JP2012008223A - Positive photosensitive resin composition, hardening film formation method, hardening film, liquid crystal display device and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition which has high sensitivity and high thermal stability and with which a hardening film with low organic solvent swelling rate can be formed.SOLUTION: A positive photosensitive resin composition includes (component A) resin including constitutional units expressed by the formula (1) and constitutional units having carboxy groups or phenol hydroxyl groups protected by acetal or ketal, (component B) acid generator, and (component C) solvent. In the formula (1), Rmeans a hydrogen atom or an alkyl group, Lmeans a bivalent connection group and Lmeans a trivalent hydrocarbon group.

Description

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

Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.
Patent Document 1 contains a structural unit having a specific acid-dissociable group and a structural unit having a functional group capable of reacting with a carboxyl group to form a covalent bond, and is alkali-insoluble or hardly alkali-soluble, and And a positive photosensitive resin composition characterized by containing at least a resin that becomes alkali-soluble when the acid-dissociable group is dissociated, and a compound that generates an acid upon irradiation with actinic rays or radiation. Yes.
Several cross-linkable photosensitive compositions using cyclic carbonates have been reported. Examples of positive photosensitive compositions include Patent Documents 2 to 5, and negative photosensitive compositions include Patent Documents 6 and 7. Is mentioned.

JP 2009-98673 A JP 2010-66503 A JP 2003-5357 A Japanese Patent Laid-Open No. 10-133377 JP-A-2005-240024 Japanese Patent Laid-Open No. 2001-100413 JP 2008-197613 A

In the case of forming a cured film applied to an interlayer insulating film or the like with a photosensitive resin composition, in addition to high sensitivity, stability against temperature (thermal stability) is required. Further, a cured film formed by crosslinking is also required to have a low swelling rate with respect to an organic solvent.
However, the conventional photosensitive resin compositions do not satisfy all of the sensitivity, stability, and organic solvent swelling rate, and the current situation is that further improvements are desired.
The present invention has been made in view of the above-described conventional situation, and solves the following problems.
That is, the problem to be solved by the present invention is to provide a positive photosensitive resin composition that can form a cured film having high sensitivity, high thermal stability, and low organic solvent swelling rate. is there.
Another problem to be solved by the present invention is to provide a method for forming a cured film using the positive photosensitive resin composition of the present invention, and a cured film formed by the method for forming the cured film. It is another object of the present invention to provide a liquid crystal display device and an organic EL display device provided with the cured film.

The above problem has been solved by the means described in <1>, <9>, <10>, <11>, <13> or <14> below. It is shown below with <2>-<8> and <12> which are preferable embodiments.
<1> (Component A) a resin comprising a structural unit represented by the following formula (1) and a structural unit having a carboxy group or a phenolic hydroxyl group protected with an acetal or ketal, (Component B) an acid generator, and (Component C) a positive photosensitive resin composition comprising a solvent,

（式（１）中、Ｒ¹は水素原子又はアルキル基を表し、Ｌ¹は二価の連結基を表し、Ｌ²は三価の炭化水素基を表す。）

(In formula (1), R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a divalent linking group, and L ² represents a trivalent hydrocarbon group.)

<2> The positive photosensitive resin composition according to <1>, wherein the component A further includes a structural unit having an alkali-soluble group.
<3> The above <1>, wherein the structural unit having a carboxy group or a phenolic hydroxyl group protected with an acetal or ketal is a structural unit represented by the following formula (A-1) or formula (A-2) Or the positive photosensitive resin composition according to <2>,

  <4> Any of the above <1> to <3>, wherein the structural unit represented by the formula (1) is a structural unit represented by the following formula (M-1) or the formula (M-2) The positive photosensitive resin composition according to one,

<5> The positive photosensitive resin composition according to any one of the above <1> to <4>, wherein the component A further has a structural unit having a hydroxyl group other than the phenolic hydroxyl group,
<6> The positive photosensitive resin composition according to any one of <1> to <5>, wherein Component B is an acid generator having an oxime sulfonate group,
<7> The positive photosensitive resin composition according to any one of <1> to <6>, wherein Component B is an oxime sulfonate compound represented by the following formula (2):

（式（２）中、Ｒ⁴はアルキル基又はアリール基を表し、Ｘはそれぞれ独立に、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の整数を表す。）

(In Formula (2), R ⁴ represents an alkyl group or an aryl group, X represents each independently an alkyl group, an alkoxy group, or a halogen atom, and m represents an integer of 0 to 3.)

<8> The positive photosensitive resin composition according to any one of <1> to <7>, further including a crosslinking agent,
<9> A cured film obtained by applying and curing at least one of light and heat to the positive photosensitive resin composition according to any one of <1> to <8> above,
<10> (1) Application step of applying the positive photosensitive resin composition according to any one of the above <1> to <8> on a substrate, (2) Applied positive photosensitive resin composition A solvent removal step for removing the solvent from the product, (3) an exposure step for exposing the positive photosensitive resin composition from which the solvent has been removed with actinic radiation, and (4) an aqueous development for the exposed positive photosensitive resin composition. A cured film forming method comprising: a developing step of developing with a liquid; and (5) a post-baking step of thermally curing the developed positive photosensitive resin composition,
<11> A cured film formed by the method for forming a cured film according to <10> above,
<12> The cured film according to <11>, which is an interlayer insulating film,
<13> A liquid crystal display device comprising the cured film according to <9>, <11> or <12> above,
<14> An organic EL display device comprising the cured film according to <9>, <11>, or <12>.

According to the present invention, it was possible to provide a positive photosensitive resin composition that can form a cured film having high sensitivity, high thermal stability, and low organic solvent swelling rate.
In addition, according to the present invention, there is provided a method for forming a cured film using the positive photosensitive resin composition of the present invention, a cured film formed by the method for forming the cured film, and the cured film. Thus, the liquid crystal display device and the organic EL display device can be provided.

It is a structure conceptual diagram which shows an example of the organic electroluminescence display using the photosensitive resin composition of this invention. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. It is a conceptual sectional view showing an example of an active matrix type liquid crystal display device applicable as a liquid crystal display device using the photosensitive resin composition of the present invention.

Hereinafter, the present invention will be described in detail.
In the specification, the description of “lower limit to upper limit” represents “more than the lower limit and less than the upper limit”, and the description of “upper limit to lower limit” represents “the upper limit and less than the lower limit”. That is, it represents a numerical range including an upper limit and a lower limit. In addition, “(component A) a resin containing a structural unit represented by the following formula (1) and a structural unit having a carboxy group or a phenolic hydroxyl group protected by an acetal or ketal” or the like is simply referred to as “component A” or the like. Say.

(Positive photosensitive resin composition)
The positive photosensitive resin composition of the present invention comprises (Component A) a resin comprising a structural unit represented by the following formula (1) and a structural unit having a carboxy group or a phenolic hydroxyl group protected with an acetal or ketal, It contains (Component B) an acid generator and (Component C) a solvent.

（式（１）中、Ｒ¹は水素原子又はアルキル基を表し、Ｌ¹は二価の連結基を表し、Ｌ²は三価の炭化水素基を表す。）

(In formula (1), R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a divalent linking group, and L ² represents a trivalent hydrocarbon group.)

Hereinafter, the positive photosensitive resin composition of the present invention (hereinafter, appropriately referred to as “photosensitive resin composition”) will be described in detail.
The cured film obtained by the photosensitive resin composition of the present invention can be suitably used as an interlayer insulating film, a planarizing film, etc. provided in a liquid crystal display device or an organic EL display device.
When the sensitivity of an insulating film included in a liquid crystal display device or an organic EL display device is high, exposure energy is small, so that the tact time (manufacturing time per unit) can be shortened and the productivity is increased. Moreover, since the thermal stability of the composition itself is high, a special frozen storage etc. are not required and cost can be reduced. Moreover, when the swelling rate with respect to an organic solvent is low, since the washing | cleaning process by an organic solvent can be performed smoothly, a tact time can be shortened and it is beneficial.
The photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).

Hereinafter, the resin and the acid generator, which are characteristic components constituting the photosensitive resin composition of the present invention, will be described.
In addition, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The method for introducing the structural 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 constituent unit using a reactive group contained in the constituent unit of the obtained copolymer.
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 alkali dissolution rate of the resin in the present invention is more preferably less than 0.005 μm / second. Moreover, when the residue in which the alkali-soluble group of the resin is protected is decomposed, the alkali dissolution rate is preferably 0.05 μm / second or more.

(Component A) Resin comprising a structural unit represented by the formula (1) and a structural unit having a carboxy group or phenolic hydroxyl group protected with acetal or ketal The positive photosensitive resin composition of the present invention comprises (component A) A resin containing a structural unit represented by the formula (1) and a structural unit having a carboxy group or phenolic hydroxyl group protected with an acetal or ketal is contained.
The cyclic carbonate structure in the structural unit represented by the formula (1) in Component A can react with a carboxy group or a phenolic hydroxyl group in the post-baking step described later to form a crosslinked structure.
Hereinafter, a structural unit represented by the following formula (1), a structural unit having a carboxy group protected by acetal or ketal, or a phenolic hydroxyl group, which is a partial structure of the resin, will be described in detail.

[Structural Unit Represented by Formula (1)]
Component A includes a structural unit represented by the following formula (1).

In formula (1), R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a divalent linking group, and L ² represents a trivalent hydrocarbon group.
In the formula (1), R ¹ represents a hydrogen atom or an alkyl group.
Alkyl group carbon number of the R ^1, preferably from 1 to 20 is, more preferably 1 to 10, more preferably 1-7. In addition, the alkyl group in R < ¹ > may have a substituent, and when it has a substituent, carbon number of a substituent is also contained.
The alkyl group in R ¹ is, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, n-pentyl group, neopentyl group, n- A hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, etc. can be mentioned. The alkyl group for R ¹ is preferably a methyl group.
R ¹ is particularly preferably a methyl group.
In the formula (1), L ¹ represents a divalent linking group.
Preferred examples of the divalent linking group for L ¹ include a divalent aliphatic group, a divalent aromatic group, and a group obtained by combining these groups. Specific examples include a methylene group, an ethylene group, a propylene group, a phenylene group, and a naphthylene group.
The divalent aliphatic group may further have a substituent, and examples thereof include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydroxy group.
The divalent aromatic group may have a substituent on the aromatic ring, and the substituent is an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.). , C 3-10 cycloalkyl group, C 6-10 aryl group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxy group, carbon number 1-10 Can be exemplified by these alkoxy groups, oxo groups and the like, and these substituents may be further substituted with the above substituents.
Moreover, an ether bond, an ester bond, an amide bond, an amino group, and a thioether bond may be inherent in the divalent linking group in L ¹ . For example, a polyalkyleneoxy group, a polyalkyleneoxyalkyl group, —CH ₂ CH ₂ N (CH ₃ ) —, —CH ₂ CH ₂ OC (═O) —, and the like can be exemplified.

In the formula (1), L ² represents a trivalent linking group. L ² is an organic linking group that cyclizes the carbonate structure and further binds to L ¹ .
Although there is no restriction | limiting in particular in the number of ring members of the cyclic carbonate structure in said Formula (1), What is comprised by 5-7 atoms is preferable, 5 (ethylene carbonate ring) or 6 (1,3-propylene carbonate ring) Is more preferable, and 5 is still more preferable. In the above embodiment, a cured film having excellent transparency and heat-resistant transparency and a lower organic solvent swelling ratio can be formed. Further, in terms of thermal stability, those having 6 ring members are preferable.
The trivalent linking group in L ² is preferably a trivalent hydrocarbon group.
The trivalent hydrocarbon group may have a branch or may have a substituent, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxy group. Etc. can be exemplified. The trivalent hydrocarbon group is preferably a group composed of only carbon atoms and hydrogen atoms. Furthermore, the carbon number of the trivalent hydrocarbon group is preferably 2 to 10, more preferably 2 to 8, and still more preferably 2 to 5.
Moreover, the component A may have 1 type of structural units represented by Formula (1), or may have 2 or more types.

  Preferable specific examples of the structural unit represented by the formula (1) include the following structural units. Needless to say, the structural unit represented by the formula (1) is not limited thereto.

Among these, M-1 and M-2 are preferable, and M-1 is most preferable.
10-60 mol% is preferable, as for the content rate of the monomer unit which forms the structural unit represented by said Formula (1) in all the monomer units which comprise component A, 5-50 mol% is more preferable, 40 mol% is particularly preferred. When component A contains the structural unit represented by the following formula (1) at the above ratio, the cured film properties are improved and the swelling ratio with respect to the organic solvent is also reduced.

[Structural unit having carboxy group or phenolic hydroxyl group protected with acetal or ketal]
Component A has a structural unit having at least one carboxy group protected with an acetal or ketal or a phenolic hydroxyl group protected with an acetal or ketal.
Component A may have one structural unit having a carboxy group or a phenolic hydroxyl group protected with an acetal or ketal, or two or more structural units.
In addition, the structural unit having a carboxyl group or phenolic hydroxyl group protected with an acetal or ketal has two or more kinds even if it has only one kind of carboxyl group or phenolic hydroxyl group protected with an acetal or ketal. The structural unit may have two or more of the same groups.
Preferred examples of the carboxy group or phenolic hydroxyl group protected with acetal or ketal include groups represented by the following formula (Ia), formula (Ib), formula (IIa) or formula (IIb). In the following, the structural unit having a group represented by the formula (Ia) and / or the formula (Ib) is also referred to as a structural unit (a1), and the group represented by the formula (IIa) and / or the formula (IIb). Is also referred to as a structural unit (a2).

In the above formula, R ¹ represents an alkyl group or a cycloalkyl group, and R ² represents an alkyl group. R ³ represents a tertiary alkyl group, 2-tetrahydropyranyl group or 2-tetrahydrofuranyl group, and R ⁴ represents a tertiary alkyl group, tert-butoxycarbonyl group, 2-tetrahydropyranyl group or 2-tetrahydrofuranyl group. Represents a group. Ar ¹ and Ar ² represent an aryl group, and the wavy line represents a bonding site with another structure.
As the structural unit having a carboxyl group or phenolic hydroxyl group protected with an acetal or ketal, it is preferable to include at least one of the structural unit (a1) and the structural unit (a2), and the structural unit (a1) And the structural unit (a2) may be included.
Among these, as the carboxy group or phenolic hydroxyl group protected with an acetal or ketal, a group represented by the formula (Ia) or a group represented by the formula (Ib) is preferable, and further represented by the formula (Ia) Are preferred.
In the present invention, Component A is preferably a resin that is insoluble in alkali and becomes alkali-soluble when a carboxy group or phenolic hydroxyl group protected with acetal or ketal is deprotected.

Component A in the present invention is preferably an acrylic polymer.
The “acrylic polymer” in the present invention is an addition polymerization type resin, is a polymer containing a structural unit derived from (meth) acrylic acid and / or its ester, and (meth) acrylic acid and / or its You may have structural units other than the structural unit derived from ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
Component A is preferably a monomer unit derived from (meth) acrylic acid and / or an ester thereof in an amount of 50 mol% or more, more preferably 80 mol% or more based on all monomer units in the polymer. Particularly preferred is a polymer consisting only of monomer units derived from (meth) acrylic acid and / or its ester.
The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”. (Meth) acrylic acid is a generic term for methacrylic acid and acrylic acid.

<Structural unit (a1) having at least one of group represented by formula (Ia) or group represented by formula (Ib)>
The structural unit (a1) having at least one of the group represented by the formula (Ia) and the group represented by the formula (Ib) will be described in more detail.

In Formula (Ia) and Formula (Ib), R ¹ represents an alkyl group or a cycloalkyl group. The alkyl group in R ¹ may be linear or branched.
Alkyl group carbon number of the R ^1, preferably from 1 to 20 is, more preferably 1 to 10, more preferably 1-7.
The number of carbon atoms of the cycloalkyl group in R ^1, preferably from 3 to 20, more preferably from 3 to 10, more preferably 5-7.
In addition, when these carbon numbers have a substituent, the carbon number of a substituent is also included.

The alkyl group in R ¹ is, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, n-pentyl group, neopentyl group, n- A hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, etc. can be mentioned.
Examples of the cycloalkyl group in R ¹ 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.
In addition, the alkyl group and cycloalkyl group in R ¹ may have a substituent.
Examples of the substituent in the alkyl group and the cycloalkyl group include alkyl groups having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.), cycloalkyl groups having 3 to 10 carbon atoms, and 6 to 6 carbon atoms. 10 aryl groups, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxy group, alkoxy group having 1 to 10 carbon atoms, and the like. It may be further substituted with a substituent.
In addition, the alkyl group or cycloalkyl group in R ¹ is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms. Is more preferably an alkyl group having 1 to 6, a cycloalkyl group having 3 to 6 carbon atoms, or a benzyl group, more preferably an ethyl group or a cyclohexyl group, and particularly preferably an ethyl group.

In formula (Ia) and formula (Ib), R ² represents an alkyl group. The alkyl group in R ² may be linear or branched.
Alkyl group carbon number of the R ^2, preferably from 1 to 20 is, more preferably 1 to 10, more preferably 1-7. In addition, when these carbon numbers have a substituent, the carbon number of a substituent is also included.
The alkyl group for R ² is particularly preferably a methyl group.

As the carboxylic acid monomer capable of forming the structural unit (a1) containing the partial structure represented by the formula (Ia) by protecting the carboxy group, the structural unit (a1) is obtained by protecting the carboxy group. Carboxylic acid monomers that can be used, for example, monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-methyl-p-carboxystyrene; maleic acid, fumaric acid, citraconic acid, mesaconic acid, Mention may be made of dicarboxylic acids such as itaconic acid. Moreover, as a structural unit (a1), the structural unit derived from the carboxylic acid by which these carboxy groups were protected can be mentioned as a preferable thing.
As a monomer having a phenolic hydroxyl group that can form the structural unit (a1) containing the group represented by the formula (Ib) by protecting the phenolic hydroxyl group, the phenolic hydroxyl group is protected to form a structural unit. Any one can be used as long as it can be (a1). Examples thereof include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene, and paragraphs 0011 to 0016 of JP-A-2008-40183. Compound, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, addition of 4-hydroxybenzoic acid and glycidyl acrylate Reaction materials and the like can be mentioned as preferable ones.
Among these, α-methyl-p-hydroxystyrene, compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, and 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454 An addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate and an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable.
Particularly preferred as the structural unit (a1) is a structural unit represented by the following formula (III).

In formula (III), R ⁵ represents an alkyl group or a cycloalkyl group, and a preferred embodiment of R ⁵ is the same as the preferred embodiment of R ¹ in formula (Ia) and formula (Ib).
In the general formula (III), R ⁶ represents a hydrogen atom or a methyl group.
Preferable specific examples of the radical polymerizable monomer used for forming the structural unit represented by the formula (III) include, for example, 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl methacrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, 1-isobutoxyethyl acrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1- ( 2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl methacrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl methacrylate, 1-cyclohexyloxyethyl acrylate, 1- ( - cyclohexyl) ethyl methacrylate, 1- (2-cyclohexyl) ethyl acrylate, 1-benzyloxy-ethyl methacrylate, and the like 1-benzyloxy-ethyl acrylate. Among these, 1-ethoxyethyl methacrylate and 1-ethoxyethyl acrylate are particularly preferable. These monomers can be used singly or in combination of two or more.

  As the radical polymerizable monomer used for forming the structural unit (a1), commercially available monomers may be used, or those synthesized by a known method may be used. For example, as shown below, it can be synthesized by reacting (meth) acrylic acid with a vinyl ether compound in the presence of an acid catalyst.

Here, R ⁵ and R ⁶ are respectively synonymous with R ⁵ and R ⁶ in formula (III).
Further, the structural unit (a1) is polymerized with the monomer or precursor thereof forming the structural units (a2) to (a4) described above or later, the carboxy group or phenolic hydroxyl group-containing monomer to be protected, It can also be formed by reacting a carboxy group or a phenolic hydroxyl group with a vinyl ether compound. In addition, the specific example of the preferable structural unit formed in this way is the same as the structural unit derived from the preferable specific example of the said radical polymerizable monomer.
Preferable specific examples of the structural unit (a1) include the following structural units.

  The content of monomer units forming the structural unit (a1) in all monomer units constituting Component A is preferably 10 to 80 mol%, more preferably 15 to 70 mol%, particularly preferably 20 to 60 mol%. . By containing the structural unit (a1) at the above ratio, a photosensitive resin composition having high sensitivity and wide exposure latitude can be obtained.

<Structural unit (a2) having at least one of group represented by formula (IIa) and group represented by formula (IIb)>
The structural unit (a2) having at least one of the group represented by the following formula (IIa) and the group represented by the following formula (IIb) will be described in more detail.

In formula (IIa) and formula (IIb), R ³ represents a tertiary alkyl group, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, R ⁴ represents a tertiary alkyl group, a tert-butoxycarbonyl group, It represents a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, Ar ² represents a divalent aromatic group, and a wavy line represents a bonding site with another structure.
Tertiary alkyl group in R ³ , 2-tetrahydropyranyl group and 2-tetrahydrofuranyl group, Tertiary alkyl group in R ⁴ , tert-butoxycarbonyl group or 2-tetrahydropyranyl group and 2-tetrahydrofuranyl group, In addition, the divalent aromatic group in Ar ² may have a substituent. Examples of the substituent include alkyl groups having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.), cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, halogen atoms ( A fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, and the like. These substituents may be further substituted with the above substituents.

The tertiary alkyl group for R ³ and R ⁴ is more preferably a group represented by the following formula (V).
-C (R ⁹ R ¹⁰ R ¹¹ ) (V)
In the formula (V), R ⁹ , R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a carbon number. 7 to 12 aralkyl groups may be represented, and any two of R ⁹ , R ¹⁰ and R ¹¹ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.
The alkyl group having 1 to 12 carbon atoms of R ⁹ , R ¹⁰ and R ¹¹ in formula (V) may be linear or branched, and examples thereof include a methyl group, an ethyl group, and n- Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group (2,3-dimethyl- 2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
Examples of the cycloalkyl group having 3 to 12 carbon atoms of R ⁹ , R ¹⁰ and R ¹¹ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, and the like. Can be mentioned.
Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
R ⁹ , R ¹⁰ and R ¹¹ can be bonded to each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , or R ¹⁰ and R ¹¹ are bonded to each other include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group Group, tetrahydropyranyl group and the like.

R ³ in formula (IIa) is preferably a tertiary alkyl group having 4 to 12 carbon atoms, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, and a tertiary alkyl group having 4 to 8 carbon atoms. It is more preferably an alkyl group, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, more preferably a t-butyl group, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, and a t-butyl group. Or 2-tetrahydrofuranyl group is particularly preferred.
R ⁴ in formula (IIb) is preferably a tertiary alkyl group having 4 to 12 carbon atoms, a 2-tetrahydropyranyl group, a tert-butoxycarbonyl group or a 2-tetrahydrofuranyl group, and has 4 carbon atoms. More preferably, it is a tertiary alkyl group of -12, 2-tetrahydropyranyl group or 2-tetrahydrofuranyl group, more preferably t-butyl group, 2-tetrahydropyranyl group or 2-tetrahydrofuranyl group. A 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group is particularly preferable.
In Formula (IIb), Ar ² represents a divalent aromatic group and has —OCH (OR ¹ ) (R ² ) on the aromatic ring.
The preferred embodiment of Ar ² in formula (IIb) is the same as the preferred embodiment of Ar ¹ in formula (IIa).

As the carboxylic acid monomer capable of forming the structural unit (a2) having the group represented by the formula (IIa) by protecting the carboxy group, the structural unit (a2) can be obtained by protecting the carboxy group. And the carboxylic acid monomer described above for the structural unit (a1) can be preferably exemplified.
As the monomer having a phenolic hydroxyl group capable of forming the structural unit (a2) having the partial structure represented by the formula (IIb) by protecting the phenolic hydroxyl group, the phenolic hydroxyl group is protected. As long as it can become the structural unit (a2), it can be used, and the monomer having a phenolic hydroxyl group described above for the structural unit (a1) can be preferably exemplified.
Particularly preferred as the structural unit (a2) is a structural unit represented by the following formula (IV).

In formula (IV), R ⁷ represents a tertiary alkyl group, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, and R ⁸ represents a hydrogen atom or a methyl group.
In formula (IV), the preferred embodiment of R ^{7 is the same as} the preferred embodiment of R ³ in formula (IIa).
Preferable specific examples of the radical polymerizable monomer used to form the structural unit represented by the formula (IV) include, for example, tert-butyl methacrylate, tert-butyl acrylate, tetrahydro-2H-methacrylate. Pyran-2-yl, tetrahydro-2H-pyran-2-yl acrylate, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 1-methylcyclohexyl methacrylate, 1-methyl acrylate Examples include cyclohexyl, tetrahydrofuran-2-yl methacrylate, tetrahydrofuran-2-yl acrylate, and the like. Tert-butyl methacrylate, tert-butyl acrylate, tetrahydrofuran-2-yl methacrylate, tetrahydrofuran-2-acrylate I especially like Arbitrariness.
These structural units can be used individually by 1 type or in combination of 2 or more types.
Preferable specific examples of the structural unit (a2) include the following structural units (a2-1) to (a2-10). Among these, the structural unit (a2-8) and the structural unit (a2-10) can be particularly preferably exemplified.

  The content of monomer units forming the structural unit (a2) in all monomer units constituting Component A is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and particularly preferably 10 to 40 mol%. . By containing the structural unit (a2) at the above ratio, a photosensitive resin composition having high sensitivity and wide exposure latitude can be obtained.

[Structural unit having an alkali-soluble group]
Component A preferably contains a structural unit having an alkali-soluble group as long as component A is not alkali-soluble.
Examples of the alkali-soluble group include acid groups such as a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group, an acid anhydride residue, and a phenolic hydroxyl group.
The alkali-soluble group is a component A composed of a structural unit having one or more acid groups selected from a carboxy group, a carboxylic acid anhydride residue, and a phenolic hydroxyl group (hereinafter also referred to as “structural unit (a3)” as appropriate). It is preferable to be contained in. The structural unit having an alkali-soluble group is more preferably a structural unit having a carboxy group and / or a phenolic hydroxyl group.
Examples of the radical polymerizable monomer used to form the structural unit having a carboxy group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, Preferable examples include unsaturated carboxylic acids such as dicarboxylic acids such as itaconic acid.
Moreover, as a radically polymerizable monomer used in order to form the structural unit which has a carboxylic anhydride residue, maleic anhydride, itaconic anhydride, etc. can be mentioned as a preferable thing, for example.
Examples of the radical polymerizable monomer used to form a structural unit having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene, and JP-A-2008-40183. Compounds described in paragraphs 0011 to 0016 of the publication, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of the patent No. 2888454, an addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, 4-hydroxy An addition reaction product of benzoic acid and glycidyl acrylate can be mentioned as a preferable example.

Among these, methacrylic acid, acrylic acid, compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, 4- An addition reaction product of hydroxybenzoic acid and glycidyl methacrylate, and an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable. Compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, Patent No. In particular, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of No. 2888454, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate preferable.
The structural unit which has an alkali-soluble group can be used individually by 1 type or in combination of 2 or more types.
Preferable specific examples of the structural unit having an alkali-soluble group include the following structural units (a3-1) to (a3-11).

  The content of the monomer unit forming the structural unit having an alkali-soluble group in all monomer units constituting Component A is preferably 2 to 35 mol%, more preferably 5 to 20 mol%, and 8 to 12 mol%. Particularly preferred. When component A contains a structural unit having an alkali-soluble group in the above proportion, high sensitivity is obtained and developability is improved.

<Other structural units>
Component A may contain other structural units as long as the effects of the present invention are not hindered.
Examples of the radical polymerizable monomer used for forming other structural units include compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623.

Moreover, it is preferable that the component A further has a structural unit which has hydroxyl groups other than a phenolic hydroxyl group. It is excellent in a sensitivity and heat-resistant transparency as it is the said aspect.
Preferred examples of the structural unit having a hydroxyl group other than the phenolic hydroxyl group include a structural unit derived from a (meth) acrylate compound having a hydroxy group.
Examples of the polymerizable compound capable of forming a structural unit having a hydroxyl group other than the phenolic hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4 -Preferred is hydroxybutyl (meth) acrylate. Among these, 2-hydroxyethyl (meth) acrylate is particularly preferable.

Moreover, as a preferable example of another structural unit, the structural unit derived from the at least 1 sort (s) selected from the group which consists of alicyclic structure containing unsaturated carboxylic acid ester, styrene, and N substituted maleimide is mentioned.
Among these, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, (meth) acrylic acid tricyclo [5.2.1.0 ² ] from the viewpoint of improving electrical characteristics. ^{, 6} ] decan-8-yloxyethyl, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid esters containing an alicyclic structure such as 2-methylcyclohexyl (meth) acrylate, Alternatively, a hydrophobic monomer such as styrene is preferable, and (meth) acrylic acid esters containing an alicyclic structure are more preferable. Further, from the viewpoint of sensitivity, N-substituted maleimide is preferable.

These other structural units can be used individually by 1 type or in combination of 2 or more types.
The content of monomer units forming other structural units in the case where other structural units are contained in all monomer units constituting Component A is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, 5-30 mol% is especially preferable.

Moreover, you may use the oxetanyl group which is another crosslinkable group further as a structure which supplements the crosslinking reaction of the structural unit represented by the said Formula (1), and an alkali-soluble group. The group having an oxetanyl group is not particularly limited as long as it has an oxetane ring, but a (3-ethyloxetane-3-yl) methyl group can be preferably exemplified.
The structural unit having an oxetanyl group only needs to have at least one oxetanyl group in one structural unit, and may have two or more oxetanyl groups. It is more preferable to have one or two, and it is even more preferable to have one oxetanyl group.
Examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, (meth) acrylic acid having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Examples include esters.
Examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group are preferably a monomer containing a methacrylic ester structure and a monomer containing an acrylic ester structure.
Among these radical polymerizable monomers, more preferable are (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A-2001-330953, and particularly preferable. Is a (meth) acrylic acid ester having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Among these, acrylic acid (3-ethyloxetane-3-yl) methyl and methacrylic acid (3-ethyloxetane-3-yl) methyl are particularly preferable, and methacrylic acid (3-ethyloxetane-3-yl) methyl is preferred. Is most preferred. These structural units can be used individually by 1 type or in combination of 2 or more types.
Preferable specific examples of the structural unit having an oxetanyl group (also referred to as “structural unit (a4)”) include the following structural units.

  The content of the monomer unit forming the structural unit having an oxetanyl group in all monomer units constituting Component A is preferably 5 to 50 mol%, more preferably 10 to 30 mol%, and particularly preferably 10 to 20 mol%. preferable. By containing the structural unit having an oxetanyl group in the above ratio, the physical properties of the cured film formed from the photosensitive resin composition are improved.

Specific preferred examples of the combination of the structural units constituting Component A include the structural unit represented by the formula (1), a structural unit having an alkali-soluble group derived from methacrylic acid, and acetal-protected. A combination including a structural unit having a carboxy group or a phenolic hydroxyl group is exemplified.
The weight average molecular weight (Mw) of component A in the present invention is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and 5,000 to 15,000. More preferably. In addition, it is preferable that the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC).
Various methods for synthesizing the resin are known. If an example of the synthesis method for Component A is given, radical polymerizability used to form at least the structural unit represented by the formula (1). A radical polymerizable monomer mixture containing a monomer and a radical polymerizable monomer used to form a structural unit having an acetal or ketal protected carboxy group or phenolic hydroxyl group, in an organic solvent, It can synthesize | combine by superposing | polymerizing using a radical polymerization initiator.

Hereinafter, although what is preferable as the component A used by this invention is illustrated as resin A-N, this invention is not limited to this. In addition, the weight average molecular weight of each resin A-N illustrated below is the range of 5,000-15,000.
Resin A: Copolymer of MAA / MAEVE / M-1 / HEMA (molar ratio: 10/40/30/20)
Resin B: Copolymer of MAA / MAEVE / M-1 / HEMA (molar ratio: 8/42/30/20)
Resin C: Copolymer of MAA / MAEVE / M-1 / HEMA (molar ratio: 10/40/35/15)
Resin D: MAA / MATHF / M-1 / HEMA copolymer (molar ratio: 10/40/30/20)
Resin E: Copolymer of MAA / MATHF / M-1 / HEMA (molar ratio: 8/42/30/20)
Resin F: Copolymer of MAA / MATHF / M-1 / HEMA (molar ratio: 10/40/35/15)
Resin G: Copolymer of MAA / MAEVE / M-2 / HEMA (molar ratio: 10/40/30/20)
Resin H: MAA / MATHF / M-2 / HEMA copolymer (molar ratio: 10/40/30/20)
Resin I: pHS / MAEVE / M-1 / HEMA copolymer (molar ratio: 10/40/30/20)
Resin J: copolymer of pHS / MATHF / M-1 / HEMA (molar ratio: 10/40/30/20)
Resin K: Copolymer of MAA / MATHF / M-1 / HEMA / DCPM (molar ratio: 10/40/20/20/10)
Resin L: Copolymer of MAA / MAEVE / M-1 / HEMA / OXE-30 (molar ratio: 10/40/20/20/10)
Resin M: Copolymer of MAA / MATHF / M-1 / HEMA / OXE-30 (molar ratio: 10/40/20/20/10)
Resin N: MAA / StOEVE / M-1 / HEMA copolymer (molar ratio: 10/40/30/20)

The details of the abbreviations of the monomers constituting each resin are as follows. The following M-1 and M-2 are monomers corresponding to the structural units (M-1) and (M-2), respectively.
MAA: methacrylic acid MAEVE: 1-ethoxyethyl methacrylate MATH: tetrahydrofuran-2-yl methacrylate OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate HEMA: hydroxyethyl methacrylate StOEVE: 4- (1-ethoxyethyloxy) styrene DCPM: dicyclopentanyl methacrylate pHS: p-hydroxystyrene

The content of Component A in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, and preferably 40 to 97% by weight, based on the total solid content of the photosensitive resin composition. More preferably, it is 60 to 95% by weight. When the content is within this range, the pattern formability upon development is good. In addition, the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.
In addition, in the photosensitive resin composition of this invention, you may use together resin other than the component A in the range which does not prevent the effect of this invention. However, the content of the resin other than Component A is preferably smaller than the content of Component A from the viewpoint of developability.

(Component B) Acid generator The photosensitive resin composition of the present invention contains an acid generator.
Preferred examples of the acid generator that can be used in the present invention include a radiation-sensitive acid generator. The radiation-sensitive acid generator is preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, more preferably a wavelength of 300 to 450 nm, and generates an acid, but is not limited to its chemical structure. Further, an acid generator that is not directly sensitive to actinic rays having a wavelength of 300 nm or more is also a sensitizer as long as it is a compound that reacts with actinic rays having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer described later. It can be preferably used in combination.
The acid generator that can be used in the present invention is preferably an acid generator that generates an acid having a pKa of 4 or less, and more preferably an acid generator that generates an acid having a pKa of 3 or less.
Examples of the acid 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 high sensitivity. These acid generators can be used singly or in combination of two or more.

The following can be illustrated as a specific example of these acid generators.
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 -Piperonylbis (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-methylphenyl) Thenyl] bis (4,6-trichloromethyl) -s-triazine, or 2- (4-methoxynaphthyl) bis (4,6-trichloromethyl) -s-triazine.
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, or phenyl-4- (2'-hydroxy-1'-) Tetradecaoxy) phenyliodonium p-toluenesulfonate and the like.

Triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoro. Lomethanesulfonate or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate.
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, or the like.
Examples of the diazomethane derivative include bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, and bis (p-toluenesulfonyl) diazomethane.
As an imide sulfonate derivative, trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-ene-dicarboximide, succinimide trifluoromethyl sulfonate, phthalimido trifluoromethyl sulfonate, N-hydroxynaphthalimide methane sulfonate, or N-hydroxy-5-norbornene-2,3-dicarboximide propane sulfonate and the like.

  The photosensitive resin composition of the present invention preferably contains an oxime sulfonate compound having at least one oxime sulfonate group represented by the following formula (B1) as an acid generator.

The oxime sulfonate compound having at least one oxime sulfonate group represented by the formula (1) is preferably a compound represented by the following formula (B2).
^{R 1A -C (R 2A) =} N-O-SO 2 -R 3A (B2)
In formula (B2), R ^1A represents an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, or a 2-thienyl group. Represents an alkoxy group having 1 to 4 carbon atoms or a cyano group, and when R ^1A is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom, a hydroxyl group, or a carbon atom number. It may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and a nitro group.
In the formula (B2), R ^2A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogen having 1 to 5 carbon atoms. Represents an alkoxy group, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, an anthranyl group optionally substituted with W, a dialkylamino group, a morpholino group, or a cyano group. R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or 6-membered ring may have one or two arbitrary substituents. It may be bonded to a benzene ring.
In the formula (B2), R ^3A represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogen having 1 to 5 carbon atoms. Represents an alkoxy group, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, or an anthranyl group optionally substituted with W.
W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 represents a halogenated alkoxy group.

The alkyl group having 1 to 6 carbon atoms in R ^1A may be a linear or branched alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, A t-butyl group, an n-pentyl group, an isoamyl group, an n-hexyl group, or a 2-ethylbutyl group may be mentioned.
As a C1-C4 halogenated alkyl group in R ^<1A >, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, or 2-bromopropyl group is mentioned, for example.
A methoxy group or an ethoxy group is mentioned as a C1-C4 alkoxy group in R ^<1A >.
When R ^1A represents a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, an alkyl having 1 to 4 carbon atoms. Group (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group), alkoxy group having 1 to 4 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group) and a substituent selected from the group consisting of a nitro group.

Specific examples of the alkyl group having 1 to 10 carbon atoms in R ^2A include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t -Butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like can be mentioned.
Specific examples of the alkoxy group having 1 to 10 carbon atoms in R ^2A include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an n-amyloxy group, an n-octyloxy group, An n-decyloxy group etc. are mentioned.
Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms in R ^2A include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro-n. -An amyl group etc. are mentioned.
Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms for R ^2A include trifluoromethoxy group, pentafluoroethoxy group, perfluoro-n-propoxy group, perfluoro-n-butoxy group, perfluoro-n. -An amyloxy group etc. are mentioned.

Specific examples of the phenyl group optionally substituted with W in R ^2A include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group. Group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s-butyl) phenyl Group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group, m- Methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group, p- (N Butoxy) phenyl, p- (i-butoxy) phenyl, p- (s-butoxy) phenyl, p- (t-butoxy) phenyl, p- (n-amyloxy) phenyl, p- (i- (Amyloxy) phenyl group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4 -Difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group, Examples thereof include a p-biphenyl group.

Specific examples of the naphthyl group optionally substituted with W in R ^2A include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl- 1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, Examples include 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group and the like.
Specific examples of the anthranyl group optionally substituted with W in R ^2A include 2-methyl-1-anthranyl group, 3-methyl-1-anthranyl group, 4-methyl-1-anthranyl group, 5-methyl- 1-anthranyl group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1-anthranyl group, 1-methyl-2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7-methyl-2 -Anthranyl group, 8-methyl-2-anthranyl group, 9-methyl-2-anthranyl group, 10-methyl-2-anthranyl group and the like can be mentioned.
^Examples of the dialkylamino group in R ^2A include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, and a diphenylamino group.

Specific examples of the alkyl group having 1 to 10 carbon atoms in R ^3A include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t -Butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like can be mentioned.
Specific examples of the alkoxy group having 1 to 10 carbon atoms in R ^3A include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group, n-octyloxy group, An n-decyloxy group etc. are mentioned.
Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms in R ^3A include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro-n. -An amyl group etc. are mentioned.
Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms in R ^3A include trifluoromethoxy group, pentafluoroethoxy group, perfluoro-n-propoxy group, perfluoro-n-butoxy group, perfluoro-n. -An amyloxy group etc. are mentioned.

  Specific examples of the optionally substituted phenyl group in W include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, p -(N-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s-butyl) phenyl group, p -(T-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group, m-methoxyphenyl group , P-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group, p- (n- Buto Ii) phenyl group, p- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i- (Amyloxy) phenyl group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4 -Difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group, Examples thereof include a p-biphenyl group.

Specific examples of the optionally substituted naphthyl group in W include a 2-methyl-1-naphthyl group, a 3-methyl-1-naphthyl group, a 4-methyl-1-naphthyl group, and a 5-methyl-1-naphthyl group. Group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl Examples include 2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group and the like.
Specific examples of the optionally substituted anthranyl group in W include 2-methyl-1-anthranyl group, 3-methyl-1-anthranyl group, 4-methyl-1-anthranyl group, and 5-methyl-1-anthranyl. Group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1-anthranyl group, 1-methyl 2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7-methyl-2-anthranyl group , 8-methyl-2-anthranyl group, 9-methyl-2-anthranyl group, 10-methyl-2-anthranyl group and the like.

Specific examples of the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, the halogenated alkyl group having 1 to 5 carbon atoms, and the halogenated alkoxy having 1 to 5 carbon atoms in W Is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a halogen having 1 to 5 carbon atoms in R ^2A or R ^3A The thing similar to what was mentioned as a specific example of the oxyalkoxy group is mentioned.
R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring.
When R ^2A and R ^1A are bonded to each other to form a 5-membered ring or a 6-membered ring, examples of the 5-membered ring or 6-membered ring include carbocyclic groups and heterocyclic ring groups. It may be a cyclopentane, cyclohexane, cycloheptane, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazine ring. The 5-membered ring or 6-membered ring may be bonded to an optionally substituted benzene ring, and examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chroman, fluorene, xanthene or thiol. Xanthene ring system. The 5-membered or 6-membered ring may contain a carbonyl group, examples of which include cyclohexadienone, naphthalenone and anthrone ring systems.
One of the suitable aspects of the compound represented by Formula (B2) is a compound represented by following formula (2). The compound represented by the formula (2) is a compound in which R ^2A and R ^1A in the formula (B2) are bonded to form a 5-membered ring.

（式（２）中、Ｒ⁴はアルキル基又はアリール基を表し、Ｘはそれぞれ独立に、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の整数を表す。）

(In Formula (2), R ⁴ represents an alkyl group or an aryl group, X represents each independently an alkyl group, an alkoxy group, or a halogen atom, and m represents an integer of 0 to 3.)

In formula (2), R ⁴ has the same meaning as R ^3A in formula (B2), and the preferred range is also the same. When m is 2 or 3, the plurality of X may be the same or different.
The alkyl group in X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group for X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
As a halogen atom in X, a chlorine atom or a fluorine atom is preferable.
As m, 0 or 1 is preferable.
In the formula (2), m is 1, X is a methyl group, the substitution position of X is an ortho position, R ⁴ is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl. A compound which is a 2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.
Specific examples of the oxime sulfonate compound represented by the formula (2) include the following compound (i), compound (ii), compound (iii), compound (iv) and the like. Compounds (i) to (iv) can be obtained as commercial products. These compounds may be used alone or in combination of two or more. It can also be used in combination with other types of acid generators.

As one of the preferable embodiments of the compound represented by the formula (B2),
R ^1A represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methoxyphenyl group, a 4-biphenyl group, a naphthyl group, or an anthranyl group;
R ^2A represents a cyano group;
R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, 1 to 1 carbon atoms It represents a 10 alkyl group, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.
The compound represented by the formula (B2) is preferably a compound represented by the following formula (B3).

In the formula (B3), R ^4A represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, and L is an integer of 0 to 5 Represents. R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, 1 to 1 carbon atoms Represents an alkyl group having 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.
R ^3A in the formula (B3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro group. A fluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and a methyl group, ethyl group, n-propyl group, n-butyl group or p-tolyl group is particularly preferable. .
The halogen atom in R ^4A is preferably a fluorine atom, a chlorine atom or a bromine atom.
The alkyl group having 1 to 4 carbon atoms in R ^4A is preferably a methyl group or an ethyl group.
The alkoxy group having 1 to 4 carbon atoms in R ^4A is preferably a methoxy group or an ethoxy group.
As L, 0-2 are preferable, and 0-1 are particularly preferable.

Among the acid generators represented by the formula (B2), as a preferred embodiment of the compound included in the acid generator represented by the formula (B3), in the formula (B2), R ^1A is a phenyl group or 4 This is an embodiment in which -methoxyphenyl group is represented, R ^2A represents a cyano group, and R ^3A represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 4-tolyl group.
Hereinafter, among the compounds represented by the formula (B2), particularly preferable examples of the compounds included in the compound represented by the formula (B3) are shown, but the present invention is not limited thereto.
α- (Methylsulfonyloxyimino) benzylcyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = methyl group)
α- (ethylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = ethyl group)
α- (n-propylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = n-propyl group)
α- (n-butylsulfonyloxyimino) benzylcyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = n-butyl group)
α- (4-Toluenesulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = 4-tolyl group)
α-[(Methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = methyl group)
α-[(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = ethyl group)
α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = n-propyl group)
α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = n-butyl group)
α-[(4-Toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = 4-tolyl group)

The photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as an acid generator sensitive to actinic rays. The reason is that the 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is 1 or less and is less sensitive than the oxime sulfonate compound.
In contrast, the oxime sulfonate compound acts as a catalyst for the deprotection of acid-protected acid groups (carboxy groups and phenolic hydroxyl groups) produced in response to actinic rays. The acid produced 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. It is guessed.

  In the photosensitive resin composition of the present invention, the acid generator is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of Component A.

  The photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as a photoacid generator sensitive to actinic rays. The reason is that the 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is always 1 or less and its sensitivity is low. On the other hand, a photoacid generator such as an oxime sulfonate compound or the like generates a single photon because an acid generated in response to actinic light acts as a catalyst for deprotection of a protected acidic group. The acid produced 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. It is guessed.

(Component C) Solvent The photosensitive resin composition of the present invention contains a solvent.
The photosensitive resin composition of the present invention is preferably prepared as a solution in which components A and B, which are essential components, and optional components of various additives are dissolved in a solvent.
A known solvent can be used as the solvent used in the photosensitive resin composition of the present invention.
Solvents include 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 And diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones and the like.

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

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

(11) 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;
(12) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate;
(13) 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;
(14) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropion methyl, 3-ethoxypropion ethyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, aceto Other esters such as methyl acetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate;
(15) Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
(16) Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
(17) 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.
Of the above-mentioned solvents, diethylene glycol dialkyl ethers and / or propylene glycol monoalkyl ether acetates are preferable, and diethylene glycol ethyl methyl ether and / or propylene glycol monomethyl ether acetate are particularly preferable.
These solvents can be used alone or in combination of two or more.
The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight per 100 parts by weight of Component A, and 150 to More preferably, it is 1,500 parts by weight.

<Other ingredients>
In addition to Component A, Component B, and Component C, the photosensitive resin composition of the present invention may contain other components.
Other components preferably contain a sensitizer and a development accelerator from the viewpoint of sensitivity, and preferably contain a crosslinking agent from the viewpoint of film properties.
Furthermore, the photosensitive resin composition of the present invention preferably contains an adhesion improver from the viewpoint of substrate adhesion, and preferably contains a basic compound from the viewpoint of liquid storage stability. From the viewpoint, it is preferable to contain a fluorine-based surfactant and / or a silicone-based surfactant.
Furthermore, if necessary, the photosensitive resin composition of the present invention includes an antioxidant, a plasticizer, a thermal radical generator, a thermal acid generator, an acid multiplier, an ultraviolet absorber, a thickener, and an organic material. Alternatively, a known additive such as an inorganic suspending agent can be added.
Hereinafter, other components that can be included in the photosensitive resin composition of the present invention will be described.

<Sensitizer>
In the photosensitive resin composition of the present invention, it is preferable to add a sensitizer in order to accelerate the decomposition in the combination with the acid generator described above. 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 acid generator, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the acid generator undergoes a chemical change and decomposes to generate an acid.
Examples of preferable sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the 350 to 450 nm region.
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 (eg, 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2, 3, 6 , 7-tetrahydro-9-methyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine-11-non).
Among these sensitizers, sensitizers that absorb an actinic ray or radiation to be in an electronically excited state and have an electron transfer action to an acid generator are preferred. Polycyclic aromatics, acridones, coumarins, base styryl Are more preferred, and polycyclic aromatics are more preferred. Among polynuclear aromatics, anthracene derivatives are most preferred. Commercially available sensitizers may be used, or they may be synthesized by known synthesis methods.
A sensitizer may be used individually by 1 type, or may use 2 or more types together.
The addition amount of the sensitizer is preferably 20 to 300 parts by weight, particularly preferably 30 to 200 parts by weight with respect to 100 parts by weight of the acid generator, from the viewpoint of achieving both sensitivity and transparency.

<Development accelerator>
The photosensitive resin composition of the present invention preferably contains a development accelerator.
As the development accelerator, any compound having a development acceleration effect can be used, but a compound having at least one structure selected from the group consisting of a carboxy group, a phenolic hydroxyl group, and an alkyleneoxy group is preferable. , A compound having a carboxy group or a phenolic hydroxyl group is more preferred, and a compound having a phenolic hydroxyl group is most preferred.
The molecular weight of the development accelerator is preferably 100 to 2,000, more preferably 150 to 1,500, and most preferably 150 to 1,000.
Examples of development accelerators having an alkyleneoxy group include polyethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester, polybutylene glycol, Examples thereof include polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, and compounds described in JP-A-9-222724.
Examples of compounds having a carboxy group include compounds described in JP-A 2000-66406, JP-A 9-6001, JP-A 10-20501, JP-A 11-338150, and the like.
Examples of those having a phenolic hydroxyl group include JP-A No. 2005-346024, JP-A No. 10-133366, JP-A No. 9-194415, JP-A No. 9-222724, JP-A No. 11-171810, Examples thereof include compounds described in JP 2007-121766, JP-A-9-297396, JP-A 2003-43679, and the like. Among these, a phenol compound having 2 to 10 benzene rings is preferable, and a phenol compound having 2 to 5 benzene rings is more preferable. Particularly preferred is a phenolic compound disclosed as a dissolution accelerator in JP-A-10-133366.
A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight, preferably 0.2 to 30 parts by weight, when the component A is 100 parts by weight from the viewpoints of sensitivity and residual film ratio. 20 parts by weight is more preferable, and 0.5 to 10 parts by weight is most preferable.

<Crosslinking agent>
It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent as needed.
By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
Examples of the crosslinking agent include a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, or a compound having at least one ethylenically unsaturated double bond. Can be added.
Among these crosslinking agents, particularly preferred are compounds having two or more epoxy groups or oxetanyl groups in the molecule.

-Compounds having two or more epoxy groups or oxetanyl groups in the molecule-
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.
These are available as commercial products. For example, 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.).
As bisphenol F type epoxy resins, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, made by DIC Corporation), LCE-21, RE- 602S (Nippon Kayaku Co., Ltd.) etc. are mentioned.
Phenol novolac type epoxy resins include JER152, JER154, JER157S70, JER157S65 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC) Etc.).
Cresol novolac type epoxy resins include 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 (manufactured by Nippon Kayaku Co., Ltd.) and the like.
As the aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, Examples thereof include PB 4700 (manufactured by Daicel Chemical Industries, Ltd.).
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation) 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, and phenol novolac type epoxy resin are preferable, and bisphenol A type epoxy resin is particularly preferable.

As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Moreover, the compound containing an oxetanyl group can be used individually or in mixture with the compound containing an epoxy group.
The addition amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule to the photosensitive resin composition of the present invention is preferably 1 to 50 parts by weight when the total amount of component A is 100 parts by weight, 3-30 weight part is more preferable.

-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 methyl group is particularly 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 preferably 0.05 to 50 parts by weight with respect to 100 parts by weight of Component A. 0.5 to 10 parts by weight is more preferable. 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 tri- or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
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, and 30 parts by weight or less with respect to 100 parts by weight of Component A. It is more preferable that By containing at least one compound having an ethylenically unsaturated double bond in such a ratio, the heat resistance and surface hardness of the cured 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 described later.

<Adhesion improver>
The photosensitive resin composition of the present invention preferably contains an adhesion improving agent.
The 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, a metal such as gold, copper, or aluminum and an insulating film. It is a compound that improves adhesion. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as an 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.
Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.
An adhesion improving agent can be used individually by 1 type or in combination of 2 or more types. These are effective in improving the adhesion to the substrate and are also effective in adjusting the taper angle with the substrate.
0.1-20 weight part is preferable with respect to 100 weight part of component A, and, as for content of the adhesion improving agent in the photosensitive resin composition of this invention, 0.5-10 weight part is more preferable.

<Basic compound>
The photosensitive resin composition of the present invention preferably contains a basic compound.
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.
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. Preferably, two kinds of heterocyclic amines are used in combination.
The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by weight, and 0.002 to 0.2 part by weight with respect to 100 parts by weight of Component A. Is more preferable.

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

In the formula (W), 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, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and L represents a branched alkylene group having 3 to 6 carbon atoms in total. Represents. p and q are weight percentages representing a polymerization ratio, p represents a numerical value of 10% by weight to 80% by weight, and q represents a numerical value of 20% by weight to 90% by weight. r represents an integer of 1 to 18. n represents an integer of 1 to 10. In addition, the total carbon number of the said L means all the carbon number which comprises an alkylene group.
The L is preferably an alkylene group represented by the following formula (L ′). Here, R ⁵ 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 with respect to the coated surface. An alkyl group is more preferred.

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

The photosensitive resin composition of the present invention preferably contains a fluorine-based surfactant and / or a silicone-based surfactant as a surfactant.
As these fluorosurfactants and silicone surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-62-170950 Examples of the surfactants described in JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, and JP-A-2001-330953. A commercially available surfactant can also be used.
Examples of commercially available surfactants that can be used include F-top EF301, EF303 (above, Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (above, made by Sumitomo 3M Ltd.), MegaFuck F171, F173, F176 , F189, R08 (above, manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox series (produced by OMNOVA), etc. And a surfactant based on a silicone or a surfactant based on a silicone. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.
Surfactant can be used individually by 1 type or in mixture of 2 or more types. Moreover, you may use together a fluorine-type surfactant and a silicone type surfactant.
The addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of Component A, and 0 More preferably, the content is 0.01 to 1 part by weight.

<Antioxidant>
The photosensitive resin composition of the present invention may contain an antioxidant.
As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, a phenolic antioxidant is particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness.
An antioxidant may be used individually by 1 type, and 2 or more types may be mixed and used for it.
As a commercial item of a phenolic antioxidant, ADK STAB AO-60, ADK STAB AO-80 (above, the product made from ADEKA), and Irganox 1098 (made by Ciba Japan Co., Ltd.) are mentioned, for example.
The content of the antioxidant is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by weight. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.

<Plasticizer>
The photosensitive resin composition of the present invention may contain a plasticizer.
Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
A plasticizer may be used individually by 1 type, or may use 2 or more types together.
The content of the plasticizer in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of Component A.

<Thermal radical generator>
The photosensitive resin composition of the present invention may contain a thermal radical generator, and when it contains an ethylenically unsaturated compound such as the aforementioned compound having at least one ethylenically unsaturated double bond, It is preferable to contain a thermal radical generator.
As the thermal radical generator in the present invention, a known thermal radical generator can be used.
The thermal radical generator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the obtained cured film becomes tougher and heat resistance and solvent resistance may be improved.
Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon Examples thereof include compounds having a halogen bond, azo compounds, and bibenzyl compounds.
A thermal radical generator may be used individually by 1 type, and it is also possible to use 2 or more types together.
The content of the thermal radical generator in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, when component A is 100 parts by weight, from the viewpoint of improving film properties. Part by weight is more preferable, and 0.5 to 10 parts by weight is most preferable.

<Heat acid generator>
In the present invention, a thermal acid generator may be used in order to improve film physical properties and the like at low temperature curing.
The thermal acid generator in the present invention is a compound that generates an acid by heat, and preferably includes a compound having a thermal decomposition point in the range of 130 ° C to 250 ° C, more preferably 150 ° C to 220 ° C.
The thermal acid generator is, for example, a compound that generates a low nucleophilic acid such as sulfonic acid, carboxylic acid, or disulfonylimide by heating.
As the generated acid, pKa is as strong as 2 or less, sulfonic acid or alkyl substituted with an electron withdrawing group is preferably arylcarboxylic acid, disulfonylimide substituted with an electron withdrawing group, or the like. Examples of the electron withdrawing group include a halogen atom such as a fluorine atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.
In the present invention, it is also preferable to use a sulfonic acid ester that does not substantially generate an acid by exposure to exposure light and generates an acid by heat.
The fact that acid is not substantially generated by exposure to exposure light is determined by the fact that there is no change in the spectrum by measuring infrared absorption (IR) spectrum and nuclear magnetic resonance (NMR) spectrum before and after exposure of the compound. Can do.
The molecular weight of the sulfonic acid ester is preferably 230 to 1,000, and more preferably 230 to 800.
As the sulfonic acid ester usable in the present invention, a commercially available one may be used, or one synthesized by a known method may be used. The sulfonic acid ester can be synthesized, for example, by reacting a sulfonyl chloride or a sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.
A thermal acid generator may be used individually by 1 type, or may use 2 or more types together.
The content of the thermal acid generator in the photosensitive resin composition is preferably 0.5 to 20 parts by weight, particularly preferably 1 to 15 parts by weight, when Component A is 100 parts by weight.

<Acid multiplication agent>
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The strength of the acid is preferably 3 or less, particularly preferably 2 or less, as the acid dissociation constant, pKa.
Specific examples of the acid proliferating agent include paragraphs 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39, line 12 of JP-T 9-512498. Examples of the compounds described in the first to page 47, line 2 are listed.
Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.
The acid proliferating agent may be used alone or in combination of two or more.
The content of the acid multiplication agent in the photosensitive resin composition is preferably 10 to 1,000 parts by weight with respect to 100 parts by weight of the acid generator, from the viewpoint of dissolution contrast between the exposed part and the unexposed part. More preferably, the lifespan is 20 to 500 parts by weight.

(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 is not particularly limited except that the photosensitive resin composition of the present invention is used, but preferably includes the following steps (1) to (5).
(1) Application step of applying the photosensitive resin composition of the present invention onto a substrate (2) Solvent removal step of removing the solvent from the applied photosensitive resin composition (3) Applying the applied photosensitive resin composition An exposure step of exposing with an actinic ray (4) A development step of developing the exposed photosensitive resin composition with an aqueous developer (5) A post-baking step of thermally curing the developed photosensitive resin composition The cured film of the present invention In the formation method of (4), after the exposure in the exposure step, the developing step (4) may be performed without performing the heat treatment.
Moreover, before the said post-baking process, you may include the process of further exposing (6) the developed photosensitive resin composition to the whole surface.

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, the acid generator is decomposed to generate an acid. Due to the catalytic action of the generated acid, the carboxy group and / or phenolic hydroxyl group protected by the acetal or ketal contained in Component A is deprotected to produce a carboxy group and / or a phenolic hydroxyl group.
In order to accelerate the decomposition reaction in the region where the acid catalyst is generated, PEB (Post Exposure Bake) may be performed as necessary. By PEB, the production | generation of the carboxy group and / or phenolic hydroxyl group from an acid-decomposable group can be accelerated | stimulated.
The carboxyl group or phenolic hydroxyl group protected with an acetal or ketal in Component A has low activation energy for acid decomposition, and is easily decomposed by an acid derived from an acid generator by exposure to carboxy group and / or phenolic hydroxyl group. Therefore, PEB is not necessarily performed. Therefore, a positive image can be formed by performing development in the development step (4) without performing PEB after the exposure step (3).
In addition, by performing PEB at a relatively low temperature, decomposition of the acid-decomposable group can be promoted without causing a crosslinking reaction. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 90 ° C. or lower.

In the developing step (4), the exposed area containing the component A that has become alkali-soluble by exposure is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a photosensitive resin composition having a carboxy group and / 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 carboxy group and / or phenolic hydroxyl group protected by the acetal or ketal in Component A to obtain the carboxy group and / or phenolic hydroxyl group. A cured film can be formed by forming and crosslinking with the structural unit represented by the formula (1). 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.
Furthermore, it is preferable to include a re-exposure step (6) that exposes the entire surface of the developed photosensitive resin composition before the post-baking step, and actinic rays, preferably ultraviolet rays are applied to the pattern of the developed photosensitive resin composition. If a step of irradiating the entire surface is added, the crosslinking reaction can be promoted by an acid generated by irradiation with actinic rays.
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)
A solvent is mixed with the essential components of Component A and Component B at a predetermined ratio and by any method, and dissolved by stirring to prepare a photosensitive resin composition. For example, it is possible to prepare a photosensitive resin composition by preparing a solution in which component A or component B is previously dissolved in a solvent and then mixing them in a predetermined ratio. The solution of the photosensitive resin composition prepared as described above can be used after being filtered using a filter having a pore size of 0.1 μm or the like.
An example of a suitable embodiment of the photosensitive resin composition of the present invention includes Component A in a range of 60 to 95% by weight and Component B in an amount of 0.1 to 0.1% based on the total solid content of the photosensitive resin composition. It is an embodiment containing in the range of 10% by weight.
Moreover, the other example of the suitable aspect of the photosensitive resin composition of this invention contains the component A in the range of 40 to 70 weight% with respect to the total solid of the photosensitive resin composition, and the component B is 0.00. It is an embodiment containing 1 to 10% by weight and containing 3 to 40% by weight of a crosslinking agent.

<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 device, 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. Here, the large substrate means a substrate having a side of 1 m or more on each side.
Also, (2) the heating conditions in the solvent removal step are such that the carboxy group or phenolic hydroxyl group protected with acetal or ketal is decomposed in component A in the unexposed area, and component A is not soluble in an alkaline developer. Although it varies depending on the type and blending ratio of each component, it is preferably about 70 to 120 ° C. for about 30 to 300 seconds.

<Exposure process>
(3) In the exposure step, the substrate provided with the dry coating film of the photosensitive resin composition is irradiated with actinic rays having a predetermined pattern. Exposure may be performed through a mask, or a predetermined pattern may be drawn directly. Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. After the exposure process, PEB is performed as necessary.
For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a laser generator, or the like can be used.
When a mercury lamp is used, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used. Mercury lamps are preferred in that they are suitable for large area exposure compared to lasers.
When a laser is used, 343 nm and 355 nm are used for a solid (YAG) laser, 351 nm (XeF) is used for an excimer laser, and 375 nm and 405 nm are used for a semiconductor laser. Among these, 355 nm and 405 nm are more preferable from the viewpoints of stability and cost. The coating can be irradiated with the laser once or multiple times.

The energy density per pulse of the laser is preferably 0.1 mJ / cm ² or more and 10,000 mJ / cm ² or less. In order to sufficiently cure the coating film, 0.3 mJ / cm ² or more is more preferable, and 0.5 mJ / cm ² or more is most preferable. cm ² or less is more preferable, and 100 mJ / cm ² or less is most preferable.
The pulse width is preferably 0.1 nsec or more and 30,000 nsec or less. In order to prevent the color coating film from being decomposed due to the ablation phenomenon, 0.5 nsec or more is more preferable, and 1 nsec or more is most preferable. Most preferred is 50 nsec or less.
Furthermore, the frequency of the laser is preferably 1 Hz to 50,000 Hz, more preferably 10 Hz to 1,000 Hz.
Furthermore, the frequency of the laser is more preferably 10 Hz or more, most preferably 100 Hz or more for shortening the exposure processing time, and more preferably 10,000 Hz or less for improving the alignment accuracy at the time of scan exposure. 000 Hz or less is most preferable.
Compared with a mercury lamp, a laser is preferable in that the focus can be easily reduced and a mask for forming a pattern in the exposure process is not necessary and the cost can be reduced.
There are no particular restrictions on the exposure apparatus that can be used in the present invention, but commercially available devices include Callisto (buoy technology), AEGIS (buoy technology), and DF2200G (large). Nippon Screen Manufacturing Co., Ltd.) can be used. Further, devices other than those described above are also 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.

<Development process>
(4) In the development step, the exposed area is removed using a basic developer (alkaline developer) to form an image pattern.
Examples of the basic compound used in the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium bicarbonate, bicarbonate Alkali metal bicarbonates such as potassium; 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, a shower method, and the like. After development, washing with running water is preferably performed for 10 to 90 seconds to form a desired pattern.

<Post-bake process (crosslinking process)>
For a pattern corresponding to an unexposed area obtained by development, a heating device such as a hot plate or an oven is used for a predetermined temperature, preferably 180 to 250 ° C. for a predetermined time, for example, 5 to 5 on a hot plate. By heating for 60 minutes, preferably 30 to 90 minutes in an oven, the carboxy group and / or phenolic hydroxyl group protected by the acetal or ketal in component A is decomposed to produce a carboxy group and / or phenolic hydroxyl group. A protective film excellent in heat resistance, hardness, etc. by reacting with the cyclic carbonate structure in the structural unit represented by the formula (1) in component A or its thermally decomposed structure An interlayer insulating film 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 pattern-formed substrate is re-exposed with actinic rays and then post-baked (re-exposure / post-bake) to generate an acid from the acid generator present in the unexposed portion, thereby crosslinking. It is preferable to function as a promoting catalyst.
That is, it is preferable that the method for forming a cured film in the present invention includes the (6) re-exposure step in which re-exposure is performed with active light 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 .

By the photosensitive resin composition of the present invention, a cured film having a high sensitivity, generation of residues during development, and a surface having excellent smoothness is obtained, and the cured film is used as an interlayer insulating film. Useful. In addition, the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency, can form a good pattern shape, and has excellent surface smoothness. It is useful for applications of display devices and liquid crystal display devices.
As an organic EL display device and a liquid crystal display device to which the photosensitive composition of the present invention can be applied, a cured film formed using the photosensitive resin composition of the present invention is used as a planarizing film or an interlayer insulating film. Are not particularly limited, and may include various known organic EL display devices and liquid crystal display devices having various structures.

FIG. 1 is a conceptual diagram showing an example of an organic EL display device using the photosensitive resin composition of the present invention. 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 thin film transistor (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, a planarizing film 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 an active matrix liquid crystal display device that can be applied as a liquid crystal display device using the photosensitive resin composition of the present invention.
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. Unless otherwise specified, “part” and “%” are based on weight.

The abbreviations of each compound used in the following synthesis examples of resins A to N represent the following compounds, respectively.
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
pHS: p-hydroxystyrene (synthetic product)
StOEVE: 4- (1-ethoxyethyloxy) styrene (synthetic product)
DCPM: Dicyclopentanyl methacrylate (FA-511A, manufactured by Hitachi Chemical Co., Ltd.)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
PGMEA: Methoxypropyl acetate (manufactured by Showa Denko KK)
HS-EDM: High Solve EDM (manufactured by Toho Chemical Industry Co., Ltd.)
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
BnMA: benzyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
CHMA: cyclohexyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MAEVE and StOEVE were synthesized by the same method as MATHF described later.

<Synthesis of Tetrahydrofuran-2-yl Methacrylate (MATHF)>
Methacrylic acid (86 g, 1 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added. 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the solution. 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 1: Synthesis of Resin A>
PGMEA (23.4 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. MAA (1.72 g), MAEVE (12.65 g), M-1 (11.16 g), HEMA (5.20 g), V-65 (2.98 g, 6 mol% based on monomers) were added to the solution to PGMEA. (23.4 g) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, resin A was obtained. The weight average molecular weight was 8,200.

<Synthesis Example 2: Synthesis of Resin B>
PGMEA (23.4 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. MAA (1.377 g), MAEVE (13.28 g), M-1 (13.03 g), HEMA (5.20 g), V-65 (2.98 g, 6 mol% based on monomers) were added to the solution to PGMEA. (23.4 g) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, resin B was obtained. (The weight average molecular weight was 8,100.

<Synthesis Example 3: Synthesis of Resin C>
HS-EDM (23.4 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. In the solution, MAA (1.72 g), MAEVE (12.65 g), M-1 (13.03 g), HEMA (3.90 g), V-601 (2.76 g, 6 mol% with respect to the monomer) were added to HS. -It dissolved in EDM (34.25g), and was dripped over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 2 hours. Thereby, resin C was obtained. The weight average molecular weight was 8,000.

<Synthesis Example 4: Synthesis of Resin D>
PGMEA (22.75 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. MAA (1.72 g), MATHF (12.49 g), M-1 (11.16 g), HEMA (5.20 g), V-65 (0.99 g, 2 mol% with respect to the monomer) were added to the solution to PGMEA. (22.75 g) was dissolved and added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, resin D was obtained. The weight average molecular weight was 18,000.

<Synthesis Example 5: Synthesis of Resin E>
HS-DEM (23.1 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. MAA (1.377 g), MATHF (13.11 g), M-1 (11.16 g), HEMA (5.20 g), V-65 (0.99 g, 2 mol% with respect to the monomer) were added to the solution. -It dissolved in EDM (23.1g) and it was dripped over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, resin E was obtained. The weight average molecular weight was 17,500.

<Synthesis Example 6: Synthesis of Resin F>
PGMEA (23.25 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. MAA (1.72 g), MATHF (12.49 g), M-1 (13.03 g), HEMA (3.90 g), V-601 (0.92 g, 2 mol% with respect to the monomer) were added to the solution to PGMEA. (23.25 g) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, resin F was obtained. The weight average molecular weight was 17,800.

<Synthesis Example 7: Synthesis of Resin G>
PGMEA (23.5 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. MAA (1.72 g), MAEVE (12.65 g), M-2 (12.01 g), HEMA (5.20 g), V-65 (2.98 g, 6 mol% based on monomers) were added to the solution to PGMEA. (23.5 g) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 2 hours. Thereby, resin G was obtained. The weight average molecular weight was 7,900.

<Synthesis Example 8: Synthesis of Resin H>
PGMEA (23.5 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. MAA (1.72 g), MATHF (12.49 g), M-2 (12.01 g), HEMA (5.20 g), V-65 (0.99 g, 2 mol% based on monomers) were added to the solution to PGMEA. (23.5 g) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, resin H was obtained. The weight average molecular weight was 18,000.

<Synthesis Example 9: Synthesis of Resin I>
PGMEA (23.5 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. To this solution, pHS (2.40 g), MAEVE (12.65 g), M-1 (11.16 g), HEMA (5.20 g), V-65 (2.98 g, 6 mol% based on monomer) were added to PGMEA. (23.5 g) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, resin I was obtained. The weight average molecular weight was 7,900.

<Synthesis Example 10: Synthesis of Resin J>
PGMEA (25.3 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. To this solution, pHS (2.40 g), MATHF (12.49 g), M-1 (11.16 g), HEMA (5.20 g), V-65 (0.99 g, 2 mol% based on monomers) were added to PGMEA. (23.5 g) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, resin J was obtained. The weight average molecular weight was 18,000.

<Synthesis Example 11: Synthesis of Resin K>
HS-DEM (23.5 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. MAA (1.72 g), MATHF (12.49 g), M-1 (7.44 g), HEMA (5.20 g), DCPM (4.40 g), V-65 (0.99 g, monomer) 2 mol%) was dissolved in HS-EDM (23.5 g) and added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, resin K was obtained. The weight average molecular weight was 16,900.

<Synthesis Example 12: Synthesis of Resin L>
PGMEA (23.0 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. MAA (1.72 g), MAEVE (12.65 g), M-1 (7.44 g), HEMA (5.20 g), OXE-30 (3.68 g), V-65 (2.98 g, 6 mol% relative to the monomer) was dissolved in PGMEA (23.0 g) and added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, resin L was obtained. The weight average molecular weight was 7,900.

<Synthesis Example 13: Synthesis of Resin M>
PGMEA (23.0 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. MAA (1.72 g), MATHF (12.49 g), M-1 (7.44 g), HEMA (5.20 g), OXE-30 (3.68 g), V-65 (0.99 g, 2 mol% relative to the monomer) was dissolved in PGMEA (23.0 g) and added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, resin M was obtained. The weight average molecular weight was 17,000.

<Synthesis Example 14: Synthesis of Resin N>
HS-DEM (23.4 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. In the solution, MAA (1.72 g), StOEVE (12.65 g), M-1 (11.16 g), HEMA (5.20 g), V-65 (2.98 g, 6 mol% based on the monomer) were added to HS. -It dissolved in EDM (23.4g) and it was dripped over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, resin N was obtained. The weight average molecular weight was 8,100.

<Comparative Synthesis Example 1: Synthesis of Comparative Resin R1>
A resin described as Synthesis Example A-1 in Japanese Patent Application Laid-Open No. 2010-66503 was synthesized as Resin R1 for comparison. The weight average molecular weight was 7,300.

<Comparative Synthesis Example 2: Synthesis of Comparative Resin R2>
A resin described as Synthesis Example A2-7 in JP-A-2009-98673 was synthesized to obtain a comparative resin R2 (MAA / GMA / BnMA copolymer). The weight average molecular weight was 6,500.

<Comparative Synthesis Example 3: Synthesis of Comparative Resin R3>
A resin described as Synthesis Example 3 in JP-A No. 2003-5357 was synthesized to obtain a comparative resin R3 (MAA / M-1 / CHMA copolymer). The weight average molecular weight was 16,000.

<Comparative Synthesis Example 4: Synthesis of Comparative Resin R4>
A resin described as Synthesis Example 2 in Japanese Patent No. 4207604 was synthesized as a comparative resin R4. The weight average molecular weight was 8,000.

<Comparative Synthesis Example 5: Synthesis of Comparative Resin R5>
Resin described as Synthesis Example 3 in Japanese Patent No. 3693199 was synthesized as Resin R5 for comparison. The weight average molecular weight was 8,000.

<Comparative Synthesis Example 6: Synthesis of Comparative Resin R6>
PGMEA (21.5 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. To the solution, MAA (2.403 g), MAEVE (12.65 g), GMA (8.529 g), HEMA (5.20 g), V-65 (2.98 g, 6 mol% with respect to the monomer) were added to HS-EDM. (21.5 g) was dissolved and added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, a comparative resin R6 was obtained. The weight average molecular weight was 8,200.

<Comparative Synthesis Example 7: Synthesis of Comparative Resin R7>
HS-DEM (23.5 g) was placed in a three-necked flask and heated to 70 ° C. in a nitrogen atmosphere. In the solution, MAA (2.403 g), MAEVE (12.65 g), OXE-30 (11.05 g), HEMA (5.20 g), V-65 (2.98 g, 6 mol% based on the monomer) were added to HS. -It dissolved in EDM (23.5g) and it was dripped over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, a comparative resin R7 was obtained. The weight average molecular weight was 8,300.

(Examples 1-14 and Comparative Examples 1-7)
After mixing each component shown in Table 1 and making it a uniform solution, it filtered using the filter made from a polytetrafluoroethylene which has a 0.2 micrometer pore size, and Examples 1-14 and Comparative Examples 1-7 Each photosensitive resin composition was prepared. In addition, the usage-amount of resin AN shown in Table 1, or comparative resin R1-R7 is a weight part of the resin solution obtained by the synthesis | combination of each resin.

In addition, the symbol in Table 1 is as follows.
B1: CGI-1397 (the following structure, manufactured by Ciba Japan Co., Ltd.)
B2: CGI-1325 (the following structure, manufactured by Ciba Japan)
B3: PAI-1001 (the following structure, manufactured by Midori Chemical Co., Ltd.)
B4: PAI-1003 (the following structure, manufactured by Midori Chemical Co., Ltd.)
C1: Propylene glycol monomethyl ether acetate (manufactured by Daicel Chemical Industries)
C2: Diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Industry Co., Ltd.)
D1: ADK STAB AO-60 (the following structure, manufactured by ADEKA Corporation)
E1: JER-157S70 (polyfunctional novolac type epoxy resin (epoxy equivalent: 200 to 220 g / eq), manufactured by Japan Epoxy Resins Co., Ltd.)
F1: KBM-403 (the following structure, manufactured by Shin-Etsu Chemical Co., Ltd.)
G1: 4-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.)
G2: 1,5-diazabicyclo [4.3.0] -5-nonene (manufactured by Wako Pure Chemical Industries, Ltd.)
H1: Megafax R-08 (perfluoroalkyl group-containing nonionic surfactant, manufactured by DIC Corporation)
H2: W-3 (perfluoroalkyl group-containing nonionic surfactant, the following structure)
I1: DBA (9,10-dibutoxyanthracene, the following structure, manufactured by Kawasaki Chemical Industry Co., Ltd.)
I2: DEA (9,10-diethoxyanthracene, the following structure, manufactured by Kawasaki Chemical Industry Co., Ltd.)

(2) Sensitivity evaluation After slit coating the photosensitive resin compositions of the examples and comparative examples on a silicon wafer having a silicon oxide film, it was pre-baked on a hot plate at 95 ° C. for 90 seconds to obtain a film thickness of 3 μm. The coating film was formed.
Next, it exposed through the predetermined | prescribed mask using i line | wire stepper (Canon Co., Ltd. product FPA-3000i5 ^<+> ). After the exposure, the resist film was developed with a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 80 seconds and rinsed with ultrapure water for 1 minute. By these operations, the optimum exposure amount when resolving a 10 μm line and space at 1: 1 was defined as sensitivity. It can be said that the sensitivity is high when the exposure dose is lower than 100 mJ / cm ² .

(3) Evaluation of unexposed part residual film ratio Initial thickness of unexposed part after development of the coating film formed in the same manner as the sensitivity evaluation was measured with a stylus type film thickness meter. The ratio of the remaining film thickness to the film thickness was evaluated as the remaining film ratio. That is, “unexposed portion remaining film ratio = film thickness after development (unexposed portion) ÷ film thickness before development (unexposed portion) × 100”. A case where the remaining film ratio of the unexposed portion is 85% or more is within the practical range and can be said to be favorable.

(4) Evaluation of transparency After coating the photosensitive resin composition solution on a glass substrate “Corning 1737 (manufactured by Corning)”, pre-baking on a hot plate at 95 ° C. for 90 seconds, a coating film having a thickness of 3 μm Formed. The obtained coating film was exposed to a cumulative irradiation amount of 200 mJ / cm ² (illuminance: 20 mW / cm ² ) using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Was heated in an oven at 230 ° C. for 1 hour to obtain a cured film. The obtained cured film was further heated in an oven at 230 ° C. for 2 hours, and the light transmittance was in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam (manufactured by Hitachi, Ltd.)”. Measured at a wavelength of. The evaluation of the transmittance of 400 nm at that time was set as the evaluation of transparency. If this value is 90% or more, it can be said that the heat-resistant transparency is good.

(5) Evaluation of solvent swell ratio After the photosensitive resin composition solution was slit-coated on a glass substrate “Corning 1737 (manufactured by Corning)”, it was pre-baked on a hot plate at 95 ° C. for 90 seconds to apply a film having a thickness of 3 μm A film was formed. The obtained coating film was exposed to a cumulative irradiation amount of 200 mJ / cm ² (illuminance: 20 mW / cm ² ) with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Was heated in an oven at 230 ° C. for 1 hour to obtain a cured film.
The cured film was immersed in a solution of monoethanolamine / dimethyl sulfoxide (DMSO) = 70/30 for 6 minutes, the film thickness immediately after the immersion was measured, and the swelling ratio was compared with the film thickness before immersion. Calculated.
Swell ratio (%) = film thickness after immersion (μm) / film thickness before immersion (μm) × 100
When this value is 103% or less, the solvent swelling ratio of the cured film is low and it can be said that the value is good.

(6) Evaluation of thermal stability After obtaining each photosensitive resin composition solution in the same manner as the evaluation of sensitivity, it was left to stand in a thermostatic bath (50 ° C.) for 7 days, and the sensitivity was evaluated again. A comparison was made between the initial sensitivity and the sensitivity of the composition forcedly aged by a thermostat.
Change amount (%) = sensitivity of composition subjected to forced aging (mJ / cm ² ) / initial sensitivity (mJ / cm ² ) × 100
The evaluation criteria are as follows. A thing with a small sensitivity fluctuation can be said to have high thermal stability.
A: Less than 105% and more than 95% (sensitivity fluctuation: small)
B: The range of 110 to 115% or 95 to 90% (sensitivity fluctuation: medium)
C: Range exceeding 115% or range less than 90% (sensitivity fluctuation: large)

  From Table 2, the photosensitive resin composition of each Example containing the resin of the present invention has a high sensitivity, a low swelling ratio with respect to the organic solvent in comparison with the photosensitive resin composition of each Comparative Example, and further heat It can be seen that good results with high stability are obtained.

(Example 15)
The photosensitive resin composition solution used in Example 4 was slit coated on a silicon wafer having a silicon oxide film, and then pre-baked on a hot plate at 95 ° C. for 90 seconds to form a coating film having a thickness of 3 μm.
Next, a predetermined photomask was set through the coating film at an interval of 150 μm, and a laser having a wavelength of 355 nm was irradiated with an exposure amount of 15 mJ / cm ² . The laser device used was “AEGIS” manufactured by Buoy Technology Co., Ltd. (wavelength 355 nm, pulse width 6 nsec), and the exposure was measured using “PE10B-V2” manufactured by OPHIR. After the exposure, the resist film was developed with a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 80 seconds and rinsed with ultrapure water for 1 minute. By these operations, a 10 μm line and space could be resolved 1: 1.

(Example 16)
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 planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 12 on a substrate, pre-baking on a hot plate (90 ° C. × 2 minutes), and then applying high pressure from above the mask. After irradiating 15 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. The insulating film 8 was formed by the same method as described above using the photosensitive resin composition of Example 7. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

(Example 17)
In the active matrix type liquid crystal display device shown in FIGS. 1 and 2 of Japanese Patent No. 332003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 17 was obtained.
That is, by using the photosensitive resin composition of Example 12, 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 16.
When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

  1: TFT (thin film transistor), 2: wiring, 3: insulating film, 4: planarization 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: Transparent ITO electrode, 20: Liquid crystal, 22: Color filter

Claims (14)

(Component A) a resin comprising a structural unit represented by the following formula (1) and a structural unit having a carboxy group or phenolic hydroxyl group protected with an acetal or ketal,
(Component B) an acid generator, and
(Component C) A positive photosensitive resin composition comprising a solvent.

(In formula (1), R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a divalent linking group, and L ² represents a trivalent hydrocarbon group.)   The positive photosensitive resin composition according to claim 1, wherein Component A further has a structural unit having an alkali-soluble group. The structural unit which has the carboxy group or phenolic hydroxyl group protected by the acetal or ketal is a structural unit represented by the following formula (A-1) or formula (A-2). A positive photosensitive resin composition.

The positive unit according to any one of claims 1 to 3, wherein the structural unit represented by the formula (1) is a structural unit represented by the following formula (M-1) or the formula (M-2). Type photosensitive resin composition.

  The positive photosensitive resin composition of any one of Claims 1-4 in which the component A further has a structural unit which has hydroxyl groups other than a phenolic hydroxyl group.   The positive photosensitive resin composition of any one of Claims 1-5 whose component B is an acid generator which has an oxime sulfonate group. The positive photosensitive resin composition of any one of Claims 1-6 whose component B is an oxime sulfonate compound represented by following formula (2).

(In Formula (2), R ⁴ represents an alkyl group or an aryl group, X represents each independently an alkyl group, an alkoxy group, or a halogen atom, and m represents an integer of 0 to 3.)   The positive photosensitive resin composition according to any one of claims 1 to 7, further comprising a crosslinking agent.   A cured film obtained by applying and curing at least one of light and heat to the positive photosensitive resin composition according to claim 1. (1) A coating step of coating the positive photosensitive resin composition according to any one of claims 1 to 8 on a substrate,
(2) a solvent removal step of removing the solvent from the applied positive photosensitive resin composition;
(3) An exposure step of exposing the positive photosensitive resin composition from which the solvent has been removed with actinic radiation,
(4) a development step of developing the exposed positive photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermosetting the developed positive photosensitive resin composition;
A method for forming a cured film comprising:   A cured film formed by the method for forming a cured film according to claim 10.   The cured film according to claim 11, which is an interlayer insulating film.   A liquid crystal display device comprising the cured film according to claim 9, 11 or 12.   An organic EL display device comprising the cured film according to claim 9, 11 or 12.

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