KR101789813B1 - Photosensitive resin composition, method for forming cured film, cured film, organic electroluminescence display device, and liquid crystal display device - Google Patents

Abstract

(식 (c1) 중, R¹ 및 R² 는 각각 독립적으로 메틸기 또는 tert-부틸기를 나타내고, R¹ 및 R² 중 적어도 하나는 tert-부틸기이고, R³ 은 -O- 또는 -NH- 를 나타낸다) assignment
A photosensitive resin composition excellent in curing sensitivity, transmittance, ITO sputter suitability, and contact hole forming ability.
Solution
(A) a copolymer containing a monomer unit having a carboxyl group protected with an acid-decomposable group or a monomer unit (a1) having a phenolic hydroxyl group protected with an acid-decomposable group and a monomer unit (a2) having a crosslinking group, (B) a photoacid generator, (C) a compound having at least two partial structures represented by the formula (c1) in the molecule and having a molecular weight of from 600 to 2,000, and (D) a solvent.

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

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a method of forming a cured film, a cured film, an organic EL display device, and a liquid crystal display device. BACKGROUND ART [0002]

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

Conventionally, in electronic parts such as liquid crystal display elements, integrated circuit elements, solid-state image pickup elements, and organic EL elements, a flattening film for imparting flatness to the surface of electronic components, a protective film Or a photosensitive resin composition is used for forming an interlayer insulating film for maintaining insulation. For example, a TFT type liquid crystal display element is a liquid crystal display element in which a polarizing plate is formed on a glass substrate, a transparent conductive circuit layer such as indium tin oxide (ITO) and a thin film transistor (TFT) are formed, On the other hand, a polarizing plate is formed on a glass substrate, a pattern of a black matrix layer and a color filter layer is formed as required, and a transparent conductive circuit layer and an interlayer insulating film are sequentially formed to form a top plate, And the liquid crystal is sealed between the both plates with the plate facing the spacer. Among them, the photosensitive resin composition used for forming the interlayer insulating film is required to have excellent sensitivity and transparency.

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

Japanese Laid-Open Patent Publication No. 2004-254623 Japanese Laid-Open Patent Publication No. 2009-98616 Japanese Laid-Open Patent Publication No. 2009-116223 Japanese Laid-Open Patent Publication No. 2006-265322

A problem to be solved by the present invention is to provide a photosensitive resin composition which is excellent in curing sensitivity, transmittance, ITO sputter suitability, and contact hole forming property.

Another object of the present invention is to provide a method for forming a cured film using the photosensitive resin composition, a cured film formed by the forming method, and an organic EL display device and a liquid crystal display device including the cured film .

The above object of the present invention is solved by the means described in the following <1>, <10>, <12>, <14> or <15>. <2> to <9>, <11> and <13> which are preferred embodiments are described below.

(1) A method for producing a resin composition, which comprises the steps of: (A) mixing a monomer unit (a1) having a carboxyl group protected with an acid-decomposable group or a monomer unit having a moiety protected with an acid-decomposable group by a phenolic hydroxyl group (B) a photoacid generator, (C) a compound having at least two partial structures represented by the formula (c1) in the molecule and having a molecular weight of from 600 to 2,000, and (D) a solvent. ,

[Chemical Formula 1]

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

&Lt; 2 &gt; A photosensitive resin composition according to &lt; 1 &gt;, which is a chemically amplified positive photosensitive resin composition,

(3) The compound of (C) is at least one compound selected from the group consisting of compounds represented by formulas (c1-1), (c1-2) and (cl-3) , A photosensitive resin composition described in

(2)

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

(3)

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

[Chemical Formula 4]

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

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

[Chemical Formula 5]

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

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

[Chemical Formula 6]

(In the formula (b2), R ⁵ represents an alkyl group, a cycloalkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m represents an integer of 0 to 3, and when m is 2 or 3, May be the same or different from each other)

<8> The photosensitive resin composition according to any one of <1> to <7>, further comprising (E) a crosslinking agent,

<9> The resin composition according to any one of <1> to <8>, wherein the monomer unit (a2) having a crosslinking group contains at least one selected from the group consisting of a cyclic ether residue of a three- A photosensitive resin composition described in any one of &lt; RTI ID = 0.0 &gt;

(2) a solvent removing step of removing the solvent from the applied photosensitive resin composition; (3) a step of removing the solvent from the applied photosensitive resin composition; and (4) a step of applying the photosensitive resin composition described in any one of (4) a developing step of developing with an aqueous developer, and (5) a post-baking step of thermally curing the coating film,

<11> The method for forming a cured film according to <10>, which comprises a step of exposing the entire surface after the above-described development step and before the post-baking step,

<12> A cured film formed by the forming method described in <10> or <11>

<13> A cured film according to <12> which is an interlayer insulating film,

<14> An organic EL display device comprising the cured film according to <12> or <13>

<15> A liquid crystal display device comprising the cured film according to <12> or <13>.

According to the present invention, it is possible to provide a photosensitive resin composition excellent in curing sensitivity, transmittance, ITO sputtering suitability, and contact hole forming property.

Further, according to the present invention, it is possible to provide a method of forming a cured film using the photosensitive resin composition, a cured film formed by the forming method, and an organic EL display device and a liquid crystal display device including the cured film.

Fig. 1 shows a configuration diagram of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.
2 is a conceptual diagram showing an example of the configuration of a liquid crystal display device. Sectional view of an active matrix substrate in a liquid crystal display device and has a cured film 17 as an interlayer insulating film.

(Photosensitive resin composition)

The photosensitive resin composition of the present invention comprises (A) a monomer unit having a carboxyl group protected with an acid-decomposable group or a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group, (a2) a monomer unit having a crosslinking group, (B) a photoacid generator, (C) a compound having at least two partial structures represented by the formula (c1) in the molecule and having a molecular weight of from 600 to 2,000, and (D) a solvent, do. Hereinafter, each of the components (A) to (D) is also referred to as "component (A)" to "component (D)". In the present specification, the description of "A to B" indicating numerical ranges indicates "A or more and B or less" unless otherwise specified. That is, it means a numerical range including A and B which are end points.

(7)

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

The photosensitive resin composition of the present invention is a positive photosensitive resin composition. The photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition). The photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as a photoacid generator that is sensitive to an actinic ray. The 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, and its quantum yield is necessarily 1 or less. On the other hand, the photoacid generator (B) used in the present invention acts as a catalyst for the deprotection of an acid-protected acid generated by the action of an actinic ray, so that the acid generated by the action of one photo- Contributes to the reaction, and the quantum yield exceeds 1, for example, becomes a large value such as a power of 10, and a high sensitivity is obtained as a result of so-called chemical amplification. Further, the photosensitive resin composition of the present invention preferably contains a cross-linking agent (E), which will be described later, from the viewpoint of the solvent resistance.

Hereinafter, the present invention will be described in detail. In the notation of the group (atomic group) in the present specification, the notation in which substitution or non-substitution is not described includes those having a substituent and having 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 of introducing the monomer unit contained in the copolymer used in the present invention may be a polymerization method or a polymer reaction method. In the polymerization method, monomers containing a predetermined functional group are synthesized in advance, and then these monomers are copolymerized. In the polymer reaction method, a necessary functional group is introduced into the monomer unit by using a reactive group contained in the monomer unit of the obtained copolymer after the polymerization reaction. Examples of the functional group include a crosslinking group such as a protecting group, an epoxy group, or an oxetanyl group for protecting the phenolic hydroxyl group or the carboxyl group and decomposing in the presence of strong acid to liberate them.

The introduction of the monomer unit (a1) and the monomer unit (a2) into the copolymer (A) may be carried out by a polymerization method or a polymer reaction method, and these two methods may be used in combination.

In the polymerization method, for example, an ethylenically unsaturated compound having a phenolic hydroxyl group or a carboxyl group protected by an acid-decomposable group and an ethylenically unsaturated compound having an epoxy group or an oxetanyl group are mixed and subjected to addition polymerization to obtain a desired copolymer Is obtained.

In the polymer reaction method, for example, a method of introducing an epoxy group by reacting epichlorohydrin with a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate can be exemplified. As described above, after the ethylenically unsaturated compound having a reactive group is copolymerized, a reactive group remaining on the side chain is utilized to remove a phenolic hydroxyl group or a carboxyl group by a polymeric reaction, such as a residue protected with an acid-decomposable group and / Can be introduced into the side chain.

(A) Copolymer

The copolymer (A) contained in the photosensitive resin composition of the present invention is preferably a copolymer

(a1) a monomer unit having a carboxyl group protected with an acid-decomposable group or a monomer unit having a phenolic hydroxyl group protected with an acid-decomposable group (hereinafter also referred to as "monomer unit (a1)")

(a2) a monomer unit (a2) having a crosslinking group (hereinafter also referred to as &quot; monomer unit (a2) &quot;).

The component (A) may contain other monomer unit (a3) in addition to the monomer unit (a1) and the monomer unit (a2).

It is preferable that the (A) copolymer is a resin that is alkali-insoluble and becomes alkali-soluble when the acid-decomposable group of the monomer unit (a1) is decomposed. Herein, the acid-decomposable group means a functional group which can be decomposed in the presence of an acid. That is, a monomer unit having a carboxyl group-bearing residue with an acid-decomposable group can generate a carboxyl group by decomposition of a protecting group by an acid, and a monomer unit having a residue whose phenolic hydroxyl group is protected with an acid- Can be decomposed to generate a phenolic hydroxyl group. Here, in the present invention, the term "alkali solubility" means that the coating solution (thickness: 3 μm) of the compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating it at 90 ° C. for 2 minutes, Means that the dissolution rate in 0.4% tetramethylammonium hydroxide aqueous solution at 23 占 폚 is not less than 0.01 占 퐉 / second, and the term "alkali insoluble" means that the solution of the compound (resin) is applied on a substrate, Refers to a dissolution rate of a coating film (thickness 3 占 퐉) of the compound (resin) formed by heating for minute in a 0.4% tetramethylammonium hydroxide aqueous solution at 23 占 폚 of less than 0.01 占 퐉 / second.

The above (A) copolymer does not exclude the introduction of an acidic group as long as the whole of the copolymer (A) is kept insoluble in alkali, but it does not exclude the presence of a carboxyl group, a carboxylic acid anhydride residue and / or a phenolic hydroxyl group And may have other monomer units or the like.

The copolymer (A) is preferably an addition polymerization type resin, more preferably a polymer containing a monomer unit derived from (meth) acrylic acid and / or an ester thereof. Further, a monomer unit other than the monomer unit derived from (meth) acrylic acid and / or an ester thereof, for example, a monomer unit derived from styrene or a monomer unit derived from a vinyl compound may be contained.

The (A) copolymer preferably contains monomer units derived from (meth) acrylic acid and / or esters thereof in an amount of 50 mol% or more, more preferably 90 mol% or more, based on the total monomer units in the polymer More preferably a polymer consisting solely of monomer units derived from (meth) acrylic acid and / or esters thereof.

The "monomer unit derived from (meth) acrylic acid and / or its ester" is also referred to as "acrylic monomer unit". In addition, "(meth) acrylic acid" means "methacrylic acid and / or acrylic acid".

Hereinafter, the monomer unit (a1) and the monomer unit (a2) will be respectively described.

(a1) a monomer unit having a carboxyl group protected with an acid-decomposable group or a monomer unit having a phenolic hydroxyl group protected with an acid-decomposable group

(A) has a monomer unit in which the carboxyl group has a moiety protected with an acid-decomposable group or a monomer unit in which a phenolic hydroxyl group has a moiety protected with an acid-decomposable group. By having the component (A) have the monomer unit (a1), a highly sensitive photosensitive resin composition can be obtained.

(a1-1) a monomer unit having a carboxyl group protected with an acid-decomposable group

(a1-1-1) a monomer unit having a carboxyl group

Examples of the monomer unit having a carboxyl group include monomer units derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid and an unsaturated tricarboxylic acid. .

As the unsaturated carboxylic acid used for obtaining a monomer unit having a carboxyl group, the same ones as those shown below are used. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid used to obtain the monomer unit having a carboxyl group may be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. The unsaturated polycarboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polycarboxylic acid, for example, mono (2-acryloyloxyethyl) succinate, mono Mono (2-acryloyloxyethyl) phthalate mono (2-methacryloyloxyethyl), and the like.

The unsaturated polycarboxylic acid may be a mono (meth) acrylate of the both terminal dicarboxylic polymer. Examples of the unsaturated polycarboxylic acid include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. have.

Examples of the unsaturated carboxylic acid include acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester and 4-carboxystyrene.

Among them, in order to form a monomer unit having a carboxyl group from the viewpoint of developability, it is preferable to use acrylic acid, methacrylic acid, or an anhydride of an unsaturated polycarboxylic acid, and more preferably use acrylic acid or methacrylic acid Do.

The monomer unit (a1-1-1) having a carboxyl group may be composed of one kind alone, or two or more kinds.

(a1-1-2) a monomer unit having an ethylenic unsaturated group and an acid anhydride moiety together

The monomer unit (a1-2) having both an ethylenic unsaturated group and an acid anhydride residue is preferably a unit derived from a monomer obtained by reacting a hydroxyl group and an acid anhydride present in a monomer unit having an ethylenic unsaturated group.

As the acid anhydride, known ones can be used, and specific examples include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and anhydrous chlorendic acid; And acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, and biphenyltetracarboxylic acid anhydride. Of these, phthalic anhydride, tetrahydrophthalic anhydride or succinic anhydride are preferable from the viewpoint of developability.

The reaction rate of the acid anhydride to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol% from the viewpoint of developability.

(a1-1-3) a monomer unit having a carboxyl group protected with an acid-decomposable group

The monomer unit having a carboxyl group protected with an acid-decomposable group is preferably a monomer unit in which the carboxyl groups described in (a1-1-1) and (a1-1-2) are protected by an acid-decomposable group Lt; / RTI &gt;

As the acid decomposable group, those known as acid decomposable groups in the positive resist for KrF and the positive resist for ArF can be used, and there is no particular limitation. Conventionally, examples of the acid-decomposable group include a group that is relatively easily decomposed by an acid (e.g., an acetal-based functional group such as a tetrahydropyranyl group) or a group that is relatively difficult to decompose by an acid (e.g., a t- -Butyl group-containing functional group such as a butylcarbonate group) are known.

Among these acid decomposable groups, the carboxyl group is a monomer unit having an acetal-protected residue or a carboxyl group-having a ketal-protected residue. The basic properties of the resist, particularly, the sensitivity and pattern shape, the contact hole forming property and the storage stability of the photosensitive resin composition . Among the acid decomposable groups, from the viewpoint of sensitivity, it is more preferable that the carboxy group is an acetal or ketal-protected residue represented by the following formula (a1-1). When the carboxy group is an acetal or ketal-protected residue represented by the following formula (a1-1), the residue has a structure of - (C═O) -O-CR ¹ R ² (OR ³ ) as a whole.

[Chemical Formula 8]

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

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

In the formula (a1-1), when R ¹ , R ² and R ³ represent an alkyl group, the alkyl group may be any of linear, branched or cyclic.

The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec- Butyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When R ¹ , R ² and R ³ are a haloalkyl group and have an aryl group as a substituent, R ¹ , R ² and R ³ are aralkyl groups when they have a halogen atom as a substituent.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Specific examples thereof include phenyl group,? -Methylphenyl group and naphthyl group. Examples of the aryl group include an aryl group Examples of the alkyl group as a whole, that is, the aralkyl group, include a benzyl group, an? -Methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.

When the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent. When the alkyl group is a linear or branched alkyl group, May have a cycloalkyl group having 3 to 12 carbon atoms.

These substituents may be further substituted with the substituent.

In the formula (a1-1), when R ¹ , R ² and R ³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent. As the substituent, an alkyl group having 1 to 6 carbon atoms can be preferably exemplified. As the aryl group, for example, a phenyl group, a tolyl group, a silyl group, a cumenyl group, a 1-naphthyl group and the like can be mentioned.

Further, R ¹ , R ² and R ³ may combine with each other to form a ring together with the carbon atoms to which they are bonded. Examples of the ring structure in the case where R ¹ and R ² , R ¹ and R ³ or R ² and R ³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, An adamantyl group, and a tetrahydropyranyl group.

In formula (a1-1), either one of R ¹ and R ² is preferably a hydrogen atom or a methyl group.

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

[Chemical Formula 9]

R ¹¹ represents a hydrogen atom or an alkyl group, and the alkyl group is the same as the alkyl group represented by R ¹ to R ³ in the formula (a1-1). As R ¹¹ , a hydrogen atom or a methyl group is preferable.

R ¹² and R ¹³ are -CH (R ¹² ) (R ¹³ ), have the same meaning as R ² in formula (a1-1), and R ¹⁴ has the same meaning as R ¹ in formula (a) , R &lt; ¹⁵ &gt; have the same meanings as R &lt; ³ &gt; in formula (a1-1) and their preferred ranges are also the same.

The above-mentioned synthesis may be conducted by previously copolymerizing (meth) acrylic acid with other monomers, and thereafter reacting with vinyl ether in the presence of an acid catalyst.

As specific preferred examples of the monomer unit (a1-1) having a carboxyl group-protected residue by an acid-decomposable group, the following monomer units can be exemplified. R represents a hydrogen atom or a methyl group.

[Chemical formula 10]

(a1-2) a monomer unit having a phenolic hydroxyl group protected with an acid-decomposable group

(a1-2-1) a monomer unit having a phenolic hydroxyl group

Examples of the monomer unit having a phenolic hydroxyl group include a monomer unit derived from a hydroxystyrene monomer unit or a novolac resin. Of these monomer units derived from? -Methylhydroxystyrene, . Among the monomer units having a phenolic hydroxyl group, monomer units represented by the formula (a1-2) are preferable from the viewpoints of transparency and sensitivity.

(11)

, R ²⁰ (wherein (a1-2) is a hydrogen atom or a methyl group, R ²¹ represents a single bond or a linking group, R ²² represents a halogen atom or an alkyl group, a is an integer of 1 ~ 5, b Is an integer of 0 to 4, and a + b is not more than 5. When two or more R ²² are present, these R ²² may be different from each other or may be the same)

In formula (a1-2), R ²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.

R ²¹ represents a single bond or a divalent linking group. In the case of a single bond, the sensitivity can be improved and the transparency of the cured film can be further improved. Examples of the divalent linking group of R ²¹ include an alkylene group and specific examples of R ²¹ is an alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among them, R ²¹ is preferably a single bond, a methylene group or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.

A is an integer of 1 to 5, and a is preferably 1 or 2, and more preferably a is 1, from the viewpoint of the effects of the present invention or from the viewpoint of easy production.

It is preferable that the bonding position of the hydroxyl group in the benzene ring is bonded at the 4-position when the carbon atom bonded to R ²¹ is the reference (1-position).

R ²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert- butyl group, a pentyl group, an isopentyl group and a neopentyl group . Among them, chlorine atom, bromine atom, methyl group or ethyl group is preferable in view of easiness of production.

B represents 0 or an integer of 1 to 4;

Among the monomer units having a phenolic hydroxyl group, when R &lt; ²¹ &gt; in the formula (a1-2) is not an alkylene group, the monomer unit represented by the formula (a1-2 ') is more preferable in terms of transparency and sensitivity. As the connecting group of R ²¹ , an alkyleneoxycarbonyl group and the like can be preferably exemplified (from the main chain side of the copolymer) in addition to the alkylene group. In this case, the monomer unit having a phenolic hydroxyl group is preferably represented by the following formula (a1- 2 ').

[Chemical Formula 12]

(In the formula (a1-2 '), R ³⁰ has the same meaning as R ²⁰ in the formula (a1-2), R ³² has the same meaning as R ²² in the formula (a1-2) b is the same as a and b in formula (a1-2), respectively, and the preferred range is also the same)

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

(a1-2-2) a monomer unit having a phenolic hydroxyl group protected with an acid-decomposable group

The monomer unit in which the phenolic hydroxyl group has a moiety protected by an acid-decomposable group is a monomer unit in which the phenolic hydroxyl group of the monomer unit having (a1-2-1) the phenolic hydroxyl group is a residue protected by an acid- Lt; / RTI &gt; As the acid-decomposable group, those known in the art can be used, and there is no particular limitation. Of the acid-decomposable groups, those in which the phenolic hydroxyl group is a monomer unit having an acetal-protected residue or a phenolic hydroxyl group-protected ketal-protected monomer unit are preferred because the basic physical properties of the resist, particularly the sensitivity and pattern shape, the storage stability of the photosensitive resin composition, From the viewpoint of formability. Among the acid decomposable groups, from the viewpoint of sensitivity, it is more preferable that the phenolic hydroxyl group is an acetal or ketal-protected residue represented by the formula (a1-1). When the phenolic hydroxyl group is an acetal or ketal-protected residue represented by the formula (a1-1), the residue has a structure of -Ar-O-CR ¹ R ² (OR ³ ) as a whole. Ar represents an arylene group.

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

Examples of the radical polymerizable monomer used for forming the monomer unit having a phenolic hydroxyl group having an acetal or ketal protected moiety include a 1-alkoxyalkyl protected product of hydroxystyrene, a tetrahydrofuran derivative of hydroxystyrene Alkoxyalkyl protecting group of? -Methyl-hydroxystyrene, a tetrahydropyranyl protecting group of? -Methyl-hydroxystyrene, a 1-alkoxyalkyl protective group of 4-hydroxyphenyl methacrylate , A tetrahydro pyranyl protective group of 4-hydroxyphenyl methacrylate, a 1-alkoxyalkyl protected group of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, a 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester of 4-hydroxybenzoic acid, 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester of 4-hydroxybenzoic acid Oxyethyl) ester, a 1-alkoxyalkyl protected form of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, a 4-hydroxybenzoic acid (3-methacryloyloxypropyl) Alkoxyalkyl protecting group of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxyphenyl) Hydroxy-2-hydroxypropyl) ester, and the like.

Among them, a 1-alkoxyalkyl protected derivative of 4-hydroxyphenyl methacrylate, a tetrahydropyranyl protected derivative of 4-hydroxyphenyl methacrylate, a 4-hydroxybenzoic acid (1-methacryloyloxymethyl) (2-methacryloyloxyethyl) ester of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, a protected tetrahydro pyranyl of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, a tetrahydrothiopyranyl protected derivative of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester of 4-hydroxybenzoic acid, a tetrahydrothiopyranyl protected derivative of 4- Alkoxyalkyl protecting group of ester, 4-hydroxy When acid (3-methacryloyloxy-2-hydroxypropyl-yloxy) is preferred in view of transparency tetra hydro pyranyl esters of body protection.

Specific examples of the acetal protecting group and the ketal protecting group of the phenolic hydroxyl group include a 1-alkoxyalkyl group, and examples thereof include a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, (1-cyclohexyloxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- ) Ethyl group, 1-benzyloxyethyl group, etc. These may be used alone or in combination of two or more.

The radically polymerizable monomer used for forming the monomer unit (a1) may be a commercially available one or a synthesized by a known method. For example, by reacting a compound having a phenolic hydroxyl group with a vinyl ether in the presence of an acid catalyst. The above-mentioned synthesis may be carried out by previously copolymerizing a monomer having a phenolic hydroxyl group with another monomer, and then reacting with a vinyl ether in the presence of an acid catalyst.

Specific preferred examples of the monomer unit (a1-2) include the following monomer units, but the present invention is not limited thereto.

[Chemical Formula 13]

The content of the monomer unit (a1) among the monomer units constituting the component (A) is preferably from 3 to 70 mol%, more preferably from 5 to 60 mol%, more preferably from 5 to 60 mol% , More preferably from 10 to 50 mol%.

The monomer unit in which the carboxyl group has a residue protected by an acid-decomposable group is characterized in that the phenolic hydroxyl group is faster than the monomer unit having a residue protected by an acid-decomposable group. Therefore, when a rapid development is desired, a monomer unit having a residue whose carboxyl group is protected with an acid-decomposable group is preferable. On the contrary, when it is desired to slow the development, it is preferable to use a monomer unit having a residue in which the phenolic hydroxyl group is protected with an acid-decomposable group.

(a2) a monomer unit having a crosslinking group

(A) has a monomer unit (a2) having a crosslinking group. The crosslinking group is not particularly limited as long as it is a group which causes a curing reaction by a heat treatment. As a mode of the monomer unit having a preferred crosslinking group, there may be mentioned a monomer unit containing at least one selected from the group consisting of a cyclic ether residue of a triple ring and / or a four-membered ring, and an ethylenic unsaturated group. More specifically, the following can be mentioned.

(a2-1) a monomer unit having a cyclic ether residue of a 3-atomic ring and / or a 4-membered ring

The copolymer (A) preferably contains a monomer unit (monomer unit (a2-1)) having a cyclic ether residue of a three-membered ring and / or a four-membered ring. The cyclic ether residue of the triple ring is also called an epoxy group, and the cyclic ether residue of the four-membered ring is also called an oxetanyl group. The monomer unit (a2-1) having an epoxy group and / or an oxetanyl group is preferably a monomer unit having an alicyclic epoxy group and / or an oxetanyl group, and more preferably a monomer unit having an oxetanyl group.

The monomer unit having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one monomer unit, and may contain at least one epoxy group and at least one oxetanyl group, at least two epoxy groups, An oxetanyl group, and it is not particularly limited, but it is preferable to have 1 to 3 epoxy groups and / or oxetanyl groups in total, more preferably 1 or 2 epoxy groups and / or oxetanyl groups in total, More preferably an epoxy group or an oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the monomer unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl alpha -ethyl acrylate, alpha -n-propyl acrylate Glycidyl,? -N-butyl acrylate glycidyl, acrylate-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7 -Epoxyheptyl,? -Ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, Japanese Patent No. 4168443, And compounds containing an alicyclic epoxy skeleton as described in [0035].

Specific examples of the radical polymerizable monomer used for forming the monomer unit having an oxetanyl group include (meth) acrylate ester having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953 And the like.

Specific examples of the radically polymerizable monomer used for forming the monomer unit having an epoxy group and / or an oxetanyl group are monomers containing a methacrylic acid ester structure and monomers containing an acrylic ester structure.

Among these monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and compounds having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A-2001-330953 ) Acrylate, and particularly preferred is a (meth) acrylic acid ester having an oxetanyl group as described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Among these, preferred are acrylic esters such as 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetan-3-yl) Yl) methyl, and most preferred are methyl (3-ethyloxetan-3-yl) acrylate and methacrylic acid (3-ethyloxetan-3-yl) methyl. These monomer units may be used singly or in combination of two or more.

It is preferable that the monomer unit (a2-1) has a residue selected from the group consisting of the following formulas (a2-1-1) and (a2-1-2).

[Chemical Formula 14]

The fact that the monomer unit (a2-1) has any of the three residues represented by the above formula (a2-1-1) means that the structure having the group excluding one or more hydrogen atoms from the structure represented by the formula (a2-1-1) .

More preferably, the monomer unit (a2-1) has a 3,4-epoxycyclohexyl group, a 2,3-epoxycyclohexyl group and a 2,3-epoxycyclopentyl group.

[Chemical Formula 15]

(Wherein R ^1b and R ^6b each independently represents a hydrogen atom or an alkyl group, and R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b , R ^10b Each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group)

In formula (a2-1-2), R ^1b and R ^6b each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms Hereinafter also referred to as &quot; lower alkyl group &quot;).

R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, more preferably a fluorine atom and a chlorine atom, and more preferably a fluorine atom.

The alkyl group may be any of linear, branched, and cyclic, and may have a substituent. The linear and branched alkyl groups preferably have 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. The cyclic alkyl group preferably has 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 5 to 7 carbon atoms. The linear or branched alkyl group may be substituted with a cyclic alkyl group, and the cyclic alkyl group may be substituted with a linear and / or branched alkyl group.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms.

The alkyl group and the aryl group may further have a substituent. Examples of the substituent which the alkyl group may have include a halogen atom and an aryl group. Examples of the substituent which the aryl group may have include a halogen atom and an alkyl group .

Of these, R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, More preferably a perfluoroalkyl group.

As the group having a residue represented by the formula (a2-1-2), a (3-ethyloxetan-3-yl) methyl group can be preferably exemplified.

As specific preferred examples of the monomer unit (a2-1), the following monomer units can be exemplified. And R represents a hydrogen atom or a methyl group.

[Chemical Formula 16]

In the present invention, from the viewpoint of curing sensitivity, an oxetanyl group is preferable among the cyclic ether residue of three-membered ring and four-membered ring. In the present invention, an alicyclic epoxy group and an oxetanyl group are preferable from the viewpoint of transmittance (transparency). From the above, in the present invention, the cyclic ether residue of a triple ring and a four-membered ring is preferably an alicyclic epoxy group and an oxetanyl group, and an oxetanyl group is particularly preferable.

(a2-3) a monomer unit having an ethylenic unsaturated group

One monomer unit (a2) having a crosslinking group includes a monomer unit (a2-3) having an ethylenic unsaturated group (hereinafter also referred to as "monomer unit (a2-3)"). The monomer unit (a2-3) having an ethylenically unsaturated group is preferably a monomer unit having an ethylenic unsaturated group in the side chain, a monomer unit having an ethylenic unsaturated group at the end and having a side chain of 3 to 16 carbon atoms And more preferably a monomer unit having a side chain represented by the formula (a2-3-1).

[Chemical Formula 17]

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

R ¹ is a divalent linking group having 1 to 13 carbon atoms, which may include an alkenyl group, a cycloalkenyl group, an arylene group, or a combination thereof, and may include a bond such as an ester bond, an ether bond, an amide bond or a urethane bond. The divalent linking group may have a substituent such as a hydroxyl group or a carboxy group at an arbitrary position. Specific examples of R ¹ include divalent linking groups represented by formulas (A-1) to (A-10).

[Chemical Formula 18]

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

The ethylenic unsaturated group contained in the side chain represented by the formula (a2-3-1) is preferably contained in an amount of 1 mole per 150 g to 2,000 g of the polymer (A), more preferably in an amount of 1 mole per 200 g to 1,300 g .

The method for obtaining the monomer unit (a2-3) having a side chain represented by the formula (a2-3-1) is not particularly limited, but for example, a polymer having a specific functional group is produced by a polymerization method such as radical polymerization in advance (A2-3) can be obtained by reacting a compound having an ethylenic unsaturated group at its terminal and a compound (hereinafter referred to as a specific compound) reacting with the specific functional group.

Examples of the specific functional group include a carboxyl group, an epoxy group, a hydroxyl group, an amino group having an active hydrogen, a phenolic hydroxyl group, and an isocyanate group. Monomers having specific functional groups for synthesizing a polymer having a specific functional group will be described later.

Examples of the combination of the specific functional group and the group reacting with the specific functional group possessed by the specific compound include a combination of a carboxyl group and an epoxy group, a combination of a carboxyl group and an oxetanyl group, a combination of a hydroxy group and an isocyanate group, a combination of a phenolic hydroxyl group and an epoxy group, A combination of a carboxyl group and an isocyanate group, a combination of an amino group and an isocyanate group, a combination of a hydroxy group and an acid chloride, and the like.

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

Preferred examples of the combination of the specific functional group and the specific compound include a combination of a carboxyl group as a specific functional group and glycidyl methacrylate as a specific compound and a combination of a hydroxy group as a specific functional group and isocyanate ethyl methacrylate as a specific compound.

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

[Chemical Formula 19]

(Formula (a2-3-2) of, R ¹ is the same from the preferable range is the same meaning as that of R ¹ in the formula ^{(a2-3-1). R 2, R} 3 are each independently a hydrogen atom or a methyl group Lt; / RTI &

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

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono (2- (acryloyloxy) ethyl) phthalate, mono (2- (methacryloyloxy) (Carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.

Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, Epoxy-5-hexene, 1,7-octadiene monoepoxide, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl acrylate.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl Acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, Caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5- Acryloyloxy-6-hydroxy norbornene-2-carboxy-6-lactone, 5-methacryloyloxy-6-hydroxy norbornene-2-carboxy-6- have.

Examples of the monomer having an amino group having an active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide and N- (hydroxyphenyl) maleimide. have.

Examples of the monomer having an isocyanate group include acryloylethyl isocyanate, methacryloyl isocyanate, m-tetramethyl xylene isocyanate and the like.

In the present invention, in the case of obtaining a polymer having a specific functional group, the above-mentioned monomer having a specific functional group and (a1) a monomer unit having a carboxyl group protected with an acid-decomposable group or a monomer unit having a phenolic hydroxyl group protected with an acid- Are used in combination. Monomers other than the above-mentioned (a1) and (a2) which are other monomer units (a3) may be used in combination.

The method for obtaining the polymer having a specific functional group to be used in the present invention is not particularly limited. For example, in a solvent in which a monomer having a specific functional group, a monomer other than the monomer, and a polymerization initiator are co- Lt; 0 &gt; C. In this case, the solvent to be used is not particularly limited as long as it dissolves the monomer constituting the polymer having a specific functional group and the polymer having a specific functional group. Specific examples include the solvents described in the solvent (D) described later. The polymer having the specific functional group thus obtained is usually in a solution state dissolved in a solvent.

Then, the polymer having the specific functional group thus obtained is reacted with a specific compound to obtain a monomer unit (a2-3) having an ethylenic unsaturated group at the end of the side chain. Typically, a solution of a polymer having a specific functional group is then provided to the reaction. For example, glycidyl methacrylate is reacted with a solution of an acrylic polymer having a carboxyl group at a temperature of 80 ° C to 150 ° C in the presence of a catalyst such as benzyltriethylammonium chloride to obtain a monomer unit (a2-3) .

Further, in order to form the monomer unit (a2-3), in addition to the above-mentioned polymer reaction, allyl methacrylate, allylacrylate and the like may be used as the radical polymerizable monomer. These monomer units may be used alone or in combination of two or more.

The content of the monomer unit (a2) among the monomer units constituting the component (A) is preferably from 5 to 60 mol%, more preferably from 10 to 55 mol%, still more preferably from 20 to 50 mol%, from the viewpoints of various resistance and transparency of the formed film. More preferably 50 mol%. Within the above range, the transparency of the cured film obtained from the photosensitive resin composition and the ITO sputter resistance are improved.

(a3) Other monomer units

In the present invention, the component (A) may have other monomer units (a3) except for the monomer units (a1) and (a2). Examples of the other monomers to be the monomer unit (a3) include styrene, alkyl (meth) acrylate, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds can be given.

Specific examples include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene,? -Methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, vinylbenzoate, ethyl vinylbenzoate, Propyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, isopropyl (meth) acrylate, isopropyl Acrylate, 2-hydroxypropyl acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl methacrylate, acrylonitrile and the like. In addition, the compounds described in paragraphs 0021 to 0024 of Japanese Laid-Open Patent Publication No. 2004-264623 can be mentioned. Among them, a group in which a group reacting with the monomer unit (a2) or a separately added crosslinking agent is produced by the (final) heating treatment is preferable from the viewpoint of film strength. Specifically, a tertiary alkyl ester of (meth) acrylic acid is preferable, and tert-butyl (meth) acrylate is more preferable. The monomers to be the monomer unit (a3) may be used singly or in combination of two or more.

The (A) copolymer preferably contains 1 to 15 mol% of an unprotected monomer unit having a carboxyl group or a monomer unit having an unprotected phenolic hydroxyl group from the viewpoint of sensitivity.

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

Various methods are also known for the method of synthesizing the component (A). For example, at least a radically polymerizable monomer containing a radical polymerizable monomer used for forming the monomer unit represented by the above (a1) and (a2) Can be synthesized by polymerization of a monomer mixture in an organic solvent using a radical polymerization initiator.

(B)

The photosensitive resin composition of the present invention contains (B) a photoacid generator. As the photoacid generator (also referred to as "component (B)") used in the present invention, a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, But is not limited to a chemical structure. In the case of a photoacid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, a compound capable of generating an acid upon exposure to an actinic ray having a wavelength of 300 nm or more by being used in combination with a sensitizer can be preferably used in combination with a sensitizer have. As the photoacid generator used in the present invention, a photoacid generator that generates an acid with a pKa of 4 or less is preferable, and a photoacid generator that generates an acid with a pKa of 3 or less is more preferable.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds and oxime sulfonate compounds. Among them, it is preferable to use an oxime sulfonate compound from the standpoint of insulation. These photoacid generators may be used alone or in combination of two or more.

Specific examples thereof include the following.

As trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) Triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan- (4,6-trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine or 2- (4-methoxynaphthyl) -s-triazine, 2- [ (4,6-trichloromethyl) -s-triazine and the like;

As the diaryl iodonium salts, there may be mentioned diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethane sulfonate, 4-methoxyphenyl phenyl iodonium trifluoromethane sulfonate, 4-methoxyphenylphenyl iodonium Phenyl-iodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecarboxy) phenyl, iodonium trifluoromethanesulfonate, Iodonium hexafluoroantimonate, phenyl, 4- (2'-hydroxy-1'-tetradecarboxy) phenyliodonium-p-toluenesulfonate and the like;

As the triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenyl 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate; and the like;

Examples of the quaternary ammonium salts include tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) (P-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate, and the like can be used. ;

Diazomethane derivatives such as bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane and the like;

As the imidosulfonate derivative, trifluoromethylsulfonyloxybicyclo [2.2.1] hepto-5-endocarboximide, succinimide trifluoromethylsulfonate, phthalimide trifluoromethylsulfonate, N -Hydroxynaphthalimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimide propanesulfonate and the like;

As the oxime sulfonate compound, the following compounds.

As the oxime sulfonate compound, that is, the compound having an oxime sulfonate moiety, a compound containing an oxime sulfonate moiety represented by formula (b1) can be preferably exemplified.

[Chemical Formula 20]

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

The alkyl group in R ⁵ may be linear, branched or cyclic. The permissible substituents are described below.

As the alkyl group for R ⁵ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R &lt; ⁵ &gt; is preferably an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a cycloalkyl group (including a cycloaliphatic group having a bridge such as a 7,7-dimethyl-2-oxonorbornyl group, A cycloalkyl group or the like).

As the aryl group for R ^5, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R &lt; ⁵ &gt; may be substituted by a lower alkyl group, an alkoxy group or a halogen atom.

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

[Chemical Formula 21]

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

In the above formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ¹ may have a substituent.

Of the above-mentioned formulas (OS-3) to (OS-5), the alkyl group for R ¹ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

Examples of the substituent which the alkyl group in R ¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group.

Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, N-decyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group , A phenoxycarbonylethyl group, and a dimethylaminocarbonylethyl group.

Of these, preferred are a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- An n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.

Of the above-mentioned formulas (OS-3) to (OS-5), the aryl group in R ¹ is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which the aryl group in R ¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, A sulfonyl group, and an alkoxysulfonyl group.

Examples of the aryl group for R ¹ include a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, Phenylthiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, and p-dimethylaminocarbonylphenyl group.

Among them, a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group and p-phenoxyphenyl group are preferable.

Of the above-mentioned formulas (OS-3) to (OS-5), the heteroaryl group for R ¹ is preferably a heteroaryl group having 4 to 30 total carbon atoms which may have a substituent.

The substituent which R ¹ may have as a heteroaryl group includes a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, An aminosulfonyl group, and an alkoxysulfonyl group.

Among the above-mentioned formulas (OS-3) to (OS-5), the heteroaryl group for R ¹ may be at least one of the rings may be a heterocyclic ring. For example, the heterocyclic ring and the benzene ring may be covalently bonded.

Examples of the heteroaryl group for R ¹ include a group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring and a benzoimidazole ring, which may have a substituent And a group in which one hydrogen atom is removed from the ring selected in the group.

In the formulas (OS-3) to (OS-5), R ² is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

Of these formulas (OS-3) to (OS-5), one or two of R ² present in two or more of the compounds are preferably an alkyl group, an aryl group or a halogen atom, and one of R ² is preferably an alkyl group, More preferably an atom, and it is particularly preferable that one is an alkyl group and the remainder is a hydrogen atom.

Among the above-mentioned formulas (OS-3) to (OS-5), the alkyl group or aryl group in R ² may have a substituent.

Examples of the substituent that the alkyl group or aryl group in R ² may have include the same group as the substituent that the alkyl group or aryl group in R ¹ may have.

The alkyl group in R ² is preferably an alkyl group having 1 to 12 carbon atoms in total which may have a substituent and more preferably an alkyl group having 1 to 6 carbon atoms in total which may have a substituent.

Specific examples of the alkyl group for R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, A perfluorohexyl group, a chloromethyl group, a bromomethyl group, a methoxymethyl group, a benzyl group, a phenoxyethyl group, a methylthioethyl group, a naphthyl group, a naphthyl group, , A phenylthioethyl group, an ethoxycarbonylethyl group, a phenoxycarbonylethyl group, and a dimethylaminocarbonylethyl group.

Among them, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s- , A benzyl group is preferable and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n- butyl group, Propyl group, n-butyl group and n-hexyl group are more preferable, and methyl group is particularly preferable.

The aryl group in R ² is preferably an aryl group having a total of 6 to 30 carbon atoms which may have a substituent.

Specific examples of the aryl group for R ² include a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, Thiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, and p-dimethylaminocarbonylphenyl group.

Among them, a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group and a p-phenoxyphenyl group are preferable.

Examples of the halogen atom in R ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Of these, a chlorine atom and a bromine atom are preferable.

Of the above formulas (OS-3) to (OS-5), X represents O or S, and is preferably O.

In the formulas (OS-3) to (OS-5), the ring containing X as a ring source is a five-membered ring or a six-membered ring.

In the formulas (OS-3) to (OS-5), n represents 1 or 2, and when X is O, n is preferably 1. When X is S, n is 2 desirable.

Among the above-mentioned formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group in R ⁶ may have a substituent.

Among the above-mentioned formulas (OS-3) to (OS-5), the alkyl group for R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

Examples of the substituent which the alkyl group in R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group.

Examples of the alkyl group for R ⁶ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- N-decyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group , A phenoxycarbonylethyl group, and a dimethylaminocarbonylethyl group.

Of these, preferred are a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- An n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.

Of the above-mentioned formulas (OS-3) to (OS-5), the alkyloxy group in R ⁶ is preferably an alkyloxy group having 1 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which the alkyloxy group in R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group.

Examples of the alkyloxy group in R ⁶ include a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, an ethoxyethyloxy group, a methylthioethyloxy group, A phenylthioethyloxy group, an ethoxycarbonylethyloxy group, a phenoxycarbonylethyloxy group, and a dimethylaminocarbonylethyloxy group.

Of these, methyloxy, ethyloxy, butyloxy, hexyloxy, phenoxyethyloxy, trichloromethyloxy or ethoxyethyloxy groups are preferred.

Of the above-mentioned formulas (OS-3) to (OS-5), examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group and an aminosulfonyl group .

Of the above-mentioned formulas (OS-3) to (OS-5), examples of the alkoxysulfonyl group for R ⁶ include a methoxysulfonyl group, ethoxysulfonyl group, propyloxysulfonyl group and butyloxysulfonyl group .

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

It is particularly preferable that the compound containing an oxime sulfonate residue represented by the formula (b1) is an oxime sulfonate compound represented by any of the following formulas (OS-6) to (OS-11).

[Chemical Formula 22]

Wherein R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, and R ⁸ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R ¹⁰ represents a hydrogen atom or a methyl group, a halogen atom, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, Lt; / RTI &

Expression and (OS-6) ~ (OS -11) R 1 has the same meaning as R ¹ in the formula (OS-3) ~ (OS -5) in the, preferred embodiments are also the same.

R ⁷ in the formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

R ⁸ in the formulas (OS-6) to (OS-11) represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, And is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group.

R ⁹ in formulas (OS-8) and (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

R ¹⁰ in the formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

In the oxime sulfonate compound, the three-dimensional structure (E, Z) of oxime may be either one of them or a mixture thereof.

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

(23)

&Lt; EMI ID =

(25)

(26)

(27)

(28)

[Chemical Formula 29]

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

(30)

(Wherein R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group Lt; ² &gt; represents an alkyl group or an aryl group)

X is ^{-O-, -S-, -NH-, -NR 5} -, -CH 2 -, -CR 6 H- or -CR ⁶ R ⁷ - represents a, R ⁵ ~ R ⁷ represents an alkyl group or an aryl group .

R ²¹ to R ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an aryl group. Two of R ²¹ to R ²⁴ may be bonded to each other to form a ring.

As R ²¹ to R ²⁴ , a hydrogen atom, a halogen atom and an alkyl group are preferable, and at least two of R ²¹ to R ²⁴ are bonded to each other to form an aryl group. Among them, embodiments in which all of R ²¹ to R ²⁴ are hydrogen atoms are preferable from the viewpoint of sensitivity.

All of the above-described functional groups may further have a substituent.

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

(31)

In the formula (OS-2), R ¹ , R ² and R ²¹ to R ²⁴ have the same meanings as those of the formula (OS-1), and preferable examples are also the same.

Among them, the embodiment wherein R ^{1 in the} formulas (OS-1) and (OS-2) is a cyano group or an aryl group is more preferable and an embodiment in which R ¹ is a cyano group, Naphthyl group is most preferable.

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

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

(32)

(33)

(34)

(35)

Among these compounds, b-9, b-16, b-31 and b-33 are preferable from the viewpoint of compatibility between sensitivity and stability.

It is more preferable that the compound containing an oxime sulfonate residue represented by the formula (b1) is an oxime sulfonate compound represented by the following formula (b2).

(36)

(In the formula (b2), R ⁵ represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m represents an integer of 0 to 3, and when m is 2 or 3, They may be the same or different)

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.

The halogen atom as X is preferably a chlorine atom or a fluorine atom.

m is preferably 0 or 1.

In the formula (b2), m is 1, X is a methyl group, X is a substituted position in the ortho position, R ⁵ is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorbornyl Methyl group, or p-toluyl group is particularly preferable.

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

(37)

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

Examples of R ⁵ in the formula (b3) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoro- N-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and n-octyl group is particularly preferable.

As X ', an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group is more preferable.

L is preferably 0 to 2, and particularly preferably 0 to 1.

Specific examples of the compound represented by the formula (b3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) Benzyl cyanide,? - (methylsulfonyloxyimino) -4-methoxyphenyl, benzyl cyanide,? - (n-butylsulfonyloxyimino) benzyl cyanide, - [(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, alpha - [(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, and? - [(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile.

Specific examples of the preferable oxime sulfonate compounds include the following compounds (i) to (viii), and they may be used singly or in combination of two or more. The compounds (i) to (viii) are commercially available. In addition, it may be used in combination with other types of (B) photoacid generators.

(38)

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

(C) a compound having at least two partial structures represented by formula (c1) in the molecule and having a molecular weight of 600 or more and 2,000 or less

(C) a compound having at least two partial structures represented by the formula (c1) in the molecule and having a molecular weight of from 600 to 2,000 (hereinafter appropriately referred to as "component (C)", "specific phenol compound (C) &quot;).

[Chemical Formula 39]

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

R ¹ and R ² are each independently a methyl group or represents a tert- butyl, at least one of R ¹ and R ² is the tert- butyl group, and both of R ¹ and R ² is preferably tert- butyl group.

R ³ represents -O- or -NH- and is preferably -O-.

By containing the specific phenol compound (C), the coloring in the baking step is reduced, and an interlayer insulating film (cured film) having excellent transparency can be obtained. In addition, when the specific phenol compound (C) and the resin having an acetal structure are used in combination, the contact hole diameter of the interlayer insulating film does not change before and after the baking. In addition, only when a specific phenol compound (C) and an acrylic resin are used in combination, a remarkable effect of lowering the relative dielectric constant of the interlayer insulating film is exhibited.

The specific phenol compound (C) has two or more partial structures represented by the formula (c1) in the molecule in the molecule, and it is preferable that the partial structure contains two or more and six or less partial structures, more preferably two Or more and 4 or less.

Examples of such compounds include tetrakis {methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate} methane, tetrakis {methylene- Methylphenyl) propionate} methane, 3,9-bis [2- [3- (3-tert- butyl-4-hydroxy- Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [2- [3- (3,5-di- tert- ) Propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, N, N'- Di-tert-butyl-4-hydroxyphenylpropionamide)], N, N'-octane-1,8-diylbis [3- (3,5- Propionamide)] and the like.

The specific phenolic compound (C) used in the present invention has a molecular weight of 600 or more and 2,000 or less, preferably a molecular weight of 700 or more. From the viewpoint of compatibility with the copolymer of the component (A), it is preferably a monomolecular compound, not a polymer (polymer compound) containing a repeating unit having a partial structure as described above.

From the viewpoint of transparency after baking, it is preferable that the specific phenol compound (C) used in the present invention contains an ester bond in which R ³ is -O-.

Among the specific phenol compounds, specific phenolic compounds more preferable in terms of transparency after baking include compounds represented by the formulas (c1-1), (c1-2) and (c1-3) Is a compound represented by the formula (c1-1).

(40)

The specific phenolic compound (C) can also be obtained as a commercially available product. Examples of the compound represented by the formula (c1-1) include Irganox 1010 (manufactured by Ciba Specialty Chemicals), Adecastab AO -60 (manufactured by ADEKA Co., Ltd.) and the trade name of the compound represented by the above formula (c1-2) may be SUMIRIZER GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Adekastab AO- ) Manufactured by ADEKA), and the compound represented by the above formula (c1-3) can be exemplified by Irganox 1098 (manufactured by Chiba Specialty Chemicals Co., Ltd.) and the like.

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

(D) Solvent

The photosensitive resin composition of the present invention contains (D) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution prepared by dissolving the aforementioned components (A) to (D) as essential components, the component (E) described below as a preferable component, Do.

As the solvent (D) used in the photosensitive resin composition of the present invention, known solvents may be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl There may be mentioned ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers , Dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like.

As the (D) solvent used in the photosensitive resin composition of the present invention, for example,

(A) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;

(B) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol dipropyl ether;

Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate and ethylene glycol monobutyl ether acetate;

(D) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether;

Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate and diethylene glycol monobutyl ether acetate;

Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether;

Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol ethyl methyl ether;

Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate and dipropylene glycol monobutyl ether acetate;

Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, isobutyl lactate, isobutyl lactate, n-amyl lactate and isoamyl lactate;

N-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, ethyl 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, Aliphatic carboxylic acid esters such as butyl, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate and isobutyl butyrate;

Hydroxyethyl methacrylate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxypropionic acid, 3-methoxypropionic acid, Methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl acetate, Methoxybutylbutylate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate and the like;

Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone;

Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone;

And lactones such as? -Butyrolactone.

In addition to these solvents, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, Solvents such as 1-octanol, 1-nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate may be added. These solvents may be used alone or in combination of two or more. The solvent usable in the present invention is preferably used alone or in combination of two or more, more preferably two solvents in combination, and the use of propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers in combination More preferable.

The content of the solvent (D) 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, more preferably 150 to 1,500 parts by weight, per 100 parts by weight of the component (A) Do.

(E) a cross-linking agent, (F) an adhesion improver, (G) a basic compound, and (C) an antioxidant may be added to the positive-working photosensitive resin composition of the present invention in addition to the components (A) Known additives such as (H) a surfactant, (I) a plasticizer and (J) a thermal radical generator and a thermal acid generator, an ultraviolet absorber, a thickener and an organic or inorganic precipitation inhibitor.

(E) Crosslinking agent

The photosensitive resin composition of the present invention preferably contains (E) a crosslinking agent, if necessary.

As the crosslinking agent (E), for example, a compound having two or more epoxy groups or oxetanyl groups in the molecule, an alkoxymethyl group-containing crosslinking agent, and a compound having at least one ethylenically unsaturated double bond may be added. By adding the crosslinking agent (E), the cured film can be made into a stronger film. As the crosslinking agent, the following may be added.

&Lt; Compounds having two or more epoxy groups in the molecule &

Specific examples of the compound having two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin and aliphatic epoxy resin.

These are available as commercial products. Examples of the bisphenol A type epoxy resin include JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 JER4005, JER4007, JER4010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (manufactured by DIC Corporation), and the like can be used as the bisphenol F type epoxy resin. JER152, JER154, JER157S65, and JER157S70 (manufactured by Japan Epoxy Resin Co., Ltd.) were used as the phenol novolak type epoxy resin, and LCE-21 and RE-602S (manufactured by Nippon Kayaku Co., EPICLON N-760, EPICLON N-770 and EPICLON N-775 (manufactured by DIC Corporation), EPICLON N-760 and EPICLON N-760 were used as the cresol novolak type epoxy resin. EPICLON N-690 (manufactured by DIC Corporation), EOCN-1020 (manufactured by NIPPON KAYAKU CO., LTD.), EPICLON N-670, EPICLON N-670, To the aliphatic Examples of the epoxy resin include ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE 3150, EPOLEAD PB 3600, and PB 4700 (manufactured by Daicel Chemical Industries, Ltd.). NC-2000, NC-3000, NC-7300, XD-1000, EPP-4010S (manufactured by ADEKA) -501, and EPPN-502 (manufactured by ADEKA Corporation). These may be used alone or in combination of two or more.

Of these, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, phenol novolak type epoxy resin and cresol novolak type epoxy resin. Particularly preferred are bisphenol A type epoxy resins, phenol novolak type epoxy resins and aliphatic epoxy resins.

&Lt; Compounds having two or more oxetanyl groups in the molecule &gt;

As specific examples of the compound having two or more oxetanyl groups in the molecule, OXT-121, OXT-221, OX-SQ and PNOX (manufactured by TOA Corporation) can be used.

The amount of the compound having an epoxy group or oxetanyl group added to the photosensitive resin composition is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, based on 100 parts by weight of the total amount of the component (A).

<Crosslinking agent containing alkoxymethyl group>

As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea are preferable. These are obtained by converting methylol groups of methylol melamine, methylol benzoguanamine, methylol glycoluryl or methylol urea into alkoxymethyl groups, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of the amount of generated outgas, a methoxymethyl group is particularly preferable Do. Of these crosslinking compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are preferable crosslinking compounds, and from the viewpoint of transparency, alkoxymethylated glycoluril is particularly preferable.

These alkoxymethyl group-containing crosslinking agents are commercially available, for example, as cyclamates 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (manufactured by Mitsui Cyanamid), NIKARAK MX-750, -032, -706, -708, -40, -31, -270, -280, -290, NIKARAK MS-11, NIKARAK MW-30HM, -100 LM, -390 (manufactured by SANWA CHEMICAL Co., Ltd.), and the like can be preferably used.

When the crosslinking agent containing an alkoxymethyl group 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, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the component (A) . Addition in this range provides favorable alkali solubility during development and excellent solvent resistance of the film after curing.

&Lt; Compounds having at least one ethylenically unsaturated double bond &gt;

As the compound having at least one ethylenic unsaturated double bond, a (meth) acrylate compound such as monofunctional (meth) acrylate, bifunctional (meth) acrylate or trifunctional or more (meth) acrylate is preferably used .

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, and the like.

Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol (meth) acrylate, polypropylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, and bisphenoxyethanol fluorene diacrylate.

Examples of the trifunctional or more (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

These compounds having at least one ethylenic unsaturated double bond among them may be 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, more preferably 30 parts by weight or less based on 100 parts by weight of the component (A). By containing a compound having at least one ethylenically unsaturated double bond in such a ratio, the heat resistance and surface hardness of the insulating film obtained from the photosensitive resin composition of the present invention can be improved. When a compound having at least one ethylenically unsaturated double bond is added, it is preferable to add the heat radical generator (J).

(F) Adhesion improver

The photosensitive resin composition of the present invention may contain (F) an adhesion improver. The adhesion improver (F) that can be used in the photosensitive resin composition of the present invention improves the adhesion of an inorganic substance as a base material, for example, a silicone compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, . Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent as the (F) adhesion improver used in the present invention is not specifically limited and known ones can be used for the purpose of modifying the interface.

Preferable silane coupling agents include, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? -Methacryloxypropylalkyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyl tri Alkoxysilane, and vinyltrialkoxysilane. Among these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable, and? -Glycidoxypropyltrialkoxysilane is more preferable. These may be used alone or in combination of two or more. These are effective for improving the adhesion with the substrate, and are also effective in adjusting the taper angle with the substrate.

The content of the (F) adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the component (A).

(G) Basic compound

The photosensitive resin composition of the present invention may contain (G) a basic compound. As the basic compound (G), any of those used in the chemically amplified resist may be selected and used. For example, aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like.

Examples of the aliphatic amine include aliphatic amines such as trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di- , Triethanolamine, 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-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8 Diazabicyclo [4.3.0] -5-nonenes, such as oximequinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4- methylmorpholine, , 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. have.

Examples of the quaternary ammonium salt of the carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate and tetra-n-butylammonium benzoate.

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

The content of the basic compound (G) in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.2 part by weight based on 100 parts by weight of the component (A).

(H) Surfactant

The photosensitive resin composition of the present invention may contain (H) a surfactant. As the surfactant (H), any of anionic, cationic, nonionic or amphoteric surfactants may be used. Preferred nonionic surfactants are nonionic surfactants.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicones, and fluorine surfactants. (Trade name) manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyowa Chemical Co., Ltd.), F-top (manufactured by JEMCO), Megapack (manufactured by DIC) (Manufactured by Sumitomo 3M Ltd.), Asahi Guard, Surfron (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like.

The surfactant preferably has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography in the case of using tetrahydrofuran (THF) as a solvent and containing the constituent unit A and the constituent unit B represented by the following formula (1) Mw) of not less than 1,000 and not more than 10,000 is a preferable example.

(41)

(Wherein R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms and R ⁴ represents a hydrogen atom or a C1- P represents an alkylene group having 3 to 6 carbon atoms, p and q represent weight percentages indicating polymerization ratios, p represents a value of 10 to 80 wt%, q represents 20 wt% Or more and 90% or less by weight, r is an integer of 1 or more and 18 or less, and n is an integer of 1 or more and 10 or less)

It is preferable that L is a branched alkylene group represented by the following formula (2). R ⁵ in the formula (2) represents an alkyl group having 1 to 4 carbon atoms, and from the viewpoints of compatibility and wettability with respect to the surface to be coated, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 2 or 3 carbon atoms is more preferable desirable. The sum (p + q) of p and q is preferably p + q = 100, i.e., 100% by weight.

(42)

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

These surfactants may be used singly or in combination of two or more.

The amount of the surfactant (H) added to 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, and most preferably 0.01 to 1 part by weight, per 100 parts by weight of the component (A) More preferable.

(I) a plasticizer

The photosensitive resin composition of the present invention may contain (I) a plasticizer. (I) plasticizers include, for example, dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerine phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.

The amount of the plasticizer (I) added to the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight, more preferably 1 to 10 parts by weight based on 100 parts by weight of the component (A).

(J) Thermal radical generator

The photosensitive resin composition of the present invention may contain (J) a thermal radical generator, and when it contains an ethylenically unsaturated compound such as a compound having at least one ethylenically unsaturated double bond as described above, (J) Containing agent. As the thermal radical generator in the present invention, a known thermal radical generator may be used.

The thermal radical generator is a compound which generates radicals by the energy of heat to initiate or promote the polymerization reaction of the polymerizable compound. The addition of the heat radical generator may make the obtained cured film stronger and improve the heat resistance and solvent resistance in some cases.

Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbimidazole compounds, ketooxime ester compounds, borate compounds, adionium compounds, metallocene compounds, active ester compounds, A compound having a bond, an azo-based compound, and a non-benzyl compound. (J) One kind of thermal radical generator may be used alone, or two or more kinds may be used in combination.

The amount of the heat radical generator (J) to be added to the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polymer (A) And most preferably 0.5 to 10 parts by weight.

<Increase / decrease>

The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with the photoacid generator (B) in order to accelerate the decomposition thereof. The sensitizer absorbs an actinic ray or radiation to become an electron-excited state. The sensitizer in the electron-excited state comes into contact with the photoacid generator to generate electron transfer, energy transfer, heat generation, and the like. As a result, the photoacid generator decomposes by chemical change to generate an acid. Examples of preferable sensitizers include compounds having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm belonging to the following compounds.

Polynuclear aromatic compounds such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- ), Xanthones (such as xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), xanthones (e. G., Fluorene, eosin, erythrosine, rhodamine B, (E.g., thiocarbocyanine, oxacarbocyanine), a merocyanine (e.g., merocyanine, carbomerocyanine), a rhodacyanine, oxonol, a thiazine (Such as thionine, methylene blue, toluidine blue), acridines (such as acridine orange, chloroflavin, acriflavine), acridones (such as acridone, (For example, anthraquinone), squarylium (for example squalium), styryls, basestirrins (for example, For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7- 2,3,6,7-Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizin-11-one).

Among these sensitizers, polynuclear aromatic compounds, acridones, styryls, base styryls and coumarins are preferable, and polynuclear aromatic compounds are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

(Method of forming a cured film)

Next, a method of forming the cured film of the present invention will be described.

The method for forming a cured film of the present invention includes the following steps (1) to (5).

(1) a coating step of applying the photosensitive resin composition of the present invention onto a substrate

(2) a solvent removing step of removing the solvent from the applied photosensitive resin composition

(3) an exposure process for exposing by an actinic ray

(4) a development step of developing with an aqueous developer

(5) Post-baking process for thermosetting

Each step will be described below in order.

(1), the photosensitive resin composition of the present invention is applied onto a substrate to form a wet film containing a solvent.

In the solvent removing step (2), the solvent is removed from the coated film by reduced pressure (bubbling) and / or heating to form a dried coating film on the substrate.

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

Post-exposure baking (hereinafter, also referred to as &quot; PEB &quot;) may be performed as needed in order to accelerate the hydrolysis reaction in the region where the acid catalyst is produced. With PEB, the generation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group can be promoted.

The acid decomposable group in the monomer unit represented by the formula (a1-1) in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator upon exposure to form a carboxyl group or a phenolic hydroxyl group Therefore, a positive image can be formed by development without necessarily performing PEB.

Further, by conducting PEB at a relatively low temperature, the hydrolysis of the acid decomposable group can be promoted without causing a crosslinking reaction. The temperature at which PEB is carried out is preferably 30 占 폚 to 130 占 폚, more preferably 40 占 폚 to 110 占 폚, and particularly preferably 50 占 폚 to 80 占 폚.

(4), a liberated carboxyl group or a copolymer having a phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing the exposed region containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.

(A1) by thermal decomposition of the acid-decomposable group in the post-baking step (5) to form a carboxyl group or phenolic hydroxyl group, and crosslinking the crosslinked group of the monomer unit (a2) . This heating is preferably performed at a high temperature of 150 ° C or higher, more preferably 180 ° C to 250 ° C, and particularly preferably 200 ° C to 250 ° C. The heating time can be appropriately set depending on the heating temperature and the like, and is preferably within a range of 10 to 90 minutes.

If a step of irradiating the entire surface with an actinic ray, preferably ultraviolet light, in a development pattern is added before the post-baking step, the crosslinking reaction can be promoted by an acid generated by actinic light irradiation.

Next, a method for forming a cured film using the photosensitive resin composition of the present invention will be described in detail.

&Lt; Preparation method of photosensitive resin composition &gt;

The essential components of (A) to (D) are mixed at a predetermined ratio and by any method, and dissolved by stirring to prepare a photosensitive resin composition. For example, it is also possible to prepare a solution in which the components (A) to (C) are each dissolved in the solvent (D) in advance, and then mix them in a predetermined ratio to prepare a resin composition. The composition solution prepared as described above may be used after being filtered using a filter having a pore size of 0.2 탆 or the like.

<Coating Process and Solvent Removal Process>

A desired dry film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by reduced pressure and / or heating (prebaking). Examples of the substrate include a polarizing plate in the production of a liquid crystal display device, a glass plate in which a black matrix layer and a color filter layer are formed if necessary, and a transparent conductive circuit layer is additionally formed. The coating method for the substrate is not particularly limited, and for example, slit coat method, spray method, roll coating method, spin coating method and the like can be used. Among them, the slit coat method is preferable from the viewpoint of being suitable for a large-size substrate. If it is manufactured by a large-sized substrate, it is preferable because productivity is high. Here, a large substrate refers to a substrate having a size of 1 m or more on each side.

(2) The heating conditions in the solvent removal step are such that the acid-decomposable group is decomposed in the monomer unit (a1) in the component (A) in the unexposed portion and the component (A) is not soluble in the alkali developing solution, But it is preferably about 80 to 130 占 폚 for about 30 to 120 seconds.

&Lt; Exposure step and development step (pattern formation method) &gt;

In the exposure step, the substrate on which the coating film is formed is irradiated with an actinic ray through a mask having a predetermined pattern. After the exposure process, the substrate is subjected to heat treatment (PEB) as required. In the development process, an exposed area is removed using an alkaline developer to form an image pattern.

(436 nm), i-line (365 nm), h-line (405 nm), and the like can be used for the exposure by the active light beam. Nm) or the like having a wavelength of 300 nm or more and 450 nm or less can be preferably used. If necessary, the irradiation light may be adjusted by passing through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

It is preferable that a developer to be used in the developing process contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Ammonium hydroxides such as sodium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydroxide, potassium hydroxide and the like; An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the aqueous alkaline solution may be used as a developer.

The pH of the developing solution is preferably 10.0 to 14.0.

The developing time is preferably 30 to 180 seconds, and the developing method may be liquid mounting, dipping or the like. After the development, water washing can be carried out for 30 to 90 seconds to form a desired pattern.

&Lt; Post baking step (crosslinking step) &gt;

For example, 180 to 250 DEG C for a predetermined time, for example, in the case of a hot plate, the pattern corresponding to the unexposed area obtained by the development is heated at a predetermined temperature, for example, from 5 to 60 (A) by dissolving the acid-decomposable group in the component (A) to generate a carboxyl group or a phenolic hydroxyl group by reacting with the crosslinkable group in the monomer unit (a2) , Hardness, and the like can be formed. When the heat treatment is carried out, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

Further, after the substrate having the pattern formed thereon is re-exposed by an actinic ray before the heat treatment, an acid is generated from the component (B) present in the unexposed portion by post-baking (re-exposure / post-baking) It is preferable to function as a catalyst for promoting the process.

That is, it is preferable that the cured film forming method of the present invention includes a re-exposure step of re-exposing by the actinic ray between the developing step and the post-baking step. The exposure in the re-exposure step may be carried out by the same means as in the above exposure step. In the re-exposure step, it is preferable to perform the entire surface exposure on the side of the substrate where the film is formed by the photosensitive resin composition of the present invention Do.

The preferable exposure amount of the re-exposure process is 100 to 1,000 mJ / cm &lt; 2 &gt;.

By the photosensitive resin composition of the present invention, an interlayer insulating film having high transparency can be obtained even when the insulating resin is excellent in bake at a high temperature. The interlayer insulating film formed using the photosensitive resin composition of the present invention is useful for an organic EL display device or a liquid crystal display device because it has high transparency and excellent physical properties of a cured film.

The organic EL display device and the liquid crystal display device of the present invention are not particularly limited except that they have a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention and various known organic EL displays Device or a liquid crystal display device.

In addition, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above-mentioned applications and can be used for various applications. For example, a protective film for a color filter, a spacer for keeping the thickness of the liquid crystal layer in a liquid crystal display device constant, or a microlens formed on a color filter in a solid-state image pickup device, in addition to a planarizing film or an interlayer insulating film .

Fig. 1 shows a configuration diagram of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.

A bottom gate type TFT 1 is formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ is formed in a state of covering the TFT 1. A wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 after forming a contact hole (not shown) in the insulating film 3. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or the subsequent steps and the TFT 1. [

The flattening layer 4 is formed on the insulating film 3 in a state of embedding unevenness by the wiring 2 in order to planarize the unevenness due to the formation of the wiring 2. [

On the flattening film 4, a bottom emission type organic EL element is formed. That is, a first electrode 5 made of ITO is formed on the planarization film 4 by being connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.

The insulating film 8 is formed so as to cover the periphery of the first electrode 5. By forming the insulating film 8, the short circuit between the first electrode 5 and the second electrode, which is formed in the subsequent step, Can be prevented.

1, a hole transporting layer, an organic light emitting layer, and an electron transporting layer are sequentially deposited by evaporation through a desired pattern mask, then a second electrode made of Al is formed on the entire surface above the substrate, An organic EL display device of an active matrix type in which an encapsulating glass plate and an ultraviolet curing type epoxy resin are used to bond each other to each other and the TFT 1 for driving each organic EL element is connected is obtained.

Fig. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. Fig. This color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on its back surface and the liquid crystal panel has TFTs (not shown) corresponding to all pixels arranged between two glass substrates 14, 16 are disposed on the substrate. In each element formed on the glass substrate, an ITO transparent electrode 19 for forming a pixel electrode is wired 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 layer of the liquid crystal 20 and a black matrix are arranged is formed.

Example

EXAMPLES The present invention will now be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.

[Synthesis Example 1: Synthesis of A-1]

(0.24 mol) of 1-n-butoxyethyl methacrylate, 21.1 g (0.12 mol) of benzyl methacrylate, 30.9 g (0.36 mol) of methacrylic acid, and 300 mL of methyl isobutyl ketone were placed in a 500 mL three- And a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) as a radical polymerization initiator was added thereto, followed by polymerization in a nitrogen stream at 70 ° C for 6 hours. Subsequently, 71 g (0.5 mol) of glycidyl methacrylate and 1 g of dimethylbenzylamine were added, and the mixture was stirred at 70 캜 for 4 hours. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in propylene glycol monomethyl ether acetate, and heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A-1 as a 50 wt% solution of propylene glycol monomethyl ether acetate .

(43)

[Synthesis Example 2: Synthesis of A-2]

47.5 g (0.3 mol) of 1-ethoxyethyl methacrylate, 25.6 g (0.18 mol) of glycidyl methacrylate, 21.2 g (0.12 mol) of benzyl methacrylate and 300 ml of methyl isobutyl ketone were dissolved in 500 ml of 3 And a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) as a radical polymerization initiator was added thereto, followed by polymerization in a nitrogen stream at 70 ° C for 6 hours. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol dimethyl ether, and heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A-2 (1-ethoxyethyl methacrylate / Cidyl / benzyl methacrylate) as a 50 wt% solution of diethylene glycol dimethyl ether.

The composition ratio of the 1-ethoxyethyl methacrylate unit, the glycidyl methacrylate unit and the benzyl methacrylate unit of the obtained polymer was about 50:30:20 from the NMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 7,000 and the molecular weight distribution (Mw / Mn) was 1.7.

(44)

[Synthesis Example 3: Synthesis of A-3]

(0.36 mol) of 1-benzyloxyethyl methacrylate, 23.1 g (0.18 mol) of glycidyl acrylate, 7.8 g (0.06 mol) of 2-hydroxyethyl methacrylate and 300 mL of methyl isobutyl ketone were added to 500 mL , And a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) as a radical polymerization initiator was added thereto, followed by polymerization in a nitrogen stream at 70 ° C for 6 hours. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A-3 (1-benzyloxyethyl methacrylate / glycidyl acrylate Dile / 2-hydroxyethyl methacrylate) as a 50 wt% solution of diethylene glycol ethyl methyl ether.

The composition ratio of the 1-benzyloxyethyl methacrylate unit, the glycidyl acrylate unit and the 2-hydroxyethyl methacrylate unit of the obtained polymer was about 60:30:10 from the NMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 10,000 and the molecular weight distribution (Mw / Mn) was 1.8.

[Chemical Formula 45]

[Synthesis Example 4: Synthesis of A-4]

43.3 g (0.3 mol) of 1-ethoxyethyl acrylate, 25.6 g (0.18 mol) of glycidyl methacrylate, 21.2 g (0.12 mol) of benzyl methacrylate and 300 ml of methyl isobutyl ketone were placed in a 500 ml three- And a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) as a radical polymerization initiator was added thereto, followed by polymerization in a nitrogen stream at 70 ° C for 6 hours. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in propylene glycol monomethyl ether acetate, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A-4 (1-ethoxyethyl acrylate / glycidyl methacrylate Dl / benzyl methacrylate) as a 50 wt% solution of propylene glycol monomethyl ether acetate.

The composition ratio of the 1-ethoxyethyl acrylate unit, glycidyl methacrylate unit and benzyl methacrylate unit of the obtained polymer was about 50:30:20 from NMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 8,000 and the molecular weight distribution (Mw / Mn) was 1.7.

(46)

[Synthesis Example 5: Synthesis of A-5]

(0.38 mol) of 1-cyclohexyloxyethyl methacrylate, 35.3 g (0.18 mol) of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100, manufactured by Daicel Chemical Industries, Ltd.) 7.8 g (0.06 mol) of 2-hydroxyethyl and 300 ml of methyl isobutyl ketone were placed in a 500 ml three-necked flask, and a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate ), And the mixture was polymerized at 70 DEG C for 6 hours under a nitrogen stream. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol dimethyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain Polymer A-5 (1-cyclohexyloxyethyl methacrylate / 3,4 -Epoxycyclohexylmethyl methacrylate / 2-hydroxyethyl methacrylate) as a 50 wt% solution of diethylene glycol dimethyl ether.

The composition ratio of 1-cyclohexyloxyethyl methacrylate unit, 3,4-epoxycyclohexylmethyl methacrylate unit and 2-hydroxyethyl methacrylate unit of the obtained polymer was about 60:30:10 from NMR measurement . As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 6,000 and the molecular weight distribution (Mw / Mn) was 1.8.

(47)

[Synthesis Example 6: Synthesis of A-6]

57.7 g (0.36 mol) of 2-tetrahydropyranyl methacrylate, 31.7 g (0.18 mol) of p-vinylphenylglycidyl ether, 7.8 g (0.06 mol) of 2-hydroxyethyl methacrylate, 300 ml was injected into a 500 ml three-necked flask, and a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) was added thereto as a radical polymerization initiator, followed by polymerization in a nitrogen stream at 70 ° C for 6 hours . The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A-6 (2-tetrahydropyranyl methacrylate / p- Vinyl phenyl glycidyl ether / 2-hydroxyethyl methacrylate) as a 50 wt% solution of diethylene glycol ethyl methyl ether.

The composition ratio of the 2-tetrahydropyranyl methacrylate unit, the p-vinylphenylglycidyl ether unit and the 2-hydroxyethyl methacrylate unit of the obtained polymer was about 60:30:10 from the NMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 7,000 and the molecular weight distribution (Mw / Mn) was 1.8.

(48)

[Synthesis Example 7: Synthesis of A-7]

, Methacrylic acid (5.2 g, 0.06 mole), and methyl (3-methylphenyl) methacrylate were dissolved in a mixture of 38.0 g (0.24 mol) of 1-ethoxyethyl methacrylate, 21.3 g (0.15 mol) of glycidyl methacrylate, Azobis (2-methylpropionate) as a radical polymerization initiator was added to the flask, and the mixture was stirred at 70 占 폚 for 6 Lt; / RTI &gt; The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in a mixed solvent of propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether, and heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A-7 Acid 1-ethoxyethyl / glycidyl methacrylate / benzyl methacrylate / methacrylic acid) as a 50% by weight solution of a mixed solvent of propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether.

The composition ratio of the 1-ethoxyethyl methacrylate unit, the glycidyl methacrylate unit, the benzyl methacrylate unit, and the methacrylic acid of the obtained polymer was about 40:25:25:10 as measured by NMR. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 7,000 and the molecular weight distribution (Mw / Mn) was 1.7.

(49)

[Synthesis Example 8: Synthesis of A-8]

(0.18 mol) of methacrylic acid (1-ethyl-3-oxacyclobutyl) methyl, 21.2 g (0.12 mol) of benzyl methacrylate, and 47.5 g (0.3 mol) of 1-ethoxyethyl methacrylate, Azobis (methyl 2-methylpropionate) as a radical polymerization initiator was added to the flask, and the mixture was stirred at 70 ° C for 6 hours Lt; / RTI &gt; The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol dimethyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A-8 (1-ethoxyethyl methacrylate / Ethyl-3-oxacyclobutyl) methyl / benzyl methacrylate) as a 50 wt% solution of diethylene glycol dimethyl ether.

The composition ratio of the 1-ethoxyethyl methacrylate unit, the methacrylic acid (1-ethyl-3-oxacyclobutyl) methyl unit and the benzyl methacrylate unit of the obtained polymer was about 50:30:20 from NMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 8,000 and the molecular weight distribution (Mw / Mn) was 1.7.

(50)

[Synthesis Example 9: Synthesis of A-9]

A-5 was synthesized in the same manner as in A-5 except that the amount of the polymerization initiator was reduced.

As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 25,000 and the molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis Example 10: Synthesis of A-10]

A-8 was synthesized in the same manner as in A-8 except that the amount of the polymerization initiator was reduced.

As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 35,000 and the molecular weight distribution (Mw / Mn) was 1.9.

[Synthesis Example 11: Synthesis of A-11]

0.4 mol of 1-ethoxyethyl methacrylate, 0.6 mol of glycidyl methacrylate, and 300 mL of methyl isobutyl ketone were charged in a 500 mL three-necked flask, and a catalytic amount of 2,2'- Azobis (methyl 2-methylpropionate) was added, and polymerization was carried out at 70 占 폚 for 6 hours under a nitrogen stream.

Next, 0.4 mol of glycidyl methacrylate and 1 g of dimethylbenzylamine were added, and the mixture was stirred at 60 캜 for 4 hours. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol dimethyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A-11 as a 50 wt% solution of diethylene glycol dimethyl ether. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 8,000 and the molecular weight distribution (Mw / Mn) was 1.8.

(51)

[Synthesis Example 12: Synthesis of A-12]

47.5 g (0.3 mole) of 1-ethoxyethyl methacrylate, 25.6 g (0.18 mole) of glycidyl methacrylate, 0.12 mole of t-butyl methacrylate and 300 ml of methyl isobutyl ketone were placed in a 500 ml three- And a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) as a radical polymerization initiator was added thereto, followed by polymerization in a nitrogen stream at 70 ° C for 6 hours. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol dimethyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A-12 as a 50 wt% solution of diethylene glycol dimethyl ether.

As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 7,000 and the molecular weight distribution (Mw / Mn) was 1.7.

(52)

[Synthesis of phenol 1 (4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester]

To a solution of 21 g of 4-hydroxybenzoic acid (2-hydroxyethyl) ester in 100 ml of acetonitrile, 20 ml of N, N-dimethylacetamide was added with stirring, and further 20 g of methacrylic acid chloride was added . The reaction mixture was poured into ice water and the precipitated crystals were collected by filtration and recrystallized from ethyl acetate / n-hexane to give 4-hydroxybenzoic acid (2-methacryloyloxy Ethyl) ester.

[Synthesis of phenol 2 (4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester]

To a solution of 23 g of 4-hydroxybenzoic acid (3-hydroxypropyl) ester in 100 ml of acetonitrile, 20 ml of N-methylpyrrolidone was added with stirring, and further 16 g of methacrylic acid chloride was added. The reaction mixture was poured into ice water and the precipitated crystals were collected by filtration and recrystallized from ethyl acetate / n-hexane to give 4-hydroxybenzoic acid (3-methacryloyloxy Propyl) ester.

[Synthesis of phenol 3 (4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester]

100 g of p-hydroxybenzoic acid, 100 g of glycidyl methacrylate, and 9.7 g of tetrabutylammonium bromide were added to a 250 ml solution of N-methylpyrrolidone and reacted at 90 DEG C for 6 hours with stirring, The mixture was poured into a water / ethyl acetate mixed solvent and the precipitated crystals were collected by filtration and recrystallized from ethyl acetate / n-hexane to give 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) .

[Synthesis of protected phenol]

Phenol 1, 2, and 3 were reacted with ethyl vinyl ether, respectively, with an acid catalyst to obtain an ethyl acetal protective group (protective phenol 1, 2, 3) of a phenolic hydroxyl group.

[Synthesis Example 13: synthesis of A-13]

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

[Synthesis Example 14: Synthesis of A-14]

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

[Synthesis Example 15: Synthesis of A-15]

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

[Synthesis Example 16: Synthesis of A-16]

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

[Synthesis Example 17: Synthesis of A-17]

A three-necked flask was charged with 12.4 g of propylene glycol monomethyl ether acetate (PGMEA), and the temperature was raised to 70 占 폚 under a nitrogen atmosphere. To this solution, 0.603 g of methacrylic acid (MAA), 1.821 g of 2-hydroxyethylmethacrylate (HEMA), 4.373 g of methacrylic acid tetrahydrofuran-2-ylmethacrylate (OXE- 30, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 1.217 g (7 mol% based on the monomer) of V-65 (polymerization initiator, Wako Pure Chemical Industries, Ltd.) were dissolved in 12.4 g of PGMEA, / RTI &gt; After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. The weight average molecular weight was 6,500. The molecular weight distribution (Mw / Mn) was 1.7.

(53)

[Synthesis Example 18: Synthesis of A-18]

32.75 g of propylene glycol monomethyl ether acetate (PGMEA) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 under a nitrogen atmosphere. To the solution was added 1.54 g of methacrylic acid (MAA), 5.20 g of 2-hydroxyethyl methacrylate (HEMA), 12.80 g of methacrylic acid tetrahydrofuran-2-yl (MATHF), glycidyl methacrylate ) And 3.477 g (7 mol% based on the monomer) of V-65 (polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in PGMEA (32.75 g) and added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. The weight average molecular weight was 7,100. The molecular weight distribution (Mw / Mn) was 1.4.

(54)

The MATHF used in Synthesis Examples A-17 and A-18 was synthesized as follows.

&Lt; Synthesis of MATHF (tetrahydrofuran-2-yl methacrylate)

Methacrylic acid (86 g, 1 mol) was cooled to 15 DEG C and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2,3-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, a saturated aqueous sodium hydrogen carbonate solution (500 ml) was added, extracted with ethyl acetate (500 ml), dried over magnesium sulfate, The yellow oily phase was distilled under reduced pressure to obtain 125 g of methacrylic acid tetrahydrofuran-2-yl methacrylate (MATHF) having a boiling point (bp.) Of 54 to 56 ° C / 3.5 mmHg as a colorless oily product 80%).

[Synthesis Example 19: Synthesis of A-19]

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

(55)

[Synthesis Example 20: Synthesis of A-20]

A-20 was synthesized in the same manner as in the synthesis of A-20, except that styrene was further added as a monomer.

(56)

[Synthesis Example 21: Synthesis of B10]

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 ml), and the mixture was heated to 40 캜 for reaction for 2 hours . Under ice cooling, 4N HCl aqueous solution (60 ml) was added dropwise to the reaction solution, and ethyl acetate (50 ml) was added to separate the layers. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 占 폚 for 1 hour. 2N HCl aqueous solution (60 ml) was added to the mixture to separate the layers. The organic layer was concentrated and the crystals were dissolved in diisopropyl ether Slurry, filtered, and dried to obtain a ketone compound (6.5 g).

Acetic acid (7.3 g) and a 50% by weight hydroxylamine aqueous solution (8.0 g) were added to the resulting suspension of the ketone compound (3.0 g) and methanol (30 ml), and the mixture was heated to reflux. After cooling, water (50 ml) was added, and the precipitated crystals were filtered, washed with cold methanol, and then dried to obtain an oxime compound (2.4 g).

The resulting oxime compound (1.8 g) was dissolved in acetone (20 ml), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and the mixture was allowed to react at room temperature for 1 hour. Water (50 ml) was added to the reaction solution, and the precipitated crystals were filtered out and then slurry was rinsed with methanol (20 ml), followed by filtration and drying to obtain B10 (2.3 g).

(57)

[Synthesis Example 22: Synthesis of B11]

1-1. Synthesis of Synthetic Intermediate B11-A

31.3 g (manufactured by Tokyo Chemical Industry Co., Ltd.) of 2-aminobenzenethiol was dissolved in 100 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 占 폚). Then, 40.6 g of phenylacetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was reacted by stirring at room temperature for 1 hour and then at 100 DEG C for 2 hours. To the reaction solution obtained, 500 ml of water was added to dissolve the precipitated salt, the toluene oil fraction was extracted, and the extract was concentrated with a rotary evaporator to obtain a synthetic intermediate B11-A.

1-2. Synthesis of B11

2.25 g of the thus-obtained synthetic intermediate B11-A was mixed with 10 ml of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), immersed in an ice bath, and the reaction solution was cooled to 5 캜 or lower. Next, 4.37 g of tetramethylammonium hydroxide (25% by weight methanol solution, manufactured by Alfa Acer) was added dropwise, and the mixture was reacted with stirring on ice for 0.5 hour. 7.03 g of isopentyl acetate was added dropwise while keeping the internal temperature at 20 ° C or lower. After completion of dropwise addition, the reaction solution was warmed to room temperature and stirred for 1 hour.

Subsequently, the reaction solution was cooled to 5 占 폚 or lower, p-toluenesulfonyl chloride (1.9 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto, and the mixture was stirred for 1 hour while maintaining the temperature below 10 占 폚. Then, 80 ml of water was added thereto, and the mixture was stirred at 0 ° C for 1 hour. The resultant precipitate was filtered, and 60 ml of isopropyl alcohol (IPA) was added. The mixture was heated to 50 占 폚, stirred for 1 hour, filtered and dried (B11: the above structure).

From the ¹ H-NMR measurement results, it is estimated that the obtained B11 is a single geometric isomer.

(58)

(Example 1)

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

&Lt; Evaluation of sensitivity &

The photosensitive resin composition of the present invention was slit-coated on a silicon wafer having a silicon oxide film, followed by vacuum drying to form a coating film having a thickness of 3 占 퐉.

Next, using an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.), exposure was performed through a predetermined mask. Mounted on a solution at 23 deg. C for 65 seconds with an alkali developing solution (2.38 wt% tetramethylammonium hydroxide aqueous solution), and rinsed with ultrapure water for 1 minute. By these operations, the optimum exposure amount at the time of resolving the line-and-space of 5 mu m to 1: 1 was determined as the sensitivity. From the viewpoint of productivity, the optimum exposure dose is preferably 50 mJ / cm 2 or less, more preferably 20 mJ / cm 2 or less.

&Lt; Evaluation of residual film ratio at the time of development &

Further, the film thickness of the unexposed portion after development was measured, and the ratio of the film thickness after coating (unexposed film thickness after development divided by film thickness after coating 100 (%)) was evaluated to evaluate the remaining film ratio at the time of development . Any of the embodiments has a residual film ratio of 99% or more, and a clear pattern can be formed.

&Lt; Evaluation of Formability of Contact Hole &gt;

A coating film having a thickness of 3.0 mu m was formed on a silicon wafer in the same manner as described above. Next, an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.) was used to expose a pattern having a punching pattern having a diameter of 10 mu m corresponding to the contact hole through the predetermined mask at the optimum exposure dose.

Development and rinsing were carried out in the same manner as described above to form a contact hole pattern. Here, the diameter of the bottom of the formed contact hole was measured by an electron microscope. The coated film after the development in which the contact holes were formed was irradiated with light of 500 mJ / cm 2 at a wavelength of 365 nm using an ultra-high pressure mercury lamp, and then heated in an oven at 220 캜 for 60 minutes. Here, the diameter of the bottom of the contact hole was measured in the same manner as described above.

In this evaluation, the difference between the two measured values measured before and after the heating with respect to the diameter of the bottom of the formed contact hole was evaluated as &quot;? &Quot; The smaller the difference in diameter before and after the heating, the better the control of the diameter of the contact hole is.

<Transmittance>

In the evaluation of the contact hole, the entire surface-cured film was obtained in the same manner as in the evaluation of the contact hole except that the substrate was changed to glass and the final heat treatment was performed at 220 캜 for 90 minutes without pattern exposure.

The transmittance of the cured film was measured at a wavelength of 400 to 800 nm using a spectrophotometer (U-3000, manufactured by Hitachi, Ltd.). The lowest transmittance is shown in Tables 1 to 5. The minimum transmittance is preferably 90% or more, and more preferably 95% or more.

<ITO sputter suitability>

The cured film after the final heat treatment was obtained in the same manner as in the evaluation of the transmittance. On this cured film, an ITO transparent electrode was formed by sputtering (SIH-3030, manufactured by ULVAC, sputtering temperature: 200 占 폚). The surface of the cured film after the sputtering was observed with an optical microscope (500 times) and evaluated according to the following criteria.

◎: No wrinkles on the surface of the cured film at all

○: Some wrinkles appear on the surface of the cured film (allowable range)

X: Wrinkles occur on the surface of the cured film

When wrinkles are observed on the surface of the cured film after the ITO transparent electrode is formed by sputtering, the transmittance of the cured film is lowered, which is undesirable.

(Examples 2 to 113 and Comparative Examples 1 to 22)

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

The abbreviations in Tables 1 to 5 are as follows.

Component (B)

B1: IRGACURE PAG 103 (manufactured by Chiba Specialty Chemicals)

B2: IRGACURE PAG 108 (manufactured by Chiba Specialty Chemicals)

B3: CGI 1380 (manufactured by Chiba Specialty Chemicals)

B4: IRGACURE PAG 121 (manufactured by Chiba Specialty Chemicals)

B5: CGI 725 (manufactured by Chiba Specialty Chemicals)

B6: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

B7:? - [(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (PAI-1001, manufactured by Midori Kagaku Co., Ltd.)

B8:? - (4-Toluenesulfonyloxyimino) benzyl cyanide (synthesized according to the method described in paragraph 0108 of Japanese Unexamined Patent Publication No. 2002-528451)

B9:? - [(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (PAI-101, manufactured by Midori Kagaku Co., Ltd.)

B10: The oxime sulfonate compound

B11: The oxime sulfonate compound

[Chemical Formula 59]

(C) Component

AO60: Adecastab AO-60 (manufactured by ADEKA Corporation)

AO70: Adecastab AO-70 (manufactured by ADEKA Corporation)

AO80: Adecastab AO-80 (manufactured by ADEKA Corporation)

AO30: adecastab AO-30 (1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenol) butane manufactured by ADEKA)

AO330: adecastab AO-330 (1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene manufactured by ADEKA)

1098: Irganox 1098 (manufactured by Chiba Specialty Chemicals)

TP-D: Sumilizer TP-D (sulfur-based antioxidant manufactured by Sumitomo Chemical Co., Ltd.)

LA-62: Adecastab LA-62 (amine antioxidant manufactured by ADEKA Co., Ltd.)

PEP-36: adecastab PEP-36 (manufactured by ADEKA, Inc., phosphorus-based antioxidant)

Table 6 summarizes the molecular weight of the component (C), the presence or absence of an ester group or an amide group.

(60)

(Basic compound)

D1: 4-dimethylaminopyridine

D2: 1,5-Diazabicyclo [4.3.0] -5-nonene

(Crosslinking agent)

MX-270: NIKARAK MX-270 (manufactured by Sanwa Chemical Co., Ltd.)

JER157S70: JER157S70 manufactured by Japan Epoxy Resin Co., Ltd.

(61)

(Adhesive agent)

KBM403: silane coupling agent KBM403 manufactured by Shin-Etsu Chemical Co.,

(62)

(Surfactants)

F780F: fluorochemical surfactant F780F manufactured by DIC Co., Ltd.

PF6320: PolyFox PF-6320 (manufactured by OMNOVA)

W-3: The following compound

(63)

Comparison of Examples and Comparative Examples, in particular, comparison of Comparative Examples 1 to 10 and Examples 18 and 23 to 29: The transmittance was remarkably improved only when a specific phenol compound (C) was added as the component (C). This effect was more remarkable as the molecular weight of a specific phenolic compound was larger and the addition amount was larger.

Comparison of Examples and Comparative Examples 11 to 14: The case of containing (a1) was highly sensitive.

Comparative Example 10 Except for (a2), the film strength required for the interlayer insulating film was not obtained.

Comparison of Examples 1 to 3 and Examples 8 to 10, Examples 4 to 6, and Examples 11, 15, and 18: Onium salt-based photoacid generators containing an oxime sulfonate residue represented by formula (b1) And it was found that the sensitivity was higher than that.

Comparison of Examples 1 to 3 and Examples 4 to 6, Examples 8 to 10, and Examples 11, 15, and 18: It was found that the crosslinking agent is effective for improving the film strength (ITO sputter suitability).

Comparison of Examples 1 to 45 and Examples 46 to 79: In Examples 46 to 79, the component (B) was changed to B10 and the basic compound was increased in comparison with Examples 1 to 45. It can be seen that Examples 46 to 79 can be made particularly sensitive to use Compound B10 represented by the formula (OS-3) because the sensitivity is equal to or higher than that of Examples 1 to 45.

(Examples a to c and l, and Comparative Examples d to k, m and n)

<Measurement of Permittivity>

A cured film after the final heat treatment was obtained in the same manner as in the evaluation of the transmittance except that the substrate was changed to a bare wafer (N type low resistance) (manufactured by SUMCO). The relative dielectric constant of this cured film was measured using CVmap92A (manufactured by Four Dimensions Inc.) at a measurement frequency of 1 MHz. As shown in Table 7, the difference in dielectric constant was measured to confirm the effect of reducing the dielectric constant by the specific phenol compound (C).

The specific dielectric constant decreased only when the component (A) and the specific phenol compound (C) were used in combination. This effect was more remarkable as the amount added was larger and the molecular weight was larger.

In Comparative Example h and Comparative Example i, since the monomer unit (a1) was absent in the resin component, the relative dielectric constant did not decrease even when the specific phenol compound (C) was contained.

(Example 114)

Using the photosensitive resin composition of Example 74, the same evaluations as those of Example 74 were carried out using a UV-LED light source exposure apparatus instead of an ultra-high pressure mercury lamp. As a result, the same results as in Example 74 were obtained.

(Example 115)

An organic EL display device using a thin film transistor (TFT) was produced by the following method (see Fig. 1).

A bottom gate type TFT 1 was formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ was formed in a state of covering the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 . This wiring 2 is for connecting the organic EL element formed between the TFTs 1 or the subsequent steps and the TFT 1. [

In order to planarize the irregularities due to the formation of the wirings 2, the planarization layer 4 was formed on the insulating film 3 in the state of embedding the irregularities by the wirings 2. [ The planarizing film 4 was formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 18 on a substrate, pre-baking (90 占 폚 for 2 minutes) on a hot plate, (365 nm) was irradiated with 45 mJ / cm 2 (illuminance: 20 mW / cm 2) using a mercury lamp, and then developed with an aqueous alkaline solution to form a pattern and subjected to heat treatment at 230 ° C. for 60 minutes. The coating property when the photosensitive resin composition was applied was good, and wrinkles and cracks were not observed in the cured film obtained after exposure, development and firing. The mean step of the wiring 2 was 500 nm, and the thickness of the planarization film 4 was 2,000 nm.

Next, a bottom emission type organic EL device was formed on the obtained flattening film 4. Then, First, a first electrode 5 made of ITO was formed on the flattening film 4 by connecting it to the wiring 2 through the contact hole 7. Thereafter, the resist was applied, pre-baked, exposed through a mask of a desired pattern, and developed. Using this resist pattern as a mask, patterning was carried out by wet etching using ITO etchant. Thereafter, the resist pattern was peeled off using a resist stripping solution (a mixture of monoethanolamine and dimethyl sulfoxide (DMSO)). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film, the insulating film 8 was formed in the same manner as above using the photosensitive resin composition of Example 7. By forming this insulating film, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent step.

Further, a hole transporting layer, an organic light emitting layer, and an electron transporting layer were sequentially deposited by vapor deposition in a vacuum deposition apparatus through a desired pattern mask. Subsequently, a second electrode made of Al was formed on the entire surface above the substrate. The obtained substrate was taken out from the evaporator, and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an active matrix type organic EL display device in which TFTs 1 for driving the organic EL elements are connected to each organic EL element was obtained. As a result of applying a voltage through the driving circuit, it was found that the organic EL display device exhibits good display characteristics and is highly reliable.

(Example 116)

An organic EL device was prepared in the same manner as in Example 115 except that the photosensitive resin composition of Example 7 was changed to the photosensitive resin composition of Example 74. [ The organic EL display device exhibits good display characteristics and is highly reliable.

(Example 117)

An organic EL device was prepared in the same manner as in Example 115 except that the photosensitive resin composition of Example 7 was changed to the photosensitive resin composition of Example 108. [ The organic EL display device exhibits good display characteristics and is highly reliable.

(Example 118)

In the active matrix type liquid crystal display device shown in Figs. 1 and 2 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film in the following manner, and a liquid crystal display device of Example 118 was obtained.

That is, the cured film 17 was formed as an interlayer insulating film in the same manner as the method for forming the planarization film 4 of the organic EL display device in Example 115, using the photosensitive resin composition of Example 19.

As a result of applying the driving voltage to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibited good display characteristics and was highly reliable.

(Example 119)

A liquid crystal display device was prepared in the same manner as in Example 118 except that the photosensitive resin composition of Example 19 was changed to the photosensitive resin composition of Example 74. The liquid crystal display device exhibits good display characteristics and is a highly reliable liquid crystal display device.

(Example 120)

A liquid crystal display device was prepared in the same manner as in Example 118 except that the photosensitive resin composition of Example 18 was changed to the photosensitive resin composition of Example 108. The liquid crystal display device exhibits good display characteristics and is a highly reliable liquid crystal display device.

1: TFT (thin film transistor)
2: Wiring
3: Insulating film
4: Planarizing film
5: First electrode
6: glass substrate
7: Contact hole
8: Insulating film
10: Liquid crystal display
12: Backlight unit
14, 15: glass substrate
16: TFT
17:
18: Contact hole
19: ITO transparent electrode
20: liquid crystal
22: Color filter

Claims (15)

(A) a copolymer containing a monomer unit having a carboxyl group protected by an acid-decomposable group or a monomer unit (a1) having a phenolic hydroxyl group protected by an acid-decomposable group and a monomer unit (a2)
(B) a photoacid generator that generates an acid having a pKa of 3 or less,
(C) a compound having at least two partial structures represented by formula (c1) in the molecule and having a molecular weight of 600 or more and 2,000 or less, and
(D) a solvent.
[Chemical Formula 1]

(In the formula (c1), R ¹ and R ² each independently represents a methyl group or a tert-butyl group, at least one of R ¹ and R ² is a tert-butyl group, R ³ is -O- or -NH- ) The method according to claim 1,
A photosensitive resin composition which is a chemically amplified positive type photosensitive resin composition. 3. The method according to claim 1 or 2,
Wherein the compound (C) is at least one compound selected from the group consisting of compounds represented by formulas (c1-1), (c1-2) and (c1-3).
(2)

3. The method according to claim 1 or 2,
Wherein the compound (C) is a compound represented by the formula (c1-1).
(3)

3. The method according to claim 1 or 2,
Wherein the photoacid generator (B) is a compound containing an oxime sulfonate residue represented by formula (b1).
[Chemical Formula 4]

(In the formula (b1), R ⁵ represents an alkyl group, a cycloalkyl group or an aryl group) 3. The method according to claim 1 or 2,
Wherein the photoacid generator (B) is a compound represented by formula (OS-3), formula (OS-4) or formula (OS-5).
[Chemical Formula 5]

(Formula (OS-3) ~ formula (OS-5) of, R ¹ is an alkyl group, an aryl group or a heteroaryl group, R ² are each independently a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ (OS-3) and (OS-3) independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, OS-4), m represents an integer of 0 to 6, and m in the formula (OS-5) represents an integer of 0 to 4) 3. The method according to claim 1 or 2,
Wherein the photoacid generator (B) is a compound represented by the formula (b2).
[Chemical Formula 6]

(In the formula (b2), R ⁵ represents an alkyl group, a cycloalkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m represents an integer of 0 to 3, and when m is 2 or 3, May be the same or different from each other) 3. The method according to claim 1 or 2,
(E) a crosslinking agent. 3. The method according to claim 1 or 2,
Wherein the monomer unit (a2) having a crosslinking group contains at least one member selected from the group consisting of a cyclic ether residue of a three-membered ring or a four-membered ring, and an ethylenic unsaturated group. (1) a coating step of applying the photosensitive resin composition according to claim 9 onto a substrate,
(2) a solvent removing step of removing the solvent from the applied photosensitive resin composition,
(3) an exposure process for exposing with active radiation,
(4) a development process for developing with an aqueous developer, and
(5) a post-baking step of thermally curing the cured film. 11. The method of claim 10,
And a step of exposing the entire surface after the development step and before the post-baking step. A cured film formed by the forming method according to claim 10. 13. The method of claim 12,
A cured film which is an interlayer insulating film. An organic EL display device comprising the cured film according to claim 12. A liquid crystal display device comprising the cured film according to claim 12.

Images