KR101888862B1 - Photosensitive resin composition, pattern, and method for forming pattern - Google Patents

Abstract

A positive photosensitive resin composition excellent in resolution and heat resistance is provided.
, Wherein the total of the repeating unit (a1) represented by the following general formula (I) and the repeating unit (a2) represented by the following general formula (II) is 95 mol% or more of the total repeating units, Wherein the positive photosensitive resin composition contains a polymer (A) having a weight average molecular weight (number average molecular weight / number average molecular weight) of more than 2.0, a photo acid generator (B) and a solvent (C).

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a pattern, and a method of manufacturing the same. BACKGROUND ART [0002]

The present invention relates to a photosensitive resin composition, a pattern and a method for producing the same. Further, the present invention relates to an electronic device such as an organic EL display device, a liquid crystal display device, and a semiconductor device using the pattern. More specifically, the present invention relates to a positive photosensitive resin composition suitable for forming a planarizing film, a protective film, or an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, an integrated circuit device, And a method of manufacturing the pattern.

In an organic EL display device, a liquid crystal display device, or the like, a patterned ITO film is provided. For forming the pattern of the ITO film, a method is known in which the ITO film is etched using the formed pattern as a mask, and the processing is performed by applying (coating) the photosensitive resin composition on the ITO film, removing the solvent, exposing and developing the film.

Further, in recent years, high resolution of ITO processing has been required in order to make the display characteristics of the organic EL display device and the liquid crystal display device high definition. In order to finely process ITO, high resolution of a photosensitive resin composition which functions as a mask at the time of etching is required.

In order to further improve the productivity of the organic EL display device and the liquid crystal display device, improvement of the process margin is a problem. From this point of view, it is required to improve the sensitivity of the photosensitive resin composition. Further, recently, when the photosensitive resin composition is exposed to light when the mask pattern is formed, the amount of light irradiation fluctuates due to blur, or fluctuates due to deviation of light irradiation amount depending on the type of the exposure apparatus And it is also desired that the photosensitive resin composition which is hardly changed in the line width of the obtained pattern and has a large exposure margin. There is also a demand for a resin composition which has less resist flow due to heating, has a good taper shape, and is unlikely to change in line width of a pattern obtained by flow.

Here, in JP-A-11-75864, JP-A-10-121029 and JP-A-11-190904, a resin in which a part of polyhydroxystyrene is protected with a tetrahydrofuran compound Based on the total weight of the positive photosensitive resin composition.

The inventors of the present invention have studied the Japanese Unexamined Patent Application, First Publication No. H11-75864 and the Japanese Unexamined Patent Application, First Publication No. H10-121029, and it has been found that the obtained positive photosensitive resin composition has poor resolution and heat resistance. It is an object of the present invention to solve such a problem, and an object thereof is to provide a positive photosensitive resin composition capable of satisfying both heat resistance and resolution.

Under such circumstances, the present inventors have conducted intensive studies, and as a result, it has been found that when tetrahydrofuranyl groups are used as protective groups in JP-A-11-75864 and JP-A-10-121029, (Weight average molecular weight / number average molecular weight, Mw / Mn) of the resin is small. In the positive photosensitive resin composition, it is known that the degree of polydispersity of a resin such as polyhydroxystyrene is preferably as small as possible, and it is very surprising that the effect of the present invention improves by increasing the polydispersity.

Specifically, the problem of the present invention has been solved by the following means.

(1) the total of the repeating unit (a1) represented by the following general formula (I) and the repeating unit (a2) represented by the following general formula (II) A positive photosensitive resin composition characterized by containing a polymer (A) having a polydispersity (weight average molecular weight / number average molecular weight) of more than 2.0, a photo acid generator (B) and a solvent (C).

In general formula (I)

(In the general formula (I), Ra ^{1 to} Ra ⁶ each represent a hydrogen atom, an alkyl group which may have a substituent having 1 to 20 carbon atoms, or an aryl group which may have a substituent, Ra ⁷ is a hydrogen atom or a methyl group, Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and n 1 is an integer of 0 to 4)

In general formula (II)

(Ra ⁹ is a hydrogen atom or a methyl group, Ra ¹⁰ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and n2 is an integer of 0 to 4)

(2) The positive photosensitive resin composition according to (1), wherein the polymer (A) has a weight average molecular weight of 5000 or more.

(3) The positive photosensitive resin composition according to (1) or (2), wherein the photo acid generator (B) has an oxime sulfonate structure represented by the following general formula (b1)

In general formula (b1)

(In the general formula (b1), R ¹ represents an alkyl group which may have a substituent, a cyclic alkyl group which may have a substituent, a heteroaryl group which may have a substituent or an aryl group which may have a substituent)

(4) The positive resist composition as described in any one of (1) to (4), wherein the basic compound (D) is at least one compound selected from the group consisting of a compound represented by the following general formula (a), a compound represented by the following general formula (b) The positive photosensitive resin composition according to any one of (1) to (3).

In general formula (a)

(In the general formula (a), R ² represents an alkyl group which may have a substituent having 1 to 6 carbon atoms or a cyclic alkyl group which may have a substituent having 3 to 10 carbon atoms, and X represents an oxygen atom or a sulfur atom. Y ¹ represents an oxygen atom or -NH- group, p ¹ represents an integer of 1 to 3,

In general formula (b)

(Wherein R ⁸ , R ⁹ and R ¹⁰ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a substituent having 3 to 10 carbon atoms Or a cyclic alkyl group which may have a substituent

(C)

(5) The positive photosensitive resin composition according to any one of (1) to (4), wherein Ra ¹ , Ra ² , Ra ³ and Ra ^{5 in} the general formula (I) are hydrogen atoms.

(6) The positive photosensitive resin composition according to any one of (1) to (5), wherein n1 in the general formula (I) and n2 in the general formula (II)

(7) The positive photosensitive resin composition according to any one of (1) to (6), wherein the repeating unit represented by the general formula (I) is represented by the following general formula (III)

In general formula (III)

(8) The photoacid generator according to the above (B), wherein the photoacid generator is represented by the following formula (OS-3), the following formula (OS-4), the following formula (OS- (1) to (7), wherein the compound represented by the general formula (OS-2) is a compound represented by the general formula (OS-2)

(In the formulas (OS-3) to (OS-5), R ²² , R ²⁵ and R ²⁸ represent an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ , R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and X ¹ To X ³ each independently represents an oxygen atom or a sulfur atom, n ^{1 to} n ³ each independently represents 1 or 2, and m ¹ to m ³ each independently represent an integer of 0 to 6)

In general formula (b2)

(In the formula (b2), R ³¹ represents an alkyl group, a cyclic alkyl group or an aryl group, X ¹¹ represents an alkyl group, an alkoxy group or a halogen atom, and m ¹¹ represents an integer of 0 to 3. When m ¹¹ represents 2 or 3 The plurality of X < ¹¹ > may be the same or different)

The formula (B3)

(In the formula (B3), R ⁴³ represents an alkyl group which may have a substituent, a cyclic alkyl group which may have a substituent, a heteroaryl group which may have a substituent or an aryl group which may have a substituent, X ¹ represents a halogen atom, An alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and n4 is an integer of 0 to 5)

Wherein R ¹⁰¹ is 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, represents an aryl group. R ¹⁰² is an alkyl group, or an aryl group. R ¹²¹ ~R ¹²⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, An amide group, a sulfo group, a cyano group, or an aryl group, two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring)

(9) The positive resist composition according to any one of (1) to (8), wherein the polymer (A) has a weight average molecular weight of 5000 or more and the photoacid generator (B) has an oxime sulfonate structure represented by the following general formula (b1) Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.

In general formula (b1)

(In the general formula (b1), R ¹ represents an alkyl group which may have a substituent, a cyclic alkyl group which may have a substituent, a heteroaryl group which may have a substituent or an aryl group which may have a substituent)

(10) The polymer (A) has a weight average molecular weight of 5000 or more,

(1) to (4), wherein the basic compound (D) is at least one compound selected from the group consisting of a compound represented by the following formula (a), a compound represented by the following formula (b) and a compound represented by the following formula (9) The positive photosensitive resin composition described in any one of (1) to (9) above.

In general formula (a)

(In the general formula (a), R ² represents an alkyl group which may have a substituent having 1 to 6 carbon atoms or a cyclic alkyl group which may have a substituent having 3 to 10 carbon atoms, and X represents an oxygen atom or a sulfur atom. Y ¹ represents an oxygen atom or -NH- group, p ¹ represents an integer of 1 to 3,

In general formula (b)

(Wherein R ⁸ , R ⁹ and R ¹⁰ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a substituent having 3 to 10 carbon atoms Or a cyclic alkyl group which may have a substituent

(C)

(11) The polymer (A) has a weight average molecular weight of 5000 or more,

Wherein Ra ¹ in the formula ^{(Ⅰ), Ra 2, Ra} 3, Ra 5 is a hydrogen atom, the formula (Ⅰ) n2 is 0 (1 in the n1 and the general formula (Ⅱ) in To (10), wherein the positive photosensitive resin composition is a positive photosensitive resin composition.

(12) A process for producing a photosensitive resin composition, comprising the steps of (1) applying the photosensitive resin composition according to any one of (1) to (11)

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

(3) a step of exposing with active radiation,

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

(5) etching the substrate using the formed resist pattern as a mask, and

(6) A method for producing a pattern, which comprises peeling the resist pattern.

(13) The method of manufacturing a pattern according to (12), which comprises post-baking the resist pattern at 100 to 160 캜 before the etching step after the developing step.

(14) The pattern manufacturing method according to (12) or (14), wherein the substrate is an ITO substrate, a molybdenum substrate, or a silicon substrate.

(15) A pattern formed by the method for producing a pattern described in any one of (12) to (14).

(16) An ITO pattern formed by the method for producing a pattern described in any one of (12) to (14).

(17) An organic EL display device or liquid crystal display device comprising the ITO pattern described in (16).

According to the present invention, it is possible to provide a photosensitive resin composition excellent in high resolution and high heat resistance of the photosensitive resin composition.

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

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, the term " ~ " is used to mean that the numerical values described before and after the lower limit and the upper limit are included.

≪ Polymer (A) >

The photosensitive resin composition of the present invention (hereinafter also referred to as " photosensitive composition of the present invention " or " composition of the present invention ") comprises repeating units (a1) represented by the following general formula (I) (A2) represented by the following general formula (II) is 95 mol% or more of the total repeating units, and the polymer having a polydispersity (weight-average molecular weight / number-average molecular weight) A).

In general formula (I)

(In the general formula (I), Ra ¹ to Ra ⁶ each represent a hydrogen atom, an alkyl group which may have a substituent having 1 to 20 carbon atoms, or an aryl group which may have a substituent, and may be bonded to each other to form a ring Ra ⁷ is a hydrogen atom or a methyl group, Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, n 1 is an integer of 0 to 4,

Examples of the alkyl group represented by Ra ^{1 to} Ra ⁶ include a linear, branched, cyclic alkyl group having 1 to 20 carbon atoms, which may have a substituent, and a phenyl group, which may have a substituent, Linear or branched alkyl group having from 3 to 12 carbon atoms or a cyclic alkyl group having from 5 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, A cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group.

Specific examples of the aryl group in Ra ^{1 to} Ra ⁶ include a phenyl group and a naphthyl group.

Each of Ra ^{1 to} Ra ⁶ is preferably a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having from 1 to 12 carbon atoms, or a phenyl group having from 3 to 12 carbon atoms, More preferably a hydrogen atom, a straight chain alkyl group having 1 to 12 carbon atoms or a phenyl group, and still more preferably a hydrogen atom, a methyl group and a phenyl group.

Ra ¹ , Ra ² , Ra ³ and Ra ⁵ are each preferably a hydrogen atom, and Ra ¹ , Ra ² , Ra ³ and Ra ⁵ are hydrogen atoms, and Ra ⁴ and Ra ⁶ are the same as those described above desirable.

Ra ⁷ is a hydrogen atom or a methyl group, preferably a hydrogen atom.

Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and is preferably a chlorine atom, a bromine atom, a hydroxyl group or a methyl group.

n1 is an integer of 0 to 4, and n1 is preferably 0.

In general formula (II)

(Ra ⁹ is a hydrogen atom or a methyl group, Ra ¹⁰ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and n1 is an integer of 0 to 4)

Ra ⁹ is a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

Ra ¹⁰ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and is preferably a chlorine atom, a bromine atom, a hydroxyl group or a methyl group.

n2 is an integer of 0 to 4, and 0 is preferable.

The component (A) is preferably insoluble or sparingly soluble in alkali, and is preferably a resin that becomes alkali-soluble when the protected hydroxyl group of the monomer unit (a1) is decomposed by the action of an acid. As a resin which increases the solubility in an alkali developing solution by the action of an acid, it has a repeating unit corresponding to hydroxystyrene having the monomer unit (a1), decomposes by the action of an acid and increases the solubility in alkali Can be used. Here, in the present invention, "alkali solubility" means that the solution of the compound (resin) is coated on a substrate and the coating film (thickness 3 μm) of the compound (resin) formed by heating at 90 ° C. for 2 minutes is 23 Refers to a dissolution rate of not less than 0.01 mu m / second in a 2.38% aqueous solution of tetramethylammonium hydroxide at 20 DEG C, and the term " alkali insoluble " means that the solution of the compound (resin) is applied onto a substrate and heated at 90 DEG C for 2 minutes Means that the dissolution rate of the coating film (thickness 3 占 퐉) of the compound (resin) formed in the aqueous solution of 2.38% tetramethylammonium hydroxide at 23 占 폚 is less than 0.01 占 퐉 / second.

The photosensitive resin composition of the present invention is preferably a resin which is deprotected by an acid generated from a photo-acid generator by light irradiation to increase the solubility in an alkali developing solution.

The skeleton of the monomer unit of hydroxystyrene may be partially hydrogenated.

Specific examples of the polymer (A) used in the present invention are shown below, but the present invention is not limited thereto.

In the present invention, the content of the monomer unit (a1) in the polymer (A) is preferably 5 to 90 mol%, more preferably 10 to 75 mol%, and still more preferably 10 to 75 mol% 45 mol%. The content of the monomer unit (a2) is preferably 5 to 95 mol%, more preferably 10 to 85 mol%, based on all repeating units. The sum of the repeating unit (a1) represented by the following general formula (I) and the repeating unit (a2) represented by the following general formula (II) is more preferably 98 mol% or more of the total repeating units.

The polydispersity (weight average molecular weight / number average molecular weight, Mw / Mn, and molecular weight distribution) of the polymer (A) is preferably 2.01 to 7.00, more preferably 2.01 to 5.00, Particularly preferably 4.00. By setting the polydispersity to 7.00 or less, resolution tends to be improved and the resist pattern can be more effectively suppressed from being tapered. Further, when it is less than 2.00, the resolution is lowered or a residual residue is generated. Here, the weight average molecular weight and the number average molecular weight are defined as polystyrene equivalents of gel permeation chromatography.

The weight average molecular weight (Mw) of the polymer (A) is preferably in the range of 5,000 to 300,000, more preferably 5,000 to 100,000, and most preferably 5,000 to 60,000. By setting the amount of the solvent to 5,000 or more, film reduction due to the development of the unexposed portion can be suppressed. When it is 300,000 or less, the dissolution rate of the resin itself to the alkali is slowed down and the sensitivity is lowered more effectively. Here, the weight average molecular weight is defined as a polystyrene conversion value of the gel permeation chromatography.

The polymer (A) of the photosensitive composition of the present invention may be used in a mixture of two or more. The amount of the polymer (A) to be used is preferably 40 to 99% by weight, more preferably 60 to 98% by weight, and more preferably 80 to 80% by weight, based on the entire weight of the photosensitive composition (excluding the solvent) To 98% by weight.

The photosensitive resin composition of the present invention is dissolved in a solvent for dissolving each of the above components, and is usually adjusted as a solution by filtration with a filter having a pore diameter of about 0.05 to 0.2 mu m, for example. Examples of the solvent to be used herein include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol Monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl beta -methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, , Xylene, cyclohexyl acetate, diacetone alcohol, N-methylpyrrolidone, N, N-dimethylformamide,? -Butyrolactone, N, N-dimethylacetamide, propylene carbonate and ethylene carbonate have. These solvents may be used alone or in combination. The selection of the solvent is important because it affects the solubility in the positive type photoresist composition of the present invention, the applicability to the substrate, the storage stability, and the like. In addition, the moisture contained in the solvent affects various properties of the resist, so that it is preferable that the amount is small.

In the photosensitive resin composition of the present invention, it is preferable to reduce metal impurities such as metal and impurity components such as halogen ions to 100 ppb or less. The presence of a large amount of these impurities causes undesirable operation defects, defects, and yield reduction in the production of semiconductor devices.

It is preferable that the solid content of the photosensitive resin composition is dissolved in the above-mentioned solvent and dissolved in a solid content concentration of 3 to 40%. And more preferably 5 to 30%.

<< Synthesis of Polymer (A) >>

The polymer to be used as the polymer (A) can be synthesized by using a method of using vinyl ether for acetalization or an acetal exchange method using an alcohol and an alkyl vinyl ether. In addition, a dehydration method (dehydration azeotropic method) described in the following examples may be used for efficient and stable synthesis. However, the synthesis method is not limited thereto.

&Lt; Photo acid generator (B) >

The photosensitive resin composition of the present invention contains a photo acid generator (B). As the radiation-sensitive acid generator to be used in the present invention, a compound which generates an acid in response to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, is preferred, but its chemical structure is not particularly limited . In the case of a radiation-sensitive acid generator that does not directly react with an actinic ray having a wavelength of 300 nm or more, a compound capable of generating an acid upon exposure to an actinic ray having a wavelength of 300 nm or more by being used in combination with a sensitizer, Can be used. As the radiation-sensitive acid generator used in the present invention, a radiation-sensitive acid generator that generates an acid with a pKa of 4 or less is preferable, and a radiation-sensitive acid generator that generates an acid with a pKa of 3 or less is more preferable.

In general formula (b1)

(In the general formula (b1), R ¹ represents an alkyl group which may have a substituent, a cyclic alkyl group which may have a substituent, a heteroaryl group which may have a substituent or an aryl group which may have a substituent)

The alkyl group in R ¹ may be linear, branched or cyclic. The permissible substituents are described below.

The alkyl group represented by R ¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R ¹ is preferably an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cyclic alkyl group (including bridged alicyclic ring such as 7,7-dimethyl-2-oxonorbornyl) Group, preferably a bicycloalkyl group, or the like).

The aryl group represented by R ¹ is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of R ¹ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

The heteroaryl group of R ¹ is the same as the heteroaryl group of R ²² , R ²⁵ and R ²⁸ in the general formulas (OS-3) to (OS-5) described later.

The two bonders extending from the carbon atom of the general formula (b1) are bonded to a substituent or an atom. Here, the carbon atom of the general formula (b1) is preferably a part of a cyclic structure or is bonded to a substituent having a cyclic structure. Such a cyclic structure is preferably a 5-membered ring, a 6-membered ring, or two or three condensed rings thereof. The molecular weight of the compound represented by the general formula (b1) is preferably 100 to 600.

It is also preferable that the compound containing an oxime sulfonate structure represented by the general formula (b1) is an oxime sulfonate compound represented by the following general formula (b2).

In general formula (b2)

(In the general formula (b2), R ³¹ represents an alkyl group or an aryl group, X ¹¹ represents an alkyl group, an alkoxy group or a halogen atom, m 11 represents an integer of 0 to 3, and when m 11 represents 2 or 3, The plurality of X &lt; ¹¹ &gt; may be the same or different)

The alkyl group as X ¹¹ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

The alkoxy group as X ¹¹ is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.

The halogen atom as X &lt; ¹¹ &gt; is preferably a chlorine atom or a fluorine atom.

m11 is preferably 0 or 1.

Wherein the general formula (b2), and m11 is 1, and X ¹¹ is a methyl group, the substitution position of X ¹¹ are ortho position, R ³¹ is a straight chain alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2 An oxonoboronylmethyl group, or a p-toluyl group is particularly preferable.

It is more preferable that the compound containing the oxime sulfonate structure represented by the general formula (b1) is an oxime sulfonate compound represented by the following general formula (B3).

(In the formula (B3), R ⁴³ is the same as R ¹ in the formula (b1), and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, And n4 represents an integer of 0 to 5)

Examples of R ⁴³ in general formula (B3) include a methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, , A perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group are preferable, and an n-octyl group is particularly preferable.

X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group.

n4 is preferably 0 to 2, and particularly preferably 0 to 1.

Specific examples of the compound represented by the general 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, Phenyl] acetonitrile, α - [(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α - [(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, (n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, and? - [(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile.

Specific examples of preferable oxime sulfonate compounds include the following compounds (i) to (vii), and they may be used singly or in combination of two or more. The compounds (i) to (vii) are commercially available. It may also be used in combination with other types of photo acid generators (B).

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

In the general formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Lt; / RTI &gt; R ¹⁰² represents an alkyl group or an aryl group.

¹⁰¹ X is ^{-O-, -S-, -NH-, -NR 105} -, -CH 2 -, -CR 106 H-, or, -CR ¹⁰⁵ R ¹⁰⁷ - represents a, R ¹⁰⁵ ~R ¹⁰⁷ is an alkyl group, Or an aryl group.

R ¹²¹ to R ¹²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an aryl group. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.

As R ¹²¹ to R ¹²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, and at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group. Among them, the case where all of R ¹²¹ to R ¹²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.

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

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

Of the above general formula (OS-2), R ¹⁰¹ , R ¹⁰² and R ¹²¹ to R ¹²⁴ are the same as those in formula (OS-1), and preferable examples are also the same.

Among them, the moiety in which R ^{101 in} the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable and is represented by the general formula (OS-2) , And R &lt; ¹⁰¹ &gt; is a cyano group, a phenyl group or a naphthyl group.

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

Specific examples (Exemplary Compounds b-1 to b-34) of the compound represented by the above general formula (OS-1) that can be 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, Ts represents a tosyl group, and Ph represents a phenyl group.

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

(OS-3), the following general formula (OS-4) or the following general formula (OS-5) as the compound containing the oxime sulfonate structure represented by the general formula (b1) It is also preferable that the oximesulfonate compound is a displayed oxime sulfonate compound.

(Formula (OS-3) ~ formula (OS-5) of, R ^22, R ²⁵ and R ²⁸ are each alkyl group independently represents an aryl group or a heteroaryl group, R ^23, R ²⁶ and R ²⁹ are each An alkyl group, an aryl group or a halogen atom; R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group; X ^{1 to} X ³ each independently represents an oxygen atom or a sulfur atom, n ^{1 to} n ³ each independently represent 1 or 2, and m ^{1 to} m ³ each independently represent an integer of 0 to 6)

In the general formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.

Of the above formulas (OS-3) to (OS-5), the alkyl group for R ²² , R ²⁵ and R ²⁸ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

Examples of the alkyl group for R ²² , R ²⁵ and R ²⁸ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group and benzyl group are preferable.

Examples of the substituent which the alkyl group in R ²² , R ²⁵ and R ²⁸ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group .

In the general formulas (OS-3) to (OS-5), as the aryl group for R ²² , R ²⁵ and R ²⁸ , an aryl group having 6 to 30 total carbon atoms which may have a substituent is preferable.

As the aryl group in R ²² , R ²⁵ and R ²⁸ , a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group or p- .

Examples of the substituent which the aryl group in R ²² , R ²⁵ and R ²⁸ 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, , A sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

Of the above-mentioned general formulas (OS-3) to (OS-5), the heteroaryl group for R ²² , R ²⁵ and R ²⁸ is preferably a heteroaryl group having 4 to 30 total carbon atoms which may have a substituent .

The heteroaryl group in R ²² , R ²⁵ and R ²⁸ in the general formulas (OS-3) to (OS-5) may be any of a heteroaromatic ring in which at least one ring is a heteroaromatic ring. (Condensed ring).

Examples of the heteroaryl group for R ²² , R ²⁵ and R ²⁸ include a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, Imidazole ring, and a group excluding one hydrogen atom from a ring selected from the group consisting of imidazole rings.

Examples of the substituent which the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have include a halogen atom, alkyl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, amino A carbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

In the general formulas (OS-3) to (OS-5), R ²³ , R ²⁶ and R ²⁹ are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

Of the general formulas (OS-3) to (OS-5), one or two of R ²³ , R ²⁶ and R ²⁹ present in two or more of the compounds are preferably an alkyl group, an aryl group or a halogen atom, An alkyl group, an aryl group or a halogen atom, more preferably one is an alkyl group, and the remainder is a hydrogen atom.

In the general formulas (OS-3) to (OS-5), the alkyl group or aryl group in R ²³ , R ²⁶ and R ²⁹ may have a substituent. Here, examples of the substituent which the alkyl group or aryl group in R ²³ , R ²⁶ and R ²⁹ may have include the same groups as the substituent which the alkyl group or aryl group in R ²² , R ²⁵ and R ²⁸ may have have.

The alkyl group for R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having a total of 1 to 12 carbon atoms which may have a substituent and more preferably an alkyl group having a total of 1 to 6 carbon atoms which may have a substituent.

Examples of the alkyl group in R ²³ , R ²⁶ and R ²⁹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, , A chloromethyl group, a bromomethyl group, a methoxymethyl group and a benzyl group are preferable and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, More preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group or an n-hexyl group, and a methyl group is preferable.

The aryl group for R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having a total of 6 to 30 carbon atoms which may have a substituent.

Specific examples of the aryl group for R ²³ , R ²⁶ and R ²⁹ include a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group and a p-phenoxyphenyl group.

Examples of the halogen atom in R ²³ , R ²⁶ and R ²⁹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

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

In the general formulas (OS-3) to (OS-5), X ^{1 to} X ³ each independently represents O or S, and is preferably O.

In the general formulas (OS-3) to (OS-5), the ring containing X ^{1 to} X ³ as a ring member is a 5-membered ring or a 6-membered ring.

In the general formulas (OS-3) to (OS-5), n ^{1 to} n ³ independently represent 1 or 2, and when X ^{1 to} X ³ are O, n ^{1 to} n ³ each independently When X ^{1 to} X ³ are S, it is preferable that n ^{1 to} n ³ are each independently 2.

In the general formulas (OS-3) to (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. Among them, it is preferable that R ²⁴ , R ²⁷ and R ³⁰ are each independently an alkyl group or an alkyloxy group.

The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.

Of the general formulas (OS-3) to (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

Examples of the alkyl group for R ²⁴ , R ²⁷ and R ³⁰ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group and benzyl group are preferable.

Examples of the substituent which the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, .

In the general formulas (OS-3) to (OS-5), the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyloxy group having 1 to 30 total carbon atoms which may have a substituent.

Examples of the alkyloxy group for R ²⁴ , R ²⁷ and R ³⁰ include methyloxy, ethyloxy, butyloxy, hexyloxy, phenoxyethyloxy, trichloromethyloxy, Group is preferable.

Examples of the substituent which the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group .

In the formulas (OS-3) to (OS-5), examples of the aminosulfonyl group for R ^{24 ,} R ²⁷ and R ³⁰ include methylaminosulfonyl group, dimethylaminosulfonyl group, phenylaminosulfonyl group, An aminosulfonyl group, and the like.

In the general formulas (OS-3) to (OS-5), examples of the alkoxysulfonyl group for R ²⁴ , R ²⁷ and R ³⁰ include a methoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, And a plant fluoro group.

In the formulas (OS-3) to (OS-5), m ^{1 to} m ³ each independently represent an integer of 0 to 6, preferably an integer of 0 to 2, , And particularly preferably 0.

The compound containing an oxime sulfonate structure represented by the general formula (B1) is particularly preferably an oxime sulfonate compound represented by any one of the following general formulas (OS-6) to (OS-11).

(Wherein (OS-6) ~ (OS -11), R 301 ~R 306 represents an alkyl group, an aryl group or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, R ³⁰⁸ ~R ^310, R ³¹³ , R ³¹⁶ and R ³¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ³¹¹ and R ³¹⁴ A halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group)

The formula ^{(OS-6) ~ R 301} ~R 306 in (OS-11) is the general formula ^{(OS-3) ~ R 22} , R 25 and R ²⁸ in (OS-5) and Agreement, and the preferred embodiment is also the same.

R ³⁰⁷ in the above general formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

R ³⁰⁸ to R ³¹⁰ , R ³¹³ , R ³¹⁶ and R ³¹⁸ in the general formulas (OS-6) to (OS-11) each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, A methyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, and is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, More preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

R ³¹¹ and R ³¹⁴ in the general formulas (OS-8) and (OS-9) each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and are preferably hydrogen atoms.

R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ in the general formulas (OS-8) to (OS-11) represent a hydrogen atom or a methyl group and are preferably hydrogen atoms.

In the oxime sulfonate compound, any of the three-dimensional structures (E, Z) of oxime may be a mixture or a mixture thereof.

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

In the positive photosensitive resin composition of the present invention, the photoacid generator represented by the formula (1) or (2) may also be used.

(Wherein R ⁵ , R ⁶ and R ⁷ each independently represent an alkyl group or an aromatic group which may have a substituent, and in the case of an alkyl group, R ⁸ and R ⁹ may each independently be a ring, X ^- represents a monovalent anion represented by BY ₄ ^- , PY ₆ ^- , AsY ₆ ^- , SbY ₆ ^- , or the formula (3) or (4), and Y represents an aromatic group which may have a substituent Each independently represent a halogen atom)

(Wherein R ²¹ , R ²² and R ²³ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkyl group having a fluorine atom having 1 to 10 carbon atoms, or R ²¹ and R ²² , An alkylene group having a number of 2 to 6 or an alkylene group having a fluorine atom having 2 to 6 carbon atoms)

As the alkyl group in R ⁵ , R ⁶ and R ⁷ in the formula (1), an alkyl group having 1 to 10 carbon atoms is preferable, and for example, a methyl group, an ethyl group and a tertiary butyl group (tert-butyl group) Do. When at least two of R ⁵ , R ⁶ and R ⁷ in the formula (1) is an alkyl group, it is preferable that the two or more alkyl groups are connected to each other to form a ring. (Thacyclopentane), and a 6-membered ring (thiacyclohexane) are more preferable, and a 5-membered ring is more preferable.

The aromatic group in R ⁵ , R ⁶ and R ⁷ is preferably an aromatic group having 6 to 30 carbon atoms and may have a substituent. Examples of such aromatic groups include a phenyl group, a naphthyl group, a 4-methoxyphenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 4-tertiary butylphenyl group, Methoxy-1-naphthyl group, and 4- (4'-diphenylsulfonylphenylthio) phenyl group.

In the formula (2), preferred examples of the aromatic group in R ⁸ and R ⁹ are the same as those of R ⁵ , R ⁶ and R ⁷ .

The substituent in R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is preferably an aromatic group, specifically, a phenyl group, a 4-methoxyphenyl group, a 4-chlorophenyl group, a 4- Phenylthio) phenyl group is particularly preferable.

The acid generator represented by the formula (1) or (2) may be combined with any of R ⁵ to R ⁹ to form a multimer such as a dimer. For example, the 4- (4'-diphenylsulfonylphenylthio) phenyl group is an example of a dimer, and the relative anion in the 4- (4'-diphenylsulfonylphenylthio) phenyl group is BY ₄ ^- , PY ₆ ^- , AsY ₆ ^- , SbY ₆ ^- , or a monovalent anion represented by the formula (3) or (4).

In BY ₄ ^{- -} Formula (1) and (2) ^{_{of, X, PY 6 -, AsY}} 6 -, SbY 6 - of the Y is preferably a fluorine atom, a chlorine atom and a fluorine atom in view of the negative ion stability Particularly preferred.

Examples of the alkyl group having 1 to 10 carbon atoms in R ²¹ , R ²² and R ²³ in the formulas (3) and (4) include a methyl group, an ethyl group, a butyl group, a tertiary butyl group, , Octyl group and the like. Examples of the alkyl group having a fluorine atom having 1 to 10 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a dodecafluoropentyl group, a perfluoro And rouxthyl group. Among them, R ²¹ , R ²² and R ²³ are preferably an alkyl group having a fluorine atom having 1 to 10 carbon atoms, more preferably an alkyl group having a fluorine atom having 1 to 6 carbon atoms, 4 &lt; / RTI &gt; fluorine atom is particularly preferred in terms of sensitivity.

Examples of the alkylene group having 2 to 6 carbon atoms in the formulas (3) and (4) when R ²¹ and R ²² are bonded to each other to form a ring include an ethylene group, a propylene group, a butylene group, a pentylene group, And a silylene group. Examples of the alkylene group containing a fluorine atom having 2 to 6 carbon atoms include a tetrafluoroethylene group, a hexafluoropropylene group, an octafluorobutylene group, a decafluoropentylene group, a dodecafluorohexylene group and the like . Among them, when R ²¹ and R ²² are bonded to each other to form a ring, they are preferably bonded with an alkylene group having a fluorine atom having 2 to 6 carbon atoms, and alkyl having a fluorine atom with 2 to 4 carbon atoms It is more preferable to bond with an alkylene group, and it is particularly preferable to bond with an alkylene group having a fluorine atom having 3 carbon atoms from the viewpoint of sensitivity.

In the formulas (3) and (4), it is preferable that R ²¹ and R ²² are each an alkylene group having 2 to 6 carbon atoms or a ring bonded with an alkylene group having a fluorine atom having 2 to 6 carbon atoms .

In the formulas (1) and (2), X ^- is preferably a monovalent anion represented by BY ₄ ^- , PY ₆ ^- , or Formula (3) or Formula (4) A monovalent anion is particularly preferable in terms of sensitivity,

As the acid generator represented by the formula (1), an acid generator represented by the following formula (5) may also be used.

(Wherein R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent an alkyl group or aromatic group which may have a substituent, and Ar ³ and Ar ⁴ each independently represent a divalent aromatic group which may have a substituent , X ^{1 -} and X ^{2 -} are each independently selected from the group consisting of BY ₄ ^- , PY ₆ ^- , AsY ₆ ^- , SbY ₆ ^- or a monovalent anion represented by the formula (3) or the formula (4) And each Y independently represents a halogen atom)

Preferable examples of the alkyl group and the aromatic group in R ¹⁰ , R ¹¹ , R ¹² and R ¹³ in the formula (5) are the preferred examples of the alkyl group and aromatic group in R ⁵ , R ⁶ and R ⁷ of the formula (1) It is like the sun.

As the divalent aromatic group in Ar ³ and Ar ⁴ in the formula (5), a phenylene group or a naphthylene group is preferable, and a phenylene group is particularly preferable.

Examples of the compound represented by the formula (1) or the formula (2) are given below. Among them, PAG-7, PAG-12 and PAG-14 are preferable, and PAG-12 is particularly preferable.

As the photoacid generator used in the present invention, trichloromethyl-s-triazine and quaternary ammonium salts can also be preferably used.

In the present invention, the following photo acid generation system can be used suitably.

As the (B) photoacid generator used in the present invention, the oxime sulfonate system is the most preferable from the viewpoint of higher heat resistance and resolution, but the onium system can also be suitably used.

In the photosensitive resin composition of the present invention, the photoacid generator (B) is used in an amount of 0.1 to 10 parts by mass relative to 100 parts by mass of the total (all) resin component (preferably solid component, more preferably polymer (A) By mass, more preferably 0.5 to 10 parts by mass.

The photosensitive resin composition of the present invention may contain a 1,2-quinonediazide compound as a photoacid generator which is sensitive to an actinic ray. The 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, and its quantum yield is necessarily 1 or less.

&Lt; Solvent (C) >

The photosensitive resin composition of the present invention contains a solvent (C). The photosensitive resin composition of the present invention is preferably prepared as a solution in which the optional components (D) to (I) are dissolved in the solvent (C) in addition to the polymer (A) and the photoacid generator .

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

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

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

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

(3) ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate and ethylene glycol monobutyl ether acetate;

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

(5) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

(6) propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate;

(7) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether;

(8) diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate and diethylene glycol monobutyl ether acetate;

(9) dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether;

(10) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol ethyl methyl ether;

(11) dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate and dipropylene glycol monobutyl ether acetate;

(12) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, isobutyl lactate, isobutyl lactate, n-amyl lactate, and lactic acid /

(13) A process for producing a compound represented by the following formula (1), wherein n is 1, Aliphatic carboxylic acid esters such as isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate and isobutyl butyrate;

(14) A process for producing a compound represented by the general formula (1), which comprises reacting a compound represented by the general formula 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxypropionate, Methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate and the like;

(15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone;

(16) amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone;

(17) lactones such as? -Butyrolactone, and the like.

If necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1- It is also possible to add a solvent such as octanol, 1-nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate. These solvents may be used singly or in combination of two or more kinds. The solvent that can be used in the present invention is preferably one type or two types of solvents in combination, more preferably two types, more preferably propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates And diethylene glycol dialkyl ethers, or a combination of esters and butylene glycol alkyl ether acetates.

The component (C) is preferably a solvent having a boiling point of 130 ° C or higher but lower than 160 ° C, a solvent having a boiling point of 160 ° C or higher, or a mixture thereof, preferably a solvent having a boiling point of 130 ° C or higher but lower than 160 ° C, And more preferably a mixture of a solvent having a boiling point of 130 DEG C or more and less than 160 DEG C and a solvent having a boiling point of 160 DEG C or more and 200 DEG C or less.

Propylene glycol monomethyl ether acetate (boiling point: 146 占 폚), propylene glycol monoethyl ether acetate (boiling point: 158 占 폚), propylene glycol methyl n-butyl ether (boiling point: 155 占 폚), propylene glycol monomethyl ether acetate And glycol methyl-n-propyl ether (boiling point 131 DEG C).

Examples of the solvent having a boiling point of 160 캜 or more include ethyl 3-ethoxypropionate (boiling point: 170 캜), diethylene glycol methyl ethyl ether (boiling point: 176 캜), propylene glycol monomethyl ether propionate (Boiling point: 162 占 폚), propylene glycol diacetate (boiling point: 171 占 폚), diethylene glycol diethyl ether (boiling point: 189 占 폚), diethylene glycol dimethyl ether Diethylene glycol monoethyl ether acetate (boiling point 220 占 폚), dipropylene glycol dimethyl ether (boiling point 175 占 폚), and 1,3-butylene glycol diacetate (boiling point 232 占 폚).

The content of the solvent (C) in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by mass per 100 parts by mass of the total resin component (preferably solid content, more preferably polymer (A)) in the photosensitive resin composition More preferably 100 to 2,000 parts by mass, and still more preferably 150 to 1,500 parts by mass.

&Lt; Basic compound (D) >

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

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.

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

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

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

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

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

The photosensitive resin composition of the present invention is preferably at least one of the compound represented by the following formula (a), the compound represented by the following formula (b) and the compound represented by the following formula (c) , And a compound represented by the general formula (a) are more preferable.

In general formula (a)

(In the general formula (a), R ² represents an alkyl group which may have a substituent having 1 to 6 carbon atoms or a cyclic alkyl group which may have a substituent having 3 to 10 carbon atoms, and X represents an oxygen atom or a sulfur atom. Y ¹ represents an oxygen atom or -NH- group, p ¹ represents an integer of 1 to 3,

In general formula (b)

(Wherein R ⁸ , R ⁹ and R ¹⁰ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a substituent having 3 to 10 carbon atoms Or a cyclic alkyl group which may have a substituent

(C)

The compound represented by the general formula (a) is preferably a thiourea compound represented by the following general formula (II), in which X is a sulfur atom in view of the exposure margin, that is, a compound having a partial structure represented by a thioether bond desirable.

In general formula (II)

(In the general formula (II), R ³ represents an alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, Y ² represents an oxygen atom or -NH- group, p ² represents an integer of 1 to 3, )

The compound (D) is further preferably a thio urea compound represented by the following general formula (III), that is, a compound containing a morpholino group.

In general formula (III)

(In the general formula (III), R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and p3 represents an integer of 1 to 3)

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ² to R ⁴ in the compounds represented by the above general formulas (a), (II) and (III) include methyl group, ethyl group, An alkyl group having 1 to 4 carbon atoms such as a methyl group, a butyl group and a tert-butyl group is preferable, and an alkyl group having 1 to 4 carbon atoms of a straight chain is more preferable, and a methyl group is particularly preferable.

Examples of the cyclic alkyl group having 3 to 10 carbon atoms represented by R ² to R ⁴ in the compounds represented by the general formulas (a), (II) and (III) include cyclopropyl group, cyclobutyl group, cyclohexyl group, A cyclic alkyl group having 3 to 10 carbon atoms such as a tyl group is preferable, a cyclic alkyl group having 5 to 10 carbon atoms is more preferable, and a cyclohexyl group is particularly preferable.

Specific examples of the basic compound (D) represented by the general formula (a) include the following compounds, but the present invention is not limited thereto.

These basic compounds (D) may be used alone or in combination of two or more.

In the present invention, the amount of the basic compound (D) to be added is preferably such that the total amount of the resin component (preferably the solid component, more preferably the component (A)) in the photosensitive resin composition, Is usually used in the range of 0.001 to 20% by weight, preferably 0.005 to 10% by weight, and most preferably 0.01 to 5% by weight based on the weight of the copolymer.

&Lt; Other components >

(N) a sensitizer, (G) an adhesion improver, (I) an antioxidant, and (I) an antioxidant, if necessary, in addition to the components (A), ) Surfactants may be added preferably. In the positive photosensitive resin composition of the present invention, known additives such as plasticizers, heat radical generators, antioxidants, thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic precipitation inhibitors may be added.

Increasing agent (N)

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

Polynuclear aromatic compounds such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- Xanthones such as xanthone, thioxanthone, dimethylthioxanthone, and diethylthioxanthone), xanthan derivatives such as xanthone (e.g., fluorene, eosin, erythrosine, rhodamine B and rose bengal) (Such as thiocarbocyanine, oxacarbocyanine), melocyanines (e.g., melocyanine, carbomeroxy), rhodacyanines, oxonols, thiazines (Such as acridine orange, chloroflavin, acriflavine), acridones (such as acridone, 10-butyl-2-chloro-thiophene, (Such as anthraquinone), squaluminium (for example squalium), styryls, basestirrins (for example, Benzooxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2 , 3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-pne).

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

Adhesion improver (G)

The photosensitive resin composition of the present invention may contain the adhesion improver (G). The adhesion improver (G) that can be used in the photosensitive resin composition of the present invention can be obtained by a method in which an inorganic material to be a base material such as silicon, silicon oxide, silicon compound such as silicon nitride, metal such as gold, Thereby improving the adhesion of the insulating film. Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent as the adhesion improver (G) for use in the present invention is not specifically limited and known ones can be used for the purpose of modifying the interface.

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

The content of the adhesion improver (G) in the photosensitive resin composition of the present invention is preferably from 0.1 to 20 parts by weight per 100 parts by weight of the total resin component (preferably solid content, more preferably polymer (A)) in the photosensitive resin composition. By mass, more preferably 0.5 to 10 parts by mass.

Surfactant (I)

The photosensitive resin composition of the present invention may contain a surfactant (I). As the surfactant (I), any of anionic, cationic, nonionic, or amphoteric surfactants may be used, but a preferred surfactant is a nonionic surfactant.

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

Further, as the surfactant, the weight in terms of polystyrene measured by gel permeation chromatography when tetrahydrofuran (THF) is used as a solvent, including the constituent unit A and the constituent unit B represented by the following general formula (1) A preferred example is a copolymer having an average molecular weight (Mw) of 1,000 or more and 10,000 or less.

In general formula (1)

(In the formula (1), R ⁴⁰¹ and R ⁴⁰⁴ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴⁰⁴ represents a hydrogen atom or a C1- P represents an alkylene group having 3 to 6 carbon atoms, p and q each represent a weight percentage representing a polymerization ratio, p represents a value of 10 mass% or more and 80 mass% or less, q represents an amount of 20 mass% Or more and 90% or less by mass, r is an integer of 1 or more and 18 or less, and s 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 general formula (2). R ⁴⁰⁵ in the general formula (2) represents an alkyl group having 1 to 4 carbon atoms and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the surface to be coated , And an alkyl group having 2 or 3 carbon atoms is more preferable. The sum (p + q) of p and q is preferably p + q = 100, that is, 100 mass%.

In general formula (2)

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

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

The amount of the surfactant (I) added to the photosensitive resin composition of the present invention is preferably 10 to 10 parts by weight based on 100 parts by weight of the total resin component (preferably solid component, more preferably the above (A) copolymer) in the photosensitive resin composition. By mass, more preferably from 0.01 to 10% by mass, and most preferably from 0.01 to 1% by mass.

Antioxidant

The photosensitive resin composition of the present invention may contain an antioxidant. As the antioxidant, a known antioxidant may be contained. The addition of the antioxidant has the advantage that the cured film can be prevented from being colored or the reduction in film thickness due to decomposition can be reduced and the heat resistance and transparency are excellent.

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

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

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

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

[Method of manufacturing pattern]

Next, a method of producing the pattern of the present invention will be described.

The method for producing a pattern of the present invention is characterized by including the following steps (1) to (6).

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

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

(3) a step of exposing with active radiation,

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

(5) etching the substrate using the formed resist pattern as a mask, and

(6) A step of peeling the resist pattern.

Each step will be described below in order.

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

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

In the exposure step of (3), an active ray having a wavelength of 300 nm or more and 450 nm or less is irradiated to the obtained coating film. In this step, (B) the photoacid generator is decomposed to generate acid. The protected hydroxyl group of the monomer unit (a1) of the hydroxystyrene contained in the component (A) is hydrolyzed by the catalytic action of the generated acid to generate a phenolic hydroxyl group.

Post-exposure baking (Post-baking): Post Exposure Bake (hereinafter, also referred to as &quot; PEB &quot;) may be performed in the region where the acid catalyst is generated, if necessary, to accelerate the hydrolysis reaction. With PEB, the generation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group can be promoted. In the method for producing a pattern of the present invention, it is preferable that the step of post-baking and thermally curing the resist pattern after the development step and before the etching step is preferable.

In the method for producing a pattern of the present invention, PEB is preferably performed at a relatively low temperature to accelerate the hydrolysis of the acid decomposable group without causing a crosslinking reaction. The temperature at which PEB is carried out is preferably 30 占 폚 to 130 占 폚, more preferably 40 占 폚 to 110 占 폚, and particularly preferably 50 占 폚 to 100 占 폚. The heating time can be suitably set according to the heating temperature and the like, but is preferably within a range of 1 to 60 minutes.

(4), the polymer having a free (free) phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing the exposed region containing the resin composition having a phenolic hydroxyl group which is easy to dissolve in an alkaline developer.

In the method for producing a pattern of the present invention, it is preferable to include a post-baking step between the developing step (4) and an etching step described later. After the developing step, before the etching step, Lt; RTI ID = 0.0 &gt; C, &lt; / RTI &gt; In the post-baking step after the developing step of the step (4), the obtained positive image is heated to obtain the effect of improving the etching dimensional stability.

After the development step, the post-baking step before the etching step is more preferably 120 to 150 ° C. By performing PEB at a relatively low temperature, an effect of improving the etching dimensional stability without causing a heat flow of the resist pattern can be obtained.

The heating time can be appropriately set depending on the heating temperature and the like, but is preferably within a range of 1 to 60 minutes.

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

&Lt; Preparation method of photosensitive resin composition >

The essential components of (A) to (C) are mixed in a predetermined ratio and optionally, and dissolved by stirring to prepare a photosensitive resin composition. For example, the components (A) to (C) may be previously dissolved in the solvent (D), and the mixture may be mixed at a predetermined ratio to prepare a resin composition. The composition solution prepared as described above may be used after being filtered using a filter having a pore size of 0.2 탆 or the like.

<Coating Process and Solvent Removal Process>

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

(2) The heating condition of the solvent removing step is such that the acid decomposable group decomposes in the monomer unit (a1) in the component (A) in the unexposed portion, and the component (A) is soluble in an alkali developing solution , And it is preferably about 80 to 130 캜 for about 30 to 120 seconds although it varies depending on the kind of each component and blending ratio.

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

In the exposure step, the substrate provided with a coating film is irradiated with an actinic ray through a mask having a predetermined pattern. After the exposure step, the substrate is subjected to heat treatment (PEB) if necessary, and in the development step, an exposed area is removed using an alkaline developer to form an image pattern.

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

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

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

The development time is preferably 30 to 180 seconds, and the developing method may be any of a liquid method, a dipping method, and the like. After the development, a desired pattern can be formed by conducting water washing for 30 to 90 seconds.

<Etching Process>

The method for manufacturing a pattern of the present invention includes a step of etching the substrate using the resist pattern formed as described above (5) as a mask.

A method of etching the substrate using the resist pattern as a mask is not particularly limited, and a known method can be used.

&Lt; Step of peeling resist pattern >

The method for producing a pattern of the present invention includes the step (6) of peeling the resist pattern.

The method of peeling the resist pattern is not particularly limited, and a known method can be used.

<Substrate>

The substrate used in the method of manufacturing the pattern of the present invention is not particularly limited, and examples thereof include a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, a tantalum alloy film, an indium oxide (ITO) film doped with tin oxide, A metal substrate such as a tin film, Ni, Cu, Fe, or Al; Silicon substrates such as quartz, glass, silicon nitride film, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon film, SOG, silicon wafers for manufacturing semiconductor devices, glass substrates for liquid crystal device fabrication; A polymer substrate such as paper, a polyester film, a polycarbonate film, a polyimide film, and other polymer substrates used in organic EL display devices; A ceramic material or the like can be used. Among them, in the present invention, an ITO substrate, a molybdenum substrate, or a silicon substrate is preferable, and an ITO substrate is more preferable.

The shape of the substrate may be a plate shape or a roll shape.

[pattern]

The pattern of the present invention is a pattern obtained by etching the substrate using a resist pattern obtained by curing the photosensitive resin composition of the present invention as a mask. The pattern of the present invention can be preferably used as an ITO pattern, a molybdenum pattern, or a silicon pattern, and can be more preferably used as an ITO pattern.

Since the photosensitive resin composition of the present invention is excellent in sensitivity, resolution and exposure margin, a resist pattern excellent in rectangularity can be obtained. Since the pattern of the present invention is obtained by the method for producing a pattern of the present invention using the above resist pattern, fine processing can be performed, and the display characteristics of the organic EL display device and the liquid crystal display device can be made high.

[Organic EL display device, liquid crystal display device]

The organic EL display device and the liquid crystal display device of the present invention are characterized by having the pattern of the present invention. The organic EL display and the liquid crystal display of the present invention preferably have an ITO pattern.

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

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

Fig. 1 shows a configuration diagram of an example of an organic EL display device. Sectional schematic view of a substrate in a bottom emission type organic EL display device and has a planarization film 4. [

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

The planarization layer 4 is formed on the insulating film 3 so as to fill the irregularities formed by the wirings 2 in order to planarize the irregularities formed by the formation of the wirings 2.

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

The insulating film 8 is formed so as to cover the periphery of the first electrode 5. By providing the insulating film 8, the first electrode 5 and the second electrode Can be prevented.

Although not shown in FIG. 1, a hole transporting layer, an organic light emitting layer, and an electron transporting layer are sequentially deposited by a desired pattern mask, and then a second electrode made of Al is formed on the entire surface above the substrate An active matrix type organic EL display device in which a sealing glass plate and an ultraviolet curing type epoxy resin are used to seal each other and the TFT 1 for driving each organic EL element is connected, Can be obtained.

Fig. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. Fig. This color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on its back surface and the liquid crystal panel corresponds to all pixels disposed between two glass substrates 14 and 15 to which a polarizing film is pasted The element of the TFT 16 is disposed. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 which passes through the contact hole 18 formed in the cured film 17 and forms a pixel electrode. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of the liquid crystal 20 and a black matrix are arranged is provided.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts to be used, the ratios, the contents of the treatments, the processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. Unless otherwise specified, &quot; part &quot; and &quot;% &quot; are based on mass.

(Synthesis Example)

Resin (R-1)

(0.7 mol) of p-acetoxystyrene was dissolved in 500 ml of propylene glycol monomethyl ether acetate (PGMEA), and a solution of dimethyl 2,2'-azobis (2-methylpropyl) 6.6 g (0.025 mol) of PGMEA solution (V-601) was added thereto, and stirring was further continued for 6 hours to carry out a polymerization reaction. Methanol, and 14 g of a sodium methoxide methanol solution (SM-28) was added and reacted for 3 hours. The solution was neutralized with hydrochloric acid, diluted by adding 200 ml of water, and 300 ml of ethyl acetate was added thereto to separate the solution, and the solution was washed three times with water. Thereafter, a white resin was precipitated. This resin was separated by filtration, washed with water and dried. Further, the solution was dissolved in 200 ml of acetone, and dropwise and reprecipitated (reprecipitated) in 3 liters of a hexane / ethyl acetate = 10/1 solution with stirring. The obtained resin was dried in a vacuum drier at 40 DEG C for 24 hours to obtain a poly (p-hydroxystyrene) alkali-soluble resin (R-1). The weight average molecular weight of the obtained resin was 15000 and the polydispersity was 3.50.

Resin (R-2)

Poly (p-hydroxystyrene) (Maruka Linker S-4P, manufactured by Maruzen Sekiyu Kagaku Co., Ltd.) was used. The weight average molecular weight was 9400 and the polydispersity was 2.19.

Resin (R-3)

Poly (p-hydroxystyrene) (Maruka Linker H-2P, manufactured by Maruzen Sekiyu Kagaku Co., Ltd.) was used. The weight average molecular weight was 21400 and the polydispersity was 5.78.

Resin (R-4)

(R-1) were synthesized to obtain (R-4). However, the amount of V-601 was changed to 19.8 g (0.075 mol) and the amount of PGMEA as a solvent was changed to 820 ml. The weight average molecular weight of the resin was 4000 and the polydispersity was 3.20.

Resin (R-5)

(R-5) was synthesized by the same method as (R-1). However, the above polymerization reaction was dissolved in 50 ml of propylene glycol monomethyl ether acetate (PGMEA), and 113.5 g (0.7 mol) of p-acetoxystyrene and 75 g of dimethyl 2,2'-azo A solution prepared by dissolving 6.6 g (0.025 mol) of bis (2-methylpropionate) (V-601) in 200 ml of PGMEA was added dropwise over 2 hours, and further stirring was continued for 4 hours. The weight average molecular weight of the obtained resin was 12500 and the polydispersity was 1.57.

Resin (R-6)

(R-6) was synthesized in the same manner as in (R-1). However, the above polymerization reaction was dissolved in 50 ml of propylene glycol monomethyl ether acetate (PGMEA), and 113.5 g (0.7 mol) of p-acetoxystyrene and 75 g of dimethyl 2,2'-azo A solution prepared by dissolving 8.0 g (0.035 mol) of bis (2-methylpropionate) (V-601) in 200 ml of PGMEA was added dropwise over 1 hour, and further stirring was continued for 4 hours. The weight average molecular weight of the obtained resin was 13000 and the polydispersity was 1.81.

Resin (R-7)

(Maruka Linker MB, manufactured by Maruzen Sekiyu Kagaku Co., Ltd.) of polyparabinylphenol was used. The weight average molecular weight was 7200 and the polydispersity was 3.05.

Synthesis of polymer (A-1)

15.6 g of the alkali-soluble resin (R-2) obtained above and 100 g of propylene glycol monomethyl ether acetate (PGMEA) were dissolved in a flask and subjected to vacuum distillation to distill off water and PGMEA. After the function (water content) was confirmed to be sufficiently low, 3.2 g of 2,3-dihydrofuran and 0.015 g of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature for 2 hours. 0.090 g of triethylamine was added thereto to stop the reaction. Ethyl acetate was added to the reaction solution and further washed with water. Ethyl acetate and water were then distilled off under reduced pressure to obtain a polymer (A-1) as a soluble resin with a protection ratio of 30 mol%.

Synthesis of polymers (A-2) to (A-5)

Polymers (A-2) to (A-5) having a protection ratio shown in the following table were obtained in the same manner as in the synthesis example of the polymer (A-1) except that the addition amount of 2,3-dihydrofuran was changed, ).

Polymers (A-6), (A-7)

In the synthesis example of the polymer (A-1), 2,3-dihydro-4-methylfuran or 2,3-dihydro-4,5-diphenylbenzo Furan was used to synthesize a polymer having the protection ratio shown below.

Polymers (A-8) to (A-10), (A-14)

(R-1), (R-3), (R-4) and (R-7) were used in place of (R-2) as the alkali- Thereby synthesizing a polymer having the following protection ratio.

Polymers (A-11), (A-12)

(R-5) and (R-6) were used in place of (R-2) as the alkali-soluble resin in the synthesis example of the polymer (A-1) .

Polymer (A-13)

In the synthesis example of the polymer (A-1), a polymer was synthesized using (R-1) instead of (R-2) and using ethyl vinyl ether instead of 2,3-dihydrofuran .

[Table 1]

(B)

B-1: CGI-1397 (trade name, structure shown below, manufactured by Ciba Specialty Chemicals)

B-2: A structure shown below (a synthesis example will be described later)

B-3: Structure shown below (synthesis example will be described later)

B-4: Structure shown below (synthesis example will be described later)

B-5: Structure shown below (synthesis example will be described later)

B-6: Structure shown below (synthesis example will be described later)

B-7: Structure shown below (synthesis example will be described later)

B-8: Structure shown below (synthesized by the method described in US4329300 A1)

B-9: Structure shown below (synthesized by the method described in US6965040 B1)

B-10: The structure shown below (synthesized by the method described in Angew. Chem. Int. Ed., 2005, vol.44, p.6685)

B-11: Structure shown below (synthesized by the method described in Tetrahedron 1994, 50, p 3195)

<Synthesis of B-2>

Α- (p-toluenesulfonyloxyimino) phenylacetonitrile (Compound B-2) was synthesized according to the method described in the paragraph [0108] of Japanese Patent Application No. 2002-528451.

<Synthesis of B-3>

1-1. Synthesis of synthetic intermediate B-3A

31.3 g (manufactured by Tokyo Chemical Industry Co., Ltd.) of 2-aminobenzenethiol was dissolved in 100 mL of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 占 폚). Next, 40.6 g of phenylacetyl chloride (manufactured by TOKYO KASEI KOGYO CO., LTD.) Was added dropwise to the obtained solution, and the mixture was reacted for 1 hour at room temperature, followed by stirring at 100 占 폚 for 2 hours. To the reaction solution obtained, 500 mL of water was added to dissolve the precipitated salt, and the toluene oil (oil component) was extracted. The extract was concentrated with a rotary evaporator to obtain a synthetic intermediate B-3A.

1-2. Synthesis of B-3

2.25 g of the thus-obtained synthetic intermediate B-3A 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 캜 or lower. Then, 4.37 g (25% by weight methanol solution, manufactured by Alfa Acer) of tetramethylammonium hydroxide was added dropwise to the reaction solution, and the mixture was reacted for 0.5 hour with stirring in an ice bath. Further, 7.03 g of isopentyl nitrite was added dropwise while keeping the temperature at 20 ° C or lower, and after the dropwise addition, the reaction solution was heated to room temperature and stirred for one hour.

Subsequently, the reaction solution was cooled to 5 캜 or lower, p-toluenesulfonyl chloride (1.9 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto, and the mixture was stirred for 1 hour while maintaining the temperature at 10 캜 or lower. Then, 80 mL of water was added, and the mixture was stirred at 0 ° C for 1 hour. The resultant precipitate was filtered, and 60 mL of isopropyl alcohol (IPA) was added. The mixture was heated to 50 占 폚 and stirred for 1 hour, filtered, and dried to obtain 1.8 g of B-3 (the structure described above).

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

From the above ¹ H-NMR measurement results, it was estimated that the obtained B-3 was a single geometric isomer.

<Synthesis of B-4>

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 mL) and the mixture was heated to 40 占 폚 for reaction for 2 hours. 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution under ice-cooling, and ethyl acetate (50 mL) was added to the reaction solution. 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 thereto to separate the layers. The organic layer was concentrated, and the crystals were reslurried with diisopropyl ether , Filtered and dried to obtain a ketone compound (6.5 g).

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

The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and the mixture was allowed to react at room temperature for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered out and then slurry with methanol (20 mL), followed by filtration and drying to obtain 2.3 g of B-4 (the above structure).

In addition, ¹ H-NMR spectrum of _{B-4 (300MHz, 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 (q,

<Synthesis of B-5>

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 48 wt% aqueous sodium hydroxide solution (23 g), ethanol (50 mL) and water (50 mL) . The reaction solution was transferred to a 1N HCl aqueous solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid. Then, 30 g of polyphosphoric acid was added and reacted at 170 DEG C for 30 minutes. The reaction solution was transferred into water (300 mL), and ethyl acetate (300 mL) was added to separate the layers. The organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).

Sodium acetate (30.6 g), hydrochloric acid hydroxyamine (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 partitioned four times with 80 mL of water, concentrated, and then purified by silica gel column chromatography to obtain an oxime compound (5.8 g).

The obtained oxime (3.1 g) was sulfonated as in B-4 to obtain 3.2 g of B-5 (the above-described structure).

In addition, ¹ H-NMR spectrum of _{B-5 (300MHz, CDCl 3} ) is, δ = 8.3 (d, 1H ), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.5 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 ddt, 1H), 1.4-1.2 (m, 8H), 0.8 (t, 3H).

<Synthesis of B-6>

B-6 (the above-described structure) was synthesized in the same manner as in B-5 except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in B-5.

In addition, ¹ H-NMR spectrum of _{B-6 (300MHz, CDCl 3} ) is, δ = 8.3 (d, 1H ), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.7 (M, 4H), 7.4 (dd, 1H), 7.1 (d, 1H), 5.6 (q,

(D) a basic compound

D-2: Toyo is older and fellowship, CMTU

D-3: 1,5-diazabicyclo [4.3.0] -5-nonene, manufactured by Tokyo Kasei K.K., D1313

D-5: dicyclohexylmethylamine, D0820 manufactured by Tokyo Chemical Industry Co., Ltd.

D-8: 2,4,5-triphenylimidazole, manufactured by Tokyo Kasei Kogyo Co., Ltd., T0999

(N) Thinner

N-1: DBA (trade name, 9,10-dibutoxyanthracene, Kawasaki Chemical Industries Co., Ltd.)

N-2: DETX (trade name, diethylthioxanthone, manufactured by Sankyo Chemical Co., Ltd.)

(I) Surfactant

I-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula

(C) Solvent

MEDG: diethylene glycol ethyl methyl ether (manufactured by Tohoku Kagaku Kogyo K.K.)

PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Mitsui Chemicals, Inc.)

[Example 1]

Each component was dissolved and mixed so that the following composition A was obtained and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 탆 to obtain a photosensitive resin composition of Example 1.

<Composition A>

Polymer (A): A solution of polymer A-1 in polyethylene glycol methyl ether acetate

100.0 parts by solid content

Photoacid generator (B): 2.0 parts of B-1 shown below

Compound (D): 0.2 parts of D-2 shown above

Surfactant (I): 0.02 part of I-1 shown below

[Examples 2 to 29 and Comparative Examples 1 to 3]

As in Example 1, except that each component was blended as shown in Table 2 to obtain a photosensitive resin composition of the examples. However, when the sensitizer N is used, it is used in the same amount as the photoacid generator (B).

[Comparative Example 4]

As the photosensitive resin composition, the composition described in Example 1 of Japanese Patent Application Laid-Open No. 2011-75864 was prepared.

The following evaluations were performed on the examples and comparative examples obtained as described above.

&Lt; Evaluation of sensitivity &

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (Corning Co.)), and then prebaked on a hot plate at 90 DEG C for 120 seconds to volatilize the solvent to obtain a photosensitive resin composition Layer.

Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a PLA-501F exposure device (ultra-high pressure mercury lamp) manufactured by CANON CO., LTD. Then, the exposed photosensitive composition layer was developed with an alkali developing solution (2.38 mass% of tetramethylammonium hydroxide aqueous solution) at 23 占 폚 for 60 seconds and then rinsed with ultrapure water for 20 seconds.

With these operations, the optimum i-line exposure amount (Eopt) at the time of resolving the line-and-space of 10 mu m at a ratio of 1: 1 was taken as the sensitivity. The evaluation criteria are as follows. The results are shown in the following table. When the optimum i-line exposure amount is less than 20 mJ / cm 2, that is, when the evaluation is "1", the sensitivity is the best.

1: less than 20 mJ / cm 2

2: 20 mJ / cm2 or more and less than 30 mJ / cm2

3: 30 mJ / cm2 or more and less than 40 mJ / cm2

4: 40 mJ / cm 2 or more and less than 50 mJ / cm 2

5: 50 mJ / cm 2 or more

&Lt; Evaluation of resolution >

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (Corning Co.)), and then the solvent was removed from the hot plate at 90 DEG C for 120 seconds to form a photosensitive resin composition layer having a thickness of 1.5 mu m .

Subsequently, the obtained photosensitive resin composition layer was exposed to light having an exposure amount (illuminance: 20 mW / cm 2, i) capable of obtaining a line-and-space of 10 μm after development for 60 seconds at 23 ° C. using a 2.38% tetramethylammonium hydroxide aqueous solution Line) through a mask having a line-and-space of 1 to 10 mu m.

The exposed substrate was subjected to paddle development at 23 DEG C for 60 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer.

The glass substrate with the patterned photosensitive resin composition layer was cut, and the patterned line and space was observed with a field emission scanning electron microscope S-4800 (HITACHI CHASE), and the resolution was evaluated.

The evaluation criteria are as follows. The results are shown in the following table. When the contact hole of 3 mu m can be resolved, that is, in the case of evaluation "1" or "2", resolution is a practical level.

1: 2 μm line and space can be resolved

2: 2 μm line-and-space can not resolve, 3 μm line-and-space can be resolved

3: 3 μm line-and-space can not be resolved, and 5 μm line-and-space can be resolved.

4: 5 μm line-and-space can not resolve, 10 μm line-and-space can be resolved

5: A line and space of 10 μm can not be resolved

&Lt; Evaluation of heat resistance &

The shape of the resist pattern resolved to 2 mu m was observed using a scanning electron microscope and the resist pattern was heated on a hot plate at 130 DEG C for 5 minutes (post baking) Was observed and evaluated as follows.

1: No change in pattern shape before and after heating, Line width variation compared with after development < 0.1 탆

2: Change of pattern shape before and after heating slightly, Line width variation compared with after development 0.1 to 0.2 m

3: Variation of pattern shape before and after heating, line width variation compared with after development 0.2 - 0.5 m

4: As the pattern shape changes before and after heating, the line width variation is 0.5 to 1 탆

5: pattern deterioration due to heat deflection after heating,

The evaluation results of the resist materials, examples and comparative examples are shown in the following table.

[Table 2]

As shown in Table 2, it was found that the photosensitive resin compositions of the respective Examples had excellent results in terms of sensitivity, resolution and heat resistance in comparison with the photosensitive resin compositions of the respective comparative examples there was. Here, Comparative Example 4 is a follow-up of the embodiment of Japanese Patent Application Laid-Open No. 2011-75864, and it was found that evaluation of heat resistance was inferior in particular.

[Example 28]

Example 28 was the same as Example 28 except that the photosensitive resin composition of Example 1 was used and the substrate was changed from a glass substrate (Corning 1737, 0.7 mm thick (Corning Co.)) to a 6 inch silicon wafer. The sensitivity, resolution and heat resistance of the composition were evaluated in the same manner as in the evaluation of sensitivity, resolution and heat resistance.

The results are shown in Table 3 below.

[Example 30] - [Example 31]

In Examples 30 and 31, except that the photosensitive resin composition of Example 1 was used and the exposure machine was changed from a PLA-501F exposure device manufactured by Canon Inc. to a FX-803M (gh-Line stepper) manufactured by Nikon Corporation Was evaluated for sensitivity, resolution and heat resistance in the same manner as in the evaluation of the sensitivity, resolution and heat resistance of the photosensitive resin composition of Example 1.

The results are shown in Table 3 below.

[Example 32]

Example 32 was the same as Example 1 except that the photosensitive resin composition of Example 1 was used and the exposure machine was changed from a PLA-501F exposure device manufactured by Canon Inc. to a 355 nm laser exposure device and 355 nm laser exposure was performed. The resolution, the resolution and the heat resistance were evaluated in the same manner as in the evaluation of the sensitivity, resolution and heat resistance of the photosensitive resin composition.

As the 355 nm laser exposure device, "AEGIS" (wavelength 355 nm, pulse width 6 nsec) was used, and the amount of exposure was measured using "PE10B-V2" OPHIR SHARSE. The results are shown in Table 3 below.

[Example 33]

Example 33 was repeated except that the photosensitive resin composition of Example 1 was used and the exposure apparatus was changed from a PLA-501F exposure device manufactured by Canon Inc. to a UV-LED light source exposing device. The sensitivity, resolution and heat resistance were evaluated in the same manner as in the evaluation of the sensitivity, resolution and heat resistance.

The results are shown in Table 3 below.

[Table 3]

As shown in Table 3, the photosensitive resin composition of the examples had excellent sensitivity and exposure margin irrespective of the substrate and the exposure apparatus. Further, it was found that the photosensitive resin composition of the examples was excellent in resolution, that is, the shape of the formed pattern was excellent also in rectangularity.

[Example 32]

(Organic EL display device)

An organic EL display device having an ITO pattern was produced by the following method (see Fig. 1).

The bottom gate type TFT 1 was formed on the glass substrate 6 and the insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, 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 a subsequent step to the TFT 1. [

In order to planarize the irregularities due to the formation of the wirings 2, the flattening film 4 was formed on the insulating film 3 in a state in which the irregularities by the wirings 2 were filled. The formation of the planarization film 4 on the insulating film 3 can be carried out by spin coating the photosensitive resin composition described in Example 1 of JP-A-2009-98616 on the substrate and prebaking on a hot plate (90 DEG C x 2 minutes ), Irradiated with i-line (365 nm) at 45 mJ / cm 2 (illuminance of 20 mW / cm 2) using a high-pressure mercury lamp on the mask, developed with an aqueous alkaline solution to form a pattern, and subjected to heat treatment at 230 ° C. for 60 minutes .

The coating properties at the time of application of the photosensitive resin composition were satisfactory, and wrinkles and cracks were not observed in the cured films obtained after exposure, development and firing. In addition, the average step of the wiring 2 was 500 nm, and the film thickness of the prepared planarization film 4 was 2,000 nm.

Next, a bottom-emission type organic EL device was formed on the obtained flattening film (4). First, a first electrode 5 made of ITO was formed on the flattening film 4 by being connected to the wiring 2 via the contact hole 7. Thereafter, the photosensitive resin composition of Example 1 was spin-coated on an ITO substrate and pre-baked (90 DEG C x 2 minutes) on a hot plate. Then, an i-line (365 nm) was irradiated with a high pressure mercury lamp at 20 mJ / (Illumination: 20 mW / cm 2), and then developed with an aqueous alkaline solution to form a pattern. Thereafter, post-baking heat treatment was performed at 140 占 폚 for 3 minutes before the etching step. Using this resist pattern as a mask, ITO was patterned by wet etching by immersing the wafer in a ITO etchant (3% oxalic acid aqueous solution) at 40 DEG C for 1 minute. Thereafter, the resist pattern was dipped in a resist stripping solution (MS2001, manufactured by Fuji Film Electronics Co., Ltd.) at 70 DEG C for 7 minutes, and the resist pattern was peeled off. 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. In the insulating film 8, the insulating film 8 was formed by the above-described method using the photosensitive resin composition described in Example 1 of JP-A-2009-98616. By providing 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 by evaporation through a desired pattern mask in a vacuum vapor deposition apparatus. Then, a second electrode made of Al was formed on the entire surface above the substrate. The obtained substrate was removed from the evaporator and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an organic EL display device including an active matrix ITO pattern in which TFTs 1 for driving the organic EL elements are connected to each organic EL element was obtained. When a voltage was applied through the driving circuit, it was found that the organic EL display device exhibited good display characteristics and was highly reliable.

[Example 33]

(Liquid crystal display device)

A liquid crystal display device having an ITO pattern was produced by the following method.

In the active matrix type liquid crystal display device shown in Fig. 1 of Japanese Patent No. 3321003, a cured film 17 as an interlayer insulating film was formed as follows to obtain a liquid crystal display device of Example 16.

That is, the cured film 17 was formed as an interlayer insulating film in the same manner as in the method of forming the planarization film 4 of the organic EL display device of Example 32 above.

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

One… Bottom gate type TFT, 2 ... Wiring, 3 ... Insulating film, 4 ... Planarization film, 5 ... The first electrode, 6 ... Glass substrate, 7 ... Contact hole, 8 ... Insulating film, 10 ... Liquid crystal displays, 12 ... Backlight unit, 14, 15 ... Glass substrate, 16 ... TFT, 17 ... Cured film, 18 ... Contact hole, 19 ... ITO transparent electrode, 20 ... LCD, 22 ... RGB color filter

Claims (18)

, Wherein the total of the repeating unit (a1) represented by the following general formula (I) and the repeating unit (a2) represented by the following general formula (II) is 95 mol% or more of the total repeating units, Wherein the positive photosensitive resin composition comprises a polymer (A) having a weight average molecular weight (weight average molecular weight / number average molecular weight) of more than 2.0 and a weight average molecular weight of 11100 or more, a photo acid generator (B) and a solvent (C) .
In general formula (I)

(In the general formula (I), Ra ^{1 to} Ra ⁶ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent and are bonded to each other to form a ring Ra ⁷ is a hydrogen atom or a methyl group, Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, n 1 is an integer of 0 to 4,
In general formula (II)

(Ra ⁹ is a hydrogen atom or a methyl group, Ra ¹⁰ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and n2 is an integer of 0 to 4) delete The method according to claim 1,
Wherein the photoacid generator (B) has an oxime sulfonate structure represented by the following general formula (b1).
In general formula (b1)

(In the general formula (b1), R ¹ represents an alkyl group which may have a substituent, a cyclic alkyl group which may have a substituent, a heteroaryl group which may have a substituent or an aryl group which may have a substituent) The method according to claim 1,
(D) a positive photosensitive resin containing at least one of a compound represented by the following general formula (a), a compound represented by the following general formula (b) and a compound represented by the following general formula (c) Composition.
In general formula (a)

(In the general formula (a), R ² represents an alkyl group which may have a substituent having 1 to 6 carbon atoms or a cyclic alkyl group which may have a substituent having 3 to 10 carbon atoms, and X represents an oxygen atom or a sulfur atom. Y ¹ represents an oxygen atom or -NH- group, p ¹ represents an integer of 1 to 3,
In general formula (b)

(Wherein R ⁸ , R ⁹ and R ¹⁰ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a substituent having 3 to 10 carbon atoms Or a cyclic alkyl group which may have a substituent
(C)

The method according to claim 1,
Ra ¹ , Ra ² , Ra ³ , and Ra ^{5 in} the general formula (I) are hydrogen atoms. The method according to claim 1,
Wherein n1 in the general formula (I) and n2 in the general formula (II) are zero. The method according to claim 1,
Wherein the repeating unit represented by the general formula (I) is represented by the following general formula (III).
In general formula (III)

The method according to claim 1,
Wherein the photoacid generator (B) is at least one compound represented by the following general formula (OS-3), the following general formula (OS-4), the following general formula (OS- Is a compound represented by any one of the formulas (OS-2) and (OS-2).

(In the formulas (OS-3) to (OS-5), R ²² , R ²⁵ and R ²⁸ represent an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ , R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and X ¹ ~X ³ each independently represents an oxygen atom or a sulfur atom, n1~n3 each independently represents 1 or 2, m1~m3 represents an integer of 0 to 6, each independently)
In general formula (b2)

(In the formula (b2), R ³¹ represents an alkyl group, a cyclic alkyl group or an aryl group, X ¹¹ represents an alkyl group, an alkoxy group or a halogen atom, and m ¹¹ represents an integer of 0 to 3. When m ¹¹ represents 2 or 3 The plurality of X &lt; ¹¹ &gt; may be the same or different)
The formula (B3)

(In the formula (B3), R ⁴³ represents an alkyl group which may have a substituent, a cyclic alkyl group which may have a substituent, a heteroaryl group which may have a substituent or an aryl group which may have a substituent, X ¹ represents a halogen atom, An alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and n4 is an integer of 0 to 5)

Wherein R ¹⁰¹ is 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, represents an aryl group. R ¹⁰² is an alkyl group, or an aryl group. R ¹²¹ ~R ¹²⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, An amide group, a sulfo group, a cyano group, or an aryl group, two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring) The method according to claim 1,
Wherein the photoacid generator (B) has an oxime sulfonate structure represented by the following general formula (b1).
In general formula (b1)

(In the general formula (b1), R ¹ represents an alkyl group which may have a substituent, a cyclic alkyl group which may have a substituent, a heteroaryl group which may have a substituent or an aryl group which may have a substituent) delete The method according to claim 1,
Wherein Ra ¹ in the formula ^{(Ⅰ), Ra 2, Ra} 3, Ra 5 is a hydrogen atom, the formula (Ⅰ) n2 is 0. The positive in the n1 and the general formula (Ⅱ) in Sensitive resin composition. (1) a step of applying the positive-working photosensitive resin composition according to any one of claims 1, 3 to 9 and 11 onto a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition,
(3) a step of exposing with active radiation,
(4) a step of developing with an aqueous developer,
(5) etching the substrate using the formed resist pattern as a mask, and
(6) A method for producing a pattern, which comprises peeling the resist pattern. 13. The method of claim 12,
Post-baking the resist pattern at 100 to 160 占 폚 after the developing step and before the etching step. 13. The method of claim 12,
Wherein the substrate is an ITO substrate, a molybdenum substrate, or a silicon substrate. A pattern formed by the method for producing a pattern according to claim 12. An ITO pattern formed by the method for producing a pattern according to claim 12. An organic EL display device comprising the ITO pattern according to claim 16. A liquid crystal display device comprising the ITO pattern according to claim 16.

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