JP2015094898A - Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which can allow a residue to hardly remain at the bottom of a hole of a developed film and the developed film to have excellent surface uniformity, and to provide a method for producing a cured film, the cured film, a liquid crystal display device, and an organic EL display device.SOLUTION: The photosensitive resin composition contains a polymer component (A), which contains: a polymer having a constituent unit having a group, the acid group of which is protected by an acid-decomposable group, and another constituent unit having a crosslinkable group; another polymer having the constituent unit having the group, the acid group of which is protected by the acid-decomposable group; and a different polymer having the constituent unit having the crosslinkable group, a photoacid generator (B), a solvent (C-1), and lactone (S). The lactone (S) contains an alkylene group having 6 or more carbon atoms in a group constituting a lactone ring and/or a substituent having the lactone ring and has 1,000 or lower molecular weight.

Description

The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Moreover, it is related with the manufacturing method of the cured film using the said photosensitive resin composition, the cured film formed by hardening | curing the photosensitive composition, and various image display apparatuses using the said cured film.
More specifically, a photosensitive resin composition suitable for forming a flattening film, a protective film and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL (organic electroluminescence) display device, an integrated circuit element, and a solid-state imaging element. The present invention relates to an article and a method for producing a cured film using the article.

  An organic EL display device, a liquid crystal display device, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.

  In addition to the properties of the cured film, such as insulating properties, solvent resistance, heat resistance, hardness, and indium tin oxide (ITO) sputtering suitability, the interlayer insulating film in the above display device is desired to have high transparency. Yes. For this reason, an attempt has been made to use an acrylic resin having excellent transparency as a film forming component. For example, those described in Patent Document 1 and Patent Document 2 are known.

JP2010-072273 JP2010-018573

  However, the photosensitive resin compositions described in Patent Document 1 and Patent Document 2 have a problem that a residue is likely to remain at the bottom of the hole of the film after development, and the surface uniformity of the film after development is deteriorated.

  The present invention solves such a problem, a residue is difficult to remain at the bottom of the hole of the film after development, and the photosensitive resin composition that can improve the surface uniformity of the film after development, And it aims at providing the manufacturing method of a cured film using this photosensitive resin composition, a cured film, a liquid crystal display device, and an organic EL display device.

（一般式（Ｓ１）中、Ｇは、５〜７員環の脂環構造を表す。Ｒ¹は、水素原子または炭素数１〜３のアルキル基を表す。Ｒ²は、無置換の炭素数５〜８の直鎖状のアルキレン基を表す。）
＜８＞上記一般式中のＲ¹が、水素原子または炭素数１〜３のアルキル基を表す、＜７＞に記載の感光性樹脂組成物。
＜９＞（Ｓ）ラクトンとして、γーデカノラクトン、γーウンデカノラクトン、γードデカノラクトン、δーデカノラクトン、δーウンデカノラクトン、δードデカノラクトン、γーメチルーγーデカノラクトンおよび１５−ペンタデカノラクトンから選択されるいずれか１種を含む、＜１＞〜＜６＞のいずれかに記載の感光性樹脂組成物。
＜１０＞（Ｓ）ラクトンの含有量が、感光性樹脂組成物の全固形分に対し０.５〜１０質量％である、＜１＞〜＜９＞のいずれかに記載の感光性樹脂組成物。
＜１１＞上記架橋性基を有する構成単位が、エポキシ基、オキセタニル基およびＮＨ−ＣＨ₂−Ｏ−Ｒで表される基から選ばれる少なくとも１種を含む構成単位である、＜１＞〜＜１０＞のいずれかに記載の感光性樹脂組成物；但し、Ｒは水素原子または炭素数１〜２０のアルキル基である。
＜１２＞（１）＜１＞〜＜１１＞のいずれかに記載の感光性樹脂組成物を基板上に塗布する工程、
（２）塗布された感光性樹脂組成物から溶剤を除去する工程、
（３）溶剤が除去された感光性樹脂組成物を活性光線により露光する工程、
（４）露光された感光性樹脂組成物を水性現像液により現像する工程、および、
（５）現像された感光性樹脂組成物を熱硬化するポストベーク工程、
を含む硬化膜の製造方法。
＜１３＞上記現像工程後、上記ポストベーク工程前に、（６）現像された感光性樹脂組成物を全面露光する工程を含む、＜１２＞に記載の硬化膜の製造方法。
＜１４＞＜１＞〜＜１１＞のいずれかに記載の感光性樹脂組成物を硬化した硬化膜、または、＜１２＞または＜１３＞に記載の硬化膜の製造方法により形成された硬化膜。
＜１５＞層間絶縁膜である、＜１４＞に記載の硬化膜。
＜１６＞＜１４＞または＜１５＞に記載の硬化膜を有する有機ＥＬ表示装置または液晶表示装置。 As a result of investigation by the present inventors under such circumstances, by incorporating a lactone having a molecular weight of 1000 or less ((S) component) containing an alkylene group having 6 or more carbon atoms into the photosensitive resin composition. The present inventors have found that the above problems can be solved.
Specifically, the above-mentioned problem has been solved by the following means <1>, preferably <2> to <16>.
<1> (A-1) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1-1) a polymer having a structural unit having an acid group protected by an acid-decomposable group and (a1-2) a structural unit having a crosslinkable group,
(2) (a1-1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a1-2) a polymer having a structural unit having a crosslinkable group,
(B-1) a photoacid generator,
(C-1) contains a solvent, and (S) a lactone,
The photosensitivity in which the (S) lactone contains an alkylene group having 6 or more carbon atoms in a group constituting the lactone ring and / or a substituent of the lactone ring, and the molecular weight of the (S) lactone is 1000 or less. Resin composition.
<2> (A-2) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) a polymer having (a2-1) a structural unit having an acid group, and (a2-2) a structural unit having a crosslinkable group,
(2) (a2-1) a polymer having a structural unit having an acid group, and (a2-2) a polymer having a structural unit having a crosslinkable group,
(B-2) a quinonediazide compound,
(C-2) contains a solvent and (S) lactone,
The photosensitivity in which the (S) lactone contains an alkylene group having 6 or more carbon atoms in a group constituting the lactone ring and / or a substituent of the lactone ring, and the molecular weight of the (S) lactone is 1000 or less. Resin composition.
<3> The photosensitive resin composition according to <1> or <2>, wherein the molecular weight of (S) lactone is 140 to 500.
<4> The photosensitive resin composition according to <1> or <2>, wherein the molecular weight of (S) lactone is 160 to 300.
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the alkylene group having 6 or more carbon atoms is unsubstituted or substituted with a hydrophobic group.
<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the alkylene group having 6 or more carbon atoms has 9 to 14 carbon atoms.
<7> The photosensitive resin composition according to any one of <1> to <6>, in which (S) lactone is represented by the following general formula (S1).
General formula (S1)

(In General Formula (S1), G represents a 5- to 7-membered alicyclic structure. R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ² represents an unsubstituted carbon number. Represents a linear alkylene group of 5 to 8.)
<8> The photosensitive resin composition according to <7>, wherein R ¹ in the general formula represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
<9> As (S) lactone, γ-decanolactone, γ-undecanolactone, γ-dodecanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, γ-methyl-γ-decanolactone and 15-pentadecanolactone The photosensitive resin composition in any one of <1>-<6> containing any 1 type selected from these.
<10> The photosensitive resin composition according to any one of <1> to <9>, wherein the content of (S) lactone is 0.5 to 10% by mass with respect to the total solid content of the photosensitive resin composition. object.
<11> The structural unit having a crosslinkable group is a structural unit including at least one selected from a group represented by an epoxy group, an oxetanyl group, and NH—CH ₂ —O—R, <1> to <10>; wherein R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
<12> (1) The process of apply | coating the photosensitive resin composition in any one of <1>-<11> on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermosetting the developed photosensitive resin composition;
The manufacturing method of the cured film containing this.
<13> The method for producing a cured film according to <12>, including (6) a step of exposing the entire surface of the developed photosensitive resin composition after the development step and before the post-baking step.
<14> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <11>, or a cured film formed by the method for producing a cured film according to <12> or <13> .
<15> The cured film according to <14>, which is an interlayer insulating film.
<16> An organic EL display device or a liquid crystal display device having the cured film according to <14> or <15>.

  ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the photosensitive resin composition which cannot make a residue remain in the hole bottom part of the film | membrane after image development, and can make the surface uniformity of the film | membrane after image development favorable. .

1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film. 1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.

  The photosensitive resin composition of the present invention contains a polymer component, (S) lactone described later, and a solvent. Such a photosensitive resin composition is applied onto a substrate, the solvent is removed, exposed to actinic rays, developed with an aqueous developer (preferably an alkali developer), and thermally cured to form a cured film. Can do. The developed film thus obtained is less likely to leave a residue at the bottom of the hole and can achieve good surface uniformity. Furthermore, a film excellent in solvent resistance (particularly resistance to NMP) can be obtained.

  Although this mechanism is presumed, it is considered as follows. The (S) lactone used in the present invention contains an alkylene group having 6 or more carbon atoms with high hydrophobicity. Therefore, (S) lactone has a structure having a high hydrophilicity and a tendency to be easily dissolved in an alkali developer, and a structure having a high hydrophobicity. As a result, when the photosensitive resin composition of the present invention is used, the non-exposed portion is hardly dissolved in an alkali developer during development, the developed film is less likely to remain at the bottom of the hole, and good surface uniformity is achieved. It can be achieved.

  Hereinafter, the composition of the present invention will be described in the order of the first aspect and the second aspect. The first and second aspects of the composition of the present invention are preferably used as a positive photosensitive resin composition.

[First embodiment of the present invention]
The photosensitive resin composition of the first aspect of the present invention is
(A-1) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1-1) a polymer having a structural unit having an acid group protected by an acid-decomposable group and (a1-2) a structural unit having a crosslinkable group,
(2) (a1-1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a1-2) a polymer having a structural unit having a crosslinkable group,
(B-1) a photoacid generator,
(C-1) contains a solvent, and (S) a lactone,
The (S) lactone contains an alkylene group having 6 or more carbon atoms in the group constituting the lactone ring and / or the substituent of the lactone ring, and the molecular weight of the (S) lactone is 1000 or less. Features.

<(A-1) Polymer component>
The composition of the present invention includes a polymer having (a1-1) a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a1-2) a structural unit having a crosslinkable group as a polymer component. (1) and (a1-1) a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group, and (a1-2) a polymer having a structural unit having a crosslinkable group (2) , At least one of the above. Furthermore, polymers other than these may be included. The polymer component (A-1) in the present invention includes, in addition to the polymer (1) and / or the polymer (2), other polymers added as necessary, unless otherwise specified. Means things.
(2) When (a1-1) includes a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group and (a1-2) a polymer having a structural unit having a crosslinkable group The ratio of (a1-1) the polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a1-2) the polymer having a structural unit having a crosslinkable group is 95: 5: 5: 95 is preferable, 80: 20-20: 80 is more preferable, and 70: 30-30: 70 is more preferable.

  (A-1) The polymer component is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc. The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”.

<< (a1-1) Structural unit having a group in which an acid group is protected by an acid-decomposable group >>
(A-1) The polymer component has at least a structural unit (a1-1) having a group in which an acid group is protected with an acid-decomposable group. (A-1) When a polymer component has a structural unit (a1-1), it can be set as the highly sensitive photosensitive resin composition.
As the “group in which the acid group is protected with an acid-decomposable group” in the present invention, those known as an acid group and an acid-decomposable group can be used, and are not particularly limited.
Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group.
Specific acid-decomposable groups include groups that are relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group, which will be described later), or an acid. A group that is relatively difficult to decompose (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group) can be used.

The structural unit (a1-1) is preferably a structural unit having a protected carboxyl group protected with an acid-decomposable group or a structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group.
Hereinafter, the structural unit (a1-1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group Each will be described in turn.

<<< (a1-1-1) Structural unit having a protected carboxyl group protected with an acid-decomposable group >>>>
The structural unit (a1-1-1) is a structural unit having a protected carboxyl group in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below.
There is no restriction | limiting in particular as a structural unit which has the said carboxyl group which can be used for the said structural unit (a1-1-1), A well-known structural unit can be used. For example, a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid (a1-1-1-1) Is mentioned.
Hereinafter, the structural unit (a1-1-1-1) used as the structural unit having a carboxyl group will be described.

<<<<< (a1-1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>>
Examples of the unsaturated carboxylic acid used in the present invention include those listed below.
That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acrylic acid. Examples include leuoxyethyl hexahydrophthalic acid and 2- (meth) acryloyloxyethyl-phthalic acid.
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of the dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among them, from the viewpoint of developability, in order to form the structural unit (a1-1-1-1), acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meta It is preferable to use acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or an anhydride of an unsaturated polyvalent carboxylic acid. Acrylic acid, methacrylic acid, 2- (meta It is more preferable to use acryloyloxyethyl hexahydrophthalic acid.
The structural unit (a1-1-1-1) may be composed of one type alone, or may be composed of two or more types.

<<<< acid-decomposable group that can be used for the structural unit (a1-1-1) >>>>
As the acid-decomposable group that can be used for the structural unit (a1-1-1), the acid-decomposable groups described above can be used.
Among these acid-decomposable groups, a group having a structure protected in the form of an acetal is preferable. For example, it is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, the basic physical properties of the photosensitive resin composition, particularly the sensitivity and pattern shape, the formation of contact holes, the storage stability of the photosensitive resin composition From the viewpoint of Furthermore, it is more preferable from the viewpoint of sensitivity that the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the general formula (a1-10). In addition, when the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10), the entire protected carboxyl group is — (C═O) —O—CR ^101. The structure is R ¹⁰² (OR ¹⁰³ ).

（式（ａ１−１０）中、Ｒ¹⁰¹およびＲ¹⁰²は、それぞれ独立に水素原子またはアルキル基を表し、但し、Ｒ¹⁰¹とＲ¹⁰²とが共に水素原子の場合を除く。Ｒ¹⁰³は、アルキル基を表す。Ｒ¹⁰¹またはＲ¹⁰²と、Ｒ¹⁰³とが連結して環状エーテルを形成してもよい。） Formula (a1-10)

(In formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom or an alkyl group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms, and R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.)

In the general formula (a1-10), R ^{101 to} R ¹⁰³ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched, or cyclic. Here, both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group.

In the general formula (a1-10), R ¹⁰¹ ~R ¹⁰³ each independently represent a hydrogen atom or an alkyl group. The alkyl group may be linear, branched or cyclic. Here, both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become an aralkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
Moreover, as said aryl group, a C6-C20 aryl group is preferable, More preferably, it is C6-C12, Specifically, a phenyl group, (alpha) -methylphenyl group, a naphthyl group etc. can be illustrated. Examples of the entire alkyl group substituted with an aryl group, that is, an aralkyl group, include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
As said alkoxy group, a C1-C6 alkoxy group is preferable, More preferably, it is C1-C4, and a methoxy group or an ethoxy group is more preferable.
In addition, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is directly In the case of a chain or branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.

In the general formula (a1-10), when R ¹⁰¹ , R ^102, and R ¹⁰³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, and preferably 6 to 10 carbon atoms. More preferred. The aryl group may have a substituent, and the substituent is preferably an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ can be bonded to each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ¹⁰³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.
In the general formula (a1-10), it is preferable that any one of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

  As the radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the general formula (a1-10), a commercially available one may be used, or it may be synthesized by a known method. Things can also be used. For example, it can synthesize | combine with the synthesis | combining method etc. of Paragraph Nos. 0037-0040 of Unexamined-Japanese-Patent No. 2011-221494, The content is integrated in this-application specification.

（式（Ａ２’）中、Ｒ¹およびＲ²は、それぞれ、水素原子、アルキル基またはアリール基を表し、少なくともＲ¹およびＲ²のいずれか一方がアルキル基またはアリール基を表し、Ｒ³は、アルキル基またはアリール基を表し、Ｒ¹またはＲ²と、Ｒ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は、水素原子またはメチル基を表し、Ｘは単結合またはアリーレン基を表す。）
Ｒ¹およびＲ²がアルキル基の場合、炭素数は１〜１０のアルキル基が好ましい。Ｒ¹およびＲ²がアリール基の場合、フェニル基が好ましい。Ｒ¹およびＲ²は、それぞれ、水素原子または炭素数１〜４のアルキル基が好ましい。
Ｒ³は、アルキル基またはアリール基を表し、炭素数１〜１０のアルキル基が好ましく、１〜６のアルキル基がより好ましい。
Ｘは単結合またはアリーレン基を表し、単結合が好ましい。 A first preferred embodiment of the structural unit (a1-1-1) is a structural unit represented by the following general formula (A2 ′).

(In the formula (A2 ′), R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² represents an alkyl group or an aryl group, and R ³ represents Represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or arylene. Represents a group.)
When R ¹ and R ² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
X represents a single bond or an arylene group, and a single bond is preferred.

（式（１−１２）中、Ｒ¹²¹は水素原子または炭素数１〜４のアルキル基を表し、Ｌ¹はカルボニル基またはフェニレン基を表し、Ｒ¹²²〜Ｒ¹²⁸はそれぞれ独立に、水素原子または炭素数１〜４のアルキル基を表す。）
Ｒ¹²¹は水素原子またはメチル基が好ましい。
Ｌ¹はカルボニル基が好ましい。
Ｒ¹²²〜Ｒ¹²⁸は、水素原子が好ましい。 A second preferred embodiment of the structural unit (a1-1-1) is a structural unit represented by the following general formula (1-12).
Formula (1-12)

(In formula (1-12), R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ^{122 to} R ¹²⁸ each independently represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms.)
R ¹²¹ is preferably a hydrogen atom or a methyl group.
L ¹ is preferably a carbonyl group.
R ^{122 to} R ¹²⁸ are preferably a hydrogen atom.

  Preferable specific examples of the structural unit (a1-1-1) include the following structural units. In the structural units below, R represents a hydrogen atom or a methyl group.

<<< (a1-1-2) Structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group >>>
The structural unit (a1-1-2) is a structural unit (a1-1-2-1) having a protected phenolic hydroxyl group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below. ).

<<<<< (a1-1-2-1) Structural Unit Having Phenolic Hydroxyl Group >>>>
Examples of the structural unit having a phenolic hydroxyl group include a structural unit in a hydroxystyrene-based structural unit and a novolac-based resin. Among these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene is, It is preferable from the viewpoint of sensitivity. Moreover, as a structural unit having a phenolic hydroxyl group, a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.

（一般式（ａ１−２０）中、Ｒ²²⁰は水素原子またはメチル基を表し、Ｒ²²¹は単結合または二価の連結基を表し、Ｒ²²²はハロゲン原子または炭素数１〜５の直鎖または分岐鎖状のアルキル基を表し、ａは１〜５の整数を表し、ｂは０〜４の整数を表し、ａ＋ｂは５以下である。なお、Ｒ²²²が２以上存在する場合、これらのＲ²²²は相互に異なっていてもよいし同じでもよい。） Formula (a1-20)

(In General Formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, and R ²²² represents a halogen atom or a straight chain having 1 to 5 carbon atoms or Represents a branched alkyl group, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less, and when R ²²² is 2 or more, these R ²²² may be different from each other or the same.)

In the general formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R ²²¹ represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved. The divalent linking group of R ²²¹ may be exemplified alkylene groups, specific examples R ²²¹ is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group, etc. are mentioned. Among these, it is preferable that R ²²¹ is a single bond, a methylene group, or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. Moreover, although a represents the integer of 1-5, from the viewpoint of the effect of this invention and the point that manufacture is easy, it is preferable that a is 1 or 2, and it is more preferable that a is 1. .
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R ²²¹ is defined as the reference (first position).
R ²²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.
Specific examples include fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
B represents 0 or an integer of 1 to 4;

<<<< acid-decomposable group that can be used for the structural unit (a1-1-2) >>>>
The acid-decomposable group that can be used for the structural unit (a1-1-2) is the same as the acid-decomposable group that can be used for the structural unit (a1-1-1). It can be used and is not particularly limited. Among the acid-decomposable groups, a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability. Furthermore, among acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-10). When the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of the acetal represented by the general formula (a1-10), the entire protected phenolic hydroxyl group is -Ar-O-CR ¹⁰¹ R. The structure is ¹⁰² (OR ¹⁰³ ). Ar represents an arylene group.
Preferable examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group, R ¹⁰¹ = R ¹⁰² = methyl group and R ¹⁰³ = benzyl group.
Moreover, as a radically polymerizable monomer used for forming a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of acetal, for example, paragraph number 0042 of JP2011-215590A is disclosed. And the like.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.

  Specific examples of the acetal protecting group for the phenolic hydroxyl group include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group. 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually or in combination of 2 or more types.

  A commercially available thing may be used for the radically polymerizable monomer used in order to form the said structural unit (a1-1-2), and what was synthesize | combined by the well-known method can also be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.

  Preferable specific examples of the structural unit (a1-1-2) include the following structural units, but the present invention is not limited thereto.

<<< Preferred Aspect of Structural Unit (a1-1) >>>
When the polymer containing the structural unit (a1-1) is substantially free of the structural unit (a1-2), the content of the structural unit (a1-1) is 20 to 100 in the polymer. The mol% is preferable, and 30 to 90 mol% is more preferable.
When the polymer containing the structural unit (a1-1) contains the structural unit (a1-2), the content of the single structural unit (a1-1) is 3 to 3 from the viewpoint of sensitivity in the polymer. 70 mol% is preferable and 10-60 mol% is more preferable. In particular, when the acid-decomposable group that can be used for the structural unit (a1-1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, 20 to 50 mol% is contained. preferable.

  The structural unit (a1-1-1) is characterized by faster development than the structural unit (a1-1-2). Therefore, when it is desired to develop quickly, the structural unit (a1-1-1) is preferable. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-1-2).

<< (a1-2) Structural Unit Having a Crosslinkable Group >>
(A-1) The polymer component has a structural unit (a1-2) having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment. As a preferred embodiment of the structural unit having a crosslinkable group, an epoxy group, an oxetanyl group, a group represented by —NH—CH ₂ —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and ethylene And a structural unit containing at least one selected from the group consisting of an unsaturated group, an epoxy group, an oxetanyl group, and —NH—CH ₂ —O—R (R is a hydrogen atom or a carbon number of 1 to 20). It is preferable that it is a structural unit containing at least 1 sort (s) chosen from the group represented by this alkyl group. Among these, it is preferable that the photosensitive resin composition of this invention contains the structural unit in which (A-1) polymer component contains at least 1 among an epoxy group and oxetanyl group. In more detail, the following are mentioned.

<<< (a1-2-1) Structural Unit Having Epoxy Group and / or Oxetanyl Group >>>
The (A-1) polymer component preferably contains a structural unit having an epoxy group and / or an oxetanyl group (hereinafter also referred to as a structural unit (a1-2-1)).
The structural unit (a1-2-1) may have at least one epoxy group or oxetanyl group in one structural unit, and one or more epoxy groups and one or more oxetanyl groups, two or more The epoxy group may have two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups. Are preferably 1 or 2 in total, and more preferably 1 epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraph Nos. 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic And compounds containing epoxy backbone can be cited, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include (meth) having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A No. 2001-330953, for example. Examples thereof include acrylate esters and compounds described in paragraph No. 0027 of JP2012-088459A, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit (a1-2-1) having the epoxy group and / or oxetanyl group include a monomer having a methacrylate structure and an acrylate ester. A monomer containing a structure is preferred.

  Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl are preferred. Ether, acrylic acid (3-ethyloxetane-3-yl) methyl, and methacrylic acid (3-ethyloxetane-3-yl) methyl are preferred from the viewpoints of copolymerization reactivity and improved properties of the cured film. These structural units can be used individually by 1 type or in combination of 2 or more types.

  Preferable specific examples of the structural unit (a1-2-1) include the following structural units. In the structural units below, R represents a hydrogen atom or a methyl group.

<<< (a1-2-2) Structural unit having an ethylenically unsaturated group >>>
As one of the structural units (a1-2) having a crosslinkable group, there may be mentioned a structural unit (a1-2-2) having an ethylenically unsaturated group. As said structural unit (a1-2-2), the structural unit which has an ethylenically unsaturated group in a side chain is preferable, the structure which has an ethylenically unsaturated group at the terminal and has a C3-C16 side chain Units are more preferred.
In addition, as for the structural unit (a1-2-2), compounds described in paragraph numbers 0072 to 0090 of JP2011-215580A and paragraph numbers 0013 to 0031 of JP2008-256974A are preferable. The contents of which are incorporated herein by reference.

（一般式（ａ２−３０）中、Ｒ¹は水素原子またはメチル基を表し、Ｒ²は水素原子または炭素数１〜２０のアルキル基を表す。）
Ｒ²は、炭素数１〜９のアルキル基が好ましく、炭素数１〜４のアルキル基がさらに好ましい。また、アルキル基は、直鎖、分岐または環状のアルキル基のいずれであってもよいが、好ましくは、直鎖または分岐のアルキル基である。
Ｒ²の具体例としては、メチル基、エチル基、ｎ−ブチル基、ｉ−ブチル基、シクロヘキシル基、およびｎ−ヘキシル基を挙げることができる。中でもｉ−ブチル基、ｎ−ブチル基、メチル基が好ましい。 <<< constituent unit having a group represented by (a1-2-3) -NH—CH ₂ —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) >>
The polymer component (A-1) used in the present invention is a structural unit (a1-) having a group represented by —NH—CH ₂ —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). 2-3) is also preferable. By having the structural unit (a1-2-3), a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The structural unit (a1-2-3) is more preferably a structural unit having a group represented by the following general formula (a2-30).
Formula (a2-30)

(In general formula (a2-30), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)
R ² is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.

<<< Preferred Aspect of Structural Unit (a1-2) Having Crosslinkable Group >>>
When the polymer containing the structural unit (a1-2) is substantially free of the structural unit (a1-1), the content of the structural unit (a1-2) is 5 to 90 in the polymer. Mol% is preferable and 20-80 mol% is more preferable.
When the polymer containing the structural unit (a1-2) contains the structural unit (a1-1), the content of the structural unit (a1-2) is 3 in the polymer from the viewpoint of chemical resistance. -70 mol% is preferable and 10-60 mol% is more preferable.
In the present invention, the content of the structural unit (a1-2) is preferably 3 to 70 mol% in all structural units of the polymer component (A-1) regardless of any embodiment. More preferably, it is -60 mol%.
By setting it within the above numerical range, a cured film having excellent characteristics can be formed.

<< (a1-3) Other structural units >>
In the present invention, the polymer component (A-1) has other structural units (a1-3) in addition to the structural unit (a1-1) and / or the structural unit (a1-2). You may do it. The structural unit (a1-3) may be contained in the polymer (1) and / or (2). In addition to the polymer (1) or (2), the weight having the other structural unit (a1-3) substantially not including the structural unit (a1-1) and the structural unit (a1-2). You may have union.

  There is no restriction | limiting in particular as a monomer used as another structural unit (a1-3), For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, Unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, other unsaturated compounds Can be mentioned. Moreover, you may have the structural unit which has an acid group so that it may mention later. The monomer which becomes another structural unit (a1-3) can be used individually or in combination of 2 or more types.

  Specific examples of the structural unit (a1-3) include styrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4 -Hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acryloylmorpholine, N-cyclohexylmaleimide, acrylonitrile, ethylene glycol mono It can be mentioned a structural unit due Seto acetate mono (meth) acrylate. In addition, compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

  Moreover, the group which has styrenes and an aliphatic cyclic skeleton as another structural unit (a1-3) is preferable from a viewpoint of an electrical property. Specific examples include styrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and the like.

  Furthermore, (meth) acrylic acid alkyl ester is preferable as another structural unit (a1-3) from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.

As the other structural unit (a1-3), a repeating unit containing an acid group is preferably included. By containing an acid group, it becomes easy to dissolve in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Amide groups, sulfonylimide groups and the like are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. . For example, the compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein. Of these, structural units derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are preferred.

As a method for introducing the repeating unit containing an acid group, it can be introduced into the same polymer as the (a1-1) structural unit and / or (a1-2) structural unit, or (a1-1) the structural unit and ( a1-2) It can also be introduced as a structural unit of a polymer different from the structural unit.
As such a polymer, a resin having a carboxyl group in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

For example, benzyl (meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid Copolymer and the like.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein.
These polymers may contain only 1 type and may contain 2 or more types.

  SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Cray Valley), ARUFON UC-3000, ARUFON UC-3510, ARUFON are commercially available as these polymers. UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncry 690, Joncry 678, Joncry 67, Joncry 586 (above, made by BASF) You can also.

  In the present invention, it is particularly preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group. For example, the compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein.

  The structural unit containing an acid group is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, still more preferably 5 to 40 mol%, and particularly preferably 5 to 30 mol% of the structural units of all polymer components. 5 to 25 mol% is particularly preferable.

Although preferable embodiment of the polymer component of this invention is given to the following, this invention is not limited to these.
(First embodiment)
The aspect in which the polymer (1) further has one or more other structural units (a1-3).
(Second Embodiment)
In the polymer (2), the polymer (a1-1) having a structural unit having a group in which an acid group is protected with an acid-decomposable group is further replaced with one or more other structural units (a1- The aspect which has 3).
(Third embodiment)
The aspect which the polymer which has a structural unit which has (a1-2) crosslinkable group in a polymer (2) further has 1 type, or 2 or more types of other structural units (a1-3).
(Fourth embodiment)
In any one of the first to third embodiments, the other structural unit (a1-3) includes a structural unit containing at least an acid group.
(Fifth embodiment)
In addition to the polymer (1) or (2), the polymer further includes the structural unit (a1-1) and the structural unit (a1-2) and the other structural unit (a1-3). Embodiment with coalescence.
(Sixth embodiment)
The form which consists of 2 or more combinations of the said 1st-5th embodiment.

In an embodiment having a polymer having other structural unit (a1-3) substantially free of (a1-1) and (a1-2), (a1-1) and / or (a1-2) The ratio by weight of the total amount of the polymer having the above and the total amount of the polymer having the other structural unit (a1-3) substantially not including (a1-1) and (a1-2) is 99. : 1 to 5:95 is preferable, 97: 3 to 30:70 is more preferable, and 95: 5 to 50:50 is more preferable.
It is preferable that the composition of the 1st form of this invention contains the polymer component in the ratio of 70 mass% or more of (A-1) polymer component of the solid content of a composition.

<< (A-1) Molecular Weight of Polymer Component >>
(A-1) The molecular weight of the polymer component is a polystyrene-equivalent weight average molecular weight, preferably 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable in the range of said numerical value. The ratio (dispersion degree) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
(A-1) The weight average molecular weight and dispersion degree of a polymer component are defined as a polystyrene conversion value by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer component are, for example, HLC-8120 (manufactured by Tosoh Corporation), and TSK gel Multipore HXL-M (Tosoh ( 7.8 mm ID × 30.0 cm can be obtained by using THF (tetrahydrofuran) as an eluent.

<< (A-1) Production Method of Polymer Component >>
Various methods are also known for synthesizing the polymer component (A-1). To give an example, at least the configuration represented by (a1-1) and (a1-3) above. It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer used to form units in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
(A-1) The polymer preferably contains 50 mol% or more, and 80 mol% or more of the structural units derived from (meth) acrylic acid and / or its ester with respect to all the structural units. More preferred.

<(B-1) Photoacid generator>
The photosensitive resin composition of the present invention contains (B-1) a photoacid generator. The photoacid generator used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate.

Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts (for example, the following compounds), quaternary ammonium salts, and diazomethane derivatives include paragraph numbers 0083 to JP-A-2011-221494. The compounds described in 0088 can be exemplified, the contents of which are incorporated herein.

（一般式（Ｂ１−１）中、Ｒ²¹は、アルキル基またはアリール基を表す。波線は他の基との結合を表す。） Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1-1).
General formula (B1-1)

(In the general formula (B1-1), R ²¹ represents an alkyl group or an aryl group. A wavy line represents a bond with another group.)

In general formula (B1-1), any group may be substituted, and the alkyl group for R ²¹ may be linear, branched, or cyclic. Acceptable substituents are described below.
As the alkyl group for R ^21, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group for R ²¹ is a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group, etc.). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.

（式（Ｂ１−２）中、Ｒ⁴²は、置換されていても良いアルキル基またはアリール基を表し、Ｘは、アルキル基、アルコキシ基、または、ハロゲン原子を表し、ｍ４は、０〜３の整数を表し、ｍ４が２または３であるとき、複数のＸは同一でも異なっていてもよい。） The compound containing the oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-2).
General formula (B1-2)

(In formula (B1-2), R ⁴² represents an optionally substituted alkyl group or aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, and m4 represents 0-3. Represents an integer, and when m4 is 2 or 3, a plurality of Xs may be the same or different.

Preferred ranges of R ^42, the same as the preferable range of the R ^21.
The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Moreover, the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4 is preferably 0 or 1. In the above general formula (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.

（式（Ｂ１−３）中、Ｒ⁴³は式（Ｂ１−２）におけるＲ⁴²と同義であり、Ｘ¹は、ハロゲン原子、水酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、シアノ基またはニトロ基を表し、ｎ４は０〜５の整数を表す。） The compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-3).
General formula (B1-3)

(In formula (B1-3), R ⁴³ has the same meaning as R ⁴² in formula (B1-2), and X ¹ is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group, a cyano group or a nitro group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the general formula (B1-3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n—. A propyl group, a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
As n4, 0-2 are preferable and 0-1 are especially preferable.
As specific examples of the compound represented by the general formula (B1-3) and preferable examples of the oxime sulfonate compound, description in paragraphs 0080 to 0082 of JP2012-163937A can be referred to. Incorporated in the description.

The compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably a compound represented by the following general formula (OS-1).

In the general formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group. ^R102 represents an alkyl group or an aryl group.
X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ² —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, wherein R ^{105 to} R ¹⁰⁷ are alkyl groups. Or an aryl group.
R ^{121 to} R ¹²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R ^{121 to} R ¹²⁴ may be bonded to each other to form a ring.
As R ^{121 to} R ¹²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, and an embodiment in which at least two of R ^{121 to} R ¹²⁴ are bonded to each other to form an aryl group is also preferable. Among these, an embodiment in which R ^{121 to} R ¹²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.
The compound represented by the general formula (OS-1) is, for example, a compound represented by the general formula (OS-2) described in paragraph numbers 0087 to 0089 of JP2012-163937A Which is incorporated herein by reference.

（一般式（ＯＳ−３）〜一般式（ＯＳ−５）中、Ｒ²²、Ｒ²⁵およびＲ²⁸はそれぞれ独立にアルキル基、アリール基またはヘテロアリール基を表し、Ｒ²³、Ｒ²⁶およびＲ²⁹はそれぞれ独立に水素原子、アルキル基、アリール基またはハロゲン原子を表し、Ｒ²⁴、Ｒ²⁷およびＲ³⁰はそれぞれ独立にハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基またはアルコキシスルホニル基を表し、Ｘ¹〜Ｘ³はそれぞれ独立に酸素原子または硫黄原子を表し、ｎ¹〜ｎ³はそれぞれ独立に１または２を表し、ｍ¹〜ｍ³はそれぞれ独立に０〜６の整数を表す。）
上記一般式（ＯＳ−３）〜（ＯＳ−５）については、例えば、特開２０１２−１６３９３７号公報の段落番号００９８〜０１１５の記載を参酌でき、この内容は本願明細書に組み込まれる。 Specific examples of the compound represented by the general formula (OS-1) that can be suitably used in the present invention include the compounds described in paragraphs 0128 to 0132 of JP2011-221494A (Exemplary compounds b-1 to 1). b-34), but the present invention is not limited thereto.
In this invention, as a compound containing the oxime sulfonate structure represented by the said general formula (B1-1), the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-) The oxime sulfonate compound represented by 5) is preferred.

(In the general formula (OS-3) to general formula (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ^{1 to} X ³ each independently represents an oxygen atom or a sulfur atom, n ^{1 to} n ³ each independently represents 1 or 2, and m ^{1 to} m ³ each independently represents an integer of 0 to 6 Represents.)
Regarding the general formulas (OS-3) to (OS-5), for example, the description of paragraph numbers 0098 to 0115 of JP2012-163937A can be referred to, and the contents thereof are incorporated in the present specification.

Moreover, the compound containing the oxime sulfonate structure represented by the above general formula (B1-1) is, for example, described in the general formula (OS-6) described in paragraph 0117 of JP2012-163937A. A compound represented by any of (OS-11) is particularly preferred, the contents of which are incorporated herein.
Preferred ranges in the above general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. The contents of which are incorporated herein by reference.
Specific examples of the oxime sulfonate compound represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. The contents of which are incorporated herein by reference. The present invention is not limited to these.

（一般式（Ｂ１−４）中、Ｒ¹は、アルキル基またはアリール基を表し、Ｒ²は、アルキル基、アリール基、またはヘテロアリール基を表す。Ｒ³〜Ｒ⁶は、それぞれ、水素原子、アルキル基、アリール基、ハロゲン原子を表す。但し、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵、またはＲ⁵とＲ⁶が結合して脂環または芳香環を形成してもよい。Ｘは、−Ｏ−またはＳ−を表す。） The compound containing the oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-4).
General formula (B1-4)

(In General Formula (B1-4), R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, an aryl group, or a heteroaryl group. R ^{3 to} R ⁶ each represent a hydrogen atom. Represents an alkyl group, an aryl group, or a halogen atom, provided that R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may combine to form an alicyclic ring or aromatic ring. , -O- or S-.

R ¹ represents an alkyl group or an aryl group. The alkyl group is preferably a branched alkyl group or a cyclic alkyl group.
The alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable, and when the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable.
Examples of the alkyl group include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. , 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
Carbon number of an aryl group becomes like this. Preferably it is 6-12, More preferably, it is 6-8, More preferably, it is 6-7. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The alkyl group and aryl group represented by R ¹ may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.

In the photosensitive resin composition of the present invention, R ¹ is preferably an alkyl group from the viewpoint of transparency, and R ¹ has a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity. An alkyl group, an alkyl group having a cyclic structure having 5 to 7 carbon atoms, or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. . By adopting such a bulky group (particularly a bulky alkyl group) as R ¹ , it becomes possible to further improve the transparency.
Among the bulky substituents, an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.

R ² represents an alkyl group, an aryl group, or a heteroaryl group. As the alkyl group represented by R ² , a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. It is a group.
As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a naphthyl group, and a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
The alkyl group, aryl group, and heteroaryl group represented by R ² may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which R < ¹ > may have.
R ² is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group. As the substituent for the phenyl group, a methyl group is preferred.

R ^{3 to} R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom). The alkyl group represented by R ^{3 to} R ⁶ has the same meaning as the alkyl group represented by R ² , and the preferred range is also the same. The aryl group represented by R ^{3 to} R ⁶ has the same meaning as the aryl group represented by R ¹ , and the preferred range is also the same.
Among R ^{3 to} R ⁶ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may combine to form a ring, and the ring forms an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
R ^{3 to} R ⁶ are each a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ^6. A benzene ring is preferably formed, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are combined to form a benzene ring Is more preferable.
Preferred embodiments of R ^{3 to} R ⁶ are as follows.
(Aspect 1) At least two are hydrogen atoms.
(Aspect 2) The number of alkyl groups, aryl groups, or halogen atoms is one or less.
(Aspect 3) R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are combined to form a benzene ring.
(Aspect 4) An aspect satisfying the above aspects 1 and 2 and / or an aspect satisfying the above aspects 1 and 3.
X represents -O- or S-.

  Specific examples of the general formula (B1-4) include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Ts represents a tosyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.

  In the photosensitive resin composition of the present invention, the content of the (B-1) photoacid generator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. 0.5-10 mass parts is more preferable, and 0.5-5 mass parts is still more preferable. Only 1 type may be used for a photo-acid generator, and it can also use 2 or more types together.

<(C-1) Solvent>
The photosensitive resin composition of the present invention contains (C-1) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent. As a solvent used for the preparation of the composition of the present invention, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
As the solvent used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl. Ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like. Moreover, as a specific example of the solvent used for the photosensitive resin composition of this invention, the solvent of paragraph number 0174-0178 of Unexamined-Japanese-Patent No. 2011-221494, paragraph number 0167-0168 of Unexamined-Japanese-Patent No. 2012-194290. And the contents thereof are incorporated herein by reference.

  In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.

Further, the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C. or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C.), diethylene glycol methyl ethyl ether (boiling point 176 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.

  The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, more preferably 60 to 90 parts by mass, per 100 parts by mass of all components in the photosensitive resin composition. preferable. Only one type of solvent may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.

<(S) Lactone>
The (S) lactone used in the present invention is an alkylene group having 6 or more carbon atoms in the group constituting the lactone ring and / or the substituent of the lactone ring (hereinafter also simply referred to as “(S) lactone has”). The molecular weight is 1000 or less.

The (S) lactone-containing alkylene group having 6 or more carbon atoms may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear.
The alkylene group having 6 or more carbon atoms may be substituted or unsubstituted, but is preferably unsubstituted or substituted with a hydrophobic group, and more preferably unsubstituted. .
The hydrophobic group is a structure having a particularly low affinity for an aqueous alkali solution, and specific examples include a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an aromatic ring, and a fluoro group. -10 alkyl groups, C6-C10 aryl groups, and fluoro groups are preferred.
(S) The number of carbon atoms of the alkylene group having 6 or more carbon atoms contained in the lactone is preferably 8 to 14, more preferably 9 to 14, and still more preferably 9 to 12.

（一般式（Ｓ１）中、Ｇは、５〜７員環の脂環構造を表す。Ｒ¹は、水素原子または炭素数１〜３のアルキル基を表す。Ｒ²は、無置換の炭素数５〜８の直鎖状のアルキレン基を表す。） (S) The lactone is preferably represented by the following general formula (S1).
General formula (S1)

(In General Formula (S1), G represents a 5- to 7-membered alicyclic structure. R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ² represents an unsubstituted carbon number. Represents a linear alkylene group of 5 to 8.)

In General Formula (S1), G represents a 5- to 7-membered alicyclic structure and includes a —C—O—C— structure. G is preferably a 5- or 6-membered alicyclic structure. G may be monocyclic or polycyclic, but is preferably monocyclic. The number of carbon atoms constituting G is preferably 4-8, and more preferably 4 or 5. G may be substituted or unsubstituted, but is preferably unsubstituted or substituted with a hydrophobic group, more preferably unsubstituted. The hydrophobic group has the same meaning as the hydrophobic group described above.
In General Formula (S1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 1 or 2 is preferable and, as for carbon number of a C1-C3 alkyl group, 1 is more preferable. The alkyl group having 1 to 3 carbon atoms may be linear, branched or cyclic, but is preferably linear. The alkyl group having 1 to 3 carbon atoms may be substituted or unsubstituted, but is preferably unsubstituted, and more preferably an unsubstituted methyl group.
R ² represents an unsubstituted linear alkylene group having 5 to 8 carbon atoms. As for carbon number of a C5-C8 linear alkylene group, 6-8 are preferable.

（一般式（Ｓ２）および一般式（Ｓ３）中、Ｒ¹は、水素原子または炭素数１〜３のアルキル基を表す。Ｒ²は、無置換の炭素数５〜８の直鎖状のアルキレン基を表す。） (S) The lactone is more preferably represented by the following general formula (S2) and / or general formula (S3).
General formula (S2) General formula (S3)

(In General Formula (S2) and General Formula (S3), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ² is an unsubstituted linear alkylene having 5 to 8 carbon atoms. Represents a group.)

In the general formula (S2), R ¹ and R ² of the general formula (S1) in the same meaning as R ¹ and R ^2, and preferred ranges are also the same.
In formula (S3), R ¹ and R ² of the general formula (S1) in the same meaning as R ¹ and R ^2, and preferred ranges are also the same.

(S) Lactone is 4,5-dicarboxy-γ-pentadecanolactone (having an alkylene group having 14 carbon atoms), γ-nonanolactone (having an alkylene group having 8 carbon atoms), γ-decanolactone (having 9 carbon atoms). Having an alkylene group), γ-undecanolactone (having an alkylene group having 10 carbon atoms), γ-dodecanolactone (having an alkylene group having 11 carbon atoms), δ-nonanolactone (having an alkylene group having 8 carbon atoms) , Δ-decanolactone (having an alkylene group having 9 carbon atoms), δ-undecanolactone (having an alkylene group having 10 carbon atoms), δ-dodecanolactone (having an alkylene group having 11 carbon atoms), γ-methyl-γ-decanolactone (Having an alkylene group having 10 carbon atoms) and 15-pentadecanolactone (alkylene having 14 carbon atoms) It is preferable that any one selected from (having a hydrogen group) is included.
In particular, (S) lactone is selected from γ-decanolactone, γ-undecanolactone, γ-dodecanolactone, δ-decanolactone, δ-undecanolactone, δdodecanolactone, γ-methyl-γ-decanolactone and 15-pentadecanolactone. It is preferable to include any one selected from γ-decanolactone, γ-undecanolactone, γ-dodecanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, and γ-methyl-γ-decanolactone. And is selected from γ-methyl-γ-decanolactone, γ-decanolactone, γ-undecanolactone, γdodecanolactone, δ-decanolactone, δ-undecanolactone and δ-dodecanolactone. Including any one Theft is more preferable.
For example, in the following γ-undecanolactone, 15-pentadecanolactone and 4,5-dicarboxy-γ-pentadecanolactone, the broken line portion represents an alkylene group having 6 or more carbon atoms which (S) lactone has. Equivalent to.

  The molecular weight of (S) lactone is 1000 or less, preferably 140 to 500, and more preferably 160 to 300. When the molecular weight exceeds 1000, the solubility in the developer is insufficient, a residue remains at the bottom of the hole in the film after development, and the surface uniformity of the film after development deteriorates. When the molecular weight of (S) lactone is 140 or more, it is possible to more effectively suppress a decrease in content caused by volatilization of component (S) during pre-baking.

The photosensitive resin composition of the present invention preferably contains 0.1 to 20% by mass of component (S), more preferably 0.5 to 20% by mass, based on the total solid content of the photosensitive resin composition. Preferably, it contains 0.5-10 mass%, More preferably, it contains 2.0-10 mass%. By making content of (S) component 10 mass% or less, solvent resistance (especially tolerance with respect to NMP) can be made more favorable.
(S) A component may be only one type and may be two or more types. When there are two or more types of component (S), the total is preferably in the above range.

<Other ingredients>
In addition to the above components, a sensitizer, a crosslinking agent, a basic compound, a silane coupling agent, a surfactant, and an antioxidant may be preferably added to the photosensitive resin composition of the present invention as necessary. it can. Furthermore, the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives such as can be added. In addition, as these compounds, for example, compounds described in paragraph numbers 0201 to 0224 of JP2012-88459A can be used, and the contents thereof are incorporated in the present specification. Each of these components may be used alone or in combination of two or more.

<< Sensitizer >>
The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote the decomposition in combination with the photoacid generator. The sensitizer absorbs actinic rays and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squariums (eg, squalium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

When the photosensitive resin composition of this invention has a sensitizer, the addition amount of a sensitizer shall be 0.001-100 mass parts with respect to 100 mass parts of all the solid components in the photosensitive resin composition. Is preferred, 0.1-5
More preferably, it is 0 mass part, and it is further more preferable that it is 0.5-20 mass part. Two or more sensitizers can be used in combination.

<< Crosslinking agent >>
It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
The crosslinking agent is not limited as long as a crosslinking reaction is caused by heat. For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. Can be added.
When the photosensitive resin composition of this invention has a crosslinking agent, the addition amount of a crosslinking agent is 0.01-50 mass parts with respect to a total of 100 mass parts of said (A-1) polymer component. Preferably, it is 0.1-30 mass parts, More preferably, it is 0.5-20 mass parts. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained. A plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.

<<< Compound having two or more epoxy groups or oxetanyl groups in the molecule >>>
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.

These are available as commercial products. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.) and the like are commercially available products described in paragraph No. 0189 of JP2011-221494A. EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX- 211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, X-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (manufactured by Nagase Chemtech), YH-300, YH-301 YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel Chemical Co., Ltd.) and the like. These can be used alone or in combination of two or more.
Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.
As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

  Further, as other crosslinking agent, an alkoxymethyl group-containing crosslinking agent described in paragraph Nos. 0107 to 0108 of JP2012-8223A and a compound having at least one ethylenically unsaturated double bond are also preferable. These contents can be used and are incorporated herein. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

<<< Blocked isocyanate compound >>>
In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably employed as a crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group other than the compound represented by the general formula (S1) described above, but from the viewpoint of curability, two or more blocked isocyanate groups in one molecule. It is preferable that it is a compound which has this.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. Moreover, it is preferable that the said blocked isocyanate group is a group which can produce | generate an isocyanate group with the heat | fever of 90 to 250 degreeC.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic. Polyisocyanate may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2 2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1 , 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′-diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate , Isocyanation of hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, etc. A compound and a prepolymer type skeleton compound derived from these compounds can be preferably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.

Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.

  The blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (and above) , Manufactured by Asahi Kasei Chemicals Corporation, Death Module BL 100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.), etc. are preferably used can do.

<< basic compound >>
The photosensitive resin composition of the present invention may contain a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in JP-A-2011-221494, paragraphs 0204 to 0207, and the contents thereof are incorporated in the present specification.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo [5.3.0] -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, benzyltrimethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide. And so on.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
The basic compounds that can be used in the present invention may be used singly or in combination of two or more.

  When the photosensitive resin composition of the present invention has a basic compound, the content of the basic compound is 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid component in the photosensitive resin composition. Is preferable, and it is more preferable that it is 0.005-1 mass part.

<< Silane coupling agent >>
The photosensitive resin composition of the present invention may contain a silane coupling agent as an adhesion improving agent. When a silane coupling agent is used, the adhesion between the film formed of the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed of the photosensitive resin composition of the present invention are adjusted. be able to. The silane coupling agent that can be used in the photosensitive resin composition of the present invention is an inorganic material serving as a base material, for example, silicon compounds such as silicon, silicon oxide, and silicon nitride, gold, copper, molybdenum, titanium, aluminum, and the like. A compound that improves the adhesion between the metal and the insulating film is preferable. Known silane coupling agents are also effective.
Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropyl dialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane, An example is decyltrimethoxysilane. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.

The silane coupling agent in the photosensitive resin composition of this invention is not specifically limited to these, A well-known thing can be used.
As for content of the silane coupling agent in the photosensitive resin composition of this invention, 0.1-30 mass parts is preferable with respect to 100 mass parts of total solids in the photosensitive composition, 0.5-20 masses Part is more preferred.

<< Surfactant >>
The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. Examples of the surfactant used in the composition of the present invention include those described in paragraph numbers 0201 to 0205 of JP2012-88459A and paragraph numbers 0185 to 0188 of JP2011-215580A. Can be used and these descriptions are incorporated herein.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Mitsubishi Materials Kasei Co., Ltd.), MegaFac (manufactured by DIC Corporation), Florard Novec FC-4430 (manufactured by Sumitomo 3M Corporation), Surflon S-242 (Manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox PF-6320 (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and footgent FTX-218G (manufactured by Neos).
Further, as a surfactant, it is measured by gel permeation chromatography using the structural unit A and the structural unit B represented by the following general formula (I-1-1) and using tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having a polystyrene-reduced weight average molecular weight (Mw) of 1,000 or more and 10,000 or less.

（式（Ｉ−１−１）中、Ｒ⁴⁰¹およびＲ⁴⁰³はそれぞれ独立に、水素原子またはメチル基を表し、Ｒ⁴⁰²は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ⁴⁰⁴は水素原子または炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐおよびｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｓは１以上１０以下の整数を表す。） Formula (I-1-1)

(In formula (I-1-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents hydrogen. Represents an atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10 mass% to 80 mass%. The following numerical values are represented, q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.

L is preferably a branched alkylene group represented by the following general formula (I-1-2). R ⁴⁰⁵ in the general formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms,
From the viewpoint of compatibility and wettability to the coated surface, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 2 or 3 carbon atoms is more preferable. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

Formula (I-1-2)

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.
When the photosensitive resin composition of the present invention has a surfactant, the addition amount of the surfactant is preferably 10 parts by mass or less with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. The amount is more preferably 0.001 to 10 parts by mass, and further preferably 0.01 to 3 parts by mass.
<< Antioxidant >>
The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Of these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing film thickness, with phenol-based antioxidants being the most preferred. preferable. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraph Nos. 0026 to 0031 of JP-A-2005-29515 and the compounds described in paragraph Nos. 0106 to 0116 of JP-A-2011-227106. It is incorporated herein.
As a preferable commercial item, ADK STAB AO-60, ADK STAB AO-80, Irganox 1035, and Irganox 1098 can be mentioned.

  When the photosensitive resin composition of this invention has antioxidant, content of antioxidant is 0.1-10 mass parts with respect to 100 mass parts of all the solid components in the photosensitive resin composition. Is more preferable, 0.2 to 5 parts by mass is more preferable, and 0.5 to 4 parts by mass is particularly preferable. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.

<< Acid Proliferator >>
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
Specific examples of such an acid proliferating agent include the acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.

<< Development accelerator >>
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, those described in paragraph Nos. 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
When the photosensitive resin composition of this invention has a development accelerator, the addition amount of a development accelerator is 0-30 with respect to 100 mass parts of total solid of a photosensitive composition from a viewpoint of a sensitivity and a residual film rate. Mass parts are preferred, 0.1 to 20 parts by mass are more preferred, and 0.5 to 10 parts by mass are most preferred.
In addition, as other additives, a thermal radical generator described in paragraph Nos. 0120 to 0121 of JP2012-8223A, a nitrogen-containing compound and a thermal acid generator described in WO2011 / 136074A1, can be used. Is incorporated herein by reference.

[Second embodiment of the present invention]
Hereinafter, the second aspect of the composition of the present invention will be described.
The composition of the second aspect of the present invention comprises
(A-2) A polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) a polymer having (a2-1) a structural unit having an acid group, and (a2-2) a structural unit having a crosslinkable group,
(2) (a2-1) a polymer having a structural unit having an acid group, and (a2-2) a polymer having a structural unit having a crosslinkable group,
(B-2) a quinonediazide compound,
(C-2) contains a solvent and (S) lactone,
The (S) lactone contains an alkylene group having 6 or more carbon atoms in the group constituting the lactone ring and / or the substituent of the lactone ring, and the molecular weight of the (S) lactone is 1000 or less. Features.

<(A-2) Polymer component>
The polymer component (A-2) used in the present invention includes (a2-1) a structural unit having an acid group and (a2-2) a polymer containing a structural unit having a crosslinkable group, and (a2-1) It includes at least one of a polymer having a structural unit having an acid group and (a2-2) a polymer having a structural unit having a crosslinkable group. Furthermore, (A-2) polymer component may contain polymers other than these.

<< (a2-1) Structural Unit Having Acid Group >>
By including (a2-1) the structural unit having an acid group in the polymer component (A-2), the polymer component is easily soluble in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group is usually incorporated into the polymer as a structural unit having an acid group using a monomer capable of forming an acid group. By including such a structural unit having an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Amide groups, sulfonylimide groups and the like are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred. In particular, the structural unit having an acid group used in the present invention is preferably a structural unit having a carboxyl group and / or a phenolic hydroxyl group.
The structural unit having an acid group used in the present invention is preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid and / or an ester thereof. For example, the compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein. Of these, structural units derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are preferred.
In the present invention, it is particularly preferable from the viewpoint of sensitivity to contain a repeating unit having a carboxyl group or a repeating unit having a phenolic hydroxyl group. For example, the compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein.

<< (a2-2) Structural Unit Having a Crosslinkable Group >>
In addition, the structural unit (a2-2) having a crosslinkable group is represented by an epoxy group, an oxetanyl group, —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). It is preferable to contain a structural unit containing at least one selected from the group consisting of a group and an ethylenically unsaturated group.
(A2-2) The structural unit which has a crosslinkable group is synonymous with the structural unit which has the (a1-2) crosslinkable group in the (A-1) polymer mentioned above, A preferable range is the same except content. It is.

<< (a2-3) Other structural units >>
Furthermore, the (A-2) polymer component includes the structural unit (a2-1) and the structural unit (a2-2), as well as the structural unit (a2-1) and the structural unit (a2-2). The structural unit (a2-3) may be included.
The monomer to be the structural unit (a2-3) is not particularly limited as long as it is an unsaturated compound other than the structural units (a2-1) and (a2-2).
For example, styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatics Examples thereof include compounds, conjugated diene compounds, and other unsaturated compounds. The monomer which becomes a structural unit (a2-3) can be used individually or in combination of 2 or more types.

(A-2) It is preferable that 3-70 mol% of structural units (a2-1) are contained in all the structural units of a polymer component, and it is more preferable that 10-60 mol% is contained, 15 More preferably, it is contained in an amount of ˜50 mol%.
(A-2) It is preferable that 3-70 mol% of structural units (a2-2) are contained in all the structural units of a polymer component, and it is more preferable that 10-60 mol% is contained, 15 More preferably, it is contained in an amount of ˜40 mol%.
(A-2) It is preferable that 1-80 mol% of structural units (a2-3) are contained in all the structural units of a polymer component, and it is more preferable that 5-50 mol% is contained, 8 More preferably, it is contained in an amount of ˜30 mol%.
It is preferable that the composition of the 2nd form of this invention contains (A-2) polymer component in the ratio of 70 mass% or more of solid content of a composition.

<(B-2) Quinonediazide compound>
As the quinonediazide compound used in the composition of the present invention, a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with actinic rays can be used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used. As specific examples of these compounds, for example, description of paragraphs 0075 to 0078 of JP2012-088459A can be referred to, and the contents thereof are incorporated in the present specification.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazide sulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the 1,2-quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1,2. -Naphthoquinonediazide-4-sulfonic acid amide etc. are also used suitably. Also, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfone Condensate with acid chloride (3.0 mol), 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) Mol)), 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44 mol), etc. It may be used.

These quinonediazide compounds can be used alone or in combination of two or more. The content of the quinonediazide compound in the photosensitive resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. 10-25 mass parts is further more preferable.
(B-2) By making content of a quinonediazide compound into the said range, the difference of the solubility of the irradiated part of the actinic light with respect to the alkaline aqueous solution used as a developing solution and a non-irradiated part is large, patterning performance becomes favorable, and is obtained. The solvent resistance of the cured film is improved.

<(S) component>
The composition of the 2nd form of this invention contains the same (S) component as the (S) component in the composition of the 1st form mentioned above, and its preferable range is also the same.
The content of the component (S) is preferably 0.1 to 20% by mass, more preferably 0.5 to 20% by mass, and preferably 0.5 to the total solid content of the photosensitive resin composition of the second form. 10 mass% is further more preferable, and 2.0-10 mass% containing is especially preferable. (S) A component may be only one type and may be two or more types. When there are two or more types of component (S), the total is preferably in the above range.

<(C-2) Solvent>
The photosensitive resin composition of the present invention contains a solvent. As the solvent used in the photosensitive resin composition of the present invention, the above-described solvent (C-1) of the first aspect can be used, and the preferred range is also the same.
The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, more preferably 60 to 90 parts by mass, per 100 parts by mass of all components in the photosensitive resin composition. preferable. Only one type of solvent may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.

<Other ingredients>
In the composition of the present invention, a crosslinking agent, a basic compound, a surfactant, and an antioxidant can be preferably added as necessary within the range not impairing the effects of the present invention in addition to the above components. Furthermore, the photosensitive resin composition of the present invention includes known development accelerators, plasticizers, thermal radical generators, thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic precipitation inhibitors. Additives can be added. These components are the same as those in the first embodiment described above, and the preferred ranges are also the same. Each of these components may be used alone or in combination of two or more.

<Method for preparing photosensitive resin composition>
Each component is mixed in a predetermined ratio and by any method, stirred and dissolved to prepare a photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore diameter of 0.2 μm.

<The manufacturing method of the cured film of the 1st aspect of this invention>
The method for producing a cured film according to the first aspect of the present invention preferably includes the following steps (1-1) to (5-1).
(1-1) The process of apply | coating the photosensitive resin composition of the 1st aspect of this invention on a board | substrate;
(2-1) The process of removing a solvent from the apply | coated photosensitive resin composition;
(3-1) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays;
(4-1) A step of developing the exposed photosensitive resin composition with an aqueous developer;
(5-1) A post-baking step of thermosetting the developed photosensitive resin composition.
Each step will be described below in order.

In the application step (1-1), the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the photosensitive resin resin composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound And the like.
These substrates are rarely used in the above-described form, and usually a multilayer laminated structure such as a TFT element is formed depending on the form of the final product.
The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used.
In the case of the slit coating method, the relative moving speed between the substrate and the slit die is preferably 50 to 120 mm / sec.
The wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but is usually used in the range of 0.5 to 10 μm.
Furthermore, before applying the composition used in the present invention to the substrate, it is also possible to apply a so-called prewetting method as described in JP-A-2009-145395.

  In the solvent removal step (2-1), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.

In the exposure step (3-1), the substrate provided with the coating film is irradiated with an actinic ray having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used. Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mJ / cm ² .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used.
In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
However, since the acid-decomposable group in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group, PEB is not necessarily performed. A positive image can also be formed by development.

In the development step (4-1), a copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
The developer used in the development step preferably contains an aqueous solution of a basic compound. Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamines such as diamine; Alcohol amines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0 ] Cycloaliphatic amines such as -5-nonene can be used.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.

In the post-baking step (5-1), the obtained positive image is heated to thermally decompose the acid-decomposable group to generate a carboxyl group or a phenolic hydroxyl group, and to crosslink with a crosslinkable group, a crosslinking agent, or the like. Thus, a cured film can be formed. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on a hot plate, 30 to 120 minutes for an oven. It is preferable to By proceeding the crosslinking reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. As a preferable exposure amount when including a post-exposure step, 100 to 3,000 mJ / cm ² is preferable, and 100 to 500 mJ / cm ² is particularly preferable.

  Furthermore, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. In the case where a cured film obtained by thermal curing in a post-baking process is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.

<The manufacturing method of the cured film of the 2nd aspect of this invention>
The method for producing a cured film according to the second aspect of the present invention preferably includes the following steps (1-2) to (5-2).
(1-2) The process of apply | coating the photosensitive resin composition of the 2nd aspect of this invention on a board | substrate;
(2-2) The process of removing a solvent from the apply | coated photosensitive resin composition;
(3-2) a step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays;
(4-2) Developing the exposed photosensitive resin composition with an aqueous developer;
(5-2) A post-baking step of thermosetting the developed photosensitive resin composition.

Steps (1-2) to (5-2) of the method for producing a cured film of the present invention are respectively (1-1) to (5-1) of the method for producing a cured film of the first aspect described above. It can carry out similarly to the process of this, and preferable conditions are also the same.
The cured film obtained from the composition of the present invention can also be used as an etching resist.

[Curing film]
The cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition of the first and second aspects of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of the 1st and 2nd aspect of this invention mentioned above.
With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for liquid crystal display devices and organic EL display devices.

[Liquid Crystal Display]
The liquid crystal display device of the present invention comprises the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal displays having various structures. An apparatus can be mentioned.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
In addition, as a liquid crystal driving method that can be taken by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (Optical) method. Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) disclosed in JP-A-2005-284291 or JP-A-2005-346054 is used. It can be used as an organic insulating film (212). Specific examples of the alignment method of the liquid crystal alignment film that can be taken by the liquid crystal display device of the present invention include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, a flexible type can also be used, and it is used as the second interlayer insulating film (48) described in JP 2011-145686 A and the interlayer insulating film (520) described in JP 2009-258758 A. Can do.
In addition, a statically driven liquid crystal display device can display a pattern with high designability by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A No. 2001-125086.

[Organic EL display device]
The organic EL display device of the present invention comprises the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 2 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening film 4 is formed on the insulating film 3 with the unevenness due to the wiring 2 being embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

  Since the photosensitive resin composition of the present invention is excellent in curability and cured film characteristics, a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part. Examples of such MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

  Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010- The partition wall (12) and the planarization film (102) described in FIG. 4A of 9793, and the bank layer (221) and third interlayer insulating film (216b) described in FIG. 10 of JP 2010-27591A. ), Second interlayer insulating film (125) and third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and flatness described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical film (12) and a pixel isolation insulating film (14). In addition, spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices, imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
NBMA: n-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry)
HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate V-601: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)

[First embodiment]
<Synthesis of MATHF>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a residual yellow oily product. Distillation under reduced pressure afforded 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.

<Synthesis Example of Polymer A-1>
PGMEA (propylene glycol monomethyl ether acetate) (89 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. MAA (amount to be 9.5 mol% in all monomer components), MATH (amount to be 43 mol% in all monomer components), GMA (47.5 mol% in all monomer components) And V-65 (corresponding to 4 mol% with respect to 100 mol% in total of all monomer components) was added dropwise over 2 hours in PGMEA (89 g) at room temperature. After completion of the dropwise addition, the mixture was stirred for 2 hours to complete the reaction. Thereby, a polymer A-1 was obtained. In addition, it adjusted so that the density | concentration of components (referred to as solid content) other than a solvent might be 40 mass%.
Monomers and the like were changed as shown in the following table, and other polymers were synthesized.

  In the above table, the numerical values not particularly given in the table are in mol%. The numerical value of a polymerization initiator and an additive is mol% when a monomer component is 100 mol%. The solid content concentration is shown as monomer mass / (monomer mass + solvent mass) × 100 (unit mass%). When V-601 was used as the polymerization initiator, the reaction temperature was 90 ° C., and when V-65 was used, the reaction temperature was 70 ° C.

<Adjustment of photosensitive resin composition>
Each component is blended so as to have the solid content ratio shown in the following table, and dissolved and mixed in a solvent (PGMEA: MEDG = 1: 1) until the solid content concentration becomes 15%. It filtered with the filter made from ethylene, and obtained the photosensitive resin composition of various Examples and a comparative example.

Ｂ−１−２：下記に示す構造（合成例は後述する）

Ｂ−１−３：下記に示す構造（特表２００２−５２８４５１号公報の段落０１０８に記載の方法に従って合成した）

Ｂ−１−４：ＰＡＧ−１０３（商品名、下記に示す構造、ＢＡＳＦ社製）

Ｂ−１−５：ＧＳＩＤ−２６−１、トリアリールスルホニウム塩（ＢＡＳＦ社製）

The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.
(Photoacid generator)
B-1-1: Structure shown below (synthesis examples will be described later)

B-1-2: Structure shown below (synthesis examples will be described later)

B-1-3: Structure shown below (synthesized according to the method described in paragraph 0108 of JP-T-2002-528451)

B-1-4: PAG-103 (trade name, structure shown below, manufactured by BASF)

B-1-5: GSID-26-1, triarylsulfonium salt (manufactured by BASF)

(Quinonediazide compound)
B-2-1: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide Condensate with -5-sulfonic acid chloride (3.0 mol) B-2-2: 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide- Condensate with 5-sulfonic acid chloride (2.0 mol) B-2-3: 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfone Condensate with acid ester (2.44 mol)

Ｓ−２：１５−ペンタデカノラクトン

Ｓ−３：γーメチルーγーデカノラクトン

Ｓ−４：γ-ノナノラクトン

Ｓ−５：４，５−ジカルボキシ−γ−ペンタデカノラクトン

Ｓ’−１：γ−カプロラクトン
Ｓ’−２：ＤＬ−パントラクトン
Ｓ’−３：Ｄ−グルコノ−６，３−ラクトン ((S) Lactone)
S-1: γ-undecanolactone

S-2: 15-pentadecanolactone

S-3: γ-methyl-γ-decanolactone

S-4: γ-nonanolactone

S-5: 4,5-dicarboxy-γ-pentadecanolactone

S′-1: γ-caprolactone S′-2: DL-pantolactone S′-3: D-glucono-6,3-lactone

(Sensitizer)
DBA: 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd.)

(Basic compound)
H-1: Compound having the following structure

<Silane coupling agent>
G-1: 3-glycidoxypropyltrimethoxysilane (KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.))

Ｗ−２：シリコーン系界面活性剤 ＳＨ8400 ＦＬＵＩＤ（（株）東レ・ダウコーニング製）
Ｗ−３：フッ素系界面活性剤 ＦＴＸ−２１８（（株）ネオス製） (Surfactant)
W-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)

W-2: Silicone surfactant SH8400 FLUID (manufactured by Toray Dow Corning)
W-3: Fluorosurfactant FTX-218 (manufactured by Neos)

(solvent)
MEDG (diethylene glycol ethyl methyl ether): Hisolv EDM (manufactured by Toho Chemical Industry Co., Ltd.)
PGMEA (propylene glycol monomethyl ether acetate): (Showa Denko)

(Other additives)
F-1: JER828 (manufactured by Mitsubishi Chemical Holdings Corporation)
F-2: JER1007 (manufactured by Mitsubishi Chemical Holdings Corporation)
F-3: JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation)
J-1: ADK STAB AO-60 (manufactured by ADEKA)
J-2: Irganox 1035 (manufactured by BASF)
J-3: Irganox 1098 (manufactured by BASF)

<Synthesis of B-1-1>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated, and the crystals were diluted with diisopropyl ether (10 mL). The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain the compound of B-1-1 (the above structure) (2.3 g). It was.
In addition, the 1H-NMR spectrum (300 MHz, CDCl3) of B-1-1 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).

<Synthesis of B-1-2>
After 4.0 g of 1-amino-2-naphthol hydrochloride (manufactured by Tokyo Chemical Industry) is suspended in 16 g of N-methylpyrrolidone (Wako Pure Chemical Industries), 3.4 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries) is added, 4.9 g of methyl 4,4-dimethyl-3-oxovalerate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise and heated at 120 ° C. for 2 hours in a nitrogen atmosphere. After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-1-2A. Crude B-1-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-1-2A.
B-1-2A (1.7 g) and p-xylene (6 mL) were mixed, and 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated at 140 ° C. for 2 hours. . After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated. The organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-1-2B.
THF (2 mL) and the entire amount of crude B-1-2B were mixed, and 2 mL hydrochloric acid / THF solution 6.0 mL was added dropwise under ice cooling, and then isopentyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (0.84 g) was added dropwise. The mixture was stirred for 2 hours after warming. Water and ethyl acetate were added to the obtained reaction mixture for liquid separation, and the organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated to obtain Intermediate Intermediate B-1-2C.
The total amount of intermediate crude B-1-2C was mixed with acetone (10 mL), and triethylamine (Wako Pure Chemical Industries, Ltd.) (1.2 g), p-toluenesulfonyl chloride (Tokyo Chemical Industry) (1.4 g) under ice cooling. Then, the mixture was warmed to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the obtained reaction mixture for liquid separation, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-1-2. Crude B-1-2 was reslurried with cold methanol, filtered and dried to obtain B-1-2 (1.2 g).
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-1-2 is δ = 8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7 .7-7.6 (m, 2H), 7.6-7.5 (m, 1H), 7.4 (d.2H), 2.4 (s, 3H), 1.4 (s, 9H) )Met.

<Evaluation of hole bottom residue>
Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning), 10 cm × 10 cm) and then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent. Thus, a photosensitive resin composition layer having a film thickness of 4.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (extra high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive resin composition layer was developed with an alkali developer (0.4 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
When a 10 μm contact hole was formed by this method, the residue at the bottom of the hole was observed and evaluated by SEM.
5: No residue 4: There is a little residue at the end of the hole 3: There is a residue at the end of the hole 2: There is a little residue at the center of the hole 1: There is a residue at the center of the hole

<Evaluation of surface roughness after development>
A substrate having a contact hole of 10 μm was prepared by the same method as the evaluation of the hole bottom residue, and the roughness of the film surface other than the hole (presence of white cloudiness) was visually evaluated.
5: No cloudiness is observed on the film surface 4: Slight cloudiness is observed in the range from the edge of the substrate to 2 cm 3: Cloudiness is observed in the range from the edge of the substrate to 2 cm 2: Over the entire surface of the substrate Slightly cloudy 1: Cloudy over the entire surface of the substrate

<Evaluation of NMP resistance>
A glass substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition is spin-coated on the substrate, and then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent. A photosensitive resin composition layer having a thickness of 3.0 μm was formed.
Subsequently, exposure was performed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and the substrate was heated in an oven at 230 ° C./30 minutes.
The film thickness (T1) of the obtained cured film was measured. And after immersing the board | substrate with which this cured film was formed in the NMP solution temperature-controlled at 80 degreeC for 10 minutes, the film thickness (t1) of the cured film after immersion is measured, and the film thickness change rate by immersion {| T1-T1 | / T1} × 100 [%] was calculated. The results are shown in the table below.
The film thickness change rate is preferably as small as possible, and 3 to 5 is a level causing no practical problem.
5: Less than 2% 4: 2% or more but less than 3% 3: 3% or more but less than 4% 2: 4% or more but less than 6% 1: 6% or more

<Comprehensive evaluation>
Based on the total score of “Evaluation of hole bottom residue” and “Evaluation of surface roughness after development”, comprehensive evaluation was performed. The results are shown in the table below. An overall rating of 6 or higher is a level that is not problematic in practice.

As is clear from the above results, it was found that the photosensitive resin compositions of the examples had little hole bottom residue and little surface roughness after development. Moreover, it turned out that NMP tolerance is also favorable.
On the other hand, it was found that the photosensitive resin composition of the comparative example had many hole bottom residue and surface roughness after development. It was also found that NMP resistance was not good.

[First embodiment]
<Example 52>
In the active matrix type liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 52 was obtained. That is, using the photosensitive resin composition of Example 1, a cured film 17 was formed as an interlayer insulating film.
That is, as a pretreatment for improving the wettability of the substrate and the interlayer insulating film 17 in paragraph 0058 of Japanese Patent No. 3321003, the substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then the photosensitive film of Example 1 is used. After spin-coating the photosensitive resin composition, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 3 μm. Next, the obtained photosensitive resin composition layer was subjected to 40 mJ / cm ² (energy intensity: 20 mW / cm ² ) through a hole pattern mask of 10 μmφ using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. , I-line). The exposed photosensitive resin composition layer was subjected to paddle development at 23 ° C./60 seconds with an alkaline developer (0.4% tetramethylammonium hydroxide aqueous solution), and then rinsed with ultrapure water for 20 seconds. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking.

  When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

<Example 53>
A liquid crystal display device similar to that of Example 52 was changed to obtain the same liquid crystal display device. That is, even if the exposure apparatus is changed from Canon Inc. MPA 5500CF (high pressure mercury lamp) to Nikon Corporation FX-803M (gh-Line stepper), the performance as a liquid crystal display device is the same as in Example 52. It was very good.

<Example 54>
A liquid crystal display device similar to that of Example 52 was changed to obtain the same liquid crystal display device. That is, even if the exposure apparatus is changed from Canon Inc. MPA 5500CF (high pressure mercury lamp) to “AEGIS” manufactured by Buoy Technology Co., Ltd. (wavelength 355 nm, pulse width 6 nsec), the liquid crystal display device The performance was also good as in Example 52.

<Example 55>
A liquid crystal display device similar to that of Example 52 was changed to obtain the same liquid crystal display device. That is, even when the photosensitive resin composition of Example 1 was applied without the hexamethyldisilazane (HMDS) treatment, which is a pretreatment of the substrate, the resulting cured film was good with no chipping or peeling off of the pattern. It was a state. Further, the performance as a liquid crystal display device was good as in Example 52. This is presumably because the composition of the present invention has excellent adhesion to the substrate. From the viewpoint of improving productivity, it is also preferable to omit the substrate pretreatment step.

<Example 56>
A similar liquid crystal display device was obtained by changing only the following process from Example 52. That is, even if a vacuum drying step (VCD) was introduced after pre-baking, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 52. It is also preferable to introduce a reduced-pressure drying step from the viewpoint of suppressing coating unevenness according to the solid content concentration and the film thickness of the composition.

<Example 57>
A liquid crystal display device similar to that of Example 52 was changed to obtain the same liquid crystal display device. That is, even if the PEB process was introduced between the development process and the mask exposure, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 52. From the viewpoint of improving dimensional stability, it is also preferable to introduce a PEB process.

<Example 58>
A liquid crystal display device similar to that of Example 52 was changed to obtain the same liquid crystal display device. That is, even when the alkaline developer is changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 2.38% tetramethylammonium hydroxide aqueous solution, the resulting cured film has good pattern free of chipping and peeling. It was a state. Further, the performance as a liquid crystal display device was good as in Example 52. This is presumably because the composition of the present invention has excellent adhesion to the substrate.

<Example 59>
A liquid crystal display device similar to that of Example 52 was changed to obtain the same liquid crystal display device. That is, even when the alkali development method was changed from paddle development to shower development, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 52. This is presumably because the composition of the present invention has excellent adhesion to the substrate.

<Example 60>
A similar liquid crystal display device was obtained by changing only the following process from Example 52. That is, even when the alkaline developer was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 0.04% KOH aqueous solution, the resulting cured film was in a good state with no pattern chipping or peeling. It was. Further, the performance as a liquid crystal display device was good as in Example 52. This is presumably because the composition of the present invention has excellent adhesion to the substrate.

<Example 61>
A liquid crystal display device similar to that of Example 52 was changed to obtain the same liquid crystal display device. That is, the entire surface exposure step after development and rinsing was omitted, and the cured film was obtained by heating in an oven at 230 ° C. for 30 minutes. The performance of the obtained liquid crystal display device was as good as in Example 52. This seems to be because the composition of the present invention is excellent in chemical resistance. From the viewpoint of improving productivity, it is also preferable to omit the entire exposure process.

<Example 62>
A liquid crystal display device similar to that of Example 52 was changed to obtain the same liquid crystal display device. That is, a step of heating on a hot plate at 100 ° C. for 3 minutes was added between the entire surface exposure step and the 230 ° C./30 minute heating step in the oven. The performance of the obtained liquid crystal display device was as good as in Example 52. It is also preferable to add this process from the viewpoint of adjusting the shape of the hole pattern.

<Example 63>
A similar liquid crystal display device was obtained by changing only the following process from Example 52. That is, a process of heating on a hot plate at 100 ° C. for 3 minutes was added between the development / rinse process and the entire surface exposure process. The performance of the obtained liquid crystal display device was as good as in Example 52. It is also preferable to add this process from the viewpoint of adjusting the shape of the hole pattern.

An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiation with i-line (365 nm) at 45 mJ / cm ² (energy intensity 20 mW / cm ² ) using a mercury lamp, development is performed with an alkaline aqueous solution (0.4% TMAH aqueous solution) to form a pattern. Was used to expose the entire surface so that the integrated dose was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and a heat treatment was performed at 230 ° C./30 minutes.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

  Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photosensitive resin composition of Example 1 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

  Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.

  As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

[Second embodiment]
<Example 64>
A liquid crystal display device was obtained using the photosensitive resin composition of Example 34 in the same manner as in the first example. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

  Similarly to the first example described above, an organic EL display device using a thin film transistor (TFT) was produced using the photosensitive resin composition of Example 34. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter 100: Substrate

Claims (16)

(A-1) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1-1) a polymer having a structural unit having an acid group protected by an acid-decomposable group and (a1-2) a structural unit having a crosslinkable group,
(2) (a1-1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a1-2) a polymer having a structural unit having a crosslinkable group,
(B-1) a photoacid generator,
(C-1) contains a solvent, and (S) a lactone,
The photosensitivity in which the (S) lactone contains an alkylene group having 6 or more carbon atoms in a group constituting the lactone ring and / or a substituent of the lactone ring, and the molecular weight of the (S) lactone is 1000 or less. Resin composition. (A-2) A polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) a polymer having (a2-1) a structural unit having an acid group, and (a2-2) a structural unit having a crosslinkable group,
(2) (a2-1) a polymer having a structural unit having an acid group, and (a2-2) a polymer having a structural unit having a crosslinkable group,
(B-2) a quinonediazide compound,
(C-2) contains a solvent and (S) lactone,
The photosensitivity in which the (S) lactone contains an alkylene group having 6 or more carbon atoms in a group constituting the lactone ring and / or a substituent of the lactone ring, and the molecular weight of the (S) lactone is 1000 or less. Resin composition. (S) The photosensitive resin composition of Claim 1 or 2 whose molecular weight of lactone is 140-500. (S) The photosensitive resin composition of Claim 1 or 2 whose molecular weight of lactone is 160-300. The photosensitive resin composition according to any one of claims 1 to 4, wherein the alkylene group having 6 or more carbon atoms is unsubstituted or substituted with a hydrophobic group. The photosensitive resin composition according to any one of claims 1 to 5, wherein the alkylene group having 6 or more carbon atoms has 9 to 14 carbon atoms. The photosensitive resin composition of any one of Claims 1-6 by which (S) lactone is represented by the following general formula (S1).
General formula (S1)

(In General Formula (S1), G represents a 5- to 7-membered alicyclic structure. R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ² represents an unsubstituted carbon number. Represents a linear alkylene group of 5 to 8.) The photosensitive resin composition of Claim 7 in which R < ¹ > in the said general formula represents a hydrogen atom or a C1-C3 alkyl group. (S) The lactone is selected from γ-decanolactone, γ-undecanolactone, γ-dodecanolactone, δ-decanolactone, δ-undecanolactone, δdodecanolactone, γ-methyl-γ-decanolactone and 15-pentadecanolactone. The photosensitive resin composition of any one of Claims 1-6 containing any 1 type. The photosensitive resin composition of any one of Claims 1-9 whose content of (S) lactone is 0.5-10 mass% with respect to the total solid of the photosensitive resin composition. Structural unit having the crosslinking group, an epoxy group, a structural unit containing at least one selected from the groups represented by oxetanyl group and NH-CH ₂ -O-R, any one of claims 1 to 10, 2. The photosensitive resin composition according to 1, wherein R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. (1) The process of apply | coating the photosensitive resin composition of any one of Claims 1-11 on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermosetting the developed photosensitive resin composition;
The manufacturing method of the cured film containing this. The manufacturing method of the cured film of Claim 12 including the process of exposing the developed photosensitive resin composition to the whole surface after the said image development process and before the said post-baking process. The cured film which hardened the photosensitive resin composition of any one of Claims 1-11, or the cured film formed by the manufacturing method of the cured film of Claim 12 or 13. The cured film of Claim 14 which is an interlayer insulation film. An organic EL display device or a liquid crystal display device having the cured film according to claim 14 or 15.

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