KR101650903B1 - Photosensitive resin composition, method for forming cured film, cured film, organic el display device, and liquid crystal display device - Google Patents

Abstract

A cured film having a high transmittance after curing and a small decrease in transmittance even when heated can be obtained and a photosensitive resin composition having extremely high sensitivity can be provided even when PEB is not performed. Wherein the composition comprises (A) an acetal resin, (B) a photoacid generator, and (C) a solvent, wherein the acetal resin (A) has a structure having a structure in which a carboxy group is produced by an acid (A1), a structural unit (a2) having a carboxyl group or a phenolic hydroxyl group, a structural unit (a3) having an epoxy group or an oxetanyl group, and a structural unit (a4) having a hydroxyl group or an alkyleneoxy group, (A2): (a3) :( a4) = 0.2 to 0.65: 0.02 to 0.2: 0.2 to 0.6: 0.005 to 0.3 in terms of molar ratio, (A4) in the acetal-based resin is in the range of 3 to 30 mass%.

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,

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

In an organic EL display device, a liquid crystal display device, or the like, a patterned interlayer insulating film is provided. In forming this interlayer insulating film, a photosensitive resin composition is widely used in that the number of steps for obtaining a required pattern shape is small, and furthermore, sufficient flatness is obtained.

The interlayer insulating film in the display device is required to have high transparency in addition to physical properties of a cured film which is excellent in insulating property, solvent resistance, heat resistance, and indium tin oxide (ITO) sputter suitability. For this reason, it has been attempted to use an acrylic resin having excellent transparency as a film forming component.

On the other hand, as an optical system material of an optical system or an optical fiber connector of an on-chip color filter such as a facsimile, an electronic copying machine, or a solid-state imaging element, a micro lens having a lens diameter of about 3 m to 100 m, A lens array is used.

In order to form a microlens or a microlens array, a method in which a resist pattern corresponding to a lens is formed and then subjected to a heat treatment to perform a melt flow to use it as a lens or a dry etching process using a lens pattern to be subjected to a melt flow as a mask, And a method of transferring a shape are known. For the formation of the lens pattern, a radiation-sensitive resin composition is widely used.

(A) an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, (b) a radically polymerizable compound having an epoxy group, and (c) a A resin soluble in an aqueous alkali solution, which is a copolymer of a radically polymerizable compound, and (B) a radiation-sensitive (radiation sensitive) acid-generating compound.

Japanese Patent Application Laid-Open No. 2004-264623 discloses a high molecular weight material having (A) an acetal structure and / or a ketal structure and an epoxy structure and having a weight average molecular weight of 2000 or more as measured by gel permeation chromatography, and (B A radiation-sensitive resin composition containing a compound capable of generating an acid having a pKa of 4.0 or less by irradiation with radiation has been proposed.

Japanese Patent Application Laid-Open No. 2009-98616 discloses a resin composition containing (A) a structural unit having a specific structure containing an acid-dissociable group and a structural unit having a functional group capable of reacting with a carboxyl group to form a covalent bond, A positive photosensitive resin composition containing at least a resin that is insoluble or alkali-sparingly soluble and becomes alkali-soluble when the acid-dissociable group is decomposed, and (B) a compound that generates an acid upon irradiation with an actinic ray or radiation, .

The photosensitive resin composition described in Japanese Patent Application Laid-Open No. 5-165214 does not have sufficient sensitivity and stability over time, and the cured film obtained by the photosensitive resin composition has a problem of large coloring due to bake .

Further, even in the photosensitive resin compositions described in JP-A-2004-264623 and JP-A-2009-98616, sufficient sensitivity was not obtained.

It is an object of the present invention to provide a cured film having a high transmittance after curing and a small decrease in transmittance even when heated, and a photosensitive resin composition having a very high sensitivity even when heating (PEB: post exposure baking) And the like.

It is another object of the present invention to provide a cured film using the photosensitive resin composition of the present invention and a method for producing the same, an organic EL display device provided with the cured film, and a liquid crystal display device.

An aspect of the present invention is described below.

<1> A photosensitive resin composition containing (A) an acetal resin, (B) a photoacid generator, and (C)

(A3) having a carboxyl group or a phenolic hydroxyl group, a structural unit (a3) having an epoxy group or an oxetanyl group, a structural unit (a1) having a structure capable of forming a carboxyl group by an acid, , And a structural unit (a4) having a hydroxyl group or an alkyleneoxy group, and having an acetal structure or a ketal structure,

Wherein the content ratio of the structural units (a1) to (a4) in the acetal-based resin (A) is in the molar ratio of the acetal-based resin (A) (A2): structural unit (a3): structural unit (a4) = 0.2 to 0.65: 0.02 to 0.2: 0.2 to 0.6: 0.005 to 0.3,

The content of the structural unit (a4) in the acetal-based resin (A) is in the range of 3 to 30 mass% based on mass.

&Lt; 2 > The positive photosensitive composition as described in any one of (1) to (3), further comprising (M) a development accelerator and the (M) development accelerator having at least one structure selected from a carboxyl group, a phenolic hydroxyl group, &Lt; 1 >.

<3> The photosensitive resin composition according to <1> or <2>, further comprising (E) a crosslinking agent.

<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the photoacid generator (B) is an oxime sulfonate compound.

(5) The photo-acid generator (B) is at least one selected from compounds represented by the following formulas (OS-3), OS-4 and OS- The photosensitive resin composition according to any one of < 1 > to < 4 &

In the general formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, and the plurality of R ^{2 s} present each independently represent a hydrogen atom, an alkyl group, R ⁶ represents a halogen atom, 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, and n represents 1 or 2, and m represents an integer of 0 to 6;

<6> The photosensitive resin composition according to any one of <1> to <5>, further containing (N) a sensitizer.

<7> The resin composition according to <7>, wherein the structural unit (a3) in the acetal-based resin is at least one selected from the group consisting of acrylic acid (3-ethyloxetan- Methyl group, or a methyl group. The photosensitive resin composition according to any one of < 1 > to &lt; 6 &gt;

<8> The photosensitive resin composition according to any one of <1> to <7>, further comprising (F) an adhesion improver.

<9> The photosensitive resin composition according to any one of <1> to <8>, further comprising (G) a basic compound.

<10> The photosensitive resin composition according to any one of <1> to <9>, further comprising a fluorine-based surfactant or a silicon-based surfactant.

Further, since the photosensitive resin composition of the present invention has the above-described constitution, the curing sensitivity is high, and a pattern of a good shape is formed on the cured film after exposure without performing a heat treatment. In addition, when the microlenses are formed by using them, there is an advantage that a microlens having a high transmittance can be formed.

(11) A method for producing a photosensitive resin composition, which comprises applying the photosensitive resin composition according to any one of <1> to <10>

(2) removing the solvent from the applied photosensitive resin composition,

(3) exposing the applied photosensitive resin composition to actinic rays,

(4) developing the exposed photosensitive resin composition with an aqueous developer, and

(5) heat-curing the developed photosensitive resin composition

To form a cured film.

<12> A cured film formed by the method according to <11>.

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

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

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

According to one aspect of the present invention, a cured film having a high transmittance after curing and a small decrease in transmittance even when heated can be obtained and a photosensitive resin composition having extremely high sensitivity can be provided even when heating (PEB) is not performed after exposure do.

According to another aspect of the present invention, there is provided a cured film using the photosensitive resin composition, a method of manufacturing the same, an organic EL display device provided with the cured film, and a liquid crystal display device.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a configuration diagram of an example of an organic EL display device in which a cured film using the photosensitive resin composition of the present invention is used as an insulating film and a planarization film.
Fig. 2 is a structural view of an example of a liquid crystal display device to which a cured film using the photosensitive resin composition of the present invention is applied. Fig.

Photosensitive resin composition

Hereinafter, the photosensitive resin composition of the present invention will be described in detail.

The photosensitive resin composition of the present invention comprises (A) an acetal resin, (B) a photoacid generator, and (C) a solvent, wherein the acetal resin (A) has a structure in which a carboxyl group is formed by an acid (A2) a structural unit having a carboxyl group or a phenolic hydroxyl group, a structural unit (a3) having an epoxy group or an oxetanyl group, and a structural unit (a4) having a hydroxyl group or an alkyleneoxy group, (A1) to (a4) in the acetal-based resin (A) is a polymer having an acetal structure or a ketal structure and the content ratio of the structural units (A2): structural unit (a3): structural unit (a4) = 0.2 to 0.65: 0.02 to 0.2: 0.2 to 0.6: 0.005 to 0.3, ) The content of the structural unit (a4) in the acetal-based resin is in the range of 3 to 30 mass% on a mass basis.

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).

In the present specification, post exposure baking after exposure is sometimes referred to as PEB.

The photosensitive resin composition of the present invention contains the above-mentioned components (A) to (C), whereby a photosensitive resin composition having extremely high sensitivity is obtained. Further, it is possible to provide a photosensitive resin composition which has a high transmittance after curing and a cured film having a small decrease in transmittance even when heated.

In the present invention, the property that the transmittance after curing is high and the decrease in transmittance is small even when heated is referred to as &quot; heat resistance transparency &quot;.

Hereinafter, each component constituting the photosensitive resin composition will be described.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

(A) acetal resin

The photosensitive resin composition of the present invention contains (A) an acetal resin.

The acetal-based resin (A) contained in the photosensitive resin composition of the present invention is preferably a structural unit (a1) having a structure which generates a carboxyl group by an acid, a structural unit (a2) having a carboxyl group or a phenolic hydroxyl group, (A3) having a hydroxyl group or an alkyleneoxy group and a structural unit (a4) having a hydroxyl group or an alkyleneoxy group, and further has an acetal structure or a ketal structure.

The acetal-based resin (A) may further contain a structural unit (a5) having a structure other than the above structural units (a1) to (a4).

The acetal-based resin (A) is preferably a resin that is alkali-insoluble and becomes alkali-soluble when the acid-decomposable group in the structural unit (a1) having a structure generating a carboxyl group by an acid decomposes.

"Alkali solubility" in the present invention means that the solution of the compound (resin) is coated on a substrate and the coating film (thickness: 3 μm) of the compound (resin) formed by heating at 90 ° C. for 2 minutes is 23 The dissolution rate in 0.4 mass% aqueous solution of tetramethylammonium hydroxide at 0.01 占 폚 / ° C is 0.01 占 퐉 / second or more. "Alkali insoluble" means that a solution of the compound (resin) is coated on a substrate, and a coating film (thickness 3 μm) of the compound (resin) formed by heating at 90 ° C. for 2 minutes at 0.4 ° C. % &Lt; / RTI &gt; aqueous solution of tetramethylammonium hydroxide is less than 0.01 mu m / second, preferably less than 0.005 mu m / second.

The acetal resin (A) is preferably an acrylic polymer.

The "acrylic polymer" in the present invention is an addition polymerizable type resin, which is a polymer containing a structural unit derived from (meth) acrylic acid or an ester thereof, and has a structure other than a structural unit derived from (meth) acrylic acid or an ester thereof Units, for example, structural units derived from styrene, structural units derived from vinyl compounds, and the like. Also. (Meth) acrylic acid and a structural unit derived from the ester thereof.

The acetal-based resin (A) preferably contains a structural unit derived from (meth) acrylic acid or an ester thereof in an amount of 50 mol% or more based on the total structural units in the acetal-based resin (A) % Or more, and is particularly preferably a polymer comprising only structural units derived from (meth) acrylic acid or an ester thereof.

In the present specification, the "structural unit derived from (meth) acrylic acid or an ester thereof" is also referred to as "acrylic structural unit". Further, (meth) acrylic acid is collectively referred to as methacrylic acid and acrylic acid.

The acetal-based resin (A) has an acetal structure or a ketal structure, and may have both an acetal structure and a ketal structure.

The acetal structure or ketal structure is preferably a structure represented by the following general formula (I).

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom, a linear or branched alkyl group or a cycloalkyl group. Provided that at least one of R ¹ and R ² represents an alkyl group or a cycloalkyl group.

R ³ represents a linear or branched alkyl group, a cycloalkyl group, or an aralkyl group.

R ¹ and R ³ may be connected to form a cyclic ether, or R ² and R ³ may be connected to form a cyclic ether.

The alkyl group as R ¹ or R ² in the general formula (I) is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. The cycloalkyl group as R ¹ or R ² is preferably a cycloalkyl group having 3 to 6 carbon atoms.

The alkyl group as R ³ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The cycloalkyl group as R ³ is preferably a cycloalkyl group having 3 to 10 carbon atoms.

The aralkyl group as R ³ is preferably an aralkyl group having 7 to 10 carbon atoms.

When R ¹ and R ³ or R ² and R ³ are connected to form a cyclic ether, R ¹ and R ³ or R ² and R ³ are connected to form an alkylene chain having 2 to 5 carbon atoms desirable.

The alkyl group, cycloalkyl group and aralkyl group as R ³ may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group and a halogen atom. The substituent preferably has 6 or less carbon atoms.

Examples of R ⁷ in the acetal ester structure (-COOR ⁷ ) of the carboxylic acid when one of R ¹ and R ² in the general formula (I) is a hydrogen atom include 1-methoxyethyl group, 1- Butoxyethyl group, 1-sec-butoxyethyl group, 1-t-butoxyethyl group, 1-n-propoxyethyl group, 1- (1-cyclohexyloxy) ethyl, 1-cyclohexyloxyethyl, 1-cyclohexyloxyethyl, 1-norbornyloxyethyl, 1-bornyloxyethyl, 1-benzyloxyethyl, (Cyclohexyl) (cyclohexyl) methyl group, (cyclohexyl) (ethoxy) methyl group, (cyclohexyl) (Phenyl) (n-propoxy) methyl group, (phenyl) (i-propoxy) methyl group, (Phenyl) (cyclohexyloxy) methyl (Benzyl) (n-propoxy) methyl group, (benzyl) (i-propoxy) methyl group, (Benzyl) (cyclohexyloxy) methyl group, (benzyl) (benzyloxy) methyl group, 2-tetrahydrofuranyl group and 2-tetrahydropyranyl group.

Examples of R ⁸ in the ketal ester structure (-COOR ⁸ ) of the carboxylic acid in the case where both of R ¹ and R ² in the general formula (I) are not hydrogen atoms include 1-methyl-1-methoxyethyl Methyl-1-n-propoxyethyl group, 1-methyl-1-n-butoxyethyl group, 1-methyl Methyl-1-t-butoxyethyl group, 1-methyl-1-cyclopentyloxyethyl group, 1-methyl- Methyl-1-norbornyloxyethyl group, 1-methyl-1-bornyloxyethyl group, 1-methyl-1-benzyloxyethyl group, 1-methyl- -Cyclohexyl-1-i-propoxyethyl group, 1-cyclohexyl-1-i-propoxyethyl group, 1-cyclohexyl- 1-cyclohexyloxyethyl group, 1-cyclohexyl-1-benzyloxyethyl group, 1-phenyl-1-methoxyethyl group, 1- Phenyl-1-i-propoxyethyl group, 1-phenyl-1-cyclohexyloxyethyl group, 1-phenyl-1-benzyl Benzyl-1-i-propoxyethyl group, 1-benzyl-1-i-propoxyethyl group, 1-benzyl- Methyl-2-tetrahydropyranyl group, a 1-methoxycyclopentyl group, a 1-benzyl-1-benzyloxyethyl group, Methoxy-cyclohexyl group, and the like.

In the acetal structure or the ketal structure of the carboxylic acid, an acetal structure is more preferable from the viewpoint of process stability. As preferable R ⁷ in the acetal ester structure (-COOR ⁷ ) of carboxylic acid, a 1-ethoxyethyl group, a 1-cyclohexyloxyethyl group, a 2-tetrahydrofuranyl group and a 2-tetrahydropyranyl group are preferable, From the viewpoint of solubility, 1-ethoxyethyl group and 1-cyclohexyloxyethyl group are particularly preferable.

(A1) having a structure which forms a carboxy group by an acid,

The acetal-based resin (A) in the present invention contains a structural unit (a1) (hereinafter appropriately referred to as "structural unit (a1)") having a structure which generates a carboxyl group by an acid. The structural unit (a1) contains a structure in which a carboxyl group is protected.

The compound used for forming the structural unit (a1) can be used as long as it can be a compound used for forming the structural unit (a1) by protecting the carboxyl group. Examples of the compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and? -Methyl-p-carboxystyrene; And dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. Of these, acrylic acid and methacrylic acid are particularly preferable. As the structural unit (a1), a structural unit derived from a carboxylic acid in which these carboxyl groups are protected is preferable.

Specific preferred examples of the radical polymerizable monomer used for forming the structural unit (a1) include 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl methacrylate, 1 1-n-butoxyethyl acrylate, 1-i-butoxyethyl acrylate, 1- (n-butoxyethyl methacrylate, 1-n-propyl methacrylate, 1-n-propyl methacrylate, 1-n-propyl methacrylate, 1- (1-cyclohexylethoxy) ethyl acrylate, 1-cyclohexyloxyethyl acrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1- Methacrylate, 1-benzyloxyethyl acrylate, tetrahydro-2H-pyran-2-yl methacrylate, 2-yl methacrylate, tetrahydrofuran-2-yl methacrylate, tetrahydrofuran-2-yl acrylate and the like. Particularly preferred examples thereof include 1-ethoxyethyl methacrylate , 1-ethoxyethyl acrylate, tetrahydrofuran-2-methacrylate tetrahydrofuran-2-yl acrylate, 1-cyclohexyloxyethyl methacrylate, and 1-cyclohexyloxyethyl acrylate. These structural units (a1) may be used alone or in combination of two or more.

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

In the formula (II), R ⁶ represents a hydrogen atom or a methyl group, and R ⁵ is the same as R ³ in the formula (I).

The structural unit (a1) can also be formed by reacting a carboxyl group with a vinyl ether compound after the protected carboxyl group is polymerized with the structural units (a2) to (a5) described below or a precursor thereof. Specific examples of the preferable structural unit thus formed are the same as the structural units derived from the preferred specific examples of the radical polymerizable monomer.

The structural unit (a1) is preferably a structural unit represented by the following general formula (5).

In the general formula (5), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, R ²¹ to R ²⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms Alkyl group.

As specific preferred examples of the structural unit (a1), the following structural units (a1-1) to (a1-8) can be exemplified. Especially preferred among these are structural units represented by (a1-1) to (a1-4), (a1-7) and (a1-8).

The content of the structural unit (a1) in the total structural units constituting the acetal-based resin (A) is 20 to 60 mol%, more preferably 25 to 60 mol%, and particularly preferably 25 to 55 mol%. By containing the structural unit (a1) in the above ratio, a photosensitive resin composition having high sensitivity can be obtained.

The structural unit (a2) having a carboxyl group or a phenolic hydroxyl group

The acetal-based resin (A) contains a structural unit (a2) having a carboxyl group or a phenolic hydroxyl group (hereinafter appropriately referred to as "structural unit (a2)").

Examples of the structural unit (a2-1) having a carboxyl group include a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid.

As the unsaturated carboxylic acid used for obtaining the structural unit (a2-1) having a carboxyl group, those exemplified below can be 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 for obtaining the structural unit (a2-1) 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 polyvalent carboxylic acid, and examples thereof include monosaccharide mono (2-acryloyloxyethyl), succinic acid mono Ethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like.

Further, the unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, 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, acrylic acid and methacrylic acid are preferably used in order to form the structural unit (a2-1) having a carboxyl group from the viewpoint of developability.

The structural unit (a2-1) having a carboxyl group can also be obtained by reacting a structural unit having a hydroxyl group with an acid anhydride.

As the acid anhydride, known dicarboxylic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and anhydride anhydride; Acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride and biphenyltetracarboxylic anhydride. Of these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride are preferable from the viewpoint of developability.

Examples of the radically polymerizable monomer used for forming the structural unit (a2-2) having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and? -Methyl-p-hydroxystyrene, Compounds described in paragraphs [0011] to [0016] of JP-A-2008-40183, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of JP 2888454, 4-hydroxy- An addition reaction product of benzoic acid and glycidyl methacrylate, an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate, and the like.

Of the radical polymerizable monomers used for forming the structural unit (a2), methacrylic acid, acrylic acid, compounds described in paragraphs 0011 to 001 of Japanese Patent Application Laid-Open No. 2008-40183, Hydroxyhexanoic acid derivative as described in JP-A-11010, an addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable, Methacrylic acid, and acrylic acid are particularly preferable. These structural units may be used alone or in combination of two or more.

The structural unit (a2) is preferably introduced in such a range that the acetal resin (A) does not become alkali soluble. The content of the structural unit (a2) in the total structural units constituting the acetal-based resin (A) is 2 to 20 mol%, more preferably 2 to 15 mol%, and particularly preferably 3 to 15 mol%. By containing the structural unit (a2) in the above ratio, a high sensitivity can be obtained and the developing property can be improved. In particular, by using the structural unit (a4) and the structural unit (a2) described later in combination, a very high sensitivity can be obtained.

(A3) having an epoxy group and / or an oxetanyl group,

The acetal-based resin (A) contains a structural unit (a3) having an epoxy group or an oxetanyl group (hereinafter appropriately referred to as "structural unit (a3)"). The structural unit (a3) may contain both a structural unit having an epoxy group and an oxetanyl group.

As the group having an epoxy group, a glycidyl group and a 3,4-epoxycyclohexylmethyl group can be preferably exemplified, as long as they have an epoxy ring, although there is no particular limitation.

The group having an oxetanyl group is not particularly limited as long as it has an oxetanyl ring, and (3-ethyloxetan-3-yl) methyl group is preferably exemplified.

The structural unit (a3) may contain at least one epoxy group or oxetanyl group in one structural unit, and may contain at least one epoxy group and at least one oxetanyl group, at least two epoxy groups, or at least two oxetanyl groups Group, and it is preferable that the epoxy group and / or oxetanyl group 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, And it is more preferable to have one setlanyl group.

Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate Dicumyl acrylate, glycidyl alpha-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl acrylate, Heptyl,? -Ethyl acrylate-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p- vinylbenzyl glycidyl ether, paragraphs of Japanese Patent No. 4168443 Compounds containing an alicyclic epoxy skeleton described in [0031] to [0035], and the like.

Examples of the radically polymerizable monomer used for forming the oxetanyl group-containing structural unit include (meth) acrylates having an oxetanyl group as described in paragraphs [0011] to [0016] of JP 2001-330953 A, Acrylic acid esters and the like.

Examples of the radically polymerizable monomer used for forming the structural unit (a3) include monomers containing a methacrylic acid ester structure and monomers containing an acrylic ester structure.

Of these monomers, glycidyl methacrylate, glycidyl acrylate, compounds containing an alicyclic epoxy skeleton described in paragraphs [0034] to [0035] of Japanese Patent No. 4168443, (Meth) acrylic acid ester having an oxetanyl group as described in paragraphs [0011] to [0016] of JP-A-2001-330953.

Particularly preferable structural units derived from acrylic acid (3-ethyloxetan-3-yl) methyl and methacrylic acid (3-ethyloxetan-3-yl) methyl are particularly preferable from the viewpoint of heat resistance transparency.

These structural units (a3) may be used alone or in combination of two or more.

As specific preferred examples of the structural unit (a3), the following structural units can be exemplified.

The content of the structural unit (a3) in the total structural units constituting the acetal-based resin (A) is 20 to 55 mol%, more preferably 25 to 55 mol%, and particularly preferably 25 to 50 mol%. By containing the structural unit (a3) in the above ratio, physical properties of the cured film are improved.

The structural unit (a4) having a hydroxyl group or an alkyleneoxy group

The acetal-based resin (A) contains a structural unit (a4) having a hydroxyl group or an alkyleneoxy group (hereinafter appropriately referred to as "structural unit (a4)"). And may contain both a hydroxyl group and a structural unit having an alkyleneoxy group.

The hydroxyl group in the structural unit (a4) refers to a hydroxyl group other than the phenolic hydroxyl group. When the above structural units (a1) to (a3) have a hydroxyl group, they are not treated as the structural unit (a4) but are treated as the respective structural units (a1) to (a3).

As the structural unit (a4), any structural unit having a hydroxyl group and / or an alkyleneoxy group can be used, and preferred examples thereof include a (meth) acrylic acid ester containing a hydroxyl group, a (meth) acrylic acid ester of an alkyl group-terminated polyalkylene glycol And (meth) acrylic acid esters of aryl-terminated polyalkylene glycols.

Examples of the hydroxyl group-containing (meth) acrylic acid esters include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Hydroxyalkyl esters of (meth) acrylic acid such as dihydroxypropyl and 4-hydroxybutyl (meth) acrylate, polyethyleneglycol mono (meth) acrylate, polypropyleneglycol mono (meth) acrylate, poly Propylene glycol-mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) -mono (meth) acrylate, polyethylene glycol-polypropylene glycol- ) -Mono (meth) acrylate, and propylene glycol · polybutylene glycol-mono (meth) acrylate.

Examples of the (meth) acrylic acid esters of alkyl-terminated polyalkylene glycols include methoxypolyethylene glycol- (meth) acrylate, octoxypolyethylene glycol-polypropylene glycol- (meth) acrylate, lauroxypolyethylene glycol- ) Acrylate, and stearoxypolyethylene glycol- (meth) acrylate.

Examples of the (meth) acrylic acid ester of the aryl group-terminated polyalkylene glycol include phenoxypolyethylene glycol- (meth) acrylate, phenoxypolyethylene glycol-polypropylene glycol- (meth) acrylate, nonylphenoxypolyethylene glycol (Meth) acrylate, nonylphenoxy-polypropylene glycol- (meth) acrylate and nonylphenoxy-poly (ethylene glycol-propylene glycol) - (meth) acrylate.

A commercially available (meth) acrylic acid ester of a hydroxyl group, a (meth) acrylic acid ester of an alkyl group-terminated polyalkylene glycol and a (meth) acrylic acid ester of an aryl-terminated polyalkylene glycol can be used. Representative examples include, but are not limited to, blemmers E, blemmer PE-90, blemmer PE-200, blemmer PE-350, blemmer p, blemmer PP-1000, Blemmer AE-200, Blemmer AE-400, Blemmer AP-300, Blemmer 70PEP-350, Blemmer 55PET-800, 150, Blemmer AP-400, Blemmer AP-550, Blemmer PME-100, Blemmer PME-200, Blemmer PME-400, BLEMER PSE-400, BLEMMER PSE-1300, BLEMMER PAE-50, BLEMMER PAE-100, BLEMMER 43PAPE-600B, BLEMMER AME-400, BLEMMER ALE series, BLEMMER ANP-300, - 600, Blemmer AAE-50, Blemmer AAE-300 (trade name, manufactured by Nichiyu K.K.) and the like.

In the structural unit (a4), the number of hydroxyl groups is preferably 1 to 10, more preferably 1 to 5, and most preferably 1 to 3. The number of repeating units of the alkyleneoxy group is preferably 1 to 25, more preferably 1 to 15, and most preferably 1 to 10.

Specific preferred structures of the structural unit (a4) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Methoxypolyethylene glycol- (meth) acrylate having 2 to 10 ethylene glycol repeating units, methoxypolypropylene glycol- (meth) acrylate having 2 to 10 propylene glycol repeating units, ethylene glycol repeating units and Methoxypolyethylene glycol-polypropylene glycol- (meth) acrylate having a sum of propylene glycol repeating units of 2 to 10, octoxypolyethylene glycol-polypropylene glycol having a sum of repeating units of ethylene glycol and propylene glycol of 2 to 10 - (meth) acrylate, polyethylene glycol mono (meth) acrylate having 2 to 10 ethylene glycol repeating units, 2 to 10 propylene glycol repeating units Poly (ethylene glycol-propylene glycol) -mono (meth) acrylate having a sum of ethylene glycol repeating units and propylene glycol repeating units of 3 to 10, ethylene glycol repeating units and propylene glycol (meth) Polypropylene glycol mono (meth) acrylate having a sum of repeating units of 3 to 10, and more preferably 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) (Meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate having 2 to 10 ethylene glycol repeating units, ethylene glycol repeating units and propylene glycol repeating units Octoxypolyethylene glycol-polypropylene glycol- (meth) acrylate having a sum of units of 2 to 10, and most preferably an ethylene glycol repeating unit Methoxypolyethylene glycol- (meth) acrylate and 2-hydroxyethyl (meth) acrylate having a stericity of 2 to 10.

The structural unit (a4) may be used alone or in combination of two or more.

The content of the structural unit (a4) in the total structural units constituting the acetal-based resin (A) is 0.5 to 30 mol%, more preferably 0.5 to 25 mol%, and particularly preferably 1 to 25 mol%.

The content of the structural unit (a4) in the total structural units (A) constituting the acetal resin is 3 to 30 mass%, more preferably 3 to 25 mass%, and particularly preferably 5 to 25 mass% . By containing the structural unit (a4) in the above ratio, the developability is improved and a photosensitive composition with high sensitivity can be obtained. Particularly, by combining the above-mentioned structural unit (a2) and structural unit (a4), a photosensitive resin composition with extremely high sensitivity can be obtained.

Other structural units (a5)

The acetal-based resin (A) may contain a structure other than the above structural units (a1) to (a4) (hereinafter appropriately referred to as "structural unit (a5)") within a range not hindering the effect of the present invention .

Examples of the radical polymerizable monomer used for forming the structural unit (a5) include the compounds described in paragraphs [0021] to [0024] of JP 2004-264623 A (however, Excluding units (a1) to (a4)).

Among them, (meth) acrylic acid esters containing an alicyclic structure such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate and cyclohexyl acrylate are preferable from the viewpoint of improvement of electrical characteristics. From the viewpoint of transparency, methyl (meth) acrylate is preferable. From the viewpoint of etching resistance, styrenes such as styrene and? -Methylstyrene are preferable.

The structural unit (a5) may be used alone or in combination of two or more.

The content of the structural unit (a5) in the total structural units constituting the acetal-based resin (A) is 0 to 40 mol%. When the acetal resin (A) contains the structural unit (a5), the content of the structural unit (a5) in the total structural units (A) constituting the acetal-based resin is preferably from 1 to 40 mol% To 30 mol%, and particularly preferably from 5 to 25 mol%.

The weight average molecular weight of the acetal resin (A) in the present invention is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and most preferably 3,000 to 12,000.

The weight average molecular weight in the present invention is the polystyrene reduced weight average molecular weight determined by gel permeation chromatography (GPC).

The method for introducing each structural unit contained in the acetal-based resin (A) 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 these monomers are copolymerized. That is, the radical polymerization (hereinafter also referred to as &quot; radical polymerization &quot;) containing a radical polymerizable monomer used for forming the structural unit (a1), the structural unit (a2), the structural unit (a3), the structural unit Can be synthesized by polymerization of a monomeric monomer mixture in an organic solvent using a radical polymerization initiator.

In the polymer reaction method, a necessary functional group is introduced into the structural unit by using a reactive group contained in the structural unit of the obtained copolymer after the polymerization reaction.

The introduction of the above structural units (a1) to (a5) into the acetal-based resin (A) may be carried out by a polymerization method or a polymer reaction method.

Preferred examples of the acetal resin (A) used in the present invention are illustrated below, but the present invention is not limited thereto.

The weight average molecular weight of the acetal-based resin (A) shown below is 2,000 to 30,000. (%) In mole%.

1-ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer (45/8/35/12),

Methoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / styrene copolymer (40/8/35/12/5),

1-cyclohexyloxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / styrene copolymer (40/8/35/12/5),

2-yl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer (40/10/30/20),

2-yl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / styrene copolymer (35/10/30/15/10),

Ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / dicyclopentyl methacrylate copolymer (42/11/25/18/4),

Methoxyethyl methacrylate, 1-ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / cyclohexyl methacrylate copolymer (35/10/30/20/5),

Methacrylic acid / glycidyl methacrylate / poly (ethylene glycol / propylene glycol) -monomethacrylate (Blemmer 50PEP-300, manufactured by Nichiyu Corporation) / methacrylic acid Acid dicyclopentyl copolymer (55/9/30/2/4),

Methacrylic acid / glycidyl methacrylate / methoxypolyethylene glycol methacrylate (Blemmer PME-400, manufactured by Nichiyu Corporation) copolymer (44 / 4.5 / 50 / 1.5),

Copolymer of 1-cyclohexyloxyethyl methacrylate / acrylic acid / glycidyl methacrylate / methoxypolyethylene glycol methacrylate (Blemmer PME-400, manufactured by Nichiyu Corporation) (45/10/43/2 ),

Methacrylic acid / glycidyl methacrylate / methoxypolyethylene glycol methacrylate (Blemmer PME-400, manufactured by Nichiyu Corporation) / di-cyclopentanyl methacrylate copolymer (43/15/30/2/10),

Methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer (40/12/28/20), methacrylic acid / glycidyl methacrylate /

Methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / styrene copolymer (35/12/28/15/10), methacrylic acid / glycidyl methacrylate /

Methacrylic acid / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid 2-hydroxyethyl copolymer (40/10/30/20), 1-ethoxyethyl methacrylate /

(40/10/30/20) methacrylic acid tetrahydrofuran-2-yl / methacrylic acid / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid 2-hydroxyethyl copolymer ,

Methacrylic acid / 3-ethyloxetane-3-yl) methyl / methacrylic acid 2-hydroxyethyl copolymer (35/10/33/12 / 10),

Methacrylic acid / methacrylic acid (3-ethyloxetan-3-yl) methyl / methoxypolyethylene glycol methacrylate (Blemmer PME-400, manufactured by Nichiyu Corporation) Copolymer (40/10/46/4),

Methacrylic acid / methacrylic acid (3-ethyloxetan-3-yl) methyl / methoxypolyethylene glycol methacrylate (Blemmer PME-400, manufactured by Nichiyu Corporation) / Methacrylic acid 2-hydroxyethyl copolymer (45/10/30/1/14),

Methacrylic acid / 3-ethyloxetane-3-yl) methyl methacrylate / 2-hydroxyethyl methacrylate / dicyclopentyl methacrylate copolymer (40/10 / 25/20/5),

Methacrylic acid / 3-ethyloxetane-3-yl) methyl methacrylate / 2-hydroxyethyl methacrylate / methyl methacrylate copolymer (38/7/35 / 15/5),

Methacrylic acid / methacrylic acid (3-ethyloxetan-3-yl) methyl / methoxypolyethylene glycol methacrylate (Blemmer PME-200, manufactured by Nichiyu K.K.) Copolymer (50/8/37/5),

Methacrylic acid / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid 2,3-dihydroxypropyl copolymer (40/7/30/23 ),

Methacrylic acid / methacrylic acid (3-ethyloxetan-3-yl) methyl / methoxypolyethylene glycol methacrylate (Blemmer PME-400, manufactured by Nichiyu K.K.) ) Copolymer (41/14/41/4),

(40/10/25/25), methacrylic acid / methacrylic acid (3-ethyloxetan-3-yl) methyl methacrylate / 2-hydroxyethyl copolymer

2-yl methacrylate / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid 2,3-dihydroxypropyl copolymer (40 / 5/30/25),

(Blemmer PME-200, manufactured by Nichiyu Corporation) copolymer (manufactured by Nippon Oil & Fats Co., Ltd.) (methacrylic acid-1-cyclohexyloxyethyl methacrylate / acrylic acid / 40/12/44/4),

Methacrylic acid / (3-ethyloxetan-3-yl) methyl methacrylate / 2-hydroxyethyl copolymer (40/10/32/18), methacrylic acid /

Methacrylic acid / 3,4-epoxycyclohexylmethyl methacrylate / 2-hydroxyethyl methacrylate copolymer (40/5/35/20), methacrylic acid / methacrylic acid /

Methacrylic acid / methacrylic acid / 3,4-epoxycyclohexylmethyl methacrylate / methoxypolyethylene glycol methacrylate (Blemmer PME-200, manufactured by Nichiyu Corporation) / methyl methacrylate copolymer Coalescence (40/15/35/5/5),

(3-methacryloyloxy-2-hydroxypropyl) ester / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer (30 / 12/38/20),

Methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer (40/7/35/35) was added to the mixture of 1-ethoxyethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) 18).

The acetal-based resin (A) may be used alone or in combination of two or more kinds in the photosensitive resin composition.

The content ratio of the structural units (a1) to (a5) in the acetal-based resin (A) is preferably in a molar ratio of the structural unit (a1) : Structural unit (a3): structural unit (a4): structural unit (a5) = (0.2-0.65): (0.02-0.2) :( 0.2-0.60) :( 0.005-0.3): (0-0.4) (0.25 to 0.6) :( 0.02 to 0.15) :( 0.25 to 0.55) :( 0.005 to 0.25) :( 0 to 0.3), more preferably (0.25 to 0.55) :( 0.03 to 0.15) 0.5): (0.01 to 0.25): (0 to 0.25).

The content of the structural unit (a4) in the total structural units (A) constituting the acetal resin is 3 to 30 mass%, more preferably 3 to 25 mass%, and particularly preferably 5 to 25 mass% .

The content of the acetal-based resin (A) in the photosensitive resin composition of the present invention is preferably 20 to 99% by mass, more preferably 40 to 97% by mass, more preferably 60 to 95% by mass with respect to the total solid content of the photosensitive resin composition % Is more preferable. When the content is within this range, the pattern forming property upon development becomes good. The solid content of the photosensitive resin composition means an amount excluding a volatile component such as a solvent.

In the photosensitive resin composition of the present invention, a resin other than the acetal resin (A) may be used in combination within a range not hindering the effect of the present invention. However, the content of the resin other than the acetal-based resin (A) is preferably smaller than the content of the acetal-based resin (A) from the viewpoint of developability.

(B)

The photosensitive resin composition of the present invention contains (B) a photoacid generator.

As the (B) photoacid generator used in the present invention, a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or longer, preferably 300-450 nm is preferable, but its chemical structure is not limited . 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, 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, imide sulfonate compounds and oxime sulfonate compounds . Of these, oxime sulfonate compounds are preferably used from the viewpoint of high sensitivity. These photoacid generators may be used alone or in combination of two or more.

Specific examples of these photoacid generators 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-methylphenyl) ethenyl] -bis Naphthyl) -bis (4,6-trichloromethyl) -s-triazine;

As the diaryl iodonium salts, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethane sulfonate, 4-methoxyphenylphenyl iodonium trifluoromethane sulfonate, 4-methoxy (2'-hydroxy-1'-tetradecarboxy) phenyl iodonium trifluoromethanesulfonate, phenyl 4- (2'-hydroxy-1'- -Tetradecaoxy) phenyliodonium hexafluoroantimonate or phenyl-4- (2'-hydroxy-1'-tetradecarboxy) phenyl iodonium p-toluenesulfonate;

As the triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenyl Sulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethane sulfonate, 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 imide sulfonate derivative, trifluoromethylsulfonyloxybicyclo [2.2.1] -hept-5-ene-dicarboxyimide, succinimide trifluoromethylsulfonate, phthalimide trifluoromethylsulfone N-hydroxynaphthalimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimidopropane sulfonate, and the like.

The photosensitive resin composition of the present invention preferably contains an oxime sulfonate compound having at least one oxime sulfonate moiety represented by the following structure (1) as the (B) photoacid generator.

Examples of the compound having at least one oxime sulfonate residue represented by the above structure (1) include oximesulfosuccinimide represented by the following general formula (OS-3), general formula (OS-4) It is preferably a compound of the formula (I).

In the general formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and the plurality of R ^{2 s} present may be independently selected from the group consisting of a hydrogen atom, an alkyl group, R ⁶ represents 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, and n represents 1 or 2, And m represents an integer of 0 to 6;

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

In the general formulas (OS-3) to (OS-5), the alkyl group represented by 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 represented by 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 represented by R ¹ in the general formulas (OS-3) to (OS-5) include an alkyl group such as a methyl group, ethyl group, n-propyl group, N-hexyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, etc. .

In the general formulas (OS-3) to (OS-5), the aryl group represented by R ¹ is preferably an aryl group having a total of 6 to 30 carbon atoms and may have a substituent.

Examples of the substituent which the aryl group represented by R ¹ may have include halogen atoms, alkyl groups, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, aminocarbonyl groups, An alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group,

As the aryl group represented by R ¹ , 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 general formulas (OS-3) to (OS-5), the heteroaryl group represented by R ¹ is preferably a heteroaryl group having 4 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which the heteroaryl group represented by 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.

In the above general formulas (OS-3) to (OS-5), the heteroaryl group represented by R ^{1 may} be at least one heteroaromatic ring, and for example, a heterocyclic ring and a benzene ring may be condensed .

Examples of the heteroaryl group represented by 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 excluding one hydrogen atom from the selected ring.

In the general 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 the general 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, More preferably a halogen atom, particularly preferably one is an alkyl group and the remainder is a hydrogen atom.

In the general formulas (OS-3) to (OS-5), the alkyl group or aryl group represented by R ² may have a substituent.

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

In the general formulas (OS-3) to (OS-5), the alkyl group represented by R ² is preferably an alkyl group having a total of 1 to 12 carbon atoms which may have a substituent, More preferably an alkyl group having 1 to 6 carbon atoms.

Examples of the alkyl group represented by 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, More preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, , An ethyl group, an n-propyl group, an n-butyl group and an n-hexyl group are more preferable, and a methyl group is particularly preferable.

In the general formulas (OS-3) to (OS-5), the aryl group represented by R ² is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

As the aryl group represented by R ² , a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group and p-phenoxyphenyl group are preferable.

Examples of the halogen atom represented by 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.

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

In the general formulas (OS-3) to (OS-5), the ring containing X as a reduction is a 5-membered ring or a 6-membered ring.

In the general 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.

In the general formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group represented by R ⁶ may have a substituent.

In the general formulas (OS-3) to (OS-5), the alkyl group represented by 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 represented by 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.

In the above general formulas (OS-3) to (OS-5), examples of the alkyl group represented by R ⁶ include a methyl group, ethyl group, n-propyl group, i- Pentyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group and benzyl group are preferable.

In the general formulas (OS-3) to (OS-5), the alkyloxy group represented by 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 represented by 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.

In the general formulas (OS-3) to (OS-5), examples of the alkyloxy group represented by R ⁶ include a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, A methyloxy group, or an ethoxyethyloxy group is preferable.

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.

Examples of the alkoxysulfonyl group represented by R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group and a butyloxysulfonyl group.

In the general 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, desirable.

The compound represented by the above general formula (OS-3) is particularly preferably a compound represented by the following general formula (OS-6), (OS-10) or (OS- OS-4) is particularly preferably a compound represented by the following general formula (OS-7), and the compound represented by the general formula (OS-5) Or (OS-9).

In the general formulas (OS-6) to (OS-11), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, R ⁸ represents a hydrogen atom, 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 chlorine atom, .

R ¹ in the general formula (OS-6) ~ (OS -11) is, and R ¹ and agreed in the general formula (OS-3) ~ (OS -5), as a preferred aspect.

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

R ⁸ in formulas (OS-6) to (OS-11) 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, Or a chlorophenyl 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, desirable.

R ⁹ in the general 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 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, any of the three-dimensional structures (E, Z) of oxime may be a mixture or a mixture thereof.

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

Another favorable embodiment of the oxime sulfonate compound having at least one oxime sulfonate group represented by the above structure (1) includes a compound represented by the following general formula (OS-1).

In the general formula (OS-1), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Lt; / RTI &gt; R ² represents an alkyl group or an aryl group.

X is ^{-O-, -S-, -NH-, -NR 5} -, -CH 2 -, -CR 6 H-, or -CR ⁶ R ⁷ - represents a, R ⁵ ~R ⁷ is an alkyl group, or aryl Lt; / RTI &gt;

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, the case where all of R ²¹ to R ²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.

Each of the substituents described above may further have a substituent.

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

The formula (OS-2) ^{of, R 1, R 2, R} 21 ~R 24 is each and ^{R 1, R 2, R 21} ~R 24 and copper in the formula (OS-1), preferred examples It is also the same.

Of these, formula (OS-1), and in the formula (OS-2) R ¹ is a cyano group, or an aryl group sun is more preferred, and represented by the formula (OS-2), R ¹ A cyano group, a phenyl group or a naphthyl group is most preferable.

In the oxime sulfonate compound, the stereostructure (E, Z, etc.) of oxime or benzothiazole ring may be either or both of them.

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

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

The oxime sulfonate compound having at least one of the oxime sulfonate moieties represented by the above structure (1) is preferably a compound represented by the following general formula (2).

^{R 1A -C (R 2A) =} NO-SO 2 -R 3A (2)

In the general formula (2), R ^1A is an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, A halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a cyano group, and when R ^1A is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, An alkoxy group having 1 to 4 carbon atoms, and a nitro group. R ^2A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group optionally substituted with W , A naphthyl group which may be substituted with W, or an anthranyl group, a dialkylamino group, a morpholino group, or a cyano group which may be substituted with W; R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or 6-membered ring may be bonded to a benzene ring which may have 1 or 2 arbitrary substituents. R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group , A naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms Lt; / RTI &gt;

The alkyl group having 1 to 6 carbon atoms represented by R ^1A may be a straight chain or branched chain alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, An n-pentyl group, an isoamyl group, an n-hexyl group, or a 2-ethylbutyl group.

Examples of the halogenated alkyl group having 1 to 4 carbon atoms represented by R ^1A include a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, and a 2-bromopropyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ^1A include a methoxy group and an ethoxy group.

When R ^{1 A} represents a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups may be substituted with a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom and the like), a hydroxyl group, Butyl group, a tert-butyl group), an alkoxy group having 1 to 4 carbon atoms (e.g., a methoxy group, an ethoxy group, an n-propoxy group, Propoxy group, i-propoxy group, n-butoxy group) and a nitro group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^2A include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- , n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group.

Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^2A include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, N-decyloxy group, n-decyloxy group and the like.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ^2A include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, n-amyl group and the like.

Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ^2A include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group , Perfluoro-n-amyloxy group, and the like.

Specific examples of the phenyl group which may be substituted with W represented by R ^2A include o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p- (Propyl) phenyl group, p- (i-propyl) phenyl group, p- p-phenylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, (n-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (P-amyloxy) phenyl group, p- (t-butoxy) phenyl group, p- ) Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4 , A 6-trifluorophenyl group, a pentachlorophenyl group, a pentabromophenyl group, a pentafluorophenyl group, and a p-biphenylyl group.

Specific examples of the naphthyl group which may be substituted with W represented by R ^2A include a 2-methyl-1-naphthyl group, a 3-methyl-1-naphthyl group, Methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4- Methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group and 8-methyl-2-naphthyl group.

Specific examples of the anthranyl group which may be substituted with W represented by R ^2A include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, Anthranyl group, a 10-methyl-1-anthranyl group, a 1- methyl-1-anthranyl group, Anthranyl group, 6-methyl-2-anthranyl group, 7-methyl-2-anthranyl group, Methyl-2-anthranyl group, 9-methyl-2-anthranyl group and 10-methyl-2-anthranyl group.

^Examples of the dialkylamino group represented by R ^2A include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group and diphenylamino group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^3A include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- , n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group.

Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^3A include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, N-decyloxy group, n-decyloxy group and the like.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ^3A include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, n-amyl group and the like.

Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ^3A include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group , Perfluoro-n-amyloxy group, and the like.

Specific examples of the phenyl group which may be substituted with W represented by R ^3A include o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m- (Propyl) phenyl group, p- (i-propyl) phenyl group, p- p-phenylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, (n-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (P-amyloxy) phenyl group, p- (t-butoxy) phenyl group, p- ) Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4 , A 6-trifluorophenyl group, a pentachlorophenyl group, a pentabromophenyl group, a pentafluorophenyl group, and a p-biphenylyl group.

Specific examples of the naphthyl group which may be substituted with W represented by R ^3A include a 2-methyl-1-naphthyl group, a 3-methyl-1-naphthyl group, Methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4- Methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group and 8-methyl-2-naphthyl group.

Specific examples of the anthranyl group which may be substituted with W represented by R ^3A include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, Anthranyl group, a 10-methyl-1-anthranyl group, a 1- methyl-1-anthranyl group, Anthranyl group, 6-methyl-2-anthranyl group, 7-methyl-2-anthranyl group, Methyl-2-anthranyl group, 9-methyl-2-anthranyl group and 10-methyl-2-anthranyl group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by W, the alkoxy group having 1 to 10 carbon atoms, the halogenated alkyl group having 1 to 5 carbon atoms, and the halogenated alkoxy having 1 to 5 carbon atoms include R ^2A or Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^3A , the alkoxy group having 1 to 10 carbon atoms, the halogenated alkyl group having 1 to 5 carbon atoms, and the halogenated alkoxy group having 1 to 5 carbon atoms And the like.

R ^2A and R ^1A may be bonded to each other to form a 5-membered or 6-membered ring.

When R ^2A and R ^1A are bonded to each other to form a 5-membered or 6-membered ring, examples of the 5-membered or 6-membered ring include a carbon ring group and a heterocyclic ring group, and examples thereof include cyclopentane, cyclohexane, , Pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazine ring. The 5-membered or 6-membered ring may be bonded to a benzene ring which may have an arbitrary substituent. Examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chroman, fluorene, xanthene or thioxanthene ring systems. . The 5-membered or 6-membered ring may contain a carbonyl group, and examples thereof include cyclohexadieneone, naphthalenone and anthrone ring systems.

One of the favorable aspects of the compound represented by the general formula (2) is a compound represented by the following general formula (2-1). The compound represented by the general formula (2-1) is a compound in which R ^2A and R ^1A in the general formula (2) combine to form a 5-membered ring.

In the general formula (2-1), R ^3A are R ^3A and copper in the formula (2), X is an alkyl group, an alkoxy group, or a halogen atom, t represents an integer 0 to 3 a, t Is 2 or 3, the plural Xs may be the same or different.

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

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

The halogen atom represented by X is preferably a chlorine atom or a fluorine atom.

As t, 0 or 1 is preferable.

In the general formula (2-1), t is 1, X is a methyl group, X is a substituted position in an ortho position, R ^3A is a straight-chain alkyl group having 1 to 10 carbon atoms, 7,7- Oxonoboronylmethyl group, or p-toluyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the general formula (2-1) include the following compounds (i), (ii), (iii) and (iv) They may be used alone or in combination of two or more. The compounds (i) to (iv) are commercially available.

These compounds may be used in combination with other kinds of specific photoacid generators.

As a preferred embodiment of the photoacid generator represented by the general formula (2)

R ^1A represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methoxyphenyl group, a 4-biphenyl group, a naphthyl group or an anthranyl group;

R ^2A represents a cyano group;

R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group optionally substituted with W , A naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms , A halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms.

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

In formula (2-2), R ^4A represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group, and 1 represents an integer of 0 to 5 . R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group , A naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms , A halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms.

Examples of R ^3A in general formula (2-2) include a methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, Propyl group, an n-butyl group or a p-tolyl group is particularly preferable, and a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and a methyl group, Do.

As the halogen atom represented by R ^4A , a fluorine atom, a chlorine atom or a bromine atom is preferable.

The alkyl group having 1 to 4 carbon atoms represented by R ^4A is preferably a methyl group or an ethyl group.

As the alkoxy group having 1 to 4 carbon atoms represented by R ^4A , a methoxy group or an ethoxy group is preferable.

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

Among the photoacid generators represented by the general formula (2), preferable examples of the compound contained in the photoacid generator represented by the general formula (2-2) include those in which R ^1A is a phenyl group or 4- R ^2A represents cyano group, and R ^3A represents a methyl group, ethyl group, n-propyl group, n-butyl group or 4-tolyl group.

Hereinafter, among the photoacid generators represented by the general formula (2), particularly preferred examples of the compound included in the photoacid generator represented by the general formula (2-2) are shown, but the present invention is not limited thereto.

? - (methylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = methyl group)

? - (ethylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = ethyl group)

(R ^1A = phenyl group, R ^2A = -CN group, R ^3A = n-propyl group)

? - (n-butylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = n-butyl group)

(R ^1A = phenyl group, R ^2A = -CN group, R ^3A = 4-tolyl group)

methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = methyl group)

methoxyphenyl) acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = ethyl group)

methoxyphenyl) acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = n-propyl group)

(R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = n-butyl group)

methoxyphenyl) acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = 4-tolyl group)

The photosensitive resin composition of the present invention preferably does not contain a 1,2-quinonediazide compound as the photoacid generator (B) which is sensitive to an actinic ray. The reason is that the 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is 1 or less, and the sensitivity is lower than that of the oxime sulfonate compound.

On the other hand, the oxime sulfonate compound acts as a catalyst against deprotection of an acidic group protected by an acid generated by the action of an actinic ray, so that an acid generated by the action of one photon contributes to a number of deprotection reactions, It is presumed that the quantum yield exceeds 1 and becomes a large value such as, for example, a power of 10, resulting in a high sensitivity as a result of so-called chemical amplification.

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 mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the acetal resin (A) Do.

(C) Solvent

The photosensitive resin composition of the present invention contains (C) a solvent.

The photosensitive resin composition of the present invention is prepared by preparing an acetal-based resin (A) as an essential component, a photoacid generator (B), and optional components of various additives described below as preferable components in a solution of desirable.

As the solvent (C) used in the photosensitive resin composition of the present invention, known solvents can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers Propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, 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.

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

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

(11) dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate and dipropylene glycol monobutyl ether acetate; (12) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, isobutyl lactate, isobutyl lactate, n-amyl lactate, and lactic acid / (13) A process for producing a compound represented by the following formula (1), wherein n is 1, Aliphatic carboxylic acid esters such as isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate and isobutyl butyrate; (14) A process for producing a compound represented by the above formula (1), which comprises dissolving at least one compound selected from the group consisting of ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methoxypropionyl acetate, 3-methoxypropionyl acetate, Methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate and the like;

(15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; (16) amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; (17) lactones such as? -Butyrolactone, and the like.

These solvents may optionally contain one or more solvents selected from the group consisting of benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, It is also possible to add a solvent such as octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate.

Of the above solvents, particularly preferred are diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate.

The solvent which can be used in the present invention is preferably a single solvent or a combination of two solvents, more preferably two solvents, more preferably propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers It is more preferable to use them in combination.

The content of the solvent (C) in the photosensitive resin composition of the present invention is preferably from 50 to 3,000 parts by mass, more preferably from 100 to 2,000 parts by mass, and still more preferably from 150 to 1,500 parts by mass per 100 parts by mass of the acetal resin (A) It is more desirable to deny it.

Other components

The photosensitive resin composition of the present invention preferably contains other components.

As other components, it is preferable to contain a (M) developing accelerator from the viewpoint of sensitivity, and (E) a crosslinking agent in view of the physical properties of the film. Further, from the viewpoint of sensitivity, it is preferable to add (N) sensitizer.

The photosensitive resin composition of the present invention preferably contains (F) an adhesion improver from the viewpoint of substrate adhesion, and preferably contains (G) a basic compound from the viewpoint of liquid storage stability, H) surfactant (a fluorine-based surfactant, a silicon-based surfactant, etc.).

(D) an antioxidant, (I) a plasticizer, (J) a heat radical generator, (K) a thermal acid generator, (L) an acid generator, an ultraviolet absorber , A thickener, and an organic or inorganic precipitation inhibitor.

Hereinafter, other components that can be contained in the photosensitive resin composition of the present invention will be described.

(N) Thinner

In the photosensitive resin composition of the present invention, in combination with the above-mentioned (B) photoacid generator, it is preferable to add (N) sensitizer 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 and generates acid.

Examples of preferred sensitizers include compounds having an absorption wavelength in the range of 350 nm to 450 nm belonging to the following compounds.

Examples of the sensitizer include polynuclear aromatic compounds (e.g., pyrene, perylene, triphenylene, anthracene), xanthenes (such as fluorescein, eosine, erythrosine, rhodamine B and rose bengal), xanthones For example, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), melothiocyanates (For example, thiophene, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, (Such as acridine, 10-butyl-2-chloroacridone), anthraquinones (such as anthraquinone), squaryliums (such as squarylium) Diethylamino, 4-methylcoumarin), and the like. Of these sensitizers, a sensitizer having an electron-transporting effect to the photoacid generator is preferable, and a polycyclic aromatic compound, acridone, coumarin, and base styryl Do. Among them, anthracene compounds are most preferable.

A commercially available sensitizer may be used, or may be synthesized by a known synthesis method.

The addition amount of the sensitizer is preferably from 20 to 300 parts by mass, more preferably from 30 to 200 parts by mass, based on 100 parts by mass of the (B) photoacid generator from the viewpoints of both sensitivity and transparency.

(M) Development accelerator

The photosensitive resin composition of the present invention preferably contains (M) a development accelerator.

(M) As the development accelerator, any compound having a phenomenon of promoting development may be used, but it is preferably a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group and an alkyleneoxy group, Compounds having a phenolic hydroxyl group are more preferable, and compounds having a phenolic hydroxyl group are most preferred.

The molecular weight of the development accelerator (M) is preferably 100 to 2000, more preferably 150 to 1500, and most preferably 150 to 1,000.

As examples of the development accelerator, those having an alkyleneoxy group include polyethylene glycol, monomethyl ether of polyethylene glycol, dimethyl ether of polyethylene glycol, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester , Polybutylene glycol, polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, alkyl ether of polyoxyethylene, alkyl ester of polyoxyethylene, and compounds described in Japanese Patent Application Laid-Open No. 9-222724 .

Examples of compounds having a carboxyl group include compounds described in JP 2000-66406 A, JP 9-6001 B, JP 10-20501 A, JP 11-338150 A, and the like have.

Examples of those having a phenolic hydroxyl group include those disclosed in JP-A-2005-346024, JP-A-10-133366, JP-A-9-194415, JP-A-9-222724, The compounds described in JP-A-11-171810, JP-A-2007-121766, JP-A-9-297396, JP-A-2003-43679, etc. Among them, phenol compounds having 2 to 10 benzene ring numbers are favorable, and phenol compounds having 2 to 5 benzene ring numbers are more favorable. Particularly preferred examples include phenolic compounds disclosed as dissolution accelerators in JP-A-10-133366.

(M) The development accelerator may be used alone or in combination of two or more.

The addition amount of the development promoter (M) in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass based on 100 parts by mass of the acetal resin (A) from the viewpoints of sensitivity and residual film- More preferably 0.5 to 10 parts by mass.

(E) Crosslinking agent

The photosensitive resin composition of the present invention preferably contains (E) a crosslinking agent, if necessary. By adding the crosslinking agent (E), the cured film can be made into a stronger film.

As the crosslinking agent (E), for example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, or a compound having at least one ethylenically unsaturated double bond can be added .

Of these crosslinking agents, particularly preferred are compounds having two or more epoxy groups or oxetanyl groups in the molecule.

A compound having two or more epoxy groups or oxetanyl 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 epoxy resin include epoxy resins such as JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (Trade names, manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by DIC Corporation), and the like. Examples of the bisphenol F type epoxy resin include JER806, JER807, JER4004, JER4005, JER4007 and JER4010 JER152, JER157S70, JER157S65 (manufactured by Nippon Kayaku Co., Ltd.), and the like can be given as phenol novolak type epoxy resins. EPICLON N-770, EPICLON N-770 and EPICLON N-775 (all trade names, manufactured by DIC Corporation), and the like, and cresol (trade name, manufactured by Japan Epoxy Resin Co., EPICLON N-660, EPICLON N-660, EPICLON N-670, EPICLON N-670, EPICLON N-680, EPICLON N-690, EPICLON N- ), EOCN-1020 (Trade name, manufactured by Nippon Kayaku Co., Ltd.), and examples of the aliphatic epoxy resin include ADEKA RESIN EP-4080S, EP-4085S, EP-4088S ), Suloxide 2021P, Suloxide 2081, Suloxide 2083, Suloxide 2085, EHPE 3150, EPOLEAD PB 3600 and PB 4700 (trade names, manufactured by Daicel Chemical Industries, Ltd.). NC-2000, NC-3000, NC-7300, XD-1000 (trade name, manufactured by ADEKA Corporation), and EP- , EPPN-501, and EPPN-502 (all trade names, manufactured by ADEKA). These may be used alone or in combination of two or more.

Among these, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolak type epoxy resin. Particularly, a bisphenol A type epoxy resin is preferable.

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

The oxetanyl group-containing compound may be used alone or in combination with a compound containing an epoxy group.

The amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule to be added to the photosensitive resin composition is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass based on 100 parts by mass of the total amount of the acetal resin component (A) desirable.

Crosslinking agent containing alkoxymethyl group

As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea are preferable. These can be obtained by converting methylol melamine, methylol benzoguanamine, methylol glycoluryl, or the methylol group of the methylol moiety into an alkoxymethyl group, respectively. The kind 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, in particular, a methoxymethyl group desirable.

Among these crosslinkable 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 Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (trade names, manufactured by Mitsui Cyanamid Co., Ltd.), NIKARAK MX-750, -032, -706, -708, -40, -31, -270, -280, 290, NIKARAK MS-11, NIKARAK MW-30HM, -100 LM, and -390 (trade names, manufactured by Sanwa Chemical Co., Ltd.).

When the crosslinking agent having an alkoxymethyl group is used in the photosensitive resin composition of the present invention, the amount of the alkoxymethyl group-containing crosslinking agent to be added is preferably 0.05 to 50 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the acetal resin component (A) More preferable. When added in this range, it is possible to obtain favorable alkali solubility at the time of development and excellent solvent resistance of the film after curing.

A compound having at least one ethylenically unsaturated double bond

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 higher functional (meth) have.

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

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 trifunctional or higher (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol 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 alone 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 mass or less based on 100 parts by mass of the acetal resin component (A), more preferably 30 parts by mass or less More preferable. By containing a compound having at least one ethylenically unsaturated double bond in such a ratio, the heat resistance and surface hardness of the cured film obtained from the photosensitive resin composition of the present invention can be improved. When a compound having at least one ethylenically unsaturated double bond is added, it is preferable to add a heat radical generator (J) described later.

(F) Adhesion improver

The photosensitive resin composition of the present invention preferably contains (F) an adhesion improver.

The adhesion improver (F) that can be used in the photosensitive resin composition of the present invention is a compound which improves the adhesiveness between an inorganic substance to be a substrate and a silicon compound such as silicon, silicon oxide, or silicon nitride, 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 intended to modify the interface and is not particularly limited, and a known silane coupling agent can be used.

Preferable silane coupling agents include, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? - Methacryloxypropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? - Silane, 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 for 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 mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the acetal resin component (A).

(G) Basic compound

The photosensitive resin composition of the present invention preferably contains (G) a basic compound.

As the basic compound (G), any of chemical compounds used as a chemical amplification resistor may be selected and used. For example, aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

Examples of the aliphatic amine include aliphatic amines such as trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di- Amine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl- Benzimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxy 4-methyl morpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1, 2-diazabicyclo [4.3.0] -naphthalene, pyrazine, pyridazine, pyridine, pyrrolidine, piperidine, piperazine, morpholine, , 8-diazabicyclo [5.3.0] -7-undecene, and the like.

Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide and tetra-n-hexylammonium hydroxide .

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

The basic compounds which can be used in the present invention may be used singly or in combination of two or more kinds. However, two or more kinds of basic compounds are preferably used together, and more preferably two kinds of basic compounds are used. 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 mass, more preferably 0.002 to 0.2 part by mass based on 100 parts by mass of the acetal resin component (A).

(H) Surfactants (fluorine surfactants, silicone surfactants, etc.)

The photosensitive resin composition of the present invention preferably contains (H) a surfactant (such as a fluorine-based surfactant or a silicon-based surfactant).

As the surfactant, a copolymer (3) containing the repeating unit A and the repeating unit B shown below may be mentioned as a preferable example. The weight average molecular weight (Mw) of the copolymer is 1000 or more and 10000 or less, preferably 1500 or more and 5000 or less. The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography.

In the copolymer (3), R ²¹ and R ²³ each independently represent a hydrogen atom or a methyl group, R ²² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ²⁴ represents a hydrogen atom or a C1- P represents an integer of not less than 10 mass% and not more than 80 mass%, q represents an amount of not less than 20 mass% N is an integer of 1 or more and 10 or less;

L in the repeating unit B is preferably an alkylene group represented by the following formula (4).

In the formula (4), R ²⁵ represents an alkyl group having 1 to 4 carbon atoms and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to a coated surface, 2 or 3 is more preferable.

It is also preferable that the sum (p + q) of p and q is p + q = 100, that is, 100 mass%.

Specific examples of the fluorine-based surfactant and the silicon-based surfactant include those described in JP 62-36663 A, JP 61-226746 A, JP 61-226745 A, JP 62-170950 A, JP-B-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, 330953, etc., and commercially available surfactants may be used. As commercial surfactants that can be used, for example, FEFTAX EF301 and EF303 (trade names, manufactured by Shin-Aida Chemical Industry Co., Ltd.), Prolide FC 430 and 431 (products of Sumitomo 3M Co., , Megafac F171, F173, F176, F189 and R08 (trade names, manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105 and 106 (trade names, available from Asahi Glass Co., (Trade name), and PolyFox series (trade name, OMNOVA SHAHASE), and silicone surfactants. In addition, polysiloxane polymer KP-341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

These surfactants may be used singly or in combination of two or more. Further, a fluorine-based surfactant and a silicon-based surfactant may be used in combination.

The amount of the (H) surfactant (containing the fluorine surfactant and / or the silicon surfactant) in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less based on 100 parts by mass of the acetal resin component (A) More preferably from 0.01 to 10 parts by mass, and still more preferably from 0.01 to 1 part by mass.

(D) Antioxidants

The photosensitive resin composition of the present invention may contain (D) an antioxidant. As the antioxidant (D), a known antioxidant may be contained. (D) the addition of an antioxidant can prevent coloring of the cured film, reduce the film thickness reduction due to decomposition, and have an advantage of excellent heat-resistant transparency.

Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrite salts, sulfites, thiosulfates, hydroxyl Amine derivatives and the like. Among them, a phenol-based antioxidant is particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness. These may be used alone or in combination of two or more.

Examples of commercially available products of phenolic antioxidants include ADEKASTOP AO-60, ADEKA STOP AO-80 (trade name, manufactured by ADEKA), Irganox 1098 (trade name, manufactured by Ciba Japan Co., Ltd.) .

The content of the antioxidant (D) is preferably 0.1 to 6% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.5 to 4% by mass based on the total solid content of the photosensitive resin composition. Within this range, sufficient transparency of the formed film can be obtained, and sensitivity at the time of pattern formation is also improved.

As the additives other than the antioxidant, various ultraviolet absorbers, metal deactivators, and the like described in &quot; New developments of the polymer additive &quot; (Ilgan Kogyo Shimbun) may be added to the photosensitive resin composition of the present invention.

(I) a plasticizer

The photosensitive resin composition of the present invention may contain (I) a plasticizer.

Examples of the plasticizer (I) include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate and triacetyl glycerin.

The content of the plasticizer (I) in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the acetal resin 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) a thermal radical It is preferable to further contain an initiator.

As the thermal radical generator in the present invention, a known thermal radical generator may be used.

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

Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, A compound having a bond, an azo-based compound, and a non-benzyl compound.

As the thermal radical generator (J), one kind may be used alone, or two or more kinds may be used in combination.

The content of the heat radical generator (J) in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 50 parts by mass, based on 100 parts by mass of the acetal resin (A) More preferably 20 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass.

(K) Thermal acid generator

In the present invention, a (K) thermal acid generator may be used in order to improve physical properties of the film due to low-temperature curing.

The thermal acid generator of the present invention is a compound which generates acid by heat and is generally a compound having a thermal decomposition point in the range of 130 to 250 캜, preferably 150 to 220 캜, for example, (Lower) nucleophilic acid such as carboxylic acid, disulfonylimide and the like.

As the generated acid, a strong or stronger pKa of 2 or less, such as a sulfonic acid or an alkylcarboxylic acid or an arylcarboxylic acid substituted with an electron attractive group, or a disulfonylimide in which an electron attractive group is substituted is preferable. Examples of the electron-withdrawing group include a halogen atom such as a fluorine atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

In the present invention, it is also preferable to use a sulfonic acid ester which generates an acid by heat without generating an acid substantially by irradiation with exposure light.

It can be judged that there is no change in the spectrum by measurement of the IR spectrum and NMR spectrum before and after exposure of the compound, in which substantially no acid is generated by irradiation of the exposure light.

The molecular weight of the sulfonic acid ester is generally 230 to 1000, preferably 230 to 800.

The sulfonic acid ester which can be used in the present invention may be a commercially available sulfonic acid ester or may be synthesized by a known method. Sulfonic acid esters can be synthesized, for example, by reacting a sulfonyl chloride or a sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.

The content of the sulfonic acid ester in the photosensitive resin composition is preferably from 0.5 to 20 parts by mass, more preferably from 1 to 15 parts by mass, based on 100 parts by mass of the acetal resin component (A).

(L) Acid growth agent

In the photosensitive resin composition of the present invention, (L) an acid propagating agent may be used for the purpose of improving the sensitivity. The acid-proliferating agent used in the present invention is a compound that can generate an acid by further catalyzing acid-catalysis to increase the acid concentration in the reaction system, and is a compound stably present in the absence of acid. In such a compound, since at least one acid increases in a single reaction, the reaction proceeds acceleratively with the progress of the reaction. However, since the generated acid itself induces self-decomposition, The strength is preferably 3 or less, more preferably 2 or less, as the acid dissociation constant, pKa.

Specific examples of acid proliferating agents include the compounds described in JP-A-10-1508 [0203] to [0223], JP-A-10-282642 [0016] to [0055] A compound described in the publication line 2 on page 39 line 12 to page 47 line 2 can be mentioned.

Examples of the acidic proliferative agent that can be used in the present invention include acids decomposed by acids generated from an acid generator and decomposed with pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid and phenylphosphonic acid And compounds capable of generating an acid of 3 or less.

The content of the acid proliferating agent in the photosensitive resin composition is preferably 10 to 1000 parts by mass based on 100 parts by mass of the (B) photoacid generator from the viewpoint of dissolution contrast between the exposed portion and the unexposed portion, and is preferably 20 to 500 parts by mass Is more preferable.

Method of forming a cured film

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

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

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

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

(3) exposing the applied photosensitive resin composition by an actinic ray (exposure step);

(4) developing the exposed photosensitive resin composition with an aqueous developing solution (development step);

(5) Heat-curing the developed photosensitive resin composition (post-baking step).

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 of (2), the solvent is removed from the coated film by reduced pressure (baking) 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 in the structural unit (a1) contained in the acetal-based resin (A) is decomposed to produce a carboxyl group.

In the region where the acid catalyst is produced, PEB (post-exposure heat treatment) can be performed as needed in order to accelerate the decomposition reaction. By PEB, the generation of carboxyl groups from the acid decomposable group can be promoted.

The acid-decomposable group in the structural unit (a1) in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group. Therefore, , And a positive image may be formed by development.

Further, by performing 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 90 占 폚.

(A) acetal resin having a liberated carboxyl group is developed using an alkaline developer in the developing step of (4). A positive image is formed by removing the exposed region containing a resin composition having a carboxyl group which is liable to dissolve in an alkaline developer.

A cured film can be formed by thermally decomposing an acid-decomposable group in the structural unit (a1) to produce a carboxyl group by heating the obtained positive image in the post-baking step of the step (5) and crosslinking the epoxy group and / or oxetanyl group . The 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, but is preferably within a range of 10 to 90 minutes.

When a step of irradiating the active ray, preferably ultraviolet ray, with the development pattern in front of the post-baking step is added, the crosslinking reaction can be promoted by the acid generated by the actinic ray irradiation.

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

Method for preparing photosensitive resin composition

The essential components of the acetal resin (A), the photoacid generator (B), and the solvent (C) are mixed in an arbitrary manner at a predetermined ratio, and the mixture is stirred and dissolved to prepare a photosensitive resin composition. For example, a solution prepared by previously dissolving (A) an acetal resin or (B) a photoacid generator in a solvent beforehand may be prepared and then mixed at a predetermined ratio to prepare a photosensitive resin composition. The solution of the photosensitive resin composition prepared as described above may be used after being filtered using a filter having a pore diameter of 0.1 mu m or the like.

Application Process and Solvent Removal Process

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

(2) The heating condition of the solvent removal step is such that the acid decomposable group decomposes in the structural unit (a1) in the acetal-based resin (A) in the unexposed portion, and the acetal- And it varies depending on the kind of each component and blending ratio, and is preferably about 70 to 120 DEG C for 30 to 300 seconds.

Exposure process

(3) In the exposure step, an actinic ray of a predetermined pattern is irradiated to the substrate provided with the dry film. The exposure may be performed via a mask, or a predetermined pattern may be directly drawn. An active ray having a wavelength of 300 nm or more and 450 nm or less can be preferably used. After the exposure process, PEB is performed if necessary.

A low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a laser generator, an LED light source, or the like can be used for exposure by an actinic ray.

When a mercury lamp is used, an actinic ray having a wavelength of g-line (436 nm), i-line (365 nm) and h-line (405 nm) can be preferably used. The mercury lamp is preferable in that it is suitable for exposure of a large area as compared with a laser.

When a laser is used, 343 nm and 355 nm are used as the solid (YAG) laser, 351 nm (XeF) is used as the excimer laser, and 375 nm and 405 nm are available as the semiconductor laser. Of these, 355 nm and 405 nm are more preferable in terms of stability and cost. The laser can be applied to the coating film once or plural times.

The energy density per pulse of the laser is preferably from 0.1 mJ / cm 2 to 10000 mJ / cm 2. More preferably not less than 0.3 mJ / cm 2, most preferably not less than 0.5 mJ / cm 2, and more preferably not more than 1000 mJ / cm 2 in order to prevent the coating film from being decomposed by the ablation phenomenon , And most preferably 100 mJ / cm 2 or less.

The pulse width is preferably from 0.1 nsec to 30000 nsec. In order to prevent decomposition of the color coating film due to ablation, it is more preferably 0.5 nsec or more, most preferably 1 nsec or more, and more preferably 1000 nsec or less and 50 nsec or less desirable.

The frequency of the laser is preferably 1 to 50000 Hz, more preferably 10 to 1000 Hz. When the frequency of the laser is less than 1 Hz, the exposure processing time is increased. When the frequency is more than 50000 Hz, the accuracy of alignment at the time of scanning exposure is lowered.

The frequency of the laser is preferably 1 Hz or more and 50000 Hz or less. In order to shorten the exposure processing time, more preferably 10 Hz or more, most preferably 100 Hz or more, and more preferably 10000 Hz or less, and most preferably 1000 Hz or less, in order to improve the fitting precision at the time of the scan exposure.

Compared with a mercury lamp, a laser is preferable in that it is easy to narrow the focus, and a mask for forming a pattern in an exposure process is unnecessary, and cost can be reduced.

Examples of the exposure apparatus that can be used in the present invention include, but are not limited to, commercially available products such as Callisto (trade name, manufactured by V Technology Corporation), AEGIS (trade name, manufactured by V Technology Corporation), DF2200G Ltd.) and the like can be used. Also, devices other than those described above can be used suitably.

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.

Development process

(4) In the developing process, an exposed pattern area is removed by using a basic developing solution to form an image pattern. Examples of the basic compound include alkali metal hydroxide 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 tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline hydroxide; An aqueous solution of sodium silicate, sodium metasilicate or the like can be used. 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 usually from 30 to 180 seconds, and the developing method may be any of a liquid method, a dipping method, and a shower method. After the development, a desired pattern can be formed by performing an aqueous (water) cleaning for 10 to 90 seconds.

Post baking process (crosslinking process)

For a predetermined time at a predetermined temperature, for example, 180 to 250 캜 for a predetermined time, for example, on a hot plate, using a heating apparatus such as a hot plate or an oven for a pattern corresponding to the unexposed region obtained by development (A) decomposing an acid-decomposable group in the acetal-based resin to generate a carboxyl group, and (A) reacting an epoxy group and / or an oxetanyl group in the acetal-based resin with a crosslinkable group And a crosslinking reaction is carried out to form a protective film or an interlayer insulating film excellent in heat resistance, hardness and the like. Further, when the heat treatment is performed, transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

In addition, prior to the heat treatment, an acid is generated from the (B) photoacid generator present in the unexposed portion by post-baking (re-exposure / post-baking) It is preferable to function as a catalyst for promoting crosslinking.

That is, the method of forming a cured film in the present invention preferably includes a re-exposure step of re-exposing the resist film by the actinic ray between the developing step and the post-baking step.

The exposure in the re-exposure step may be performed by the same means as in the exposure step, but in the re-exposure step, it is preferable to perform the entire exposure on the side of the substrate where the film is formed by the photosensitive resin composition of the present invention. The preferable exposure amount of the re-exposure process is 100 to 1,000 mJ / cm &lt; 2 &gt;.

With the photosensitive resin composition of the present invention, a cured film having excellent insulating properties and having high transparency even when baked at a high temperature can be obtained and is useful as an interlayer insulating film. 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 the cured film formed using the photosensitive resin composition of the present invention is used as a planarizing film or an interlayer insulating film, Organic EL display devices and liquid crystal display devices.

Fig. 1 shows a configuration diagram of an example of an organic EL display device. Sectional view of a substrate in a bottom emission type organic EL display device and has a planarizing 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 so as to cover the TFT 1. A wiring 2 (height 1.0 mu m) connected to the TFT 1 via the contact hole is formed on the insulating film 3 after forming a contact hole (not shown) in the insulating film 3 here. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or a later step to the TFT 1. [

The flattening film 4 is formed on the insulating film 3 so as to fill the irregularities formed by the wirings 2 in order to planarize the irregularities due to the formation of the wirings 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 providing the insulating film 8, the first electrode 5 and the second electrode Can be prevented.

Although not shown in FIG. 1, a hole transporting layer, an organic light emitting layer, and an electron transporting layer are sequentially deposited by a desired pattern mask, and subsequently, a second electrode made of Al is formed on the entire upper surface of the substrate, An active matrix type organic EL display device in which an encapsulating glass plate and an ultraviolet curing type epoxy resin are used to encapsulate and seal each organic EL element and a 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 is a liquid crystal display panel in which all of the two glass substrates 14 and 15 that are stuck Elements of the TFT 16 corresponding to the pixel are disposed. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 which passes through the contact hole 18 formed in the cured film 17 and forms a pixel electrode. 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 provided.

Example

Next, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited by these examples. Unless otherwise specified, &quot; part &quot; and &quot;% &quot; are based on mass.

In the following Synthesis Examples, the following abbreviations respectively represent the following compounds.

V-65: 2,2'-azobis (2,4-dimethylvaleronitrile)

GMA: glycidyl methacrylate

PGMEA: Propylene glycol monomethyl ether acetate

Synthesis of Polymer A-1

(1 molar equivalent) of methacrylic acid was added dropwise to 144.2 parts (2 molar equivalents) of ethyl vinyl ether while 0.5 part of phenothiazine was added to the reaction system while cooling the reaction system to 10 DEG C or lower, and the mixture was stirred at room temperature (25 DEG C) for 4 hours Lt; / RTI &gt; 5.0 parts of p-toluenesulfonic acid pyridinium was added, and the mixture was stirred at room temperature for 2 hours and allowed to stand at room temperature overnight. 5 parts of sodium hydrogencarbonate and 5 parts of sodium sulfate were added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The insoluble material was filtered and then concentrated under reduced pressure at 40 DEG C or lower to obtain a yellow oil- Distillation to obtain 134.0 parts of 1-ethoxyethyl methacrylate having a boiling point (bp.) Of 43 to 45 DEG C / 7 mmHg as a colorless oil.

The obtained methacrylic acid was mixed with 66.41 parts (0.4 molar equivalent) of methacrylic acid, 6.89 parts (0.08 molar equivalent) of methacrylic acid, 49.75 parts (0.35 molar equivalent) of GMA, 19.52 parts (0.15 mol) of 2-hydroxyethyl methacrylate Equivalent) and 132.5 parts of PGMEA was heated to 70 占 폚 under a nitrogen stream. While stirring the mixed solution, a mixed solution of a radical polymerization initiator V-65 (12.4 parts by Wako Pure Chemical Industries, Ltd.) and 100.0 parts of PGMEA was added dropwise over 2.5 hours. After completion of the dropwise addition, the PGMEA solution (solid content concentration: 40%) of Polymer A-1 was obtained by reacting at 70 DEG C for 4 hours. The polymer A-1 thus obtained had a weight average molecular weight of 8,000 as determined by gel permeation chromatography (GPC).

Synthesis of Polymers A-2 to A-19, A-30, A-31, A-34 to A-36, and A'-20 to 29

Polymer A-1 was obtained in the same manner as in Polymer A-1 except that the respective monomers used in the synthesis of Polymer A-1 were changed to the respective structural units (a1) to (a5) shown in Table 1 and the usage amounts of the respective structural units were changed to those shown in Table 1. Polymers A-2 to 19, A-30, A-31, A-34 to A-36, and A'-20 to 29 were synthesized in the same manner as in Synthesis. The addition amount of the radical polymerization initiator V-65 was adjusted so as to have the molecular weights shown in Table 1, respectively.

[Table 1]

In addition, the molar ratio shown in Table 1 is the copolymerization ratio of each structural unit, and (a4) the mass% of the structural unit is the mass% of the structural unit (a-4) in the polymer. "-" in Table 1 indicates that the structural unit thereof is not used, and in the polymer A-8, (a4) HEMA and PME-400 are used as structural units of 10 mol% and 1 mol% respectively, -26, (a4) indicates that 10 mol% of HEMA and 5 mol% of PME-400 were used as structural units.

The abbreviations in Table 1 are as follows.

MAEVE: 1-ethoxyethyl methacrylate

CHOEMA: 1- (cyclohexyloxy) ethyl methacrylate

MATHF: tetrahydrofuran-2-yl methacrylate

GMA: glycidyl methacrylate

OXE-30: Methacrylic acid (3-ethyloxetan-3-yl) methyl (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

OXE-10: Acrylic acid (3-ethyloxetan-3-yl) methyl (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

M100: 3,4-epoxycyclohexylmethyl methacrylate (trade name, manufactured by Daicel Chemical Industries, Ltd.)

MAA: methacrylic acid

AA: Acrylic acid

Ph-2: 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester

HEMA: 2-hydroxyethyl methacrylate

PME-400: methyl-terminated polyethylene glycol methacrylate (Blemmer PME-400, trade name, manufactured by Nichiyu Corporation)

MMA: methyl methacrylate

DCPM: di-cyclopentanyl methacrylate

CHMA: cyclohexyl methacrylate

BzMA: Benzyl methacrylate

St: Styrene

C1: Propylene glycol monomethyl ether acetate

C2: diethylene glycol ethyl methyl ether

CHOEMA and MATHF were synthesized by the same method as the above-mentioned 1-ethoxyethyl methacrylate.

Ph-2 was synthesized by the following method.

20 ml of N, N-dimethylacetamide was added to a solution of 21 g of 4-hydroxybenzoic acid (2-hydroxyethyl) ester in 100 ml of acetonitrile under stirring, and 20 g of methacrylic chloride was further 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-methacryloyl Yloxyethyl) ester.

Synthesis of polymer A'-32

Diethylene glycol ethyl methyl ether (25 g) was added to the three-necked flask, and the flask was placed under a nitrogen atmosphere and the temperature was raised to 70 占 폚. MAA (1444 g), MAEVE (14.23 g), benzyl methacrylate (12.33 g) and V-65 (3.477 g, 7 mol% based on the monomer) were dissolved in diethylene glycol ethyl methyl ether , And the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 4 hours, and the reaction was terminated to obtain a diethylene glycol ethyl methyl ether solution (solid concentration: 40%) of the polymer A'-32. The polymer A'-32 thus obtained had a weight average molecular weight measured by gel permeation chromatography (GPC) of 7,200.

Synthesis of Polymer A-33

Diethylene glycol ethyl methyl ether (24.5 g) was added to the three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. MAEVE (12.65 g), GMA (10.23 g), HEMA (6.24) and V-65 (3.477 g, 7 mol% based on monomer) were dissolved in diethylene glycol ethyl methyl ether (24.5 g) . After completion of dropwise addition, the mixture was stirred for 4 hours. Thereafter, the temperature was elevated to 90 DEG C as an aging step of thermally decomposing a small amount of MAEVE, and the reaction was terminated by stirring for 3 hours to obtain a diethylene glycol ethyl methyl ether solution (solid concentration: 40%) of the polymer A-33 . NMR and the measured acid value, the composition ratio (molar ratio) of the polymer A-33 was MAA / MAVEV / GMA / HEMA = 4.5 / 35.5 / 36/24 and the weight average molecular weight measured by gel permeation chromatography 7,500. The mass% of the structural unit (a4) was 22%.

Examples 1 to 119, Comparative Examples 1 to 11, and Comparative Example 14

(1) Preparation of Photosensitive Resin Composition

Each of the components shown in Table 2 below was mixed to obtain a homogeneous solution, which was then filtered using a polytetrafluoroethylene filter having a pore size of 0.1 mu m to obtain a comparative example 1 to a comparative example 1 to 11, A solution of the photosensitive resin composition of Example 14 was prepared.

In Tables 2 to 5, in Example 30, Example 70, and Example 107, two kinds of polymers A'-32 and A-33 were used. In Table 2, two types are used, and two types are used. For example, the amount of crosslinking agent in Example 37 is 8 parts of E2 and 1.5 parts of E3.

[Table 2]

[Table 3]

[Table 4]

[Table 5]

The abbreviations in Tables 2 to 5 are as follows.

B1: CGI1397 (trade name, the following structure, manufactured by Ciba Japan Co., Ltd.)

B2: CGI1325 (trade name, the following structure, manufactured by Ciba Japan K.K.)

B3: PAI-1001 (trade name, the following structure, manufactured by Midori Kagaku Co., Ltd.)

B4: PAI-101 (trade name, the following structure, manufactured by Midori Kagaku Co., Ltd.)

B5:? - (p-toluenesulfonyloxyimino) phenylacetonitrile (synthesis method is shown below)

B6: Compound

B7: The following compounds

B8: Compound

B9: Compound

N1: NBCA (trade name, the following structure, manufactured by Kuraray Chemical Industries, Ltd.)

N2: DBA (trade name, 9,10-dibutoxyanthracene, structure shown below, Kawasaki Chemical Industries, Ltd.)

C1: Propylene glycol monomethyl ether acetate

C2: diethylene glycol ethyl methyl ether

E1: JER-157S70 (trade name, polyfunctional novolak type epoxy resin (epoxy equivalent: 200 to 220 g / eq), Japan Epoxy Resin Co.,

E2: JER-157S65 (trade name, polyfunctional novolac epoxy resin (epoxy equivalents: 200 to 220 g / eq), Japan Epoxy Resin Co.,

E3: NIKARAK MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.)

E4: NIKARAK MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.)

E5: KAYARAD DPHA (trade name, manufactured by Nihon Kayaku Co., Ltd.)

H1: PolyFox PF-6320 (trade name, fluorine-based surfactant, OMNOVA ShaZee)

H2: Compound W-3 of the following structure

G1: 4-Dimethylaminopyridine

G2: 1,5-Diazabicyclo [4.3.0] -5-nonene

G3: Triphenylimidazole

G4: Diazabicyclo undecene

G5: 1,4-diazabicyclo [2.2.2] octane

F1: 3-glycidoxypropyltrimethoxysilane (KBM-403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.))

M1: The following compounds

M2: The following compounds

J1: (2,3-dimethyl-2,3-diphenylbutane) (NOFUMAR BC-90 (trade name, manufactured by Nichiyu Corporation))

K1: Compound K-1 shown below

L1: Compound L-1 of the following structure

Synthesis of B5

Α- (p-toluenesulfonyloxyimino) phenylacetonitrile was synthesized according to the method described in the paragraph [0108] of Japanese Patent Application No. 2002-528451.

Synthesis of B6

1-1. Synthesis of Synthetic Intermediate B-6A

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). Subsequently, 40.6 g of phenylacetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was reacted at room temperature for 1 hour and then at 100 占 폚 for 2 hours with stirring. To the reaction solution obtained, 500 mL of water was added to dissolve the precipitated salt, the toluene oil was extracted, and the extract was concentrated with a rotary evaporator to obtain a synthetic intermediate B-6A.

1-2. Synthesis of B-6

2.25 g of the thus-obtained synthetic intermediate B-6A was mixed with 10 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) and then immersed in an ice bath to cool the reaction solution to 5 ° C or less. Next, 4.37 g of tetramethylammonium hydroxide (25% by weight methanol solution, Alfa Acer Co., Ltd.) was added dropwise and the mixture was reacted with stirring in an ice bath for 0.5 hour. Further, 7.03 g of isopentyl nitrite was added dropwise while keeping the temperature at 20 ° C or lower, and after the dropwise addition, the reaction solution was heated to room temperature and stirred for one hour.

Subsequently, the reaction solution was cooled to 5 캜 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 at 10 캜 or lower. Then, 80 mL of water was added, and the mixture was stirred at 0 ° C for 1 hour. The resulting precipitate was filtered, and 60 mL of isopropyl alcohol (IPA) was added. The mixture was heated to 50 DEG C and stirred for 1 hour, filtered and dried (B6: the above structure) to obtain 1.8 g.

The resulting ¹ H-NMR spectrum of the obtained B6 (300 MHz, DMSO ((D ₃ C) ₂ S = O)) was found to be δ = 8.2-8.17 (m, 1H), 8.03-8.00 7.9 (m, 2H), 7.6-7.45 (m, 9H), 2.45 (s, 3H).

It is estimated that B6 obtained from the above ¹ H-NMR measurement results is a single cis or trans isomer.

Synthesis of B7

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 separate the layers. The organic layer was concentrated, and the crystals were reslurried with diisopropyl ether , Filtered and dried to obtain a ketone compound (6.5 g).

Acetic acid (7.3 g) and a 50 mass% 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 allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).

The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and the 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 B7 (2.3 g).

In addition, ¹ H-NMR spectrum of the B7 (300㎒, CDCl ₃₎ is, δ = 8.3 (d, 1H ), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 ( (d, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d.1H), 5.6

Synthesis of B8

2-Naphthol (20 g) was dissolved in N, N-dimethylacetamide (150 ml). Potassium carbonate (28.7 g) and ethyl 2-bromoacetate (52.2 g) were added and reacted at 100 ° C for 2 hours. Water (300 mL) and ethyl acetate (200 mL) were added to the reaction mixture and the mixture was separated. The organic layer was concentrated, and 48 wt% aqueous sodium hydroxide solution (23 g), ethanol (50 mL) and water (50 mL) . The reaction solution was poured into 1N HCl aqueous solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid. Then, 30 g of polyphosphoric acid was added and reacted at 170 DEG C for 30 minutes. The reaction solution was poured into water (300 mL), and ethyl acetate (300 mL) was added thereto for liquid separation. The organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).

Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g) and magnesium sulfate (4.5 g) were added to the resulting suspension of the ketone compound (10.0 g) and methanol (100 mL) and the mixture was refluxed for 24 hours. After cooling, water (150 mL) and ethyl acetate (150 mL) were added to separate the layers. The organic layer was separated into four portions of 80 mL of water, concentrated, and then purified by silica gel column chromatography to obtain an oxime compound (5.8 g).

The resulting oxime (3.1 g) was sulfonated as in B7 to give B8 (3.2 g).

In addition, ¹ H-NMR spectrum of B8 (300㎒, CDCl ₃₎ is, δ = 8.3 (d, 1H ), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 ( (dd, 1H), 7.5 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 , 1H), 1.4-1.2 (m, 8H), 0.8 (t, 3H).

Synthesis of B9

B9 was synthesized in the same manner as B7 except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in the synthesis of B7.

In addition, ¹ H-NMR spectrum of B9 (300㎒, CDCl ₃₎ is, δ = 8.3 (d, 1H ), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.7- (M, 4H), 7.4 (dd, 1H), 7.1 (d, 1H), 5.6 (q,

The composition used in Comparative Example 12 is the composition described in Example 1 of Japanese Patent Application Laid-Open No. 2004-264623. The composition used in Comparative Example 13 is the composition described in Example 7 of JP-A-2009-98616. The composition used in Comparative Example 14 is the composition described in Example 1 of Japanese Patent Application Laid-Open No. 10-26829.

(2) Evaluation of Photosensitive Resin Composition

(2-1) Evaluation of sensitivity (without PEB)

The solutions of the photosensitive resin compositions of Examples 1 to 119 and Comparative Examples 1 to 14 were each spin-coated on a silicon wafer having a silicon oxide film and then pre-baked on a hot plate at 90 캜 for 120 seconds to form a coating film having a film thickness of 3 탆 did.

Next, using an i-line stepper (trade name: FPA-3000i5 +, manufactured by Canon Inc.), exposure was performed through a predetermined mask. The substrate was allowed to stand at room temperature for 10 minutes after exposure, developed with a 0.4% tetramethylammonium hydroxide aqueous solution at 23 占 폚 for 60 seconds by a liquid method, and further rinsed with ultrapure water for 45 seconds. With these operations, the optimum exposure amount (Eopt) when resolving a line-and-space of 10 mu m at a ratio of 1: 1 was taken as sensitivity. The sensitivity can be said to be high sensitivity when the amount of exposure is lower than 70 mJ / cm 2. The evaluation results are shown in Tables 6 and 7.

"**" in the column of sensitivity (PEB free) in Tables 6 and 7 means that the patterning could not be performed due to peeling at the time of development, and "*" indicates that the patterning was impossible at 200 mJ / Indicating that the pattern could not be formed.

(2-2) Evaluation of heat resistance transparency

A solution of the photosensitive resin composition of Examples 1 to 119 and Comparative Examples 1 to 14 (except that the pattern could not be formed at 200 mJ / cm 2) was spin-coated on a glass substrate (trade name: Eagle 2000, Corning) And then prebaked on a hot plate at 90 캜 for 120 seconds to form a coating film having a film thickness of 3 탆. The obtained coating film was developed with a 0.4% tetramethylammonium hydroxide aqueous solution at 23 占 폚 for 60 seconds by a liquid method and further rinsed with ultrapure water for 45 seconds. Thereafter, a PLA-501F exposure device (trade name: Ultra High Pressure Mercury Lamp ) So as to have an integrated irradiation amount of 300 mJ / cm 2 (light intensity: 20 mW / cm 2). Thereafter, this substrate was heated in an oven at 230 ° C for 1 hour to obtain a cured film. The obtained cured film was further heated in an oven at 230 DEG C for 2 hours, and then the light transmittance was measured using a spectrophotometer &quot; 150-20 type double beam (trade name, manufactured by Hitachi Seisakusho Co., Ltd.) . The evaluation of the lowest light transmittance (evaluation of heat resistance and transparency) at that time is shown in Tables 6 and 7.

The evaluation criteria are as follows. Further, the value of the lowest light transmittance is converted into a value per 2 mu m of film thickness after heating at 230 DEG C for 2 hours.

0: 92% or more

1: 87% or more and less than 92%

2: 85% or more and less than 87%

3: 82% or more and less than 85%

4: less than 82%

(2-3) Evaluation of ITO sputter resistance

The photosensitive resin compositions of Examples 1 to 119 and Comparative Examples 1 to 14 (except that the pattern could not be formed at 200 mJ / cm 2) were spin-coated on a glass substrate &quot; Eagle 2000 (trade name, On a hot plate for 120 seconds to form a coating film having a thickness of 3 m. The resulting coating film was exposed with a PLA-501F exposure apparatus (trade name, ultra-high pressure mercury lamp) manufactured by Canon Inc. so as to have a cumulative dose of 300 mJ / cm 2 (illuminance: 20 mW / cm 2) And heated for a time to obtain a cured film. Each of the obtained cured films was subjected to ITO sputtering at a substrate temperature of 210 DEG C in ULVAC SHARSE SIH-3030 (trade name), and an ITO film of 0.14 mu m was formed on the cured film. The surface after the sputtering was observed with an optical microscope to evaluate the surface roughness. The evaluation results are shown in Tables 6 and 7. The evaluation criteria were as follows.

1: no surface roughness observed

2: Surface roughness slightly observed, but practically no problem level

3: Surface roughness is observed, and practically unacceptable levels

4: The surface is violently rough

(2-4) Sensitivity when PEB (post exposure baking) is performed

The photosensitive resin compositions of Examples 9 to 12, Examples 50 to 52, Examples 87 to 89, and Comparative Example 13 were subjected to PEB at 80 캜 for 60 seconds with a hot plate 1 minute after exposure (2-1) Evaluation of sensitivity (without PEB), the sensitivity in the case of performing PEB was evaluated. The results are shown in Tables 6 and 7.

[Table 6]

[Table 7]

From Table 6 and Table 7, it can be seen that all the photosensitive resin compositions of the present invention have high sensitivity even when PEB is not performed, good heat-resistant transparency, and excellent ITO sputter resistance. Further, in the photosensitive resin composition of the present invention, the sensitivity is very high even without PEB, but it can be seen that the sensitivity is further increased by performing PEB.

On the other hand, the comparative example in which the present invention is not used shows low sensitivity when PEB is not performed and low sensitivity compared to the embodiment of the present invention even when PEB is performed.

(2-5) Adhesion on glass substrate

The photosensitive resin compositions of Examples 1 to 119 were prepared by using the glass substrate "Eagle 2000 (trade name, Corning Co.)" instead of the silicon wafer in the evaluation of the sensitivity (PEB) (2-1) A coating film was formed as in the above (2-1) except that a predetermined mask was closely contacted with a proximity exposure apparatus (UX-1000SM, product name: UX-1000SM), so that the light intensity at 365 nm was 16 mW / Cm &lt; 2 &gt;. The glass substrate was subjected to ordinary cleaning, and two kinds of the photosensitive resin composition were further washed and then exposed to hexamethyldisilazane vapor for 3 minutes in a desiccator.

The exposure was carried out at an exposure amount of 1: 1 in a line-and-space of 10 mu m. Subsequently, the substrate was allowed to stand at room temperature for 10 minutes after the exposure as described in (2-1), and developed with a 0.4% tetramethylammonium hydroxide aqueous solution at 23 DEG C for 60 seconds by the liquid method. Rinse. At this time, patterning of the pattern and peeling did not occur in any of the photosensitive resin compositions of Examples 1 to 119.

(2-6) 355 nm laser exposure

The photosensitive resin compositions of Examples 1 to 119 were subjected to the same procedure as in (2-1) above except that the exposure was evaluated in the evaluation of the sensitivity (PEB) (2-1) , And pattern formation was performed. That is, a predetermined photomask was set through an interval of 150 mu m from the coating film, and a laser beam having a wavelength of 355 nm was irradiated at an exposure amount of 10 to 100 mJ / cm &lt; 2 &gt;. The laser device used was "AEGIS" (trade name) manufactured by Kabushiki Kaisha V Technology Co., Ltd. (wavelength: 355 nm, pulse width: 6 nsec) and the exposure amount was measured using "PE10B-V2" (trade name) .

It was found that patterns could be formed even at 355 nm laser exposure in any of the photosensitive resin compositions of Examples 1 to 119.

(2-7) UV-LED exposure

Evaluation of the sensitivity (without PEB) was carried out in the same manner as in the above (2-1) evaluation of sensitivity (PEB free), except that the exposure was changed from an i-line stepper to a UV- It was found that pattern formation was possible in all cases.

Example 120

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

The bottom gate type TFT 1 was formed on the glass substrate 6 and the insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, after a contact hole was formed in the insulating film 3, a wiring 2 (height 1.0 mu m) connected to the TFT 1 via the contact hole was formed on the insulating film 3.

In order to planarize the irregularities due to the formation of the wirings 2, the flattening film 4 was formed on the insulating film 3 in a state in which the irregularities by the wirings 2 were filled. The planarizing film 4 on the insulating film 3 was formed by spin-coating the photosensitive resin composition of Example 11 on a substrate, pre-baking it on a hot plate (90 占 폚 for 2 minutes) (365 nm) was irradiated with 25 mJ / cm 2 (illuminance: 20 mW / cm 2) and then developed with an aqueous alkali solution to form a pattern, and heat treatment was performed at 230 ° C. for 60 minutes. The coating properties upon application of the photosensitive resin composition were satisfactory, and wrinkles and cracks were not observed in the cured films obtained after exposure, development and firing. The average step of the wiring 2 was 500 nm, and the film thickness of the planarization film 4 was 2.000 nm.

Next, a bottom emission type organic EL device was formed on the obtained planarization film 4. Then, First, a first electrode 5 made of ITO was formed on the flattening film 4 by being connected to the wiring 2 via the contact hole 7. Thereafter, the resist was coated and prebaked, 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 at 50 캜 using a resist stripping solution (Remover 100, AZ Electronic Materials Co., Ltd.). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. The insulating film 8 was formed using the photosensitive resin composition of Example 12 by the same method as described above.

Further, a hole transporting layer, an organic light emitting layer, and an electron transporting layer were sequentially deposited by evaporation through a desired pattern mask in a vacuum vapor deposition apparatus. Subsequently, a second electrode made of Al was formed on the entire upper surface of the substrate. The obtained substrate was taken out of 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 each organic EL element are connected is obtained. When the voltage was applied through the driving circuit, it was found that the organic EL display device exhibited good display characteristics and was highly reliable.

Example 121

The photosensitive resin composition of Example 11 in which the planarizing film 4 was formed and the photosensitive resin composition of Example 12 in which the insulating film 8 was formed were all changed to the photosensitive resin composition of Example 43 An organic EL display device was produced in the same manner as in Example 120 except for the above. The obtained organic EL display device exhibited good display characteristics and was found to be an organic EL display device with high reliability.

Example 122

The photosensitive resin composition of Example 11 in which the planarizing film 4 was formed in Example 120 and the photosensitive resin composition of Example 12 in which the insulating film 8 was formed were all changed to the photosensitive resin composition of Example 80 An organic EL display device was produced in the same manner as in Example 120 except for the above. The obtained organic EL display device exhibited good display characteristics and was found to be an organic EL display device with high reliability.

Example 123

The photosensitive resin composition of Example 11 in which the planarizing film 4 was formed in Example 120 and the photosensitive resin composition of Example 12 in which the insulating film 8 was formed were all changed to the photosensitive resin composition of Example 119 An organic EL display device was produced in the same manner as in Example 120 except for the above. The obtained organic EL display device exhibited good display characteristics and was found to be an organic EL display device with high reliability.

Example 124

In the active matrix type liquid crystal display device described in Figs. 1 and 2 of Japanese Patent No. 3321003, a cured film 17 as an interlayer insulating film was formed as follows to obtain a liquid crystal display device of Example 124. [

That is, using the photosensitive resin composition of Example 11, a cured film 17 was formed as an interlayer insulating film in the same manner as in the method of forming the planarization film 4 of the organic EL display device in Example 120. [

When the driving voltage was applied to the obtained liquid crystal display device, good display characteristics were exhibited and it was found that the liquid crystal display device was highly reliable.

Example 125

A liquid crystal display device was produced in the same manner as in Example 124 except that the photosensitive resin composition of Example 11 was changed to the photosensitive resin composition of Example 43. The obtained liquid crystal display device exhibited good display characteristics, and it was found that the liquid crystal display device was highly reliable.

Example 126

A liquid crystal display device was produced in the same manner as in Example 124 except that the photosensitive resin composition of Example 11 was changed to the photosensitive resin composition of Example 80. [ The obtained liquid crystal display device exhibited good display characteristics, and it was found that the liquid crystal display device was highly reliable.

Example 127

A liquid crystal display device was produced in the same manner as in Example 124 except that the photosensitive resin composition of Example 11 was changed to the photosensitive resin composition of Example 119. [ The obtained liquid crystal display device exhibited good display characteristics, and it was found that the liquid crystal display device was highly reliable.

Example 128

In the liquid crystal display device shown in Fig. 2 of Japanese Patent Application Laid-Open No. 2008-146004, a protective film 141 was formed by using the photosensitive resin composition of Example 119 to obtain a liquid crystal display device of Example 128. Fig.

When the driving voltage was applied to the obtained liquid crystal display device, good display characteristics were exhibited and it was found that the liquid crystal display device was highly reliable.

Example 129

In the liquid crystal display device shown in Fig. 1 of Japanese Patent Application Laid-Open No. 2000-267073, an overcoat 15 was formed by using the photosensitive resin composition of Example 119 to obtain a liquid crystal display device of Example 129. Fig.

When the driving voltage was applied to the obtained liquid crystal display device, good display characteristics were exhibited and it was found that the liquid crystal display device was highly reliable.

Claims (15)

1. A photosensitive resin composition comprising (A) an acetal resin, (B) a photoacid generator, and (C) a solvent,
(A3) having a carboxyl group or a phenolic hydroxyl group, a structural unit (a3) having an epoxy group or an oxetanyl group, a structural unit (a1) having a structure capable of forming a carboxyl group by an acid, And a structural unit (a4) which is a structural unit which does not correspond to the structural units (a1) to (a3) and which has a hydroxyl group or an alkyleneoxy group and has an acetal structure or a ketal structure,
Wherein the content ratio of the structural units (a1) to (a4) in the acetal-based resin (A) is in the molar ratio of the acetal-based resin (A) (A2): structural unit (a3): structural unit (a4) = 0.2 to 0.65: 0.02 to 0.2: 0.2 to 0.6: 0.005 to 0.3,
The content of the structural unit (a4) in the acetal-based resin (A) is in the range of 3 to 30 mass% based on mass. The method according to claim 1,
(M) a development accelerator, wherein the (M) development accelerator has at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group and an alkyleneoxy group in the molecule and has a molecular weight in the range of 100 to 2000 &Lt; / RTI &gt; 3. The method according to claim 1 or 2,
(E) a crosslinking agent. 3. The method according to claim 1 or 2,
Wherein the photoacid generator (B) is an oxime sulfonate compound. 3. The method according to claim 1 or 2,
Wherein the photoacid generator (B) is at least one compound selected from the group consisting of compounds represented by the following general formula (OS-3), general formula (OS-4), and general formula (OS- Resin composition:

In the general formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, and the plurality of R ^{2 s} present each independently represent a hydrogen atom, an alkyl group, R ⁶ represents a halogen atom, 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, and n represents 1 or 2, and m represents an integer of 0 to 6; 3. The method according to claim 1 or 2,
(N) a sensitizer. 3. The method according to claim 1 or 2,
Wherein the structural unit (a3) in the acetal resin (A) is at least one selected from the group consisting of acrylic acid (3-ethyloxetan-3-yl) methyl and methacrylic acid (3-ethyloxetan- Wherein the photosensitive resin composition is a structural unit derived from one. 3. The method according to claim 1 or 2,
(F) an adhesion improver. 3. The method according to claim 1 or 2,
(G) a basic compound. 3. The method according to claim 1 or 2,
A fluorine-based surfactant or a silicone-based surfactant. (1) applying the photosensitive resin composition according to any one of claims 1 to 3 on a substrate,
(2) removing the solvent from the applied photosensitive resin composition,
(3) exposing the applied photosensitive resin composition to actinic rays,
(4) developing the exposed photosensitive resin composition with an aqueous developer, and
(5) heat-curing the developed photosensitive resin composition
To form a cured film. A cured film formed by the method for forming a cured film according to claim 11. 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