Neopentyl glycol diacrylate is commercially available as A-NPG (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), and nonanediol diacrylate is FA-129 (trade name, Hitachi Chemical Co., Ltd.). It is commercially available as a company).

  Examples of the bisphenol A-based (meth) acrylate compound include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypoly). Propoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc. Is mentioned. 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) acryloxynonane) Xyl) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane. These are used individually by 1 type or in combination of 2 or more types.

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

  The photopolymerizable compound having a urethane bond and an ethylenically unsaturated group in the molecule has, for example, a urethane bond derived from a reaction between a dihydroxyl group and an isocyanate group of a diisocyanate compound, and an isocyanate group at a plurality of terminals. It can be obtained by subjecting a urethane compound having a hydroxyl group and an ethylenically unsaturated group to a condensation reaction.

  Examples of available photopolymerizable compounds having a urethane bond and an ethylenically unsaturated group in the molecule include TMCH-5 (trade name, manufactured by Hitachi Chemical Co., Ltd.), Hitaroid 9082 (trade name, manufactured by Hitachi Chemical Co., Ltd.). ), UA-11, UA-21 (trade names, manufactured by Shin-Nakamura Chemical Co., Ltd.).

  The compound obtained by reacting the glycidyl group-containing compound with an α, β-unsaturated carboxylic acid includes a novolac type epoxy resin, a bisphenol type A type epoxy resin or a bisphenol F type epoxy resin and a salicylaldehyde type epoxy resin. It is preferable to include a resin obtained by reacting at least one epoxy resin selected from the group consisting of a vinyl group-containing monocarboxylic acid.

  Examples of the novolac type epoxy resin include a phenol novolac type epoxy resin and a cresol novolac type epoxy resin. These novolak type epoxy resins can be obtained by reacting a phenol novolak resin and a cresol novolak resin with epichlorohydrin, respectively, by a known method.

  The bisphenol A type epoxy resin or bisphenol F type epoxy resin can be obtained, for example, by reacting the hydroxyl group of bisphenol A type epoxy resin or bisphenol F type epoxy resin with epichlorohydrin.

  Specific examples of the salicylaldehyde type epoxy resin include FAE-2500, EPPN-501H, and EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the vinyl group-containing monocarboxylic acid include acrylic acid, dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and α-cyanocinnamic acid. Can be mentioned. In addition, a half-ester compound, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester and a saturated or unsaturated dibasic acid anhydride, which is a reaction product of a hydroxyl group-containing acrylate and a saturated or unsaturated dibasic acid anhydride The half-ester compound which is a reaction product of is mentioned. These half ester compounds are obtained by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio. These vinyl group-containing monocarboxylic acids can be used singly or in combination of two or more.

  Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the half ester compound include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxybutyl acrylate. , Hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, Guri Jill acrylate, glycidyl methacrylate.

  Examples of the saturated or unsaturated dibasic acid anhydride used in the synthesis of the half ester compound include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, and ethyltetrahydrophthalic anhydride. Examples thereof include acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.

  If necessary, a vinyl group-containing monocarboxylic acid and a polybasic acid anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like can be used in combination.

  In the reaction of the saturated or unsaturated group-containing polybasic acid anhydride with the vinyl group-containing epoxy resin, 0 to 1.0 equivalent of the saturated or unsaturated group-containing polybasic acid anhydride is reacted with 1 equivalent of the hydroxyl group. Thus, an acid-modified vinyl group-containing epoxy resin can be obtained.

  The acid value of the acid-modified vinyl group-containing epoxy resin (A) is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, and further preferably 70 mgKOH / g or less. When the acid value exceeds 150 mgKOH / g, the film swells during development or the water absorption rate of the film tends to increase.

  Examples of the photopolymerizable compound having an acid-modified vinyl group-containing epoxy resin that can be obtained include HITAROID 7661 (trade name, manufactured by Hitachi Chemical Co., Ltd.), KAYARAD CCR-1159 (trade name, manufactured by Nippon Kayaku Co., Ltd.), KAYARAD. TCR-1310 (trade name, manufactured by Nippon Kayaku Co., Ltd.) may be mentioned.

  Among these, as the component (B), from the viewpoint of compatibility with (A) polyamic acid, solubility in a developer, and heat resistance of a cured film, HITAROID 7661 which is an acid-modified vinyl group-containing novolak resin is used. preferable. These may be used alone or in combination of two or more.

  In the photosensitive resin composition, the content of the component (B) is preferably 20 to 80 parts by weight, based on a total of 100 parts by weight of the component (A) and the component (B), and 30 to 70 parts by weight. It is more preferable that it is 40-60 mass parts. When the content is less than 20 parts by mass, the resolution tends to decrease or the imidization rate at low temperature tends to decrease. When the content exceeds 80 parts by mass, the content is within the above range. Compared to the above, the developability tends to be lowered.

<(C) component>
The photopolymerization initiator as component (C) is not particularly limited as long as it generates a free radical by active light. For example, aromatic ketone, quinones, benzoin ether compound, benzyl derivative, 2, 4, 5 -Triarylimidazole dimer, acridine derivative, N-phenylglycine, N-phenylglycine derivative, phosphine oxide derivative, oxime ester derivative, coumarin compound.

  Examples of the aromatic ketone include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (that is, Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4. '-Dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Propan-1-one is mentioned.

  Examples of quinones include 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenyl. Examples include anthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone.

  Examples of the benzoin ether compound include benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether. Examples of commercially available products include Irgacure-369 and Irgacure-907 (trade name, manufactured by Ciba Specialty Chemicals).

  Examples of the benzyl derivative include benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin, and benzyldimethyl ketal. Examples of commercially available products include Irgacure-651 (trade name, manufactured by Ciba Specialty Chemicals), which is benzyldimethyl ketal.

  Examples of the 2,4,5-triarylimidazole dimer include 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1,3-diazol-2- Yl] -4,5-diphenylimidazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer is mentioned.

  Examples of the acridine derivative include 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane.

  Examples of the phosphine derivative include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Examples of commercially available products include Darocur-TPO (trade name, manufactured by Ciba Specialty Chemicals) which is 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

  Examples of the oxime ester derivative include 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) -1,2-octanedione.

  (C) A photoinitiator may be synthesize | combined by a conventional method and a commercially available thing may be obtained. Examples of commercially available (C) photopolymerization initiators include Darocur-TPO, Irgacure-369, Irgacure-907, Irgacure-651, Irgacure-819, Irgacure-OXE-01 (all of which are Ciba Specialty. Chemicals, product name).

  The said (C) photoinitiator can be used individually by 1 type or in combination of 2 or more types. Among the above-described (C) photopolymerization initiators, Irgacure-651 and Irgacure-OXE-01 are particularly preferable from the viewpoint of improving sensitivity and compatibility with a solvent. In addition, when Darocur-TPO is used as a photopolymerization initiator, the sensitivity tends to be slightly improved as compared with the case where Irgacure-651 and Irgacure-OXE-01 are combined, but the resolution tends to be improved.

  In the photosensitive resin composition of the present invention, the content of (C) the photopolymerization initiator is preferably 1 to 20% by mass, based on the total solid content of the photosensitive resin composition, and preferably 2 to 10% by mass. % Is more preferable, and 2.5 to 8% by mass is particularly preferable. (C) When the content of the photopolymerization initiator is out of the above range, the sensitivity of the photosensitive resin composition is decreased or the compatibility is decreased as compared with the case where the content is in the above range. There is a tendency.

<Other ingredients>
((D) Crosslinking agent)
Moreover, you may add (D) crosslinking agent further to the photosensitive resin composition of this invention. (D) Although it does not restrict | limit especially as a crosslinking agent, An epoxy compound, a blocked isocyanate compound, etc. are mentioned. Specifically, YH-434L (amine type epoxy resin, manufactured by Tohto Kasei Co., Ltd., trade name) is preferable as the epoxy compound. Specifically, BL-3175 (blocked isocyanate, manufactured by Sumika Bayer Urethane Co., Ltd., trade name) is preferable as the blocked isocyanate compound. When these crosslinking agents are added, the adhesiveness of the cured photosensitive resin composition to the substrate can be further improved.

  When (D) a crosslinking agent is contained in the photosensitive resin composition, the content is preferably 10 to 60 parts by mass, and 30 to 40 parts by mass with respect to 100 parts by mass of (A) polyamic acid. More preferably. When the content of the (D) crosslinking agent is out of the above range, the cured film after curing becomes fragile as compared with the case where the content is within the above range, or (A) the polyamic acid and (D) the crosslinking agent. There is a tendency that the compatibility with is reduced.

((E) sensitizer)
Further, (E) a sensitizer can be further added to the photosensitive resin composition of the present invention. Examples of (E) sensitizers include Michler's ketone, 4,4-diethylaminobenzophenone, 3,3′-carbonylbis (diethylaminocoumarin), and the like. (E) As a sensitizer, from the viewpoints of sensitivity of the photosensitive resin composition and compatibility with a solvent, coumarins are preferable, and Coumarin 102 (trade name, manufactured by Acros Co., Ltd.) is particularly preferable. (E) A sensitizer is used individually by 1 type or in mixture of 2 or more types.

  The content of the (E) sensitizer in the photosensitive resin composition is preferably 0.1 to 1% by mass based on the total solid content of the photosensitive resin composition. (E) When the content of the sensitizing dye is out of the above range, the sensitivity of the photosensitive resin composition is decreased or the compatibility with the solvent is decreased as compared with the case where the content is within the above range. There is a tendency to.

  The photosensitive resin composition of the present invention comprises (A) a polyamic acid, (B) a photopolymerizable compound and (C) a photopolymerization initiator, and (D) a crosslinking agent and / or ( E) It can be obtained by mixing a sensitizer with a solvent.

(solvent)
The solvent used at this time is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, propylene glycol monomethyl ether acetate, and γ-butyrolactone. These solvents are used alone or as a mixture of two or more.

(Adhesion aid)
If necessary, an adhesion assistant may be added to the photosensitive resin composition in order to improve the adhesion between the photosensitive resin composition and the substrate. Examples of the adhesion assistant include silane coupling agents such as γ-glycidoxysilane, aminosilane, γ-ureidosilane, and 3-methacryloxypropyltrimethoxysilane. As adhesion aids that are generally available, KBM-503 (3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone, trade name), AY-43031 (γ-ureidopropyltriethoxysilane, manufactured by Toray Dow Co., Ltd.) , Product name). These may be used alone or in combination of two or more.

  The photosensitive resin composition of the present invention obtained as described above can obtain sufficient developability and can perform image formation with a thick film with high resolution. It can be used as a surface protective film or an interlayer insulating film of a semiconductor element.

[Pattern formation method]
A method for forming a cured body (cured film) using the photosensitive resin composition of the present invention will be described.

  First, the photosensitive resin composition is applied on a substrate. As the substrate, silicon, alumina ceramic, glass, glass ceramic, aluminum nitride, a substrate on which a semiconductor is formed, or the like is used. Examples of the coating method include, but are not limited to, spin coating using a spinner, spray coating, dipping, and roll coating.

  The coating thickness varies depending on the coating means, the solid content concentration and the viscosity of the photosensitive resin composition, and the like. For use as an interlayer insulating film, the film thickness of the dried film (photosensitive resin composition layer) is preferably 1 to 300 μm, more preferably 15 to 150 μm, and particularly preferably 20 to 100 μm. preferable. In order to make the film thickness after drying become 1 to 300 μm, it is preferable to dissolve the photosensitive resin composition of the present invention with a solvent and adjust the viscosity to 1 to 50 Pa · s, preferably 20 to 20 μm. It is more preferable to adjust to 40 Pa · s. The solid content concentration of the photosensitive resin composition is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. When the film thickness of the obtained film exceeds 300 μm, the resolution tends to decrease.

  Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition layer made of the photosensitive resin composition. Drying is preferably carried out in the range of 60 to 120 ° C. for 1 minute to 1 hour using an oven, a hot plate or the like.

  Next, a mask having a desired pattern is placed on the photosensitive resin composition layer as necessary, and exposure is performed by irradiating actinic rays through the mask. Examples of the actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. Among these, ultraviolet rays and visible rays are particularly preferable.

  A pattern can be formed by removing an unexposed part using a developing solution after exposure. Here, as the developer, an organic solvent such as N-methylpyrrolidone or ethanol, or an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, or tetraethylammonium hydroxide is used. be able to. Among these, since there are few metallic ion compounds, it is preferable to use tetramethylammonium hydroxide for development of the photosensitive resin composition.

  Further, after the development, if necessary, rinse with water or an alcohol such as methanol, ethanol, isopropyl alcohol or the like.

  Furthermore, after the development, a cured product made of the photosensitive resin composition can be obtained by curing. In the curing after development, it is preferable to adjust the heating temperature as appropriate, for example, it is preferable to carry out for 1 to 2 hours while raising the temperature stepwise. The heating temperature is preferably adjusted between 120 and 225 ° C. Specifically, after development, for example, heat treatment is performed at 120 ° C., 150 ° C., and 180 ° C. for 20 minutes, and then heat treatment is performed at 225 ° C. for 40 minutes to further heat cure the pattern after photocuring. A cured product can be obtained.

  The cured body formed from the photosensitive resin composition according to the present invention is useful as a surface protective film or an interlayer insulating film of a semiconductor element.

[Photosensitive element]
The photosensitive resin composition of this invention can also be used with the form of the photosensitive element in which the photosensitive resin composition layer (photosensitive layer) which consists of a photosensitive resin composition was formed on the support body.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. The photosensitive element 1 shown in FIG. 1 includes a support 10 and a photosensitive layer 14 provided on the support 10. The photosensitive layer 14 is a layer made of the above-described photosensitive resin composition of the present invention. In the photosensitive element 1 of the present invention, the surface F1 opposite to the support 10 on the photosensitive layer 14 may be covered with a protective film.

  The photosensitive layer 14 is formed by dissolving the photosensitive resin composition of the present invention in the above solvent or mixed solvent to obtain a solution having a solid content of about 30 to 70% by mass, and then applying the solution onto the support 10. It is preferable.

  Although the thickness of the photosensitive layer 14 changes with uses, it is the thickness after drying which removed the solvent by heating and / or hot air spraying, and it is preferable that it is 10-100 micrometers, and it is more preferable that it is 20-70 micrometers.

  Examples of the support 10 included in the photosensitive element 1 include polymer films having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester.

  The thickness of the support 10 is preferably 5 to 100 μm, and more preferably 10 to 30 μm.

  The photosensitive element 1 composed of two layers of the support 10 and the photosensitive layer 14 as described above or the photosensitive element composed of three layers of the support 10, the photosensitive layer 14 and the protective film can be stored as it is, for example. Alternatively, it may be wound around a roll core and stored with a protective film interposed.

  When the photosensitive element 1 is used in the pattern forming process described above, the photosensitive element 1 is disposed so that the photosensitive layer 14 is in contact with the substrate, and a predetermined portion of the photosensitive layer 14 is irradiated with an actinic ray so that the photosensitive layer 14 is photocured. After forming the part, the support 10 can be peeled off and developed.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a reference example, this invention is not limited to these.

<Measurement of molecular weight>
Moreover, in the following synthesis examples, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of polyamic acid are measured by gel permeation chromatography (GPC) and calculated by a calibration curve using standard polystyrene. It was. The measurement conditions for GPC are shown below.

(GPC conditions)
Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd., trade name)
Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., trade name)
Column: Gelpack GL-S300MDT-5 (two in total) (above, manufactured by Hitachi Chemical Co., Ltd., trade name)
Eluent: DMF (dimethylformamide) / THF (tetrahydrofuran) (mass ratio 1/1)
Flow rate: 1 mL / min

[Synthesis of polyamic acid]
(Synthesis Example 1)
In a 300 mL four-necked separable flask, “Versamine 551” ([3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene, manufactured by Cognis Japan, trade name) 15 .73 g (0.028 mol), 4,4′-diaminodiphenylsulfone (hereinafter referred to as “DDS”) 3.54 g (0.014 mol) and N-methylpyrrolidone (hereinafter referred to as “NMP”) 30 To the solution stirred for 15 minutes at room temperature, 22.24 g (0.043 mol) of 1,10- (decamethylene) bis (trimellitate) dianhydride (hereinafter referred to as “DBTA”) and 30. 00 g of the mixed solution was added over 15 minutes. After completion of the addition, the resulting mixture was heated to 60 ° C. and stirred for 8 hours to obtain an NMP solution of polyamic acid. Solid content in the obtained solution was 40 mass%, and Mw of the polyamic acid was 29000.

(Synthesis Example 2)
1.12-dodecanediamine (hereinafter referred to as “DDO”) 2.20 g (0.011 mol), DDS 1.39 g (0.006 mol), DBTA 10.00 g (0.019 mol) in a 300 mL four-necked separable flask ) And 20.00 g of NMP were added and stirred at room temperature for 10 minutes. The reaction solution was heated to 60 ° C. and stirred for 8 hours to obtain an NMP solution of polyamic acid. Solid content in the obtained solution was 40 mass%, and Mw of the polyamic acid was 27000.

(Synthesis Example 3)
In a 300 mL 4-neck separable flask, DBTA 10 g (0.019 mol), “Versamine 551” 4.76 g (0.009 mol), DDS 1.56 g (0.006 mol), “N-12” (dodecanedioic acid dihydrazide, Japan Made by Finechem, trade name: 1.20 g (0.004 mol) and NMP 18.00 g were added and suspended at room temperature. When a white precipitate appeared, the mixture was stirred at 120 ° C. for 15 minutes, stirred at room temperature for 1 hour, and further stirred at 60 ° C. for 3 hours to obtain an NMP solution of the desired polyamic acid. Solid content in the obtained solution was 50 mass%, and Mw of the polyamic acid was 32000.

(Synthesis Example 4)
To a 300 mL four-necked separable flask, 19.61 g (0.035 mol) of DBASamine 551, 20.39 g (0.039 mol) of DBTA and 60 g of NMP were added and stirred at room temperature for 10 minutes. Next, the reaction solution was heated to 60 ° C. and stirred for 8 hours to obtain an NMP solution of polyamic acid. Solid content in the obtained solution was 40 mass%, and Mw of the polyamic acid was 20000.

(Synthesis Example 5)
In a 300 mL four-necked separable flask, 21.06 g (0.038 mol) of “Versamine 551”, 14.60 g (0.028 mol) of DBTA, 4.33 g of 4,4′-oxydiphthalic dianhydride (ODPA) ( 0.014 mol) and 60 g of NMP were added and stirred at room temperature for 10 minutes. Next, the reaction solution was heated to 60 ° C. and stirred for 8 hours to obtain an NMP solution of polyamic acid. Solid content in the obtained solution was 40 mass%, and Mw of the polyamic acid was 20000.

(Synthesis Example 6)
DBTA 27.13 g (0.052 mol), DDS 12.89 g (0.052 mol) and NMP 60 g were added to a 300 mL four-necked separable flask and stirred at room temperature for 10 minutes. Next, the reaction solution was heated to 60 ° C. and stirred for 8 hours to obtain an NMP solution of polyamic acid. Solid content in the obtained solution was 40 mass%, and Mw of the polyamic acid was 18000.

  Table 1 summarizes the compounding ratio (mol%) and Mw in each component in the polyamic acid obtained in Synthesis Examples 1 to 6.

[Preparation of photosensitive resin composition]
The solutions of polyamic acid, photopolymerizable compounds, photoinitiators and other components synthesized in each of the above synthesis examples were mixed at the blending ratios shown in Table 2 below, and Examples 1 to 4 and Comparative Examples 1 to 3 were mixed. A solution of the photosensitive resin composition was obtained. In addition, the number in Table 2 has shown the mass part of solid content. Moreover, each component in Table 2 is shown below.

“Hitaroid 7661”: acid-modified phenol novolac epoxy acrylate, manufactured by Hitachi Chemical Co., Ltd., trade name “I-651”: benzyldimethyl ketal, manufactured by Ciba Specialty Chemicals, trade name “I-OXE-01”: 1, 2-octanedione-1- [4- (phenylthio) -phenyl-2- (o-benzoyloxime)], manufactured by Ciba Specialty Chemicals, Inc., trade name “D-TPO”: 2,4,6-trimethylbenzoyl- Diphenyl-phosphine oxide, manufactured by Ciba Specialty Chemicals, trade name “AY-43031”: Ureidopropyltriethoxysilane, manufactured by Toray Dow Co., Ltd., trade name “KBM-503”: 3-methacryloxypropyltrimethoxysilane, Shin-Etsu Silicone Product name

[Evaluation of photosensitive resin composition]
Using the solutions of the photosensitive resin compositions obtained in the above Examples and Comparative Examples, the compatibility, solubility, developability, and water absorption were evaluated by the following methods. The results are shown in Table 3.

<Compatibility evaluation>
The photosensitive resin composition obtained in the above Examples and Comparative Examples was applied to a silicon substrate using a spin coater, dried on a hot plate at 110 ° C. for 5 minutes, and then formed. The coating film appearance of the composition layer was visually observed. Here, when there is turbidity in the solution or coating film of the photosensitive resin composition, the compatibility of the photosensitive resin composition components is poor, and it is deposited in the photosensitive resin composition solution or the photosensitive resin composition layer. it seems to do.
A: The solution appearance and the coating film appearance are uniform without turbidity.
B: The solution appearance and / or coating appearance is turbid and non-uniform.

<Measurement of water absorption rate>
The photosensitive resin composition solutions of the above examples and comparative examples were uniformly applied on a glass plate having a thickness of 1 mm using an applicator, dried on a hot plate at 110 ° C. for 5 minutes, and photosensitive having a thickness of 70 μm. A resin composition layer was formed. About the test board | substrate which formed this photosensitive resin composition layer, the whole surface exposure was performed by the exposure amount of 500 mJ / cm < ² > using the proximity exposure machine (Ushio Electric make, brand name: UX-1000SM). Then, it was cured by heating at 120 ° C. for 40 minutes and then at 200 ° C. for 60 minutes to obtain a cured film having a thickness of 50 μm. This cured film was immersed in purified water for 24 hours together with the glass plate, and the water absorption was determined from the following formula (a) from the weight change before and after.
Water absorption (%) = (weight of cured film after immersion−weight of cured film before immersion) / (weight of cured film before immersion) × 100 (a)

<Evaluation of developer solubility in unexposed areas>
The photosensitive resin composition solution was uniformly coated on a silicon substrate using a spin coater and dried on a 110 ° C. hot plate for 5 minutes to form a photosensitive resin composition layer having a thickness of 70 μm. An aqueous 2.38 mass% tetramethylammonium hydroxide solution was dropped into the photosensitive resin composition layer, the time taken for the film to completely dissolve was measured, and the dissolution rate was determined by the following formula (b).
Dissolution rate (nm / second) = film thickness (nm) / dissolution time (second) (b)
A: Dissolution rate of 500 nm / second or more B: Dissolution rate of less than 500 nm / second

<Developability evaluation>
The photosensitive resin composition solutions of the above examples and comparative examples were uniformly applied on a silicon substrate using a spin coater, dried on a hot plate at 110 ° C. for 5 minutes, and a photosensitive resin composition having a thickness of 70 μm. A layer was formed. About the test board | substrate which formed this photosensitive resin composition layer, a proximity exposure machine (USHIO Corporation make, brand name) is passed through the negative mask which has a wiring pattern whose line width / space width is 50/400 (unit: micrometer). : UX-1000SM), the photosensitive resin composition layer was exposed at an exposure amount of 500 mJ / cm ² . Here, the exposure amount is the UV illuminance meter (Ushio Electric Co., Ltd., trade name: UIT-150-A, also usable as an illuminometer) and the light receiver “UVD-S365” (Sensitivity wavelength range: 320 nm to 470 nm, absolute calibration wavelength: 365 nm), and obtained from the relationship of exposure amount = illuminance × exposure time. Thereafter, the test substrate was immersed in an aqueous 2.38% by mass tetramethylammonium hydroxide solution and developed until the unexposed portion of the photosensitive resin composition layer was completely dissolved. From the film thickness of the exposed portion of the photosensitive resin composition layer after development, the remaining film ratio was determined by the following formula (c), and developability was evaluated based on the following evaluation criteria.
Residual film ratio (%) = (film thickness of exposed area after development (μm) / initial film thickness (μm)) × 100 (c)
A: The remaining film rate is 80% or more.
B: The remaining film rate is 20% or more and less than 80%.
C: Remaining film ratio is less than 20%.

  As can be seen from Table 3, the photosensitive resin compositions obtained in Examples 1 to 4 are excellent in developability and have a sufficiently low water absorption. From the above, according to the photosensitive resin composition of the present invention, sufficient alkali developability can be obtained, image formation can be performed well even with a thick film, and water absorption is sufficient. It was confirmed that a low cured film could be formed.

It is a schematic cross section which shows suitable one Embodiment of the photosensitive element of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body, 14 ... Photosensitive layer.

Claims (7)

(A) a polyamic acid having a structural unit represented by each of the following general formulas (1), (2) and (3);
(B) a photopolymerizable compound;
(C) a photopolymerization initiator;
A photosensitive resin composition comprising:

[In the formulas (1), (2) and (3), Ar ¹ represents a tetravalent group having an alkylene group having 5 to 20 carbon atoms, and Ar ² is a divalent group having an alkylene group having 5 to 20 carbon atoms. Ar ³ represents a divalent group having an aromatic hydrocarbon group. ] The photosensitive resin composition of Claim ¹ whose said Ar1 is a tetravalent group represented by following General formula (4).

[In the formula (4), X represents an alkylene group having 5 to 20 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. M and n each independently represent an integer of 1 to 3. When m is 2 or more, a plurality of R ¹ may be the same or different, and when n is 2 or more, a plurality of R ² are present. May be the same or different. ] Wherein Ar ² is a divalent group represented by the following general formula (5), according to claim 1 or 2 photosensitive resin composition.

[In Formula (5), Z represents a single bond or a divalent organic group, and Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms. ] The photosensitive resin composition according to claim 3, wherein Z is at least one group selected from the group consisting of divalent groups represented by the following general formulas (6), (7) and (8). object.

[In the formulas (6), (7) and (8), R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or carbon. 1 to 3 represent an alkoxy group, q, r and s each independently represent an integer of 1 to 4, and when q is 2 or more, a plurality of R ³ may be the same or different, and r When R is 2 or more, a plurality of R ⁴ may be the same or different, and when s is 2 or more, a plurality of R ⁵ may be the same or different. ] Wherein Ar ³ is a group represented by even arylene group or the following general formula have a substituent (8), the photosensitive resin composition according to any one of claims 1-4.

[In the formula (8), D represents a single bond, an ether bond, a thioether bond, a carbonyl group, a sulfonyl group, a methylene group, an ethylene group, an isopropylidene group, a hexafluoroisopropylidene group, a group represented by the following formula (i) Or a group represented by the following formula (ii), wherein R ⁶ and R ⁷ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, t1 And t2 each independently represents an integer of 1 to 4. When t1 is 2 or more, a plurality of R ⁶ may be the same or different, and when t2 is 2 or more, a plurality of R ⁷ may be the same or different. ]

  The photosensitive resin composition of Claim 5 whose said D is a sulfonyl group.   A photosensitive element provided with a support body and the layer which consists of a photosensitive resin composition in any one of Claims 1-6 formed on this support body.

Images