JP2015187634A - Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic el display device, and touch panel display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which has excellent sensitivity, and has excellent pattern adhesion at the time of development even in the case of a substrate which is not subjected to hydrophobic treatment such as HMDS; and a method for producing a cured film, a cured film, a liquid crystal display device, an organic EL display device, and a touch panel display device using the photosensitive resin composition.SOLUTION: A photosensitive resin composition contains (A) a polymer component, (B) a photoacid generator, (C) a solvent, and (S) a polymer having a structural unit having a specific hindered amine structure and a structural unit having a carboxyl group. In the polymer (S), a molar ratio of the structural unit having the carboxyl group in the total repeating units of the polymer (S) is 0.3-5 times a molar ratio of the structural unit having the specific hindered amine structure in the total repeating units of the polymer (S).

Description

  The present invention relates to a photosensitive resin composition. More specifically, it is suitable for forming a flattening film, a protective film, an interlayer insulating film, and the like of electronic components such as a liquid crystal display device, an organic EL (organic electroluminescence) display device, a touch panel display device, an integrated circuit element, and a solid-state imaging device. And relates to a photosensitive resin composition. The present invention also relates to a method for producing a cured film, a cured film obtained by curing a photosensitive resin composition, a liquid crystal display device using the cured film, an organic EL display device, and a touch panel display device.

  Image display devices such as organic EL display devices, liquid crystal display devices, and touch panel display devices are provided with a patterned interlayer insulating film. In forming an interlayer insulating film, a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.

  The interlayer insulating film in the image display device is required to have high transparency in addition to the properties of the cured film, such as excellent insulation, heat resistance, hardness, and indium tin oxide (ITO) sputtering suitability. 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 Documents 1 and 2 are known.

JP 2011-227106 A JP 2011-95433 A

With the recent increase in pixel density of flat panel displays, there has been a strong demand for miniaturization of each pixel pattern size. With the miniaturization of the pattern size, it is essential to miniaturize the wiring used for manufacturing and the dimensions of various structures, and similar characteristics are required for the photosensitive resin composition for forming them.
On the other hand, in the conventional process for producing an interlayer insulating film and protective film, hexamethyldiethylene is used as a pretreatment of the substrate in order to improve the adhesion (development adhesion) between the photosensitive resin composition and the substrate during development. Surface hydrophobization treatment such as silazane (HMDS) treatment has been performed. In recent years, from the viewpoint of cost reduction and process simplification, there has been an increasing demand for omitting surface hydrophobization treatment and the like.
Further, along with the miniaturization of patterns and the omission of surface hydrophobization treatment, the development adhesiveness of the photosensitive resin composition to the substrate is insufficient, causing problems such as pattern chipping and peeling during development. As a result, the in-plane uniformity of the pattern dimensions finished after the development deteriorates, and the problem that it becomes difficult to ensure the dimensional accuracy has become apparent.

  Here, when the inventors examined, it turned out that image development adhesiveness improves by adding hindered amines to the photosensitive resin composition. However, as a result of further studies by the inventors, it has been found that if the amount of hindered amines added is too large, the sensitivity decreases.

  The present invention solves such problems, and is a photosensitive resin composition excellent in pattern adhesion at the time of development even if the substrate has good sensitivity and is not subjected to a hydrophobic treatment such as HMDS. Another object of the present invention is to provide a cured film manufacturing method, a cured film, a liquid crystal display device, an organic EL display device, and a touch panel display device using the photosensitive resin composition.

式（１）および（２）中、Ｒ¹⁰およびＲ¹¹は、それぞれ独立に、水素原子またはメチル基を表し、Ｌ¹およびＬ²は、それぞれ独立に、単結合、または、２価の連結基を表し、Ｒ¹〜Ｒ⁴は、それぞれ独立に、炭素数１〜１２のアルキル基または炭素数１〜１２のアルコキシ基を表し、Ｒ⁵は、水素原子、炭素数１〜１２の１アルキル基または炭素数１〜１２のアルコキシ基を表す。
＜２＞ （Ａ）重合体成分と（Ｓ）重合体の合計１００質量部に対し、（Ｓ）重合体を０．１〜１０質量部含有する＜１＞に記載の感光性樹脂組成物。
＜３＞ （Ａ）重合体成分と（Ｓ）重合体の合計１００質量部に対し、一般式（１）で表される構成単位を０．０５〜３質量部含有する、＜１＞または＜２＞に記載の感光性樹脂組成物。
＜４＞ （Ｓ）重合体は、全繰り返し単位中における一般式（２）で表される構成単位のモル比率が、全繰り返し単位中における一般式（１）で表される構成単位のモル比率の０．５〜３倍である、＜１＞〜＜３＞のいずれかに記載の感光性樹脂組成物。
＜５＞ （Ｓ）重合体は、全繰り返し単位中における一般式（１）で表される構成単位のモル比率が５〜５０モル％である、＜１＞〜＜４＞のいずれかに記載の感光性樹脂組成物。
＜６＞ （Ｓ）重合体は、一般式（１）におけるＲ¹〜Ｒ⁴が、それぞれ独立に、炭素数１〜５のアルキル基であり、Ｒ⁵が、水素原子または炭素数１〜５のアルキル基である、＜１＞〜＜５＞のいずれかに記載の感光性樹脂組成物。
＜７＞ ＜１＞〜＜６＞のいずれかに記載の感光性樹脂組成物を塗布する工程、塗布された感光性樹脂組成物から溶剤を除去する工程、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、露光された感光性樹脂組成物を現像液により現像する工程、および、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。
＜８＞ 現像する工程後、ポストベーク工程前に、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、＜７＞に記載の硬化膜の製造方法。
＜９＞ ポストベーク工程で熱硬化して得られた硬化膜を有する基板に対し、ドライエッチングを行う工程を含む、＜７＞または＜８＞に記載の硬化膜の製造方法。
＜１０＞ ＜１＞〜＜６＞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、＜７＞〜＜９＞のいずれかに記載の硬化膜の製造方法により形成された硬化膜。
＜１１＞ 層間絶縁膜である、＜１０＞に記載の硬化膜。
＜１２＞ ＜１０＞または＜１１＞に記載の硬化膜を有する、液晶表示装置。
＜１３＞ ＜１０＞または＜１１＞に記載の硬化膜を有する、有機ＥＬ表示装置。
＜１４＞ ＜１０＞または＜１１＞に記載の硬化膜を有する、タッチパネル表示装置。 As a result of investigations by the inventors, the photosensitive resin composition contains a polymer containing a specific unit having a hindered amine structure and a structural unit having a carboxyl group in a specific ratio. I found that the problem could be solved.
Specifically, the above-mentioned problem has been solved by the following solution <1>, preferably <2> to <14>.
<1> (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a-1) a polymer having a structural unit having an acid group protected by an acid-decomposable group, and (a-2) a structural unit having a crosslinkable group,
(2) (a-1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a-2) a polymer having a structural unit having a crosslinkable group,
(B) a photoacid generator,
(C) a solvent, and (S) a polymer having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2),
In the polymer (S), the molar ratio of the structural unit represented by the general formula (2) in all the repeating units of the polymer (S) is the general formula (1) in all the repeating units of the polymer (S). A photosensitive resin composition that is 0.3 to 5 times the molar ratio of the structural unit represented by:

In formulas (1) and (2), R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a methyl group, and L ¹ and L ² each independently represent a single bond or a divalent linking group. R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Or represents a C1-C12 alkoxy group.
<2> The photosensitive resin composition according to <1>, wherein 0.1 to 10 parts by mass of the (S) polymer is contained with respect to 100 parts by mass of the total of the (A) polymer component and the (S) polymer.
<3> 0.05 to 3 parts by mass of the structural unit represented by the general formula (1) with respect to a total of 100 parts by mass of the (A) polymer component and the (S) polymer, <1> or <1. 2>. The photosensitive resin composition as described in 2>.
<4> The (S) polymer is such that the molar ratio of the structural unit represented by the general formula (2) in all repeating units is the molar ratio of the structural unit represented by the general formula (1) in all repeating units. The photosensitive resin composition in any one of <1>-<3> which is 0.5-3 times.
The <5> (S) polymer is described in any one of <1> to <4>, in which the molar ratio of the structural unit represented by the general formula (1) in all repeating units is 5 to 50 mol%. Photosensitive resin composition.
In the <6> (S) polymer, R ^{1 to} R ⁴ in the general formula (1) are each independently an alkyl group having 1 to 5 carbon atoms, and R ⁵ is a hydrogen atom or 1 to 5 carbon atoms. The photosensitive resin composition in any one of <1>-<5> which is the alkyl group of these.
<7> A step of applying the photosensitive resin composition according to any one of <1> to <6>, a step of removing a solvent from the applied photosensitive resin composition, and a photosensitive resin composition from which the solvent has been removed. A method for producing a cured film comprising a step of exposing a product with actinic rays, a step of developing the exposed photosensitive resin composition with a developer, and a post-baking step of thermally curing the developed photosensitive resin composition .
<8> The method for producing a cured film according to <7>, including a step of exposing the entire surface of the developed photosensitive resin composition after the step of developing and before the post-baking step.
<9> The method for producing a cured film according to <7> or <8>, including a step of performing dry etching on a substrate having a cured film obtained by thermal curing in a post-bake process.
<10> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <6> or a cured film production method according to any one of <7> to <9>. Cured film.
<11> The cured film according to <10>, which is an interlayer insulating film.
<12> A liquid crystal display device having the cured film according to <10> or <11>.
<13> An organic EL display device having the cured film according to <10> or <11>.
<14> A touch panel display device having the cured film according to <10> or <11>.

  According to the present invention, a photosensitive resin composition capable of achieving both pattern adhesion and sensitivity during development, a method for producing a cured film using the photosensitive resin composition, a cured film, a liquid crystal display device, An organic EL display device and a touch panel display device can be provided.

It is a figure for demonstrating the measuring method of a contact angle. 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. It is sectional drawing which shows the structural example of an electrostatic capacitance type input device. It is explanatory drawing which shows an example of a front plate. It is explanatory drawing which shows an example of a 1st transparent electrode pattern and a 2nd transparent electrode pattern.

  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 solid content in the present invention is a solid content at 25 ° C.

  In this specification, a weight average molecular weight and a number average molecular weight 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) are, for example, HLC-8220 (manufactured by Tosoh Corporation) and TSKgel Super AWM-H (manufactured by Tosoh Corporation), 6 0.0 mm ID × 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.

  The photosensitive resin composition of the present invention comprises (A) a polymer component, (B) a photoacid generator, (C) a solvent, and (S) a structural unit having a specific hindered amine structure to be described later and a carboxyl group to be described later. The polymer which contains the structural unit which has a predetermined ratio. Since the (S) polymer contains a structural unit having a hindered amine structure and a structural unit having a carboxyl group, the carboxyl group can exist in the vicinity of the hindered amine structure. And since both are included by the predetermined ratio, the outstanding adhesiveness is acquired, without raise | generating the sensitivity fall by a hindered amine structure. Furthermore, since the (S) polymer has a structural unit having a carboxyl group, an improvement in sensitivity can be obtained. For this reason, according to the photosensitive resin composition of the present invention, the sensitivity is good and the pattern adhesion at the time of development is excellent even on a substrate without a hydrophobizing treatment such as HMDS.

  Hereinafter, each component of the photosensitive resin composition of the present invention will be described in more detail.

<(A) Polymer component>
The photosensitive resin composition of this invention contains the (A) polymer component containing the polymer which satisfy | fills at least one of following (1) and (2).
(1) A polymer having (a-1) a structural unit having a group in which an acid group is protected with an acid-decomposable group and (a-2) a structural unit having a crosslinkable group.
(2) (a-1) A polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a-2) a polymer having a structural unit having a crosslinkable group.
Hereinafter, the structural unit (a-1) having a group in which an acid group is protected with an acid-decomposable group is also referred to as a structural unit (a-1). Moreover, the structural unit (a-2) having a crosslinkable group is also referred to as a structural unit (a-2).
The (A) polymer component in this invention may contain other polymers other than the (S) polymer mentioned later.

  The aspect (1) is an aspect including at least one type of polymer, the polymer having the structural unit (a-1) and the structural unit (a-2). Such a polymer may further contain other repeating units. Each of the structural unit (a-1) and the structural unit (a-2) may include two or more types.

In the above aspect (2), the polymer contains at least two types of polymers, at least one of the polymers has the structural unit (a-1), and at least one other type of the polymer has the structural unit (a -2). In the aspect (2), the polymer containing the structural unit (a-1) may further contain the structural unit (a-2) or another structural unit. Similarly, the polymer containing the structural unit (a-2) may contain the structural unit (a-1) or another structural unit. In such a case, the aspect satisfies both (1) and (2).
In the case of the above aspect (2), the mass ratio of the polymer having the structural unit (a-1) and the polymer having the structural unit (a-2) is preferably 95: 5 to 5:95, 80:20 to 20:80 is more preferable, and 70:30 to 30:70 is more preferable.

  The (A) polymer component is preferably an addition polymerization type polymer, 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”.

<< (a-1) Structural Unit Having Acid Group Protected with Acid Decomposable Group >>
(A) The polymer component has at least a structural unit (a-1) having a group in which an acid group is protected with an acid-decomposable group. (A) When a polymer component has a structural unit (a-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 (a-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 (a-1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a-1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group Each will be described in turn.

<<< (a-1-1) Structural Unit Having a Protected Carboxyl Group Protected with an Acid-Decomposable Group >>>
The structural unit (a-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 a carboxyl group which can be used for a structural unit (a-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 (a-1-1-1) Is mentioned.
Hereinafter, the structural unit (a-1-1-1) used as the structural unit having a carboxyl group will be described.

<<<<< (a-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 these, from the viewpoint of developability, in order to form the structural unit (a-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 unsaturated polyvalent carboxylic acid. Acrylic acid, methacrylic acid, 2- (meta It is more preferable to use acryloyloxyethyl hexahydrophthalic acid.
The structural unit (a-1-1-1) may be composed of one kind alone, or may be composed of two or more kinds.

<<<< acid-decomposable group that can be used for the structural unit (a-1-1) >>>>
As the acid-decomposable group that can be used for the structural unit (a-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 represent a hydrogen atom or an alkyl group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms. 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.

  A first preferred embodiment of the structural unit (a-1-1) is a structural unit represented by the following general formula (A2 ′).

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。

In 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 combine to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group Represents.

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.

  A second preferred embodiment of the structural unit (a-1-1) is a structural unit represented by the following general formula (1-12).

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。 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 a carbon atom. The alkyl group of number 1-4 is represented.

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 (a-1-1) include the following structural units. In the structural units below, R represents a hydrogen atom or a methyl group.

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

<<<< (a-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 linear or branched group having 1 to 5 carbon atoms. A chain alkyl group is represented, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less. In addition, when two or more ^R222 exists, these ^R222 may mutually differ or may be 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 (a-1-2) >>>>
As the acid-decomposable group that can be used for the structural unit (a-1-2), as in the case of the acid-decomposable group that can be used for the structural unit (a-1-1), known acid-decomposable groups can be used. 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 a structural unit (a-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 (a-1-2) include the following structural units, but the present invention is not limited thereto.

<<< Preferred Aspect of Structural Unit (a-1) >>>
When the polymer containing the structural unit (a-1) does not substantially contain the structural unit (a-2), the content of the structural unit (a-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 (a-1) contains the structural unit (a-2), the content of the single structural unit (a-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 (a-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 preferable.

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

<< (a-2) Structural Unit Having Crosslinkable Group >>
(A) The polymer component has a structural unit (a-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. It is preferably at least one selected from the group represented by an epoxy group, an oxetanyl group, and —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Among them, in the photosensitive resin composition of the present invention, it is preferable that the (A) polymer component includes a structural unit including at least one of an epoxy group and an oxetanyl group. In more detail, the following are mentioned.

<< (a-2-1) Structural Unit Having Epoxy Group and / or Oxetanyl Group >>
The (A) polymer component preferably contains a structural unit having an epoxy group and / or an oxetanyl group (hereinafter also referred to as a structural unit (a-2-1)).
The structural unit (a-2-1) only needs to 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 to form the structural unit (a-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 (a-2-1) include the following structural units. In the structural units below, R represents a hydrogen atom or a methyl group.

<<< (a-2-2) Structural unit having an ethylenically unsaturated group >>>
As one of the structural units (a-2) having a crosslinkable group, there may be mentioned a structural unit (a-2-2) having an ethylenically unsaturated group. As the structural unit (a-2-2), a structural unit having an ethylenically unsaturated group in the side chain is preferable, and a structural unit having an ethylenically unsaturated group at the terminal and having a side chain having 3 to 16 carbon atoms. Is more preferable.
In addition, as the structural unit (a-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.

<<< a structural unit having a group represented by (a-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) used in the present invention is a structural unit having a group represented by —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) (a-2- 3) is also preferable. By having the structural unit (a-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 (a-2-3) is more preferably a structural unit having a group represented by the following general formula (a2-30).

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。 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 iso-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, an iso-butyl group, an n-butyl group, and a methyl group are preferable.

<<< Preferred Aspect of Structural Unit Having (a-2) Crosslinkable Group >>>
When the polymer containing the structural unit (a-2) is substantially free of the structural unit (a-1), the content of the structural unit (a-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 (a-2) contains the structural unit (a-1), the content of the structural unit (a-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 (a-2) is preferably 3 to 70 mol% in all the structural units of the polymer component (A) regardless of any embodiment. More preferably, it is mol%.
By setting it within the above numerical range, a cured film having excellent characteristics can be formed.

<< (a-3) Other structural units >>
In the present invention, the (A) polymer component has, in addition to the structural unit (a-1) and / or the structural unit (a-2), another structural unit (a-3) other than these. Also good. The structural unit (a-3) includes a polymer having the structural unit (a-1) and the structural unit (a-2), a polymer having the structural unit (a-1), and the structural unit (a-2). At least one of the polymers having may be included. Separately from the polymer having the structural unit (a-1) and the structural unit (a-2), the polymer having the structural unit (a-1), and the polymer having the structural unit (a-2). In addition, a polymer having other structural unit (a-3) may be included without substantially including the structural unit (a-1) and the structural unit (a-2).

  There is no restriction | limiting in particular as a monomer used as another structural unit (a-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 (a-3) can be used individually or in combination of 2 or more types.

  Specifically, the structural unit (a-3) is styrene, methyl styrene, hydroxy styrene, α-methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, 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 monoa It can be mentioned a structural unit due preparative 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 styrene and an aliphatic cyclic skeleton as another structural unit (a-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 (a-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 (a-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 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 structural unit (a-1) and / or (a-2), or (a-1) the structural unit and ( a-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 (A) polymer component of this invention is given to the following, this invention is not limited to these.
(First embodiment)
In the above aspect (1), the polymer having the structural unit (a-1) and the structural unit (a-2) further has one or more other structural units (a-3). Aspect.
(Second Embodiment)
In the aspect of (2) described above, the polymer having the structural unit (a-1) further has one or more other structural units (a-3).
(Third embodiment)
In the above-described aspect (2), the polymer having the structural unit (a-2) further has one or more other structural units (a-3).
(Fourth embodiment)
In any one of the first to third embodiments, the other structural unit (a-3) includes a structural unit containing at least an acid group.
(Fifth embodiment)
In the above aspect (1) and / or (2), the polymer having the structural unit (a-1) and the structural unit (a-2), the polymer having the structural unit (a-1), and the structure In addition to the polymer having the unit (a-2), the polymer having the other structural unit (a-3) substantially not including the structural unit (a-1) and the structural unit (a-2). 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 (a-3) substantially not including the structural unit (a-1) and the structural unit (a-2), the structural unit (a-1) and / or Or the total amount of the polymer having the structural unit (a-2) and the other structural unit (a-3) substantially not including the structural unit (a-1) and the structural unit (a-2). The mass ratio with the total amount of the polymer is preferably 99: 1 to 5:95, more preferably 97: 3 to 30:70, and still more preferably 95: 5 to 50:50.
The photosensitive resin composition of the present invention preferably contains (A) the polymer component in a proportion of 70% by mass or more, and more preferably 70 to 90% by mass, based on the solid content of the photosensitive resin composition.

<< (A) Molecular Weight of Polymer Component >>
(A) The molecular weight of the polymer contained in the polymer component is a polystyrene-reduced 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) The weight average molecular weight and dispersion degree of the polymer contained in 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) Production Method of Polymer Component >>
(A) Although various methods are known as a manufacturing method of a polymer component, when an example is given, it uses in order to form the structural unit represented by (a-1) and (a-3) at least. It can synthesize | combine by superposing | polymerizing the radically polymerizable monomer mixture containing the radically polymerizable monomer obtained using a radical polymerization initiator in an organic solvent. It can also be synthesized by a so-called polymer reaction.
The polymer component (A) preferably contains 50 mol% or more, more preferably 80 mol% or more of the structural unit derived from (meth) acrylic acid and / or its ester with respect to all the structural units. preferable.

<(B) Photoacid generator>
The photosensitive resin composition of the present invention contains (B) a photoacid generator. The photoacid generator is preferably a compound that reacts with an actinic ray 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 a pKa of 2 or less. Photoacid generators that generate acids are most preferred. In addition, pKa of this invention points out pKa in water of 25 degreeC fundamentally. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement. Specifically, the pKa described in the chemical handbook can be referred to. The acid having a pKa of 3 or less is preferably sulfonic acid or phosphonic acid, and more preferably sulfonic acid.

  Examples of photoacid generators include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. . Among these, an imide sulfonate compound and an oxime sulfonate compound are preferable from the viewpoint of insulating properties. A photo-acid generator can be used individually by 1 type or in combination of 2 or more types. 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 and the compounds described in paragraph numbers 0013 to 0049 of JP 2011-105645 A can be exemplified, and the contents thereof are incorporated in the present specification. Specific examples of the imide sulfonate compound include compounds described in paragraph numbers 0065 to 0075 of WO2011 / 087011, and the contents thereof are incorporated in the present specification.

  Examples of the onium salt compound include diphenyl iodonium salt, triarylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, and the like.

  Examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium. Butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarsenate Bis (4-t-butylphenyl) iodonium trifluorome Sulphonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonic acid, etc. .

  Examples of the triarylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium. And butyl tris (2,6-difluorophenyl) borate. Specifically, the following compounds are exemplified.

  Examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts and the like.

  Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate and the like can be mentioned.

  Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenyl. Methylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenyl Examples include methylsulfonium hexafluorophosphate.

  Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, and dibenzyl-4-methoxyphenylsulfonium. Hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl- Examples include 4-hydroxyphenylsulfonium hexafluorophosphate.

  Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethyl. Sulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3- Examples include chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3- (p-methoxybenzyl). ) Benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

  Examples of tetrahydrothiophenium salts include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethane. Sulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1 , 2,2-Tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo) [2.2.1] Heptan-2-yl) -1,1, , 2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl ) -1,1,2,2-tetrafluoroethanesulfonate and the like.

Examples of the imidosulfonate compound include compounds represented by general formula (ZV).

In General Formula (ZV), R ²⁰⁸ represents an alkyl group or an aryl group. A represents an alkylene group, an alkenylene group or an arylene group. When the alkyl group is a cyclic alkyl group, a ring may be formed via a carbonyl group.
The alkyl group for R ²⁰⁸ is preferably a linear alkyl group or a cyclic alkyl group. R ²⁰⁸ is preferably a linear or branched alkyl group or an aryl group. These groups may be substituted or unsubstituted. When the alkyl group is a cyclic alkyl group, a ring may be formed via a carbonyl group, and the cyclic alkyl group may be polycyclic. Preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group or pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group). Or a norbornyl group). The alkyl group for R ²⁰⁸ may be further substituted with, for example, a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, and / or a nitro group.

The aryl group for R ²⁰⁸ is preferably a phenyl group or a naphthyl group.
The aryl group for R ²⁰⁸ may be further substituted with, for example, a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, and / or a nitro group, but preferably has 1 to 10 carbon atoms. A linear or branched alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (a cyclopentyl group, a cyclohexyl group or a norbornyl group). Can be mentioned.

  The alkylene group of A is an alkylene group having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 carbon atoms. ˜12 alkenylene groups (for example, ethenylene group, propenylene group, butenylene group, etc.), and as the arylene group of A, C 6-10 arylene groups (for example, phenylene group, tolylene group, naphthylene group, etc.) Each can be mentioned.

The imide sulfonate compound preferably has the following structure.

  R each independently represents a hydrogen atom and an organic group composed of a carbon atom and / or an oxygen atom (other than C, H, and O). Two or more Rs may be bonded to each other to form a ring. The total number of carbon atoms and oxygen atoms in each R is 16 or less.

  Although the example of an imide sulfonate compound is given to the following, this invention is not limited to these. In the following formulae, Me represents a methyl group, Et represents an ethyl group, t-Bu represents a tert-butyl group, and Ph represents a phenyl group.

  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).

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。 General formula (B1-1)

In General Formula (B1-1), R ²¹ represents an alkyl group or an aryl group. Wavy lines represent bonds with other groups.

In general formula (B1-1), any group may be substituted, and the alkyl group in 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.

  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).

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。 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 an integer of 0 to 3. And when m4 is 2 or 3, the plurality of X 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.

  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).

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。 General formula (B1-3)

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

上記一般式（ＯＳ−１）中、Ｒ¹⁰¹は、水素原子、アルキル基、アルケニル基、アルコキシ基、アルコキシカルボニル基、アシル基、カルバモイル基、スルファモイル基、スルホ基、シアノ基、アリール基、または、ヘテロアリール基を表す。Ｒ¹⁰²は、アルキル基、または、アリール基を表す。

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.

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.

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。

In 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 are 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 Represent.

  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.

  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).

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。 General formula (B1-4)

In General Formula (B1-4), R ¹ represents an alkyl group or an aryl group, and R ² represents an alkyl group, an aryl group, or a heteroaryl group. R ^{3 to} R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. However, 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. X represents -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.

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

<(C) Solvent>
The photosensitive resin composition of the present invention contains (C) 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 the solvent, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
In the present invention, a known solvent can be used as the solvent. For example, 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 (for example, Diethylene glycol diethyl ether), diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, etc. it can. 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.
Also, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2 -Alcohols, such as methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol, cyclohexanol, etc. can also be used.

  A solvent can be used individually by 1 type or in mixture of 2 or more types. It is more preferable to use two kinds of solvents together, and propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetates are used in combination. Is more preferable.

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.

  It is preferable that content of the solvent in the photosensitive resin composition of this invention is 50-95 mass parts with respect to 100 mass parts of all the components in the photosensitive resin composition, and it is 60-90 mass parts. Further preferred. 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) Polymer>
The (S) polymer is a polymer having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2).

式（１）、（２）中、Ｒ¹⁰およびＲ¹¹は、それぞれ独立に、水素原子またはメチル基を表し、Ｌ¹およびＬ²は、それぞれ独立に、単結合、または、２価の連結基を表し、Ｒ¹〜Ｒ⁴は、それぞれ独立に、炭素数１〜１２のアルキル基または炭素数１〜１２のアルコキシ基を表し、Ｒ⁵は、水素原子、炭素数１〜１２のアルキル基または炭素数１〜１２のアルコキシ基を表す。

In formulas (1) and (2), R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a methyl group, and L ¹ and L ² each independently represent a single bond or a divalent linking group. R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or An alkoxy group having 1 to 12 carbon atoms is represented.

R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. These groups may have a substituent, but preferably have no substituent. These groups may be linear, branched or cyclic, but are preferably linear.
The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
The alkoxy group is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms.
R ^{1 to} R ⁴ are particularly preferably a methyl group.

R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. These groups may have a substituent, but preferably have no substituent. These groups may be linear, branched or cyclic, but are preferably linear.
The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
The alkoxy group is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms.
R ⁵ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, still more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Or a methyl group is particularly preferable.

L ¹ and L ² each independently represents a single bond or a divalent linking group.
Examples of the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, -O-, and -NR '-(R' may have a hydrogen atom or a substituent. Represents a good alkyl group or an aryl group which may have a substituent, and is preferably a hydrogen atom), a structure represented by —SO ₂ —, —CO—, —COO—, and —S—. Examples include groups containing at least one.
The alkylene group and arylene group may have a substituent or may be unsubstituted. Examples of the substituent include hydrocarbon groups (aliphatic hydrocarbon groups and aromatic hydrocarbon groups). Specific examples include an alkyl group having 1 to 30 carbon atoms and an alkenyl group having 1 to 30 carbon atoms. When the alkylene group or arylene group has two or more substituents, the substituents may be connected to form a ring.
L ¹ and L ² are preferably groups obtained by combining the above divalent linking groups or the above divalent linking groups.
L ¹ is preferably a divalent linking group containing at least one selected from an alkylene group having 1 to 30 carbon atoms, —COO—, —NH—, —CO— and —CONH—.
L ² is preferably a single bond or a divalent linking group containing at least one selected from an alkylene group having 1 to 30 carbon atoms, —COO—, —CO—, —NH— or —CONH—.

  Examples of the structural unit represented by the general formula (1) include the following.

  Examples of the structural unit represented by the general formula (2) include the following.

  In the polymer (S), the molar ratio of the structural unit represented by the general formula (2) in all the repeating units of the polymer (S) is the general formula (1) in all the repeating units of the polymer (S). Is 0.3 to 5 times the molar ratio of the structural unit represented by the formula, preferably 0.5 to 3 times, and more preferably 0.7 to 3 times. If it is the said range, development adhesiveness and a sensitivity can be made compatible.

  In the (S) polymer, the molar ratio of the structural unit represented by the general formula (1) in all repeating units is preferably 5 to 50 mol%, and more preferably 10 to 40 mol%. According to this, excellent development adhesion can be obtained.

  In the (S) polymer, the molar ratio of the structural unit represented by the general formula (2) in all repeating units is preferably 10 to 70 mol%, and more preferably 10 to 65 mol%. According to this, excellent sensitivity can be obtained.

The (S) polymer includes a structural unit other than the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) (hereinafter also referred to as other structural units). Also good.
Other structural units include (a-1) a structural unit having a group in which an acid group is protected with an acid-decomposable group, and (a-2) a crosslinkable group, as described in the above (A) polymer component. Structural units, (a-3) other structural units, and the like.
For example, styrene, methyl styrene, hydroxy styrene, α-methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chloro styrene, methyl vinyl benzoate, ethyl vinyl benzoate, 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, (meth) 2-hydroxypropyl acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acryloylmorpholine, N-cyclohexylmaleimide, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) Mention may be made of a structural unit due to acrylate.
(S) The polymer may not contain other structural units, but when it contains other structural units, the molar ratio of the other structural units in all repeating units may be 70 mol% or less. Preferably, it is 60 mol%.

  (S) The weight average molecular weight of the polymer is preferably 5000 to 50000, more preferably 8000 to 30000.

  Examples of the (S) polymer include the following. The numerical value written together with the main chain repeating unit) represents the molar content (mol%) of each structural unit.

The photosensitive resin composition of the present invention preferably contains 0.1 to 10 parts by mass of the (S) polymer with respect to 100 parts by mass in total of the (A) polymer component and the (S) polymer. It is more preferable to contain 5-10 mass parts.
The photosensitive resin composition of this invention contains 0.05-3 mass parts of structural units represented by General formula (1) with respect to a total of 100 mass parts of (A) polymer component and (S) polymer. It is preferable to contain, 0.1 to 3 parts by mass is more preferable, and 0.5 to 3 parts by mass is particularly preferable.
The photosensitive resin composition of the present invention preferably contains the (S) polymer in a proportion of 0.1 to 15% by mass, more preferably 0.5 to 10% by mass of the solid content of the photosensitive resin composition. .
(S) Only one type of polymer 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 addition to the above components, a silane coupling agent, a sensitizer, a crosslinking agent, a basic compound, 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.

<Silane coupling agent>
The photosensitive resin composition of the present invention may contain a silane coupling agent. The silane coupling agent in the present invention refers to a compound containing a silicon atom and having at least two different reactive groups. One type of reactive group contained in the silane coupling agent is preferably a hydrolyzable group, and more preferably an alkoxy group. Examples of other reactive groups contained in the silane coupling agent include vinyl groups, epoxy groups, styryl groups, (meth) acryloyloxy groups, amino groups, ureido groups, mercapto groups, sulfide groups, and isocyanate groups. .

The content of the silane coupling agent is preferably 0.001 to 15 parts by mass and more preferably 0.005 to 10 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. preferable.
Only one type of silane coupling agent 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.

  As a silane coupling agent, what is represented by the following general formula (SC1) is preferable.

一般式（ＳＣ１）中、Ｒ¹およびＲ²は、それぞれ独立してアルキル基またはアリール基を表し、ｎは０〜２の整数を表し、Ｌ¹は単結合または２価の連結基を表し、Ａ¹は、官能基を表す。 General formula (SC1)

In general formula (SC1), R ¹ and R ² each independently represents an alkyl group or an aryl group, n represents an integer of 0 to 2, L ¹ represents a single bond or a divalent linking group, A ¹ represents a functional group.

R ¹ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms. 1-10 are preferable, as for carbon number of an alkyl group, 1-5 are more preferable, and 1-3 are more preferable. 6-12 are preferable and, as for carbon number of an aryl group, 6 is more preferable.
R ² is preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
n represents an integer of 0 to 2, and 0 or 1 is preferable.
When L ¹ represents a divalent linking group, a group consisting of — (CH ₂ ) _n1 — or a combination of — (CH ₂ ) _n1 — and —O— is preferable. Here, n1 is preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3. A ¹ is vinyl group, epoxy group, styryl group, methacryloxy group, acryloxy group, amino group, ureido group, mercapto. At least one functional group selected from a group, a sulfide group and an isocyanate group is preferred, and an epoxy group, a methacryloxy group or an acryloxy group is more preferred.

  Examples of the silane coupling agent include vinyl silane, epoxy silane, styryl silane, methacryloxy silane, acryloxy silane, amino silane, ureido silane, chloropropyl silane, mercapto silane, polyfluoride silane, isocyanate silane, and the like.

  Specific examples of the silane coupling agent include, for example, 3-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ -Glycidoxypropyl dialkoxysilane, γ-methacryloxypropyl trialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4- Epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane, 3-acryloxypropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide and the like.

  50-500 are preferable and, as for the weight average molecular weight of a silane coupling agent, 100-300 are more preferable.

  As the silane coupling agent, a structural unit having a partial structure represented by the following general formula (SC2), a vinyl group, an epoxy group, a styryl group, a (meth) acryloyloxy group, an amino group, a ureido group, a mercapto group, What contains the polymer containing the structural unit which has at least 1 type of group (X) chosen from the group which consists of a sulfide group and an isocyanate group can also be used. This polymer has a plurality of each of the respective structural units, and it is usually preferable that each polymer has 5 or more.

一般式（ＳＣ２）中、Ｒ¹およびＲ²はそれぞれ独立に炭素数１〜４のアルキル基を表し、ｎは０〜２の整数を表す。 General formula (SC2)

In General Formula (SC2), R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 2.

In the general formula (SC2), R ¹ and R ² each independently represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. is there. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tert-butyl group. R ¹ and R ² preferably represent the same group.
n represents an integer of 0 to 2, an integer of 0 or 1 is preferable, and 0 is more preferable.

  The structural unit having a partial structure represented by the general formula (SC2) is preferably represented by the following general formula (I).

一般式（Ｉ）中、Ｒ¹およびＲ²はそれぞれ独立に炭素数１〜４のアルキル基を表し、ｎは０〜２の整数を表す。Ｒ³は水素原子またはメチル基を表す。Ｌ¹は単結合、または連結部の原子数が１〜６の連結基を表す。 Formula (I)

In the general formula (I), R ¹ and R ² represents an alkyl group having 1 to 4 carbon atoms each independently, n is an integer of 0 to 2. R ³ represents a hydrogen atom or a methyl group. L ¹ represents a single bond or a linking group having 1 to 6 atoms in the linking part.

R ¹ and R ² in the general formula (I) has the same meaning as R ¹ and R ² in the general formula (SC2), and preferred ranges are also the same.
N in general formula (I) is synonymous with n in general formula (SC2), and its preferable range is also the same.
R ³ represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.
L ¹ represents a single bond or a linking group having 1 to 6 atoms in the linking part, preferably a divalent linking group having 2 to 6 atoms in the linking part, and 3 to 6 atoms in the linking part. The divalent linking group is more preferable.

Here, the number of atoms in the linking portion refers to the number of chains connecting the carbon atoms and silicon atoms constituting the main chain in the general formula (I). The number of atoms that make up the chain. Specifically, as represented by the following formula (A), when L ¹ is a propylene group, the chain connecting the main chain and the silicon atom is three carbon atoms, so the number of atoms of the connecting portion is 3. In addition, when L ¹ is a cyclohexylene group as represented by the following formula (B), there are three cases and five cases where the main chain and the silicon atom are connected to each other. The number of atoms in the connecting portion is 3. Even when the main chain in L ¹ has a carbonyl group as represented by the following formula (C), the number of atoms in the linking portion is 3.

Specific examples of the linking group having 1 to 6 atoms in the linking portion represented by L ¹ include alkylene groups having 1 to 6 carbon atoms (for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group). Cyclohexylene group), an arylene group having 6 to 10 carbon atoms (for example, a phenylene group or a naphthylene group), and the like. Among these, an alkylene group having 1 to 6 carbon atoms is preferable.

The group (X) is synonymous with A ¹ in the general formula (SC1), and is preferably selected from the group consisting of an epoxy group, a mercapto group, and a (meth) acryloyl group. More preferably, it is a mercapto group. The groups (X) may be different from each other, but the groups (X) are preferably the same.

  The structural unit having at least one group (X) is preferably represented by the following general formula (II).

一般式（ＩＩ）中、Ｒ⁴はそれぞれ独立に水素原子またはメチル基を表す。Ｌ²は単結合、または連結部の原子数が１〜６の連結基を表す。Ｒ⁵は、エポキシ基、メルカプト基、（メタ）アクリロイル基、ビニル基、またはアミノ基を表す。 Formula (II)

In general formula (II), each R ⁴ independently represents a hydrogen atom or a methyl group. L ² represents a single bond or a linking group having 1 to 6 atoms in the linking part. R ⁵ represents an epoxy group, a mercapto group, a (meth) acryloyl group, a vinyl group, or an amino group.

R ⁴ represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.
R ⁵ has the same meaning as A ¹ in formula (SC1), and is preferably an epoxy group, a mercapto group, or a (meth) acryloyl group, and more preferably an epoxy group or a mercapto group.
L ² has the same meaning as L ¹ in formula (I), and the preferred range is also the same.

  The silane coupling agent preferably includes a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), and the structural unit represented by the general formula (I) and the general formula ( It is preferable that the structural unit represented by II) occupies 60 mol% or more of all the structural units of the polymer, and more preferably 80 mol% or more.

  A structural unit having a partial structure represented by the general formula (SC2) (preferably a structural unit represented by the general formula (I)) and a structural unit having at least one group (X) (preferably the general formula (II) 15 to 85:85 to 15 is preferable, and 25 to 75:75 to 25 is more preferable.

  Illustrative compounds are shown below, but it goes without saying that the present invention is not limited thereto. Me represents a methyl group, and Et represents an ethyl group.

  As the polymer type silane coupling agent, commercially available products may be used. For example, X-12-981S, X-12-984S, X-12-1154, X-12-1048, X-12-972F ( Both are manufactured by Shin-Etsu Silicone Co., Ltd.).

<< Sensitizer >>
The photosensitive resin composition of the present invention may contain a sensitizer. 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. For this reason, decomposition | disassembly of a photo-acid generator can be accelerated | stimulated by containing a sensitizer. 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 preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 20 parts by mass. Two or more sensitizers can be used in combination. When two or more sensitizers are used in combination, the total amount is preferably within the above range.

<< Crosslinking agent >>
The photosensitive resin composition of the present invention may contain a crosslinking agent. By containing a crosslinking agent, a harder cured film can be obtained.
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.

<<< 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, MFA-100, E402-B80B, SBN-70D, SBB-70P , K6000 (above, manufactured by Asahi Kasei Chemicals Corporation) Modules BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumijour BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) and the like are preferable Can be used.

  When the photosensitive resin composition of the present invention has a crosslinking agent, the addition amount of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass in total of the polymer component (A), It is more preferable that it is 0.1-30 mass parts, and it is further more preferable that 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.

<< 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 following compounds can also be used.

  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.

<< 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 photosensitive resin composition of the present invention include those described in paragraph numbers 0201 to 0205 of JP2012-88459A, and paragraph number 0185 of JP2011-215580A. The ones described in 0188 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.), MegaFuck (manufactured by DIC Corporation), F-554 (manufactured by DIC Corporation), Florard Novec FC-4430 (Sumitomo) 3M Co.), Surflon S-242 (AGC Seimi Chemical Co., Ltd.), PolyFox PF-6320 (OMNOVA Co., Ltd.), SH-8400 (Toray Dow Corning Silicone Co., Ltd.), Footgent FTX-218G (Neos Co., Ltd.), etc. Can be mentioned.
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 a hydrogen atom. Alternatively, it represents 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%. 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 formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. And an alkyl group having 2 or 3 carbon atoms is more preferred. 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.

Surfactant 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 the present invention has a development accelerator, the addition amount of the development accelerator is 0 to 100 parts by mass of the total solid content of the photosensitive resin composition from the viewpoints of sensitivity and residual film ratio. 30 mass parts is preferable, 0.1-20 mass parts is more preferable, and it is most preferable that it is 0.5-10 mass parts.
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.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition of the present invention can be prepared by mixing each component at a predetermined ratio and by any method, stirring and dissolving. For example, the photosensitive resin composition of the present invention can also be prepared by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent. 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.

<Method for producing cured film>
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of apply | coating the photosensitive resin composition of this invention on a board | substrate (application | coating process)
(2) Step of removing the solvent from the applied photosensitive resin composition (solvent removal step)
(3) Step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays (exposure step)
(4) Step of developing the exposed photosensitive resin composition with a developer (exposure step)
(5) Step of thermosetting the developed photosensitive resin composition (post-baking step)
Each step will be described below in order.

In the application step (1), the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent.
In the application step, the photosensitive resin composition of the present invention may be applied on a substrate having a contact angle of 15 ° or less when water is dropped, that is, a highly hydrophilic substrate, or when water is dropped. The photosensitive resin composition of the present invention may be applied to a substrate having a contact angle of more than 15 °, that is, a substrate that is not so hydrophilic.
In the present invention, even on a substrate having a contact angle of 15 ° or less when water is dropped, for example, a substrate that has not been subjected to a hydrophobic treatment such as HMDS, development is performed by using the photosensitive resin composition of the present invention. The pattern adhesion at the time is good.
The contact angle in the present invention can employ the θ / 2 method. That is, as shown in FIG. 1, when it is assumed that the shape of the water droplet dropped onto the substrate is a part of a sphere, the angle θ with respect to the solid surface of the tangent line a from the left and right end points of the water droplet, and the radius r of the sphere The contact angle can be obtained by obtaining the height h and substituting it into the following equation. In the θ / 2 method, the angle θ ₁ of the straight line connecting the left and right end points of the water droplet and the apex b with respect to the substrate surface is obtained, and the contact angle can also be obtained by doubling this.

  The contact angle of the substrate with respect to water can be measured according to JIS R3257 using a contact angle measuring device such as DM-500 (manufactured by Kyowa Interface Science).

In the application step (1), before applying the photosensitive resin composition to the substrate, the substrate may be cleaned by alkali cleaning or plasma cleaning. Moreover, you may process the board | substrate surface with HMDS with respect to the board | substrate after washing | cleaning. The method of treating the substrate surface with HMDS is not particularly limited, and examples thereof include a method of exposing the substrate to HMDS 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 method for applying the photosensitive resin composition to 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 may be used. it can.
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 the photosensitive resin composition is 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.
Before applying the photosensitive resin composition of 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 removing step (2), the solvent is removed from the wet film formed by applying the photosensitive resin composition by vacuum (vacuum) and / or heating to form a dry 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), the substrate provided with the dry 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 addition, exposure using a so-called super-resolution technique can be performed. Examples of the super-resolution technique include multiple exposure in which exposure is performed a plurality of times, a method using a phase shift mask, and an annular illumination method. By using these super-resolution techniques, it is possible to form a higher definition pattern, which is preferable.
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, if the acid-decomposable group has a low activation energy for acid decomposition and is easily decomposed by an acid derived from a photoacid generator by exposure to easily generate a carboxyl group or a phenolic hydroxyl group, PEB is necessarily performed. There is no.

In the developing step (4), a copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using a developer. A positive image is formed by removing an exposed area having a carboxyl group and / or a phenolic hydroxyl group that is easily dissolved in the 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 Alkyl amines such as dimethyl alcohol; alcohol amines such as dimethyl ethanol amine and triethanol amine; 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), the obtained positive image is heated to thermally decompose the acid-decomposable group to form 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.

<Curing film>
The cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition of the present invention. 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 this invention mentioned above.
The cured film of the present invention can be suitably used as an interlayer insulating film.
The photosensitive resin composition of the present invention can provide an interlayer insulating film having high transparency even when baked at a high temperature. The interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and is useful for applications such as a liquid crystal display device, an organic EL display device, and a touch panel display device.

<Liquid crystal display device>
The liquid crystal display device of the present invention has 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 planarizing film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal display devices having various structures. 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. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel is disposed on all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. Corresponding TFT 16 elements 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.
Further, even in a static drive type liquid crystal display device, a pattern with high designability can be displayed 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 has 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 organic materials having various structures. An EL display device and a liquid crystal display device can be given.
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. 3 is 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.
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. be able to.
Further, although not shown in FIG. 3, 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 has good sensitivity and excellent pattern adhesion at the time of development, a resist pattern formed using the photosensitive resin composition of the present invention is used as a partition as a structural member of a MEMS device. Or used as part of a mechanical drive component. 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.

<Touch panel display device>
The touch panel display device of the present invention includes a capacitive input device having the cured film of the present invention. Moreover, the capacitance-type input device has the cured film of the present invention. That is, the touch panel display device of the present invention has the cured film of the present invention.
The capacitive input device has at least the following elements (1) to (5) on the front plate and the non-contact side of the front plate, and the insulating layer of (4) is the photosensitive resin composition of the present invention. It is preferable that it is a cured film using.
(1) Mask layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) First transparent electrode pattern and electrical And a plurality of second transparent electrode patterns comprising a plurality of pad portions formed extending in a direction crossing the first direction. (4) First transparent electrode pattern and second transparent electrode pattern (5) The first transparent electrode pattern and the second transparent electrode pattern are electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern. Another conductive element In the capacitive input device of the present invention, it is preferable that a transparent protective layer is further provided so as to cover all or a part of the elements (1) to (5). The cured film of the present invention is more preferable. Arbitrariness.

  First, the configuration of the capacitive input device will be described. FIG. 4 is a cross-sectional view illustrating a configuration example of the capacitive input device. In FIG. 4, the capacitive input device 30 includes a front plate 31, a mask layer 32, a first transparent electrode pattern 33, a second transparent electrode pattern 34, an insulating layer 35, and a conductive element 36. And a transparent protective layer 37.

  The front plate 31 is made of a light-transmitting substrate such as a glass substrate, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used. Moreover, in FIG. 4, the side in which each element of the front plate 31 is provided is called a non-contact surface. In the capacitive input device 30, input is performed by bringing a finger or the like into contact with the contact surface of the front plate 31 (the surface opposite to the non-contact surface). Hereinafter, the front plate may be referred to as a “base material”.

A mask layer 32 is provided on the non-contact surface of the front plate 31. The mask layer 32 is a frame-like pattern around the display area formed on the non-contact side of the touch panel front plate, and is formed so as not to show the lead wiring and the like.
As shown in FIG. 5, the electrostatic capacitance type input device is provided with a mask layer 32 so as to cover a part of the front plate 31 (a region other than the input surface in FIG. 5). Further, the front plate 31 can be provided with an opening 38 in part as shown in FIG. A mechanical switch by pressing can be installed in the opening 38.

As shown in FIG. 6, on the contact surface of the front plate 31, a plurality of first transparent electrode patterns 33 formed with a plurality of pad portions extending in the first direction via the connection portions, A plurality of second transparent electrode patterns 34 each including a plurality of pad portions that are electrically insulated from one transparent electrode pattern 33 and extend in a direction crossing the first direction; An insulating layer 35 that electrically insulates the electrode pattern 33 and the second transparent electrode pattern 34 is formed. The first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 to be described later are, for example, translucent conductive materials such as ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide). It can be made of a metal oxide film. Examples of such metal films include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO ₂ . At this time, the film thickness of each element can be 10 to 200 nm. Further, since the amorphous ITO film is made into a polycrystalline ITO film by firing, the electrical resistance can be reduced. Moreover, the 1st transparent electrode pattern 33, the 2nd transparent electrode pattern 34, and the electroconductive element 36 mentioned later are manufactured using the photosensitive transfer material which has the photosensitive resin composition using a conductive fiber. You can also In addition, when the first conductive pattern or the like is formed by ITO or the like, paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to, and the contents thereof are incorporated in this specification.

  Further, at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 extends over both the non-contact surface of the front plate 31 and the region opposite to the front plate 31 of the mask layer 32. Can be installed. In FIG. 4, a diagram is shown in which the second transparent electrode pattern is installed across both areas of the non-contact surface of the front plate 31 and the surface of the mask layer 32 opposite to the front plate 31. Yes.

  The first transparent electrode pattern 33 and the second transparent electrode pattern 34 will be described with reference to FIG. FIG. 6 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern. As shown in FIG. 6, the first transparent electrode pattern 33 is formed such that the pad portion 33a extends in the first direction via the connection portion 33b. The second transparent electrode pattern 34 is electrically insulated by the first transparent electrode pattern 33 and the insulating layer 35, and extends in a direction intersecting the first direction (second direction in FIG. 6). It is constituted by a plurality of pad portions that are formed. Here, when the first transparent electrode pattern 33 is formed, the pad portion 33a and the connection portion 33b may be manufactured integrally, or only the connection portion 33b is manufactured, and the pad portion 33a and the second transparent electrode pattern 33 are formed. The electrode pattern 34 may be integrally formed (patterned). When the pad portion 33a and the second transparent electrode pattern 34 are integrally formed (patterned), as shown in FIG. 6, a part of the connection part 33b and a part of the pad part 33a are connected and an insulating layer is formed. Each layer is formed so that the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by 35.

  In FIG. 4, a conductive element 36 is provided on the side of the mask layer 32 opposite to the front plate 31. The conductive element 36 is electrically connected to at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34, and is different from the first transparent electrode pattern 33 and the second transparent electrode pattern 34. Is another element. In FIG. 4, a view in which the conductive element 36 is connected to the second transparent electrode pattern 34 is shown.

  Moreover, in FIG. 4, the transparent protective layer 37 is installed so that all of each component may be covered. The transparent protective layer 37 may be configured to cover only a part of each component. The insulating layer 35 and the transparent protective layer 37 may be made of the same material or different materials.

  Capacitance type input device and touch panel display device comprising capacitance type input device as constituent elements are “latest touch panel technology” (Techno Times, issued July 6, 2009), supervised by Yuji Mitani, The configurations disclosed in “Technology and Development”, CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. can be applied.

<Touch panel and manufacturing method thereof>
In the touch panel of the present invention, it is preferable that all or part of the insulating layer is composed of a cured film of the photosensitive resin composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an ITO electrode, and an insulating layer at least. Preferred examples of the transparent substrate include a glass substrate, a quartz substrate, a transparent resin substrate, and the like.
The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention.

The touch panel of the present invention can be manufactured, for example, as follows.
That is, the photosensitive resin composition of the present invention is applied by various methods such as an inkjet coating method so as to be in contact with the ITO electrode, and an opening pattern having a predetermined shape is formed on the photosensitive resin composition applied to the ITO electrode. It can be manufactured through Step 2 in which a mask is placed and exposed by irradiation with active energy rays, Step 3 in which the exposed photosensitive resin composition is developed, and Step 4 in which the photosensitive resin composition after development is heated. .

In Step 1, when the photosensitive resin composition is applied so as to be in contact with the ITO electrode, it is sufficient that at least a part of the applied photosensitive resin composition of the present invention is in contact with the ITO electrode.
Step 2 can be performed in the same manner as the exposure step described above, and the preferred embodiment is also the same.
Step 3 can be performed in the same manner as the development step described above, and the preferred embodiment is also the same.
Step 4 can be performed in the same manner as the post-baking step described above, and the preferred embodiment is also the same.
Moreover, as an example of the ITO electrode pattern in the touch panel of this invention, the pattern shown in FIG. 6 mentioned above is mentioned preferably.

  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 raw material manufacturers and abbreviations used are described below.
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
GMA: Glycidyl methacrylate (manufactured by 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.)
PGMEA: Propylene glycol monomethyl ether acetate (Showa Denko)
Dicyclopentanyl methacrylate (manufactured by Tokyo Chemical Industry)
Tetrahydrofurfuryl methacrylate (manufactured by Tokyo Chemical Industry)
Methacrylic acid 1,2,2,6,6-pentamethyl-4-piperidyl (manufactured by Tokyo Chemical Industry)
2,2,6,6-Tetramethyl-4-piperidyl methacrylate (manufactured by Tokyo Chemical Industry)

<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 (89 g) was placed in a three-necked flask and heated to 90 ° 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) ), V-601 (corresponding to 4 mol% with respect to 100 mol% in total of all monomer components) was dissolved dropwise in PGMEA (89 g) at room temperature over 2 hours. 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%.

<Synthesis of Polymers A-2 to A-5>
Polymers A-2 to A-5 were synthesized in the same manner as the polymer A-1, except that the raw materials were changed as shown in the following table.
In the table below, the numerical values without particular units in the table are in mol%. The numerical value of the polymerization initiator is mol% when the monomer component is 100 mol%. The solid content concentration is shown as monomer mass / (monomer mass + solvent mass) × 100 (unit mass%).

<Synthesis Example of Polymer A′-1>
PGMEA (89 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. In the solution, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (amount to be 2 mol% in all monomer components), MAA (amount to be 20 mol% in all monomer components) , GMA (amount to be 48 mol% in all monomer components), dicyclopentanyl methacrylate (corresponding to 15 mol% in all monomer components), tetrahydrofurfuryl methacrylate (in all monomer components) 15 mol%), a solution prepared by dissolving V-601 (corresponding to 4 mol% with respect to 100 mol% in total of all monomer components) in PGMEA (89 g) at room temperature was added dropwise over 2 hours. 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 solid content might be 40 mass%.

<Synthesis Example of Polymer A′-2>
Polymer A′-2 was synthesized in the same manner as polymer A′-1, except that the raw materials were changed as shown in the following table.

<Synthesis of Polymer S-1>
Polymer S-1 was synthesized as follows. 29,92 g of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 17.22 g of methacrylic acid and 52.86 g of benzyl methacrylate were added to 400 g of propylene glycol monomethyl ether acetate (PGMEA), and 75 under a nitrogen atmosphere. Stir at 1 ° C. for 1 hour. Next, 0.5 g of V-601 (manufactured by Wako Pure Chemical Industries) was added and heated for 2 hours. Next, 0.5 g of V-601 was further added and heated for 2 hours, and then heated at 95 ° C. for 2 hours to synthesize polymer S-1.

<Synthesis of Polymers S-2 to S-9>
Polymers S-2 to S-9 were synthesized in the same manner as the polymer S-1, except that the raw materials were changed as shown in the following table.

<Preparation of photosensitive resin composition>
Each component is blended so as to have a solid content ratio (unit: mass%) described in the following table, and dissolved and mixed in a solvent (PGMEA: MEDG = 1: 1) until the solid content concentration becomes 15 mass%. It filtered with the 0.2 micrometer filter made from a polytetrafluoroethylene, and obtained the photosensitive resin composition of various Examples and a comparative example.

  The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.

Ｂ−２：下記に示す構造（合成例を後述する）

Ｂ−３：ＧＳＩＤ−２６−１、トリアリールスルホニウム塩（ＢＡＳＦ社製）

Ｂ−４：４，７− ジ− ｎ−ブトキシ−１−ナフチルテトラヒドロチオフェニウムトリフルオロメタンスルホネート (A) Polymer components A-1 to A-5, A′-1, A′-2: Polymers A-1 to A-5, A′-1, A′-2 synthesized by the method described above
(B) Photoacid generator B-1: Structure shown below (synthesis examples will be described later)

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

B-3: GSID-26-1, triarylsulfonium salt (manufactured by BASF)

B-4: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

Ｓ’−２：Ｔｉｎｕｖｉｎ ７６５ （ＢＡＳＦ社製）（下記構造）

(S) Components S-1 to S-9: Polymers S-1 to S-9 synthesized by the method described above
S′-1: 4-hydroxy-1,2,2,6,6-pentamethylpiperidine (the following structure)

S′-2: Tinuvin 765 (manufactured by BASF) (the following structure)

(Silane coupling agent)
SC-1: KBM-403 (3-glycidoxypropyltrimethoxysilane)

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

(Surfactant)
Surfactant) W-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)

(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: EX-321L (manufactured by Nagase ChemteX Corporation)
F-3: Takenate B870N (Mitsui Chemicals, Inc.)
F-4: Duranate MF-K60X (manufactured by Asahi Kasei Chemicals Corporation)
F-5: Duranate MFA-100 (Asahi Kasei Chemicals Corporation)
F-6: Irganox 1035 (manufactured by BASF)
F-7: Dibutoxyanthracene (sensitizer) (manufactured by Kawasaki Kasei)

<Synthesis of B-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, then reslurried with methanol (20 mL), filtered and dried to obtain the compound of B-1 (the above structure) (2.3 g).
In addition, the 1H-NMR spectrum (300 MHz, CDCl3) of B-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-2>
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), and 3.4 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries) is added. , 4-dimethyl-3-oxovalerate methyl (4.9 g, 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-2A. Crude B-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-2A.
Intermediate B-2A (1.7 g) and p-xylene (6 mL) were mixed, 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was 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-2B.
THF (2 mL) and the whole amount of crude B-2B were mixed, and 2 mL of 2M hydrochloric acid / THF solution was added dropwise under ice cooling, followed by dropwise addition of isopentyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (0.84 g) The mixture was heated up to 2 hours and stirred. 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-2C.
The whole amount of intermediate crude B-2C was mixed with acetone (10 mL), and triethylamine (Wako Pure Chemical Industries, Ltd.) (1.2 g) and p-toluenesulfonyl chloride (Tokyo Chemical Industry) (1.4 g) were added under ice cooling. Then, it heated up 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-2. Crude B-2 was reslurried with cold methanol, filtered and dried to obtain B-2 (1.2 g).
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-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) there were.

<Development adhesion evaluation>
Each photosensitive resin composition is slit-coated on a glass substrate (EAGLE XG, 0.7 mm thick (manufactured by Corning)) that has been washed with water, 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.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive resin composition layer was developed with an alkali developer (2.38% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 60 seconds. The mask used for the evaluation is a mask in which 15 extraction patterns and 15 floating patterns of 10 μm to 100 μm are respectively formed. By these operations, the remaining pattern was observed when resolving line patterns of various line widths. It is more preferable that there is no pattern peeling with a finer line. 5 to 3 is a practical range in the following evaluation criteria.

評価は１０μｍ、２０μｍ、５０μｍの各パターンで剥がれ量の評価を行い、その中で最も低い評価点をそのサンプルの評価点とした。

In the evaluation, the amount of peeling was evaluated for each pattern of 10 μm, 20 μm, and 50 μm, and the lowest evaluation score among them was set as the evaluation score of the sample.

<Sensitivity evaluation>
Each photosensitive resin composition is slit-coated on a glass substrate (EAGLE XG, 0.7 mm thick (manufactured by Corning)) that has been washed with water, 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.
Next, the obtained photosensitive resin composition layer was exposed to a 6.0 μm hole pattern using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc.
After the exposure, the resist film was developed with an alkali developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) (24 ° C., 60 seconds), and rinsed with ultrapure water for 20 seconds. The exposure amount at which a hole pattern having a lower bottom diameter of 6.0 μm was formed was defined as sensitivity. The smaller the required exposure (the higher the sensitivity), the better. 5 to 3 is a practical range on the following criteria.
[Evaluation criteria]
5: 40mJ / cm ² less than 4: 40mJ / cm ² or more 70 mJ / cm ² less than 3: 70mJ / cm ² or more 100 mJ / cm ² less than ^2: 100mJ / cm 2 or more 300 mJ / cm ² less than 1: 300mJ / cm ² or more

As is clear from the above results, the photosensitive resin compositions of Examples 1 to 16 had good sensitivity, and even in a substrate without hydrophobizing treatment such as HMDS, the pattern adhesiveness during development was excellent. .
On the other hand, Comparative Examples 4, 7, and 8 in which (S) the polymer was not used were inferior in development adhesion.
Moreover, the comparative examples 1-3 which used S'-1, S'-2, and S-9 instead of the (S) polymer were inferior in sensitivity.
The molar ratio of the structural unit represented by the general formula (2) in all the repeating units of the polymer (S) is represented by the general formula (1) in all the repeating units of the polymer (S). The comparative example 5 which uses polymer S-6 of less than 0.3 times the molar ratio of the unit was inferior in sensitivity.
The molar ratio of the structural unit represented by the general formula (2) in all the repeating units of the polymer (S) is represented by the general formula (1) in all the repeating units of the polymer (S). Comparative Example 6 using the polymer S-7 exceeding 5 times the molar ratio of the units was inferior in development adhesion.

<Creation of organic EL display device>
(Example 101)
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 3).
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.

(Examples 102 to 116)
In Example 101, an organic EL display device was produced in the same manner as in Example 101 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Examples 2 to 16. When a drive voltage was applied to the obtained organic EL display device, it was found that the organic EL display device showed good display characteristics and had high reliability.

<Production of liquid crystal display device>
(Example 200)
In the active matrix liquid crystal display device described 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 201 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 HMDS vapor for 30 seconds, and then the photosensitive resin composition of Example 1 is spun. After coating application, the solvent was volatilized by prebaking on a hot plate at 90 ° C. for 2 minutes 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 201)
A liquid crystal display device similar to that of Example 200 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 that of Example 200. It was very good.

(Example 202)
A liquid crystal display device similar to that of Example 200 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 200.

(Example 203)
A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. 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 200. 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 204)
A liquid crystal display device similar to that of Example 200 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 200. From the viewpoint of improving dimensional stability, it is also preferable to introduce a PEB process.

(Example 205)
A liquid crystal display device similar to that of Example 200 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 200.

(Example 206)
A liquid crystal display device similar to that of Example 200 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 200.

(Example 207)
A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. 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 200.

(Example 208)
A liquid crystal display device similar to that of Example 200 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 200.

(Example 209)
A liquid crystal display device similar to that of Example 200 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 200.

(Example 210)
A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. 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 200. It is also preferable to add this process from the viewpoint of adjusting the shape of the hole pattern.

<Production of touch panel display device>
(Example 301)
A touch panel display device was produced by the method described below.
<Formation of first transparent electrode pattern>
<< Formation of transparent electrode layer >>
A front plate of tempered glass (300 mm × 400 mm × 0.7 mm) with a mask layer formed in advance is introduced into a vacuum chamber, and an ITO target (indium: tin = 95: 5) with a SnO ₂ content of 10% by mass. (Molar ratio)) was used to form an ITO thin film having a thickness of 40 nm by DC magnetron sputtering (conditions: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), and a transparent electrode layer was formed. A formed front plate was obtained. The surface resistance of the ITO thin film was 80Ω / □.

Next, a commercially available etching resist was applied onto ITO and dried to form an etching resist layer. The distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the etching resist layer is set to 100 μm, pattern exposure is performed at an exposure amount of 50 mJ / cm ² (i-line), and development is performed with a developer. Then, a post-baking treatment at 130 ° C. for 30 minutes was performed to obtain a front plate on which a transparent electrode layer and a photosensitive resin layer pattern for etching were formed.

The front plate on which the transparent electrode layer and the photo-sensitive resin layer pattern for etching are formed is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and etched resist. The exposed transparent electrode layer not covered with the layer was dissolved and removed to obtain a front plate with a transparent electrode layer pattern with an etching resist layer pattern.
Next, the front plate with the transparent electrode layer pattern with the etching resist layer pattern is immersed in a dedicated resist stripping solution, the photosensitive resin layer for etching is removed, and the mask layer and the first transparent electrode pattern A front plate formed was obtained.

<< Formation of insulating layer >>
On the front plate on which the mask layer and the first transparent electrode pattern were formed, the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 μm, 90 ° C., 120 seconds) to form a photosensitive resin composition layer. Got. The distance between the surface of the exposure mask (quartz exposure mask having a pattern for insulating layer) and the photosensitive resin composition layer was set to 30 μm, and pattern exposure was performed with the optimum exposure amount obtained by sensitivity evaluation.
Next, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds and rinsed with ultrapure water for 10 seconds. Subsequently, a post-bake treatment at 220 ° C. for 45 minutes was performed to obtain a front plate on which a mask layer, a first transparent electrode pattern, and an insulating layer pattern were formed.

<Formation of second transparent electrode pattern>
<< Formation of transparent electrode layer >>
In the same manner as the formation of the first transparent electrode pattern, the front plate formed up to the insulating layer pattern was subjected to DC magnetron sputtering treatment (conditions: substrate temperature 50 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa). An ITO thin film having a thickness of 80 nm was formed to obtain a front plate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 110Ω / □.
Similarly to the formation of the first transparent electrode pattern, using a commercially available etching resist, the first transparent electrode pattern, an insulating layer pattern formed using the photosensitive resin composition of Example 1, a transparent electrode layer, A front plate on which an etching resist pattern was formed was obtained (post-baking treatment; 130 ° C. for 30 minutes).
Further, etching was performed in the same manner as the formation of the first transparent electrode pattern, and the etching resist layer was removed to form the mask layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. A front plate on which an insulating layer pattern and a second transparent electrode pattern were formed was obtained.

<Formation of Conductive Element Different from First and Second Transparent Electrode Pattern>
Similar to the formation of the first and second transparent electrode patterns, the first transparent electrode pattern, the insulating layer pattern formed using the photosensitive resin composition of Example 1, and the second transparent electrode pattern The front plate on which was formed was subjected to DC magnetron sputtering to obtain a front plate on which an aluminum (Al) thin film having a thickness of 200 nm was formed.
Insulating layer formed using the first transparent electrode pattern, the photosensitive resin composition of Example 1, using a commercially available etching resist in the same manner as the formation of the first and second transparent electrode patterns. A front plate on which a pattern, a second transparent electrode pattern, and an etching resist pattern were formed was obtained (post-bake treatment; 130 ° C. for 30 minutes).
Further, in the same manner as the formation of the first transparent electrode pattern, etching (30 ° C. for 50 seconds) is performed, and the etching resist layer is removed (45 ° C. for 200 seconds). A front plate on which a conductive element different from the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns formed using the photosensitive resin composition of Example 1 was obtained was obtained.

<Formation of transparent protective layer>
In the same manner as the formation of the insulating layer, the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 μm) on the front plate formed up to the conductive element different from the first and second transparent electrode patterns. , 90 ° C. for 120 seconds) to obtain a photosensitive resin composition film. Furthermore, exposure, development, post-exposure (1,000 mJ / cm ² ), post-bake treatment were performed, and the insulating layer formed using the mask layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1 Insulating layer (transparent protection) formed using the photosensitive resin composition of Example 1 so as to cover all the conductive elements different from the pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns Layer) was obtained.

<Production of touch panel display device>
A liquid crystal display device manufactured by the method described in Japanese Patent Laid-Open No. 2009-47936 is bonded to the previously manufactured front plate, and a touch panel display device including a capacitive input device as a constituent element is manufactured by a known method. did.

<Evaluation of front plate and touch panel display>
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and other conductive elements, while the first transparent electrode pattern and the second transparent electrode pattern Between the electrode patterns, there was insulation, and good display characteristics as a touch panel were obtained. Furthermore, the 1st and 2nd transparent electrode pattern was hard to be visually recognized, and the touchscreen display apparatus excellent in the display characteristic was obtained.

a Tangent b Vertex 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 30: Capacitance type input device 31: Front plate 32: Mask layer 33: First transparent electrode pattern 33a: Pad portion 33b: Connection portion 34: second transparent electrode pattern 35: insulating layer 36: conductive element 37: transparent protective layer 38: opening 100: substrate

Claims (14)

(A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a-1) a polymer having a structural unit having an acid group protected by an acid-decomposable group, and (a-2) a structural unit having a crosslinkable group,
(2) (a-1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a-2) a polymer having a structural unit having a crosslinkable group,
(B) a photoacid generator,
(C) a solvent, and (S) a polymer having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2),
In the polymer (S), the molar ratio of the structural unit represented by the general formula (2) in all repeating units of the polymer (S) is the general formula in all repeating units of the polymer (S). A photosensitive resin composition that is 0.3 to 5 times the molar ratio of the structural unit represented by (1);

In formulas (1) and (2), R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a methyl group, and L ¹ and L ² each independently represent a single bond or a divalent linking group. R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or An alkoxy group having 1 to 12 carbon atoms is represented.   The photosensitive resin composition of Claim 1 which contains 0.1-10 mass parts of said (S) polymers with respect to a total of 100 mass parts of said (A) polymer component and said (S) polymer.   The structural unit represented by the general formula (1) is contained in an amount of 0.05 to 3 parts by mass with respect to a total of 100 parts by mass of the (A) polymer component and the (S) polymer. The photosensitive resin composition as described in 2.   In the (S) polymer, the molar ratio of the structural unit represented by the general formula (2) in all repeating units is 0. 0 of the molar ratio of the structural unit represented by the general formula (1) in all repeating units. The photosensitive resin composition of any one of Claims 1-3 which is 5 to 3 times.   (S) The photosensitivity of any one of Claims 1-4 whose molar ratio of the structural unit represented by General formula (1) in a polymer is 5-50 mol% in all the repeating units. Resin composition. (S) In the polymer, R ^{1 to} R ⁴ in the general formula (1) are each independently an alkyl group having 1 to 5 carbon atoms, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The photosensitive resin composition of any one of Claims 1-5 which are these. The process of apply | coating the photosensitive resin composition of any one of Claims 1-6,
Removing the solvent from the applied photosensitive resin composition;
Exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
Developing the exposed photosensitive resin composition with a developer; and
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 7 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 manufacturing method of the cured film of Claim 7 or 8 including the process of dry-etching with respect to the board | substrate which has a cured film obtained by thermosetting at the said post-baking process.   The cured film which hardened the photosensitive resin composition of any one of Claims 1-6, or the cured film formed by the manufacturing method of the cured film of any one of Claims 7-9 .   The cured film of Claim 10 which is an interlayer insulation film.   A liquid crystal display device comprising the cured film according to claim 10.   An organic EL display device comprising the cured film according to claim 10.   A touch panel display device comprising the cured film according to claim 10.

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