TWI541608B - Positive-type photosensitive resin composition and method for forming pattern - Google Patents

Description

Positive photosensitive resin composition and pattern manufacturing method

The present invention relates to a photosensitive resin composition, a pattern, and a method of 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 element using the pattern. More specifically, the present invention relates to a planarizing film, a protective film, or an interlayer layer suitable for forming electronic components such as a liquid crystal display device, an organic electroluminescence (EL) display device, an integrated circuit device, and a solid-state imaging device. A positive photosensitive resin composition of an insulating film and a method for producing a pattern using the positive photosensitive resin composition.

An indium tin oxide (ITO) film in which a pattern is formed is provided in an organic EL display device, a liquid crystal display device or the like. In the pattern formation of the ITO film, a method is known in which a photosensitive resin composition is applied onto an ITO film, solvent removal, exposure, and development are carried out, and the formed pattern is used as a mask to etch the ITO film, and processing is performed. .

Further, in recent years, in order to provide high-definition display characteristics for an organic EL display device or a liquid crystal display device, high resolution of ITO processing is required. In order to micro-process ITO, the high-resolution of the photosensitive resin composition which functions as a mask at the time of etching is required.

Further, in order to further improve the productivity of the organic EL display device or the liquid crystal display device, improvement in process margin has become a problem. From this point of view, the sensitivity of the photosensitive resin composition is required to be further improved. In addition, in recent years, the following photosensitive resin composition has also been sought: when a pair of mask patterns are formed When the photosensitive resin composition is exposed, the amount of light irradiation fluctuates due to shaking or varies depending on the amount of light irradiation of the type of exposure machine, and the line width of the obtained pattern is less likely to fluctuate, and the exposure margin is wide. Further, a resin composition is proposed in which the flow of the resist is small by heating, the taper shape is good, and even if it flows, the line width of the obtained pattern hardly fluctuates.

Here, a resin containing a part of polyhydroxystyrene protected with a tetrahydrofuran compound is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 2011-75864, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. A positive photosensitive resin composition.

The inventors of the present invention have studied the results of the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 10-121029. The present invention has been made to solve the above problems, and an object of the invention is to provide a positive photosensitive resin composition which can have both heat resistance and resolution.

In the case of the above-mentioned situation, the inventors of the present invention conducted an active study, and as a result, it is not possible to have both analytical properties in the case of using a tetrahydrofuranyl group as a protective group in the Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. The main reason for the heat resistance is that the degree of polymerization degree distribution (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 polymerization degree distribution of a resin such as polyhydroxystyrene is preferably small, and it is extremely surprising that some effects are improved by increasing the degree of polymerization distribution.

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

(1) A positive photosensitive resin composition comprising a polymer (A), a photoacid generator (B), and a solvent (C), wherein the polymer (A) has the following formula (I) The total of the repeating unit (a1) represented by the following formula (II) and the repeating unit (a2) represented by the following formula (II) is 95 mol% or more of the total repeating unit, and the degree of polymerization distribution (weight average molecular weight / number average molecular weight) ) is greater than 2.0:

(In the formula (I), each of Ra ¹ to Ra ⁶ is a hydrogen atom, an alkyl group having a substituent of 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; ⁷ is a hydrogen atom or a methyl group, and Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms; n1 is an integer of 0 to 4; and the general formula (II)

(In the formula (II), Ra ⁹ is a hydrogen atom or a methyl group, and Ra ¹⁰ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms; and n 2 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 5,000 or more.

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

(In the 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 photosensitive resin composition according to any one of (1) to (3), which comprises a compound represented by the following formula (a) and represented by the following formula (b) At least one of the compound and the compound represented by the following formula (c) is (D) a basic compound:

(In the formula (a), R ² represents an alkyl group which may have a substituent having 1 to 6 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent; and X represents an oxygen atom or a sulfur atom; Y ¹ represents an oxygen atom or a -NH- group; p1 represents an integer of 1 to 3)

(In the formula (b), R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having a substituent of 1 to 6 carbon atoms, an aryl group which may have a substituent, or a carbon number of 3 to 10; Cyclic alkyl group which may have a substituent)

(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 above formula (I) are hydrogen atoms.

(6) The positive photosensitive resin composition according to any one of (1) to (5), wherein n1 in the above formula (I) and n2 in the formula (II) are 0.

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

The positive photosensitive resin composition according to any one of (1) to (7), wherein the (B) photoacid generator is a formula (OS-3) having the following formula (OS-4), a compound represented by any one of the following formula (OS-5), the following formula (b2), the following formula (B3), and the formula (OS-2):

(In the general formula (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 each independently represent hydrogen. An atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ¹ to X ³ each independently represent an oxygen atom or a sulfur atom, and n1 to n3 each independently represent 1 or 2, and m1 to m3 each independently represent an integer of 0 to 6)

(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 m11 represents an integer of 0 to 3; when m11 is 2 or 3 , multiple X ¹¹ can be the same or different)

Formula (B3)

(In the formula (B3), R ⁴³ is 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, 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, a cyano group or a nitro group, and n4 represents an integer of 0 to 5)

(In the formula (OS-2), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a cyano group, An aryl group or a heteroaryl group; R ¹⁰² represents an alkyl group or an aryl group; and R ¹²¹ to R ¹²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amine group, or an alkoxycarbonyl group; Or an alkylcarbonyl group, an arylcarbonyl group, a decylamino 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 positive photosensitive resin composition according to any one of (1) to (8), wherein the polymer (A) has a weight average molecular weight of 5,000 or more, and the photoacid generator (B) has The oxime sulfonate structure represented by the following formula (b1):

(In the 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 positive photosensitive resin composition according to any one of (1) to (9), wherein the polymer (A) has a weight average molecular weight of 5,000 or more and contains the following general formula (a) At least one of the compound represented by the compound represented by the following formula (b) and the compound represented by the following formula (c) is (D) a basic compound:

(In the formula (a), R ² represents an alkyl group which may have a substituent having 1 to 6 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent; and X represents an oxygen atom or a sulfur atom; Y ¹ represents an oxygen atom or a -NH- group; p1 represents an integer of 1 to 3)

(In the formula (b), R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having a substituent of 1 to 6 carbon atoms, an aryl group which may have a substituent, or a carbon number of 3 to 10; Cyclic alkyl group which may have a substituent)

(11) The positive photosensitive resin composition according to any one of (1) to (10), wherein the polymer (A) has a weight average molecular weight of 5,000 or more, and is in the above formula (I) Ra ¹ , Ra ² , Ra ³ and Ra ⁵ are hydrogen atoms, and n1 in the above formula (I) and n2 in the formula (II) are 0.

(12) A method of producing a pattern, comprising the step of: (1) the photosensitive resin according to any one of (1) to (11) a step of coating a composition on a substrate; (2) a step of removing a solvent from the applied photosensitive resin composition; (3) a step of exposing with active radiation; and (4) developing with an aqueous developing solution. a step of (5) etching the substrate by using the formed resist pattern as a mask; and (6) a step of peeling off the resist pattern.

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

(14) The pattern manufacturing method according to (12) or (13), wherein the substrate is an ITO substrate, a molybdenum substrate or a tantalum substrate.

(15) A pattern formed by the pattern manufacturing method according to any one of (12) to (14).

(16) An ITO pattern formed by the pattern manufacturing method according to any one of (12) to (14).

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

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

Hereinafter, the contents of the present invention will be described in detail. The structure described below The description of the components is based on a representative embodiment of the present invention, but the present invention is not limited to the above embodiment. In addition, the "~" in the present specification is used in the meaning of including the numerical values described before and after the lower limit value and the upper limit value.

<Polymer (A)>

The photosensitive resin composition of the present invention (hereinafter also referred to as "the photosensitive composition of the present invention" or "the composition of the present invention") contains the following polymer (A) as a polymer (A) component: the polymer In (A), the total of the repeating unit (a1) represented by the following formula (I) and the repeating unit (a2) represented by the following formula (II) is 95 mol% or more of the total repeating unit, and The degree of polymerization distribution (weight average molecular weight / number average molecular weight) is more than 2.0.

(In the formula (I), each of Ra ¹ to Ra ⁶ is a hydrogen atom, an alkyl group having a substituent of 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; ⁷ is a hydrogen atom or a methyl group, and Ra ⁸ 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.

Examples of the alkyl group in Ra ¹ to Ra ⁶ include a linear alkyl group having 1 to 20 carbon atoms which may have a substituent, a branched alkyl group, a cyclic alkyl group, and a phenyl group which may have a substituent; A linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 5 to 10 carbon atoms is preferable. 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 decyl group, a decyl group, an undecyl group, a dodecyl group, and a tridecane group. Base, cetyl, octadecyl, eicosyl, isopropyl, isobutyl, t-butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, Isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2-norbornyl.

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

Ra ¹ to Ra ⁶ are each preferably a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 5 to 10 carbon atoms. Further, the phenyl group is more preferably a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, or a phenyl group, and particularly preferably a hydrogen atom, a methyl group or a phenyl group.

Ra ¹ , Ra ² , Ra ³ and Ra ^{5 are} preferably a hydrogen atom, and more preferably Ra ¹ , Ra ² , Ra ³ and Ra ⁵ are hydrogen atoms, and Ra ⁴ and Ra ⁶ are each a group described above.

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, preferably a chlorine atom, a bromine atom, a hydroxyl group or a methyl group.

N1 is an integer from 0 to 4, and n1 is preferably 0.

General formula (II)

(In the formula (II), Ra ⁹ is a hydrogen atom or a methyl group, and 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, preferably a hydrogen atom.

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

N2 is an integer of 0 to 4, preferably 0.

The component (A) is preferably insoluble or poorly soluble to a base, and is preferably a resin which becomes alkali-soluble when the protected hydroxyl group of the monomer unit (a1) is decomposed by the action of an acid. As the resin which increases the solubility in the alkali developing solution by the action of an acid as described above, a repeating unit corresponding to the hydroxystyrene having the above monomer unit (a1) is used, and is decomposed by the action of an acid and A resin that has increased solubility in alkali. Here, the term "alkali-soluble" in the present invention means a coating film (thickness: 3 μm) of the compound (resin) formed by applying a solution of the compound (resin) to a substrate and heating at 90 ° C for 2 minutes. The dissolution rate of the 2.38% aqueous solution of tetramethylammonium hydroxide at 23 ° C is 0.01 μm / sec or more; the term "alkali-insoluble" means coating the solution of the compound (resin) The coating film (thickness: 3 μm) of the compound (resin) formed on the substrate by heating at 90 ° C for 2 minutes had a dissolution rate of 2.38% aqueous solution of tetramethylammonium hydroxide at 23 ° C of less than 0.01 μm/sec.

In the photosensitive resin composition of the present invention, a resin which is deprotected by an acid generated by a photo-acid generator by light irradiation to increase solubility in an alkali developer is preferred.

Further, the skeleton of the monomer unit of the above 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 to the following specific examples.

In the present invention, the content of the monomer unit (a1) in the polymer (A) is preferably from 5 mol% to 90 mol%, more preferably from 10 mol% to 75 mol%, based on the total repeating unit. , especially good for 10 moles % ~ 45 moles %. Further, the monomer unit (a2) is preferably present in an amount of 5 moles per unit of total repeating unit. %~95% by mole, more preferably 10% by mole to 85% by mole. Further, the total of the repeating unit (a1) represented by the following formula (I) and the repeating unit (a2) represented by the following formula (II) is more preferably 98 mol% or more of the total repeating unit.

The degree of polymerization of the polymer (A) (also sometimes referred to as weight average molecular weight/number average molecular weight, Mw/Mn, molecular weight distribution) is preferably from 2.01 to 7.00, more preferably from 2.01 to 5.00, and particularly preferably from 2.01. ~4.00. When the degree of polymerization distribution is set to 7.00 or less, the resolution tends to be improved, and the resist pattern can be more effectively suppressed from being tapered. In addition, when the degree of polymerization distribution is 2.00 or less, the resolution is lowered or a development residue is generated. Here, the weight average molecular weight and the number average molecular weight are defined by the polystyrene equivalent value of the gel permeation chromatography.

The weight average molecular weight (Mw) of the above polymer (A) is preferably in the range of 5,000 to 300,000, particularly preferably 5,000 to 100,000, most preferably 5,000 to 60,000. By setting the weight average molecular weight (Mw) of the polymer (A) to 5,000 or more, it is possible to suppress film reduction by development of an unexposed portion, and by setting it to 300,000 or less, it is possible to more effectively suppress the resin itself to alkali. The dissolution rate becomes slow and the sensitivity decreases. Here, the weight average molecular weight is defined by a polystyrene-converted value by gel permeation chromatography.

Further, the polymer (A) of the photosensitive composition of the present invention may be used in combination of two or more kinds. The polymer (A) is preferably used in an amount of 40% by weight to 99% by weight, more preferably 60% by weight to 98% by weight, even more preferably 80% by weight based on the total mass of the photosensitive composition (excluding the solvent). %~98 weight%.

The photosensitive resin composition of the present invention is prepared by dissolving in a solvent in which the above components are dissolved, and is usually prepared by filtration using, for example, a filter having a pore diameter of about 0.05 μm to 0.2 μm. Here, examples of the solvent to be used include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether propionate. Propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl Isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate, diacetone alcohol, N-methylpyrrolidone, N,N-dimethylformamide , γ-butyrolactone, N,N-dimethylacetamide, propylene carbonate, ethylene carbonate, and the like. These solvents may be used singly or in combination. The selection of the solvent affects the solubility to the positive-type photoresist composition of the present invention, the coatability to the substrate, the storage stability, and the like, and is therefore important. Further, the moisture contained in the solvent affects the properties of the resist, and therefore it is preferably a small amount.

Furthermore, it is preferable that the photosensitive resin composition of the present invention reduces an impurity component such as a metal impurity such as a metal or a halogen ion to 100 ppb or less. If such impurities are present in a large amount, it is unsatisfactory in terms of manufacturing a semiconductor device, resulting in poor operation, defects, and a decrease in yield.

The solid content of the photosensitive resin composition is preferably dissolved in the solvent and dissolved in a solid content concentration of 3% to 40%. More preferably, it dissolves 5% to 30%.

"Synthesis of Polymer (A)"

The synthesis of the polymer used as the polymer (A) can be carried out by a method using a vinyl ether or an acetal exchange method using an alcohol and an alkyl vinyl ether. Further, for efficient and stable synthesis, a dehydration azeotropy method as shown in the following examples can also be used. However, it is not limited to these synthetic methods.

<Photoacid generator (B)>

The photosensitive resin composition of the present invention contains a photoacid generator (B). The radiation-sensitive acid generator used in the present invention is preferably a compound which generates an acid by inducing an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but the chemical structure thereof is not particularly limited. In addition, the sensitizing agent that does not directly induce the actinic ray having a wavelength of 300 nm or more is generated by inducing an actinic ray having a wavelength of 300 nm or more by using it together with a sensitizer. The compound can be preferably used in combination with a sensitizer. The radiation-sensitive acid generator used in the present invention is preferably a radiation-sensitive acid generator that generates an acid having a pKa of 4 or less, and more preferably a radiation-sensitive acid generator that produces an acid having a pKa of 3 or less.

(In the 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.)

Any one of the groups may be substituted, and the alkyl group in R ¹ may be linear, may be branched, or may be cyclic. The permissible substituents are described below.

The alkyl group of R ¹ is preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group. The alkyl group of R ¹ may be an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cyclic alkyl group (including 7,7-dimethyl-2-oxo-norbornyl group, etc.) The bridged alicyclic group, preferably a bicycloalkyl group, is substituted.

The aryl group of 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 preferred range of the heteroaryl group of R ^{1 is} the same as the preferred range of the heteroaryl group of R ²² , R ²⁵ and R ²⁸ in the following general formula (OS-3) to (OS-5).

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

The above compound containing the oxime sulfonate structure represented by the above formula (b1) is also preferably an oxime sulfonate compound represented by the following formula (b2).

(In the 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, m11 represents an integer of 0 to 3, and when m11 is 2 or 3, a plurality of X ¹¹ Can be the same or different.)

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

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

The halogen atom as X ¹¹ is preferably a chlorine atom or a fluorine atom.

M11 is preferably 0 or 1.

In the general formula (B2), particularly preferably m11 is 1, X ¹¹ is a methyl group, X ¹¹ is substituted ortho position and R ³¹ is a C 1-4 straight-chain alkyl group having 1 to 10, 7,7- A compound of dimethyl-2-oxo-norbornylmethyl or p-tolyl.

The compound containing the oxime sulfonate structure represented by the above formula (b1) is more preferably an oxime sulfonate compound represented by the following formula (B3).

(In the formula (B3), R ⁴³ has the same meaning 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, or a cyano group. Or nitro, n4 represents an integer from 0 to 5.)

R ⁴³ in the above formula (B3) is preferably methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro - n-Butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably n-octyl.

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 above formula (B3) include α-(methylsulfonyloxyimino)benzyl cyanide and α-(ethylsulfonyloxyimino)benzyl cyanide. , α-(n-propylsulfonyloxyimino)benzyl cyanide, α-(n-butylsulfonyloxyimino)benzyl cyanide, α-(4-toluenesulfonyloxy) Imino)benzyl cyanide, α-[(methylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(ethylsulfonyloxyimino)-4 -Methoxyphenyl]acetonitrile, α-[(n-propylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(n-butylsulfonyloxyimino) 4-methoxyphenyl]acetonitrile, α-[(4-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile.

Specific examples of the preferred oxime sulfonate compound include the following compounds (i) to (viii), and the like, and may be used alone or in combination of two or more. The compound (i) to the compound (viii) can be obtained as a commercial product. Further, it can also be used in combination with other types of (B) photoacid generators.

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

In the above formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a cyano group, or the like. Aryl or heteroaryl. R ¹⁰² represents an alkyl group or an aryl group.

X ¹⁰¹ represents -O-, -S-, -NH-, -NR ¹⁰⁵ -, -CH ₂ -, -CR ¹⁰⁶ H- or -CR ¹⁰⁵ R ¹⁰⁷ -, and R ¹⁰⁵ to R ¹⁰⁷ represent 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 amine group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, a decylamino group, a sulfo group or a cyano group. Or aryl. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.

R ¹²¹ to R ^{124 are} preferably a hydrogen atom, a halogen atom or an alkyl group, and it is also preferred to exemplify a state in which at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group. Among them, from the viewpoint of sensitivity, it is preferred that all of R ¹²¹ to R ¹²⁴ are hydrogen atoms.

The functional groups described may each further have a substituent.

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

In the general formula ^{(OS-2), R 101} , R 102, R 121 ~ R 124 , respectively of formula R ¹⁰¹ (OS-1) is, R ^102, R ¹²¹ ~ R ¹²⁴ same meaning, preferred examples also the same.

In these, it is more preferred that the above formula (OS-1) and R ¹⁰¹ in the above formula (OS-2) are a cyano group or an aryl group, and the above formula (OS-2) is most preferable. The aspect indicated and R ¹⁰¹ is a cyano group, a phenyl group or a naphthyl group.

Further, in the above oxime sulfonate compound, the steric structure (E, Z, etc.) of the hydrazine or the benzothiazole ring may be either a mixture or a mixture.

In the following, specific examples (exemplified compound b-1 to exemplary compound b-34) of the compound represented by the above formula (OS-1) which can be suitably used in the present invention are shown, but the present invention is not limited thereto. Further, 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.

Among the above compounds, from the viewpoint of the coexistence of sensitivity and stability, the compound b-9, the exemplified compound b-16, the exemplified compound b-31, and the exemplified compound b-33 are preferably exemplified.

In the present invention, the compound containing the oxime sulfonate structure represented by the above formula (b1) is also preferably a compound of the following formula (OS-3), the following formula (OS-4) or the following formula ( The oxime sulfonate compound represented by OS-5).

(In the general formula (OS-3) to (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represent an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ are each independently The ground represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonate. The thiol group, X ¹ to X ³ each independently represents an oxygen atom or a sulfur atom, and 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 above formula (OS-3) to formula (OS-5), the alkyl group, the aryl group or the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.

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

The alkyl group in R ²² , R ²⁵ and R ²⁸ is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl or n-hexyl, N-octyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, benzyl.

Examples of the substituent which the alkyl group in R ²² , R ²⁵ and R ²⁸ may have include a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an amine. Alkylcarbonyl.

Further, in the above formula (OS-3) to formula (OS-5), the aryl group in R ²² , R ²⁵ and R ²⁸ is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

The aryl group in R ²² , R ²⁵ and R ²⁸ is preferably phenyl, p-methylphenyl, p-chlorophenyl, pentachlorophenyl, pentafluorophenyl, o-methoxyphenyl or p-phenoxy. Phenyl.

The substituent which the aryl group in R ²² , R ²⁵ and R ²⁸ may have may be a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group or an aryloxy group. A carbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, an alkoxysulfonyl group.

Further, in the above formula (OS-3) to formula (OS-5), the heteroaryl group in R ²² , R ²⁵ and R ²⁸ is preferably a heteroaryl group having a total carbon number of 4 to 30 which may have a substituent. base.

In the above formula (OS-3) to formula (OS-5), the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be at least one ring which is a heteroaromatic ring, for example, a heteroaromatic ring and a benzene ring. Shrinkable ring.

The heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be exemplified by a substituent which may have a substituent selected from the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzene. And a group in which a hydrogen atom is removed from the ring in the group consisting of the imidazole rings.

The substituent which the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have may be a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group or an aryloxy group. A carbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, an alkoxysulfonyl group.

In the above formula (OS-3) to formula (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.

In the above formula (OS-3) to formula (OS-5), two or more of R ²³ , R ²⁶ and R ²⁹ are present in the compound, and preferably one or two are alkyl groups, aryl groups or More preferably, one halogen atom is an alkyl group, an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the remainder is a hydrogen atom.

In the above formula (OS-3) to formula (OS-5), the alkyl group or the aryl group in R ²³ , R ²⁶ and R ²⁹ may have a substituent. Here, the substituent which the alkyl group or the aryl group in R ²³ , R ²⁶ and R ²⁹ may have may be the same as the substituent which the alkyl group or the aryl group in the above R ²² , R ²⁵ and R ²⁸ may have. group.

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

The alkyl group in R ²³ , R ²⁶ and R ²⁹ is preferably: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, allyl, Chloromethyl, bromomethyl, methoxymethyl, benzyl, preferably: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl More preferably, it is methyl, ethyl, n-propyl, n-butyl or n-hexyl, preferably methyl.

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

The aryl group in R ²³ , R ²⁶ and R ²⁹ is specifically preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group or 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.

Among these halogen atoms, a chlorine atom or a bromine atom is preferred.

In the above formula (OS-3) to formula (OS-5), X ¹ to X ³ each independently represent O or S, and is preferably O.

In the above formula (OS-3) to formula (OS-5), the ring including X ¹ to X ³ as a ring member is a 5-membered ring or a 6-membered ring.

In the above formula (OS-3) to formula (OS-5), n ¹ to n ³ each independently represent 1 or 2, and when X ¹ to X ³ are 0, n ¹ to n ³ are each independently The ground is preferably 1, and when X ¹ to X ³ are S, n ¹ to n ³ are each independently preferably 2.

In the above formula (OS-3) to formula (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or Alkoxysulfonyl. Wherein R ²⁴ , R ²⁷ and R ³⁰ are each independently preferably an alkyl group or an alkoxy group.

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

In the above formula (OS-3) to formula (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

The alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is preferably: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl or n-hexyl. , n-octyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, benzyl.

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

In the above formula (OS-3) to formula (OS-5), the alkoxy group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkoxy group having a total carbon number of 1 to 30 which may have a substituent.

The alkoxy group in R ²⁴ , R ²⁷ and R ³⁰ is preferably methoxy, ethoxy, butoxy, hexyloxy, phenoxyethoxy, trichloromethoxy or ethoxyethyl. Oxygen.

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

In the above formula (OS-3) to formula (OS-5), the aminosulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may, for example, be a methylaminosulfonyl group or a dimethylaminosulfonyl group. , phenylaminosulfonyl, methylphenylaminosulfonyl, aminosulfonyl.

In the above formula (OS-3) to (OS-5), the alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may, for example, be a methoxysulfonyl group or an ethoxysulfonyl group. , propoxysulfonyl, butoxysulfonyl.

Further, in the above formula (OS-3) to formula (OS-5), m ¹ to m ³ each independently represent an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1. , especially good is 0.

Further, the compound containing the oxime sulfonate structure represented by the above formula (b1) is particularly preferably any of the following formula (OS-6) to formula (OS-11). An oxime sulfonate compound represented by the person.

(In the formula (OS-6)~(OS-11), R ³⁰¹ to R ³⁰⁶ represent an alkyl group, an aryl group or a heteroaryl group, and R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ³⁰⁸ to R ³¹⁰ and 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 ^R314 each independently represent a hydrogen atom, 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.

R ³⁰¹ to R ³⁰⁶ in the above formula (OS-6) to formula (OS-11) and R ²² , R ²⁵ and R ^{28 in the} above formula (OS-3) to formula (OS-5) The meanings are the same and the preferred aspects are the same.

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

R ³⁰⁸ to R ³¹⁰ , R ³¹³ , R ³¹⁶ and R ^{318 in the} above formula (OS-6) to formula (OS-11) each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom. , chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl or chlorophenyl, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably a carbon number of 1 The alkyl group of ~8 is particularly preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group.

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

R ³¹² , R ³¹⁵ , R ³¹⁷ and R ^{319 in the} above formula (OS-8) to formula (OS-11) represent a hydrogen atom or a methyl group, preferably a hydrogen atom.

Further, in the above oxime sulfonate compound, the steric structure (E, Z) of ruthenium may be either a mixture or a mixture.

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

Moreover, the photo-acid generator represented by Formula (1) or Formula (2) can also be used for the positive photosensitive resin composition of this invention.

(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, may be bonded to each other to form a ring, and R ⁸ and R ⁹ are each independently An aromatic group which may have a substituent, X ^- represents BY ₄ ^- , PY ₆ ^- , AsY ₆ ^- , SbY ₆ ^- , or a monovalent anion represented by formula (3) or formula (4), and Y is independently Indicates 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 1 to 10 carbon atoms having a fluorine atom, or R ²¹ and R ²² each having a carbon atom; a ring of 2 to 6 alkyl groups or an alkyl group having 2 to 6 carbon atoms and having a fluorine atom.

In the formula (1), the alkyl group in R ⁵ , R ⁶ and R ⁷ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group or a tert-butyl group. Further, in the formula (1), when two or more of R ⁵ , R ⁶ and R ⁷ are an alkyl group, it is preferred that two or more alkyl groups are bonded to each other to form a ring, and the ring form is more preferable. In the form of a sulfur atom, it is a 5-membered ring (thiolane) and a 6-membered ring (thiamethylene), and particularly preferably a 5-membered ring.

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 an aromatic group include a phenyl group, a naphthyl group, a 4-methoxyphenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 4-tert-butylphenyl group, and a 4-phenylthiobenzene group. Base, 2,4,6-trimethylphenyl, 4-methoxy-1-naphthyl, 4-(4'-diphenylmercaptophenylthio)phenyl.

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

The substituent in R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is particularly preferably an aromatic group, and particularly preferably a phenyl group, a 4-methoxyphenyl group, a 4-chlorophenyl group, or a 4- (4'-Diphenylmercaptophenylthio)phenyl.

Further, the acid generator represented by the formula (1) or the formula (2) may be bonded to any of R ⁵ to R ⁹ to form a polymer such as a dimer. For example, the above 4-(4'-diphenylmercaptophenylthio)phenyl group is an example of a dimer, and the counter anion in the above 4-(4'-diphenylmercaptophenylthio)phenyl group is preferred. It is a monovalent anion represented by BY ₄ ^- , PY ₆ ^- , AsY ₆ ^- , SbY ₆ ^- or (3) or (4).

The BY _{4 ^{- -, PY 6 -, AsY}} 6 -, SbY 6 - in the formula (1) and (2), X is Y is preferably a fluorine atom, a chlorine atom, in terms of the stability of the anion to aspects Particularly preferred is a fluorine atom.

In the formula (3) and the formula (4), examples of the alkyl group having 1 to 10 carbon atoms in R ²¹ , R ²² and R ²³ include a methyl group, an ethyl group, a butyl group, a tert-butyl group and a cyclohexyl group. , 辛基, etc. Further, 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 perfluorooctyl group, and the like. . In these groups, 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. In terms of the aspect, it is particularly preferably an alkyl group having a fluorine atom and having 1 to 4 carbon atoms.

In the formula (3) and the formula (4), in the case where R ²¹ and R ²² are bonded to each other to form a ring, the alkylene group having 2 to 6 carbon atoms may, for example, be an ethyl group, a propyl group or a butyl group. Stretching the base, stretching the base and so on. Further, examples of the alkyl group having a fluorine atom having 2 to 6 carbon atoms include a tetrafluoroethyl group, a hexafluoroexetyl group, an octafluorobutyl group, a decafluoropentyl group, and a dodecafluorohexyl group. In the above-mentioned groups, in the case where R ²¹ and R ²² are bonded to each other to form a ring, it is preferably bonded by an alkyl group having a fluorine atom having 2 to 6 carbon atoms, more preferably 2 to 2 carbon atoms. The alkyl group having a fluorine atom of 4 is bonded, and in terms of sensitivity, it is particularly preferable to bond with an alkylene group having a fluorine atom of 3 carbon atoms.

Further, in the formulae (3) and (4), it is preferred that R ²¹ and R ²² are bonded to each other by an alkylene group having 2 to 6 carbon atoms or an alkylene group having a fluorine atom having 2 to 6 carbon atoms. Ring.

In the formulae (1) and (2), X ^{- is} preferably BY ₄ ^- , PY ₆ ^- or a monovalent anion represented by the formula (3) or the formula (4), and is particularly excellent in terms of sensitivity. a monovalent anion represented by the formula (3).

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

(wherein R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent an alkyl group or an 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- each independently represent BY ₄ ^- , PY ₆ ^- , AsY ₆ ^- , SbY ₆ ^- , or a monovalent anion represented by the above formula (3) or the above formula (4), and Y are each independently The ground represents a halogen atom.)

Preferred embodiments of the alkyl group and the aromatic group in R ¹⁰ , R ¹¹ , R ¹² and R ¹³ of the formula (5) and the alkyl group and aromatic group in R ⁵ , R ⁶ and R ⁷ of the formula (1) The preferred aspects of the base are the same.

Further, the divalent aromatic group in Ar ³ and Ar ⁴ of the formula (5) is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.

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

Further, the photoacid generator used in the present invention is preferably a trichloromethyl-s-triazine or a quaternary ammonium salt.

The photoacid generator described below can also be suitably used in the present invention.

The (B) photoacid generator used in the present invention is preferably an oxime sulfonate system from the viewpoint of higher heat resistance and analytical properties, but a lanthanide system can also be suitably used.

In the photosensitive resin composition of the present invention, (B) a photoacid generator is more than 100 parts by mass based on the total resin component (preferably a solid component, more preferably a polymer (A)) in the photosensitive resin composition. It is preferably used in an amount of from 0.1 part by mass to 10 parts by mass, more preferably from 0.5 part by mass 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 induces an actinic ray. The 1,2-quinonediazide compound generates a carboxyl group by a sequential type photochemical reaction, but its quantum yield must be 1 or less.

<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 by dissolving (D) component - (I) as an optional component in addition to the polymer (A) and the photoacid generator (B) which are essential components. A solution obtained in the solvent (C).

The (C) solvent used in the photosensitive resin composition of the present invention can be used. The known solvent can be exemplified by ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers. , propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Monoalkyl ether acetates, esters, ketones, guanamines, lactones, and the like.

The solvent (C) used in the photosensitive resin composition of the present invention may, for example, be (1) ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether or ethylene glycol monobutyl ether. Glycol monoalkyl ethers; (2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether; (3) ethylene glycol monomethyl ether Ethylene glycol monoalkyl ether acetate such as ester, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate; (4) propylene glycol monomethyl ether , propylene glycol monoalkyl ether such as propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether; (5) propylene glycol dialkyl ether such as propylene glycol dimethyl ether or propylene glycol diethyl ether; (6) propylene glycol monomethyl ether acetate Propylene glycol monoalkyl ether acetate such as ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; (7) diethylene glycol dimethyl ether, diethylene glycol II Ethylene glycol, diethylene glycol ethyl methyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc. Alkyl ethers or diethylene glycol monoalkyl ethers; (8) diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, Diethylene glycol monoalkyl ether acetate such as diethylene glycol monobutyl ether acetate; (9) dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, etc. Propylene glycol monoalkyl ethers; (10) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether; (11) dipropylene glycol monomethyl ether acetate, dipropylene glycol Dipropylene glycol monoalkyl ether acetate such as diethyl ether acetate, dipropylene glycol monopropyl ether acetate or dipropylene glycol monobutyl ether acetate; (12) methyl lactate, ethyl lactate, n-propyl lactate, Lactic acid lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate, etc.; (13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate Ester, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, butyric acid Ester, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate, etc.; (14) ethyl hydroxyacetate , 2-hydroxy-2-methylpropionic acid ethyl ester, 2-hydroxy-3-methylbutyric acid ethyl ester, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate , 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, acetic acid 3-methoxybutyl ester, acetic acid 3-methyl-3-methoxy Butyl ester, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-butyrate Other esters such as methoxybutyl ester, ethyl acetoacetate, ethyl acetate, methyl pyruvate, ethyl pyruvate; (15) methyl ethyl ketone, methyl propyl ketone, methyl - Ketones such as n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; (16) N-methylformamide, N,N-di a decylamine such as methylformamide, N-methylacetamide, N,N-dimethylacetamide or N-methylpyrrolidone; (17) lactones such as γ-butyrolactone .

In addition, these solvents may be further added as needed: benzyl ethyl ether, dihexyl ether, ethyleneglycol monophenyl ether acetate, diethylene glycol Diethyleneglycol monomethyl ether, diethyleneglycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol (1- Octanol), 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate (diethyl oxalate), diethyl maleate, ethylene carbonate, propylene carbonate and other solvents. These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably used singly or in combination of two, more preferably two, and particularly preferably a propylene glycol monoalkyl ether acetate or a dialkyl ether or a diacetate. Diethylene glycol dialkyl ethers or esters are used in combination with butanediol alkyl ether acetate.

Further, the component (C) is preferably a solvent having a boiling point of 130 ° C or more and less than 160 ° C, a solvent having a boiling point of 160 ° C or more, or a mixture of the solvents. More preferably, the solvent having a boiling point of 130 ° C or more and less than 160 ° C, a solvent having a boiling point of 160 ° C or more and 200 ° C or less, or a mixture of the solvents, particularly preferably a solvent having a boiling point of 130 ° C or more and less than 160 ° C. A mixture of solvents having a boiling point of from 160 ° C to 200 ° C.

The solvent having a boiling point of 130 ° C or more and less than 160 ° C can be exemplified by propylene glycol monomethyl ether acetate (boiling point: 146 ° C), propylene glycol monoethyl ether acetate (boiling point: 158 ° C), propylene glycol methyl-n-butyl ether (boiling point) 155 ° C), propylene glycol methyl-n-propyl ether (boiling point 131 ° C).

The solvent having a boiling point of 160 ° C or higher can be exemplified by ethyl 3-ethoxypropionate (boiling point: 170 ° C), diethylene glycol methyl ether (boiling point: 176 ° C), and propylene glycol monomethyl ether propionate (boiling point: 160 ° C), dipropylene glycol methyl ether acetate (boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), two Diol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C ), 1,3-butanediol diacetate (boiling point: 232 ° C).

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

<Basic Compound (D)>

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

The basic compound can be arbitrarily selected from the compounds used in the chemical amplification resist. For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, and a quaternary ammonium salt of a carboxylic acid can be mentioned.

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

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

Examples of the heterocyclic amine include pyridine, 2-methyl pyridine, 4-methyl pyridine, 2-ethyl pyridine, and 4 -4-ethyl pyridine, 2-phenyl pyridine, 4-phenyl pyridine, N-methyl-4-phenylpyridine (N-methyl-) 4-phenyl pyridine), 4-dimethylamino pyridine, imidazole, benzimidazole, 4-methyl imidazole, 2-phenylbenzo 2-phenyl benzimidazole, 2,4,5-triphenyl imidazole, nicotine, nicotinic acid, nicotinic acid Amide), quinoline, 8-oxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, Piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo[4.3.0]-5-nonene (1,5-diazabicyclo[4.3.0]-5-nonene), 1,8-diazabicyclo[5.3.0]-7-undecene (1,8-diazabicyclo[5.3.0]-7- Undecene) and so on.

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

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

In addition, the photosensitive resin composition of the present invention is particularly preferably a compound represented by the following formula (a), a compound represented by the following formula (b), and at least a compound represented by the following formula (c). One type is more preferably a compound represented by the formula (a).

In (formula (a), R ² may have a carbon number of 1 to 6 carbons or a substituted alkyl group may have a cyclic alkyl substituent group having 3 to 10; X is an oxygen atom or a sulfur atom; Y ¹ represents an oxygen atom or a -NH- group; and p1 represents an integer of 1 to 3.)

(In the formula (b), R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having a substituent of 1 to 6 carbon atoms, an aryl group which may have a substituent or a carbon number of 3 to 10; a cyclic alkyl group having a substituent.)

From the viewpoint of the exposure margin, the compound represented by the formula (a) is preferably a thiourea compound in which the above X is a sulfur atom and represented by the following formula (II), that is, represented by a thiourea bond. Part of the structure.

(In the 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 a -NH- group; and p2 represents an integer of 1 to 3; .)

Further, the compound of the above (D) is more preferably a thiourea compound represented by the following formula (III), that is, a morpholinyl group.

General formula (III)

(In the 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.)

The alkyl group having 1 to 6 carbon atoms in R ² to R ⁴ of the compound represented by the above formula (a), formula (II) or formula (III) is preferably methyl group, ethyl group or ethyl group. The alkyl group having 1 to 4 carbon atoms such as a group, n-butyl group, t-butyl group or t-butyl group is more preferably a linear alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.

The cyclic alkyl group having 3 to 10 carbon atoms in R ² to R ⁴ in the compound represented by the above formula (a), formula (II) or formula (III) is preferably a cyclopropyl group or a cyclobutyl group. A cyclic alkyl group having 3 to 10 carbon atoms such as a group, a cyclohexyl group or an adamantyl group is more preferably a cyclic alkyl group having 5 to 10 carbon atoms, particularly preferably a cyclohexyl group.

Specific examples of the basic compound (D) represented by the above formula (a) include the compounds shown below, but the present invention is not limited to these compounds.

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

In the present invention, the total resin component (preferably a solid component, more preferably the above (A) copolymer) in the photosensitive resin composition is used as the viewpoint of satisfying the sensitivity, the resolution, and the exposure margin. The amount of the basic compound (D) to be added is usually from 0.001% by weight to 20% by weight, preferably from 0.005% by weight to 10% by weight, most preferably from 0.01% by weight to 5% by weight. The scope of use.

<Other ingredients>

In addition to the (A) component, (B), the positive photosensitive resin composition of the present invention In addition to the component, the component (C), and the component (D), a (N) sensitizer, a (G) adhesion improver, and (I) a surfactant may be preferably added as needed. Further, a positive photosensitive resin composition of the present invention may be added with a plasticizer, a thermal radical generator, an antioxidant, a thermal acid generator, an ultraviolet absorber, a tackifier, and an organic or inorganic precipitation preventive agent. And other known additives.

Sensitizer (N)

In the combination with the photoacid generator (B), the photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote decomposition thereof. The sensitizer absorbs actinic rays or radiation and becomes an electronically excited state. The sensitizer that is in an electronically excited state is brought into contact with the photoacid generator to cause electron transfer, energy transfer, heat generation, and the like. Thereby, the photoacid generator generates a chemical change to decompose to form an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength at any of the wavelength regions of 350 nm to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxy anthracene, 9, 9,10-diethoxy anthracene, 3,7-dimethoxy anthracene, 9,10-dipropoxy anthracene )), xanthene (eg fluorescein, eosin, erythrosine, rhodamine B, rose bengal), Xanthone (eg xanthone, thioxanthone, dimethyl thioxanthone) Thioxanthone), diethyl thioxanthone, cyanine (eg thiacarbocyanine, oxacarbocyanine), melocyanine (eg, merocyanine, carbomerocyanine), rhodacyanine, oxonol, thiazine (eg, thionine, methylene blue) ), toluidine blue, acridine (eg, acridine orange, chloroflavin, acriflavine), acridone Classes (eg, acridone, 10-butyl-2-chlororidone), anthraquinone (eg, hydrazine), squarylium squarylium Classes (eg, squaric acid ylide), styryl, base styryl (eg 2-[2-[4-(dimethylamino)phenyl)ethene) 2-[2-[4-(dimethylamino)phenyl]ethenyl]benzoxazole)), coumarin (eg 7-diethylamino-4-methylcoumarin) (7-diethylamino-4-methyl coumarin), 7-hydroxy-4- 7-hydroxy-4-methyl coumarin, 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H[1]benzopyrano[6,7,8 - ij] quinoxazin-11-one (2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H[1]benzopyrano[6,7,8-ij]quinolizine-11-none)).

Among these sensitizers, polynuclear aromatics, acridones, styrenes, basic styrenes, and coumarins are preferred, and polynuclear aromatics are more preferred. Among the polynuclear aromatics, the most preferred is an anthracene derivative.

Adhesion improver (G)

The photosensitive resin composition of the present invention may further contain a adhesion improving agent (G). The adhesion improver (G) which can be used in the photosensitive resin composition of the present invention is an inorganic substance to be a substrate, for example, a ruthenium compound such as ruthenium, iridium oxide or ruthenium nitride, and a metal such as gold, copper or aluminum and an insulating film. The adhesion-enhancing compound. Specific examples thereof include a decane coupling agent and a thiol compound. The decane coupling agent which is the adhesion improving agent (G) used in the present invention is not particularly limited as long as it is an interface modification, and a known compound can be used.

Preferred examples of the decane coupling agent include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrialkoxydecane, and γ-. Glycidoxypropylalkyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxy decane, γ - chloropropyl trialkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxydecane. Among these compounds, more preferred is γ-glycidoxypropyltrialkoxydecane or γ-methacryloxypropyltrialkoxydecane, and particularly preferably γ-glycidoxypropane The trialkoxy alkane is further preferably 3-glycidoxypropyltrimethoxydecane. These compounds may be used alone or in combination of two or more. These compounds are effective for improving the adhesion to the substrate, and are also effective for adjusting the taper angle of the substrate.

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

Surfactant (I)

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

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyalkylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, and fluorenone. Fluorine surfactant. In addition, the following product names can be listed: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), Eftop (manufactured by JEMCO), Megafac (manufactured by DIC), and Fluorad (Sumitomo 3M (share) manufacturing), Aashi Guard, Surflon (made by Asahi Glass Co., Ltd.), and PolyFox (made by OMNOVA).

In addition, as a surfactant, a copolymer containing a structural unit A represented by the following general formula (1) and a structural unit B, and tetrahydrofuran (THF) are mentioned as a preferable example. The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography in the case of a solvent is 1,000 or more and 10,000 or less.

(In the formula (1), R ⁴⁰¹ and R ⁴⁰⁴ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or a carbon number of 1 or more and 4 or less. The alkyl group, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are percentages by weight of the polymerization ratio, p is a numerical value of 10% by mass or more and 80% by mass or less, and q is 20% by mass or more and 90% by mass or less. In the following numerical values, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.)

The above L is preferably a branched alkyl group represented by the following formula (2). R ⁴⁰⁵ in the formula (2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and is preferably an alkyl group having 1 or more and 3 or less carbon atoms in terms of compatibility and wettability to a surface to be coated. The base is more preferably an alkyl group having 2 or 3 carbon atoms. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

The weight average molecular weight (Mw) of the above copolymer is more preferably 1,500 or more and 5,000 or less.

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

(I) Surfactant of the photosensitive resin composition of the present invention with respect to 100 parts by mass of the total resin component (preferably a solid component, more preferably the above (A) copolymer) in the photosensitive resin composition The amount of addition is preferably 10 parts by mass or less, more preferably 0.01 parts by mass to 10 parts by mass, particularly preferably 0.01 parts by mass to 1 part by mass.

Antioxidants

The photosensitive resin composition of the present invention may also contain an antioxidant. As the antioxidant, a known antioxidant can be contained. By adding an antioxidant, there is an advantage that the coloration of the cured film can be prevented or the film thickness reduction due to decomposition can be reduced, and the heat-resistant transparency is excellent.

Examples of the antioxidant include a phosphorus-based antioxidant, a hydrazide, a hindered amine-based antioxidant, a sulfur-based antioxidant, a phenol-based antioxidant, ascorbic acid, zinc sulfate, and a saccharide. , nitrite, sulfite, thiosulfate, hydroxylamine derivative, and the like. Among these antioxidants, a phenolic antioxidant is particularly preferred from the viewpoint of coloring and film thickness reduction of the cured film. These antioxidants may be used alone or in combination of two or more.

Commercial products of the phenolic antioxidants include, for example, Adekastab AO-60, Adekastab AO-80 (manufactured by ADEKA Co., Ltd.), and Irganox 1098 (manufactured by Ciba Japan Co., Ltd.).

The content of the antioxidant is preferably from 0.1% by mass to 6% by mass, more preferably from 0.2% by mass to 5% by mass, even more preferably from 0.5% by mass to 4% by mass based on the total solid content of the photosensitive resin composition. By setting it as this range, sufficient transparency of the formed film can be acquired, and the sensitivity at the time of pattern formation also becomes favorable.

In addition, various additives described in "New Polymer Additives ((Stock) Nikkan Kogyo Shimbun)" An ultraviolet absorber, a metal deactivator or the like is added to the photosensitive resin composition of the present invention.

[Method of manufacturing pattern]

Hereinafter, 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 comprising 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 a solvent from the applied photosensitive resin composition; and (3) a step of exposing with active radiation; (4) a step of developing with an aqueous developing solution; (5) a step of etching the substrate by using the formed resist pattern as a mask; and (6) a step of peeling off the resist pattern.

Each step will be described in order below.

In the coating step of (1), it is preferred 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 removal step (2), the solvent is removed from the applied film by pressure reduction (vacuum) and/or heating to form a dried coating film on the substrate.

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

In the formation region of the acid catalyst, in order to accelerate the hydrolysis reaction, post-exposure heat treatment (post-baking) may be performed as needed: Post Exposure Bake (hereinafter also referred to as "PEB"). By PEB, it is possible to promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. In the method for producing a pattern of the present invention, it is preferred to include a step of post-baking the resist pattern and thermally curing it after the developing step and before the etching step.

In the method for producing a pattern of the present invention, it is preferred to carry out hydrolysis of the acid-decomposable group without causing a crosslinking reaction by performing PEB at a relatively low temperature. The temperature in the case of performing PEB is preferably 30° C. or higher and 130° C. or lower, more preferably 40° C. or higher and 110° C. or lower, and particularly preferably 50° C. or higher and 100° C. or lower. The heating time can be appropriately set depending on the heating temperature and the like, and is preferably in the range of 1 minute to 60 minutes.

In the developing step of (4), a polymer having a free phenolic hydroxyl group is developed using an alkaline developing solution. A positive image is formed by removing an exposed portion region containing a resin composition having a phenolic hydroxyl group which is easily dissolved in an alkaline developing solution.

In the method for producing a pattern of the present invention, it is preferable to include a post-baking step between the development step of (4) and an etching step described later, and more preferably, after the developing step and before the etching step, the resist is included The step of post-baking of the agent pattern at 100 ° C to 160 ° C. In the post-baking step after the development step of (4), the effect of improving the etching dimensional stability is obtained by heating the obtained positive image.

The post-baking step after the above development step and before the etching step is more preferably from 120 ° C to 150 ° C. By performing PEB at a relatively low temperature, an effect of improving the etching dimensional stability without causing the resist pattern to flow thermally is obtained.

The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 1 minute to 60 minutes.

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

<Method for Preparing Photosensitive Resin Composition>

The essential components of (A) to (C) are mixed at a predetermined ratio and in an arbitrary manner, and stirred and dissolved to prepare a photosensitive resin composition. For example, the components (A) to (C) may be previously prepared as a solution dissolved in the solvent (D), and then the solutions may be mixed in a predetermined ratio to prepare a resin composition. The composition solution prepared in the above manner can also be filtered and then used for use using a filter having a pore size of 0.2 μm or the like.

<Coating step and solvent removal step>

The desired dry coating film can be obtained by applying a photosensitive resin composition onto a predetermined substrate, and performing pressure reduction and/or heating (prebaking) to remove the solvent. As the substrate, for example, in the production of a liquid crystal display element, a polarizing plate can be exemplified, and a black matrix layer, a color filter layer, and a glass plate provided with a transparent conductive circuit layer can be provided as needed. The method of applying the photosensitive resin composition onto the substrate is not particularly limited. In the present invention, it is preferred to apply a photosensitive resin composition to the substrate. The method of applying the substrate is not particularly limited, and for example, a method such as a slit coating method, a spray method, a roll coating method, or a spin coating method can be used. Among them, it is suitable for large substrates From the viewpoint, the slit coating method is preferred. When it is manufactured by a large substrate, productivity is high, and it is preferable. Here, the large substrate refers to a substrate having a size of 1 m or more on each side.

In addition, (2) the heating condition of the solvent removal step is a range in which the acid-decomposable group in the monomer unit (a1) in the component (A) in the unexposed portion is decomposed and the component (A) is not soluble in the alkali developer. It varies depending on the type of each component or the blending ratio, but is preferably from 80 ° C to 130 ° C for about 30 seconds to 120 seconds.

<Exposure step and development step (pattern formation method)>

In the exposure step, the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. After the exposure step, heat treatment (PEB) is performed as needed, and then in the development step, the exposed portion is removed using an alkaline developer to form an image pattern.

The exposure by actinic rays can be used: a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generating device, etc., preferably a g line (436 nm), i can be used. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as a line (365 nm) or an h line (405 nm). In addition, the illumination light may be adjusted by a spectroscopic filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as needed.

The developer used in the developing step preferably contains a basic compound. As the basic compound, for example, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; an alkali metal carbonate such as sodium carbonate or potassium carbonate; or an alkali metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate; Salt; tetramethyl hydroxide An ammonium hydroxide such as ammonium, tetraethylammonium hydroxide or choline hydroxide; or an aqueous solution of sodium citrate or sodium metasilicate. Further, an aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the aqueous solution of the above-mentioned alkali may be used as the developing solution.

The pH of the developer is preferably from 10.0 to 14.0.

The development time is preferably from 30 seconds to 180 seconds, and the development method may be any one of a puddle method and a dip method. After development, it can be washed with running water for 30 seconds to 90 seconds to form the desired pattern.

<etching step>

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

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

<Step of peeling off resist pattern>

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

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

<Substrate>

The substrate used in the method for producing a pattern of the present invention is not particularly limited, and for example, a chromium film, a molybdenum film, a molybdenum alloy film, a ruthenium film, a ruthenium alloy film, an indium oxide (ITO) film doped with tin oxide, or Tin oxide film, metal substrate such as Ni, Cu, Fe, Al; quartz, glass, tantalum nitride film, anthrone, Niobium ketone, polyfluorene ketone, decyl ketone, amorphous fluorene ketone film, spin-on-glass (SOG), fluorene ketone wafer for semiconductor element manufacturing, glass corner substrate for liquid crystal element manufacturing, etc. A substrate, a polymer substrate such as a paper, a polyester film, a polycarbonate film, a polyimide film, or another polymer substrate used in an organic EL display device; a ceramic material or the like. Among them, in the present invention, an ITO substrate, a molybdenum substrate or a tantalum 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 is preferably used as an ITO pattern, a molybdenum pattern or a ruthenium pattern, and more preferably 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 is obtained. Since the pattern of the present invention is obtained by the method for producing the pattern of the present invention using the above-described resist pattern, fine processing can be performed, and the organic EL display device or the liquid crystal display device can have high-definition display characteristics.

[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 comprising the pattern of the present invention. The organic EL display device and the liquid crystal display device of the present invention preferably have an ITO pattern.

The organic EL display device or the liquid crystal display device of the present invention is not particularly limited, and various structures are used in addition to the planarizing film or the interlayer insulating film formed using the photosensitive resin composition of the present invention. Various known organic EL display devices or liquid crystal display devices.

Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above applications, and can be used in various applications. For example, in addition to a planarizing film or an interlayer insulating film, it can be suitably used for a protective film of a color filter, a spacer for maintaining a constant thickness of a liquid crystal layer in a liquid crystal display device, or a solid-state image sensor. Microlenses and the like on a color filter.

FIG. 1 is a conceptual diagram showing an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device having a planarization film 4.

A bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si ₃ N ₄ is formed in a state of covering the TFT 1. After the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 via 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 in the step described later to the TFT 1.

Further, in order to planarize the unevenness due to the formation of the wiring 2, the planarization layer 4 is formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is buried.

A bottom emission type organic EL element is formed on the planarization film 4. That is, on the planarizing film 4, the first electrode 5 including ITO is formed by being connected to the wiring 2 via the contact hole 7. Further, the first electrode 5 corresponds to the anode of the organic EL element.

Forming an insulating film 8 covering the shape of the circumference of the first electrode 5, by Providing the insulating film 8 prevents a short circuit between the first electrode 5 and the second electrode formed in the subsequent step.

Further, in FIG. 1, not shown, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited by vapor deposition through a desired pattern mask, and then a second electrode containing Al is formed on the entire upper surface of the substrate. By sealing with a UV-curable epoxy resin using a sealing glass plate and sealing it, an active matrix organic EL display device in which the TFT 1 for driving the organic EL element is connected to each organic EL element is obtained.

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

Instance

The invention is further illustrated by the following examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "parts" and "%" are quality standards unless otherwise specified.

Synthesis example Resin (R-1)

113.5 g (0.7 mol) of ethoxylated styrene was dissolved in 500 ml of propylene glycol monomethyl ether acetate (PGMEA), and 2,2'-even was introduced at 65 ° C to 75 ° C under a nitrogen stream with stirring. A PGMEA solution of 6.6 g (0.025 mol) of nitrogen bis(2-methylpropionic acid) dimethyl ester (V-601) was further stirred for 6 hours to carry out a polymerization reaction. Then, it was dissolved in 200 ml of methanol, and 14 g of a sodium methoxide methanol solution (SM-28) was added thereto, and the mixture was reacted for 3 hours. Then, it was neutralized with hydrochloric acid, diluted with 200 ml of water, and then added with 300 ml of ethyl acetate to carry out a liquid separation operation, and washed with water three times. Then, the white resin was precipitated. The resin was separated by filtration, washed with water, and dried. Further, it was dissolved in 200 ml of acetone, and added dropwise to 3 liters of a hexane/ethyl acetate = 10/1 solution while stirring to carry out reprecipitation. The obtained resin was dried at 40 ° C for 24 hours in a vacuum dryer to obtain a poly(p-hydroxystyrene) alkali-soluble resin (R-1). The obtained resin had a weight average molecular weight of 15,000 and a degree of polymerization distribution of 3.50.

Resin (R-2)

Poly(p-hydroxystyrene) (Maruka Lyncur S-4P, manufactured by Maruzen Petrochemical Co., Ltd.) was used. The weight average molecular weight was 9,400 and the degree of polymerization distribution was 2.19.

Resin (R-3)

Poly(p-hydroxystyrene) (Maruka Lyncur H-2P, manufactured by Maruzen Petrochemical Co., Ltd.) was used. The weight average molecular weight was 21,400, and the degree of polymerization distribution was 5.78.

Resin (R-4)

The resin (R-4) was obtained by the same method as the resin (R-1). Here, the amount of V-601 was 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 4,000, and the degree of polymerization distribution was 3.20.

Resin (R-5)

The resin (R-5) was obtained by the same method as the resin (R-1). Here, the above polymerization reaction was changed to the following method: dissolving in 50 ml of propylene glycol monomethyl ether acetate (PGMEA), and dropping the acetoxy group at 75 ° C to 80 ° C for 2 hours under a nitrogen stream and stirring. a solution of styrene 113.5 g (0.7 mol) and 2,2'-azobis(2-methylpropionic acid) dimethyl ester (V-601) 6.6 g (0.025 mol) dissolved in PGMEA 200 ml, Stirring was continued for 4 hours. The obtained resin had a weight average molecular weight of 12,500 and a polymerization degree distribution of 1.57.

Resin (R-6)

The resin (R-6) was obtained by the same method as the resin (R-1). Here, the above polymerization reaction was changed to the following method: dissolving in 50 ml of propylene glycol monomethyl ether acetate (PGMEA), and dropping p-acetoxybenzene at 75 ° C to 80 ° C for 1 hour under a nitrogen stream and stirring. A solution of 113.5 g (0.7 mol) of ethylene and 2,2'-azobis(2-methylpropionic acid) dimethyl ester (V-601) 8.0 g (0.035 mol) dissolved in PGMEA 200 ml, and then continue Stir for 4 hours. The obtained resin had a weight average molecular weight of 13,000 and a polymerization degree distribution of 1.81.

Resin (R-7)

A bromide of poly(p-vinylphenol) (Maruka Lyncur MB, manufactured by Maruzen Petrochemical Co., Ltd.) was used. Weight average molecular weight is 7200, the degree of polymerization distribution 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 distilled under reduced pressure, and water and PGMEA were removed by azeotropic distillation. After confirming that the water content was sufficiently lowered, 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. Then, 0.090 g of triethylamine was added thereto to stop the reaction. Ethyl acetate was added to the reaction liquid, and after washing with water, ethyl acetate and water were distilled off by distillation under reduced pressure to obtain a polymer (A-1) as a soluble resin having a protection ratio of 30 mol%.

Synthesis of Polymer (A-2)~Polymer (A-5)

In the synthesis example of the above polymer (A-1), the amount of addition of 2,3-dihydrofuran was changed, and the same procedure was carried out to obtain a polymer having a protection ratio shown in the following table (A-2). ) ~ polymer (A-5).

Polymer (A-6), polymer (A-7)

In the synthesis example of the above polymer (A-1), 2,3-dihydro-4-methylfuran or 2,3-dihydro-4,5-di is used instead of 2,3-dihydrofuran. Phenylbenzofuran was used to synthesize a polymer having the protection ratio shown below.

Polymer (A-8)~Polymer (A-10), Polymer (A-14)

In the synthesis example of the above polymer (A-1), a resin (R-1), a resin (R-3), a resin (R-4), and a resin (R-7) are used instead of the resin (R-2). As the alkali-soluble resin, a polymer having the protection ratio shown below was synthesized.

Polymer (A-11), polymer (A-12)

In the synthesis example of the polymer (A-1), the resin (R-5) and the resin (R-6) are used as the alkali-soluble resin instead of the resin (R-2), and the synthesis is as follows. Protection rate of the polymer.

Polymer (A-13)

In the synthesis example of the above polymer (A-1), a resin (R-1) is used instead of the resin (R-2), and an ethyl vinyl ether is used instead of 2,3-dihydrofuran to synthesize a polymer. .

(B) Photoacid generator

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

B-2: Structure shown below (the synthesis example will be described below)

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

B-4: Structure shown below (the synthesis example is explained below)

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

B-6: Structure shown below (the synthesis example is explained below)

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

B-8: Structure shown below (synthesized by the method described in US 4329300 A1)

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

B-10: 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 Paragraph No. [0108] of JP-A-2002-528451.

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

2-Aminobenzenethiol: 31.3 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in toluene: 100 mL (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 ° C). Then, phenylacetonitrile chloride: 40.6 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained solution, and the mixture was stirred at room temperature for 1 hour, followed by stirring at 100 ° C for 2 hours to carry out a reaction. Add to the resulting reaction solution 500 mL of water was added to dissolve the precipitated salt, and the toluene oil fraction was extracted, and the extract was concentrated by a rotary evaporator to obtain a synthetic intermediate B-3A.

1-2. Synthesis of B-3

2.25 g of the synthetic intermediate B-3A obtained in the above manner was mixed in tetrahydrofuran: 10 mL (manufactured by Wako Pure Chemical Industries, Ltd.), and the reaction liquid was cooled to 5 ° C or lower in an ice bath. Then, tetramethylammonium hydroxide: 4.37 g (25 wt% methanol solution, manufactured by Alfa Acer Co., Ltd.) was added dropwise to the reaction liquid, and the mixture was stirred for 0.5 hour in an ice bath to cause a reaction. Further, 7.03 g of isoamyl nitrite was added dropwise while maintaining the internal temperature at 20 ° C or lower. After the completion of the dropwise addition, the reaction liquid was allowed to warm to room temperature, and then stirred for one hour.

Then, the reaction liquid was cooled to 5 ° C or lower, and then p-toluenesulfonium chloride (1.9 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged, and the mixture was stirred for 1 hour while being kept at 10 ° C or lower. Then, 80 mL of water was added, and the mixture was stirred at 0 ° C for 1 hour. After the obtained precipitate was separated by filtration, 60 mL of isopropyl alcohol (IPA) was added, and the mixture was heated to 50 ° C and stirred for 1 hour, and filtered while being hot, and dried to obtain 1.8 g of B-3 (structure described above).

The ¹ H-NMR spectrum of the obtained B-3 (300 MHz, dimethylsulfoxide-d6 (heavy DMSO) ((D ₃ C) ₂ S=O)) was: δ = 8.2 to 8.17 (m, 1H) ), 8.03~8.00 (m, 1H), 7.95~7.9 (m, 2H), 7.6~7.45 (m, 9H), 2.45 (s, 3H).

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

<Synthesis of B-4>

Add to a suspension of 2-naphthol (10g) and chlorobenzene (30mL) Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were mixed and heated to 40 ° C for 2 hours. 4N HCl aqueous solution (60 mL) was added dropwise to the reaction mixture under ice-cooling, and ethyl acetate (50 mL) was added to the mixture. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 ° C for 1 hour, and then a 2N aqueous HCl solution (60 mL) was added to carry out liquid separation. After concentrating the organic layer, the crystals were diisopropyl ether (10 mL). The syrup, filtration, and drying gave a ketone compound (6.5 g).

To a suspension solution of the obtained ketone compound (3.0 g) and methanol (30 mL), acetic acid (7.3 g) and a 50% by weight aqueous hydroxylamine solution (8.0 g) were added, and the mixture was heated under reflux. After cooling, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain a hydrazine compound (2.4 g).

The obtained hydrazine compound (1.8 g) was dissolved in acetone (20 mL), and triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added thereto under ice cooling, and the mixture was heated to room temperature to cause a reaction. hour. Water (50 mL) was added to the reaction liquid, and the precipitated crystals were filtered, and then re-pulped with methanol (20 mL), filtered and dried to obtain 2.3 g of B-4 (the above structure).

Further, the ¹ H-NMR spectrum of B-4 (300 MHz, CDCl ₃ ) was: δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).

<Synthesis of B-5>

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

Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g), and magnesium sulfate (4.5 g) were added to a suspension of the obtained ketone compound (10.0 g) and methanol (100 mL), and the mixture was heated under reflux for 24 hours. After cooling, water (150 mL) and ethyl acetate (150 mL) were added for liquid separation, and the organic layer was partitioned with water (80 mL) for 4 times, concentrated, and purified by silica gel column chromatography to obtain a hydrazine compound (5.8 g). ).

The obtained hydrazine (3.1 g) was subjected to sulfonation in the same manner as B-4 to obtain 3.2 g of B-5 (the above structure).

Further, the ¹ H-NMR spectrum of B-5 (300 MHz, CDCl ₃ ) was: 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 (dd, 1H), 2.4 (s, 3H), 2.2 (ddt, 1H), 1.9 ( Ddt, 1H), 1.4~1.2 (m, 8H), 0.8 (t, 3H).

<Synthesis of B-6>

In addition to replacing p-toluenesulfonyl chloride in B-5, benzenesulfonyl chloride is used. Further, B-6 (the above structure) was synthesized in the same manner as in the case of B-5.

Further, the ¹ H-NMR spectrum of B-6 (300 MHz, CDCl ₃ ) was: δ = 8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.7 - 7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d.1H), 5.6 (q, 1H), 1.7 (d, 3H).

(D) Basic compound

D-2: Toyo Chemical Co., Ltd., CMTU

D-3: 1,5-diazabicyclo[4.3.0]-5-pinene, manufactured by Tokyo Chemical Industry Co., Ltd., D1313

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

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

(N) sensitizer

N-1: DBA (trade name, 9,10-dibutoxy oxime, manufactured by Kawasaki Chemicals Co., Ltd.)

N-2: DETX (trade name, diethyl thioxanthone, manufactured by Sun Chemical Co., Ltd.)

(I) surfactant

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

(C) solvent

MEDG: Diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Industry Co., Ltd.)

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

[Example 1]

Each component was dissolved and mixed so as to have the following composition A, and filtered through a filter made of polytetrafluoroethylene having a diameter of 0.2 μm to obtain a photosensitive resin composition of Example 1.

<Composition A>

[Example 2 to Example 29, Comparative Example 1 to Comparative Example 3]

In the same manner as in Example 1, each component was formulated into a photosensitive resin composition as exemplified in Table 2, and an example was obtained. In the case where the sensitizer N is used, the same amount as the photoacid generator (B) is used.

[Comparative Example 4]

The composition described in Example 1 of JP-A-2011-75864 was prepared as a photosensitive resin composition.

Each of the evaluations shown below was performed on the examples and comparative examples obtained above.

<Evaluation of Sensitivity>

Each of the photosensitive resin compositions was applied to a glass substrate (Corning 1737 (0.7 mm thick (manufactured by Corning)), and then pre-baked on a hot plate at 90 ° C for 120 seconds to volatilize the solvent to form a film. A photosensitive resin composition layer having a thickness of 1.5 μm.

Then, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon. Then, the exposed photosensitive composition layer was subjected to an alkali developer (2.38 mass% aqueous solution of tetramethylammonium hydroxide). After development at 23 ° C / 60 seconds, it was rinsed with ultrapure water for 20 seconds.

By these operations, the optimum i-line exposure amount (Eopt) when the line and space of 10 μm are analyzed by 1:1 is taken as the sensitivity. In addition, 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 "1" is evaluated, the sensitivity can be said to be the best.

1: less than 20mJ/cm ²

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

3:30 mJ/cm ² or more and less than 40 mJ/cm ²

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

5:50mJ/cm ² or more

<Analytical Evaluation>

After coating each of the photosensitive resin compositions on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), the solvent was removed on a hot plate at 90 ° C / 120 seconds to form a film having a film thickness of 1.5 μm. Resin composition layer.

Then, using 2.38% aqueous solution of tetramethylammonium hydroxide as a developing solution, the obtained photosensitive resin composition layer was developed at 23 ° C for 60 seconds to obtain a line-to-space exposure amount of 10 μm (illuminance: 20 mW/cm). ² , i line), exposure is performed through a mask having a line and space of 1 μm to 10 μm.

The exposed substrate was immersed and developed at 23 ° C for 60 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide as a developing solution.

Cutting a glass base with a patterned photosensitive resin composition layer The plate was observed by a field emission type scanning electron microscope S-4800 (manufactured by HITACHI Co., Ltd.) to analyze the patterned lines and spaces.

The evaluation criteria are as follows. The results are shown in the following table. When the contact hole of 3 μm can be analyzed, that is, when "1" or "2" is evaluated, the analytical performance is a practical level.

1: Can resolve 2μm lines and spaces

2: Can't resolve 2μm line and space, can resolve 3μm line and space

3: Can't resolve 3μm line and space, can resolve 5μm line and space

4: Can't resolve 5μm line and space, can resolve 10μm line and space

5: Unable to resolve 10μm lines and spaces

<Evaluation of heat resistance>

The shape of the resist pattern analyzed at 2 μm was observed using a scanning electron microscope, and as a heat resistance test, the resist pattern was heated (post-baked) on a hot plate at 130 ° C for 5 minutes, and observed before and after heating. The change in the shape of the pattern was evaluated in the following manner.

1: There is no change in the shape of the pattern before and after heating, and the line width variation compared with that after development is <0.1 μm.

2: The shape of the pattern before and after heating is slightly changed, and the line width variation compared with that after development is 0.1 μm to 0.2 μm.

3: The change in the shape of the pattern before and after heating can be seen, and the line width variation compared with that after development is 0.2 μm to 0.5 μm.

4: The change in the shape of the pattern before and after heating is large, and the line width variation compared with that after development is 0.5 μm to 1 μm.

5: After heating, the pattern deteriorates due to overheating

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

As shown in the above Table 2, in the comparison with the photosensitive resin composition of each comparative example, the photosensitive resin composition of each of the examples obtained excellent results in terms of evaluation of sensitivity, resolution, and heat resistance. . Here, Comparative Example 4 is a follow-up test of an example of JP-A-2011-75864, and in particular, poor evaluation of heat resistance.

[Example 28]

In Example 28, except that the photosensitive resin composition of Example 1 was used, the substrate was changed from a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) to a 6 inch 矽 wafer, and was composed of the photosensitive resin of Example 1. The sensitivity, the analytical property, and the heat resistance were evaluated in the same manner as the evaluation of the sensitivity, the analytical property, and the heat resistance of the material.

The results are shown in Table 3 below.

[Example 30]~[Example 31]

In Example 30 and Example 31, except that the photosensitive resin composition of Example 1 was used, the exposure machine was changed from a PLA-501F exposure machine manufactured by Canon (Canon) to an FX-803M manufactured by Nikon (GH line). In the same manner as in the evaluation of the sensitivity, the resolution, and the heat resistance of the photosensitive resin composition of Example 1, the sensitivity, the analytical property, and the heat resistance were evaluated.

The results are shown in Table 3 below.

[Example 32]

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

Further, the 355 nm laser exposure machine was "AEGIS" (wavelength: 355 nm, pulse width: 6 nsec) manufactured by V-Technology Co., Ltd., and the exposure amount was measured using "PE10B-V2" manufactured by OPHIR Corporation. The results are shown in Table 3 below.

[Example 33]

In Example 33, except that the photosensitive resin composition of Example 1 was used, the exposure machine was changed from a PLA-501F exposure machine manufactured by Canon (Canon) to a UV-LED source exposure machine, and the photosensitive film of Example 1 was used. The sensitivity, the analytical properties, and the heat resistance were evaluated in the same manner as the evaluation of the sensitivity, the analytical property, and the heat resistance of the resin composition.

The results are shown in Table 3 below.

As shown in Table 3 above, regardless of the substrate, the exposure machine, the sense of the example The photosensitive resin composition has excellent sensitivity and exposure margin. In addition, it is understood that the photosensitive resin composition of the example is also excellent in the resolution, that is, the shape of the formed pattern is also excellent in the squareness.

[Example 32] (Organic EL display device)

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

A bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si ₃ N ₄ is formed in a state of covering the TFT 1. Then, after the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3. This wiring 2 is for connecting the organic EL element formed between the TFTs 1 or in the step described later to the TFT 1.

Further, in order to planarize the unevenness due to the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried. The flattening film 4 is formed on the insulating film 3, and the photosensitive resin composition described in Example 1 of JP-A-2009-98616 is spin-coated on a substrate, and pre-baked on a hot plate (90). After ° C × 2 minutes), an i-line (365 nm) of 45 mJ/cm ² (illuminance: 20 mW/cm ² ) was irradiated from a mask using a high-pressure mercury lamp, and then developed by an aqueous alkali solution to form a pattern, and the film was formed at 230 ° C. Minute heat treatment.

When the photosensitive resin composition was applied, the coating property was good, and no occurrence of wrinkles or cracks was observed on the cured film obtained after exposure, development, and firing. Further, the average step of the wiring 2 was 500 nm, and the produced planarizing film 4 was produced. The film thickness was 2,000 nm.

Then, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, on the planarizing film 4, the first electrode 5 containing ITO is formed by being connected to the wiring 2 via the contact hole 7. Then, the photosensitive resin composition of Example 1 was spin-coated on an ITO substrate, prebaked on a hot plate (90 ° C × 2 minutes), and then irradiated with a high-pressure mercury lamp from a mask to an i-line (365 nm) of 20 mJ. After /cm ² (illuminance: 20 mW/cm ² ), development was carried out using an aqueous alkali solution to form a pattern. Then, a post-baking heat treatment was performed at 140 ° C for 3 minutes before the etching step. Using this resist pattern as a mask, ITO was patterned by wet etching using ITO etchant (3% aqueous oxalic acid solution) at 40 ° C / 1 min. Then, the resist pattern was peeled off by immersing in a resist stripper (MS2001, manufactured by Fujifilm Electronic Materials Co., Ltd.) at 70 ° C / 7 min. The first electrode 5 obtained in the above manner corresponds to the anode of the organic EL element.

Then, an insulating film 8 covering the shape of the periphery of the first electrode 5 is formed. The insulating film 8 is formed on the insulating film 8 by the same method as described above using the photosensitive resin composition described in Example 1 of JP-A-2009-98616. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the later-described step can be prevented.

Further, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited by vapor deposition in a vacuum vapor deposition apparatus with a desired pattern. Then, a second electrode containing Al is formed on the entire upper surface of the substrate. The obtained substrate was taken out from the vapor deposition machine, and sealed by bonding with a glass plate for sealing and an ultraviolet curable epoxy resin.

In the above manner, an active matrix type organic EL display device having an ITO pattern in which the TFTs 1 for driving the organic EL elements are connected to each of the organic EL elements is obtained. When a voltage is applied via a drive circuit, it is known that the organic EL display device exhibits excellent display characteristics and high reliability.

[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 liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3,321,003, the cured film 17 is formed as an interlayer insulating film in the following manner, and the liquid crystal display device of Example 16 is obtained.

That is, the cured film 17 was formed as an interlayer insulating film by the same method as the method of forming the planarizing film 4 of the organic EL display device of the above-described Example 32.

When a driving voltage was applied to the obtained liquid crystal display device having an ITO pattern, it was found that the liquid crystal display device exhibited excellent display characteristics and high reliability.

1,16‧‧‧TFT

2‧‧‧Wiring

3‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7, 18‧‧‧ contact holes

8‧‧‧Insulation film

10‧‧‧Liquid crystal display device

12‧‧‧Backlight unit

14, 15‧‧‧ glass substrate

17‧‧‧ hardened film

19‧‧‧ITO transparent electrode

20‧‧‧LCD

22‧‧‧RGB color filter

FIG. 1 is a conceptual diagram showing an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device having a planarization film 4.

FIG. 2 is a conceptual diagram showing an example of a liquid crystal display device. A schematic cross-sectional view showing an active matrix substrate in a liquid crystal display device, having a cured film 17 as an interlayer insulating film.

1‧‧‧TFT

2‧‧‧Wiring

3‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7‧‧‧Contact hole

8‧‧‧Insulation film

Claims (11)

A positive photosensitive resin composition comprising a polymer (A), a photoacid generator (B), and a solvent (C), wherein the polymer (A) is represented by the following formula (I) The total of the repeating unit (a1) and the repeating unit (a2) represented by the following formula (II) is 95 mol% or more of the total repeating unit, and the degree of polymerization distribution (weight average molecular weight/number average molecular weight) is more than 2.0. And the weight average molecular weight is 11100 or more: (In the formula (I), each of Ra ¹ to Ra ⁶ is a hydrogen atom, an alkyl group having a substituent of 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; ⁷ is a hydrogen atom or a methyl group, and Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms; n1 is an integer of 0 to 4; and the general formula (II) (In the formula (II), Ra ⁹ is a hydrogen atom or a methyl group, and Ra ¹⁰ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms; and n 2 is an integer of 0 to 4). The positive photosensitive resin composition according to claim 1, wherein the photoacid generator (B) has an oxime sulfonate structure represented by the following formula (b1): (In the 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 positive photosensitive resin composition according to the first aspect of the invention, which comprises a compound represented by the following formula (a), a compound represented by the following formula (b), and a formula (c) At least one of the compounds represented as (D) a basic compound: (In the formula (a), R ² represents an alkyl group which may have a substituent having 1 to 6 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent; and X represents an oxygen atom or a sulfur atom; Y ¹ represents an oxygen atom or a -NH- group; p1 represents an integer of 1 to 3); (In the formula (b), R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having a substituent of 1 to 6 carbon atoms, an aryl group which may have a substituent, or a carbon number of 3 to 10; a cyclic alkyl group which may have a substituent; The positive photosensitive resin composition according to claim 1, wherein Ra ¹ , Ra ² , Ra ³ and Ra ⁵ in the above formula (I) are hydrogen atoms. Forming a positive photosensitive resin as described in claim 1 And n1 in the above formula (I) and n2 in the formula (II) are 0. The positive photosensitive resin composition according to claim 1, wherein the repeating unit represented by the above formula (I) is represented by the following formula (III): The positive photosensitive resin composition according to the first aspect of the invention, wherein the (B) photoacid generator is represented by the following formula (OS-3), the following formula (OS-4), and the following A compound represented by any one of the formula (OS-5), the following formula (b2), the following formula (B3), and the formula (OS-2): (In the general formula (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 each independently represent hydrogen. An atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ¹ to X ³ each independently represent an oxygen atom or a sulfur atom, and n1 to n3 each independently represent 1 or 2, and m1 to m3 each independently represent an integer of 0 to 6); (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 m11 represents an integer of 0 to 3; when m11 is 2 or 3 , multiple X ¹¹ may be the same or different); (In the formula (B3), R ⁴³ is 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, 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, a cyano group or a nitro group, and n4 represents an integer of 0 to 5; (In the formula (OS-2), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a cyano group, An aryl or heteroaryl group; R ¹⁰² represents an alkyl group or an aryl group; and R ¹²¹ to R ¹²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amine group, an alkoxycarbonyl group, or an alkane group; a carbonyl group, an arylcarbonyl group, a decylamino 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 positive photosensitive resin composition according to claim 1, wherein the photoacid generator (B) has an oxime sulfonate structure represented by the following formula (b1), and the positive photosensitive material The resin composition contains at least one 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 (c) as (D) basic Compound: general formula (b1) (in the 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); (In the formula (a), R ² represents an alkyl group which may have a substituent having 1 to 6 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent; and X represents an oxygen atom or a sulfur atom; Y ¹ represents an oxygen atom or a -NH- group; p1 represents an integer of 1 to 3); (In the formula (b), R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having a substituent of 1 to 6 carbon atoms, an aryl group which may have a substituent, or a carbon number of 3 to 10; a cyclic alkyl group which may have a substituent; A method for producing a pattern, comprising: (1) a coating step of applying a positive photosensitive resin composition according to any one of claims 1 to 8 on a substrate; (2) a solvent removing step, removing a solvent from the coated positive photosensitive resin composition; (3) exposing the exposure to active radiation; (4) developing the step, developing with an aqueous developing solution; (5) And an etching step of etching the substrate by using the formed resist pattern as a mask; and (6) a peeling step of peeling off the resist pattern. The method for manufacturing a pattern according to claim 9, wherein after the developing step and before the etching step, the post-baking step comprises: post-baking the resist pattern at 100 ° C to 160 ° C. grilled. The pattern manufacturing method according to claim 9, wherein the substrate is an ITO substrate, a molybdenum substrate or a germanium substrate.