JP2013190507A - Positive photosensitive resin composition, cured film manufacturing method, cured film, organic el display and liquid-crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition with a high sensitivity, a low unexposed residual film ratio, a low relative dielectric constant, and an excellent dry etching resistance.SOLUTION: The positive photosensitive resin composition contains (A) a component containing a polymer satisfying at least one of (1) and (2) described below, (B) a photoacid generator, and (D) a solvent, with: (1) a polymer comprising a constitutional unit (a1) having a residue of protecting an acid group with an acid decomposable group, and a constitutional unit (a2) represented by the specified general formula; (2) a polymer comprising the constitutional unit (a1) and a polymer comprising the constitutional unit (a2).

Description

The present invention relates to a positive photosensitive resin composition. The present invention also relates to a method for producing a cured film using the positive photosensitive resin composition, a cured film obtained by curing the positive photosensitive composition, and various image display devices using the cured film.
More specifically, a positive photosensitive resin composition suitable for forming a flattening film, a protective film, and an interlayer insulating film of electronic components such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state imaging device, and the same The present invention relates to a method for producing a cured film using the above.

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

  A photosensitive resin composition having high sensitivity is required for the interlayer insulating film and the planarizing film patterned using the positive photosensitive resin composition as described above from the viewpoint of reducing the manufacturing cost. Recently, since mobile displays such as smartphones have been widely used, a highly reliable cured film in a wide temperature environment has been particularly demanded.

  An example using a photosensitive resin composition with improved storage stability, sensitivity, etc. is known (see, for example, Patent Document 1). However, a photosensitive resin composition with high sensitivity, low unexposed residual film ratio, low relative dielectric constant, and excellent dry etching resistance is not known.

JP2011-221494A

  The present invention solves the above problems, and provides a positive photosensitive resin composition having high sensitivity, low unexposed residual film ratio, low relative dielectric constant, and excellent dry etching resistance. With the goal.

Under such circumstances, the present inventor attempted to lower the oxygen density in the polymer and increase the density of the crosslinkable group by using a structural unit derived from a compound having an oxetanyl group introduced in styrene. . As a result, while maintaining high sensitivity, the unexposed residual film ratio was lowered, the relative dielectric constant was lowered, and the dry etching resistance was successfully improved.
Here, if the oxygen density is simply lowered, it is advantageous to introduce an epoxy group as a crosslinkable group. However, when the present inventors have studied, the epoxy group may improve the dielectric constant. I understood. That is, the present inventor succeeded in comprehensively solving the above problems by adopting a structural unit derived from a compound in which an oxetanyl group is introduced into styrene, and has completed the present invention.

（一般式（Ｉ）中、Ｒ¹は水素原子またはメチル基を表し、Ｌは単結合または２価の連結基を表し、Ｒ²は水素原子、置換基を有していてもよい炭素数１〜２０のアルキル基、または、置換基を有していてもよい炭素数６〜２０のアリール基を表す。）
＜２＞上記一般式（Ｉ）における、Ｒ¹が水素原子である＜１＞に記載のポジ型感光性樹脂組成物。
＜３＞上記一般式（Ｉ）における、Ｌが、エステル結合、エーテル結合およびアミド結合の少なくとも１つを含む２価の連結基である、＜１＞または＜２＞に記載のポジ型感光性樹脂組成物。
＜４＞上記一般式（Ｉ）における、Ｌが、エステル結合、エーテル結合およびアミド結合の少なくとも１つと、−ＣＨ₂−の組み合わせからなる基である、＜１＞または＜２＞に記載のポジ型感光性樹脂組成物。
＜５＞上記一般式（Ｉ）における、Ｌの鎖部分を構成する原子数が、２〜１０である、＜１＞〜＜４＞のいずれかに記載のポジ型感光性樹脂組成物。
＜６＞上記一般式（Ｉ）における、Ｒ²がアルキル基またはヒドロキシアルキル基である＜１＞〜＜５＞のいずれかに記載のポジ型感光性樹脂組成物。
＜７＞上記一般式（Ｉ）における、Ｒ²が炭素数１〜４のアルキル基または炭素数１〜３のヒドロキシアルキル基である、＜１＞〜＜５＞のいずれかに記載のポジ型感光性樹脂組成物。
＜８＞上記一般式（Ｉ）における、Ｌが、エステル結合および／またはエーテル結合を含む２価の連結基である、＜１＞〜＜７＞のいずれかに記載のポジ型感光性樹脂組成物。
＜９＞上記（ａ１）構成単位が、下記一般式（ＩＩＩ）で表される構成単位である、＜１＞〜＜８＞のいずれかに記載の感光性樹脂組成物。
一般式（ＩＩＩ）

（一般式（ＩＩＩ）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であり、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。）
＜１０＞上記（Ａ）重合体成分に含まれる重合体のうち少なくともいずれか１つが、酸基を含有する構成単位を有する、＜１＞〜＜９＞のいずれかに記載のポジ型感光性樹脂組成物。
＜１１＞光酸発生剤（Ｂ）がオキシムスルホネート化合物、オニウム塩化合物、及び１，２−キノンジアジド化合物から選ばれる少なくとも１種を含む＜１＞〜＜１０＞のいずれかに記載のポジ型感光性樹脂組成物。
＜１２＞さらに、架橋剤（Ｆ）を含む＜１＞〜＜１１＞のいずれかに記載のポジ型感光性組成物。
＜１３＞＜１＞〜＜１２＞のいずれかに記載のポジ型感光性樹脂組成物を硬化させた硬化膜。
＜１４＞＜１３＞に記載の硬化膜を用いた層間絶縁膜。
＜１５＞＜１４＞に記載の層間絶縁膜を有する液晶表示装置または有機ＥＬ表示装置。
＜１６＞下記一般式（ＩＶ）で表される化合物。

（一般式（ＩＶ）中、Ｒ⁵はエチル基、メチル基またはヒドロキシメチル基を表す。） Specifically, the above-mentioned problem has been solved by the following means <1>, preferably <2> to <17>.
<1> (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1) a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit represented by the following general formula (I):
(2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit represented by the following general formula (I):
(B) a photoacid generator, and
(D) Solvent
A positive photosensitive resin composition comprising:
Formula (I)

(In the general formula (I), R ¹ Represents a hydrogen atom or a methyl group, L represents a single bond or a divalent linking group, R ² Represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. )
<2> R in the general formula (I) ¹ The positive photosensitive resin composition according to <1>, wherein is a hydrogen atom.
<3> The positive type photosensitivity according to <1> or <2>, wherein L in the general formula (I) is a divalent linking group containing at least one of an ester bond, an ether bond and an amide bond. Resin composition.
<4> In the above general formula (I), L represents at least one of an ester bond, an ether bond and an amide bond; ₂ The positive photosensitive resin composition according to <1> or <2>, which is a group comprising a combination of-.
<5> The positive photosensitive resin composition according to any one of <1> to <4>, wherein the number of atoms constituting the L chain portion in the general formula (I) is 2 to 10.
<6> R in the above general formula (I) ² The positive photosensitive resin composition according to any one of <1> to <5>, wherein is an alkyl group or a hydroxyalkyl group.
<7> R in the above general formula (I) ² The positive photosensitive resin composition according to any one of <1> to <5>, in which is an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms.
<8> The positive photosensitive resin composition according to any one of <1> to <7>, wherein L in the general formula (I) is a divalent linking group containing an ester bond and / or an ether bond. object.
<9> The photosensitive resin composition according to any one of <1> to <8>, wherein the (a1) structural unit is a structural unit represented by the following general formula (III).
Formula (III)

(In the general formula (III), R ¹ And R ² Each represents a hydrogen atom, an alkyl group or an aryl group, and at least R ¹ And R ² Any one of which is an alkyl group or an aryl group, and R ^Three Represents an alkyl group or an aryl group, R ¹ Or R ² And R ^Three May be linked to form a cyclic ether, R ^Four Represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. )
<10> The positive photosensitive resin according to any one of <1> to <9>, wherein at least one of the polymers contained in the polymer component (A) has a structural unit containing an acid group. Resin composition.
<11> The positive photosensitizer according to any one of <1> to <10>, wherein the photoacid generator (B) includes at least one selected from an oxime sulfonate compound, an onium salt compound, and a 1,2-quinonediazide compound. Resin composition.
<12> The positive photosensitive composition according to any one of <1> to <11>, further including a crosslinking agent (F).
<13> A cured film obtained by curing the positive photosensitive resin composition according to any one of <1> to <12>.
<14> An interlayer insulating film using the cured film according to <13>.
<15> A liquid crystal display device or an organic EL display device having the interlayer insulating film according to <14>.
<16> A compound represented by the following general formula (IV).

(In the general formula (IV), R ^Five Represents an ethyl group, a methyl group or a hydroxymethyl group. )

  According to the present invention, it is possible to provide a positive photosensitive resin composition having high sensitivity, low unexposed residual film ratio, low relative dielectric constant and excellent dry etching resistance.

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. 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.

  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 addition, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have 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).

（一般式（Ｉ）中、Ｒ¹は水素原子またはメチル基を表し、Ｌは単結合または２価の連結基を表し、Ｒ²は水素原子、置換基を有していてもよい炭素数１〜２０のアルキル基、または、置換基を有していてもよい炭素数６〜２０のアリール基を表す。） [Positive photosensitive resin composition]
The positive photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as “photosensitive resin composition”) includes (A) a polymer containing a polymer that satisfies at least one of the following (1) and (2). It contains a coalescing component, (B) a photoacid generator, and (D) a solvent.
(1) (a1) a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit represented by the following general formula (I) (hereinafter referred to as “polymer”) (1) ”),
(2) (a1) a polymer having a structural unit having a residue in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit represented by the following general formula (I) , Sometimes referred to as “polymer (2)”)
Formula (I)

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, L represents a single bond or a divalent linking group, and R ² represents a hydrogen atom or an optionally substituted carbon atom. 1 Represents an alkyl group of -20 or an aryl group of 6-20 carbon atoms which may have a substituent.)

The photosensitive resin composition of the present invention is a positive photosensitive resin composition. The photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).
Hereinafter, the preferable aspect of each component is demonstrated in order about the photosensitive resin composition of this invention.

<(A) component>
In the photosensitive resin composition of the present invention, (A) component (1) (a1) a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) general formula (I) A polymer having a structural unit represented, and (2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) the following general formula (I) At least one of the polymers having a structural unit represented by the formula:
Preferably, it contains at least (1) (a1) a structural unit having a residue in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit represented by formula (I). It is an aspect. By adopting such a configuration, chemical resistance tends to be improved.

The component (A) is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
The component (A) preferably contains 50 mol% or more, and 90 mol% or more of the structural unit derived from (meth) acrylic acid and / or its ester with respect to all the structural units in the polymer. Is more preferable, and a polymer composed only of structural units derived from (meth) acrylic acid and / or its ester is particularly preferable.
The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”. “(Meth) acrylic acid” means “methacrylic acid and / or acrylic acid”.
The component (A) may contain other structural units in addition to the structural units (a1) to (a3).

The (A) copolymer is preferably insoluble in alkali, and is preferably a resin that becomes alkali-soluble when the acid-decomposable group in the structural unit (a1) is decomposed. Here, the acid-decomposable group means a functional group that can be decomposed in the presence of an acid. That is, the structural unit having a protected carboxyl group in which the carboxyl group is protected with an acid-decomposable group can generate a carboxyl group when the protective group is decomposed by an acid, and the phenolic hydroxyl group is an acid-decomposable group. The structural unit having a protected phenolic hydroxyl group protected with can generate a phenolic hydroxyl group by the decomposition of the protecting group with an acid. Here, in the present invention, “alkali-soluble” means a coating film (thickness) of the compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating at 90 ° C. for 2 minutes. 3 μm) is a dissolution rate in a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. of 0.01 μm / second or more. “Alkali insoluble” means that the solution of the compound (resin) is a substrate. The dissolution rate of the coating film (thickness 3 μm) of the compound (resin) formed by applying the coating on the substrate and heating at 90 ° C. for 2 minutes in a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. It means less than 0.01 μm / second.
The (A) copolymer may have a carboxyl group described later, a structure derived from a carboxylic anhydride, and / or other structural units having a phenolic hydroxyl group. However, when introducing an acidic group, it is preferable to introduce it in the range which keeps the whole (A) copolymer insoluble in alkali.

<< Structural Unit (a1) >>
Component A has (a1) at least a structural unit having a residue in which an acid group is protected with an acid-decomposable group. When the component (A) has the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
The “residue in which an acid group is protected with an acid-decomposable group” in the present invention can be specified as an acid group and an acid-decomposable group, and is not particularly limited. Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group. The acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal group such as an ester structure of a group represented by the formula (A1) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group). A functional group) or a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a t-butyl ester group or a tertiary alkyl carbonate group such as a t-butyl carbonate group) can be used.

(A1) The structural unit having a residue whose acid group is protected with an acid-decomposable group is a structural unit having a protected carboxyl group protected with an acid-decomposable group, or a protected phenol protected with an acid-decomposable group A structural unit having a functional hydroxyl group is preferred.
Hereinafter, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in this order. To do.

<<< (a1-1) Structural Unit Having a Protected Carboxyl Group Protected with an Acid-Decomposable Group >>>
The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a protected carboxyl in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below. A structural unit having a group.
There is no restriction | limiting in particular as a structural unit which has the said carboxyl group as a structural unit which can be used for the structural unit (a1-1) which has the protected carboxyl group protected by the said acid-decomposable group, A well-known structural unit can be used. For example, a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid, And a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
Hereinafter, (a1-1-1) used as a structural unit having a carboxyl group, a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and (a1-1-2) ethylene The structural units having both the unsaturated group and the structure derived from the acid anhydride will be described in order.

<<<<< (a1-1-1) 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 as the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include those listed below. . That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic 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. For example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of the dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among them, from the viewpoint of developability, in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, acrylic acid, methacrylic acid, Alternatively, an unsaturated polycarboxylic acid anhydride or the like is preferably used, and acrylic acid or methacrylic acid is more preferably used.
The structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule may be composed of one kind alone or two or more kinds. May be.

<<<<< (a1-1-2) Structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride >>>>
The structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride reacts a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride. A unit derived from the obtained monomer is preferred.
As the acid anhydride, known ones can be used, specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride and the like. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, from the viewpoint of developability.

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

（式（ａ１−１）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 (a1-1)

(In formula (a1-1), R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom or an alkyl group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms. R ¹⁰³ is an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.)

In the general formula (a1-1), 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.

In the general formula (a1-1), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be linear, branched or cyclic.
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 linear Or a 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 (a1-1), when R ¹⁰¹ , R ^102, and R ¹⁰³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. preferable. The aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a silyl group, a cumenyl group, and a 1-naphthyl group.

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ can be bonded together 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 (a1-1), any one of R ¹⁰¹ and R ¹⁰² is preferably 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 (a1-1), 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 be synthesized by the synthesis method described in paragraph numbers 0037 to 0040 of JP2011-221494A.

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

(Wherein 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 is an alkyl group or an aryl group, and R ³ is an alkyl group or Represents an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group; )
When R ¹ and R ² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
X represents a single bond or an arylene group, and a single bond is preferred.

（式中、Ｒ¹²¹は水素原子または炭素数１〜４のアルキル基を表し、Ｌ¹はカルボニル基またはフェニレン基を表し、Ｒ¹²²〜Ｒ¹²⁸はそれぞれ独立に、水素原子または炭素数１〜４のアルキル基を表す。）
Ｒ¹²¹は水素原子またはメチル基が好ましい。
Ｌ¹はカルボニル基が好ましい。
Ｒ¹²²〜Ｒ¹²⁸は、水素原子が好ましい。 The 2nd preferable aspect of the structural unit (a1-1) which has the protected carboxyl group protected by the said acid-decomposable group is a structural unit of the following general formula.

(Wherein 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 1 to 4 carbon atoms. Represents an alkyl group of
R ¹²¹ is preferably a hydrogen atom or a methyl group.
L ¹ is preferably a carbonyl group.
R ^{122 to} R ¹²⁸ are preferably a hydrogen atom.

  Preferable specific examples of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group include the following structural units. R represents a hydrogen atom or a methyl group.

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

<<<< (a1-2-1) 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, and among these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene, It is preferable from the viewpoint of transparency. Among the structural units having a phenolic hydroxyl group, the structural unit represented by the following general formula (a1-2) is preferable from the viewpoints of transparency and sensitivity.

（一般式（ａ１−２）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 (a1-2)

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

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

<<<< acid-decomposable group that can be used for the structural unit (a1-2) >>>>
The acid-decomposable group that can be used for the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group has a protected carboxyl group protected with the acid-decomposable group. Similarly to the acid-decomposable group that can be used for the unit (a1-1), a known one 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 the acid-decomposable groups, the phenolic hydroxyl group is more preferably a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-1) from the viewpoint of sensitivity. When the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of the acetal represented by the general formula (a1-1), 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.

Examples of the radical polymerizable monomer used to form a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include, for example, paragraphs of JP2011-215590A The thing of number 0042 etc. are mentioned.
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.

  As the radical polymerizable monomer used to form the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group, a commercially available one may be used, or a known method may be used. What was synthesize | combined by can also be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.

  Preferable specific examples of the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group include the following structural units, but the present invention is not limited thereto.

<<< Preferred Aspect of Structural Unit (a1) >>>
From the viewpoint of sensitivity, the content of the structural unit (a1) in the structural unit constituting the polymer (A) is preferably 1 to 95 mol%, more preferably 10 to 80 mol%, based on the whole polymer. 20-70 mol% is further more preferable, and 20-50 mol% is especially preferable. In particular, when the acid-decomposable group that can be used in the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected with an acetal, a polymer containing the structural unit (a1) is formed. The content of the structural unit (a1) in the structural unit is more preferably 20 to 60 mol%, particularly preferably 30 to 50 mol%.
In particular, when the structural unit (a2) is contained in the same polymer as the structural unit (a1), the structural unit (a1) in the polymer is preferably 20 to 50 mol%, more preferably 30 to 45 mol%. .
On the other hand, when the structural unit (a2) is contained in a polymer different from the structural unit (a1), the structural unit (a1) is preferably 30 to 70 mol% in the polymer containing the structural unit (a2). -60 mol% is more preferable.

  The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred when developing quickly. Conversely, when it is desired to delay development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.

（一般式（Ｉ）中、Ｒ¹は水素原子またはメチル基を表し、Ｌは単結合または２価の連結基を表し、Ｒ²は水素原子、置換基を有していてもよい炭素数１〜２０のアルキル基、または、置換基を有していてもよい炭素数６〜２０のアリール基を表す。）
一般式（Ｉ）中、Ｒ¹は、水素原子であることが好ましい。水素原子とすることにより、本発明の効果がより効果的に発揮される傾向にある。
一般式（Ｉ）中、Ｌは、２価の連結基が好ましく、エステル結合、エーテル結合およびアミド結合の少なくとも１つを含む２価の連結基であることがより好ましく、エステル結合、エーテル結合およびアミド結合の少なくとも１つと、−ＣＨ₂−の組み合わせからなる基であることがより好ましい。さらに、本発明では、少なくとも、Ｌがエステル結合および／またはエーテル結合を含む態様が好ましく、少なくとも、エーテル結合を含む態様がさらに好ましい。このような構成とすることにより、本発明の効果がより効果的に発揮される傾向にある。
Ｌの鎖部分を構成する原子数は、２〜１０であることが好ましく、２〜８がより好ましく、２〜４がさらに好ましい。このような構成とすることにより、本発明の効果がより効果的に発揮される傾向にある。 << (a2) Structural Unit Represented by General Formula (I) >>
In this invention, it has the structural unit (a2) represented by general formula (I) as a polymer component (A).
Formula (I)

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, L represents a single bond or a divalent linking group, and R ² represents a hydrogen atom or an optionally substituted carbon atom. 1 Represents an alkyl group of -20 or an aryl group of 6-20 carbon atoms which may have a substituent.)
In general formula (I), R ¹ is preferably a hydrogen atom. By using hydrogen atoms, the effects of the present invention tend to be exhibited more effectively.
In general formula (I), L is preferably a divalent linking group, more preferably a divalent linking group containing at least one of an ester bond, an ether bond and an amide bond, and an ester bond, an ether bond and It is more preferably a group consisting of a combination of at least one amide bond and —CH ₂ —. Furthermore, in the present invention, an embodiment in which at least L includes an ester bond and / or an ether bond is preferable, and an embodiment in which at least an ether bond is included is more preferable. By setting it as such a structure, it exists in the tendency for the effect of this invention to be exhibited more effectively.
The number of atoms constituting the L chain portion is preferably 2 to 10, more preferably 2 to 8, and still more preferably 2 to 4. By setting it as such a structure, it exists in the tendency for the effect of this invention to be exhibited more effectively.

In general formula (I), R ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent. Examples of the substituent include a hydroxyl group, an aryl group, a cyano group, and a halogen atom, and a hydroxyl group is preferable. In the case where R ² is an alkyl group, the number of carbon atoms is preferably 1 to 10, and more preferably 1 to 5.
R ² is more preferably an alkyl a group or a hydroxyalkyl group, more preferably a hydroxyalkyl group R ² having 1 to 3 alkyl groups or carbon atoms having 1 to 4 carbon atoms is an alkyl group.

（一般式（ＩＩ）中、Ｒ³は水素原子またはメチル基を表し、Ｌ²およびＬ³は、それぞれ単結合、アルキレン基、アルキレンオキシ構造、又はカルボニル基を表し、Ｒ⁴は、メチル基、エチル基またはヒドロキシメチル基を表す。）
Ｒ³は水素原子が好ましい。
Ｌ²は、炭素数１または２のアルキレン基が好ましく、炭素数１のアルキレン基がより好ましい。Ｌ³は、炭素数１〜３のアルキレン基が好ましく、炭素数１または２のアルキレン基がより好ましく、炭素数１のアルキレン基がさらに好ましい。
このような構成単位は、対応するものモノマーを他の成分と重合することによって、形成することができる。一例として、下記一般式（ＩＶ）で表される化合物を用いて合成することができる。
下記一般式（ＩＶ）で表される化合物。

（一般式（ＩＶ）中、Ｒ⁵はエチル基、メチル基またはヒドロキシメチル基を表す。） The structural unit represented by the general formula (I) is preferably a structural unit represented by the following general formula (II).
Formula (II)

(In General Formula (II), R ³ represents a hydrogen atom or a methyl group, L ² and L ³ each represents a single bond, an alkylene group, an alkyleneoxy structure, or a carbonyl group, and R ⁴ represents a methyl group, Represents an ethyl group or a hydroxymethyl group.)
R ³ is preferably a hydrogen atom.
L ² is preferably an alkylene group having 1 or 2 carbon atoms, and more preferably an alkylene group having 1 carbon atom. L ³ is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and further preferably an alkylene group having 1 carbon atom.
Such structural units can be formed by polymerizing the corresponding monomers with other components. As an example, it can be synthesized using a compound represented by the following general formula (IV).
The compound represented by the following general formula (IV).

(In general formula (IV), R ⁵ represents an ethyl group, a methyl group or a hydroxymethyl group.)

Hereinafter, the monomer which comprises the structural unit represented by general formula (I) used by this invention is illustrated. However, it goes without saying that the present invention is not limited to these examples.

  In the present invention, the polymer containing the structural unit (a2) represented by the general formula (I) is substantially free of repeating units having a crosslinkable group other than the group represented by the general formula (I). Is preferred. By setting it as such a structure, an oxygen density improves more and the effect of this invention is exhibited more effectively. Here, “substantially free” means, for example, 1 mol% or less of the structural unit constituting the polymer containing the structural unit (a2).

<<< Preferred Aspect of Structural Unit (a2) >>>
From the viewpoint of sensitivity, the content of the structural unit (a2) in the structural unit constituting the polymer (A) is preferably 20 to 70 mol%, particularly preferably 30 to 70 mol%, from the viewpoint of sensitivity.
In particular, when the structural unit (a2) is contained in the same polymer as the structural unit (a1), the structural unit (a2) in the polymer is preferably 30 to 60 mol%, and more preferably 40 to 50 mol%.
On the other hand, when the structural unit (a2) is contained in a polymer different from the structural unit (a1), the structural unit (a2) in the polymer containing the structural unit (a2) is preferably 40 to 70 mol%, -65 mol% is more preferable.

<< (a3) Other structural units >>
In the present invention, the component (A) may have another structural unit (a3) in addition to the structural units (a1) and / or (a2). These structural units may be contained in the polymer (1) and / or (2). In addition to the polymer (1) or (2), a polymer component having another structural unit (a3) may be included. When a polymer having another structural unit (a3) is included in addition to the polymer (1) or (2), the blending amount of the polymer component is 60% by weight or less in the total polymer component. Is preferable, and it is more preferable that it is 40 weight% or less.

  There is no restriction | limiting in particular as a monomer used as another structural unit (a3), 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, and other unsaturated compounds be able to. Moreover, you may have the structural unit which has an acid group so that it may mention later. Furthermore, you may have a structural unit which has crosslinkable group other than the structural unit represented by general formula (I). The monomer which becomes another structural unit (a3) can be used individually or in combination of 2 or more types.

  Hereinafter, preferred embodiments of the polymer component of the present invention will be described, but it is needless to say that the present invention is not limited to these.

(First embodiment)
The aspect in which the polymer (1) further has one or more other structural units (a3).
(Second Embodiment)
The polymer having a structural unit having a residue in which the (a1) acid group of the polymer (2) is protected with an acid-decomposable group further has one or more other structural units (a3). Aspect.
(Third embodiment)
The aspect which the polymer which has a structural unit represented by (a2) following general formula (I) of polymer (2) further has 1 type, or 2 or more types of other structural units.

(Fourth embodiment)
In any one of the first to third embodiments, the other structural unit includes a structural unit containing at least an acid group.

(Fifth embodiment)
The aspect containing the structural unit which has crosslinkable groups other than the structural unit represented by general formula (I) in any one of the said 1st-3rd embodiment.

(Sixth embodiment)
The aspect which has the polymer which has another structural unit (a3) separately from the said polymer (1) or (2). Examples of the other structural unit (a3) in this case include a structural unit containing an acid group, a structural unit having a crosslinkable group other than the structural unit represented by the general formula (I), and the like.

(Seventh embodiment)
The form which consists of two or more combinations of the said 1st-6th embodiment.

  Specifically, the single structural unit (a3) is styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoate. Acid ethyl, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic Isopropyl acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate Mention may be made of a structural unit due. In addition, compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

  Moreover, the group which has styrenes and an aliphatic cyclic skeleton as another structural unit (a3) is preferable from a viewpoint of an electrical property. Specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.

  Furthermore, (meth) acrylic acid alkyl ester is preferable as another structural unit (a3) 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.

  In the structural unit constituting the copolymer (A), the content of the structural unit (a3) is preferably 60 mol% or less, more preferably 50 mol% or less, and further preferably 40 mol% or less. As a lower limit, although 0 mol% may be sufficient, it can be set as 1 mol% or more, for example, Furthermore, it can be set as 5 mol% or more. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.

The other structural unit (a3) preferably contains an acid group. By containing an acid group, it becomes easy to dissolve in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the resin 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 resin, alkali solubility tends to increase.
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. .

  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.

  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 20 mol% is particularly preferable.

The crosslinkable group possessed by the structural unit having a crosslinkable group other than the structural unit represented by the general formula (I) is not particularly limited as long as it undergoes a curing reaction by heat treatment. By including a crosslinking group, the mechanical properties of the cured film are improved. Preferred embodiments of the structural unit having a crosslinking group are represented by an epoxy group, an oxetanyl group, an ethylenically unsaturated group, and —NH—CH ₂ —O—R (R is an alkyl group having 1 to 20 carbon atoms). And at least one selected from the group represented by an epoxy group, oxetanyl group, and —NH—CH ₂ —O—R (wherein R is an alkyl group having 1 to 20 carbon atoms). Are preferable, and an epoxy group and / or an oxetanyl group are more preferable. In particular, an epoxy group is preferred from the viewpoint of improving chemical resistance. On the other hand, an oxetanyl group is preferable from the viewpoint of reducing the dielectric constant.

<<< (a3-1) Structural Unit Having Epoxy Group and / or Oxetanyl Group >>>
The (A) copolymer can contain a structural unit (structural unit (a3-1)) having an epoxy group and / or an oxetanyl group.
The structural unit (a3-1) having the epoxy group and / or oxetanyl group only needs to have at least one epoxy group or oxetanyl group in one structural unit, and one or more epoxy groups and one It may have an oxetanyl group, two or more epoxy groups, or 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, It is more preferable to have one or two epoxy groups and / or oxetanyl groups in total, and it is even more preferable to have one 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 skeleton.
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 acrylic acid esters.
Specific examples of the radical polymerizable monomer used for forming the structural unit (a3-1) having the epoxy group and / or oxetanyl group include a monomer containing a methacrylic ester structure and an acrylic ester structure. It is preferable that it is a monomer to contain.

  Among these monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraph Nos. 0034 to 0035 of Japanese Patent No. 4168443 and paragraph numbers 0011 to 0016 of JP-A No. 2001-330953. The (meth) acrylic acid ester having an oxetanyl group described in (1), and (meth) acrylic acid ester having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A-2001-330953 is particularly preferable. Among these, preferred are glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetane-3-yl) methyl acrylate, and methacrylic acid ( 3-ethyloxetane-3-yl) methyl, most preferred are (3-ethyloxetane-3-yl) methyl acrylate and (3-ethyloxetane-3-yl) methyl methacrylate. These structural units can be used individually by 1 type or in combination of 2 or more types.

  The structural unit (a3-1) having the epoxy group and / or oxetanyl group preferably has a structure selected from the group consisting of the following formula (a3-1-1) and formula (a3-1-2). .

The structural unit (a3-1) having the epoxy group and / or oxetanyl group has any one of the three structures represented by the formula (a3-1-1). ) Is a group obtained by removing one or more hydrogen atoms from the structure represented by
The structural unit (a3-1) having an epoxy group and / or oxetanyl group further preferably has a 3,4-epoxycyclohexyl group, a 2,3-epoxycyclohexyl group, or a 2,3-epoxycyclopentyl group.

（一般式（ａ３−１−２）中、Ｒ^1bおよびＲ^6bはそれぞれ独立に水素原子またはアルキル基を表し、Ｒ^2b、Ｒ^3b、Ｒ^4b、Ｒ^5b、Ｒ^7b、Ｒ^8b、Ｒ^9b、Ｒ^10bはそれぞれ独立に水素原子、ハロゲン原子、アルキル基、または、アリール基を表す。）

(In General Formula (a3-1-2), R ^1b and R ^6b each independently represent a hydrogen atom or an alkyl group, and R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b , R ^10b independently represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group.)

In the general formula (a3-1-2), R ^1b and R ^6b each independently represent a hydrogen atom or an alkyl group, and are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. It is more preferably a C 1-5 alkyl group (hereinafter also referred to as “lower alkyl group”).
R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be illustrated, a fluorine atom and a chlorine atom are more preferable, and a fluorine atom is further more preferable.
The alkyl group may be linear, branched, or cyclic, and may have a substituent. The linear and branched alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The cyclic alkyl group preferably has 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 5 to 7 carbon atoms. Note that the linear and branched alkyl groups may be substituted with a cyclic alkyl group, and the cyclic alkyl group may be substituted with a linear and / or branched alkyl group.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms.
The alkyl group and aryl group may further have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom and an aryl group, and the aryl group has Examples of the substituent that may be used include a halogen atom and an alkyl group. Among these, R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or More preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms.
Preferred examples of the group having the structure represented by the general formula (a3-1-2) include a (3-ethyloxetane-3-yl) methyl group.

  Preferable specific examples of the structural unit (a3-1) having the epoxy group and / or oxetanyl group include the following structural units. R represents a hydrogen atom or a methyl group.

<<< (a3-2) Structural unit having an ethylenically unsaturated group >>>
As one of the structural unit (a3) having a crosslinking group, there may be mentioned a structural unit (a3-2) having an ethylenically unsaturated group (hereinafter also referred to as “structural unit (a3-2)”). The structural unit (a3-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having 3 to 16 carbon atoms. A structural unit having a side chain is more preferred, and a structural unit having a side chain represented by the following general formula (a3-2-1) is more preferred.

（一般式（ａ３−２−１）中、Ｒ³⁰¹は炭素数１〜１３の二価の連結基を表し、Ｒ³⁰²は水素原子またはメチル基を表し、＊は架橋基を有する構成単位（ａ３）の主鎖に連結する部位を表す。） General formula (a3-2-1)

(In General Formula (a3-2-1), R ³⁰¹ represents a divalent linking group having 1 to 13 carbon atoms, R ³⁰² represents a hydrogen atom or a methyl group, and * represents a structural unit having a crosslinking group (a3 ) Represents a site linked to the main chain of.

R ³⁰¹ is a divalent linking group having 1 to 13 carbon atoms and includes an alkenyl group, a cycloalkenyl group, an arylene group, or a combination of these, and includes an ester bond, an ether bond, an amide bond, a urethane bond, and the like. Bonds may be included. The divalent linking group may have a substituent such as a hydroxy group or a carboxyl group at an arbitrary position. Specific examples of R ³⁰¹ include the following divalent linking groups.

Among the side chains represented by the general formula (a3-2-1), an aliphatic side chain including the divalent linking group represented by the R ³⁰¹ is preferable.

  The ethylenically unsaturated group contained in the side chain represented by the general formula (a3-2-1) is contained in an amount of 1 mol per 150 to 2,000 g based on the polymer component (A). It is preferable that 1 mol is contained with respect to 200 to 1,300 g.

  In the present invention, the structural unit (a3-2) having an ethylenically unsaturated group is preferably a structural unit represented by the following general formula (a3-2-2).

（一般式（ａ３−２−２）中、Ｒ³¹¹は、上記一般式（ａ３−２−１）におけるＲ³⁰¹と同義であり好ましい範囲も同様である。Ｒ³¹²、Ｒ³¹³はそれぞれ独立に、水素原子またはメチル基を表す。） General formula (a3-2-2)

(In general formula (a3-2-2), R ³¹¹ has the same meaning as R ³⁰¹ in general formula (a3-2-1) and the preferred range is also the same. R ³¹² and R ³¹³ are each independently Represents a hydrogen atom or a methyl group.)

The method for obtaining the structural unit (a3-2) having a side chain represented by the general formula (a3-2-1) is not particularly limited. For example, the specific functional group is previously obtained by a polymerization method such as radical polymerization. The above-mentioned general formula (a3-2-1) is produced by reacting a group that reacts with the specific functional group and a compound having an ethylenically unsaturated group at the terminal (hereinafter referred to as a specific compound). It can be set as the copolymer which has a structural unit (a3-2) which has a side chain represented by these.
Here, examples of the specific functional group include a carboxyl group, an epoxy group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxyl group, and an isocyanate group. A monomer having a specific functional group for synthesizing a polymer having a specific functional group will be described later.

  As a combination of the specific functional group and a group that reacts with the specific functional group of the specific compound, a combination of a carboxyl group and an epoxy group, a combination of a carboxyl group and an oxetanyl group, a combination of a hydroxy group and an isocyanate group, Examples include a combination of a phenolic hydroxyl group and an epoxy group, a combination of a carboxyl group and an isocyanate group, a combination of an amino group and an isocyanate group, and a combination of a hydroxy group and an acid chloride.

  Examples of the specific compound include glycidyl methacrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, isocyanate ethyl methacrylate, isocyanate ethyl acrylate, methacrylic acid chloride, acrylic acid chloride, Examples include methacrylic acid and acrylic acid.

  Preferred combinations of the specific functional group and the specific compound include a combination of a carboxyl group that is the specific functional group and a glycidyl methacrylate that is the specific compound, and a hydroxy group that is the specific functional group and the specific compound. A combination with isocyanate ethyl methacrylate is mentioned.

  Specific examples of the monomer having the specific functional group necessary for obtaining the polymer having the specific functional group are listed below, but the invention is not limited thereto.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono (2- (acryloyloxy) ethyl) phthalate, mono (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl). Maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like can be mentioned.
Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene, 1, Examples include 7-octadiene monoepoxide, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl acrylate.
Examples of the monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2, 3 -Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, Poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyl Oxy-6-hydroxy-norbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxy-norbornene-2-carboxylic-6-lactone and the like.

Examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.
Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.
Furthermore, as a monomer which has the said isocyanate group, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m-tetramethyl xylene isocyanate, etc. are mentioned, for example.

（上記式中、Ｒ¹は水素原子またはメチル基を表し、Ｒ²は炭素数１〜２０のアルキル基を表す。）
Ｒ²は、炭素数１〜９のアルキル基が好ましく、炭素数１〜４のアルキル基がさらに好ましい。また、アルキル基は、直鎖、分岐または環状のアルキル基のいずれであってもよいが、好ましくは、直鎖または分岐のアルキル基である。
Ｒ²の具体例としては、メチル基、エチル基、ｎ−ブチル基、ｉ−ブチル基、シクロヘキシル基、およびｎ−ヘキシル基を挙げることができる。中でもｉ−ブチル基、ｎ−ブチル基、メチル基が好ましい。 _{<<< (a3-3) -NH-CH 2} -O-R (R is an alkyl group having 1 to 20 carbon atoms) The structural unit having a partial structure represented by >>>
The copolymer used in the present invention has a structural unit (a3-3) having a partial structure represented by —NH—CH ₂ —O—R (R is an alkyl group having 1 to 20 carbon atoms) (hereinafter referred to as “configuration”). Unit (a3-3) ”). By having the structural unit (a3-3), a curing reaction can be caused by a gentle 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 (a3-3) is more preferably a structural unit having a group represented by the following general formula (1).
General formula (1)

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

<< (A) Molecular Weight of Copolymer >>
(A) The molecular weight of a copolymer is a polystyrene conversion weight average molecular weight, Preferably it is 1,000-200,000, More preferably, it is the range of 2,000-50,000. Various characteristics are favorable within the range of the above numerical values. The ratio (dispersity) 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) Copolymer Production Method >>
Various methods for synthesizing the component (A) are known. To give an example, at least one of the structural units represented by the above (a1) and (a3) is used. It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.

  It is preferable that the photosensitive resin composition of this invention contains (A) component in the ratio of 50-99.9 mass% with respect to the total solid, and it is more preferable to include it in the ratio of 70-98 mass%.

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

  Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, from the viewpoint of insulation, it is preferable to use an onium salt compound and an oxime sulfonate compound, and an oxime sulfonate compound is more preferable. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-221494A. It can be illustrated.

  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).

（一般式（Ｂ１）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)

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

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 represented by R ²¹ is 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 or the like It may be substituted with a cyclic 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 an oxime sulfonate structure represented by the general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B2).

（式（Ｂ２）中、Ｒ⁴²は、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。）

(In the formula (B2), R ⁴² represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m4 represents an integer of 0 to 3, and m4 represents 2 or When X is 3, the plurality of X may be the same or different.)

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
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 the oxime sulfonate structure represented by the general formula (B1) is more preferably an oxime sulfonate compound represented by the following general formula (B3).

（式（Ｂ３）中、Ｒ⁴³は式（ｂ１）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。）

(In formula (B3), R ⁴³ has the same meaning as R ⁴² in formula (b1), and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano A group or a nitro group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the general formula (B3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group. Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and 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.

  Specific examples of the compound represented by the general formula (B3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino). ) Benzyl cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4- Methoxyphenyl] acetonitrile, α-[(4- Toluene sulfonyl) -4-methoxyphenyl] can be mentioned acetonitrile.

  Specific examples of preferred oxime sulfonate compounds include the following compounds (i) to (viii) and the like, and these can be used alone or in combination of two or more. Compounds (i) to (viii) can be obtained as commercial products. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.

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

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

  The compound represented by the general formula (OS-1) is more preferably a compound represented by the following general formula (OS-2).

In the general formula (OS-2), R ¹⁰¹ , R ¹⁰² , R ^{121 to} R ¹²⁴ are respectively synonymous with those in the formula (OS-1), and preferred examples are also the same.
Among these, an embodiment in which R ¹⁰¹ in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and is represented by the general formula (OS-2). And R ¹⁰¹ is most preferably a cyano group, a phenyl group, or a naphthyl group.

  In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.

  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 paragraph numbers 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to 1). b-34), but the present invention is not limited thereto.

  In the present invention, the compound containing the oxime sulfonate structure represented by the general formula (B1) is represented by the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-5). It is preferable that it is an oxime sulfonate compound represented by these.

（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 the general formula (OS-3) to general formula (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl X ^{1 to} X ³ each independently represents an oxygen atom or a sulfur atom, n ^{1 to} n ³ each independently represents 1 or 2, and m ^{1 to} m ³ each independently represents an integer of 0 to 6 Represents.)

In the general formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.
In the above formulas (OS-3) to (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.

In the general formulas (OS-3) to (OS-5), as the aryl group in R ²² , R ²⁵ and R ^28, an aryl group having 6 to 30 carbon atoms which may have a substituent may be used. preferable.

Further, in the above general formula (OS-3) ~ (OS -5), as the heteroaryl group in R ^1, heteroaryl group having a total carbon number of 4-30 which may have a substituent is preferable.

In the general formulas (OS-3) to (OS-5), at least one ring of the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be a heteroaromatic ring. For example, a heteroaromatic ring and benzene The ring may be condensed.

In the general formulas (OS-3) to (OS-5), R ²³ , R ²⁶ and R ²⁹ are preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group. preferable.
In the general formulas (OS-3) to (OS-5), one or two of R ²³ , R ²⁶ and R ²⁹ present in the compound are an alkyl group, an aryl group or a halogen atom. It is more preferable that one is an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.

The alkyl group for R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.

The aryl group for R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.

In the general formulas (OS-3) to (OS-5), X ^{1 to} X ³ each independently represents O or S, and is preferably O.
In the general formulas (OS-3) to (OS-5), the ring containing X ^{1 to} X ³ as a ring member is a 5-membered ring or a 6-membered ring.
In the general formulas (OS-3) to (OS-5), n ^{1 to} n ³ each independently represent 1 or 2, and when X ^{1 to} X ³ are O, n ^{1 to} n ³ are each independently 1 is preferable, and when X ^{1 to} X ³ are S, n ^{1 to} n ³ are preferably 2 each independently.

In the general formulas (OS-3) to (OS-5), 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. Represent. Among them, R ²⁴ , R ²⁷ and R ³⁰ are preferably each independently an alkyl group or an alkyloxy group.
The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.
In the general formulas (OS-3) to (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. It is preferable.

In the general formulas (OS-3) to (OS-5), the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. Preferably there is.

In the general formulas (OS-3) to (OS-5), m ^{1 to} m ³ each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, preferably 0 or 1. More preferably, it is particularly preferably 0.
Further, with respect to each of the substituents of (OS-3) to (OS-5), the substitution of (OS-3) to (OS-5) described in paragraph numbers 0092 to 0109 of JP2011-221494A. The preferred range of groups is likewise preferred.

  The compound containing the oxime sulfonate structure represented by the general formula (B1) is particularly an oxime sulfonate compound represented by any one of the following general formulas (OS-6) to (OS-11). preferable.

（式（ＯＳ−６）〜（ＯＳ−１１）中、Ｒ³⁰¹〜Ｒ³⁰⁶はアルキル基、アリール基またはヘテロアリール基を表し、Ｒ³⁰⁷は、水素原子または臭素原子を表し、Ｒ³⁰⁸〜Ｒ³¹⁰、Ｒ³¹³、Ｒ³¹⁶およびＲ³¹⁸はそれぞれ独立に水素原子、炭素数１〜８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基またはクロロフェニル基を表し、Ｒ³¹¹およびＲ³¹⁴はそれぞれ独立に水素原子、ハロゲン原子、メチル基またはメトキシ基を表し、Ｒ³¹²、Ｒ³¹⁵、Ｒ³¹⁷およびＲ³¹⁹はそれぞれ独立には水素原子またはメチル基を表す。）

(In the formulas (OS-6) to (OS-11), R ^{301 to} R ³⁰⁶ represent an alkyl group, an aryl group, or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ^{308 to} R ³¹⁰ , R ³¹³ , R ³¹⁶ and R ³¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group; R ³¹¹ and R ³¹⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group.)

  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. It is the same.

  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. However, the present invention is not limited to these.

  In the photosensitive resin composition of the present invention, (B) the photoacid generator is based on 100 parts by mass of all resin components (preferably a solid content, more preferably a total of copolymers) in the photosensitive resin composition. 0.1-10 parts by mass is preferably used, more preferably 0.5-10 parts by mass. Two or more kinds can be used in combination.

<(D) Solvent>
The photosensitive resin composition of the present invention contains (D) 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 optional components described below are dissolved in the solvent (D).
As the solvent (D) used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene. Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like. Specific examples of the solvent (D) used in the photosensitive resin composition of the present invention also include the solvents described in paragraph numbers 0174 to 0178 of JP2011-221494A.

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

Component D 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, a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a boiling point of 160 ° C. or higher and 200 ° C. A solvent having a boiling point of 130 ° C. or lower or a mixture thereof is more preferable, and a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C. and a solvent having a boiling point of 160 ° C. or higher and 200 ° C. or lower is more preferable.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C. or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C.), diethylene glycol methyl ethyl ether (boiling point 176 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.

  The content of the solvent (D) in the photosensitive resin composition of the present invention is 50% based on the total resin components (preferably solid content, more preferably 100 parts by mass of the polymer (A) component) in the photosensitive resin composition. It is preferably ˜3,000 parts by mass, more preferably 100 to 2,000 parts by mass, and even more preferably 150 to 1,500 parts by mass.

<Other ingredients>
In addition to the above components, the positive photosensitive resin composition of the present invention includes (E) a sensitizer, (F) a cross-linking agent, (G) an adhesion improver, and (H) a basic compound as necessary. (I) A surfactant can be preferably added. Further, the positive photosensitive resin composition of the present invention includes a plasticizer, a thermal radical generator, an antioxidant, a thermal acid generator, an ultraviolet absorber, a thickener, a development accelerator, and an organic or inorganic precipitate. Known additives such as inhibitors can be added.

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

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

The addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1000 parts by weight, and 10 to 500 parts by weight with respect to 100 parts by weight of the photoacid generator of the photosensitive resin composition. It is more preferable that it is 50 to 200 parts by weight.
Two or more kinds can be used in combination.

(F) Crosslinking agent It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
The crosslinking agent is not limited as long as a crosslinking reaction is caused by heat. (Excluding component A). For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, or a compound having at least one ethylenically unsaturated double bond can be added. .
Among these crosslinking agents, compounds having two or more epoxy groups or oxetanyl groups in the molecule are preferable, and epoxy resins are particularly preferable.
It is preferable that the addition amount of the crosslinking agent in the photosensitive resin composition of this invention is 0.01-50 weight part with respect to 100 weight part of total solids of the photosensitive resin composition, 0.5-30 More preferably, it is more preferably 2 to 10 parts by weight. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained. A plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.

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

These are available as commercial products. For example, the commercial item etc. of the paragraph number 0189 of Unexamined-Japanese-Patent No. 2011-221494, such as JER150S70 (made by Japan epoxy resin company), are mentioned.
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), Denacol 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- 14L, EX-216L, EX-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, aliphatic epoxy, 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, 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.

  As other crosslinking agents, alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A and compounds having at least one ethylenically unsaturated double bond are also preferably used. be able to. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

(G) Adhesion improving agent The photosensitive resin composition of the present invention may contain (G) an adhesion improving agent. The adhesion improver (G) that can be used in the photosensitive resin composition of the present invention includes an inorganic substance serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, and silicon nitride, a metal such as gold, copper, and aluminum. It is a compound that improves adhesion to an insulating film. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent (G) used as an adhesion improver used in the present invention is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more. These are effective in improving the adhesion to the substrate and are also effective in adjusting the taper angle with the substrate.
The content of the (G) adhesion improving agent in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. 10 mass parts is more preferable.

(H) Basic compound The photosensitive resin composition of the present invention may contain (H) a basic compound. (H) 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 paragraph numbers 0204 to 0207 of JP2011-221494A.

  The basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. It is preferable to use two kinds of heterocyclic amines in combination.

  The content of the basic compound (H) in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. It is more preferable that it is 0.005-0.2 mass part.

(I) Surfactant The photosensitive resin composition of the present invention may contain (I) a surfactant. (I) As the surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
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. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) (Manufactured by Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and the like.
Further, the surfactant includes the structural unit A and the structural unit B represented by the following general formula (1), and is a polystyrene equivalent weight measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. Preferred examples include copolymers having an average molecular weight (Mw) of 1,000 or more and 10,000 or less.

（式（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は重合比を表す重量百分率であり、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。） General formula (1)

(In Formula (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 or carbon number. 1 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 weight percentages representing a polymerization ratio, and p is a numerical value of 10% by mass to 80% by mass. Q represents a numerical value of 20% by mass to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.

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

General formula (2)

  The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of (I) surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less with respect to 100 parts by mass of the total solid content in the photosensitive resin composition, 0.001 More preferably, it is -50 mass parts, and it is still more preferable that it is 0.01-10 mass parts.

〔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, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, a phenolic antioxidant is particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used alone or in combination of two or more.

Examples of commercially available phenolic antioxidants include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70 and ADK STAB AO manufactured by ADEKA Corporation. -80, ADK STAB AO-330, Sumitizer Chemical Co., Ltd., Sumilizer GM, Sumilizer GS, Sumilizer MDP-S, Sumizer ZBM-S, Sumizer ZX, IRGANOX10 NO. IRGANOX1135, IRGANOX1330, IRGANOX1726, IRGANOX1425WL, IR ANOX1520L, IRGANOX245, IRGANOX259, IRGANOX3114, IRGANOX565, IRGAMOD295, Yoshinox BHT, Yoshinox BB, Yoshinox T3, Yoshinox T3, Yoshinox T3, Is mentioned.
Among these, ADK STAB AO-60, ADK STAB AO-80 (manufactured by ADEKA, Inc.), and Irganox 1098 (manufactured by Ciba Japan Co., Ltd.) are preferable.

The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation can be improved.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.

In the present invention, it is also preferable to use a sulfonic acid ester that does not substantially generate an acid by irradiation with exposure light and generates an acid by heat.
The fact that acid is not substantially generated by exposure light exposure can be determined by no change in the spectrum by IR spectrum or NMR spectrum measurement before and after the exposure of the compound.
The molecular weight of the sulfonic acid ester is preferably 230 to 1,000, and more preferably 230 to 800.
As the sulfonic acid ester that can be used in the present invention, a commercially available one may be used, or one synthesized by a known method may be used. The sulfonic acid ester can be synthesized, for example, by reacting a sulfonyl chloride or sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.
The content of the thermal acid generator in the photosensitive resin composition is preferably 0.5 to 20 parts by weight and more preferably 1 to 15 parts by weight when the total content of the component (A) is 100 parts by weight. .

等を挙げることができる。
酸増殖剤の感光性樹脂組成物への含有量は、光酸発生剤１００重量部に対して、１０〜１，０００重量部とするのが、露光部と未露光部との溶解コントラストの観点から好ましく、２０〜５００重量部とするのがさらに好ましい。 [Acid multiplication agent]
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. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less.
Specific examples of the acid proliferating agent include paragraph numbers 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39 of JP-T 9-512498. The compounds described on the 12th line to the 47th line on page 2 can be mentioned.
Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.
In particular

Etc.
The content of the acid multiplier in the photosensitive resin composition is 10 to 1,000 parts by weight with respect to 100 parts by weight of the photoacid generator. To 20 to 500 parts by weight is more preferable.

[Development accelerator]
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, any compound having a development acceleration effect can be used, but it is preferably a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group. Or the compound which has a phenolic hydroxyl group is more preferable, and the compound which has a phenolic hydroxyl group is the most preferable.
The molecular weight of the (M) development accelerator is preferably 100 to 2000, more preferably 100 to 1000, and most preferably 100 to 800.

Examples of development accelerators having an alkyleneoxy group include polyethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester, polybutylene glycol, Examples thereof include polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, and compounds described in JP-A-9-222724.
Examples of those having a carboxyl group include maleic acid, fumaric acid, acetylene carboxylic acid, 1,4-cyclohexanedicarboxylic acid, suberic acid, adipic acid, citric acid, malic acid and the like. In addition, compounds described in JP-A 2000-66406, JP-A 9-6001, JP-A 10-20501, JP-A 11-338150 and the like can be mentioned.
Examples of those having a phenolic hydroxyl group include JP-A No. 2005-346024, JP-A No. 10-133366, JP-A No. 9-194415, JP-A No. 9-222724, JP-A No. 11-171810, Examples thereof include compounds described in JP 2007-121766, JP-A-9-297396, JP-A 2003-43679, and the like. Among these, a phenol compound having 2 to 10 benzene rings is preferable, and a phenol compound having 2 to 5 benzene rings is more preferable. Particularly preferred is a phenolic compound disclosed as a dissolution accelerator in JP-A-10-133366.

A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass when the component (A) is 100 parts by mass from the viewpoints of sensitivity and residual film ratio. 20 mass parts is more preferable, and it is most preferable that it is 0.5-10 mass parts.
In addition, as other additives, thermal radical generators and thermal acid generators described in paragraph numbers 0120 to 0121 of JP2012-8223A can also be used.

[Method for producing cured film]
Next, the manufacturing method of the cured film of this invention is demonstrated.
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) A step of applying the positive photosensitive resin composition of the present invention on a substrate;
(2) removing the solvent from the applied positive photosensitive resin composition;
(3) a step of exposing with actinic rays;
(4) developing with an aqueous developer;
(5) A post-bake process for thermosetting.
Each step will be described below in order.

In the application step (1), the positive photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent.
In the solvent removing step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate.

  In the exposure step (3), the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm or more and 450 nm or less. In this step, (B) the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the component (A) is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.

  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”) is 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.

  The acid-decomposable group in the structural unit represented by the formula (a1-1) in the present invention has a low activation energy for acid decomposition, and is easily decomposed by an acid derived from an acid generator by exposure to a carboxyl group or phenol. A positive image can also be formed by development without necessarily carrying out PEB, since a functional hydroxyl group is generated. However, in the method for producing a cured film of the present invention, the photosensitive resin composition of the present invention is used. By performing the post-bake process, the obtained cured film can reduce heat flow. Therefore, when the cured film obtained by the method for producing a cured film of the present invention is used for a substrate as a resist, for example, even if the cured film of the present invention is heated together with the substrate, the resolution of the pattern hardly deteriorates. In the present specification, “heat flow” means that the cross-sectional shape of a patterned cured film formed by exposure and development steps is to heat the cured film (preferably 180 ° C. or more, more preferably 200 ° C. to 240 ° C. ) When deformed and the dimensions, taper angle, etc. deteriorate.

In the developing step (4), a copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
In the post-baking step of (5), the obtained positive image is heated to thermally decompose the acid-decomposable group in the structural unit (a1) to produce a carboxyl group or a phenolic hydroxyl group, and the structural unit (a3) A cured film can be formed by crosslinking with a crosslinking group, a crosslinking agent, or the like. This heating is preferably performed at a high temperature of 150 ° C. or more, more preferably 180 to 250 ° C., and particularly preferably 200 to 240 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 10 to 120 minutes.
When a step of irradiating the entire surface with actinic rays, preferably ultraviolet rays, is added before the post-baking step, the crosslinking reaction can be promoted by an acid generated by actinic ray irradiation.
Furthermore, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist.
When the cured film obtained by thermal curing in the post-baking step (5) is used as a dry etching resist, dry etching processing such as ashing, plasma etching, ozone etching, or the like can be performed as the etching processing.
Next, the formation method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

<Method for preparing photosensitive resin composition>
The essential component (A) and component (B) are mixed at a predetermined ratio and by any method, and dissolved by stirring to prepare a photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which the components are previously dissolved in the solvent (D) and then mixing them in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

<Application process and solvent removal process>
A desired dry coating film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by decompression and / or heating (pre-baking). Examples of the substrate include, for example, a glass plate in which a polarizing plate, a black matrix layer and a color filter layer are provided as necessary, and a transparent conductive circuit layer is further provided in the production of a liquid crystal display element. Although there is no restriction | limiting in particular as a method of applying the photosensitive resin composition to a board | substrate, Among these, it is preferable to apply | coat a photosensitive resin composition to a board | substrate in this invention. The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coat method, a spin coat method, can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Manufacturing with a large substrate is preferable because of high productivity. Here, the large substrate means a substrate having a size of 1 m or more and 5 m or less on each side.

  In addition, (2) the heating conditions for the solvent removal step are ranges in which the acid-decomposable group is decomposed in the structural unit (a1) in the unexposed area and the component (A) is not soluble in the alkaline developer. However, it is preferably about 80 to 130 ° C. for about 30 to 120 seconds.

<Exposure process and development process (pattern formation method)>
In the exposure step, the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. After the exposure step, heat treatment (PEB) is performed as necessary, and then in the development step, the exposed area is removed using an alkaline developer to form an image pattern.
For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used, and g-line (436 nm), i-line (365 nm), h-line (405 nm). Actinic rays having a wavelength of 300 nm to 450 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 developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. 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.
As a preferable developing solution, a 0.4 wt% aqueous solution, a 0.5 mass% aqueous solution, and a 2.38% aqueous solution of tetraethylammonium hydroxide can be mentioned.

The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 180 seconds, and the development method may be any of a liquid piling method, a dip method, and the like. After the development, washing with running water is performed for 30 to 90 seconds, and a desired pattern can be formed.
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.

<Post-bake process (crosslinking process)>
For a pattern corresponding to an unexposed area obtained by development, using a heating device such as a hot plate or oven, at a predetermined temperature, for example, 180 to 250 ° C., for a predetermined time, for example, 5 to 90 minutes on the hot plate, In the case of an oven, a protective film or an interlayer insulating film having excellent heat resistance, hardness, etc. can be formed by a heat treatment for 30 to 120 minutes to advance the crosslinking reaction. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.
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 the heat treatment, the substrate on which the pattern is formed is re-exposed with actinic rays and then post-baked (re-exposure / post-bake) to generate an acid from the component (B) present in the unexposed portion, thereby crosslinking. It is preferable to function as a catalyst that accelerates the process.
That is, the method for forming a cured film of the present invention preferably includes a re-exposure step in which re-exposure is performed with actinic rays between the development step and the post-bake step. The exposure in the re-exposure step may be performed by the same means as in the exposure step. In the re-exposure step, the entire surface of the substrate on which the film is formed by the photosensitive resin composition of the present invention is exposed. It is preferable.
A preferable exposure amount in the re-exposure step is 100 to 1,000 mJ / cm ² .

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

[Organic EL display device, Liquid crystal display device]
The organic EL display device and the liquid crystal display device of the present invention are characterized by including the cured film of the present invention.
The organic EL display device or liquid crystal display device of the present invention is not particularly limited except that it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and has various structures. Various known organic EL display devices and liquid crystal display devices can be used.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device and 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.
Further, the liquid crystal display device that can be taken by the liquid crystal display device of the present invention includes a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, and an OCB. (Optical Compensated Bend) method and the like.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.

FIG. 1 is a conceptual diagram illustrating 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 layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 1, 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 first 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.

FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type.

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

In the following synthesis examples, the following symbols represent the following compounds, respectively.
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MATHP: 2-tetrahydropyranyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
NBMA: n-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry)
DCPM: Dicyclopentanyl methacrylate MMA: Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries)
OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
V-601: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
α-Methylstyrene dimer (Wako Pure Chemical Industries, Ltd.)
Dodecyl mercaptan (Wako Pure Chemical Industries)
PGMEA: Methoxypropyl acetate (manufactured by Showa Denko)
HS-EDM: High Solve EDM (manufactured by Toho Chemical Industry Co., Ltd.)

<Synthesis Example of Compound M-1>
25.0 g (0.244 mol) of 3-hydroxymethyl-3-methyloxetane was dissolved in 100 mL of toluene, and 20 mg of hydroxy TEMPO was added. 9.76 g (0.244 mol) of NaOH was dissolved therein and cooled to 0 ° C. with an ice bath. To this solution, 37.3 g (0.244 mol) of chloromethylstyrene was added dropwise. It returned to room temperature and stirred at 80 degreeC for 6 hours. 200 mL of ethyl acetate and 200 mL of water were added, and the organic layer was extracted, dried over magnesium sulfate, and concentrated. The composition was subjected to column chromatography, and 24 g (0.10 mol, 40%) of the target product was isolated.
H-NMR (DMSO) δ 1.21 (s, 3H), 3.49 (s, 2H), 4.13 (d, 2H), 4.33 (d, 2H), 4.50 (s, 2H) , 5.25 (d, 1H), 5.83 (d, 1H), 6.75 (dd, 1H), 7.35 (d, 2H), 7.50 (d, 2H), colorless oil.

<Synthesis Example of Compound M-2>
28.0 g (0.244 mol) of 3-hydroxymethyl-3-ethyloxetane was dissolved in 100 mL of toluene, and 20 mg of hydroxy TEMPO was added. 9.76 g (0.244 mol) of NaOH was dissolved therein and cooled to 0 ° C. with an ice bath. To this solution, 37.3 g (0.244 mol) of chloromethylstyrene was added dropwise. It returned to room temperature and stirred at 80 degreeC for 6 hours. 200 mL of ethyl acetate and 200 mL of water were added, and the organic layer was extracted, dried over magnesium sulfate, and concentrated. The composition was subjected to column chromatography, and 28 g (0.12 mol, 49%) of the target product was isolated.
H-NMR (DMSO) δ 0.72 (t, 3H), 0.61 (dd, 2H), 3.54 (s, 2H), 4.20 (d, 2H), 4.41 (d, 2H) , 4.50 (s, 2H), 5.20 (d, 1H), 5.81 (d, 1H), 6.72 (dd, 1H), 7.28 (d, 2H), 7.49 ( d, 2H), colorless oil.

<Synthesis Example of Compound M-3>
100 mL of THF was cooled to 0 ° C., and 1.9 g of NaH (0.047 mol, 60% oil dispersion) was added. To this was added 8.6 g (0.047 mol) of 3-bromomethyl-3-hydroxymethyloxetane. Next, 6.38 g (0.047 mol) of 4-vinylbenzyl alcohol was added, the temperature was returned to room temperature, and the mixture was stirred at 80 ° C. for 2 hours. 200 mL of ethyl acetate and 200 mL of water were added, and the organic layer was extracted, dried over magnesium sulfate, and concentrated. The composition was subjected to column chromatography, and 3.6 g (0.015 mol, 33%) of the target product was isolated.
H-NMR (DMSO) δ 3.60 (s, 2H), 3.79 (s, 1H), 4.30 (d, 2H), 4.34 (d, 2H), 4.51 (s, 2H) , 5.26 (d, 1H), 5.80 (d, 1H), 6.75 (dd, 1H), 7.33 (d, 2H), 7.48 (d, 2H), colorless oil.

<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 of Polymer a-1>
PGMEA (89 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. MAA (5.72 g, corresponding to 9.5 mol% in all monomer components), MATH (44.28 g, corresponding to 37.5 mol%), M-1 (57.30 g, 37.5 mol%) was added to the solution. HEMA (corresponding to 11.39 g, 12.5 mol%), V-601 (4.83 g, corresponding to 3 mol% with respect to a total of 100 mol% of all monomer components) was dissolved over 2 hours. And dripped. After completion of the dropwise addition, the mixture was stirred for 2 hours to complete the reaction. Thereby, polymer a-1 was obtained.
Monomers and the like were changed as shown in the following table, and other polymers were synthesized.

  In the said Tables 1-5, the numerical value which does not attach | subject especially the unit in a table | surface makes mol% a unit. The numerical value of a polymerization initiator and an additive is mol% when a monomer component is 100 mol%. The solid content concentration is shown as monomer weight / (monomer weight + solvent weight) × 100 (unit weight%). When V-601 was used as the polymerization initiator, the reaction temperature was 90 ° C., and when V-65 was used, the reaction temperature was 70 ° C.

<Adjustment of photosensitive resin composition>
Polymer ((A) component), photoacid generator ((B) component), sensitizer, cross-linking agent, surfactant, basic compound and adhesion improver so that the solid content ratio shown in the table below is obtained. Were dissolved and mixed in a solvent and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain photosensitive resin compositions of various Examples and Comparative Examples.

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

(Photoacid generator)
P-1: Oxime sulfonate having the following structure (synthetic product)
P-2: Oxime sulfonate having the following structure (PAI-101, manufactured by Midori Chemical Co., Ltd.)
P-3: Sulfonium sulfonate having the following structure (synthetic product)
NQD: TAS-200 (manufactured by Toyo Kasei Co., Ltd.)
(Sensitizer)
S-1: Dibutoxyanthracene having the following structure (manufactured by Kawasaki Kasei Co., Ltd.)
(Crosslinking agent)
JER: JER150S70 (epoxy crosslinking agent, manufactured by Japan Epoxy Resin Co., Ltd.)
MX: Nicarax MX-270 (methoxymethyl crosslinking agent, manufactured by Sanwa Chemical Co., Ltd.)

(Surfactant)
W-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)
W-2: Silicone surfactant SH-8400 (Toray Dow Corning Silicone)
(Basic compound)
G-1: 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
G-2: 1,5-diazabicyclo [4.3.0] -5-nonene (manufactured by Wako Pure Chemical Industries, Ltd.)
G-3: Compound having the following structure

(Adhesion improver)
F-1: γ-glycidoxypropyltrialkoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)
(solvent)
HS-EDM: High Solve EDM (manufactured by Toho Chemical Industry Co., Ltd.)

(Comparative compound)
K-1: Monomer having the following structure (manufactured by Aldrich)
K-2: Monomer having the following structure (synthetic product)
K-3: Monomer having the following structure (synthetic product)
K-4: Monomer having the following structure (synthetic product)

<Transparency evaluation>
A coating film having a thickness of 3.0 μm was formed on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)). Next, it exposed through the predetermined | prescribed mask using i line | wire stepper (Canon Co., Ltd. product FPA-3000i5 +). After liquid development with an alkaline developer (2.38 wt% tetramethylammonium hydroxide aqueous solution) at 23 ° C. for 65 seconds, the resultant was rinsed with ultrapure water for 1 minute. The developed coating film was irradiated with 300 mJ / cm ² light at a wavelength of 365 nm using an ultrahigh pressure mercury lamp, and then heated in an oven at 220 ° C. for 45 minutes. The transmittance of this cured film was measured at a wavelength of 400 nm using a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.). The minimum transmittance is shown in the table (Fresh transparency).
Furthermore, it heated at 230 degreeC for 2 hours in oven. The transmittance of the cured film was measured in the same manner (heat resistant transparency).

<Evaluation of sensitivity>
Each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) and then pre-baked on a hot plate at 95 ° C. for 140 seconds to volatilize the solvent. A photosensitive resin composition layer having a thickness of 4.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive resin composition layer was developed with an alkali developer (0.4 wt% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
By these operations, the optimum i-line exposure (Eopt) when resolving 9 μm line and space at 1: 1 was defined as sensitivity.

<Unexposed film ratio>
Each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) and then pre-baked on a hot plate at 95 ° C. for 140 seconds to volatilize the solvent. A photosensitive resin composition layer having a thickness of 4.0 μm was formed.
Next, after developing with an alkali developer (0.4 wt% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, it was rinsed with ultrapure water for 20 seconds.
The unexposed residual film ratio was measured by measuring the film thickness before and after development.

<Measurement of relative permittivity>
A photosensitive resin composition is spin-coated on a bare wafer (N-type low resistance) (manufactured by SUMCO) and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a photosensitive resin having a thickness of 0.35 μm A composition layer was formed. The obtained photosensitive resin composition layer was exposed with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. so that the integrated irradiation amount was 300 mJ / cm ² (illuminance: 20 mW / cm ² ). The cured film was obtained by heating the substrate at 220 ° C. for 1 hour in an oven. With respect to this cured film, the relative dielectric constant was measured at a measurement frequency of 1 MHz using CVmap92A (made by Four Dimensions Inc.). The results are shown in the table below. When this value is 3.4 or less, the relative dielectric constant of the cured film is good.
In addition, the rotation speed depends on the viscosity of the photosensitive resin composition. In order to adjust the film thickness to 0.35 μm, the number of rotations was changed individually.

<Dry etching resistance (DE resistance)>
After each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to obtain a film thickness of 3 A photosensitive resin composition layer having a thickness of 0.0 μm was formed.
The obtained photosensitive resin composition layer is exposed with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. so that the integrated irradiation amount is 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line). Thereafter, the substrate was heated in an oven at 230 ° C. for 1 hour to obtain a cured film. The cured film is dry etched using a dry etching apparatus “CDE-80N (manufactured by Shibaura Mechatronics Co., Ltd.)” under the conditions that the etching gas is CF4 50 ml / min, O2 10 ml / min, output 400 mW, etching time 90 seconds. The film thickness before and after the treatment was measured, and the amount of film loss with respect to time by dry etching was calculated. The unit is Å / sec.

<Example 40>
Example 40 was performed in the same manner as in Example 1 except that the exposure machine was changed from a PLA-501F exposure machine manufactured by Canon Inc. to FX-803M (gh-Line stepper) manufactured by Nikon Corporation. The evaluation of sensitivity was the same level as in Example 1.

<Example 41>
Example 41 was performed in the same manner as in Example 1 except that the exposure machine was changed from a PLA-501F exposure machine manufactured by Canon Inc. to a 355 nm laser exposure machine and 355 nm laser exposure was performed. Here, as the 355 nm laser exposure machine, “AEGIS” manufactured by Buoy Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using “PE10B-V2” manufactured by OPHIR.
The evaluation of sensitivity was the same level as in Example 1.

<Example 42>
Example 42 was performed in the same manner as in Example 1 except that the exposure machine was changed from a Canon-made PLA-501F exposure machine to a UV-LED light source exposure machine. The evaluation of sensitivity was the same level as in Example 1.

  As described above, it was found that the photosensitive resin compositions of the examples showed excellent sensitivity and excellent shape of the formed pattern regardless of the substrate and the exposure machine.

<Example 43>
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1).
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 planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 16 on the substrate, pre-baking on a hot plate (90 ° C. × 2 minutes), and then applying high pressure from above the mask. After irradiating 45 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C. for 60 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 25 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.

<Example 44>
In the active matrix liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 44 was obtained.
That is, using the photosensitive resin composition of Example 25, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 43.

  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.

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

Claims (16)

(A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1) a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit represented by the following general formula (I):
(2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit represented by the following general formula (I):
A positive photosensitive resin composition containing (B) a photoacid generator and (D) a solvent.
Formula (I)

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, L represents a single bond or a divalent linking group, and R ² represents a hydrogen atom or an optionally substituted carbon atom. 1 Represents an alkyl group of -20 or an aryl group of 6-20 carbon atoms which may have a substituent.) The positive photosensitive resin composition according to claim 1, wherein R ¹ in the general formula (I) is a hydrogen atom. The positive photosensitive resin composition according to claim 1 or 2, wherein L in the general formula (I) is a divalent linking group containing at least one of an ester bond, an ether bond and an amide bond. Wherein in Formula (I), L is an ester bond, at least one ether bond and an amide bond, -CH ₂ - is a group composed of a combination of positive photosensitive resin composition according to claim 1 or 2 object. The positive photosensitive resin composition of any one of Claims 1-4 whose number of atoms which comprises the chain | strand part of L in the said general formula (I) is 2-10. R < ² > in the said general formula (I) is an alkyl group or a hydroxyalkyl group, The positive type photosensitive resin composition of any one of Claims 1-5. The positive photosensitive resin according to claim 1, wherein R ² in the general formula (I) is an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. Composition. The positive photosensitive resin composition of any one of Claims 1-7 whose L in the said general formula (I) is a bivalent coupling group containing an ester bond and / or an ether bond. The photosensitive resin composition of any one of Claims 1-8 whose said (a1) structural unit is a structural unit represented by the following general formula (III).
Formula (III)

(In the general formula (III), 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 is an alkyl group or an aryl group, and R ³ is Represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or arylene. Represents a group.) The positive photosensitive resin composition according to any one of claims 1 to 9, wherein at least one of the polymers contained in the polymer component (A) has a structural unit containing an acid group. . The positive photosensitive resin composition according to any one of claims 1 to 10, wherein the photoacid generator (B) contains at least one selected from an oxime sulfonate compound, an onium salt compound, and a 1,2-quinonediazide compound. object. Furthermore, the positive photosensitive composition of any one of Claims 1-11 containing a crosslinking agent (F). The cured film which hardened the positive photosensitive resin composition of any one of Claims 1-12. An interlayer insulating film using the cured film according to claim 13. A liquid crystal display device or an organic EL display device having the interlayer insulating film according to claim 14. The compound represented by the following general formula (IV).

(In general formula (IV), R ⁵ represents an ethyl group, a methyl group or a hydroxymethyl group.)

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