JP5548604B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a method for forming a cured film, a cured film, an organic EL display device, and a liquid crystal display device.

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

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

  Recently, there is an increasing demand for lower power consumption of the display device, and in order to reduce the electric capacity generated in the interlayer insulating film, a lower dielectric constant of the interlayer insulating film is required. The interlayer insulating film made of acrylic resin is made of silicon nitride film (SiN, relative dielectric constant 8), silicon oxynitride film (SiON, relative dielectric constant 4.5), silicon oxide film (SiO, relative dielectric constant 4), etc. A lower dielectric constant is desired, although it is lower.

  As a method for reducing the dielectric constant of an interlayer insulating film, a method of introducing a styrene unit as a copolymer component of an acrylic resin, a method of adding a styrene-containing polymer, and the like are known.

  Further, as an important characteristic of the photosensitive resin composition constituting the interlayer insulating film, there is an adhesiveness with the base substrate. In the development process, film peeling from the substrate may occur, which is one of the problems. In recent years, it has become difficult to perform fine pattern processing as display devices become higher performance and higher definition, and further improvement in adhesion of interlayer insulating film materials is required.

However, the above-described method for reducing the dielectric constant of the interlayer insulating film has insufficient adhesion to the underlying substrate during development, and it has been difficult to impart both characteristics simultaneously.
Moreover, what is described in patent document 1 and patent document 2 is known as a photosensitive resin composition. However, these photosensitive resin compositions also have insufficient compatibility between the low dielectric constant and the adhesion to the base substrate.

JP 2002-23374 A JP-A-8-62847

  An object of the present invention is to provide a photosensitive resin composition having a cured film having a low dielectric constant and good adhesion to a base substrate during development. To do. Furthermore, it aims at providing the formation method of a cured film using such a photosensitive resin composition, a cured film, an organic electroluminescence display, and a liquid crystal display device.

  Under such circumstances, the inventors of the present application have studied, and in the photosensitive resin composition, the photoacid generator containing an oxime sulfonate compound having a specific skeleton, and represented by the following formula (c1) It has been found that by using a compound in combination, a low dielectric constant after curing and adhesion with a high substrate can be achieved, and the present invention has been completed. Specifically, the object of the present invention has been achieved by the following means.

（式（ｂ１）中、Ｒ⁵は、アルキル基、シクロアルキル基またはアリール基を表し、Ｒ¹およびＲ²は、それぞれ置換基を示し、互いに結合して、環を形成していてもよい。）
（Ｃ）式（ｃ１）で表される化合物、および、
式（ｃ１）

（式（ｃ１）中、Ｒ¹およびＲ²は、それぞれ独立に、炭素数１〜１０の分岐していてもよいアルキル基、置換基を有しても良いアリール基、置換基を有しても良いシクロアルキル基、またはモルホリノ基を表す。Ｒ³は酸素原子または硫黄原子を表し、Ａは２価の連結基を表す。）
（Ｄ）溶剤、を含有することを特徴とする感光性樹脂組成物。
（２）化学増幅ポジ型感光性樹脂組成物である、（１）に記載の感光性樹脂組成物。
（３）前記（Ｃ）の化合物が、式（ｃ２）で表されるチオ尿素化合物である、（１）または（２）に記載の感光性樹脂組成物。
式（ｃ２）

（式（ｃ２）中、Ｒ¹およびＲ²は、それぞれ独立に、炭素数１〜１０の分岐していてもよいアルキル基、置換基を有しても良いアリール基、置換基を有しても良いシクロアルキル基、またはモルホリノ基を表す。Ａは２価の連結基を表す。）
（４）前記式（ｃ２）のＲ¹がモルホリノ基である、（３）に記載の感光性樹脂組成物。
（５）前記（Ｃ）の化合物が、式（ｃ３）で表されるチオ尿素化合物である、（１）または（２）に記載の感光性樹脂組成物。
式（ｃ３）

（式（ｃ３）中、Ａは２価の連結基を表す。）
（６）前記（Ｂ）の光酸発生剤が、式（ＯＳ−３）、式（ＯＳ−４）、式（ＯＳ−５）または式（ｂ３）で表される化合物である、（１）〜（５）のいずれか１項に記載の感光性樹脂組成物。

（式（ＯＳ−３）〜式（ＯＳ−５）中、Ｒ¹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、Ｒ²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、Ｒ⁶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、ＸはＯまたはＳを表し、ｎは１または２を表し、ｍは０〜６の整数を表す。）

（式中、Ｒ^B1はアルキル基、アルコキシ基、または、ハロゲン原子を表し、Ｒ^B2はアルキル基またはアリール基を表す。）
（７）前記カルボキシ基が酸分解性基で保護された残基を有するモノマー単位（ａ１）が、アセタール構造またはケタール構造を有する、（１）〜（６）のいずれか１項に記載の感光性樹脂組成物。
（８）前記（Ｃ）の化合物が、アクリル系共重合体成分１００重量部に対し、０．０１〜２．５０重量部の範囲で含まれる。（１）〜（７）のいずれか１項に記載の感光性樹脂組成物。
（９）（１）（１）〜（８）のいずれか１項に記載の感光性樹脂組成物を基板上に適用する工程、
（２）塗布された感光性樹脂組成物から溶剤を除去する工程、
（３）溶剤が除去された感光性樹脂組成物を活性光線により露光する工程、
（４）露光された感光性樹脂組成物を水性現像液により現像する工程、および、
（５）現像された感光性樹脂組成物を熱硬化するポストベーク工程、を含む硬化膜の形成方法。
（１０）前記現像工程後、前記ポストベーク工程前に、現像された感光性樹脂組成物を全面露光する工程を含む、（９）に記載の硬化膜の形成方法。
（１１）（９）または（１０）に記載の方法により形成された硬化膜。
（１２）層間絶縁膜である、（１１）に記載の硬化膜。
（１３）
（１１または１２に記載の硬化膜を具備する有機ＥＬ表示装置または液晶表示装置。 (1) (A) a monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group, or a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group, (a1), An acrylic copolymer containing a monomer unit (a2) having a crosslinking group,
(B) a photoacid generator containing an oxime sulfonate compound represented by formula (b1),
Formula (b1)

(In Formula (b1), R ⁵ represents an alkyl group, a cycloalkyl group, or an aryl group, and R ¹ and R ² each represent a substituent, and may be bonded to each other to form a ring. )
(C) a compound represented by the formula (c1), and
Formula (c1)

(In Formula (c1), R ¹ and R ² each independently have an alkyl group which may have 1 to 10 carbon atoms, an aryl group which may have a substituent, or a substituent. Represents a good cycloalkyl group or morpholino group, R ³ represents an oxygen atom or a sulfur atom, and A represents a divalent linking group.)
(D) A photosensitive resin composition comprising a solvent.
(2) The photosensitive resin composition according to (1), which is a chemically amplified positive photosensitive resin composition.
(3) The photosensitive resin composition according to (1) or (2), wherein the compound (C) is a thiourea compound represented by the formula (c2).
Formula (c2)

(In Formula (c2), R ¹ and R ² each independently have an alkyl group which may have 1 to 10 carbon atoms, an aryl group which may have a substituent, or a substituent. Represents a good cycloalkyl group or morpholino group, and A represents a divalent linking group.)
(4) The photosensitive resin composition according to (3), wherein R ^{1 in the} formula (c2) is a morpholino group.
(5) The photosensitive resin composition according to (1) or (2), wherein the compound (C) is a thiourea compound represented by the formula (c3).
Formula (c3)

(In formula (c3), A represents a divalent linking group.)
(6) The photoacid generator of (B) is a compound represented by formula (OS-3), formula (OS-4), formula (OS-5) or formula (b3), (1) The photosensitive resin composition of any one of-(5).

(In Formula (OS-3) to Formula (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and R ² independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. R ⁶ represents each independently a halogen atom, alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group or alkoxysulfonyl group, X represents O or S, n represents 1 or 2, m Represents an integer of 0 to 6.)

(Wherein R ^B1 represents an alkyl group, an alkoxy group, or a halogen atom, and R ^B2 represents an alkyl group or an aryl group.)
(7) The photosensitive composition according to any one of (1) to (6), wherein the monomer unit (a1) having a residue in which the carboxy group is protected with an acid-decomposable group has an acetal structure or a ketal structure. Resin composition.
(8) The compound of (C) is contained in the range of 0.01 to 2.50 parts by weight with respect to 100 parts by weight of the acrylic copolymer component. (1) The photosensitive resin composition of any one of (7).
(9) (1) A step of applying the photosensitive resin composition according to any one of (1) to (8) on a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) A method for forming a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition.
(10) The method for forming a cured film according to (9), comprising a step of exposing the entire surface of the developed photosensitive resin composition after the developing step and before the post-baking step.
(11) A cured film formed by the method according to (9) or (10).
(12) The cured film according to (11), which is an interlayer insulating film.
(13)
(An organic EL display device or a liquid crystal display device comprising the cured film described in 11 or 12.

  According to the present invention, it is possible to provide a photosensitive resin composition that can achieve a low relative dielectric constant and high substrate adhesion after curing.

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. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, a “group” such as an alkyl group may or may not have a substituent unless otherwise specified. Further, in the case of a group having a limited number of carbons, the number of carbons means a number including the number of carbons that the substituent has. Moreover, an organic EL element means an organic electroluminescence element.

（式（ｂ１）中、Ｒ⁵は、アルキル基、シクロアルキル基またはアリール基を表し、Ｒ¹およびＲ²は、それぞれ置換基を示し、互いに結合して、環を形成していてもよい。）
（Ｃ）式（ｃ１）で表される化合物、および、
式（ｃ１）

（式（ｃ１）中、Ｒ¹およびＲ²は、それぞれ独立に、炭素数１〜１０の分岐していてもよいアルキル基、置換基を有しても良いアリール基、置換基を有しても良いシクロアルキル基、またはモルホリノ基を表す。Ｒ³は酸素原子または硫黄原子を表し、Ａは２価の連結基を表す。）
（Ｄ）溶剤、を含有することを特徴とする。
このような構成とすることにより、本発明の感光性樹脂組成物の硬化後の誘電率を低くでき、かつ、高い基板密着性を達成できる。特に、本発明の組成物は、化学増幅ポジ型感光性樹脂組成物に有益である。 The photosensitive resin composition of the present invention comprises (A) a monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group, or a monomer having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group. An acrylic copolymer containing a unit, (a1) and a monomer unit (a2) having a crosslinking group,
(B) a photoacid generator containing an oxime sulfonate compound represented by formula (b1),
Formula (b1)

(In Formula (b1), R ⁵ represents an alkyl group, a cycloalkyl group, or an aryl group, and R ¹ and R ² each represent a substituent, and may be bonded to each other to form a ring. )
(C) a compound represented by the formula (c1), and
Formula (c1)

(In Formula (c1), R ¹ and R ² each independently have an alkyl group which may have 1 to 10 carbon atoms, an aryl group which may have a substituent, or a substituent. Represents a good cycloalkyl group or morpholino group, R ³ represents an oxygen atom or a sulfur atom, and A represents a divalent linking group.)
(D) It contains a solvent.
By setting it as such a structure, the dielectric constant after hardening of the photosensitive resin composition of this invention can be made low, and high board | substrate adhesiveness can be achieved. In particular, the composition of the present invention is useful for a chemically amplified positive photosensitive resin composition.

(A) Acrylic copolymer (A) Acrylic copolymer contained in the photosensitive resin composition of the present invention,
(A1) A monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group, or a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group (hereinafter referred to as “monomer unit (a1)”) ")
(A2) a monomer unit (a2) having a crosslinking group (hereinafter also referred to as “monomer unit (a2)”);
Is an acrylic copolymer containing
The component (A) may contain another monomer unit (a3) in addition to the monomer unit (a1) and the monomer unit (a2).
In the present invention, among monomer units having a residue in which a carboxy group is protected with an acid-decomposable group, or monomer units having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group, the carboxy group is acid-decomposed. A monomer unit having a residue protected with a functional group is preferred.

(A) The acrylic copolymer is preferably a resin that is insoluble in alkali and becomes alkali-soluble when the acid-decomposable group of the monomer 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, a monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group can generate a carboxy group by the decomposition of the protecting group with an acid, and the phenolic hydroxyl group is an acid-decomposable group. The monomer unit having a protected residue 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) acrylic copolymer does not exclude the introduction of an acidic group as long as the entire (A) acrylic copolymer is kept insoluble in alkali. And / or other monomer units having a phenolic hydroxyl group.

The (A) acrylic copolymer is preferably an addition polymerization type resin, and is a polymer containing a monomer unit derived from (meth) acrylic acid and / or an ester thereof as a main component. Within the scope of the present invention, a monomer unit other than the monomer unit derived from (meth) acrylic acid and / or its ester, for example, a monomer unit derived from styrene or a monomer unit derived from a vinyl compound Etc. may be included.
The (A) acrylic copolymer preferably contains 50 mol% or more of monomer units derived from (meth) acrylic acid and / or its ester with respect to all monomer units in the polymer, and is 90 mol%. It is more preferable to contain the above, and it is particularly preferable that the polymer is composed of only monomer units derived from (meth) acrylic acid and / or its ester.
The “monomer unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic monomer unit”. “(Meth) acrylic acid” means “methacrylic acid and / or acrylic acid”.
Hereinafter, each of the monomer unit (a1) and the monomer unit (a2) will be described.

(A1) A monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group, or a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group (A) It has a monomer unit having a residue protected with an acid-decomposable group or a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group. When the component (A) has the monomer unit (a1), a highly sensitive photosensitive resin composition can be obtained.

(A1-1) Monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group (a1-1-1) Monomer unit having a carboxy group As a monomer unit having a carboxy group, for example, an unsaturated monocarboxylic acid Examples thereof include monomer units derived from unsaturated carboxylic acids having at least one carboxy group in the molecule, such as acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids.
Examples of the unsaturated carboxylic acid used for obtaining the monomer unit having a carboxy group 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 monomer unit which has a carboxy group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like.
Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of the dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.
As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used. Among them, from the viewpoint of developability, in order to form a monomer unit having a carboxy group, it is preferable to use acrylic acid, methacrylic acid, an anhydride of unsaturated polyvalent carboxylic acid, etc., and acrylic acid or methacrylic acid. More preferably, it is used.
The monomer unit (a1-1-1) having a carboxy group may be composed of one kind alone, or may be composed of two or more kinds.

(A1-1-2) Monomer unit having both an ethylenically unsaturated group and an acid anhydride residue The monomer unit (a1-2) having both an ethylenically unsaturated group and an acid anhydride residue is ethylenic. It is preferably a unit derived from a monomer obtained by reacting a hydroxyl group present in a monomer unit having an unsaturated group with an acid anhydride.
As the acid anhydride, known ones can be used. Specific examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride. Examples include basic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. 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.

(A1-1-3) Monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group The monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group is preferably the above (a1- 1-1) A monomer unit having a residue in which the carboxy group described in (a1-1-2) is protected by an acid-decomposable group described in detail below.
As the acid-decomposable group, known acid-decomposable groups in the positive resist for KrF and the positive resist for ArF can be used and are not particularly limited. Conventionally, as an acid-decomposable group, a group that is relatively easily decomposed by an acid (for example, an acetal functional group such as a tetrahydropyranyl group) or a group that is relatively difficult to be decomposed by an acid (for example, a t-butyl ester group, t -T-butyl functional groups such as butyl carbonate groups) are known.
Among these acid-decomposable groups, the basic physical properties of the resist, especially the sensitivity and pattern shape, should be a monomer unit having a residue in which the carboxy group is protected with an acetal or a residue in which the carboxy group is protected with a ketal. From the viewpoints of contact hole formability and storage stability of the photosensitive resin composition. Furthermore, it is more preferable from a sensitivity viewpoint that a carboxyl group is a residue protected by the acetal or ketal represented by a following formula (a1-1) among acid-decomposable groups. In addition, when the carboxy group is an acetal or ketal-protected residue represented by the following formula (a1-1), the entire residue is — (C═O) —O—CR ¹ R ² ( OR ³ ).

（式（ａ１−１）中、Ｒ¹およびＲ²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、Ｒ¹とＲ²とが共に水素原子の場合を除く。Ｒ³は、アルキル基を表す。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い。）

(In formula (a1-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, except that R ¹ and R ² are both hydrogen atoms, and R ³ represents an alkyl group. R ¹ or R ²
And R ³ may be linked to form a cyclic ether. )

In formula (a1-1), R ^{1 to} R ³ each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic. Here, both R ¹ and R ² do not represent a hydrogen atom, and at least one of R ¹ and R ² represents an alkyl group.

In the formula (a1-1), when R ¹ , R ² and R ³ 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, t-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 ¹ , R ² and R ³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹ , R ² and R ³ 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 when it is a branched alkyl group, it may have a C3-C12 cycloalkyl group as a substituent.
These substituents may be further substituted with the above substituents.

In Formula (a1-1), when R ¹ , R ^2, and R ³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, and more preferably has 6 to 10 carbon atoms. 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 ¹ , R ² and R ³ can be bonded to each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹ and R ² , R ¹ and R ³ or R ² and R ³ are bonded include, for example, 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 formula (a1-1), it is preferable that either R ¹ or R ² is a hydrogen atom or a methyl group.

  As the radical polymerizable monomer used for forming the monomer unit having a residue represented by the formula (a1-1), a commercially available one may be used, or one synthesized by a known method may be used. You can also. For example, as shown below, it can be synthesized by reacting (meth) acrylic acid with vinyl ether in the presence of an acid catalyst.

R ¹¹ represents a hydrogen atom or an alkyl group, and the alkyl group is the same as the alkyl group shown as R ^{1 to} R ³ in formula (a1-1). R ¹¹ is preferably a hydrogen atom or a methyl group.
R ¹² and R ¹³ have the same meaning as R ² in formula (a1-1) as —CH (R ¹² ) (R ¹³ ), R ¹⁴ has the same meaning as R ¹ in formula (a), and R ¹⁵ Is synonymous with R ³ in formula (a1-1), and the preferred range thereof is also the same.
In the above synthesis, (meth) acrylic acid may be previously copolymerized with other monomers and then reacted with vinyl ether in the presence of an acid catalyst.

  In the present invention, examples of the monomer unit (a1-1) include the following.

（上記式中、Ｒ¹は、それぞれ、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、Ｒ²はそれぞれ、炭素数１〜４のアルキル基を表す。ｎ１およびｎ２はそれぞれ１〜５の整数であり、ｎ３は１〜４の整数であり、ｎ４は１〜３の整数である。）
Ｒ¹は、それぞれ、水素原子または炭素数１〜４のアルキル基を表し、水素原子またはメチル基が好ましく、メチル基がさらに好ましい。
Ｌ¹はカルボニル基またはフェニレン基を表し、カルボニル基がより好ましい。
Ｒ²はそれぞれ、水素原子または炭素数１〜４のアルキル基を表し、水素原子またはメチル基が好ましく、何れも水素原子であることがより好ましい。
ｎ１、ｎ２、ｎ３およびｎ４は、それぞれ、０が好ましい。
上記の中でも、特に、（１）、（２）、（５）または（７）が好ましく、（２）、または（７）がさらに好ましく、（７）が特に好ましい。

(In the above formula, R ¹ 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 ² represents an alkyl group having 1 to 4 carbon atoms, respectively. N1 and n2 are each an integer of 1 to 5, n3 is an integer of 1 to 4, and n4 is an integer of 1 to 3.
R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
L ¹ represents a carbonyl group or a phenylene group, and a carbonyl group is more preferable.
R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
n1, n2, n3 and n4 are each preferably 0.
Among these, (1), (2), (5) or (7) is particularly preferable, (2) or (7) is more preferable, and (7) is particularly preferable.

  Preferable specific examples of the monomer unit (a1-1) having a residue in which a carboxy group is protected with an acid-decomposable group include the following monomer units. R represents a hydrogen atom or a methyl group.

(A1-2) Monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group (a1-2-1) Monomer unit having a phenolic hydroxyl group As a monomer unit having a phenolic hydroxyl group, a hydroxystyrene-based monomer unit Although the monomer unit and the monomer unit in a novolak-type resin are mentioned, Among these, the monomer unit derived from (alpha) -methylhydroxystyrene is preferable from a transparency viewpoint. Among the monomer units having a phenolic hydroxyl group, the monomer unit represented by the formula (a1-2) is preferable from the viewpoints of transparency and sensitivity.

（式（ａ１−２）中、Ｒ²⁰は水素原子またはメチル基を表し、Ｒ²¹は単結合または連結基を表し、Ｒ²²はハロゲン原子またはアルキル基を表し、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、Ｒ²²が２以上存在する場合、これらのＲ²²は相互に異なっていてもよいし同じでもよい。）

(In Formula (a1-2), R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ represents a single bond or a linking group, R ²² represents a halogen atom or an alkyl group, and a represents an integer of 1 to 5. And b represents an integer of 0 to 4, and a + b is 5 or less, and when R ²² is 2 or more, these R ²² may be different or the same.

In formula (a1-2), R ²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R ²¹ 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 for R ²¹ may be exemplified alkylene groups, specific examples R ²¹ 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, R ²¹ is preferably 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 ²¹ is the reference (first position).
R ²² 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;

Among the monomer units having a phenolic hydroxyl group, when R ²¹ is not an alkylene group in the above formula (a1-2), the monomer unit represented by the formula (a1-2 ′) is a viewpoint of transparency and sensitivity. To more preferred. Preferred examples of the linking group for R ²¹ include an alkyleneoxycarbonyl group (from the main chain side of the acrylic copolymer) other than an alkylene group. In this case, the monomer unit having a phenolic hydroxyl group is It is preferable to be represented by the formula (a1-2 ′).

（式（ａ１−２’）中、Ｒ³⁰は、式（ａ１−２）におけるＲ²⁰と同義であり、Ｒ³²は式（ａ１−２）におけるＲ²²と同義であり、ａおよびｂは式（ａ１−２）におけるａおよびｂとそれぞれ同義である。また、好ましい範囲も同様である。）

(In formula (a1-2 ′), R ³⁰ has the same meaning as R ²⁰ in formula (a1-2), R ³² has the same meaning as R ²² in formula (a1-2), and a and b are the formulas (It is synonymous with a and b in (a1-2). The preferred range is also the same.)

In the formula (a1-2 ′), R ³³ represents a divalent linking group, and an alkylene group can be preferably exemplified. The alkylene group may be linear or branched, and preferably has 2 to 6 carbon atoms, and is an ethylene group, propylene group, isopropylene group, n-butylene group, tert-butylene group, or pentylene group. , Isopentylene group, neopentylene group, hexylene group and the like. Further, the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. Among these, R ³³ is preferably an ethylene group, a propylene group, or a 2-hydroxypropylene group from the viewpoint of sensitivity.

(A1-2-2) Monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group A monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group is (a1-2-2). 1) A monomer unit having a residue in which a phenolic hydroxyl group of a monomer unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below. As the acid-decomposable group, a known group can be used as described above, and is not particularly limited. Among the acid-decomposable groups, the basic physical properties of the resist, especially the sensitivity and pattern shape, should be a monomer unit having a residue in which the phenolic hydroxyl group is protected with an acetal, or a residue in which the phenolic hydroxyl group is protected with a ketal. From the viewpoint of storage stability of the photosensitive resin composition and formability of the contact hole. Furthermore, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the phenolic hydroxyl group is a residue protected with an acetal or ketal represented by the formula (a1-1). In addition, when the phenolic hydroxyl group is an acetal or ketal-protected residue represented by the formula (a1-1), the entire residue is —Ar—O—CR ¹ R ² (OR ³ ). It has a structure. Ar represents an arylene group.

Preferred examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R ¹ = R ² = R ³ = methyl group, R ¹ = R ² = methyl group and R ³ = benzyl group.

Examples of the radical polymerizable monomer used to form a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acetal or ketal include, for example, a 1-alkoxyalkyl protector of hydroxystyrene, a hydroxystyrene Protected tetrahydropyranyl, 1-alkoxyalkyl protected α-methyl-hydroxystyrene, tetrahydropyranyl protected α-methyl-hydroxystyrene, 1-alkoxyalkyl protected 4-hydroxyphenyl methacrylate, 4-hydroxyphenyl Tetrahydropyranyl protected form of methacrylate, 1-alkoxyalkyl protected form of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester Protected trahydropyranyl, 1-alkoxyalkyl protected of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, protected tetrahydropyranyl of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, 4- 1-alkoxyalkyl protected form of hydroxybenzoic acid (3-methacryloyloxypropyl) ester, tetrahydropyranyl protected form of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxy- 2-hydroxypropyl) ester 1-alkoxyalkyl protector, 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester tetrahydropyranyl protector, and the like.
Among these, 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate, tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate, 1-alkoxyalkyl protector of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester Tetrahydropyranyl protected form of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, 1-alkoxyalkyl protected form of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, 4-hydroxybenzoic acid (2- Tetrahydropyranyl protected form of methacryloyloxyethyl) ester, 1-alkoxyalkyl protected form of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, 4-hydroxybenzoic acid (3-methacrylo) (Luoxypropyl) ester tetrahydropyranyl protected, 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester 1-alkoxyalkyl protected, 4-hydroxybenzoic acid (3-methacryloyloxy-2- A tetrahydropyranyl protected form of hydroxypropyl ester is preferred from the viewpoint of transparency.

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

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

  Preferable specific examples of the monomer unit (a1-2) include the following monomer units. R represents a hydrogen atom or a methyl group, and a methyl group is more preferable.

  In the monomer unit constituting the component (A), the content of the monomer unit (a1) is preferably 3 to 70 mol% as a whole from the acrylic copolymer of the component (A) from the viewpoint of sensitivity. 60 mol% is more preferable and 10-50 mol% is further more preferable.

  A monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group is characterized by faster development than a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group. Therefore, a monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group is preferable for rapid development. Conversely, when it is desired to delay development, it is preferable to use a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group.

(A2) Monomer unit having a crosslinking group The component (A) has a monomer unit (a2) having a crosslinking group. The crosslinking group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment. Preferred embodiments of the monomer unit having a crosslinking group include a monomer unit including at least one selected from the group consisting of a 3-membered ring and / or a 4-membered cyclic ether residue and an ethylenically unsaturated group. It is done. In more detail, the following are mentioned.

(A2-1) Monomer unit having a 3-membered ring and / or 4-membered cyclic ether residue The (A) acrylic copolymer has a 3-membered ring and / or 4-membered cyclic ether residue. It is preferable to contain a monomer unit (monomer unit (a2-1)). The 3-membered cyclic ether residue is also called an epoxy group, and the 4-membered cyclic ether residue is also called an oxetanyl group. The monomer unit (a2-1) having an epoxy group and / or oxetanyl group is preferably a monomer unit having an alicyclic epoxy group and / or oxetanyl group, more preferably a monomer unit having an oxetanyl group. preferable.
The monomer unit having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one monomer unit, one or more epoxy groups and one or more oxetanyl groups, two Although it may have the above epoxy groups or two or more oxetanyl groups and is not particularly limited, it preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and epoxy groups and / or oxetanyl groups It is more preferable to have one or two 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 monomer 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, acrylate-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, cycloaliphatic according to paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Compounds containing an epoxy skeleton It is.
Specific examples of the radical polymerizable monomer used for forming a monomer unit having an oxetanyl group include, for example, a (meth) acryl having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. An acid ester etc. can be mentioned.
Specific examples of the radical polymerizable monomer used to form a monomer unit having an epoxy group and / or an oxetanyl group include a monomer having a methacrylate structure and a monomer having an acrylate structure. Is preferred.

  Among these monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and paragraphs 0011 to 0016 of JP 2001-330953 A. (Meth) acrylic acid esters having an oxetanyl group, particularly preferred are (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Among these, preferred are 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 monomer units can be used alone or in combination of two or more.

  The monomer unit (a2-1) preferably has a residue selected from the group consisting of the following formula (a2-1-1) and formula (a2-1-2).

The monomer unit (a2-1) has any one of the three residues represented by the formula (a2-1-1) from the structure represented by the formula (a2-1-1) It means having one or more groups.
The monomer unit (a2-1) further preferably has a 3,4-epoxycyclohexyl group, a 2,3-epoxycyclohexyl group, or a 2,3-epoxycyclopentyl group.

（式（ａ２−１−２）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 formula (a2-1-2), 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 formula (a2-1-2), R ^1b and R ^6b each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and preferably a hydrogen atom or carbon number 1 It is more preferably an alkyl group of ˜5 (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 a 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, and 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 a residue represented by the above formula (a2-1-2) include a (3-ethyloxetane-3-yl) methyl group.

  Preferable specific examples of the monomer unit (a2-1) include the following monomer units. R represents a hydrogen atom or a methyl group.

  In the present invention, from the viewpoint of curing sensitivity, an oxetanyl group is preferable among 3-membered and 4-membered cyclic ether residues. In the present invention, an alicyclic epoxy group and an oxetanyl group are preferable from the viewpoint of transmittance (transparency). From the above, in the present invention, the 3-membered and 4-membered cyclic ether residues are preferably an alicyclic epoxy group and an oxetanyl group, and particularly preferably an oxetanyl group.

(A2-3) Monomer unit having an ethylenically unsaturated group As one of the monomer units (a2) having a crosslinking group, there may be mentioned a monomer unit (a2-3) having an ethylenically unsaturated group (hereinafter referred to as “monomer”). Also referred to as “unit (a2-3)”). The monomer unit (a2-3) having an ethylenically unsaturated group is preferably a monomer 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 monomer unit having a side chain is more preferable, and a monomer unit having a side chain represented by the formula (a2-3-1) is more preferable.

（式（ａ２−３−１）中、Ｒ¹は炭素数１〜１３の二価の連結基を表し、Ｒ³は水素原子またはメチル基を表す。）

(In formula (a2-3-1), R ¹ represents a divalent linking group having 1 to 13 carbon atoms, and R ³ represents a hydrogen atom or a methyl group.)

R ¹ 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 thereof, such as an ester bond, an ether bond, an amide bond, and a urethane bond. Bonds may be included. The divalent linking group may have a substituent such as a hydroxy group or a carboxy group at an arbitrary position. Specific examples of R ¹ include divalent linking groups represented by formula (A-1) to formula (A-10).

  Among the side chains represented by the formula (a2-3-1), an aliphatic side chain is preferable. Among the side chains having a linking group represented by the formula (a2-3-1), a side chain whose terminal is an acryloyl group or a methacryloyl group is more preferable.

  Moreover, it is preferable that 1 mol of ethylenically unsaturated groups contained in the side chain represented by the formula (a2-3-1) are included with respect to 150 to 2,000 g of the polymer (A). It is more preferable that 1 mol is contained with respect to ˜1,300 g.

The method for obtaining the monomer unit (a2-3) having a side chain represented by the formula (a2-3-1) is not particularly limited, but for example, a polymer having a specific functional group may be obtained in advance by a polymerization method such as radical polymerization. An acrylic system having a monomer unit (a2-3) by reacting with a compound 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 a copolymer.
Here, examples of the specific functional group include a carboxy 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 carboxy group and an epoxy group, a combination of a carboxy 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 carboxy 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 carboxy group that is a specific functional group and a glycidyl methacrylate that is a specific compound, and a combination of a hydroxy group that is a specific functional group and an isocyanate ethyl methacrylate that is a specific compound. Is mentioned.

  In the present invention, the monomer unit (a2-3) is preferably a monomer unit represented by the formula (a2-3-2).

（式（ａ２−３−２）中、Ｒ¹は、式（ａ２−３−１）におけるＲ¹と同義であり好ましい範囲も同様である。Ｒ²、Ｒ³はそれぞれ独立に、水素原子またはメチル基を表す。）

(In the formula (a2-3-2), R ¹ has the formula (a preferred range has the same meaning as R ¹ is also similar .R ^2, R ³ are each independently of A2-3-1), hydrogen atom or Represents a methyl group.)

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

Examples of the monomer having a carboxy 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.
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, 1,7. -Octadiene monoepoxide, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate and the like.
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 Shi-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 an isocyanate group, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m-tetramethyl xylene isocyanate, etc. are mentioned, for example.

  In the present invention, when obtaining a polymer having a specific functional group, the monomer unit having the specific functional group and (a1) a monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group, or And a monomer that becomes a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group. Furthermore, the monomer used as other monomer units (a3) other than (a1) and (a2) mentioned later can be used together.

  The method for obtaining the polymer having a specific functional group used in the present invention is not particularly limited. For example, in a solvent in which a monomer having a specific functional group, other monomers, and a polymerization initiator or the like coexist if desired, 50 to It can be obtained by a polymerization reaction at a temperature of 110 ° C. In that case, the solvent used will not be specifically limited if it dissolves the monomer which comprises the polymer which has a specific functional group, and the polymer which has a specific functional group. As a specific example, the solvent described in the (D) solvent mentioned later is mentioned. The polymer having the specific functional group thus obtained is usually in a solution state dissolved in a solvent.

  Next, the obtained polymer having the specific functional group is reacted with the specific compound to obtain a monomer unit (a2-3) having an ethylenically unsaturated group at the end of the side chain. At that time, a polymer solution having a specific functional group is usually subjected to the reaction. For example, a monomer unit (a2-3) can be obtained by reacting a solution of an acrylic polymer having a carboxy group with glycidyl methacrylate at a temperature of 80 ° C. to 150 ° C. in the presence of a catalyst such as benzyltriethylammonium chloride. it can.

  Moreover, in order to form a monomer unit (a2-3), in addition to using the polymer reaction as described above, allyl methacrylate, allyl acrylate, or the like may be used as a radical polymerizable monomer. These monomer units can be used alone or in combination of two or more.

 In this invention, it is preferable that a monomer unit (a2-1) is included as a monomer unit (a2).

  In the monomer unit constituting the component (A), the content of the monomer unit (a2) is preferably 5 to 60 mol%, more preferably 10 to 55 mol%, from the viewpoints of various resistances and transparency of the formed film. Preferably, 20-50 mol% is more preferable. Within the above numerical range, the cured film obtained from the photosensitive resin composition has good transparency and ITO sputtering resistance.

(A3) Other monomer units In the present invention, the component (A) may have other monomer units (a3) excluding the monomer units (a1) and (a2). Examples of other monomer units (a3) include styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclo Examples include unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds.
Specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (meth) acrylic acid , Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Examples of the structural unit include 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl methacrylate, acrylonitrile, and the like. In addition, compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be exemplified. Among them, a group in which a group that reacts with the monomer unit (a2) or a separately added cross-linking agent by (final) heat treatment is preferable from the viewpoint of film strength. Specifically, (meth) acrylic acid tertiary alkyl ester is preferable, and (meth) acrylic acid tert-butyl is more preferable. The monomer used as a monomer unit (a3) can be used individually or in combination of 2 or more types.
In addition, (A) the acrylic copolymer contains 1 to 15 mol% of a monomer unit having an unprotected carboxy group or a monomer unit having an unprotected phenolic hydroxyl group in terms of sensitivity. preferable.

  The molecular weight of the (A) acrylic copolymer is a weight average molecular weight in terms of polystyrene, preferably 1,000 to 200,000, more preferably 2,000 to 50,000. Within the above numerical range, the sensitivity and ITO suitability are good.

  Various methods for synthesizing the component (A) are also known. For example, the component (A) is used to form at least the monomer units represented by the above (a1) and (a2). 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.

(B) Photoacid generator In this invention, the oxime sulfonate compound represented by a following formula (b1) is contained.

（式（ｂ１）中、Ｒ⁵は、アルキル基、シクロアルキル基またはアリール基を表し、Ｒ¹およびＲ²は、それぞれ置換基を示し、互いに結合して、環を形成していてもよい。）

(In Formula (b1), R ⁵ represents an alkyl group, a cycloalkyl group, or an aryl group, and R ¹ and R ² each represent a substituent, and may be bonded to each other to form a ring. )

As the alkyl group for R ^5, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group represented by R ⁵ 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 other It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R ^5, 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 ⁵ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

  The oxime sulfonate compound represented by formula (b1) is preferably an oxime sulfonate compound represented by formula (OS-3), formula (OS-4) or formula (OS-5).

（式（ＯＳ−３）〜式（ＯＳ−５）中、Ｒ¹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、Ｒ²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、Ｒ⁶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、ＸはＯまたはＳを表し、ｎは１または２を表し、ｍは０〜６の整数を表す。）

(In Formula (OS-3) to Formula (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and R ² independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. R ⁶ represents each independently a halogen atom, alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group or alkoxysulfonyl group, X represents O or S, n represents 1 or 2, m Represents an integer of 0 to 6.)

In the formulas (OS-3) to (OS-5), the alkyl group, aryl group, or heteroaryl group in R ¹ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group for R ¹ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyl group in R ¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. .

Examples of the alkyl group in R ¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group, Examples include phenoxycarbonylethyl group and dimethylaminocarbonylethyl group.
Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, An n-decyl group, an n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.

In the formulas (OS-3) to (OS-5), the aryl group for R ¹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
As the substituent that the aryl group in R ¹ may have, a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group , A sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

As the aryl group in R ¹ , a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, a p-phenoxyphenyl group, a p-methylthiophenyl group, p -Phenylthiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, p-dimethylaminocarbonylphenyl group.
Among these, a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.

Further, the 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.
Examples of the substituent that the heteroaryl group in R ¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl. Group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group.

In the formulas (OS-3) to (OS-5), at least one of the heteroaryl groups in R ¹ may be a heteroaromatic ring. For example, a heteroaromatic ring and a benzene ring are condensed. May be.
The heteroaryl group in R ¹ may have a substituent, the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring And a group in which one hydrogen atom is removed from the ring selected from the above.

In the formulas (OS-3) to (OS-5), R ² is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
In the above formulas (OS-3) to (OS-5), it is preferable that one or two of R ² present in the compound is an alkyl group, an aryl group or a halogen atom, and one is an alkyl group. More preferably an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the rest is a hydrogen atom.
In the formulas (OS-3) to (OS-5), the alkyl group or aryl group in R ² may have a substituent.
Examples of the substituent that the alkyl group or aryl group in R ² may have include the same groups as the substituent that the alkyl group or aryl group in R ¹ may have.

The alkyl group for R ² is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and an alkyl group having 1 to 6 carbon atoms which may have a substituent. It is more preferable.
Specific examples of the alkyl group for R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, allyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, perfluorohexyl group, chloromethyl group, bromomethyl group, methoxymethyl group, benzyl group, phenoxyethyl group, methylthioethyl Group, phenylthioethyl group, ethoxycarbonylethyl group, phenoxycarbonylethyl group, dimethylaminocarbonylethyl group.
Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, chloromethyl group, bromomethyl group, Methoxymethyl group and benzyl group are preferable, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and n-hexyl group are more preferable, and methyl group , An ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group are more preferable, and a methyl group is particularly preferable.

The aryl group for R ² is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
Specific examples of the aryl group for R ² include phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, p-phenoxyphenyl group, p-methylthiophenyl group, p- Examples include a phenylthiophenyl group, a p-ethoxycarbonylphenyl group, a p-phenoxycarbonylphenyl group, and a p-dimethylaminocarbonylphenyl group.
Among these, a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.
Examples of the halogen atom for R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Among these, a chlorine atom and a bromine atom are preferable.

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

In the formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group in R ⁶ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group for R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyl group in R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. .

Examples of the alkyl group in R ⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group, Examples include phenoxycarbonylethyl group and dimethylaminocarbonylethyl group.
Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, An n-decyl group, an n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.

In the formulas (OS-3) to (OS-5), the alkyloxy group for R ⁶ is preferably an alkyloxy group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyloxy group in R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. It is done.

Examples of the alkyloxy group in R ⁶ include methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, ethoxyethyloxy group, methylthioethyloxy group, phenylthioethyloxy group, ethoxy Examples thereof include a carbonylethyloxy group, a phenoxycarbonylethyloxy group, and a dimethylaminocarbonylethyloxy group.
Among these, a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group is preferable.
In the formulas (OS-3) to (OS-5), examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group. It is done.
In the formulas (OS-3) to (OS-5), examples of the alkoxysulfonyl group for R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.

  In the formulas (OS-3) to (OS-5), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. It is particularly preferred.

  The compound containing the oxime sulfonate compound represented by the formula (b1) is particularly preferably an oxime sulfonate compound represented by any one of the following formulas (OS-6) to (OS-11).

（式（ＯＳ−６）〜（ＯＳ−１１）中、Ｒ¹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、Ｒ⁷は、水素原子または臭素原子を表し、Ｒ⁸は水素原子、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、Ｒ⁹は水素原子、ハロゲン原子、メチル基またはメトキシ基を表し、Ｒ¹⁰は水素原子またはメチル基を表す。）

(In formulas (OS-6) to (OS-11), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, R ⁸ represents a hydrogen atom, 1 to 8 represents an alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group; ¹⁰ represents a hydrogen atom or a methyl group.)

R ¹ in the formulas (OS-6) to (OS-11) has the same meaning as R ¹ in the formulas (OS-3) to (OS-5), and preferred embodiments thereof are also the same.
R ⁷ in formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
R ⁸ in formulas (OS-6) to (OS-11) is 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 chlorophenyl. Represents a group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Is more preferable, and a methyl group is particularly preferable.
R ⁹ in formula (OS-8) and formula (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R ¹⁰ in formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the oxime sulfonate compound, the oxime steric structure (E, Z) may be either one or a mixture.

  Specific examples of the oxime sulfonate compound represented by the formula (OS-3) to the formula (OS-5) include the following exemplified compounds, but the present invention is not limited thereto.

  The compound containing the oxime sulfonate compound represented by the formula (b1) is also preferably a compound represented by the formula (OS-1).

（式（ＯＳ−１）中、Ｒ¹は、水素原子、アルキル基、アルケニル基、アルコキシ基、アルコキシカルボニル基、アシル基、カルバモイル基、スルファモイル基、スルホ基、シアノ基、アリール基、または、ヘテロアリール基を表す。Ｒ²は、アルキル基、または、アリール基を表す。）

(In the formula (OS-1), R ¹ 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 a hetero group. Represents an aryl group, and R ² represents an alkyl group or an aryl group.)

X is -O -, - S -, - NH -, - NR 5 -, - CH 2 -, - CR 6 H-, or, -CR ⁶ R ⁷ - represents, R ⁵ to R ⁷ is an alkyl group, Or an aryl group is represented.
R ^{21 to} R ²⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group, Or an aryl group is represented. Two of R ^{21 to} R ²⁴ may be bonded to each other to form a ring.
R ^{21 to} R ²⁴ are preferably a hydrogen atom, a halogen atom, and an alkyl group, and an embodiment in which at least two of R ^{21 to} R ²⁴ are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R ^{21 to} R ²⁴ 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 formula (OS-1) is preferably a compound represented by the following formula (OS-2).

In said formula (OS-2), R < ¹ >, R < ² >, R < ²¹ > -R < ²⁴ > is synonymous with each in formula (OS-1), and its preferable example is also the same.
Among these, an embodiment in which R ¹ in the formula (OS-1) and the formula (OS-2) is a cyano group or an aryl group is more preferable, represented by the formula (OS-2), and R ¹ is a cyano group. The embodiment which is a phenyl group or a naphthyl group is most preferable.

  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 (exemplary compounds b-1 to b-34) of the compound represented by the formula (OS-1) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto. Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

  Among the above compounds, b-9, b-16, b-31, and b-33 are preferable from the viewpoint of achieving both sensitivity and stability.

  The compound containing the oxime sulfonate compound represented by the formula (b1) is also preferably an oxime sulfonate compound represented by the following formula (b2).

（式（ｂ２）中、Ｒ⁵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、ｍは、０〜３の整数を表し、ｍ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 ⁵ represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m represents an integer of 0 to 3, and m 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.
m is preferably 0 or 1.
In the formula (b2), m is 1, X is a methyl group, the substitution position of X is an ortho position, R ⁵ is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- A compound that is a 2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

  The compound containing the oxime sulfonate compound represented by the formula (b1) is also preferably an oxime sulfonate compound represented by the formula (b3).

（式中、Ｒ^B1はアルキル基、アルコキシ基、または、ハロゲン原子を表し、Ｒ^B2はアルキル基またはアリール基を表す。）

(Wherein R ^B1 represents an alkyl group, an alkoxy group, or a halogen atom, and R ^B2 represents an alkyl group or an aryl group.)

R ^B1 is preferably an alkoxy group, preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
R ^B2 is preferably an alkyl group, and includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro group. A fluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferred.

  Specific examples of preferred oxime sulfonate compounds include the following compounds (i) to (viii), and the like can be used singly 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.

（式（ｃ１）中、Ｒ¹およびＲ²は、それぞれ独立に、炭素数１〜１０の分岐していてもよいアルキル基、置換基を有しても良いアリール基、置換基を有しても良いシクロアルキル基、またはモルホリノ基を表す。Ｒ³は酸素原子または硫黄原子を表し、Ａは２価の連結基を表す。） (C) Compound represented by formula (c1) In the present invention, a compound represented by formula (c1) is used. By using the compound represented by the formula (c1) in combination with the photoacid generator (B), low dielectric constant and high substrate adhesion can be achieved.
Formula (c1)

(In Formula (c1), R ¹ and R ² each independently have an alkyl group which may have 1 to 10 carbon atoms, an aryl group which may have a substituent, or a substituent. Represents a good cycloalkyl group or morpholino group, R ³ represents an oxygen atom or a sulfur atom, and A represents a divalent linking group.)

R ¹ is preferably an aryl group which may have a substituent, an cycloalkyl group which may have a substituent, or a morpholino group, and more preferably a morpholino group.
When R ¹ is an aryl group, a phenyl group and a naphthyl group are exemplified, and a phenyl group is more preferable. The aryl group may have a substituent, but preferably has no substituent.
When R ¹ is a cycloalkyl group, a 5-membered or 6-membered cycloalkyl group is preferred, and a 6-membered cycloalkyl group is more preferred. The cycloalkyl group may have a substituent, but preferably has no substituent.

R ² is preferably an alkyl group having 1 to 10 carbon atoms which may be branched, an aryl group which may have a substituent, or a cycloalkyl group which may have a substituent.
When R < ² > is an alkyl group, a C1-C8 alkyl group is preferable.
When R ² is an aryl group, a phenyl group and a naphthyl group are exemplified, and a phenyl group is more preferable. The aryl group may have a substituent, but preferably has no substituent.
When R ² is a cycloalkyl group, a 5-membered or 6-membered cycloalkyl group is preferred, and a 6-membered cycloalkyl group is more preferred. The cycloalkyl group may have a substituent, but preferably has no substituent.
A represents a divalent linking group, an alkylene group (for example, methylene group, ethylene group, propylene group, etc.), a cycloalkylene group (for example, cyclohexylene group, cyclopentylene group, etc.), an arylene group (for example, 1 , 2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, naphthylene group, etc.), an ether group, a carbonyl group, an ester group, an amide group and a combination thereof, preferably an alkylene group, A group consisting of an ether group and a combination thereof is more preferable.

（式（ｃ２）中、Ｒ¹およびＲ²は、それぞれ独立に、炭素数１〜１０の分岐していてもよいアルキル基、置換基を有しても良いアリール基、置換基を有しても良いシクロアルキル基、またはモルホリノ基を表す。Ａは２価の連結基を表す。）
Ｒ¹、Ｒ²、Ａは、それぞれ、上記式（ｃ１）におけるＲ¹、Ｒ²、Ａと同義であり、好ましい範囲も同義である。 The compound represented by the formula (c1) is preferably a compound represented by the formula (c2).
Formula (c2)

(In Formula (c2), R ¹ and R ² each independently have an alkyl group which may have 1 to 10 carbon atoms, an aryl group which may have a substituent, or a substituent. Represents a good cycloalkyl group or morpholino group, and A represents a divalent linking group.)
R ¹ , R ² and A have the same meanings as R ¹ , R ² and A in the above formula (c1), respectively, and the preferred ranges are also the same.

（式（ｃ３）中、Ａは２価の連結基を表す。）
Ａは、上記式（ｃ１）におけるＡと同義であり、好ましい範囲も同義である。 The compound represented by the formula (c1) is more preferably a compound represented by the formula (c3).
Formula (c3)

(In formula (c3), A represents a divalent linking group.)
A is synonymous with A in the formula (c1), and a preferred range is also synonymous.

  The compound represented by the formula (c1) is preferably contained at a ratio of 0.01 to 2.50 parts by weight with respect to 100 parts by weight of the (A) acrylic copolymer, and 0.03 to 2 When the content is within the range of the above-mentioned numerical value, which is more preferably contained at a ratio of 0.000 part by weight, the effect of lowering the dielectric constant of the cured film obtained from the photosensitive resin composition is great, and at the same time, the base during development High adhesion to the substrate can be achieved.

(D) Solvent The photosensitive resin composition of the present invention usually contains (D) a solvent. It is preferable that the photosensitive resin composition of this invention is prepared as a solution which melt | dissolved the essential component, the preferable component, and arbitrary components in (D) solvent.
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.

As the (D) solvent used in the photosensitive resin composition of the present invention, for example,
(E-1) Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
(E-2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether;
(E-3) Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate;
(E-4) Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
(E-5) Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether;

(E-6) Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
(E-7) Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether;
(E-8) Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate;
(E-9) Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether; (co) dipropylene glycol dimethyl ether, dipropylene Dipropylene glycol dialkyl ethers such as glycol diethyl ether and dipropylene glycol ethyl methyl ether;

(E-10) Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate;
(E-11) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate;
(E-12) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate Aliphatic carboxylic acid esters such as isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate;
(E-13) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3- Other esters such as methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate;
(E-14) Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;

(E-15) Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
(E-16) Lactones such as γ-butyrolactone can be mentioned.
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, and a combination of propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers. More preferably.

  The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight and more preferably 100 to 2,000 parts by weight per 100 parts by weight of the resin component. Preferably, it is 150-1500 weight part.

Crosslinking agent The photosensitive resin composition of this invention contains a crosslinking agent as needed. As the crosslinking agent, for example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, and a compound having at least one ethylenically unsaturated double bond are added. be able to. By adding a crosslinking agent, the cured film can be made stronger. The following can be added as a crosslinking agent.

<Compound having two or more epoxy 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, as bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1051, EPICLON1051 , Manufactured by DIC Corporation), etc., as bisphenol F type epoxy resins, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Corporation) )), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.), etc. As the enol novolac type epoxy resin, JER152, JER154, JER157S65, JER157S70 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC) (Corporation) etc., as cresol novolac type epoxy resins, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (Above, manufactured by DIC Corporation), EOCN-1020 (above, manufactured by Nippon Kayaku Co., Ltd.), etc., as an aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP- 4085S, EP-4088S (manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, PB 4700 (above, manufactured by Daicel Chemical Industries, Ltd.), etc. Can be mentioned. In addition, ADEKA RESIN EP-4000S, EP-4003S, 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) and the like can be mentioned. These can be used alone or in combination of two or more.
Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, phenol novolak type epoxy resin, and cresol novolak type epoxy resin are preferable. In particular, bisphenol A type epoxy resin, phenol novolac type epoxy resin, and aliphatic epoxy resin are preferable.

<Compounds having two or more oxetanyl groups in the molecule>
As specific examples of the compound having two or more oxetanyl groups in the molecule, OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.) can be used.

  The addition amount of the compound having an epoxy group or oxetanyl group to the photosensitive resin composition is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, when the total amount of the resin components is 100 parts by weight.

<Alkoxymethyl group-containing crosslinking agent>
As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of the amount of outgas generated, A methoxymethyl group is preferred. Among these crosslinkable compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferable crosslinkable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.
These alkoxymethyl group-containing crosslinking agents are available as commercial products. For example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicarax MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nicarac MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

  When the alkoxymethyl group-containing crosslinking agent is used in the photosensitive resin composition of the present invention, the addition amount of the alkoxymethyl group-containing crosslinking agent is 0.05 to 50 parts by weight with respect to 100 parts by weight of the resin component. Preferably, it is 0.5 to 10 parts by weight. By adding within this range, preferable alkali solubility during development and excellent solvent resistance of the cured film can be obtained.

<Compound having at least one ethylenically unsaturated double bond>
As the compound having at least one ethylenically unsaturated double bond, a (meth) acrylate compound such as a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, or a trifunctional or higher (meth) acrylate is preferably used. be able to.
Examples of monofunctional (meth) acrylates include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. And 2-hydroxypropyl phthalate.
Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
These compounds having at least one ethylenically unsaturated double bond are used singly or in combination of two or more.

  The proportion of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is preferably 50 parts by weight or less, based on 100 parts by weight of the resin component, and 30 parts by weight. The following is more preferable. By including at least one compound having an ethylenically unsaturated double bond in such a ratio, the heat resistance and surface hardness of the insulating film obtained from the photosensitive resin composition of the present invention can be improved. it can. When adding a compound having at least one ethylenically unsaturated double bond, it is preferable to add a thermal radical generator (J).

Sensitizer The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with a radiation-sensitive acid generator in order to promote its decomposition. 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.

Silane coupling agent The photosensitive resin composition of this invention may contain a silane coupling agent. The silane coupling agent that can be used in the photosensitive resin composition of the present invention includes an inorganic material as a base material, for example, a silicon compound such as silicon, silicon oxide, and silicon nitride, a metal such as gold, copper, and aluminum, and an insulating film. It is a compound that improves the adhesion.
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, and γ-glycidoxypropyltrialkoxysilane is more preferable. 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.
0.1-20 weight part is preferable with respect to 100 weight part of resin components, and, as for content of the silane coupling agent in the photosensitive resin composition of this invention, 0.5-10 weight part is more preferable.

Surfactant The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants 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), Mega Fuck (manufactured by DIC Corporation), Florard (Sumitomo 3M) (Made by Co., Ltd.), Asahi Guard, Surflon (made by Asahi Glass Co., Ltd.), PolyFox (made by OMNOVA), and the like.
In addition, as a surfactant, it contains a structural unit A and a structural unit B represented by the following formula (1), and is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A preferable example is a copolymer having (Mw) of 1,000 or more and 10,000 or less.

（式（１）中、Ｒ¹およびＲ³はそれぞれ独立に、水素原子またはメチル基を表し、Ｒ²は炭素
数１以上４以下の直鎖アルキレン基を表し、Ｒ⁴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重量％以上８０重量％以下の数値を表し、ｑは２０重量％以上９０重量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｎは１以上１０以下の整数を表す。）

(In the formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ 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% to 80% by weight. Q represents a numerical value of 20 wt% or more and 90 wt% or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less.)

The L is preferably a branched alkylene group represented by the following formula (2). R ⁵ in the 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. More preferred is an alkyl group of 3. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by weight.

  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 (H) surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, and preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin component. More preferred is 0.01 to 1 part by weight.

Thermal radical generator The photosensitive resin composition of the present invention may contain a thermal radical generator. As the thermal radical generator in the present invention, a known thermal radical generator can be used.
The thermal radical generator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the obtained cured film becomes tougher and heat resistance and solvent resistance may be improved.
Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon Examples thereof include compounds having a halogen bond, azo compounds, and bibenzyl compounds. A thermal radical generator may be used individually by 1 type, and it is also possible to use 2 or more types together.
The addition amount of the thermal radical generator in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polymer. Most preferably, it is 5 to 10 parts by weight.

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.

  As a commercial item of a phenolic antioxidant, ADK STAB AO-60, ADK STAB AO-80 (above, the product made from ADEKA), and Irganox 1098 (made by Ciba Japan Co., Ltd.) are mentioned, for example.

The content of the antioxidant is preferably 0.1 to 6% 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 becomes good.
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.

Basic Compound The photosensitive resin composition of the present invention may contain a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7 -Undecene and the like.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
The basic compound that can be used in the present invention may be used singly or in combination of two or more, but it is preferable to use two or more in combination, and 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 in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by weight, and 0.005 to 0.2 part by weight with respect to 100 parts by weight of the resin component. It is more preferable.

(Method for forming cured film)
Next, the formation method of the cured film of this invention is demonstrated.
The method for forming a cured film of the present invention includes the following steps (1) to (5).
(1) Step of applying the photosensitive resin composition of the present invention on a substrate (2) Step of removing a solvent from the applied photosensitive resin composition (3) Step of exposing with actinic rays (4) Aqueous developer (5) Thermal curing process (post-baking process)
Each step will be described below in order.

In the application step (1), the photosensitive resin composition of the present invention is applied (usually applied) on a substrate to form a wet film containing a solvent.
In the solvent removal step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry 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 (A) the acrylic copolymer is hydrolyzed to produce a carboxy 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”) can be performed as necessary. PEB can promote the formation of a carboxy group or a phenolic hydroxyl group from an acid-decomposable group.

The acid-decomposable group in the monomer 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 carboxy group or a phenol. Since a positive hydroxyl group is generated, a positive image can be formed by development without necessarily performing PEB.
In addition, by performing PEB at a relatively low temperature, hydrolysis of an acid-decomposable group can be promoted without causing a crosslinking reaction. The temperature at which PEB is performed 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 80 ° C. or lower.

In the developing step (4), an acrylic copolymer having a liberated carboxy 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 carboxy 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 monomer unit (a1) to produce a carboxy group or a phenolic hydroxyl group, and the monomer unit (a2) A cured film can be formed by crosslinking with the crosslinking group. 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 250 ° 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 90 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.
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>
Various components are mixed in a predetermined ratio and in an arbitrary 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 each component is previously dissolved in a 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). As the substrate, for example, in the production of a liquid crystal display element, a polarizing plate, a glass plate provided with a black matrix layer and a color filter layer as required, and further a transparent conductive circuit layer can be exemplified. The application 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 side of 1 m or more on each side.

  In addition, (2) the heating condition of the solvent removal step is a range in which the acid-decomposable group is decomposed in the monomer unit (a1) in the resin component in the unexposed area and the resin component is not soluble in the alkali developer. Although it differs depending on the type and mixing ratio of each component, it is preferably about 80 to 130 ° C. for 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 ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used. 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.

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.

<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, 5-60 minutes on the hot plate, In the case of an oven, the acid-decomposable group in the resin component is decomposed by heat treatment for 30 to 90 minutes to generate a carboxy group or a phenolic hydroxyl group, which is reacted with the crosslinkable group in the monomer unit (a2). By cross-linking, a protective film and an interlayer insulating film excellent in heat resistance, hardness and the like can be formed. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.
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 .

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.
The organic EL display device or liquid crystal display device of the present invention is not particularly limited except that it has a flattening 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.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, but 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 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.

<Synthesis of Acrylic Copolymer A-1>
Copolymer A-1 was synthesized by the method shown below.
In the following synthesis examples, the following symbols represent the following compounds, respectively.
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries)
HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries)
EDM: Diethylene glycol ethyl methyl ether (manufactured by Wako Pure Chemical Industries)
PGMEA: Propylene glycol monomethyl ether acetate (Showa Denko)

  Copolymer A-1 was synthesized by the method shown below.

[Synthesis of 1-ethoxyethyl methacrylate (MAEVE)]
To 144.2 parts (2 molar equivalents) of ethyl vinyl ether, 0.5 part of phenothiazine was added, and 86.1 parts (1 molar equivalent) of methacrylic acid was added dropwise while cooling the reaction system to 10 ° C. or lower. ) For 4 hours. After adding 5.0 parts of pyridinium p-toluenesulfonate, the mixture was stirred at room temperature for 2 hours and allowed to stand overnight at room temperature. To the reaction solution, 5 parts of sodium bicarbonate and 5 parts of sodium sulfate were added, and the mixture was stirred at room temperature for 1 hour. The insoluble material was filtered and concentrated under reduced pressure at 40 ° C. or lower. .) 134.0 parts of 1-ethoxyethyl methacrylate (MAEVE) fraction of 43-45 ° C./7 mmHg was obtained as a colorless oil.

The obtained MAEVE (63.28 parts (0.4 molar equivalent)), GMA (42.65 parts (0.3 molar equivalent)), MAA (8.61 parts (0.1 molar equivalent)), HEMA ( A mixed solution of 26.03 parts (0.2 molar equivalent)) and EDM (110.8 parts) was heated to 70 ° C. under a nitrogen stream. While stirring this mixed solution, a mixed solution of radical polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 7 parts) and EDM (100.0 parts) was added dropwise over 2.5 hours. After completion of dropping, the reaction was carried out at 70 ° C. for 4 hours to obtain an EDM solution of copolymer A-1 (solid content concentration: 40%).
The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained copolymer A-1 was 15,000.

<Synthesis of Copolymers A-2 to A-7>
Copolymers A-2 to A-7 were respectively synthesized in the same manner as the synthesis of the polymer A-1, except that the monomers used and the amounts used thereof were changed to those shown in the following table.
The synthesis method of tetrahydrofuran-2-yl methacrylate (MATHF) is as follows.

[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 hydrogen carbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, filtered to insoluble matter and concentrated under reduced pressure at 40 ° C. or lower to give a yellow oily residue. Distillation under reduced pressure gave 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.

Abbreviations in Table 1 are as follows.
MAEVE: 1-ethoxyethyl methacrylate (synthetic product)
MATHF: tetrahydrofuran-2-yl methacrylate (synthetic product)
MATHP: Tetrahydro-2H-pyran-2-yl methacrylate (synthesized by the method of Synthesis Example 1 described in paragraph 0018 of JP-A-5-88367)
OXE-30: Methacrylic acid (3-ethyloxetane-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

(Examples and Comparative Examples)
The amount described below (solid content) was dissolved in a mixed solvent of diethylene glycol methyl ethyl ether: propylene glycol monomethyl ether acetate = 1: 1 (weight ratio) so that the solid content concentration was 20% by weight, and then the caliber It filtered with the 0.2 micrometer membrane filter, and prepared the photosensitive resin composition of an Example and a comparative example, respectively.

The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.
In addition, each used material is as follows.

A-8: Resin modified with poly (p-hydroxystyrene) (synthesized by the method of Synthesis Example 5 described in paragraph 0138 of JP-A-2002-23374)
B-1: Compound having the following structure (synthetic product)
B-2: Compound having the following structure (synthetic product)
B-3: Compound having the following structure (synthetic product)
B-4: CGI-1397 (manufactured by BASF)
B-5: Compound having the following structure (synthesized according to the method described in paragraph 0108 of JP-T-2002-528451)
B-6: PAI-1001 (manufactured by Midori Chemical Co., Ltd.)
B-7: Compound having the following structure B-8: 1,2-naphthoquinonediazide-5-sulfonic acid ester of 2,3,4-trihydroxybenzophenone

[Synthesis of B-1]
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. After adding potassium carbonate (19.2 g) to the organic layer and reacting at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and liquid-separated. The organic layer was concentrated, and the crystal was converted to diisopropyl ether (10 mL). ), Followed by filtration and drying to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and 50% by weight hydroxylamine aqueous solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (18 mL), and the mixture was heated to reflux for 10 hours. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain A-1 (2.3 g).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-1 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).

[Synthesis of B-2]
2-Naphthol (20 g) is dissolved in N, N-dimethylacetamide (150 mL), potassium carbonate (28.7 g) and ethyl 2-bromooctanoate (52.2 g) are added and reacted at 100 ° C. for 2 hours. It was. To the reaction solution are added water (300 mL) and ethyl acetate (200 mL), and the mixture is separated. The organic layer is concentrated, and then 48 wt% aqueous sodium hydroxide solution (23 g), ethanol (50 mL), and water (50 mL) are added. The reaction was performed for 2 hours. The reaction solution was poured into 1N HCl aqueous solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid, and then 30 g of polyphosphoric acid was added and reacted at 170 ° C. for 30 minutes. The reaction solution was poured into water (300 mL), and ethyl acetate (300 mL) was added for liquid separation, and the organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).
Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g), and magnesium sulfate (4.5 g) were added to a suspension of the resulting ketone compound (10.0 g) and methanol (100 mL) for 24 hours. Heated to reflux. After standing to cool, water (150 mL) and ethyl acetate (150 mL) were added for liquid separation, and the organic layer was separated four times with 80 mL of water, concentrated and purified by silica gel column chromatography to obtain an oxime compound (5.8 g). Got.
The obtained oxime (3.1 g) was sulfonated in the same manner as B-1, and B-2 (3.2 g) was obtained.
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-2 has δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.5 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (dd, 1H) , 2.4 (s, 3H), 2.2 (ddt, 1H), 1.9 (ddt, 1H), 1.4 to 1.2 (m, 8H), 0.8 (t, 3H) there were.

[Synthesis of B-3]
B-3 was synthesized in the same manner as B-1, except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in B-1.
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-3 is δ = 8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.7-7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d.1H), 5.6 (q, 1H), 1.7 (D, 3H).

C-1: Compound having the following structure C-2: Compound having the following structure C-3: Compound having the following structure C-4: Compound having the following structure C-5: Compound having the following structure C-6: Compound having the following structure C- 7: Compound having the following structure

C-8: Morpholine (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-9: Copolymer of styrene / MAA = 70/30 (molar ratio), Mw 3000
C-10: 1,5-diazabicyclo [4,3,0] -5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.)

D-1: JER-157S70 (polyfunctional novolac type epoxy resin (epoxy equivalent: 200 to 220 g / eq), manufactured by Japan Epoxy Resins Co., Ltd.)
E-1: DBA (9,10-dibutoxyanthracene, manufactured by Kawasaki Kasei Kogyo Co., Ltd.)

F-1: 3-Glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
G-1: Compound having the following structure

[Measurement of relative permittivity]
On a glass substrate (10 cm × 10 cm × 0.5 mm), a solution prepared by mixing material: propylene glycol monomethyl ether acetate = 1: 1 (weight ratio) with a spin coater has a dry film thickness of 0.35 μm. After being coated, it was dried at 90 ° C. for 2 minutes. Further, the film was exposed to 300 mJ with an ultra-high pressure mercury lamp, and further heated in an oven at 230 ° C. for 60 minutes to form a cured film. The cured film was conditioned at 23 ° C. and 60% RH for 24 hours, and then the relative dielectric constant was measured at 1 MHz with CV-Map (Four Dimensions, Inc.). The results are shown in the table below.

[Evaluation of adhesion to substrate]
The material was applied on a Mo substrate and a SiN substrate (10 cm × 10 cm × 0.5 mm) using a spin coater so that the dry film thickness was 3 μm, and then dried at 90 ° C. for 2 minutes. Then, after 40 mJ exposure with an ultra-high pressure mercury lamp through a mask capable of reproducing a 10 μm line / 10 μm space, an alkaline developer (0.4% by mass tetramethylammonium hydroxide aqueous solution) was used at 23 ° C. After developing for 60 seconds, it was rinsed with ultrapure water for 1 minute. The obtained board | substrate was observed with the optical microscope, and the chip | tip of the pattern of 10 micrometers line / 10micrometer space and peeling were observed. The results are shown in the table below. Less peeling is preferable.
A: No chipping or peeling B: Chipping or peeling 30% or less C: Chipping or peeling over 30% to 60% or less D: Chipping or peeling over 60% to 100% or less

  The photosensitive resin composition of the present invention was found to have a low relative dielectric constant of the cured film and excellent substrate adhesion during development.

(Example 115)
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 flattening layer 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 3 on the substrate, pre-baking (90 ° C. × 2 minutes) on a hot plate, 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 using a resist stripping solution (mixed solution of monoethanolamine and dimethyl sulfoxide (DMSO)). 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, the photosensitive resin composition of Example 3 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process can be prevented.

  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 through the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

(Example 116)
An organic EL device was produced in the same manner as in Example 115 except that the photosensitive resin composition of Example 3 was replaced with the photosensitive resin composition of Example 9. It was found that the organic EL display device had good display characteristics and high reliability.

(Example 117)
An organic EL device was produced in the same manner except that the photosensitive resin composition of Example 3 was replaced with the photosensitive resin composition of Example 10 in Example 115. It was found that the organic EL display device had good display characteristics and high reliability.

(Example 118)
In the active matrix liquid crystal display device described in FIG. 1 and FIG. 2 of Japanese Patent No. 332003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 118 was obtained.
That is, using the photosensitive resin composition of Example 3, 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 115 above.

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

(Example 119)
A liquid crystal display device was produced in the same manner as in Example 118 except that the photosensitive resin composition of Example 11 was replaced with the photosensitive resin composition of Example 1. It was found that the liquid crystal display device had good display characteristics and high reliability.

(Example 120)
A liquid crystal display device was prepared in the same manner as in Example 118 except that the photosensitive resin composition of Example 11 was replaced with the photosensitive resin composition of Example 25. It was found that the liquid crystal display device had 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 (13)

(A) a monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group, or a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group, (a1) and a crosslinking group An acrylic copolymer containing a monomer unit (a2) having,
(B) a photoacid generator containing an oxime sulfonate compound represented by formula (b1),
Formula (b1)

(In Formula (b1), R ⁵ represents an alkyl group, a cycloalkyl group, or an aryl group, and R ¹ and R ² each represent a substituent, and may be bonded to each other to form a ring. )
(C) a compound represented by the formula (c1), and
Formula (c1)

(In Formula (c1), R ¹ and R ² each independently have an alkyl group which may have 1 to 10 carbon atoms, an aryl group which may have a substituent, or a substituent. Represents a good cycloalkyl group or morpholino group, R ³ represents an oxygen atom or a sulfur atom, and A represents a divalent linking group.)
(D) A photosensitive resin composition comprising a solvent. The photosensitive resin composition of Claim 1 which is a chemically amplified positive photosensitive resin composition. The photosensitive resin composition of Claim 1 or 2 whose said compound of (C) is a thiourea compound represented by Formula (c2).
Formula (c2)

(In Formula (c2), R ¹ and R ² each independently have an alkyl group which may have 1 to 10 carbon atoms, an aryl group which may have a substituent, or a substituent. Represents a good cycloalkyl group or morpholino group, and A represents a divalent linking group.) The photosensitive resin composition of Claim 3 whose R < ¹ > of the said formula (c2) is a morpholino group. The photosensitive resin composition of Claim 1 or 2 whose said compound of (C) is a thiourea compound represented by Formula (c3).
Formula (c3)

(In formula (c3), A represents a divalent linking group.) The photoacid generator of (B) is a compound represented by formula (OS-3), formula (OS-4), formula (OS-5), or formula (b3). The photosensitive resin composition of any one.

(In Formula (OS-3) to Formula (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and R ² independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. R ⁶ represents each independently a halogen atom, alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group or alkoxysulfonyl group, X represents O or S, n represents 1 or 2, m Represents an integer of 0 to 6.)

(Wherein R ^B1 represents an alkyl group, an alkoxy group, or a halogen atom, and R ^B2 represents an alkyl group or an aryl group.) The photosensitive resin composition of any one of Claims 1-6 in which the monomer unit (a1) which has a residue in which the carboxy group is protected with an acid-decomposable group has an acetal structure or a ketal structure. The compound (C) is contained in the range of 0.01 to 2.50 parts by weight with respect to 100 parts by weight of the acrylic copolymer component. The photosensitive resin composition of any one of Claims 1-7. (1) The process of applying the photosensitive resin composition of any one of Claims 1-8 on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) A method for forming a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition. The formation method of the cured film of Claim 9 including the process of exposing the developed photosensitive resin composition to the whole surface after the said image development process and before the said post-baking process. A cured film formed by the method according to claim 9. The cured film according to claim 11, which is an interlayer insulating film. An organic EL display device or a liquid crystal display device comprising the cured film according to claim 11.

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