JP2011215580A - Photosensitive resin composition, method for forming cured film, cured film, organic electroluminescent (el) display device and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in curing sensitivity, transmittance, adaptability to ITO sputtering and forming property of a contact hole.SOLUTION: The photosensitive resin composition contains: (A) a copolymer having a monomer unit (a1) having a residue of a carboxylic group protected by an acid-decomposable group or a monomer unit having a residue of a phenolic hydroxyl group protected with an acid-decomposable group, and a monomer unit (a2) having a crosslinking group; (B) a photo-acid generator; (C) a compound having at least two moiety structures expressed by formula (c1) in the molecule and having a molecular weight of 600 or more and 2,000 or less; and (D) a solvent.

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. More specifically, a positive photosensitive resin composition suitable for forming a planarizing film, a protective film, and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state imaging device, and the same The present invention relates to a method for forming a cured film using the above.

  Conventionally, in an electronic component such as a liquid crystal display element, an integrated circuit element, a solid-state imaging element, and an organic EL, generally, a flattening film for imparting flatness to the surface of the electronic component, and for preventing deterioration and damage of the electronic component A photosensitive resin composition is used when forming a protective film or an interlayer insulating film for maintaining insulation. For example, in a TFT type liquid crystal display element, a polarizing plate is provided on a glass substrate, a transparent conductive circuit layer such as indium tin oxide (ITO) and a thin film transistor (TFT) are formed, and covered with an interlayer insulating film to form a back plate. On the other hand, a polarizing plate is provided on a glass substrate, a pattern of a black matrix layer and a color filter layer is formed as necessary, and a transparent conductive circuit layer and an interlayer insulating film are sequentially formed as a top plate, and this back plate and Manufactured by sealing the liquid crystal between both plates with the top plate facing through a spacer, but the photosensitive resin composition used when forming the interlayer insulating film in this is sensitive and transparent It is required to be excellent.

  As a highly sensitive photosensitive resin composition for an interlayer insulating film, for example, Patent Documents 1 and 2 include an acetal structure, a resin containing an epoxy group or a crosslinkable group, and an acid generator. A chemically amplified radiation sensitive resin composition has been proposed. As a photosensitive resin composition excellent in transparency, for example, Patent Documents 3 and 4 propose a photosensitive resin composition characterized by adding an antioxidant.

JP 2004-254623 A JP 2009-98616 A JP 2009-116223 A JP 2006-265322 A

The problem to be solved by the present invention is to provide a photosensitive resin composition excellent in curing sensitivity, transmittance, ITO sputtering suitability, and contact hole formation.
Another problem to be solved by the present invention is a method for forming a cured film using the photosensitive resin composition, a cured film formed by the forming method, and an organic EL display device including the cured film. And providing a liquid crystal display device.

The above-described problems of the present invention have been solved by means described in the following <1>, <10>, <12>, <14> or <15>. It is described below together with <2> to <9>, <11> and <13> which are preferred embodiments.
<1> (A) a monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group, or a monomer unit (a1) having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group, and crosslinking A monomer unit having a group (a2), a copolymer containing (B) a photoacid generator, (C) having at least two partial structures represented by formula (c1) in the molecule, and having a molecular weight A photosensitive resin composition comprising a compound that is 600 or more and 2,000 or less, and (D) a solvent,

（式（ｃ１）中、Ｒ¹及びＲ²はそれぞれ独立にメチル基又はｔｅｒｔ−ブチル基を表し、Ｒ¹及びＲ²の少なくとも１つはｔｅｒｔ−ブチル基であり、Ｒ³は−Ｏ−又は−ＮＨ−を表す。）

(In Formula (c1), R ¹ and R ² each independently represent a methyl group or a tert-butyl group, at least one of R ¹ and R ² is a tert-butyl group, and R ³ is —O— or Represents -NH-.)

<2> The photosensitive resin composition according to <1>, which is a chemically amplified positive photosensitive resin composition,
<3> The compound of (C) is at least one compound selected from the group consisting of compounds represented by formula (c1-1), formula (c1-2) and formula (c1-3). <1> or the photosensitive resin composition as described in <2>,

  <4> The photosensitive resin composition according to any one of <1> to <3>, wherein the compound (C) is a compound represented by the formula (c1-1).

  <5> The photosensitive resin composition according to any one of <1> to <4>, wherein the (B) photoacid generator is a compound containing an oxime sulfonate residue represented by the formula (b1). object,

（式（ｂ１）中、Ｒ⁵は、アルキル基、シクロアルキル基又はアリール基を表す。）

(In formula (b1), R ⁵ represents an alkyl group, a cycloalkyl group or an aryl group.)

  <6> Any of <1> to <5>, wherein (B) the photoacid generator is a compound represented by formula (OS-3), formula (OS-4), or formula (OS-5) The photosensitive resin composition according to any one of the above,

（式（ＯＳ−３）〜式（ＯＳ−５）中、Ｒ¹はアルキル基、アリール基又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、アリール基又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又はアルコキシスルホニル基を表し、ＸはＯ又はＳを表し、ｎは１又は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, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, m Represents an integer of 0 to 6.)

  <7> The photosensitive resin composition according to any one of <1> to <5>, wherein the (B) photoacid generator is a compound represented by the formula (b2);

（式（ｂ２）中、Ｒ⁵は、アルキル基、シクロアルキル基又はアリール基を表し、Ｘは、アルキル基、アルコキシ基、又は、ハロゲン原子を表し、ｍは、０〜３の整数を表し、ｍが２又は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, a cycloalkyl 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, When m is 2 or 3, a plurality of X may be the same or different.)

<8> (E) The photosensitive resin composition according to any one of <1> to <7>, further containing a crosslinking agent,
<9> The monomer unit (a2) having a crosslinking group includes a 3-membered ring and / or a 4-membered cyclic ether residue, and at least one selected from the group consisting of ethylenically unsaturated groups. <1>-<8> photosensitive resin composition as described in any one,
<10> (1) Application step of applying the photosensitive resin composition according to any one of <1> to <9> on a substrate, (2) Removing the solvent from the applied photosensitive resin composition A cured film characterized by comprising: a solvent removing step, (3) an exposure step of exposing with actinic radiation, (4) a developing step of developing with an aqueous developer, and (5) a post-baking step of thermosetting. Forming method,
<11> The method for forming a cured film according to <10>, including a step of exposing the entire surface after the development step and before the post-baking step.
<12> A cured film formed by the forming method according to <10> or <11>,
<13> The cured film according to <12>, which is an interlayer insulating film,
<14> An organic EL display device comprising the cured film according to <12> or <13>,
<15> A liquid crystal display device comprising the cured film according to <12> or <13>.

According to the present invention, it was possible to provide a photosensitive resin composition excellent in curing sensitivity, transmittance, ITO sputtering suitability, and contact hole formation.
Moreover, according to this invention, the formation method of the cured film using the said photosensitive resin composition, the cured film formed by the said formation method, the organic electroluminescence display containing the said cured film, and a liquid crystal display device Could be provided.

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.

(Photosensitive resin composition)
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. A copolymer containing a unit (a1) and a monomer unit (a2) having a crosslinking group, (B) a photoacid generator, (C) a partial structure represented by formula (c1) at least in the molecule And a compound having a molecular weight of 600 or more and 2,000 or less, and (D) a solvent. Hereinafter, these components represented by (A) to (D) are also referred to as “(A) component” to “(D) component”, respectively. In the present specification, the description of “A to B” representing a numerical range represents “A or more and B or less” unless otherwise specified. That is, it means a numerical range including A and B which are end points.

（（ｃ１）中、Ｒ¹及びＲ²はそれぞれ独立にメチル基又はｔｅｒｔ−ブチル基を表し、Ｒ¹及びＲ²の少なくとも１つはｔｅｒｔ−ブチル基であり、Ｒ³は−Ｏ−又は−ＮＨ−を表す。）

(In (c1), R ¹ and R ² each independently represent a methyl group or a tert-butyl group, at least one of R ¹ and R ² is a tert-butyl group, and R ³ represents —O— or — Represents NH-)

  The photosensitive resin composition of the present invention is a positive photosensitive resin composition. The photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition). The photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as a photoacid generator sensitive to actinic rays. A 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is always 1 or less. On the other hand, the photoacid generator (B) used in the present invention acts as a catalyst for the deprotection of the acid-protected acid group produced in response to actinic rays. The acid generated by the action contributes to a number of deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as a power of 10, and high sensitivity is obtained as a result of so-called chemical amplification. Moreover, it is preferable that the photosensitive resin composition of this invention further contains the (E) crosslinking agent mentioned later from a solvent-resistant viewpoint.

Hereinafter, the present invention will be described in detail. In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The method for introducing the monomer unit contained in the copolymer used in the present invention may be a polymerization method or a polymer reaction method. In the polymerization method, monomers containing a predetermined functional group are synthesized in advance, and then these monomers are copolymerized. In the polymer reaction method, after a polymerization reaction is performed, a necessary functional group is introduced into the monomer unit using a reactive group contained in the monomer unit of the obtained copolymer. Here, examples of the functional group include a protecting group for protecting the phenolic hydroxyl group or carboxy group and at the same time decomposing and releasing them in the presence of a strong acid, and a crosslinking group such as an epoxy group or an oxetanyl group.
The monomer unit (a1) or the monomer unit (a2) may be introduced into the (A) copolymer by a polymerization method or a polymer reaction method, or these two methods may be used in combination.
In the polymerization method, for example, an ethylenically unsaturated compound having a residue in which a phenolic hydroxyl group or a carboxy group is protected with an acid-decomposable group is mixed with an ethylenically unsaturated compound having an epoxy group or an oxetanyl group, and addition polymerization is performed. Thus, the desired copolymer is obtained.
Examples of the polymer reaction method include a method of introducing an epoxy group by reacting epichlorohydrin with a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate. Thus, after copolymerizing an ethylenically unsaturated compound having a reactive group, the reactive group remaining in the side chain is utilized to protect the phenolic hydroxyl group or carboxy group with an acid-decomposable group by a polymer reaction. Functional groups such as cross-linked groups and / or cross-linking groups can be introduced into the side chain.

(A) Copolymer The (A) copolymer contained in the photosensitive resin composition of the present invention is:
(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 a copolymer containing
The component (A) may contain another monomer unit (a3) in addition to the monomer unit (a1) and the monomer unit (a2).

(A) The 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 copolymer (A) does not exclude the introduction of an acidic group as long as the entire copolymer (A) is kept insoluble in alkali, but does not exclude the introduction of an acidic group, which will be described later, a carboxylic acid anhydride residue and / or phenol. It may have other monomer units having a functional hydroxyl group.

The (A) copolymer is preferably an addition polymerization type resin, and more preferably a polymer containing monomer units derived from (meth) acrylic acid and / or its ester. In addition, you may have monomer units other than the monomer unit derived from (meth) acrylic acid and / or its ester, for example, the monomer unit derived from styrene, the monomer unit derived from a vinyl compound, etc.
The (A) 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 contains 90 mol% or more. It is more preferable to use a polymer 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”. Further, “(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), an extremely 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. For example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like.
Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of the dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.
As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among these, 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, or an anhydride of unsaturated polyvalent carboxylic acid, 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, particularly 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, among acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the carboxy group is a residue protected with an acetal or ketal represented by the following formula (a1-1). In addition, when a carboxy group is a residue protected with an acetal or ketal represented by the following formula (a1-1), as a whole of the residue, — (C═O) —O—CR ¹ R ² ( OR ³ ).

（式（ａ１−１）中、Ｒ¹及びＲ²は、それぞれ独立に水素原子又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又は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 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.
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 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 together 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 combined 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), either R ¹ or R ² is preferably 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.

  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は水素原子又はメチル基を表し、Ｒ²¹は単結合又は連結基を表し、Ｒ²²はハロゲン原子又はのアルキル基を表し、ａは１〜５の整数を表し、ｂは０〜４の整数を表し、ａ＋ｂは５以下である。なお、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 thereof, and a is an integer of 1 to 5. 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 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 copolymer) in addition to the alkylene group. In this case, the monomer unit having a phenolic hydroxyl group is represented by the following 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及びｂは式（ａ１−２）におけるａ及び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 the formula (a1-2 ′), R ³⁰ has the same meaning as R ²⁰ in the formula (a1-2), R ³² has the same meaning as R ²² in the 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 acid-decomposable groups, the basic physical properties of the resist, in particular the sensitivity and pattern shape, are residues having a phenolic hydroxyl group protected with an acetal or a residue having a phenolic hydroxyl group 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, 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, Teto of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester Lahydropyranyl protected form, 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester 1-alkoxyalkyl protected, 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester tetrahydropyranyl protected form, 4-hydroxybenzoic acid 1-alkoxyalkyl protector of (3-methacryloyloxypropyl) ester, tetrahydropyranyl protector of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxy) 1-alkoxyalkyl protector of propyl) ester, tetrahydropyranyl protector of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester, 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, but the present invention is not limited thereto.

  In the monomer unit constituting the component (A), the content of the monomer unit (a1) is preferably from 3 to 70 mol%, and preferably from 5 to 60 mol, based on the copolymer of the component (A), from the viewpoint of sensitivity. % Is more preferable, and 10 to 50 mol% is 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 containing 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) copolymer is a monomer unit having a 3-membered ring and / or 4-membered cyclic ether residue. It is preferable to contain (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, and 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 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 described in 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 methacrylic ester 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 acrylic acid (3-ethyloxetane-3-yl) methyl and methacrylic acid (3-ethyloxetane-3-yl) methyl. These monomer units can be used singly 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及びＲ^6bはそれぞれ独立に水素原子又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、又は、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. 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 alicyclic epoxy groups and oxetanyl groups, and particularly preferably oxetanyl groups.

(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は水素原子又はメチル基を表す。）

(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 of these, 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. Copolymer having a monomer unit (a2-3) by reacting with a group that reacts with the specific functional group and a compound having an ethylenically unsaturated group at the terminal (hereinafter referred to as a specific compound). Can be combined.
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、水素原子又はメチル基を表す。）

(In the formula (a2-3-2), R ¹ are each preferable range is also the same the same meaning as R ¹ is .R ^2, R ³ in Formula (A2-3-1) independently represent a 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 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 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 transparency and ITO sputtering resistance of the cured film obtained from the photosensitive resin composition will be good.

(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 in terms of film strength. Specifically, (meth) acrylic acid tertiary alkyl ester is preferable, and (meth) acrylic acid tert-butyl is more preferable. The monomer which becomes a monomer unit (a3) can be used individually or in combination of 2 or more types.
The (A) copolymer preferably 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.

  (A) The molecular weight of a copolymer is a polystyrene conversion weight average molecular weight, Preferably it is 1,000-200,000, More preferably, it is the range of 2,000-50,000. 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 The photosensitive resin composition of the present invention contains (B) a photoacid generator. As the photoacid generator (also referred to as “component (B)”) used in the present invention, a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferable. The chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, and more preferably a photoacid generator that generates an acid having a pKa of 3 or less.

  Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators can be used singly or in combination of two or more.

Specific examples of these include the following.
As trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl)- s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s -Triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methyl) Butylphenyl) ethenyl] - bis (4,6-trichloromethyl) -s-triazine or 2- (4-methoxynaphthyl) - bis (4,6-trichloromethyl) -s-triazine and the like;

  Examples of diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl, 4- (2′-hydroxy-1 '-Tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecaoxy) phenyliodonium hexafluoroantimonate, phenyl, 4- (2'-hydroxy-1'-tetradeca) Oxy) phenyliodonium-p-toluenesulfonate and the like;

  Examples of triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoro. Lomethanesulfonate or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, etc .;

  As quaternary ammonium salts, tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) borate, benzyl Dimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate and the like;

Examples of the diazomethane derivative include bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, and bis (p-toluenesulfonyl) diazomethane;
Examples of imide sulfonate derivatives include trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-enedicarboximide, succinimide trifluoromethyl sulfonate, phthalimide trifluoromethyl sulfonate, N-hydroxynaphthalimide methanesulfonate, N-hydroxy- 5-norbornene-2,3-dicarboximidopropane sulfonate and the like;
The compound shown below as an oxime sulfonate compound.

  Preferred examples of the oxime sulfonate compound, that is, the compound having an oxime sulfonate residue include compounds containing an oxime sulfonate residue represented by the formula (b1).

（式（ｂ１）中、Ｒ⁵は、アルキル基又はアリール基を表す。）

(In the formula (b1), R ⁵ represents an alkyl group or an aryl group.)

Any group may be substituted, and the alkyl group in R ⁵ may be linear, branched or cyclic. Acceptable substituents are described below.
The alkyl group for R ⁵ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. 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 compound containing an oxime sulfonate residue represented by the formula (b1) is an oxime sulfonate compound represented by the formula (OS-3), the formula (OS-4) or the formula (OS-5). Is preferred.

（式（ＯＳ−３）〜式（ＯＳ−５）中、Ｒ¹はアルキル基、アリール基又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、アリール基又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又はアルコキシスルホニル基を表し、ＸはＯ又はＳを表し、ｎは１又は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, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an 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.
Examples of the substituent that the aryl 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. , 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 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 a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, an ethoxyethyloxy group, a methylthioethyloxy group, a phenylthioethyloxy group, and an ethoxy group. Examples thereof include carbonylethyloxy group, phenoxycarbonylethyloxy group, and 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 an oxime sulfonate residue 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、アリール基又はヘテロアリール基を表し、Ｒ⁷は、水素原子又は臭素原子を表し、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、フェニル基又はクロロフェニル基を表し、Ｒ⁹は水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、Ｒ¹⁰は水素原子又はメチル基を表す。）

(In the 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 or a carbon number. Represents an alkyl group of 1 to 8, 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 the 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 a 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 residue 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、又は、ヘテロアリール基を表す。Ｒ²は、アルキル基、又は、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 hetero. 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.
As R ^{21 to} R ²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, 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 preferable. 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 more 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, the aspect 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 an oxime sulfonate residue represented by the formula (b1) is more preferably an oxime sulfonate compound represented by the following formula (b2).

（式（ｂ２）中、Ｒ⁵は、アルキル基又はアリール基を表し、Ｘは、アルキル基、アルコキシ基、又は、ハロゲン原子を表し、ｍは、０〜３の整数を表し、ｍが２又は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 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 an oxime sulfonate residue represented by the formula (b1) is more preferably an oxime sulfonate compound represented by the formula (b3).

（式（ｂ３）中、Ｒ⁵は式（ｂ１）におけるＲ⁵と同義であり、Ｘ’は、ハロゲン原子、水酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、シアノ基又はニトロ基を表し、Ｌは０〜５の整数を表す。）

(In the formula (b3), R ⁵ has the same meaning as R ⁵ in the formula (b1), X 'is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and L represents an integer of 0 to 5.)

R ⁵ in the formula (b3) is methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro A fluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferred, and an n-octyl group is particularly preferred.
X ′ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
As L, 0-2 are preferable, and 0-1 are particularly preferable.

  Specific examples of the compound represented by the formula (b3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) benzyl. Cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- [(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl Acetonitrile, α-[(4-toluene Sulfo) -4-methoxyphenyl] can be mentioned acetonitrile.

  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.

  In the photosensitive resin composition of the present invention, (B) the photoacid generator is preferably used in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of component (A), and 0.5 to 10 parts by weight. More preferably it is used.

(C) Compound having at least two partial structures represented by formula (c1) in the molecule and having a molecular weight of 600 or more and 2,000 or less. The photosensitive resin composition of the present invention includes formula (C) ( a compound having at least two partial structures represented by c1) in the molecule and having a molecular weight of 600 or more and 2,000 or less (hereinafter referred to as “component (C)” or “specific phenol compound (C)” as appropriate) Also called).

（式（ｃ１）中、Ｒ¹及びＲ²はそれぞれ独立にメチル基又はｔｅｒｔ−ブチル基を表し、Ｒ¹及びＲ²の少なくとも１つはｔｅｒｔ−ブチル基であり、Ｒ³は−Ｏ−又は−ＮＨ−を表す。）

(In Formula (c1), R ¹ and R ² each independently represent a methyl group or a tert-butyl group, at least one of R ¹ and R ² is a tert-butyl group, and R ³ is —O— or Represents -NH-.)

R ¹ and R ² each independently represent a methyl group or a tert- butyl group, at least one of R ¹ and R ² are tert- butyl group, both of R ¹ and R ² are tert- butyl Preferably there is.
R ³ represents —O— or —NH—, and is preferably —O—.

  By including the specific phenol compound (C), coloring during the baking process is reduced, and an interlayer insulating film (cured film) having excellent transparency can be obtained. Furthermore, only when the specific phenolic compound (C) and a resin having an acetal structure are used in combination, the surprising effect that the contact hole diameter of the interlayer insulating film does not change before and after baking is exhibited. Furthermore, only when the specific phenol compound (C) and the acrylic resin are used in combination, a surprising effect of reducing the relative dielectric constant of the interlayer insulating film is exhibited.

The specific phenol compound (C) has two or more partial structures represented by the formula (c1) in the molecule, and the partial structure preferably includes two or more and six or less, Preferably, it is a compound containing in the range of 2 or more and 4 or less.
Examples of such compounds include tetrakis {methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate} methane, tetrakis {methylene-3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) propionate} methane, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, N, N′-hexane-1,6-diylbis [3- (3 5-di-tert-butyl-4-hydroxyphenylpropionamide)], N, N′-octane-1,8-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)] ] Etc. are mentioned.

The molecular weight of the specific phenol compound (C) used in the present invention is 600 or more and 2,000 or less, but the molecular weight is preferably 700 or more. Moreover, from a compatible viewpoint with the copolymer of (A) component, it is preferable that it is not a polymer (polymer compound) containing the repeating unit which has the above partial structures but a monomolecular compound.
The specific phenol compound (C) used in the present invention preferably contains an ester bond in which R ³ is —O— from the viewpoint of transparency after baking.
Among the specific phenol compounds, from the viewpoint of transparency after baking, more preferable specific phenol compounds include compounds represented by formula (c1-1), formula (c1-2), and formula (c1-3). Most preferred is a compound represented by formula (c1-1).

  The specific phenol compound (C) is also available as a commercial product. For example, as a compound represented by the above formula (c1-1), trade name Irganox 1010 (manufactured by Ciba Specialty Chemicals), Adeka Stub AO-60 (manufactured by ADEKA Co., Ltd.) and the like are trade names of compounds represented by the above formula (c1-2), such as Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Adeka Stub AO-80 ( Examples of the compound represented by the above formula (c1-3) include ADEGANOX 1098 (manufactured by Ciba Specialty Chemicals) and the like.

  As for the specific phenol compound (C), only one kind may be used in the photosensitive resin composition of the present invention, or two or more kinds may be used in combination. The content of the specific phenol compound (C) is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, based on the total solid content of the photosensitive resin composition. Preferably, 0.5 to 4% by weight is optimal. When the content is 0.1% by weight or more and 6% by weight or less, sufficient transparency of the formed film is obtained, and excellent sensitivity at the time of pattern formation is exhibited.

(D) Solvent The photosensitive resin composition of the present invention contains (D) a solvent. The photosensitive resin composition of the present invention is a solution in which the above-described components (A) to (D), which are essential components, the later-described (E) component which is a preferred component, and any later-described optional component are dissolved in a solvent (D). It is preferable to be prepared as
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,
(A) Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
(A) Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether;
(C) 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;
(D) Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
(E) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether;

(F) 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;
(G) Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether;
(H) 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;
(G) 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 dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether;

(Sa) 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;
(L) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate;
(S) 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, propionate Aliphatic carboxylic acid esters such as isobutyl acid, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate;
(C) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl Other esters such as butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate;
(So) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;

(Ta) Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
(H) Examples include lactones such as γ-butyrolactone.
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, preferably a combination of two types, and a combined use 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 100 to 2,000 parts by weight per 100 parts by weight of the component (A). Is more preferable, and it is still more preferable that it is 150-1,500 weight part.

  In addition to the component (A), the component (B), the component (C), and the component (D), the positive photosensitive resin composition of the present invention includes (E) a cross-linking agent and (F) an adhesion improvement as necessary. Agent, (G) basic compound, (H) surfactant, (I) plasticizer, and (J) thermal radical generator, thermal acid generator, ultraviolet absorber, thickener, and organic Or well-known additives, such as an inorganic precipitation inhibitor, can be added.

(E) Crosslinking agent It is preferable that the photosensitive resin composition of this invention contains (E) crosslinking agent as needed. (E) 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 Can be added. (E) By adding a cross-linking 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 DIC Co., Ltd.), etc., as bisphenol F type epoxy resin, 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 component (A) 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 outgas generation amount, 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 component (A). It is preferably 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 the monofunctional (meth) acrylate 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 with respect to 100 parts by weight of component (A), 30 It is more preferable that the amount is not more than parts by weight. 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).

(F) Adhesion improving agent The photosensitive resin composition of the present invention may contain (F) an adhesion improving agent. The (F) adhesion improver that can be used in the photosensitive resin composition of the present invention is an inorganic substance that serves as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, or aluminum. It is a compound that improves adhesion to an insulating film. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as the (F) adhesion improving agent used in the present invention is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, 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.
The content of the (F) adhesion improving agent in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the component (A). preferable.

(G) Basic compound The photosensitive resin composition of this invention may contain the (G) basic compound. (G) 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 compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. It is preferable to use two kinds of heterocyclic amines in combination.

  The content of the basic compound (G) in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the component (A), and 0.005 to 0.005. More preferably, it is 2 parts by weight.

(H) Surfactant The photosensitive resin composition of the present invention may contain (H) a surfactant. (H) As the surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) (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, the structural unit A and the structural unit B represented by the following formula (1) are included, and the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having (Mw) of 1,000 or more and 10,000 or less.

（式（１）中、Ｒ¹及びＲ³はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ²は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ⁴は水素原子又は炭素数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及び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 0.01 to 10 parts by weight with respect to 100 parts by weight of component (A). It is more preferable that the content is 0.01 to 1 part by weight.

(I) Plasticizer The photosensitive resin composition of the present invention may contain (I) a plasticizer. Examples of (I) plasticizers include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
The addition amount of the plasticizer (I) in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the component (A), and is 1 to 10 parts by weight. It is more preferable.

(J) Thermal radical generator The photosensitive resin composition of the present invention may contain (J) a thermal radical generator, such as a compound having at least one ethylenically unsaturated double bond as described above. When it contains an ethylenically unsaturated compound, it is preferable to contain (J) 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. (J) A thermal radical generator may be used individually by 1 type, and can also use 2 or more types together.
The amount of the (J) thermal radical generator added to the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight when the polymer (A) is 100 parts by weight from the viewpoint of improving film properties. 0.1 to 20 parts by weight is more preferable, and 0.5 to 10 parts by weight is most preferable.

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

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

(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) Application process for applying the photosensitive resin composition of the present invention onto a substrate (2) Solvent removal process for removing the solvent from the applied photosensitive resin composition (3) Exposure process for exposure with actinic rays (4) ) Development step for developing with aqueous developer (5) Post-bake step for thermosetting Each step will be described below in order.

In the coating step (1), the photosensitive resin composition of the present invention is coated 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 coating film on the substrate.

  In the exposure step (3), the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm or more and 450 nm or less. In this step, (B) the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the copolymer (A) 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 development step (4), a 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>
The photosensitive resin composition is prepared by mixing the essential components (A) to (D) at a predetermined ratio and by any method, and stirring and dissolving. For example, it is possible to prepare a resin composition by mixing the components (A) to (C) in advance in a solution in which the components (A) to (C) are previously dissolved in the solvent (D) and mixing them at 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.

<Coating 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 reducing pressure 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 coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coat method, a spin coat method, can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Manufacturing with a large substrate is preferable because of high productivity. Here, the large substrate means a substrate having a side of 1 m or more on each side.

  In addition, the heating condition in the (2) solvent removal step is such that the acid-decomposable group is decomposed in the monomer unit (a1) in the component (A) in the unexposed area, and the component (A) is not soluble in the alkaline developer. Although it varies depending on the type and blending 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, If it is an oven, the acid-decomposable group in the component (A) is decomposed by heat treatment for 30 to 90 minutes to generate a carboxy group or a phenolic hydroxyl group, and the crosslinkable group in the monomer unit (a2). By reacting and crosslinking, 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, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.

FIG. 1 is a conceptual diagram illustrating an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is used to connect 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.

  Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[Synthesis Example 1: Synthesis of A-1]
500 ml of 44.8 g (0.24 mol) of 1-n-butoxyethyl methacrylate, 21.1 g (0.12 mol) of benzyl methacrylate, 30.9 g (0.36 mol) of methacrylic acid and 300 ml of methyl isobutyl ketone A three-necked flask was charged, and a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added as a radical polymerization initiator, followed by polymerization at 70 ° C. for 6 hours in a nitrogen stream. Next, 71 g (0.5 mol) of glycidyl methacrylate and 1 g of dimethylbenzylamine were added and stirred at 70 ° C. for 4 hours. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals are collected by filtration, dissolved in propylene glycol monomethyl ether acetate, and heptane and methyl isobutyl ketone contained in the solution are distilled off under reduced pressure to obtain polymer A-1 as a 50% by weight solution of propylene glycol monomethyl ether acetate. It was.

[Synthesis Example 2: Synthesis of A-2]
47.5 g (0.3 mol) of 1-ethoxyethyl methacrylate, 25.6 g (0.18 mol) of glycidyl methacrylate, 21.2 g (0.12 mol) of benzyl methacrylate and 300 ml of methyl isobutyl ketone A cervical flask was charged, a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added as a radical polymerization initiator, and polymerization was performed at 70 ° C. for 6 hours in a nitrogen stream. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol dimethyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A-2 (1-ethoxyethyl methacrylate / glycidyl methacrylate / benzyl methacrylate). ) Was obtained as a 50% by weight solution of diethylene glycol dimethyl ether.
The composition ratio of 1-ethoxyethyl methacrylate unit, glycidyl methacrylate unit and benzyl methacrylate unit of the obtained polymer was about 50:30:20 from NMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 7,000, and the molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Example 3: Synthesis of A-3]
79.3 g (0.36 mol) of 1-benzyloxyethyl methacrylate, 23.1 g (0.18 mol) of glycidyl acrylate, 7.8 g (0.06 mol) of 2-hydroxyethyl methacrylate and 300 ml of methyl isobutyl ketone Was added to a 500 ml three-necked flask, and a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added as a radical polymerization initiator, followed by polymerization at 70 ° C. for 6 hours in a nitrogen stream. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A-3 (1-benzyloxyethyl methacrylate / glycidyl acrylate / 2-hydroxyethyl methacrylate) was obtained as a 50% by weight solution of diethylene glycol ethyl methyl ether.
The composition ratio of 1-benzyloxyethyl methacrylate unit, glycidyl acrylate unit and 2-hydroxyethyl methacrylate unit of the obtained polymer was about 60:30:10 from NMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 10,000, and the molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis Example 4: Synthesis of A-4]
33.3 g (0.3 mol) of 1-ethoxyethyl acrylate, 25.6 g (0.18 mol) of glycidyl methacrylate, 21.2 g (0.12 mol) of benzyl methacrylate and 300 ml of methyl isobutyl ketone A cervical flask was charged, a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added as a radical polymerization initiator, and polymerization was performed at 70 ° C. for 6 hours in a nitrogen stream. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in propylene glycol monomethyl ether acetate, and heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A-4 (1-ethoxyethyl acrylate / glycidyl methacrylate / Benzyl methacrylate) was obtained as a 50% by weight solution of propylene glycol monomethyl ether acetate.
The composition ratio of 1-ethoxyethyl acrylate unit, glycidyl methacrylate unit and benzyl methacrylate unit of the obtained polymer was about 50:30:20 from NMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 8,000, and the molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Example 5: Synthesis of A-5]
76.4 g (0.36 mol) of 1-cyclohexyloxyethyl methacrylate, 35.3 g (0.18 mol) of 3,4-epoxycyclohexylmethyl methacrylate (Daicel Chemical Industries, Ltd. Cyclomer M100), methacrylic acid 2 -7.8 g (0.06 mol) of hydroxyethyl and 300 ml of methyl isobutyl ketone were charged into a 500 ml three-necked flask, and a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) was used as a radical polymerization initiator. And polymerized at 70 ° C. for 6 hours under a nitrogen stream. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol dimethyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A-5 (1-cyclohexyloxyethyl methacrylate / 3,4-epoxycyclohexyl). Methyl methacrylate / 2-hydroxyethyl methacrylate) was obtained as a 50% by weight solution of diethylene glycol dimethyl ether.
The composition ratio of the obtained polymer 1-cyclohexyloxyethyl methacrylate unit, 3,4-epoxycyclohexylmethyl methacrylate unit and 2-hydroxyethyl methacrylate unit was about 60:30:10 from NMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 6,000 and the molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis Example 6: Synthesis of A-6]
27.0 g (0.36 mol) of 2-tetrahydropyranyl methacrylate, 31.7 g (0.18 mol) of p-vinylphenylglycidyl ether, 7.8 g (0.06 mol) of 2-hydroxyethyl methacrylate and methyl Charge 300 ml of isobutyl ketone to a 500 ml three-necked flask, add a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) as a radical polymerization initiator, and polymerize at 70 ° C. for 6 hours under a nitrogen stream. I let you. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A-6 (2-tetrahydropyranyl methacrylate / p-vinylphenyl methacrylate). Glycidyl ether / 2-hydroxyethyl methacrylate) was obtained as a 50% by weight solution of diethylene glycol ethyl methyl ether.
The constituent ratio of the 2-tetrahydropyranyl methacrylate unit, the p-vinylphenylglycidyl ether unit and the 2-hydroxyethyl methacrylate unit of the obtained polymer was about 60:30:10 from NMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 7,000, and the molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis Example 7: Synthesis of A-7]
1-Ethoxyethyl methacrylate 38.0 g (0.24 mol), glycidyl methacrylate 21.3 g (0.15 mol), benzyl methacrylate 26.4 g (0.15 mol), methacrylic acid 5.2 g (0. 06 mol) and 300 ml of methyl isobutyl ketone were charged into a 500 ml three-necked flask, and a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added thereto as a radical polymerization initiator. Polymerization was carried out at 6 ° C. for 6 hours. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, then dissolved in a mixed solvent of propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether, and heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A-7 (methacrylic acid 1 -Ethoxyethyl / glycidyl methacrylate / benzyl methacrylate / methacrylic acid) was obtained as a 50 wt% solution of a mixed solvent of propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether.
The constituent ratio of 1-ethoxyethyl methacrylate unit, glycidyl methacrylate unit, benzyl methacrylate unit and methacrylic acid in the obtained polymer was about 40: 25: 25: 10 from NMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 7,000, and the molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Example 8: Synthesis of A-8]
47.5 g (0.3 mol) of 1-ethoxyethyl methacrylate, 33.2 g (0.18 mol) of methyl methacrylate (1-ethyl-3-oxacyclobutyl), 21.2 g (0.12) of benzyl methacrylate Mole) and 300 ml of methyl isobutyl ketone were charged into a 500 ml three-necked flask, and a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added as a radical polymerization initiator to the mixture at 70 ° C. under a nitrogen stream. For 6 hours. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol dimethyl ether, and heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to give polymer A-8 (1-ethoxyethyl methacrylate / methacrylic acid (1-ethyl- 3-oxacyclobutyl) methyl / benzyl methacrylate) was obtained as a 50% by weight solution of diethylene glycol dimethyl ether.
The composition ratio of 1-ethoxyethyl methacrylate unit, (1-ethyl-3-oxacyclobutyl) methyl methacrylate unit and benzyl methacrylate unit of the obtained polymer was about 50:30:20 from NMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 8,000, and the molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Example 9: Synthesis of A-9]
The synthesis was performed in the same manner as A-5 except that the amount of the polymerization initiator was reduced.
As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 25,000, and the molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis Example 10: Synthesis of A-10]
The compound was synthesized in the same manner as A-8 except that the amount of the polymerization initiator was reduced.
As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 35,000, and the molecular weight distribution (Mw / Mn) was 1.9.

[Synthesis Example 11: Synthesis of A-11]
1 mol of 1-ethoxyethyl methacrylate, 0.6 mol of glycidyl methacrylate and 300 ml of methyl isobutyl ketone were charged into a 500 ml three-necked flask, and a catalytic amount of 2,2′-azobis ( 2-methylpropionate methyl) was added and polymerized at 70 ° C. for 6 hours under a nitrogen stream.
Next, 0.4 mol of glycidyl methacrylate and 1 g of dimethylbenzylamine were added and stirred at 60 ° C. for 4 hours. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol dimethyl ether, and heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A-11 as a 50% by weight solution of diethylene glycol dimethyl ether. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 8,000, and the molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis Example 12: Synthesis of A-12]
47.5 g (0.3 mol) of 1-ethoxyethyl methacrylate, 25.6 g (0.18 mol) of glycidyl methacrylate, 0.12 mol of t-butyl methacrylate and 300 ml of methyl isobutyl ketone were added to a 500 ml three-necked flask. Then, a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added as a radical polymerization initiator, and polymerization was carried out at 70 ° C. for 6 hours under a nitrogen stream. After cooling the reaction solution, it was poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol dimethyl ether, and heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A-12 as a 50% by weight solution of diethylene glycol dimethyl ether.
As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 7,000, and the molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis of phenol 1 (4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester)]
To a 100 ml acetonitrile solution of 21 g of 4-hydroxybenzoic acid (2-hydroxyethyl) ester, 20 ml of N, N-dimethylacetamide was added with stirring, and 20 g of methacrylic acid chloride was further added. After reacting with stirring at 35 ° C. for 8 hours, the reaction mixture was poured into ice water, the precipitated crystals were collected by filtration, recrystallized from ethyl acetate / n-hexane, and 4-hydroxybenzoic acid (2-methacryloyloxy). Ethyl) ester was obtained.

[Synthesis of phenol 2 (4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester)]
To a solution of 23 g of 4-hydroxybenzoic acid (3-hydroxypropyl) ester in 100 ml of acetonitrile, 20 ml of N-methylpyrrolidone was added with stirring, and 16 g of methacrylic acid chloride was further added. After reacting at 35 ° C. for 8 hours with stirring, the reaction mixture was poured into ice water, and the precipitated crystals were collected by filtration and recrystallized from ethyl acetate / n-hexane to give 4-hydroxybenzoic acid (3-methacryloyloxy). Propyl) ester was obtained.

[Synthesis of phenol 3 (4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester)]
After adding 100 g of p-hydroxybenzoic acid, 100 g of glycidyl methacrylate, and 9.7 g of tetrabutylammonium bromide to a solution of 250 ml of N-methylpyrrolidone and reacting at 90 ° C. for 6 hours with stirring, the reaction mixture is mixed with water / ethyl acetate. It was poured into a solvent, and the precipitated crystals were collected by filtration and recrystallized from ethyl acetate / n-hexane to obtain 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester.

(Synthesis of protected phenol)
By reacting phenols 1, 2, and 3 with ethyl vinyl ether in the presence of an acid catalyst, respectively, protected ethylacetals of protected phenolic hydroxyl groups (protected phenols 1, 2, and 3) were obtained.

[Synthesis Example 13: Synthesis of A-13]
A-13 was obtained in the same manner as A-8 except that 1-ethoxyethyl methacrylate was changed to protected phenol 1 in the synthesis of A-8. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 8,000, and the molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Example 14: Synthesis of A-14]
A-14 was synthesized in the same manner as A-8 except that 1-ethoxyethyl methacrylate was changed to protected phenol 2 in the synthesis of A-8. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 8,000, and the molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis Example 15: Synthesis of A-15]
A-15 was obtained in the same manner as A-8 except that 1-ethoxyethyl methacrylate was changed to protected phenol 3 in the synthesis of A-8. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 8,000, and the molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis Example 16: Synthesis of A-16]
Synthesis in A-9 was carried out in the same manner as in A-8 except that 1-cyclohexyloxyethyl methacrylate was changed to protected phenol 3 and the amount of initiator was further reduced to obtain A-16. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 45,000, and the molecular weight distribution (Mw / Mn) was 2.1.

[Synthesis Example 17: Synthesis of A-17]
12.4 g of propylene glycol monomethyl ether acetate (PGMEA) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. In the solution, 0.603 g of methacrylic acid (MAA), 1.821 g of 2-hydroxyethyl methacrylate (HEMA), 4.373 g of tetrahydrofuran-2-yl methacrylate (MATHF), oxetane methacrylate (OXE-30, Osaka Organic Chemical Industry ( Co., Ltd.) 3.868 g, V-65 (polymerization initiator, Wako Pure Chemical Industries, Ltd.) 1.217 g (7 mol% based on monomer) was dissolved in 12.4 g of PGMEA and added dropwise over 2 hours. . After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. The weight average molecular weight was 6,500. The molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Example 18: Synthesis of A-18]
In a three-necked flask, 32.75 g of propylene glycol monomethyl ether acetate (PGMEA) was placed and heated to 70 ° C. in a nitrogen atmosphere. In the solution, 1.54 g of methacrylic acid (MAA), 5.20 g of 2-hydroxyethyl methacrylate (HEMA), 12.80 g of tetrahydrofuran-2-yl methacrylate (MATHF), 8.53 g of glycidyl methacrylate (GMA), V-65 (Polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.) 3.477 g (7 mol% with respect to the monomer) was dissolved in PGMEA (32.75 g) and added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. The weight average molecular weight was 7,100. The molecular weight distribution (Mw / Mn) was 1.4.

Note that MATHF used in Synthesis Examples A-17 and A-18 was synthesized as follows.
<Synthesis of MATHF (tetrahydrofuran-2-yl methacrylate)>
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, 2,3-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated aqueous sodium hydrogen carbonate solution (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a yellow oily residue. Was distilled under reduced pressure to obtain 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) as a colorless oily substance having a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg (yield 80%).

[Synthesis Example 19: Synthesis of A-19]
A-19 was obtained in the same manner as A-17 except that MATH was changed to 1-ethoxyethyl methacrylate in the synthesis of A-17. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 8,000, and the molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis Example 20: Synthesis of A-20]
In the synthesis of A-17, A-20 was synthesized in the same manner as the synthesis of A-20 except that styrene was further added as a monomer.

[Synthesis Example 21: Synthesis of B10]
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated, and the crystals were diluted with diisopropyl ether (10 mL). The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and 50% by weight hydroxylamine aqueous solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain B10 (2.3 g).
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B10 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 Example 22: Synthesis of B11]
1-1. Synthesis of synthetic intermediate B11-A 2-aminobenzenethiol: 31.3 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in toluene: 100 mL (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 ° C.). . Next, phenylacetyl chloride: 40.6 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was stirred at room temperature for 1 hour and then stirred at 100 ° C. for 2 hours for reaction. 500 mL of water was added to the resulting reaction solution to dissolve the precipitated salt, the toluene oil was extracted, and the extract was concentrated with a rotary evaporator to obtain a synthetic intermediate B11-A.

1-2. Synthesis of B11 After 2.25 g of the synthetic intermediate B11-A obtained as described above was mixed with tetrahydrofuran: 10 mL (manufactured by Wako Pure Chemical Industries, Ltd.), it was put in an ice bath and the reaction solution was kept at 5 ° C. or lower. Cooled down. Next, tetramethylammonium hydroxide: 4.37 g (25% by weight methanol solution, manufactured by Alfa Acer) was added dropwise, and the mixture was stirred for 0.5 hour in an ice bath to be reacted. Furthermore, 7.03 g of isopentyl nitrite: was dropped while maintaining the internal temperature at 20 ° C. or lower, and after completion of the dropping, the reaction solution was warmed to room temperature and stirred for 1 hour.
Subsequently, after cooling the reaction liquid to 5 ° C. or lower, p-toluenesulfonyl chloride (1.9 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirred for 1 hour while maintaining 10 ° C. or lower. Thereafter, 80 mL of water was added and stirred at 0 ° C. for 1 hour. After filtration of the resulting precipitate, 60 mL of isopropyl alcohol (IPA) was added, heated to 50 ° C., stirred for 1 hour, filtered while hot, and dried to obtain 1.8 g of (B11: the structure). Obtained.
The ¹ H-NMR spectrum (300 MHz, deuterated DMSO ((D ₃ C) ₂ S═O)) of the obtained B11 is δ = 8.2 to 8.17 (m, 1H), 8.03 to 8.0. 00 (m, 1H), 7.95 to 7.9 (m, 2H), 7.6 to 7.45 (m, 9H), 2.45 (s, 3H).
From the above ¹ H-NMR measurement results, it is estimated that the obtained B11 is a single geometric isomer.

Example 1
The components shown in Table 1 were mixed, and a 1: 1 mixed solvent of propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether was added to obtain a solid concentration of 20% by weight, and a 0.2 μm polytetrafluoroethylene filter was used. And filtered to prepare a positive photosensitive resin composition.

<Evaluation of sensitivity>
The photosensitive resin composition of the present invention was slit-coated on a silicon wafer having a silicon oxide film, and then vacuum-dried to form a coating film having a thickness of 3 μm.
Next, it exposed through the predetermined | prescribed mask using i line | wire stepper (Canon Co., Ltd. product FPA-3000i5 +). After liquid development with an alkaline developer (2.38 wt% tetramethylammonium hydroxide aqueous solution) at 23 ° C. for 65 seconds, the resultant was rinsed with ultrapure water for 1 minute. By these operations, the optimum exposure amount when resolving 5 μm line and space at 1: 1 was defined as sensitivity. Optimum exposure from the viewpoint of productivity is preferably at 50 mJ / cm ² or less, more preferably 20 mJ / cm ² or less.

<Evaluation of remaining film ratio during development>
In addition, the film thickness of the unexposed part after development is measured, and the ratio to the film thickness after application (the film thickness of the unexposed part after development ÷ the film thickness after application × 100 (%)) is obtained during development. The remaining film rate was evaluated. In all the examples, the remaining film ratio was 99% or more, and the pattern could be formed cleanly.

<Evaluation of formability of contact holes>
In the same manner as described above, a coating film having a thickness of 3.0 μm was formed on a silicon wafer. Next, using an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.), an optimal exposure exposure was performed with a pattern having a 10 μm diameter extraction pattern corresponding to a contact hole through a predetermined mask.
Development and rinsing were performed in the same manner as described above to form a contact hole pattern. Here, the diameter of the bottom of the formed contact hole was measured with an electron microscope. Further, the developed coating film in which the contact hole was formed was irradiated with light of 500 mJ / cm ^{2 at} a wavelength of 365 nm using an ultrahigh pressure mercury lamp, and then heated in an oven at 220 ° C. for 60 minutes. Here, the diameter of the lower bottom of the contact hole was measured in the same manner as described above.
In this evaluation, regarding the diameter of the bottom bottom of the formed contact hole, the difference between the two measured values measured before and after heating was 0.5 μm or less as “◯”, and the difference between 0.5 μm or more as “ “×” was evaluated. The smaller the difference in diameter before and after heating, the easier it is to control the contact hole diameter, which is preferable.

<Transmissivity>
In the evaluation of contact holes, a solid cured film was obtained in the same manner except that the substrate was changed to glass, pattern exposure was not performed, and the final heat treatment was changed to 220 ° C. for 90 minutes.
The transmittance of the cured film was measured at a wavelength of 400 to 800 nm using a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.). The minimum transmittance is shown in Tables 1-5. The minimum transmittance is preferably 90% or more, and more preferably 95% or more.

<ITO sputtering suitability>
In the same manner as the transmittance evaluation, a cured film after the final heat treatment was obtained. On this cured film, an ITO transparent electrode was formed by sputtering (manufactured by ULVAC, SIH-3030, sputtering temperature 200 ° C.). The surface of the cured film after sputtering was observed with an optical microscope (500 times) and evaluated according to the following criteria.
A: No wrinkle is generated on the surface of the cured film. O: A slight wrinkle is visible on the surface of the cured film (allowable range).
X: Wrinkles are generated on the surface of the cured film. If wrinkles are observed on the surface of the cured film after the ITO transparent electrode is formed by sputtering, the transmittance of the cured film is reduced, which is not preferable.

(Examples 2-113 and Comparative Examples 1-22)
The photosensitive resin compositions of Examples 2 to 113 and Comparative Examples 1 to 22 shown in Tables 1 to 5 were prepared in the same manner as in Example 1 with the compositions shown in Tables 1 to 5, and Example 1 and Evaluation was performed in the same manner. The results are shown in Tables 1-5.

The abbreviations in Tables 1 to 5 are as follows.
(B) Component B1: IRGACURE PAG 103 (Ciba Specialty Chemicals)
B2: IRGACURE PAG 108 (Ciba Specialty Chemicals)
B3: CGI 1380 (manufactured by Ciba Specialty Chemicals)
B4: IRGACURE PAG 121 (manufactured by Ciba Specialty Chemicals)
B5: CGI 725 (Ciba Specialty Chemicals)
B6: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate B7: α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (PAI-1001, Midori Chemical Co., Ltd.) Made)
B8: α- (4-Toluenesulfonyloxyimino) benzyl cyanide (synthesized according to the method described in paragraph 0108 of JP-T-2002-528451)
B9: α-[(4-Toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (PAI-101, manufactured by Midori Chemical Co., Ltd.)
B10: The oxime sulfonate compound synthesized above B11: The oxime sulfonate compound synthesized above

(C) Component AO60: ADK STAB AO-60 (manufactured by ADEKA Corporation)
AO70: ADK STAB AO-70 (manufactured by ADEKA)
AO80: ADK STAB AO-80 (manufactured by ADEKA)
AO30: ADK STAB AO-30 (manufactured by ADEKA, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenol) butane)
AO330: ADK STAB AO-330 (manufactured by ADEKA, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene)
1098: Irganox 1098 (Ciba Specialty Chemicals)
TP-D: Sumilyzer TP-D (Sumitomo Chemical Co., Ltd., sulfur antioxidant)
LA-62: ADK STAB LA-62 (manufactured by ADEKA, amine-based antioxidant)
PEP-36: ADK STAB PEP-36 (manufactured by ADEKA Corporation, phosphorus antioxidant)
The molecular weight of component (C) and the presence or absence of ester groups or amide groups are summarized in Table 6.

(Basic compound)
D1: 4-dimethylaminopyridine D2: 1,5-diazabicyclo [4.3.0] -5-nonene (crosslinking agent)
MX-270: Nikarak MX-270 manufactured by Sanwa Chemical Co., Ltd.
JER157S70: JER157S70 manufactured by Japan Epoxy Resin Co., Ltd.

(Adhesive)
KBM403: Silane coupling agent KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.

(Surfactant)
F780F: manufactured by DIC Corporation, fluorine-based surfactant F780F
PF6320: PolyFox PF-6320 (manufactured by OMNOVA)
W-3: The following compound

-Comparison between Examples and Comparative Examples, in particular, Comparison between Comparative Examples 1-10 and Examples 18, 23-29: Only when the specific phenolic compound (C) is added as the component (C), the transmission rate jumps. Improved. This effect was more prominent as the molecular weight of the specific phenolic compound was larger and the amount added was larger.
-Comparison with an Example and Comparative Examples 11-14: The case where (a1) was included was high sensitivity.
Comparative Example 10 and others: Without (a2), the film strength necessary for the interlayer insulating film could not be obtained.
Comparison between Examples 1 to 3 and Examples 8 to 10, Examples 4 to 6 and Examples 11, 15, and 18: A photoacid generator containing an oxime sulfonate residue represented by the formula (b1) It was found to be more sensitive than the onium salt photoacid generator.
Comparison of Examples 1 to 3 and Examples 4 to 6, Examples 8 to 10 and Examples 11, 15, and 18: It was found that the crosslinking agent was effective in improving the film strength (ITO sputtering suitability).
-Comparison between Examples 1-45 and Examples 46-79: In Examples 46-79, compared to Examples 1-45, the component (B) was changed to B10, and the basic compound was further increased. . Since Examples 46 to 79 have sensitivity equal to or higher than that of Examples 1 to 45, it can be seen that particularly high sensitivity can be achieved by using Compound B10 represented by the formula (OS-3).

(Examples a to c and l, and comparative examples d to k, m and n)
<Measurement of dielectric constant>
A cured film after the final heat treatment was obtained in the same manner as the transmittance evaluation, except that the substrate was changed to a bare wafer (N-type low resistance) (manufactured by SUMCO). With respect to this cured film, the relative dielectric constant was measured at a measurement frequency of 1 MHz using CVmap92A (made by Four Dimensions Inc.). As shown in Table 7, the difference in relative dielectric constant was measured, and the dielectric constant reduction effect by the specific phenol compound (C) was confirmed.

The dielectric constant decreased only when the component (A) and the specific phenol compound (C) were used in combination. This effect was more pronounced as the amount added increased and the molecular weight increased.
In Comparative Example h and Comparative Example i, since the resin component does not have the monomer unit (a1), the relative dielectric constant did not decrease even when the specific phenol compound (C) was contained.

(Example 114)
Using the photosensitive resin composition of Example 74, the same evaluation as in Example 74 was performed using a UV-LED light source exposure machine in place of the ultrahigh pressure mercury lamp. As a result, the same result as in Example 74 was obtained.

(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 to the 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 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 18 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 7 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 7 was replaced with the photosensitive resin composition of Example 74. 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 as in Example 115 except that the photosensitive resin composition of Example 7 was replaced with the photosensitive resin composition of Example 108. 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 shown in FIGS. 1 and 2 of Japanese Patent No. 3312003, 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 19, 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 19 was replaced with the photosensitive resin composition of Example 74. 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 19 was replaced with the photosensitive resin composition of Example 108. 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 (15)

(A) a monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group, or a monomer unit (a1) having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group, and a crosslinking group A monomer unit (a2) and a copolymer containing
(B) a photoacid generator,
(C) a compound having at least two partial structures represented by the formula (c1) in the molecule and having a molecular weight of 600 or more and 2,000 or less, and
(D) A photosensitive resin composition comprising a solvent.

(In Formula (c1), R ¹ and R ² each independently represent a methyl group or a tert-butyl group, at least one of R ¹ and R ² is a tert-butyl group, and R ³ is —O— or -NH-
Represents. )   The photosensitive resin composition of Claim 1 which is a chemically amplified positive photosensitive resin composition. The compound (C) is at least one compound selected from the group consisting of compounds represented by formula (c1-1), formula (c1-2), and formula (c1-3). Or the photosensitive resin composition of 2.

The photosensitive resin composition as described in any one of Claims 1-3 whose compound of the said (C) is a compound represented by Formula (c1-1).

The photosensitive resin composition as described in any one of Claims 1-4 whose said (B) photo-acid generator is a compound containing the oxime sulfonate residue represented by Formula (b1).

(In formula (b1), R ⁵ represents an alkyl group, a cycloalkyl group or an aryl group.) The said (B) photo-acid generator is a compound represented by a formula (OS-3), a formula (OS-4), or a formula (OS-5), It is any one of Claims 1-5. Photosensitive resin composition.

(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, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, m Represents an integer of 0 to 6.) The photosensitive resin composition as described in any one of Claims 1-5 whose said (B) photo-acid generator is a compound represented by Formula (b2).

(In the formula (b2), R ⁵ represents an alkyl group, a cycloalkyl 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, When m is 2 or 3, a plurality of X may be the same or different.)   (E) The photosensitive resin composition as described in any one of Claims 1-7 which further contains a crosslinking agent.   The monomer unit (a2) having a crosslinking group includes 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. The photosensitive resin composition as described in any one of -8. (1) The application | coating process which apply | coats the photosensitive resin composition as described in any one of Claims 1-9 on a board | substrate,
(2) a solvent removal step of removing the solvent from the applied photosensitive resin composition;
(3) an exposure step of exposing with actinic radiation,
(4) a development step of developing with an aqueous developer, and
(5) A method for forming a cured film, comprising a post-bake step of thermosetting.   The formation method of the cured film of Claim 10 including the process of exposing the whole surface after the said image development process and before a post-baking process.   A cured film formed by the forming method according to claim 10.   The cured film according to claim 12, which is an interlayer insulating film.   An organic EL display device comprising the cured film according to claim 12.   A liquid crystal display device comprising the cured film according to claim 12.

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