KR101618897B1 - Process for producing cured film, photosensitive resin composition, cured film, organic electro-luminescence display and liquid crystal display - Google Patents

Abstract

(PROBLEMS) To provide a manufacturing method for manufacturing a cured film having high sensitivity and stable sensitivity and excellent in patterning performance of a contact hole, resistance to ITO sputtering, and heat resistance transparency by means of a slit coat.
A step of slitting the photosensitive resin composition on a substrate; a step of removing the solvent from the applied photosensitive resin composition; a step of removing the solvent from the photosensitive resin composition; , A step of exposing at room temperature for 45 seconds or more, a step of developing with an aqueous developing solution, and a step of thermosetting, wherein the photosensitive resin composition comprises (Component A) a structural unit having an acid group protected with an acid- , A structural unit having a crosslinking group, a copolymer containing a structural unit having a carboxyl group and / or a phenolic hydroxyl group, a component (B) a photoacid generator, and (C) a solvent.

Description

TECHNICAL FIELD [0001] The present invention relates to a process for producing a cured film, a photosensitive resin composition, a cured film, an organic EL display, and a liquid crystal display device using the cured film,

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

2. Description of the Related Art Conventionally, in electronic parts such as liquid crystal display elements, integrated circuit elements, solid-state image pickup elements, and organic EL elements, a planarizing film for imparting flatness to the surface of electronic components and a protective film for preventing deterioration or damage of the electronic components, A photosensitive resin composition is used to form an interlayer insulating film for maintaining insulation. With the recent increase in size of display devices, slit coat suitability that can be coated and manufactured by a slit coater is required. Also, with this increase in size, exposure takes time, and high sensitivity is required for shortening the exposure time.

Patent Document 1 discloses coating a slit with a photosensitive resin composition obtained by mixing a carboxyl group-containing polymer, a quinone diazide compound and a specific onium. However, the sensitivity of this composition is not sufficient. As a composition for a highly sensitive interlayer insulating film, for example, Patent Documents 2 and 3 disclose a chemically amplified radiation sensitive resin composition containing an acid generator and a resin containing an acetal structure and an epoxy group or a crosslinkable group .

Japanese Laid-Open Patent Publication No. 2009-075329 Japanese Laid-Open Patent Publication No. 2004-254623 Japanese Laid-Open Patent Publication No. 2009-098616

As a result of the studies by the present inventors, it has been found that the sensitivity is not stable when the photosensitive resin composition of Patent Documents 2 and 3 is slit-coated. It has also been found that when the insulating film is produced by slit coating, the patterning performance of the contact hole becomes insufficient. This is a new problem when the chemical amplification type photosensitive resin composition is used as an insulating film by a slit coat.

A problem to be solved by the present invention is to provide a manufacturing method of a cured film which can be manufactured with a high sensitivity and a stable sensitivity and which is excellent in patterning performance of a contact hole, ITO sputter suitability and heat resistance transparency by a slit coat, A cured film produced by the above production method, an organic EL display device including the cured film, and a liquid crystal display device.

The above problem of the present invention is solved by the means described in the following <1> to <12>.

(1) a low-temperature treatment step of setting the photosensitive resin composition to a temperature of 10 ° C or lower, (2) a coating step of slitting the photosensitive resin composition on a substrate, (3) (4) an exposure step of exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray, (5) a step of elongating at room temperature for 45 seconds or more, (6) a developing step of developing with an aqueous developer, And (7) a post-baking step of thermosetting in this order, wherein the photosensitive resin composition comprises (A) at least (a1) a structural unit having an acid group protected by an acid-decomposable group, (a2) (A3) a copolymer containing a structural unit having a carboxyl group and / or a phenolic hydroxyl group, (B) a photoacid generator, and (C) a solvent. Way,

 &Lt; 2 &gt; The process for producing a cured film according to &lt; 1 &gt;, wherein the structural unit (a1) is a structural unit having a carboxyl group in an acetal- or ketal-

<3> The method for producing a cured film according to <1> or <2>, wherein the structural unit (a1)

[Chemical Formula 1]

(In the formula (A2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ is an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group)

<4> The method for producing a cured film according to any one of <1> to <3>, wherein the structural unit (a2) has at least one group selected from the group consisting of an epoxy group, an oxetanyl group and an ethylenic unsaturated group,

<5> The method for producing a cured film according to any one of <1> to <4>, wherein the structural unit (a2) has an alicyclic epoxy group and / or an oxetanyl group,

<6> The method for producing a cured film according to any one of <1> to <5>, wherein the component B is a compound having an oxime sulfonate residue,

<7> The method for producing a cured film according to any one of <1> to <6>, wherein the component B is a compound represented by the formula (OS-3), the formula (OS-

(2)

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

<8> The method for producing a cured film according to any one of <1> to <7>, wherein the photosensitive resin composition is a chemically amplified positive photosensitive resin composition,

<9> A photosensitive resin composition for use in the method for producing a cured film according to any one of <1> to <8>

&Lt; 10 &gt; A cured film produced by the method for producing a cured film according to any one of &lt; 1 &gt; to &lt; 8 &

&Lt; 11 &gt; An organic EL display device having the cured film described in &lt; 10 &

<12> A liquid crystal display device comprising the cured film according to <10>.

The present invention provides a method for producing a cured film which can be produced with a high sensitivity and a stable sensitivity and which is produced by a slit coat with an interlayer insulating film excellent in patterning performance of a contact hole, ITO sputtering suitability and heat resistance transparency, A composition, a cured film produced by the above production method, an organic EL display including the cured film, and a liquid crystal display device.

1 is a conceptual diagram showing an example of an organic EL display device.
2 is a conceptual cross-sectional view showing an example of a liquid crystal display device.

The method for producing the cured film of the present invention comprises the steps of: (1) a low-temperature treatment step of setting the photosensitive resin composition at a temperature of 10 DEG C or lower; (2) a coating step of slitting the photosensitive resin composition on a substrate; (3) (4) a step of exposing the photosensitive resin composition from which the solvent has been removed by exposure to actinic light, (5) a step of elongating at room temperature for 45 seconds or more, (6) (A1) a structural unit having an acid group protected with an acid-decomposable group, (a2) a structural unit having an acid group protected with an acid-decomposable group, and (7) a post-baking step of thermally curing the composition, (A3) a copolymer containing a structural unit having a carboxyl group and / or a phenolic hydroxyl group, (B) a photoacid generator, and (C) a solvent. It shall be. Hereinafter, the present invention will be described in detail. In the present invention, the description of &quot; A to B &quot; indicating the numerical range means &quot; A to B &quot; unless otherwise stated, and includes numerical ranges including A and B which are end points it means.

Ⅰ. Photosensitive resin composition

The photosensitive resin composition (hereinafter also referred to as the photosensitive resin composition of the present invention) used in the method for producing a cured film of the present invention contains the above components A to C and, if necessary, a sensitizer (component D) ), A crosslinking agent (Component F), an adhesion improver, (Component G), a basic compound (Component H), and a surfactant. Hereinafter, each component will be described.

(Component A)

The photosensitive resin composition of the present invention is a photosensitive resin composition comprising (A) at least (a1) a structural unit having an acid group protected by an acid-decomposable group, (a2) a structural unit having a crosslinking group, (a3) a structure having a carboxyl group and / or a phenolic hydroxyl group Lt; / RTI &gt; units. Component A is preferably an alkali-insoluble resin which becomes alkali-soluble when the acid-decomposable group is decomposed. Here, the "acid-decomposable group" means a functional group decomposable in the presence of an acid. "Alkali solubility" is a condition in which a solution of a compound (resin) is coated on a substrate, and a coating film (thickness 3 μm) formed by heating at 90 ° C. for 2 minutes is coated with 0.4 wt% tetramethylammonium hydroxide Means that the dissolution rate in the aqueous solution of the lockside is not less than 0.01 탆 / second. On the other hand, "alkali insoluble" means that the dissolution rate is less than 0.01 μm / sec. It is more preferable that the alkali dissolution rate of the component A is less than 0.005 mu m / second.

The component A is preferably an addition polymerizable resin, more preferably a polymer comprising a constituent unit derived from (meth) acrylic acid and / or an ester thereof. The term "(meth) acrylic acid" has the same meaning as "acrylic acid and / or methacrylic acid". The component A may also contain constituent units other than the constituent units derived from (meth) acrylic acid and / or esters thereof, for example, constituent units derived from styrene or a vinyl compound.

The component A preferably contains a monomer unit derived from (meth) acrylic acid and / or an ester thereof in an amount of preferably 50 mol% or more, more preferably 90 mol% or more, and more preferably 100 mol% Polymers are particularly preferred.

Incidentally, the method of introducing the constituent unit contained in the component A may be a polymerization method, a polymer reaction method, or a combination of these two methods.

In the polymerization method, for example, an ethylenically unsaturated compound having a residue protected with an acid-decomposable group and an ethylenically unsaturated compound having a crosslinking group, an ethylenically unsaturated compound having a carboxyl group and / or a phenolic hydroxyl group, To obtain a desired copolymer.

In the polymer reaction method, epichlorohydrin may be reacted with a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate to introduce an epoxy group. After the ethylenically unsaturated compound having a reactive group is copolymerized, a reactive group remaining on the side chain is utilized to cause a functional group such as a residue protected by an acid-decomposable group and / or a crosslinking group to be a phenolic hydroxyl group or a carboxyl group Chain.

(Constituent unit (a1))

Component A contains (a1) a constituent unit in which the acid group has a moiety protected with an acid-decomposable group. As the component A has the constituent unit (a1), a photosensitive resin composition having extremely high sensitivity can be obtained. Examples of the acid group include a carboxyl group and a phenolic hydroxyl group.

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

(a1-1) The constituent unit (hereinafter also referred to as &quot; constituent unit (a1-1) &quot;) in which the carboxyl group has a residue protected by an acid- ) Is a constituent unit having a carboxyl group-protected moiety by acid decomposability.

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

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

Examples of the unsaturated monocarboxylic acid include (meth) acrylic 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 may be an acid anhydride. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. The unsaturated polycarboxylic acid may be a mono (2- (meth) acryloyloxyalkyl) ester of a polycarboxylic acid, and may be, for example, succinic acid mono (2- (meth) acryloyloxyethyl), phthalic acid mono (2- (meth) acryloyloxyethyl), and the like. Further, the unsaturated polycarboxylic acid may be a mono (meth) acrylate of the both terminal dicarboxylic polymer, for example, omega -carboxypolycaprolactone mono (meth) acrylate and the like. Examples of the unsaturated carboxylic acid include (meth) acrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester and 4-carboxystyrene. Among them, from the viewpoint of developability, in order to form a structural unit having a carboxyl group, it is preferable to use anhydride of (meth) acrylic acid or an unsaturated polycarboxylic acid, and it is more preferable to use (meth) acrylic acid.

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

(a1-1-2) a structural unit having both an ethylenic unsaturated group and an acid anhydride residue

The constituent unit (a1-1-2) having both an ethylenic unsaturated group and an acid anhydride residue is preferably a constituent unit derived from a monomer obtained by reacting a hydroxyl group and an acid anhydride present in a compound having an ethylenic unsaturated group. In the following description, the acid anhydride residue means a residue formed by reacting a hydroxyl group and an acid anhydride, and is, for example, a residue having an ester bond and a carboxyl group.

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

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

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

The constituent unit in which the carboxyl group has a moiety protected by an acid-decomposable group is preferably a moiety in which the carboxyl group contained in the constituent unit of (a1-1-1) or (a1-1-2) is protected by an acid-decomposable group .

As the acid decomposable group, those known as acid decomposable groups in positive resists for KrF and positive resists for ArF can be used, and there is no particular limitation. Examples of the acid-decomposable group include a group which is relatively well decomposed by an acid (e.g., an acetal-based functional group such as a tetrahydropyranyl group or an ethoxyethyl group) or a group which is relatively poorly decomposed by an acid (for example, Butyl ester group, t-butyl carbonate group and other t-butyl functional groups) are known. As the structural unit (a1-1), a structural unit in which a carboxyl group is protected with an acetal, or a structural unit in which a carboxyl group is protected with a ketal is preferable in view of sensitivity, pattern shape, and formation of a contact hole.

Among the acid decomposable groups, the carboxyl group is more preferably an acetal or ketal-protected residue represented by the formula (A1) from the viewpoint of sensitivity. In addition, when the carboxyl group is an acetal or ketal-protected residue represented by the formula (A1), the moiety has a structure of -C (= O) -O-CR ¹ R ² (OR ³ ) as a whole.

(3)

(In the formula (A1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether. The broken line in formula (A1) represents the bonding position with other structures.

In the formula (A1), the alkyl group in R ¹ , R ² and R ³ may be any of linear, branched or cyclic.

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

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

The alkyl group may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an aryl group having 6 to 20 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. When R ¹ , R ² and R ³ are a haloalkyl group and have an aryl group as a substituent, R ¹ , R ² and R ³ are aralkyl groups when they have a halogen atom as a substituent. The aralkyl group is preferably a benzyl group.

In the formula (A1), the aryl group in R ¹ , R ² and R ³ preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms can be preferably exemplified. As the aryl group, for example, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a 1-naphthyl group and the like can be mentioned, and a phenyl group is preferable.

In the formula (A1), R ¹ , R ² and R ³ may combine with each other to form a ring together with the carbon atoms to which they are bonded. Examples of the ring structure in the case where R ¹ and R ² , R ¹ and R ³ or R ² and R ³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group , An adamantyl group, and a tetrahydropyranyl group.

In formula (A1), it is preferable that either one of R ¹ and R ² is a hydrogen atom or a methyl group.

The commercially available radically polymerizable monomers used for forming the constituent unit having a moiety represented by the formula (A1) may be used. For example, the method described in paragraphs 0025 to 0026 of JP-A No. 2009-098616, May be used.

As the structural unit (a1-1) having a carboxyl group protected by an acid-decomposable group, the structural unit represented by the formula (A2) is more preferable.

[Chemical Formula 4]

(In the formula (A2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ is an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group)

Formula (A2) of, R ¹ ~ R ³ are the same as R ¹ ~ R ³ in the formula (A1), and are also the same preferable range.

In the formula (A2), R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. R ³ is preferably a linear, branched or cyclic alkyl group having 6 or less carbon atoms or an aralkyl group having 7 to 10 carbon atoms, more preferably an ethyl group, a cyclohexyl group or a benzyl group. As the cyclic ether in which R ¹ or R ² and R ³ are connected, a tetrahydropyranyl group or a tetrahydrofuranyl group is preferable. R ⁴ is preferably a methyl group. X is preferably a single bond or a phenylene group.

As specific preferred examples of the structural unit (a1-1), the following structural units can be exemplified. R represents a hydrogen atom or a methyl group.

[Chemical Formula 5]

As the structural unit (a1-1), the carboxyl group may be a structural unit having a residue protected with a tertiary alkyl group represented by the formula (A3). Compared with an acetal or ketal-protected residue, the sensitivity is lowered, but it is preferable from the viewpoint of excellent storage stability. Further, when the carboxyl group is a residue protected with a tertiary alkyl group represented by the formula (A3), the whole of the residue is a structure of -C (= O) -O-CR ¹ R ² R ³ .

[Chemical Formula 6]

In formula (A3), R ¹ , R ² and R ³ each independently represents an alkyl group or an aryl group, and any two of R ¹ , R ² and R ³ may be bonded to each other to form a ring. The broken line part in the formula (A3) represents a bonding position with another structure. Specific examples of the alkyl group and aryl group in R ¹ to R ³ in the formula (A3) are the same as the specific examples of the alkyl group and the aryl group in the formula (A1).

In the formula (A3), a preferable example is a combination of R ¹ = R ² = R ³ = methyl group, a combination of R ¹ = R ² = methyl group and R ³ = benzyl group.

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

(a1-2) As the constituent unit in which the phenolic hydroxyl group has a moiety protected by an acid-decomposable group, the constituent unit (a1-2-1) having a phenolic hydroxyl group of the constituent unit having a phenolic hydroxyl group has a moiety protected by an acid- A constituent unit is preferable.

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

Examples of the structural unit having a phenolic hydroxyl group include a structural unit derived from a hydroxystyrene-based structural unit or a novolak-based resin. Of these structural units, structural units derived from -methylhydroxystyrene are preferred from the viewpoint of transparency . Among the constituent units having a phenolic hydroxyl group, a constituent unit represented by the formula (A4) is preferable in view of transparency and sensitivity.

(7)

(In the formula (A4), R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ represents a single bond or a divalent linking group, R ²² independently represents a halogen atom or an alkyl group, and a represents an integer of 1 to 5 , B represents an integer of 0 to 4, and a + b is 5 or less)

R ²⁰ is preferably a methyl group.

Examples of the divalent linking group of R ²¹ include an ester bond (-COO-) in which a carbon atom is bonded to the main chain, and an alkylene group. As the alkylene group, an alkylene group having 1 to 6 carbon atoms having a linear or branched group is preferable. -COO-, it is preferable since the sensitivity can be improved and the transparency of the cured film can be improved. Among them, R ²¹ is preferably a single bond or an ester bond. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.

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

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

R ²² is a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, or a linear or branched alkyl group having 1 to 5 carbon atoms. Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferable in view of easiness of production.

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

The constituent unit in which the phenolic hydroxyl group has a moiety protected by an acid-decomposable group is a constituent unit in which the phenolic hydroxyl group of the constituent unit having a phenolic hydroxyl group (a1-2-1) has a moiety protected by an acid-decomposable group.

As the acid-decomposable group, any known acid-decomposable group can be used and is not particularly limited.

Among the residues protected with an acid-decomposable group, a phenolic hydroxyl group is a constituent unit having a residue protected by an acetal or ketal, and the basic physical properties of the resist, particularly the sensitivity and pattern shape, the storage stability of the photosensitive resin composition, . Among the residues in which the phenolic hydroxyl group is protected by an acid-decomposable group, the phenolic hydroxyl group is more preferably an acetal or ketal-protected residue represented by formula (A1) from the viewpoint of sensitivity. In this case, the whole of the residue has a structure of -Ar-O-CR ¹ R ² (OR ³ ). Ar represents an arylene group.

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

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

Specific examples of the acetal protecting group and the ketal protecting group of the phenolic hydroxyl group include a 1-alkoxyalkyl group, and examples thereof include a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, (1-cyclohexyloxy) ethyl group, 1-n-propyloxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexyloxy) ethyl group, Ethoxy) ethyl group, 1-benzyloxyethyl group and the like, among which a 1-ethoxyethyl group is preferable. These may be used alone or in combination of two or more.

The radically polymerizable monomer used for forming the structural unit (a1-2) may be a commercially available one, or a compound synthesized by a known method may be used. For example, a compound having a phenolic hydroxyl group can be synthesized by reacting with a vinyl ether in the presence of an acid catalyst. The above-mentioned synthesis may be carried out by previously copolymerizing a monomer having a phenolic hydroxyl group with another monomer, and then reacting with a vinyl ether in the presence of an acid catalyst.

Specific preferred examples of the structural unit (a1-2) include the following structural units, but the present invention is not limited thereto. R represents a hydrogen atom or a methyl group.

[Chemical Formula 8]

The constituent unit in which the carboxyl group has a moiety protected by an acid-decomposable group has a faster phenomenon than a constituent unit in which the phenolic hydroxyl group has a moiety protected with an acid-decomposable group. Therefore, when it is desired to develop quickly, a constituent unit in which the carboxyl group has a residue protected by an acid-decomposable group is preferable. On the other hand, when the development is to be slowed, it is preferable to use a constitutional unit having a residue whose phenolic hydroxyl group is protected with an acid-decomposable group.

The content of the monomer unit derived from the structural unit (a1) among the monomer units constituting the component A is preferably from 20 to 60 mol%, more preferably from 30 to 60 mol%, based on the whole monomer units of the copolymer of the component A, More preferably 50 mol%.

(The constituent unit (a2))

Component A contains (a2) a structural unit having a crosslinking group. As the crosslinking group, a group which causes a crosslinking reaction by a heat treatment is preferable. As a mode of the structural unit having a preferable crosslinking group, a structural unit containing at least one selected from the group consisting of a cyclic ether residue of a triple ring and / or a four-membered ring and an ethylenic unsaturated group is exemplified.

(a2-1) a structural unit having a cyclic ether residue of a triple ring and / or a four-membered ring

The cyclic ether residue of the triple atomic ring is also called an epoxy group, and the cyclic ether residue of the four-membered ring is also called an oxetanyl group. These cyclic ether residue reacts with a carboxyl group or a phenolic hydroxyl group by heat treatment to form a covalent bond to cause a crosslinking reaction. The structural unit (a2-1) having an epoxy group and / or an oxetanyl group is preferably a structural unit having an alicyclic epoxy group and / or an oxetanyl group, and more preferably a structural unit having an oxetanyl group.

The structural unit having an epoxy group and / or an oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, preferably has 1 to 3 epoxy groups and / or oxetanyl groups in total, / Or oxetanyl groups in total, and more preferably one having an epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (Meth) acrylate, glycidyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, glycidyl α- Vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether,? -Butyl benzyl glycidyl ether,? -Butyl benzyl glycidyl ether, Compounds containing an alicyclic epoxy skeleton described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443, and the like.

Specific examples of the radically polymerizable monomer used for forming the oxetanyl group-containing structural unit include (meth) acrylic acid having an oxetanyl group described in paragraphs 0011 to 0016 of JP 2001-330953 A Esters and the like.

In the present invention, the radical polymerizable monomer used for forming the structural unit (a2) is preferably a monomer containing a (meth) acrylic acid ester structure.

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

It is preferable that the structural unit (a2-1) has a residue selected from the group consisting of a residue obtained by removing one hydrogen atom from the structure represented by the formula (A5) and a residue represented by the formula (A6).

[Chemical Formula 9]

(Wherein R ^1b and R ^6b each independently represents a hydrogen atom or an alkyl group, and R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b each independently represents A hydrogen atom, a halogen atom, an alkyl group or an aryl group, and the broken line portion in the formula (A6) represents a bonding position with another structure)

In formula (A6), R ^1b and R ^6b each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms .

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

As the halogen atom, a fluorine atom and a chlorine atom are more preferable, and a fluorine atom is more preferable.

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

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

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

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

As the residue represented by the formula (A6), a (3-ethyloxetan-3-yl) methyl group can be preferably exemplified.

Specific preferred examples of the structural unit (a2-1) include the following structural units. R represents a hydrogen atom or a methyl group.

[Chemical formula 10]

In the present invention, an oxetanyl group is preferable from the viewpoint of the transmittance (transparency). From the viewpoint of electrical characteristics, alicyclic epoxy groups are preferred.

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

As one of the structural units (a2), structural units (a2-3) having an ethylenic unsaturated group can be mentioned. As the structural unit (a2-3), for example, structural units described in paragraphs 0010 to 0040 of Japanese Patent Application Laid-Open No. 2008-256974 may be used in the present invention. As the constituent unit (a2-3), a constituent unit having an ethylenic unsaturated group in the side chain is preferable, a constituent unit having an ethylenic unsaturated group at the terminal and having a side chain of 3 to 16 carbon atoms is more preferable, More preferably a structural unit having a side chain represented by A7).

(11)

(In the formula (A7), R ¹ represents a divalent linking group having 1 to 13 carbon atoms, and R ³ represents a hydrogen atom or a methyl group, and the broken line portion in the formula (A7) represents a bonding position with the main chain)

R ¹ is a divalent linking group having 1 to 13 carbon atoms, which may include an alkenyl group, a cycloalkenyl group, an arylene group, or a combination thereof, and may include a bond such as an ester bond, an ether bond, an amide bond or a urethane bond. The divalent linking group may have a substituent such as a hydroxyl group or a carboxyl group at an arbitrary position. Specific examples of R ^{1 include} the linkers described in paragraphs 0016 to 0017 of Japanese Laid-Open Patent Publication No. 2008-256974.

The ethylenic unsaturated group contained in the side chain represented by the formula (A7) is preferably contained in an amount of 1 mole per 150 to 2,000 g of Component A, more preferably 1 mole per 200 to 1,300 g.

In the present invention, the structural unit (a2-3) is preferably a structural unit represented by the formula (A8).

[Chemical Formula 12]

(In the formula (A8), R ¹ represents a divalent linking group having 1 to 13 carbon atoms, and R ² and R ³ each independently represent a hydrogen atom or a methyl group)

R ¹ in the formula (A8) is the same meaning as that of R ¹ in the formula (A7), the preferred range is also the same.

The method for obtaining the structural unit (a2-3) having a side chain represented by the formula (A7) is not particularly limited. For example, a polymer having a specific functional group is produced in advance by a polymerization method such as radical polymerization, A copolymer having a structural unit (a2-3) can be obtained by reacting a group reacting with a specific functional group and a compound having an ethylenic unsaturated group at an end (hereinafter referred to as a specific compound). Specific examples of specific functional groups, polymers having specific functional groups, and specific compounds are described in paragraphs 0019 to 0031 of Japanese Patent Laid-Open Publication No. 2008-256974, and they can also be used in the present invention.

In the present invention, when a polymer having a specific functional group is obtained, the aforementioned monomers having the specific functional groups described above are used in combination with the monomers constituting the constituent units (a1) and the constituent units (a3) described later.

A method for obtaining a polymer having a specific functional group to be used in the present invention and a method for obtaining a structural unit (a2-3) by reacting a specific functional group with a polymer having a specific functional group include, but are not limited to, Reference can be made to paragraphs 0038 to 0040 of Publication No. 2008-256974.

The content of the monomer unit derived from the structural unit (a2) among the total monomer units constituting the component A is preferably from 20 to 45 mol%, more preferably from 20 to 45 mol% from the viewpoint of various resistance and transparency such as ITO sputtering property of the formed film, And more preferably 40 mol%.

(The constituent unit (a3))

The component A contains (a3) a constitutional unit having a carboxyl group and / or a phenolic hydroxyl group within a range in which the component A is not soluble in an alkali. The carboxyl group also includes a carboxylic acid anhydride residue.

Examples of the radical polymerizable monomer used for forming the structural unit having a carboxyl group include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid And the like. As the radical polymerizable monomer used for forming the constituent unit having a carboxylic acid anhydride residue, for example, maleic anhydride, itaconic anhydride and the like are preferable. Examples of the radically polymerizable monomers forming the constituent unit having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and? -Methyl-p-hydroxystyrene, those disclosed in JP-A-2008-40183 4-hydroxybenzoic acid derivatives as described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, addition reaction products of 4-hydroxybenzoic acid and glycidyl methacrylate, 4-hydroxybenzoic acid and 4-hydroxybenzoic acid derivatives, Addition reaction products of glycidyl acrylate and the like are preferable. Among them, (meth) acrylic acid and hydroxystyrene are more preferable. These constituent units may be used alone or in combination of two or more.

Specific preferred examples of the structural unit (a3) include the following structural units. R represents a hydrogen atom or a methyl group.

[Chemical Formula 13]

The content of the monomer unit derived from the constituent unit (a3) is preferably from 1 to 20 mol%, more preferably from 5 to 15 mol%, of the total monomer units constituting the component A from the viewpoint of obtaining excellent sensitivity and developability desirable.

(Other constituent units)

The component A may contain other constitutional units other than the above-mentioned constitutional units (a1) to (a3) within the range not impairing the effect of the present invention. Examples of the radical polymerizable monomer used for forming other constituent units include the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 (provided that (a1) to (a3 ) Are excluded).

Among them, (meth) acrylic acid esters containing an alicyclic structure such as dicyclopentanyl (meth) acrylate and cyclohexyl (meth) acrylate are preferred from the viewpoint of improvement of electrical characteristics. From the viewpoint of transparency, methyl (meth) acrylate is preferable. From the viewpoint of sensitivity, 2-hydroxyethyl (meth) acrylate and alkyl-terminated polyalkylene glycol (meth) acrylate are preferred. Among them, 2-hydroxyethyl (meth) acrylate is more preferable. The other structural units may be used alone or in combination of two or more. The content ratio of the other structural units in the total structural units constituting the component A is preferably 0 to 30 mol%, more preferably 5 to 25 mol%.

The weight average molecular weight of the component A is preferably 1,000 to 100,000, more preferably 2,000 to 50,000. The weight average molecular weight in the present invention is the polystyrene reduced weight average molecular weight determined by gel permeation chromatography (GPC).

Various methods are also known for the method of synthesizing the copolymer of the component A. For example, the radical polymerization (hereinafter referred to as radical polymerization) used for forming the constituent unit (a1), the constituent unit A method of synthesizing a radical polymerizable monomer mixture containing a monomer by polymerization in an organic solvent using a radical polymerization initiator.

Hereinafter, preferable examples of the component A used in the present invention are illustrated, but the present invention is not limited thereto.

1-ethoxyethyl methacrylate / tert-butyl methacrylate / glycidyl methacrylate / methacrylic acid copolymer

Methoxyethyl methacrylate / 1-ethoxyethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / glycidyl methacrylate / methacrylic acid copolymer

Methacrylic acid 1-ethoxyethyl / methacrylic acid 2-hydroxyethyl / methacrylic acid 3,4-epoxycyclohexylmethyl / methacrylic acid copolymer

Methacrylic acid 1-ethoxyethyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxy- Ester copolymer

(3-methacryloyloxypropyl) ester copolymer of 1-ethoxyethyl methacrylate / 2-hydroxyethyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid

(3-methacryloyloxypropyl) ester copolymer of 1-ethoxyethyl methacrylate / 2-hydroxyethyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid

Methacrylic acid 1-ethoxyethyl / methacrylic acid 2-hydroxyethyl / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid Methyl copolymer

Methacrylic acid tetrahydro-2H-pyran-2-yl / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl)

Methacrylic acid tetrahydro-2H-pyran-2-yl / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2-hydroxy Ethyl copolymer

 (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer of methacrylic acid 1-ethoxyethyl /

Methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2-hydroxyethyl copolymer

Methacrylic acid / (methacrylic acid / 3-ethyloxetane-3-yl) methyl methacrylate / 2-hydroxyethyl methacrylate copolymer

Methoxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid 2-hydroxyethyl copolymer

Acrylic acid / acrylic acid (3-ethyloxetan-3-yl) methyl / acrylic acid 2-hydroxyethyl copolymer

1-ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / styrene copolymer

1-ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / dicyclopentyl methacrylate copolymer

2-yl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer

Methyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid / tetrahydrofuran-

Component A may be used alone or in combination of two or more.

The content of the component A in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, more preferably 40 to 97% by weight, and more preferably 60 to 95% by weight based on the total solid content of the photosensitive resin composition 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 component 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 component A is preferably smaller than the content of the component A from the viewpoint of developability.

(Component B)

The photosensitive resin composition of the present invention (component B) contains a photoacid generator. The photoacid generator used in the present invention is preferably a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, but is not limited to the chemical structure thereof. Also, 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, imidosulfonate compounds and oxime sulfonate compounds . Among them, from the viewpoint of the insulating property, it is preferable to use an oxime sulfonate compound. These photoacid generators may be used alone or in combination of two or more.

As the oxime sulfonate compound, that is, the compound having an oxime sulfonate moiety, a compound having an oxime sulfonate moiety of the formula (B1) can be preferably exemplified.

[Chemical Formula 14]

In the formula (B1), R ⁵ represents an alkyl group, an alkoxy group, an aryl group or a halogen atom. The broken line portion in the formula (B1) represents the bonding position with other structures.

As the alkyl group for R ⁵ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R &lt; ⁵ &gt; is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, aryl group of 6 to 11 carbon atoms, alkoxy group of 1 to 10 carbon atoms, -Dimethyl-2-oxononyl group and the like, preferably a bicycloaryl group, and the like).

As the alkoxy group for R ⁵ , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable. The alkoxy group may be substituted in the same manner as the alkyl group.

As the aryl group for R ^5, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R &lt; ⁵ &gt; may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a halogen atom.

The compound containing an oxime sulfonate residue represented by the formula (B1) is more preferably an oxime sulfonate compound represented by the formula (B2).

[Chemical Formula 15]

(Wherein (B2), R ⁵ is the same meaning as R ⁵ in the formula (B1), X is an alkyl group, an alkoxy group or a halogen atom, m is an integer of 0 ~ 3, m is 2 or 3, the plurality of X's may be the same or different)

The alkyl group in X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom is preferably a chlorine atom or a fluorine atom.

m is preferably 0 or 1.

In the formula (B2), m is 1, X is a methyl group, the substitution position of X is an ortho position, R ⁵ is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorbornyl Methyl group, or p-toluyl group is particularly preferable.

It is also preferable that the compound containing an oxime sulfonate group represented by the formula (B1) is an oxime sulfonate compound represented by the formula (B3).

[Chemical Formula 16]

(Formula (B3) of, R ⁵ has the formula (a same meaning as R ⁵ in B1), X 'represents a halogen atom, a hydroxyl group, an alkoxy group or a nitro group with a carbon number of alkyl group of from 1 to 4, having from 1 to 4 carbon atoms , and l represents an integer of 0 to 5)

Examples of R ⁵ in the formula (B3) include methyl, ethyl, n-propyl, n-butyl, n-octyl, N-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and n-octyl group is particularly preferable.

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

As l, an integer of 0 to 2 is preferable, and 0 or 1 is particularly preferable.

Specific examples of the compound represented by formula (B3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) Benzyl cyanide,? - (methylsulfonyloxyimino) -4-methoxyphenyl, benzyl cyanide,? - (n-butylsulfonyloxyimino) benzyl cyanide, - [(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, alpha - [(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, and? - [(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile.

Among them, specific examples of the preferable oxime sulfonate compound include (i) to (vi), and they may be used singly or in combination of two or more. The compounds (i) to (vi) are commercially available. It may also be used in combination with other types of photoacid generators.

[Chemical Formula 17]

As the compound containing an oxime sulfonate residue represented by the above formula (B1), a compound represented by the formula (OS-1) is also preferable.

[Chemical Formula 18]

In the formula (OS-1), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group . R ² represents an alkyl group or an aryl group.

The expression (OS-1), X is ^{-O-, -S-, -NH-, -NR 5} -, -CH 2 -, -CR 6 H- or -CR ⁶ R ⁷ - represents a, R ⁵ R ⁷ represents an alkyl group or an aryl group.

In the formula (OS-1), R ²¹ to R ²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, An oxygen atom or an aryl group. Two of R ²¹ to R ²⁴ may be bonded to each other to form a ring.

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

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

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

[Chemical Formula 19]

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

Among them, the embodiment wherein R ^{1 in the} formulas (OS-1) and (OS-2) is a cyano group or an aryl group is more preferable and is represented by the formula (OS-2), R ¹ is a cyano group, Or naphthyl group is most preferred.

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

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

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

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

The compound containing an oxime sulfonate residue represented by the above formula (B1) is preferably an oxime sulfonate compound represented by the formula (OS-3), the formula (OS-4) or the formula (OS-5) Do.

&Lt; EMI ID =

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

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

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

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

Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, An octyl group, an n-decyl group, an n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group.

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

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

As the aryl group for R ¹ , a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group or p-phenoxyphenyl group is preferable.

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

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

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

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

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

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

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

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

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

Examples of the alkyl group for R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, More preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s- A methyl group, an ethyl group, an n-propyl group, an n-butyl group and an n-hexyl group are more preferable, and a methyl group is particularly preferable.

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

As the aryl group for R ² , a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group or p-phenoxyphenyl group is preferable.

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

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

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

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

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

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

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

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

Examples of the alkyl group for R ⁶ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- An octyl group, an n-decyl group, an n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group.

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

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

As the alkyloxy group for R ⁶ , a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group is preferable.

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

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

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

It is particularly preferable that the compound containing an oxime sulfonate residue represented by the above formula (4) is an oxime sulfonate compound represented by any of the following formulas (OS-6) to (OS-11).

(25)

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

Expression (OS-6) ~ R ¹ in (OS-11) is the same meaning as that of R ¹ in the formula (OS-3) ~ (OS -5), a preferred embodiment is also the same meaning.

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

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

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

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

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

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

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

(32)

In the photosensitive resin composition of the present invention, the photoacid generator is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the component A from the viewpoints of sensitivity and transparency Do.

(Component C) Solvent

The photosensitive resin composition of the present invention contains (Component C) a solvent. It is preferable that the photosensitive resin composition of the present invention is prepared as a solution in which a component A and a component B as essential components and an optional component described later are dissolved in a solvent.

As the (C) solvent used in the photosensitive resin composition of the present invention, known solvents may be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol mono Alkyl 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 ether Dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like. As specific examples of these solvents, reference can be made to paragraph 0062 of Japanese Laid-Open Patent Publication No. 2009-098616. The solvents which can be used in the present invention may be used alone or in combination of two or more kinds. It is preferable to use two kinds of solvents in combination, more preferably propylene glycol monoalkyl ether acetates and other solvents. Propylene glycol mono The use of methyl ether acetate and diethylene glycol ethyl methyl ether is more preferable.

The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight, per 100 parts by weight of the component A from the viewpoint of adjusting the viscosity to a suitable level for the slit coat, More preferably 150 to 1,500 parts by weight.

The viscosity of the photosensitive resin composition is preferably 1 to 50 mPa · s, more preferably 1 to 30 mPa · s, and even more preferably 1 to 20 mPa · s. The viscosity is measured at 25 占 0.2 占 폚 by using, for example, RE-80L type rotational viscometer manufactured by Toki Kogyo KK. The rotation speed at the time of measurement is 100 rpm for 5 mPa · s, 50 rpm for 5 mPa · s or more and less than 10 mPa · s, 20 rpm for 10 mPa · s or more and 30 mPa · s or more for less than 30 mPa · s 10 rpm, respectively.

(Optional component)

In the photosensitive resin composition of the present invention, in addition to the components A to C, optional additives described below may be added, if necessary.

(Component D)

In the present invention, it is preferable to add a sensitizer (component D) in order to accelerate the decomposition of the photoacid generator. The sensitizer absorbs an actinic ray or radiation to become an electron-excited state. The sensitizer brought into the electron-excited state comes into contact with the photoacid generator to generate electron movement, energy transfer, heat generation, and the like. As a result, the photoacid generator is decomposed by a chemical change to generate an acid.

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

Specific examples of the sensitizer include polynuclear aromatic compounds such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene , 9,10-dipropyloxyanthracene), xanthines (e.g., fluorescein, eosine, erythrosine, rhodamine B, rose benzal), zotonates (e.g., xanthones, thioxanthones, (For example, oxycarbonyl, oxetane, diethylthioxanthone), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), merocyanines (Such as thionine, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavin, acrylic flavin), acridones (for example, (For example, acridone, 10-butyl-2-chloroacridone), anthraquinones (for example, anthraquinone), squaryliums Diethylamino 4-methylcoumarin), and particularly preferably a polynuclear aromatic compound, an acridone compound, a coumarin compound, and a base styryl compound. More preferably a polynuclear aromatic group and an acridone, and more preferably an anthracene derivative and 10-butyl-2-chloroacridone.

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

(Component E) Crosslinking agent

To the photosensitive resin composition of the present invention, a crosslinking agent (component E) is added, if necessary. Examples of the crosslinking agent include a compound having two or more epoxy groups or oxetanyl groups in the molecule, an alkoxymethyl group-containing crosslinking agent, and a compound having at least one ethylenically unsaturated double bond. By adding a crosslinking agent, the cured film can be made into a stronger film.

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. Specific examples thereof include JER-157S65 (polyfunctional novolak type epoxy resin) in addition to the compound described in paragraph 0042 of JP-A No. 2009-258723. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin and phenol novolak type epoxy resin are preferable, and phenol novolak type epoxy resin is more preferable.

Specific examples of the compound having two or more oxetanyl groups in the molecule include aroxoxetane OXT-121, OXT-221, OX-SQ and PNOX (manufactured by Toa Gosei Co., Ltd.). The oxetanyl group-containing compound may be used alone or in combination with a compound containing an epoxy group.

As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea are preferable. These are obtained by converting methylol groups of methylol melamine, methylol benzoguanamine, methylol glycoluryl, or methylol urea into alkoxymethyl groups, respectively. The 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.

As the compound having at least one ethylenic unsaturated bond, a (meth) acrylate compound such as monofunctional (meth) acrylate, bifunctional (meth) acrylate or trifunctional or more functional (meth) have. Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, and the like. Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, and bisphenoxyethanol fluorene diacrylate. Examples of the trifunctional or more (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

When a compound having at least one ethylenic unsaturated bond is added, it is preferable to add a heat radical generator. In the present invention, as the component E, a compound having two or more epoxy groups or oxetanyl groups in the molecule is preferable. As the thermal radical generator, a known thermal radical generator can be used, for example, described in paragraph 0037 of JP-A No. 2009-218509.

The amount of the component E to be added is preferably from 1 to 50 parts by weight, more preferably from 3 to 30 parts by weight, still more preferably from 5 to 20 parts by weight, based on 100 parts by weight of the component A from the viewpoint of obtaining heat resistance, solvent resistance and hardness of an excellent cured film More preferable.

(Component F) Adhesion improving agent

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

As the silane coupling agent, a silane coupling agent described in paragraph 0048 of Japanese Patent Laid-Open Publication No. 2009-98616 is preferable, and among them,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable ,? -glycidoxypropyltrialkoxysilane is more preferable, and? -glycidoxypropyltrimethoxysilane is particularly preferable. These may be used singly or in combination of two or more. These are effective for improving the adhesion with the substrate and adjusting the taper angle with the substrate.

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

(Component G) The basic compound

The photosensitive resin composition of the present invention may contain (Component G) a basic compound.

As the basic compound, any of those used as a chemically amplified resist may be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides and quaternary ammonium salts of carboxylic acids described in paragraphs 0051 to 0056 of JP-A No. 2009-098616 Among them, a heterocyclic amine is preferable, a heterocyclic amine having a pyridine ring and a heterocyclic amine having a bicyclo ring are more preferable, and 1,5-diazabicyclo [4.3.0] -5- Nonene, and 1,8-diazabicyclo [5.3.0] -7-undecene are more preferable.

The basic compound may be used singly or in combination of two or more, but it is preferable to use two or more kinds of them in combination, more preferably two kinds, more preferably two kinds of heterocyclic amines in combination Do. The content of the basic compound is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.2 part by weight based on 100 parts by weight of the component A from the viewpoint of sensitivity stability.

(Component H) Surfactant

The photosensitive resin composition of the present invention may contain (Component H) a surfactant.

As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants may be used, but preferred nonionic surfactants are nonionic surfactants. Specific examples thereof include nonionic surfactants described in paragraph 0058 of Japanese Patent Laid-Open Publication No. 2009-098616, and among them, fluorinated surfactants are preferred. These surfactants may be used alone or in combination of two or more.

It is also preferred that the surfactant contains a constituent unit A and a constituent unit B represented by the following formula (1) and has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography when tetrahydrofuran (THF) (Mw) of 1,000 or more and 10,000 or less.

(33)

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

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

(34)

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

The amount of the surfactant added to the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight, and most preferably 0.01 to 1 part by weight, per 100 parts by weight of the component A, The weight portion is more preferable.

(Other components)

In the photosensitive resin composition of the present invention, other components such as plasticizers, thermal radical generators, thermal acid generators, acid propagating agents, development promoters, and antioxidants may be added as necessary. As for these components, for example, those disclosed in JP-A-2009-098616, JP-A-2009-244801, and other known compounds can be used. In addition, various ultraviolet absorbers, metal deactivators, and the like described in "New Developments of Polymer Additives " (Japan Daily Newspaper) may be added to the photosensitive resin composition of the present invention.

(Method for preparing photosensitive resin composition)

The essential components of the components A to C and, if necessary, optional components are mixed in a predetermined ratio in any manner and dissolved by stirring to prepare a photosensitive resin composition. For example, it is also possible to prepare a solution in which each of the component A or the component B is previously dissolved in a solvent, and then mix them in a predetermined ratio to prepare a photosensitive resin composition. The photosensitive resin composition prepared as described above may be used after being filtered using a filter having a pore diameter of 0.2 탆 or the like.

Ⅱ. Method for producing a cured film

The method for producing a cured film of the present invention comprises the steps of: (1) a low-temperature treatment step of keeping the photosensitive resin composition at a temperature of 10 ° C or lower; (2) a coating step of slitting the photosensitive resin composition on a substrate; (3) (4) a step of exposing the photosensitive resin composition from which the solvent has been removed by exposure to actinic light, (5) a step of elongating at room temperature for 45 seconds or more, (6) And (7) a post-baking step for thermally curing the resin in this order. Each step will be described below in order.

(1) a low-temperature treatment step of bringing the photosensitive resin composition to a temperature of 10 캜 or lower

In the present invention, a low-temperature treatment step is carried out at a temperature of 10 DEG C or lower before the application of the photosensitive resin composition. The treatment temperature is not particularly limited as long as the treatment temperature is 10 占 폚 or less, but is preferably -50 to 0 占 폚, and more preferably -30 to -10 占 폚, from the viewpoints of hole forming property and ITO sputtering suitability.

The treatment time is not particularly limited, but is preferably 20 minutes or more, more preferably 30 minutes or more, and most preferably 40 minutes or more. By setting this range, performance can be further improved. The upper limit of the treatment time is not particularly limited, but is preferably 365 days or less, and more preferably 180 days or less, from the viewpoint of prevention of aging deterioration of the composition.

(2) a coating process for slit-coating the photosensitive resin composition on a substrate

(2), the photosensitive resin composition of the present invention is slit-coated (slit-coated) on a substrate to form a wet film containing a solvent.

Examples of the substrate include a polarizing plate, a glass plate on which a black matrix layer and a color filter layer are formed and a transparent electroconductive circuit layer is formed, if necessary, in the production of a liquid crystal display device. 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 width of at least 1 m × 1 m and a width of at least 5 m × 5 m.

In conventional small substrates, spin coating has been used. As the substrate becomes larger, it becomes difficult to rotate the substrate, and a spinless coater is used. Especially in a substrate larger than the sixth generation substrate (approximately 1,500 x 1,800 mm), it is considered impossible to rotate the substrate by the spin coat. In addition, the slit coater is free from liquid (slit & spin coat) to about 1/3, tact time is shortened, and fringe (thickened area of the end portion of the substrate) There is an advantage that EBR (edge, back, rinse) treatment is not required. In the case of the conventional spin coat, a force in the horizontal direction acts on the liquid. On the other hand, in the case of the slit coater, no external force acts on the liquid on the substrate merely by placing the liquid on the substrate. It is presumed that a difference in performance occurs due to the difference in history for such a liquid (photosensitive composition). In the present invention, a commercially available slit coater can be used.

(3) a solvent removing step of removing the solvent in the applied photosensitive resin composition

In the solvent removing step of (3), the solvent is removed from the applied film by depressurization (bubbling) and / or heating to form a dried coating film on the substrate. In the present invention, it is preferable to remove the solvent by heating to form a dry coating film on the substrate.

The heating conditions for the solvent removal step are those in which the acid decomposable groups in the constituent unit (a1) in the component A in the unexposed portion are decomposed and the component A is not soluble in the alkali developing solution. Depending on the kind and the compounding ratio of the components, However, it is preferably about 80 to 130 DEG C for about 30 to 120 seconds.

The thickness of the dried coating film is preferably 0.1 to 30 mu m, more preferably 1.0 to 8.0 mu m.

(4) an exposure step of exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray

(4), an active ray having a wavelength of 300 to 450 nm is irradiated to the obtained coating film. In this step, the photoacid generator is decomposed to generate acid. By the catalytic action of the generated acid, the acid-decomposable group in the constituent unit (a1) contained in the component A is decomposed to generate an acid group.

A low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an LED light source, a chemical lamp, a laser generator, 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. In this case, exposure is performed through a mask. The mercury lamp is preferable in that it is suitable for exposure of a large area as compared with a laser.

In the case of using a laser, 343 nm and 355 nm are used for a solid-state (YAG) laser and 351 nm (XeF) for an excimer laser, and 375 nm and 405 nm are used for a semiconductor laser. Of these, 355 nm and 405 nm are more preferable in terms of stability and cost. The laser beam can be irradiated onto the coating film once or plural times.

The energy density per pulse of the laser is preferably 0.1 to 10,000 mJ / cm 2. In order to sufficiently cure the coating film, it is preferably 0.3 mJ / cm 2 or more, more preferably 0.5 mJ / cm 2 or more. In order not to decompose the coating film due to the ablation phenomenon, it is preferably 1,000 mJ / cm2 or less, more preferably 100 mJ / cm2 or less.

The pulse width is preferably 0.1 to 30,000 nsec. In order not to decompose the color coated film by the ablation phenomenon, 0.5 nsec or more is more preferable, and 1 nsec or more is most preferable. In order to improve the accuracy in accordance with the scanning exposure, 1,000 nsec or less is more preferable, and 50 nsec or less is most preferable.

Further, the frequency of the laser is preferably 1 to 50,000 Hz, more preferably 10 to 1,000 Hz. If the frequency of the laser is 1 Hz or more, the exposure processing time is adequate, and if the frequency is 50,000 Hz or less, the accuracy is improved in accordance with the scanning exposure. In order to shorten the exposure processing time, more preferably 10 Hz or more, most preferably 100 Hz or more, and more preferably 10,000 Hz or less, and most preferably 1,000 Hz or less, in order to improve the precision in accordance with the scanning exposure.

Compared with a mercury lamp, a laser is preferable in that the focus can be narrowed easily, a mask for pattern formation in the exposure process is unnecessary, or a small mask can be used, which is preferable in cost reduction. Examples of commercially available products include commercially available products such as Callisto (manufactured by V Technology), AEGIS (manufactured by V Technology), DF2200G (manufactured by Dainippon Screen Co., Ltd.) And the like. If necessary, irradiation light can be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

In order to accelerate the decomposition reaction in the region where the acid catalyst is formed, Post Exposure Bake (hereinafter, also referred to as &quot; PEB &quot;) may be carried out, if necessary, after the exposure. The decomposition of the acid decomposable group can be promoted by PEB. In the present invention, a mode in which a positive image is formed by development without PEB is preferable. Further, by conducting PEB at a relatively low temperature, decomposition of the acid decomposable group can be accelerated without causing a crosslinking reaction. The temperature at which PEB is carried out is preferably 50 to 110 占 폚, more preferably 60 to 90 占 폚.

(5) Process of elongating at room temperature for 45 seconds or more

(5) is a step of passing the substrate at a room temperature for 45 seconds or more between (4) the exposure step and (6) the developing step. During the process, even if the substrate is left without moving, the substrate may be moved for transportation or the like. The elapsed time is preferably 45 seconds or more from the viewpoint of sensitivity stability, preferably 60 seconds or more, more preferably 90 seconds or more, and most preferably 120 seconds or more. Although there is no upper limit, the upper limit is preferably 10 minutes or less, more preferably 5 minutes or less, from the viewpoint of production efficiency and the like. The room temperature (temperature) is preferably 10 to 45 占 폚, more preferably 10 to 40 占 폚, and further preferably 15 to 30 占 폚. By setting this range, the sensitivity can be stabilized. In a large-sized substrate, if the sensitivity is unstable, a large amount of residue may be generated. The PEB may be performed before the process, or may be performed later (for example, after 30 seconds have elapsed after exposure, PEB is performed and again 40 seconds have elapsed). In the present invention, from the viewpoint of simplification of the process, it is preferable that the PEB is not formed before, after, or between the steps of (5).

(6) Developing process developed by aqueous developer

In the developing step of the developing roller 6, it is preferable to develop the polymer having an acid group using an alkaline developing solution. A positive image is formed by removing the exposed region including the copolymer having an acid group well dissolved in an alkaline developer.

In the development step, it is preferable to use a basic developer. 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 cholinehydroxide; 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 solution of the base may be used as a developer.

 The pH of the developing solution is preferably 10.0 to 14.0. The developing time is preferably 30 to 180 seconds, and the developing method may be any of a liquid mounting method and a dipping method. After development, cleaning may be carried out in running water for 30 to 90 seconds.

(7) Post-baking process for thermosetting

(A2) can be crosslinked by heating the obtained positive image in the post-baking step of the step (7), whereby a cured film excellent in heat resistance and hardness can be formed. The heating is preferably performed at a high temperature of 150 DEG C or higher by using a heating apparatus such as a hot plate or an oven with respect to a pattern corresponding to the unexposed area obtained by development, And particularly preferably 200 to 250 ° C.

The heating time can be suitably set according to the heating temperature and the like, and is preferably within a range of 5 to 90 minutes. For example, if it is a hot plate, heat it for 5 ~ 60 minutes, if it is an oven for 30 ~ 90 minutes. When the heat treatment is carried out, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

When the crosslinking group of the constituent unit (a2) is an epoxy group or an oxetanyl group, the substrate on which the pattern is formed is re-exposed by an actinic ray, preferably ultraviolet ray, before the heat treatment, It is preferable to function as a catalyst for promoting the crosslinking step by generating an acid from the component B present in the unexposed portion by the exposure / post-baking).

The exposure in the re-exposure step may be carried out by the same means as in the exposure step. In the re-exposure step, it is preferable to perform the entire surface exposure on the side where the film of the substrate is formed. The preferable exposure amount of the re-exposure process is 100 to 1,000 mJ / cm &lt; 2 &gt;.

Ⅲ. A cured film, an organic EL display, a liquid crystal display

By the process for producing a cured film of the present invention, a cured film having high transparency can be obtained even when it is excellent in insulation and baked at a high temperature. The interlayer insulating film formed using the photosensitive resin composition of the present invention has high transparency and is excellent in physical properties of a cured film, and thus is useful for an organic EL display device or a liquid crystal display device. The organic EL display device and the liquid crystal display device of the present invention are not particularly limited, except that the organic EL display device and the liquid crystal display device have a planarizing film, a protective layer, and a cured film as an interlayer insulating film formed by the method for producing a cured film of the present invention, And various known organic EL display devices and liquid crystal display devices.

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

Fig. 1 shows a configuration diagram of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4. A bottom gate type TFT (thin film transistor) 1 is formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ is formed with the TFT 1 covered. A wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 after forming a contact hole (not shown) in the insulating film 3. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or later and the TFT 1. [ The flattening layer 4 is formed on the insulating film 3 with the irregularities formed by the wirings 2 buried in order to planarize the irregularities formed by the formation of the wirings 2. On the planarizing film 4, a bottom-emission organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarization film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element. The insulating film 8 is formed so as to cover the periphery of the first electrode 5. By forming the insulating film 8, the short circuit between the first electrode 5 and the second electrode formed in the subsequent step Can be prevented.

Although not shown in Fig. 1, a hole transport layer, an organic luminescent layer, and an electron transport layer are sequentially deposited by evaporation through a desired pattern mask. Then, a second electrode made of Al is formed on the entire upper surface of the substrate, An organic EL display device in which an organic EL element is sealed by bonding using an ultraviolet curable epoxy resin 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. The liquid crystal display device 10 of this color is a liquid crystal panel having a backlight unit 12 on its back surface. The liquid crystal panel is a liquid crystal display panel in which TFTs corresponding to all the pixels arranged between two glass substrates 14, (16) are disposed on the substrate. In each element formed on the glass substrate, an ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal layer 20 and a black matrix are arranged is formed.

Example

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples. Unless specifically stated, "part" means "part by weight" and "%" means "% by weight".

1. Synthesis of Copolymer

&Lt; Synthesis of Copolymer A-1 &gt;

(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 and the reaction system was cooled to 10 DEG C or lower. Lt; / RTI &gt; After 5.0 parts of pyridinium p-toluenesulfonate was added, 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 the filtrate was concentrated under reduced pressure at 40 DEG C or lower. The yellow oily residue was distilled under reduced pressure to obtain the boiling point (bp. To obtain 134.0 parts of 1-ethoxyethyl methacrylate of 43 to 45 占 폚 / 7 mmHg fraction as a colorless oil.

Methacrylic acid (6.89 parts (0.08 molar equivalents)) and glycidyl methacrylate (GMA) (49.75 parts (0.35 molar equivalents)) of the obtained methacrylic acid 1-ethoxyethyl (66.41 parts (19.52 parts (0.15 mol equivalent) of methacrylic acid and 132.5 parts of propylene glycol monomethyl ether acetate (PGMEA) was heated to 70 占 폚 under a nitrogen stream. While stirring this mixed solution, a radical polymerization initiator V-65 (2,2'-azobis (2,4-dimethylvaleronitrile), 12.4 parts by Wako Pure Chemical Industries, Ltd.) and PGMEA (100.0 parts) Was added dropwise over 2.5 hours. After completion of the dropwise addition, the reaction was carried out at 70 DEG C for 4 hours to obtain a PGMEA solution (solid concentration: 40% by weight) of the copolymer A-1. The weight average molecular weight (Mw) of the obtained copolymer A-1 as measured by gel permeation chromatography (GPC) was 8,000.

(35)

<Synthesis of Copolymers A-2 to A-16 and A'-1 to A'-3>

Copolymers A-2 to A-16 and A'-1 to A'-3 were synthesized in the same manner as in the synthesis of copolymer A-1, except that the monomer species and the amount thereof used were changed to those shown in Table 1. Respectively. The addition amount of the radical polymerization initiator V-65 was adjusted so as to have the molecular weight shown in Table 1. [

The copolymerization ratios shown in Table 1 are molar ratios, and the abbreviations in Table 1 are as follows.

MAEVE: 1-ethoxyethyl methacrylate

CHOEMA: 1- (cyclohexyloxy) ethyl methacrylate

THPMA: tetrahydro-2H-pyran-2-yl methacrylate

MATHF: tetrahydrofuran-2-yl methacrylate

MATHF was synthesized as follows.

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

(36)

GMA: glycidyl methacrylate

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

ECHMMA: 3,4-epoxycyclohexylmethyl methacrylate

MAA: methacrylic acid

α-MHS: α-methylhydroxystyrene

HEMA: 2-hydroxyethyl methacrylate

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

DCPM: di-cyclopentanyl methacrylate

2. Preparation of Photosensitive Resin Composition

(Examples 1 to 44, Comparative Examples 1 to 7, Examples 101 to 139, Examples 201 to 239, and Examples 301 to 308)

The components shown in Tables 2 to 5 were mixed and the viscosity was adjusted to 3.0 mPa · s by addition of a 1: 1 mixed solvent of C1: propylene glycol monomethyl ether acetate and C2: diethylene glycol ethyl methyl ether, And then filtered through a polytetrafluoroethylene filter to prepare a positive photosensitive resin composition.

The abbreviations in Tables 2 to 5 are as follows.

(37)

B5: α- (4-Toluenesulfonyloxyimino) benzyl cyanide (synthesized according to the method described in paragraph 0108 of Japanese Unexamined Patent Publication No. 2002-528451)

B6: α - [(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (PAI-101, manufactured by Midori Kagaku Co., Ltd.)

D1: NBCA (10-butyl-2-chloroacridone, manufactured by Kurogane Kasei Co., Ltd.)

D2: DBA (9,10-dibutoxyanthracene, manufactured by Kawasaki Kasei Kogyo Co., Ltd.)

E1: JER-157S65 (polyfunctional novolac epoxy resin (epoxy equivalents: 200 to 220 g / eq), Japan Epoxy Resin Co., Ltd.)

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

G1: 4-Dimethylaminopyridine

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

H1: PolyFox PF-6320 (fluorine surfactant, manufactured by OMNOVA)

W-3: The following compound

(38)

(Synthesis of photo acid generator B-10)

1-1. Synthesis of synthetic intermediate B-10A

31.3 g (manufactured by Tokyo Kasei Kogyo Co., Ltd.) of 2-aminobenzenethiol was dissolved in 100 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 ° C). Next, 40.6 g of phenylacetyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise, and the mixture was reacted by stirring at room temperature for 1 hour and then at 100 ° C for 2 hours. 500 ml of water was added to the obtained reaction solution, and the precipitated salt was dissolved. Toluene oil was extracted and the extract was concentrated with a rotary evaporator to obtain a synthetic intermediate B-10A.

1-2. Synthesis of B-10

2.25 g of the thus-obtained synthetic intermediate B-10A 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 占 폚 or less. Next, 4.37 g of tetramethylammonium hydroxide (25% by weight methanol solution, manufactured by Alfa Acer) was added dropwise, and the mixture was stirred and reacted on ice for 0.5 hour. Further, 7.03 g of isopentyl nitrite was added dropwise while keeping the temperature at 20 캜 or lower, and after completion of dropwise addition, the temperature of the reaction solution was raised to room temperature, followed by stirring for 1 hour.

Subsequently, the reaction solution was cooled to 5 캜 or lower, p-toluenesulfonyl chloride (1.9 g) (manufactured by Tokyo Kasei Kogyo 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 thereto, and the mixture was stirred at 0 ° C for 1 hour. The resulting precipitate was filtered and then 60 ml of isopropyl alcohol (IPA) was added. The mixture was heated to 50 占 폚 and stirred for 1 hour and then filtered and dried to obtain 1.8 g of the compound (B-5: &Lt; / RTI &gt;

The ¹ H-NMR spectrum (300 MHz, heavy DMSO ((D ₃ C) ₂ S = O) of the obtained B-10 was δ = 8.2 to 8.17 (m, 1H), 8.03 to 8.00 ), 7.95-7.9 (m, 2H), 7.6-7.45 (m, 9H), 2.45 (s, 3H).

It is estimated that B-10 obtained from the above ¹ H-NMR measurement result is a single geometric isomer.

(Synthesis of photo acid generator B-11)

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

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

The resulting oxime compound (1.8 g) was dissolved in acetone (20 ml), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and the mixture was allowed to react at room temperature for 1 hour. Water (50 ml) was added to the reaction solution, and the precipitated crystals were filtered, and then slurry was reslurried with methanol (20 ml), followed by filtration and drying to obtain B-11 (2.3 g).

In addition, ¹ H-NMR spectrum of B-11 (300 MHz, 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 photo acid generator B-11)

2-Naphthol (20 g) was dissolved in N, N-dimethylacetamide (150 ml), potassium carbonate (28.7 g) and ethyl 2-bromooxinate (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 a 48 wt% aqueous sodium hydroxide solution (23 g), ethanol (50 ml) And the mixture was reacted for 2 hours. The reaction solution was poured into 1N HCl aqueous solution (500 ml), and the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid. Then, 30 g of polyphosphoric acid was added and reacted at 170 ° C for 30 minutes. The reaction solution was poured into water (300 ml), and ethyl acetate (300 ml) was added 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 4 times with 80 ml of water, concentrated and purified by silica gel column chromatography to obtain an oxime compound (5.8 g) .

The resulting oxime (3.1 g) was sulfonated in the same manner as B-11 to obtain B-12 (3.2 g).

In addition, ¹ H-NMR spectrum of B-12 (300 MHz, CDCl 3) is δ = 8.3 (d, 1H) , 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (s, 3H), 2.2 (ddt, 1H), 1.9 (ddt, 1H), 7.5 (dd, , 1H), 1.4-1.2 (m, 8H), 0.8 (t, 3H).

(Synthesis of photo acid generator B-13)

B-13 was synthesized in the same manner as B-11 except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in B-11.

In addition, ¹ H-NMR spectrum of B-13 (300 MHz, 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

[Chemical Formula 39]

B-14: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

B-15: Trifluoromethylsulfonyloxybicyclo [2.2.1] -hept-5-en-dicarboxyimide

3. Evaluation

(Example 1)

Using the photosensitive resin composition of Example 1, the following evaluations were carried out.

&Lt; Evaluation of sensitivity &

The prepared photosensitive resin composition was once subjected to low-temperature treatment under the conditions shown in Table 6, and returned to room temperature (23 캜). A photosensitive resin composition was applied to a glass substrate having a size of 2,160 mm x 2,460 mm, slit coated, and then prebaked on a hot plate at 90 DEG C for 90 seconds to remove the solvent to form a coating film having a thickness of 3 mu m. Next, exposure was performed through a predetermined mask using FX-85S (i-line specification, manufactured by Nikon Corporation). After the exposure, the coating solution was subjected to the time shown in Table 6 at the temperature shown in Table 6, showered at 25 캜 for 35 seconds with 0.4% by weight aqueous solution of tetramethylammonium hydroxide, and rinsed with ultrapure water for 1 minute. By these operations, the optimum exposure dose (Eopt) at the time of resolving a line-and-space of 10 mu m at a ratio of 1: 1 was determined. This was repeated 10 times, and the arithmetic mean was taken as the sensitivity. The sensitivity can be said to be a high sensitivity when the exposure amount is lower than 50 mJ / cm 2. The results are shown in Table 6.

<Evaluation of Sensitivity Stability>

(Emax - Emin) / (sensitivity) x 100 is 0 or more and less than 5: A, 5 or more and less than 10: B, Emax, 10 or more: C. The smaller the value is, the more stable the sensitivity, and there is no practical problem if A or B is evaluated. In the C evaluation, problems such as residues may occur, which is not permissible. The results are shown in Table 6.

&Lt; Evaluation of heat resistance transparency &

The prepared photosensitive resin composition was subjected to low-temperature treatment under the conditions shown in Table 6 and returned to room temperature (23 캜).

The photosensitive resin composition was applied to a glass substrate (manufactured by Corning Incorporated) with a slit, and then prebaked on a hot plate at 90 DEG C for 120 seconds to remove the solvent to form a coating film having a thickness of 3 mu m. The entire exposure was performed at an optimum exposure dose using FX-85S (i-ray specification, manufactured by Nikon Corporation), elapsed by the time shown in Table 6 at the temperature shown in Table 6, And rinsed with ultrapure water for 1 minute. The obtained coating film was exposed with FX-85S so that the integrated irradiation amount became 300 mJ / cm 2 (light intensity: 20 mW / cm 2), and the 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 &quot; (manufactured by Hitachi, Ltd.) to a wavelength in the range of 400 to 800 nm Respectively. Table 6 shows the evaluation results of the lowest light transmittance (evaluation results of heat resistance and transparency) at that time. The evaluation criteria are as follows.

A: 93% or more

B: 88% or more and less than 93%

C: 83% or more and less than 88%

D: Less than 83%

<ITO sputter suitability>

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

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

B: Small wrinkles were observed on the surface of the cured film (allowable range)

C: Wrinkles occur on the surface of the cured film

When wrinkles are observed on the surface of the cured film after the ITO transparent electrode is formed by sputtering, the transmittance of the cured film is lowered, which is undesirable. The results are shown in Table 6.

<Evaluation of Formability of Contact Hole>

A coating film having a thickness of 3.0 탆 was formed in the same manner as in the sensitivity evaluation except that the substrate was changed to a silicon wafer. Next, an i-line stepper (FPA-3000i5 ⁺ manufactured by Canon Inc.) was used to expose an optimal exposure amount in a mask having a hole pattern having a diameter of 10 mu m corresponding to the contact hole.

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

In this evaluation, "A" indicates a difference between two measured values measured before and after heating, "B" indicates a difference between 0.5 μm and less than 1.0 μm, "C" indicates a difference of not less than 1.0 μm with respect to the diameter of the bottom of the formed contact hole, . The smaller the difference in diameter before and after heating, the better the control of the diameter of the contact hole becomes, which is preferable. A or B is practical.

A hole cross section after heating was observed, and A, A, and B were A, B, and C, respectively. It is preferable that the taper is a net taper, and if A, practical use is possible. The results are shown in Table 6.

(Examples 2 to 21, Examples 26 to 28, Examples 30 to 44, Examples 101 to 121, Examples 126 to 129, Examples 131 to 139, Examples 201 to 221, Examples 226 to 229, Examples 231 to 239, and Examples 301 to 304)

The procedures of the low-temperature treatment as shown in Tables 6 to 9 and the conditions (temperature and time) for leaving the substrate after exposure were changed as shown in Tables 2 to 5 as shown in Tables 6 to 9, The resin composition and the cured film were evaluated.

(Examples 22 to 25)

The conditions (temperature, time) for leaving the substrate after exposure were changed to PEB at 80 캜 for 60 seconds on a hot plate after lapse of 90 seconds at 23 캜 after exposure and development was performed after elapse of 35 seconds at 23 캜, 1, the photosensitive resin composition and the cured film were evaluated. The results are shown in Table 6.

(Example 29)

Except that the pattern exposure was performed with the following laser exposure, the same procedure was performed as in Example 8 (the substrate size was appropriately adjusted). A predetermined photomask was set through a 150 占 퐉 interval from the dried film having a film thickness of 3 占 퐉, and the laser beam having a wavelength of 355nm was irradiated with the optimum exposure dose. Further, the laser device used was "AEGIS" (manufactured by V-Technology Co., Ltd.) (wavelength: 355 nm, pulse width: 6 nsec) and the exposure amount was measured using "PE10B-V2" manufactured by OPHIR. It was found that a laser can form a pattern in the same manner as a mercury lamp.

(Examples 122 to 125)

The conditions (temperature, time) for leaving the substrate after exposure were changed to PEB at 80 캜 for 60 seconds on a hot plate after lapse of 90 seconds at 23 캜 after exposure and development was performed after elapse of 35 seconds at 23 캜, 101, the photosensitive resin composition and the cured film were evaluated. The results are shown in Table 7.

(Example 130)

The procedure of Example 108 was carried out except that the pattern exposure was performed with the following laser exposure (the substrate size was appropriately adjusted). A predetermined photomask was set through a 150 占 퐉 interval from the dried film having a film thickness of 3 占 퐉, and the laser beam having a wavelength of 355nm was irradiated with the optimum exposure dose. Further, the laser device used was "AEGIS" (manufactured by V-Technology Co., Ltd.) (wavelength: 355 nm, pulse width: 6 nsec) and the exposure amount was measured using "PE10B-V2" manufactured by OPHIR. It was found that a laser can form a pattern in the same manner as a mercury lamp.

(Examples 222 to 225)

The conditions (temperature, time) for leaving the substrate after exposure were changed to PEB at 80 캜 for 60 seconds on a hot plate after lapse of 90 seconds at 23 캜 after exposure and development was performed after elapse of 35 seconds at 23 캜, 201, the photosensitive resin composition and the cured film were evaluated. The results are shown in Table 8.

(Example 230)

The procedure of Example 208 was carried out except that the pattern exposure was performed with the following laser exposure (the substrate size was appropriately adjusted). A predetermined photomask was set through a 150 占 퐉 interval from the dried film having a film thickness of 3 占 퐉, and the laser beam having a wavelength of 355nm was irradiated with the optimum exposure dose. Further, the laser device used was "AEGIS" (manufactured by V-Technology Co., Ltd.) (wavelength: 355 nm, pulse width: 6 nsec) and the exposure amount was measured using "PE10B-V2" manufactured by OPHIR. It was found that a laser can form a pattern in the same manner as a mercury lamp.

(Examples 305 to 308)

The composition (composition) was changed as shown in Table 5, and the conditions (temperature, time) for leaving the substrate after exposure were 90 seconds at 23 占 폚 after exposure and then subjected to PEB at 80 占 폚 for 60 seconds on a hot plate. , The photosensitive resin composition and the cured film were evaluated in the same manner as in Example 101. The results are shown in Table 9.

(Comparative Examples 1 to 7)

The photosensitive resin compositions of Comparative Examples 1, 2, and 4 to 6 were prepared in the same manner as in Example 1, except that the conditions (temperature, time) for leaving the substrate after the low temperature treatment and exposure were changed as shown in Table 2, , And the photosensitive resin composition and the cured film were evaluated in the same manner as in Example 1. [ In Comparative Example 3, the composition of Example 7 described in JP-A-2009-98616 was mixed with C1: a mixture of propylene glycol monomethyl ether acetate and C2: diethylene glycol ethyl methyl ether in a ratio of 3.0 mPa · s, and the photosensitive resin composition and the cured film were evaluated in the same manner as in Example 1. With respect to Comparative Example 7, the photosensitive resin composition and the cured film were evaluated in the same manner as in Example 1, using the composition of Example 17 of JP-A-2009-75329.

From the results shown in Tables 6 to 9, the following can be found.

In the first half of the example, the photosensitive resin composition containing the component A, the component B and the component C was subjected to a predetermined low-temperature treatment step and a step of elongating at room temperature for 45 seconds or more, whereby a satisfactory performance An interlayer insulating film can be obtained. Specifically, by adjusting the low-temperature treatment process, the formation of contact holes, ITO sputtering aptitude and the like can be further improved (Examples 1 to 16). In addition, it can be seen that the sensitivity is improved by slightly lengthening the elapsed time at room temperature (Examples 12, 30 to 36).

It can be seen that performance can be achieved with various compositions in the range containing Component A, Component B and Component C (Examples 18 to 29). It can be seen that all of the constituent units are composed of (meth) acrylate, and the copolymer using an oxetanyl group as the component (a2) is excellent in heat-resistant transparency. When a slit is applied without a low temperature treatment process, there is no sensitivity stability, and the performance such as the formation of contact holes and the ITO sputtering suitability are not satisfied at the same time (Comparative Examples 1 and 3). In addition, it can be seen that when the time elapsed at room temperature is short, the sensitivity is not stable, and the change in contact hole diameter is large (Comparative Example 2). (a1), (a2) and (a3), all characteristics such as sensitivity, sensitivity stability, and contact hole forming properties can not be satisfied at the same time (Comparative Examples 4 to 7).

It can be seen that the effects of the present invention are exhibited also in various polymers and photoacid generators as in Examples 101 to 139, 201 to 239 and Examples 301 to 308. In addition, as in Examples 201 to 239 and 301 to 304, it can be seen that transparency is particularly high when a photo acid generator of naphthofuran precursor is used.

(Example 45)

In the sensitivity evaluation of Example 8, evaluation was made in the same manner, except that the substrate was changed to a glass substrate surface-treated with HDMS (hexamethyldisilazane). It was possible to produce a pattern clearly as in Example 8.

(Example 140)

In the sensitivity evaluation of Example 108, evaluation was made in the same manner, except that the substrate was changed to a glass substrate surface-treated with HDMS (hexamethyldisilazane). It was possible to produce a clear pattern in the same manner as in Example 108.

(Example 240)

In the sensitivity evaluation of Example 208, evaluation was made in the same manner, except that the substrate was changed to a glass substrate surface-treated with HDMS (hexamethyldisilazane). A pattern could be produced clearly as in Example 208. [

(Example 46)

Except that the sensitivity evaluation of Example 8 was changed to an exposure apparatus provided with an i-line cut filter (FX-85S (ghi line specification, manufactured by Nikon Corporation) (that is, gh line exposure) Respectively. It was possible to produce a clear pattern in the same manner as in Example 8.

<Evaluation of Coating Properties>

(Examples 47 to 50)

The photosensitive resin composition of Example 47 was prepared in the same manner as in Example 8 except that the amount of the solvent was adjusted to adjust the viscosity to 18.0 mPa · s in the preparation of the photosensitive resin composition of Example 8. The viscosity of the photosensitive resin compositions of Examples 48 to 50 was adjusted to 22.0 mPa · s, 29.0 mPa · s, and 31.0 mPa · s, respectively, in the same manner as in Example 47.

The coating properties of the photosensitive resin compositions of Example 8 and Examples 47 to 50 were evaluated as follows. CL 1700 manufactured by Tokyo Electron Co., Ltd. was used to slit coat a 1,500 mm x 1,800 mm glass substrate so that the coated film thickness after drying was 3.0 탆. Drying was carried out on a hot plate at 90 DEG C for 90 seconds. The coated surface was visually observed to count the number of stripe-shaped unevenness, and the evaluation was made based on the following criteria. The results are shown in the table. A, B, and C are acceptable.

No streaks on the coated surface: A

Having 1-3: B

Having 4 ~ 5: C

With more than 6: D

(Examples 141 to 144)

A photosensitive resin composition of Example 141 was prepared in the same manner as in Example 108 except that the amount of the solvent was adjusted to adjust the viscosity to 18.0 mPa · s in the preparation of the photosensitive resin composition of Example 108. The viscosity of the photosensitive resin compositions of Examples 142 to 144 was adjusted to 22.0 mPa · s, 29.0 mPa · s, and 31.0 mPa · s, respectively, in the same manner as in Example 140.

The coating properties of the photosensitive resin compositions of Example 108 and Examples 141 to 144 were evaluated in the same manner as above.

(Examples 241 to 244)

A photosensitive resin composition of Example 241 was prepared in the same manner as in Example 208 except that the amount of the solvent was adjusted to adjust the viscosity to 18.0 mPa · s in the preparation of the photosensitive resin composition of Example 208. The viscosity of the photosensitive resin compositions of Examples 242 to 244 was adjusted to 22.0 mPa · s, 29.0 mPa · s, and 31.0 mPa · s, respectively, in the same manner as in Example 241.

The coating properties of the photosensitive resin compositions of Example 208 and Examples 241 to 244 were evaluated in the same manner as above.

(Comparative Example 8)

Using the photosensitive resin composition of Example 8, the liquid-tightness of the slit coat was evaluated as follows. CL 1700 manufactured by Tokyo Electron Co., Ltd. was used to slit coat a 1,500 mm x 1,800 mm glass substrate so that the coated film thickness after drying was 3.0 탆. The drying was carried out at 90 DEG C for 90 seconds on a hot plate. From the solid content remaining on the substrate as a dried film, it was found that 80 wt% or more of the photosensitive resin composition used in slit coating remained on the substrate.

A composition of Comparative Example 8 for spin coating was obtained in the same manner as in Example 8 except that the amount of the solvent was adjusted to adjust the viscosity to 35.0 mPa · s in the production of the photosensitive resin composition of Example 8. The composition of Comparative Example 8 was spin-coated on a 150 mm x 150 mm glass substrate so that the coating film thickness after drying was 3.0 占 퐉. Drying was carried out on a hot plate at 90 DEG C for 90 seconds. From the solid content remaining on the substrate as a dried film, it was found that the amount of the photosensitive resin composition remaining on the substrate during spin coating was 15 wt% or less. Further, an attempt was made to spin-coat the glass substrate with 1,500 mm x 1,800 mm, but the substrate could not be rotated. As described above, the slit coat is a coating method excellent in lubrication and large size.

(Example 51)

An organic EL display device using a thin film transistor (TFT) was manufactured 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 while covering the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 . The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or the subsequent steps and the TFT 1. [

The planarization layer 4 was formed on the insulating film 3 in a state in which the irregularities due to the wiring 2 were buried in order to planarize the irregularities due to the formation of the wiring 2. [ The planarizing film 4 was formed on the insulating film 3 by slit-coating the photosensitive resin composition of Example 12 subjected to low-temperature treatment on the substrate, pre-baking (90 DEG C x 2 minutes) on a hot plate, (365 nm) was irradiated with 20 mJ / cm 2 (illuminance: 20 mW / cm 2) from high-pressure mercury or the like, developed for 125 seconds at room temperature (23 ° C) and developed in an aqueous alkaline solution to form a pattern , And a heat treatment was performed at 230 캜 for 60 minutes. The coating property when the photosensitive resin composition was applied was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and firing. The average step of the wiring 2 was 500 nm, and the thickness of the planarizing film 4 was 2,000 nm.

Next, a bottom emission type organic EL device was formed on the obtained planarization film 4. [ First, a first electrode 5 made of ITO was formed on the flattening film 4 by connecting it to the wiring 2 through the contact hole 7. Thereafter, the resist was applied, pre-baked, exposed through a mask of a desired pattern, and developed. Using this resist pattern as a mask, patterning was performed by wet etching using ITO as a catalyst. Thereafter, the resist pattern was peeled off using a resist stripping solution (a 1: 1 mixture of monoethanolamine and dimethyl sulfoxide (DMSO)). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

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

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

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

(Example 145)

An organic EL display device was produced in the same manner as in Example 51 except that the insulating film 8 was formed using the composition of Example 107. [ As a result of applying a voltage through the driving circuit, it was found that the organic EL display device exhibits good display characteristics and is highly reliable.

(Example 245)

An organic EL display device was manufactured in the same manner as in Example 51 except that the insulating film 8 was formed using the composition of Example 207. [ As a result of applying a voltage through the driving circuit, it was found that the organic EL display device exhibits good display characteristics and is highly reliable.

(Example 52)

In the active matrix type liquid crystal display device shown in Figs. 1 and 2 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film in the following manner, and a liquid crystal display device of Example 52 was obtained.

That is, the photosensitive resin composition of Example 12 was used to form a cured film 17 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 51 above. As a result of applying the driving voltage to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibited good display characteristics and was highly reliable.

(Example 146)

A liquid crystal display device was produced in the same manner as in Example 52 except that the cured film 17 was formed using the composition of Example 138. [ As a result of application of the driving voltage, it was found that the liquid crystal display device exhibited good display characteristics and was highly reliable.

(Example 246)

A liquid crystal display device was produced in the same manner as in Example 52 except that the cured film 17 was formed using the composition of Example 238. [ As a result of application of the driving voltage, it was found that the liquid crystal display device exhibited good display characteristics and was highly reliable.

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

Claims (12)

(1) a low-temperature processing step of setting the photosensitive resin composition to a temperature of 10 占 폚 or lower,
(2) a coating step for slit-coating the photosensitive resin composition on a substrate,
(3) a solvent removing step of removing the solvent in the applied photosensitive resin composition,
(4) an exposure step of exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray,
(5) a step of elongating at room temperature for 45 seconds or more,
(6) a developing step of developing by an aqueous developing solution, and
(7) a post-baking process for thermosetting in this order,
The above photosensitive resin composition
(Component A) A resin composition comprising at least (a1) a structural unit having an acid-decomposable group-protected residue, (a2) a structural unit having a crosslinking group, (a3) a copolymer containing a structural unit having a carboxyl group and / or a phenolic hydroxyl group,
(Component B) photoacid generator,
(Component C) a solvent. The method according to claim 1,
Wherein the constituent unit (a1) is a constitutional unit having a carboxyl group as an acetal or ketal protected residue. The method according to claim 1,
Wherein the constituent unit (a1) is represented by the formula (A2).
[Chemical Formula 1]

(In the formula (A2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ is an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group) The method according to claim 1,
Wherein the structural unit (a2) has at least one group selected from the group consisting of an epoxy group, an oxetanyl group and an ethylenic unsaturated group. The method according to claim 1,
Wherein the constituent unit (a2) has an alicyclic epoxy group and / or an oxetanyl group. The method according to claim 1,
Wherein the component B is a compound having an oxime sulfonate moiety. The method according to claim 1,
Wherein the component B is a compound represented by the formula (OS-3), the formula (OS-4) or the formula (OS-5).
(2)

(Formula (OS-3) ~ formula (OS-5) of, R ¹ is an alkyl group, an aryl group or a heteroaryl group, R ² are each independently a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ An alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, and m represents an integer of 0 to 6, ) The method according to claim 1,
Wherein the photosensitive resin composition is a chemically amplified positive photosensitive resin composition. delete A cured film produced by the method for producing a cured film according to any one of claims 1 to 8. An organic EL display device comprising the cured film according to claim 10. A liquid crystal display device comprising the cured film according to claim 10.

Images