JP2009237556A - Method for producing photomask - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a photomask, which can stably provide a photomask with high resolution and can suppress development scum (sludge) over a long period. <P>SOLUTION: The method for producing a photomask comprises: exposing imagewise a photomask material having, on a transparent substrate, a photosensitive layer containing at least a light-shielding material and capable of performing image formation with near ultraviolet ray or visible light with near ultraviolet ray or visible light; and developing the exposed photomask material by use of a developer having pH of 8-13 which contains, in the total mass, 1-10 mass% of at least one surfactant selected from the group consisting of anionic surfactants and nonionic surfactants. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photomask manufacturing method, and more specifically, a photomask manufacturing method that can be used in a photolithographic process in the fields of flat panel displays such as PDP, FED, and LCD, shadow masks for CRTs, printed wiring boards, and semiconductors. About.

  Photomasks used in photolithography processes in the fields of flat panel displays, CRT shadow masks, printed wiring boards, semiconductors, etc. include Cr masks with a metallic chromium layer (Cr layer), and Em with a silver halide emulsion layer. A mask (emulsion mask) is known (for example, see Non-Patent Document 1).

  The Cr mask is formed by forming a chromium layer on a transparent substrate such as quartz or glass by a sputtering method and then applying an etching resist on the chromium layer, exposing it with a HeCd laser (442 nm), or developing with an alkaline aqueous solution. It is manufactured by patterning an etching resist, etching chrome, and removing the etching resist. The Cr mask has the merits of being capable of correcting defects such as pinholes, and being excellent in high resolution, high durability (scratch resistance), and high cleanability. On the other hand, the Cr mask is expensive because the manufacturing process is complicated, and has an environmental problem such as waste liquid treatment due to chromium etching in the manufacturing process.

The Em mask is prepared by providing a silver halide emulsion layer (photosensitive layer) on a transparent substrate such as quartz or glass, and exposing, developing and fixing with a YAG laser or the like. Since the silver halide emulsion used for the production of the Em mask has high sensitivity to light, the exposure energy may be small (˜0.1 mJ / cm ² ), and it is environmentally friendly and inexpensive. is there. On the other hand, the Em mask uses silver halide as a photosensitive material, so the resolution is not so high (about 3 μm) and is not suitable for producing an extremely fine pattern, and the photosensitive layer is a gelatin film. Therefore, it has poor durability. Further, the Em mask has a defect that defect correction is substantially difficult.

  In addition, other types of photomasks are known which are produced using a photomask material containing a black material such as a black pigment and having a photosensitive layer capable of forming an image with near ultraviolet light or visible light. (See Patent Document 1). The photosensitive layer of the photomask material is highly sensitive because of its low absorbance in the near-ultraviolet to visible region irradiated at the time of photomask fabrication, while the absorption property of light in the ultraviolet region irradiated when using the photomask is high. Since it is favorable, a photomask with excellent resolution can be obtained by exposing and developing the photosensitive layer. In addition, since this photomask does not require a metal film and is a relief image, it can be easily corrected for defects, has a good balance of sensitivity, resolution, etc., is inexpensive and has a low environmental impact. .

  By the way, in the case of using a photomask material containing a light-shielding material such as a black material in a photosensitive layer for the production of a photomask, the light-shielding material absorbs exposure light when performing image formation by exposure. Need to be exposed. However, when exposed under strong exposure conditions, an unexpected curing reaction in which a portion that should be a non-cured portion is cured may occur, resulting in a problem that the resolution of the obtained photomask is lowered. In addition, when the photosensitive layer has a light shielding material such as a black material such as a black pigment, there is a problem that the light shielding material remains in the developer after development as development residue (sludge) and contaminates the developer. .

Educational Literature Society, “Photofabrication”, published by Japan Photofabrication Association, 67-80 pages, June 1992

JP 2005-283914 A

  The present invention has been made in view of the above problems in the prior art, and a photomask manufacturing method capable of stably obtaining a photomask with high resolution and suppressing the generation of development residue (sludge) over a long period of time. The purpose is to provide.

Means for solving the above-mentioned problems are as follows.
<1> After image-wise exposure of a photomask material having a light-sensitive material containing at least a light-shielding material and capable of forming an image with near ultraviolet light or visible light on a transparent substrate with near ultraviolet light or visible light PH 8 to 13 containing at least one surfactant selected from the group consisting of an anionic surfactant and a nonionic surfactant as a photomask material after exposure in a total mass of 1% by mass to 10% by mass A method for producing a photomask, wherein the development is performed using a developing solution.
<2> The anionic surfactant contained in the developer has at least one aromatic group which has an anion group of sulfonic acid or an anion group of sulfuric monoester, and may have a substituent. <1> The method for producing a photomask according to <1>, which is an anionic surfactant.
<3> The nonionic surfactant contained in the developer is at least one surfactant selected from the group consisting of nonionic aromatic ether surfactants represented by the following general formula (1). The method for producing a photomask according to <1> or <2>, wherein:
X-Y-O- (A) _n- (B) _m- H (1)
(In general formula (1), X represents an aromatic group which may have a substituent, Y represents a single bond or an alkylene group having 1 to 10 carbon atoms, and A and B are groups different from each other. And represents either —CH ₂ CH ₂ O— or —CH ₂ CH (CH ₃ ) O—, and n and m each represent 0 or an integer of 1 to 100, provided that n and m are 0 at the same time. And when either n or m is 0, n and m are not 1.)
<4> The photosensitive layer in the photomask material further contains a polymer binder, and the polymer binder has a polyurethane resin having a crosslinkable group in the side chain or a (meth) acrylic resin having a crosslinkable group in the side chain. <1>-<3> The method for producing a photomask according to any one of <1> to <3>.
<5> The method for producing a photomask according to any one of <1> to <4>, wherein the imagewise exposure is performed using a laser that emits light of 250 nm to 540 nm.

  ADVANTAGE OF THE INVENTION According to this invention, the photomask manufacturing method which can obtain a high-resolution photomask stably and can suppress generation | occurrence | production of development waste (sludge) over a long period of time can be provided.

  The method for producing a photomask of the present invention comprises a photomask material containing at least a light shielding material and having a photosensitive layer capable of forming an image with near ultraviolet light or visible light on a transparent substrate. After imagewise exposure with light, the exposed photomask material is at least one surfactant selected from the group consisting of anionic surfactants and nonionic surfactants in a total mass of 1% by mass to 10% by mass. % Development is carried out using a developer having a pH of 8 to 13 (hereinafter referred to as “specific developer” as appropriate).

  According to the photomask manufacturing method of the present invention, a photomask with high resolution can be stably obtained, and generation of development residue (sludge) can be suppressed over a long period of time. That is, in the production method of the present invention, by using a specific developer, the resolution of an image formed on the photomask material is not lowered even when the same developer is repeatedly used for development processing. Moreover, the use of the specific developer can suppress the generation of sludge over a long period of time. As a result, it is possible to extend the service life of the developer, which also reduces the burden on the environment. This excellent effect exhibited by the present invention is sufficiently exhibited when a photomask material having a photosensitive layer containing a black material is used as a light shielding material.

  The photomask manufacturing method of the present invention (hereinafter referred to as “the manufacturing method of the present invention” as appropriate) will be described in detail below. In the following, first, a specific developer used as a characteristic element used in the manufacturing method of the present invention and a photomask material will be described, and then manufacturing of the photomask will be described.

[Developer]
The developer used in the production method of the present invention will be described.
The specific developer used in the production method of the present invention has a pH of 8 to 13 containing 1% by mass or more of at least one surfactant selected from the group consisting of an anionic surfactant and a nonionic surfactant in the total mass. Developer.

<Anionic surfactant, nonionic surfactant>
The specific developer applied to the present invention contains at least one surfactant selected from the group consisting of an anionic surfactant and a nonionic surfactant.

  The total content of the anionic surfactant and the nonionic surfactant in the specific developer is 1% by mass or more and 10% by mass or less in the total mass of the specific developer, and is a viewpoint of suppressing generation of sludge and improving unexposed area developability. Is preferably 2% by mass to 8% by mass, and more preferably 3% by mass to 7% by mass.

The anionic surfactant and the nonionic surfactant may contain only one or both of them in the specific developer.
As a content ratio (mass ratio) in the case of using an anionic surfactant and a nonionic surfactant in combination, the anionic surfactant: nonionic surfactant is preferably 1: 9 to 9: 1, and 4: 6. ~ 6: 4 is more preferable, and 3: 7 to 5: 5 is more preferable.

  As the anionic surfactant and nonionic surfactant, those described in detail below can be used.

-Anionic surfactant-
Anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, Alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkylsulfosuccinic acid monoamide disodium salts, petroleum sulfonates, sulfated castor oil, Sulfated tallow oil, sulfates of fatty acid alkyl esters, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates Salts, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, styrene-anhydrous Examples include anionic surfactants such as partially saponified products of maleic acid copolymer, partially saponified products of olefin-maleic anhydride copolymer, and naphthalene sulfonate formalin condensate.

  As the anionic surfactant, an anionic surfactant having an anionic group of sulfonic acid or anionic group of sulfuric monoester is preferable, having an anionic group of sulfonic acid or anionic group of sulfuric monoester, and having a substituent. More preferably, the anionic surfactant has at least one aromatic group which may be present.

  As a preferable aspect of an anionic surfactant, the compound represented by the following general formula (I) or the compound represented by general formula (II) is mentioned.

In general formula (I) or (II), R ¹ and R ² each represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group, and these groups further have a substituent. May be. M represents an alkali metal.

Examples of the alkyl group represented by R ¹ or R ² include an alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- Preferred examples include a butyl group, hexyl group, 2-ethylhexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, stearyl group, and the like.

The cycloalkyl group represented by R ¹ or R ² may be monocyclic or polycyclic. Examples of the monocyclic cycloalkyl group include those having 3 to 8 carbon atoms, and preferred examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Preferred examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, and the like.

Examples of the alkenyl group represented by R ¹ or R ² include alkenyl groups having 2 to 20 carbon atoms, and specific examples include vinyl, allyl, butenyl, and cyclohexenyl groups. be able to.

Examples of the aralkyl group represented by R ¹ or R ² include an aralkyl group having 7 to 12 carbon atoms, and specific examples include a benzyl group, a phenethyl group, and a naphthylmethyl group. .

The aryl group represented by R ¹ or R ² includes, for example, an aryl group having 6 to 15 carbon atoms, and specifically includes a phenyl group, a tolyl group, a dimethylphenyl group, 2, 4, 6 Preferred examples include -trimethylphenyl group, naphthyl group, anthryl group, 9,10-dimethoxyanthryl group and the like.

Examples of the substituent that can be further introduced into R ¹ and R ² include a monovalent nonmetallic atomic group excluding a hydrogen atom. Preferred examples of the substituent include a halogen atom (F, Br, Cl, I), hydroxyl group, alkoxy group, aryloxy group, acyl group, amide group, ester group, acyloxy group, carboxy group, carboxylate anion. Group, or a sulfonic acid anion group.

  Specific examples of the alkoxy group in these substituents include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, stearyloxy group, methoxyethoxy group, Examples include poly (ethyleneoxy) and poly (propyleneoxy) having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms. The aryloxy group has 6 to 18 carbon atoms such as phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group, bromophenyloxy group and naphthyloxy group. Individuals are listed. Examples of the acyl group include those having 2 to 24 carbon atoms such as an acetyl group, a propanoyl group, a butanoyl group, a benzoyl group, and a naphthoyl group. Examples of the amide group include those having 2 to 24 carbon atoms such as an acetamide group, a propionic acid amide group, a dodecanoic acid amide group, a palmitic acid amide group, a stearic acid amide group, a benzoic acid amide group, and a naphthoic acid amide group. . Examples of the acyloxy group include those having 2 to 20 carbon atoms such as an acetoxy group, a propanoyloxy group, a benzoyloxy group, and a naphthoyloxy group. Examples of the ester group include those having 1 to 24 carbon atoms such as methyl ester group, ethyl ester group, propyl ester group, hexyl ester group, octyl ester group, dodecyl ester group, stearyl ester group. The substituent may be a combination of two or more of the above substituents.

  Examples of the alkali metal represented by M include sodium, potassium, and lithium, and sodium and potassium are more preferable.

R ¹ in the general formula (I) is more preferably an aryl group which may have a substituent.

  Other preferred embodiments of the anionic surfactant include compounds represented by the following general formula (IA) and general formula (IB).

In the general formula (IA) or (IB), R ³ and R ⁵ each represent a linear or branched alkylene group having 1 to 5 carbon atoms; R ⁴ and R ⁶ are respectively Each represents a linear or branched alkylene group having 1 to 20 carbon atoms; p and q each represents 0, 1 or 2; and X ₁ and X ₂ each represent a single bond or 1 to 10 carbon atoms. And r and s each represent an integer of 1 to 100. However, when r and s are 2 or more, R ³ or R ⁵ may be selected from two or more groups. M represents an alkali metal.

  The alkali metal represented by M has the same meaning as M in the general formula (II), and the preferred range is also the same.

  Specific examples of the compounds represented by the general formulas (I), (II), (IA), and (IB) are illustrated below, but the present invention is not limited thereto.

  In addition, x and y in the said specific example represent the repeating number of an ethyleneoxy chain or a propyleneoxy chain, respectively, and represent the integer of 1-20 (each average value).

  Commercially available products may be used as the compounds represented by the general formulas (I) and (II). Examples of commercially available products include Perex NBL manufactured by Kao Corporation, New Coal B4SN, New Coal B13SN manufactured by Nippon Emulsifier Co., Ltd., and the like.

  An anionic surfactant may be used individually by 1 type in a specific developing solution, and may be used in combination of 2 or more types.

  When the specific developer contains an anionic surfactant, the content of the anionic surfactant in the specific developer is preferably 1 to 10% by mass, more preferably 2 to 8% by mass in the total mass of the specific developer. %. When the content of the anionic surfactant is within the above range, the developability during the development process and the solubility of the photosensitive layer component are better.

-Nonionic surfactant-
Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ether, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene Glycol monofatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid partial ester, polyoxyethylene glycerin fatty acid partial ester , Polyoxyethylene diglycerins, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines Polyoxyethylene alkylamine, triethanolamine fatty acid esters, trialkylamine oxides, polyoxyethylene alkyl phenyl ethers, polyoxyethylene - polyoxypropylene block copolymers, and nonionic surface active agents and the like are exemplified.

  Particularly preferable examples of the nonionic surfactant include nonionic aromatic ether surfactants represented by the following formula (1).

X-Y-O- (A) _n- (B) _m- H (1)
In general formula (1), X represents an aromatic group which may have a substituent, Y represents a single bond or an alkylene group having 1 to 10 carbon atoms, and A and B are groups different from each other. Te, -CH ₂ CH ₂ O- or -CH ₂ CH (CH ₃₎ O- represents any of, n, m each represents an integer of 0 or 1 to 100, provided that n and m are not 0 at the same time In addition, when either n or m is 0, n and m are not 1.

  In the general formula (1), examples of the aromatic group represented by X include a phenyl group, a naphthyl group, and an anthranyl group. These aromatic groups may have a substituent. Examples of the substituent include an organic group having 1 to 100 carbon atoms. Examples of the organic group include all organic groups having 1 to 100 carbon atoms described in the description of the general formulas (1-A) and (1-B) described later.

  In the general formula (1), when both A and B are present, the arrangement of A and B may be alternating, may form a block, or may be random.

  Specific examples of the compound represented by the general formula (1) include compounds represented by the following general formulas (1-A) and (1-B).

In general formula (1-A) or (1-B), R ¹⁰ and R ²⁰ each represent a hydrogen atom or an organic group having 1 to 100 carbon atoms; t and u each represent 1 or 2; Y ₁ and Y ₂ each represent a single bond or an alkylene group having 1 to 10 carbon atoms; v and w each represent 0 or an integer of 1 to 100; If both v and w are 0 at the same time, and v and w are not 1, v ′ and w ′ each represent 0 or an integer from 1 to 100, provided that v ′ and w ′ Are not 0 at the same time, and v 'and w' are not 1 if either v 'or w' is 0.

In the general formula (1-A), when t represents 2 and R ¹⁰ is an organic group having 1 to 100 carbon atoms, two R ^{10 s} may be the same or different, and two R ¹⁰ May be bonded to each other to form a ring.
In the general formula (1-B), when u represents 2 and R ²⁰ is an organic group having 1 to 100 carbon atoms, the two R ²⁰ may be the same or different, and R ²⁰ may be mutually different. It may combine to form a ring.

Specific examples of the organic group having 1 to 100 carbon atoms represented by R ¹⁰ or R ²⁰ include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, which may be saturated or unsaturated, and may be linear or branched, For example, alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, etc. Besides, alkoxy group, aryloxy group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N -Diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diaryl Carbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, acylamino group, N-al Ruacylamino group, N-arylacylamino group, acyl group, alkoxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, Examples thereof include N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, polyoxyalkylene chain, and the above organic group to which a polyoxyalkylene chain is bonded. The alkyl group may be linear or branched.

Preferred examples of R ¹⁰ and R ²⁰ include a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group, an N-alkylamino group, N, N-dialkylamino group, N-alkylcarbamoyl group, acyloxy group or acylamino group, polyoxyalkylene chain having about 5 to 20 repeating units, aryl group having 6 to 20 carbon atoms, poly having about 5 to 20 repeating units Examples include an aryl group to which an oxyalkylene chain is bonded.

  In the compounds represented by the general formulas (1-A) and (1-B), the number of repeating units of the polyoxyethylene chain is preferably 3 to 50, more preferably 5 to 30. The number of repeating units of the polyoxypropylene chain is preferably 0 to 10, more preferably 0 to 5. The arrangement of the polyoxyethylene part and the polyoxypropylene part may be alternating, random or block.

Examples of the compound represented by the general formula (1-A) include polyoxyethylene phenyl ether, polyoxyethylene methyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like.
Examples of the compound represented by the general formula (1-B) include polyoxyethylene naphthyl ether, polyoxyethylene methyl naphthyl ether, polyoxyethylene octyl naphthyl ether, and polyoxyethylene nonyl naphthyl ether.

  Examples of the nonionic aromatic ether activator represented by the general formula (1-A) or (1-B) are shown below, but the present invention is not limited to these.

  A nonionic surfactant may be used individually by 1 type in a specific developing solution, and may be used in combination of 2 or more types.

  When using a nonionic surfactant, 1-10 mass% is preferable in the total mass of a specific developing solution, and, as for content of the nonionic surfactant in a specific developing solution, More preferably, it is 2-8 mass%. When the content is within the above range, the developability during development and the solubility of the photosensitive layer components are good.

  In addition to the above-mentioned various anionic surfactants and nonionic surfactants, the specific developer also includes acetylene glycol-based and acetylene alcohol-based oxyethylene adducts, fluorine-based and silicon-based anions or nonionic surfactants. Can be used for Two or more of these surfactants can be used in combination. For example, a combination of two or more different anionic surfactants or a combination of an anionic surfactant and a nonionic surfactant is preferable. These compounds are preferably selected and used in consideration of environmental effects. The content when these surfactants are contained in the specific developer is preferably 0.01 to 10% by mass in the total mass of the specific developer.

[Other ingredients]
In addition to the above-mentioned nonionic surfactant and / or anionic surfactant, the specific developer applied to the production method of the present invention may contain other components as necessary. Examples of other components that can be contained in the specific developer include water-soluble polymer compounds, wetting agents, preservatives, chelate compounds, antifoaming agents, organic acids, organic solvents, inorganic acids, inorganic salts, and the like. .

<Water-soluble polymer compound>
The specific developer can contain a water-soluble polymer compound.
Examples of water-soluble polymer compounds include soybean polysaccharides, modified starch, gum arabic, dextrin, fibrin derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, etc.) and modified products thereof, pullulan, polyvinyl alcohol and derivatives thereof, polyvinylpyrrolidone, Examples include polyacrylamide and acrylamide copolymers, vinyl methyl ether / maleic anhydride copolymers, vinyl acetate / maleic anhydride copolymers, styrene / maleic anhydride copolymers, and the like.

  As the soybean polysaccharide, conventionally known ones can be used. For example, as a commercial product, there is a trade name Soya Five (manufactured by Fuji Oil Co., Ltd.), and various grades can be used. What can be preferably used is one in which the viscosity of a 10% by mass aqueous solution is in the range of 10 to 100 mPa / sec.

  As modified starch, the starch shown by the following general formula (A) is preferable. As the starch represented by the general formula (A), any starch such as corn, potato, tapioca, rice and wheat can be used. These starches can be modified by a method of decomposing in the range of 5 to 30 glucose residues per molecule with an acid or an enzyme, and further adding oxypropylene in an alkali.

  In general formula (A), the degree of etherification (degree of substitution) is in the range of 0.05 to 1.2 per glucose unit, n1 represents an integer of 3 to 30, and m1 represents an integer of 1 to 3.

  Among water-soluble polymer compounds, particularly preferred are soybean polysaccharides, modified starches, gum arabic, dextrin, carboxymethylcellulose, polyvinyl alcohol and the like.

  Only one type of water-soluble polymer compound may be used, or two or more types may be used in combination. The content of the water-soluble polymer compound in the specific developer is preferably from 0.1 to 20% by mass, and more preferably from 0.5 to 10% by mass.

  In addition, the water-soluble polymer compound can be contained in the specific developer in the present invention, and is also contained in a processing solution applied to a treatment (for example, a washing treatment) arbitrarily performed after the development treatment with the developer. It can also be used.

<Wetting agent>
As the wetting agent, ethylene glycol, propylene glycol, triethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, diglycerin and the like are preferably used. These wetting agents may be used alone or in combination of two or more. Generally, the wetting agent is used in an amount of 0.1 to 5% by mass based on the total mass of the specific developer.

<Preservative>
Preservatives include phenol or its derivatives, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzisothiazolin-3-one, benztriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, pyridine , Derivatives of quinoline, guanidine, etc., diazine, triazole derivatives, oxazole, oxazine derivatives, nitrobromoalcohol-based 2-bromo-2-nitropropane-1,3diol, 1,1-dibromo-1-nitro-2-ethanol 1,1-dibromo-1-nitro-2-propanol can be preferably used.
The addition amount of the preservative may be an amount that exhibits a stable effect on bacteria, mold, yeast, and the like. The amount of the preservative added is preferably in the range of 0.01 to 4% by mass in the total mass of the specific developer at the time of use, although it varies depending on the type of bacteria, mold, yeast and the like. Moreover, it is preferable to use 2 or more types of preservatives together so that it may be effective with respect to various molds and sterilization.

<Chelate compound>
Examples of chelate compounds include ethylenediaminetetraacetic acid, potassium salt thereof, sodium salt thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetraminehexaacetic acid, potassium salt thereof, sodium salt thereof, and hydroxyethylethylenediaminetriacetic acid. Nitrilotriacetic acid, sodium salt; 1-hydroxyethane-1,1-diphosphonic acid, potassium salt, sodium salt; aminotri (methylenephosphonic acid), potassium salt, sodium salt And organic phosphonic acids and phosphonoalkanetricarboxylic acids. Organic amine salts are also effective in place of the sodium and potassium salts of the chelating agents. These chelating agents are selected so that they are stably present in the specific developer composition and do not impair image-forming properties. The addition amount of the chelating agent is preferably 0.001 to 1.0% by mass in the total mass of the specific developer at the time of use.

  As the chelate compound, commercially available products may be used, and examples thereof include Kirest 400 (manufactured by Kirest Co., Ltd.), Diquest 2066 (manufactured by Solusia Japan Co., Ltd.), and the like.

<Antifoaming agent>
As the antifoaming agent, compounds such as a general silicon-based self-emulsifying type, an emulsifying type, and a surfactant nonionic HLB of 5 or less can be used. Silicon antifoaming agents are preferred. Among them, emulsification dispersion type and solubilization can be used.
The content of the antifoaming agent is preferably in the range of 0.001 to 1.0% by mass in the total mass of the specific developer at the time of use.

<Organic acid>
Examples of the organic acid include citric acid, acetic acid, succinic acid, malonic acid, salicylic acid, caprylic acid, tartaric acid, malic acid, lactic acid, levulinic acid, p-toluenesulfonic acid, xylenesulfonic acid, phytic acid, and organic phosphonic acid. . The organic acid can also be used in the form of its alkali metal salt or ammonium salt. The content of the organic acid is preferably 0.01 to 0.5% by mass in the total mass of the specific developer.

<Organic solvent>
Examples of the organic solvent include ethylene glycol and benzyl alcohol. The content of the organic solvent is preferably in the range of 0.01 to 1% by mass with respect to the total mass of the specific developer.

<Inorganic acid, inorganic salt>
Examples of inorganic acids and inorganic salts include phosphoric acid, metaphosphoric acid, primary ammonium phosphate, secondary ammonium phosphate, primary sodium phosphate, secondary sodium phosphate, primary potassium phosphate, secondary potassium phosphate, Examples include sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, magnesium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate, sodium sulfate, potassium sulfate, ammonium sulfate, sodium sulfite, ammonium sulfite, sodium hydrogen sulfate, nickel sulfate and the like. The content of the inorganic salt is preferably 0.01 to 0.5% by mass based on the total mass of the specific developer.

  The specific developer used in the present invention can be prepared by dissolving or dispersing the nonionic and / or anionic surfactants, which are essential components, and the above-described components used as necessary in water. . The solid content concentration of the specific developer at the time of use is preferably 1 to 20% by mass. The specific developer may be prepared by preparing a concentrated solution and diluting with water at the time of use.

  The pH of the specific developer used in the present invention is 8 to 13, and 8.5 to 12.8 is preferable and 9 to 12.5 is more preferable from the viewpoint of compatibility between suppression of image damage and developability.

  Adjustment of the pH of the specific developer is, for example, an alkali agent (for example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, monoethanolamine, diethanolamine, triethanolamine, etc.) Or it can carry out by addition of buffering agents (for example, phosphoric acid, a citric acid, malonic acid), etc. These may be used alone or in combination of two or more. A particularly preferable alkaline agent is an alkaline agent that exhibits a buffering action at a pH of 8 to 13, and a combined use of carbonate and bicarbonate is particularly preferred.

  In the case where two or more alkali agents are used in combination in the specific developer, preferred examples of the combination include a combination of potassium carbonate and potassium bicarbonate, sodium carbonate and sodium bicarbonate, and the like.

[Photomask material]
The photomask material used for the manufacturing method of the present invention will be described.
The photomask material used in the present invention has a photosensitive layer containing at least a light shielding material and capable of forming an image with ultraviolet light or visible light on a transparent substrate.

(Transparent substrate)
As a transparent substrate in the photomask material, a glass plate such as quartz, soda glass, and alkali-free glass, or a transparent plastic film such as polyethylene terephthalate can be used. Although the thickness of a transparent base material changes with the uses, generally it is the range of 1 mm-7 mm.

(Photosensitive layer)
The photosensitive layer included in the photomask material is a layer containing at least a light shielding material and capable of forming an image with ultraviolet light or visible light. That is, the photosensitive layer is a layer capable of forming an image by developing with the specific developer in the present invention after imagewise exposure with near ultraviolet light or visible light.

  The photosensitive layer is preferably an alkali development type in view of environmental problems, and may be either a negative type layer in which an exposed portion is cured and insolubilized in an alkaline developer, or a positive layer in which an exposed portion is soluble in an alkaline developer.

In the case of a negative photosensitive layer, a layer formed of a photosensitive composition that contains at least the light-shielding material and is polymerized and cured by exposure to near ultraviolet light or visible light is preferable. Examples of the photosensitive composition include a photopolymerizable composition containing at least a light shielding material, an alkali-soluble polymer binder, an ethylenically unsaturated bond-containing compound, and a photopolymerization initiation system.
Hereinafter, although the photosensitive layer is demonstrated by the example formed using the said photopolymerizable composition, the photosensitive layer in this invention is not limited to this.

<Light shielding material>
The photosensitive layer contains a light shielding material.
The light shielding material in the present invention refers to a light absorber that absorbs light of 250 nm to 400 nm, and preferably has an optical density (OD) of 2.5 or more at the time of coating film formation.
The light-shielding material in the present invention is a material having a function of not transmitting light by reflecting and absorbing light having an active light wavelength to which the photomask is applied. Specifically, an exposure light source used as a mask ( Mercury lamps, metal halide lamps, xenon lamps, etc.) can emit light in a wavelength range of 200 to 450 nm, preferably about 250 to 400 nm, and the optical density (OD) at the time of coating film formation is 2. It needs to be 5 or more, preferably 3.0 or more.

What is necessary is just to select the light-shielding material in this invention suitably according to the intended purpose etc. of a photomask.
Specifically, metal particles (including metal compound particles, composite particles, core / shell particles, etc.), pigments, other particles, fullerene, and the like are preferably used as the light shielding material.
The light shielding material that can be used in the present invention is preferably a black material, and the black material is preferably at least one of a black pigment and metal fine particles.
Hereinafter, the light shielding material applicable to the present invention will be described in detail.

-Metal particles-
When metal particles are used as the light shielding material, the metal particles may be composed of one kind of metal, a combination of two or more kinds of metals, or an alloy. The metal particles may be composite fine particles of a metal and a metal compound. From the viewpoint of shielding ability, light resistance, and heat resistance, particles containing a metal compound can be suitably used as the light shielding material.

  Examples of preferable metals contained in the metal particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, Mention may be made of at least one selected from titanium, bismuth, antimony, lead, and alloys thereof. More preferable metals are copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, calcium, iridium, and alloys thereof, and more preferable metals are copper, silver, gold, platinum, palladium, tin, and calcium. And at least one selected from these alloys, and particularly preferred metals are at least one selected from copper, silver, gold, platinum, tin, and alloys thereof. In particular, particles of silver are preferable (colloidal silver is preferable as silver), and particles having a silver-tin alloy part are also preferable. The particle | grains which have a silver tin alloy part are mentioned later.

The metal compound is a compound of the metal and an element other than the metal. Examples of the compound of metal and other elements include metal oxides, sulfides, sulfates, carbonates, and the like, and these particles are preferable as the metal compound particles. Of these, sulfide particles are preferred from the viewpoint of color tone and ease of fine particle formation.
Examples of metal compounds include copper oxide (II), iron sulfide, silver sulfide, copper sulfide (II), and titanium black. From the viewpoint of color tone, ease of fine particle formation and stability, silver sulfide is particularly preferable. preferable.

Composite particles are particles in which a metal and a metal compound are combined into one particle. For example, the inside of the particle and the surface are different in composition, and the two kinds of particles are combined. Further, each of the metal compound and the metal may be one type or two or more types.
Specific examples of the composite fine particles of the metal compound and the metal include preferably composite fine particles of silver and silver sulfide, and composite fine particles of silver and copper (II) oxide.

When composite particles are used as the light shielding material, the composite particles may be composite particles having a core / shell structure (core-shell particles). Core-shell type composite particles (core-shell particles) are obtained by coating the surface of a core material with a shell material.
Examples of the shell material constituting the core-shell type composite particles include Si, Ge, AlSb, InP, Ga, As, GaP, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, PbTe, Se. , Te, CuCl, CuBr, CuI, TlCl, TlBr, TlI, at least one semiconductor selected from these solid solutions and solid solutions containing 90 mol% or more of these, or copper, silver, gold, platinum, palladium, nickel, tin And at least one metal selected from cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, lead, calcium, and alloys thereof.
The shell material is also preferably used as a refractive index adjuster for the purpose of reducing the reflectance.
Preferable core materials include at least one selected from copper, silver, gold, palladium, nickel, tin, bismuth, ammotine, lead, and alloys thereof.

There is no restriction | limiting in particular in the preparation methods of the composite particle which has a core shell structure, The following (1) and (2) are mentioned as a typical method.
(1) A method of forming a metal compound shell on the surface of metal fine particles produced by a known method by oxidation, sulfurization, etc. For example, metal fine particles are dispersed in a dispersion medium such as water, and sodium sulfide or This is a method of adding a sulfide such as ammonium sulfide. By this method, the surface of the particles can be sulfided to form core / shell particles.
In this case, the metal particles to be used can be produced by a known method such as a gas phase method or a liquid phase method. The method for producing metal particles is described in, for example, “Latest Trend II in Technology and Application of Ultrafine Particles” (Sumibe Techno Research Co., Ltd., issued in 2002).
(2) A method of continuously forming a metal compound shell on the surface in the process of producing metal particles. For example, a reducing agent is added to a metal salt solution to reduce a part of metal ions to form metal fine particles. And then adding a sulfide to form a metal sulfide around the produced metal fine particles.

  As the metal particles, commercially available ones can be used, and the metal particles can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.

For example, rod-shaped silver fine particles are reduced with relatively weak reducing power such as ascorbic acid in the presence of a surfactant such as CTAB (cetyltrimethylammonium bromide) after adding silver salt after using spherical silver fine particles as seed particles. By using the agent, a silver bar or a wire can be obtained. This is described in Advanced Materials 2002, 14, 80-82. Similar descriptions are made in Materials Chemistry and Physics 2004, 84, 197-204, Advanced Functional Materials 2004, 14, 183-189.
Further, as a method using electrolysis, Materials Letters 2001, 49, 91-95 and a method of generating a silver bar by irradiating microwaves are described in Journal of Materials Research 2004, 19, 469-473. . Journal of Physical Chemistry B 2003, 107, 3679-3683 is an example in which reverse micelles and ultrasonic waves are used in combination.
Similarly, the gold particles are also described in Journal of Physical Chemistry B 1999, 103, 3073-3077 and Langmuir 1999, 15, 701-709, Journal of American Chemical Society 2002, 124, 14316-1143.
The method for forming the rod-like particles can be prepared by improving the method described above (adjusting the addition amount and controlling the pH).

The particles having a silver-tin alloy part include those made of a silver-tin alloy part, those made of a silver-tin alloy part and another metal part, and those made of a silver-tin alloy part and another alloy part.
In the particles having a silver-tin alloy part, at least a part of the particles is composed of a silver-tin alloy. For example, HD-2300 manufactured by Hitachi, Ltd. and EDS (energy dispersive X) manufactured by Noran. And a spectrum measurement of the center 15 nm □ area of each particle with an acceleration voltage of 200 kV.
Particles having a silver-tin alloy part have a high black density, can exhibit excellent light-shielding performance in a small amount or in a thin film, and have high thermal stability, so that they do not impair the black density and are high temperature (for example, 200 degrees or more). Heat treatment can be performed, and a high light-shielding property can be secured stably.

-Pigments and other particles-
As the light shielding material, pigments and other particles can be used.
When a pigment is used, the hue can be made closer to black. When a pigment is used as the light shielding material, the pigment may be used alone or in combination with the above metal particles.

  Examples of the pigment and other particles include particles made of a black material such as carbon black, titanium black, and graphite.

Examples of the black pigment include Fat Black HB (C.I. 26150), Monolite First Black B (C. I. Pigment Black 1), and carbon black.
As an example of carbon black, Pigment Black 7 (carbon black CI No. 77266) is preferable. Examples of commercially available products include Mitsubishi Carbon Black MA100 (manufactured by Mitsubishi Chemical Corporation) and Mitsubishi Carbon Black # 5 (manufactured by Mitsubishi Chemical Corporation).
As an example of titanium black, TiO ₂ , TiO, TiN and a mixture thereof are preferable. Examples of commercially available products include (trade names) 12S and 13M manufactured by Mitsubishi Materials Corporation.

  In the present invention, known pigments other than those described above can also be used as the light shielding material. The pigment is generally roughly classified into an organic pigment and an inorganic pigment, and an organic pigment is preferable. Examples of pigments that can be suitably used include azo pigments, phthalocyanine pigments, anthraquinone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and nitro pigments. Examples of the hue of such an organic pigment include a yellow pigment, an orange pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a brown pigment, and a black pigment.

Hereinafter, particles such as other pigments that can be used in the present invention are listed below. However, the present invention is not limited to these.
Specific examples include the color materials described in JP 2005-17716 A [0038] to [0040], the pigments described in JP 2005-361447 A [0068] to [0072], and JP The colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used.

Also, “Handbook of Pigments, edited by Japan Pigment Technology Association, Seibundo Shinkosha, 1989”, “COLOR”.
INDEX, THE SOCIETY OF DYES & COLORIST, THIRD EDITION, 1987 "can be used as appropriate.

  When the pigment is used together with metal particles, it is desirable to use a pigment having a complementary color relationship with the hue of the metal particles. Further, the pigments may be used alone or in combination of two or more. Preferred pigment combinations include a combination of a red and blue pigment mixture complementary to each other and a yellow and purple pigment mixture complementary to each other, or a black pigment added to the above mixture. And combinations of blue, violet and black pigments.

Carbon black is particularly preferable as the light shielding material in the present invention.
When carbon black is used as the light shielding material, the photosensitive layer may contain only carbon black, or carbon black and another colorant (for example, other colorant) may be used in combination. When carbon black and another color material are used in combination, it is preferable that 50% by mass or more of the total light-shielding material contained in the photosensitive layer is carbon black in terms of increasing the color density of the photosensitive layer. .

  The light-shielding material such as a black material preferably has an average particle diameter of 1 μm or less, and more preferably 10 nm to 50 nm.

  In addition, when using pigments, such as a black pigment, it is preferable to disperse | distribute with the dispersing agent in the photosensitive composition used for formation of a photosensitive layer.

  The content of the light shielding material in the solid content of the photosensitive composition is determined in consideration of the concentration of the photomask, the sensitivity at the time of producing the photomask, the resolution, and the like. % By mass is preferable, and more preferably 30 to 50% by mass.

<Polymer binder>
The photosensitive layer preferably contains a polymer binder. The polymer binder is not particularly limited as long as it is a polymer compound, but an alkali-soluble polymer compound is preferable from the viewpoint of developability. As such a polymer compound, a polymer compound having an alkali-soluble group in the side chain is preferable. Examples of the alkali-soluble group include an acid group or a salt thereof. As the polymer compound having a soluble group, a polymer compound having a carboxylic acid group is particularly preferably used. The polymer binder is preferably a polymer binder having a crosslinkable group in the side chain.

  Here, the crosslinkable group means a group that crosslinks the polymer binder in the course of radical polymerization reaction that occurs in the photosensitive layer when the photomask material is exposed. Although it will not specifically limit if it is a group of such a function as a crosslinkable group, For example, an ethylenically unsaturated bond group, an amino group, an epoxy group etc. are mentioned as a functional group which can be addition-polymerized. Moreover, the functional group which can become a radical by light irradiation may be sufficient, and as such a crosslinkable group, a thiol group, a halogen group, an onium salt structure etc. are mentioned, for example. Especially, an ethylenically unsaturated bond group is preferable and the functional group represented by the following general formula (a1)-(a3) is especially preferable.

In the general formula (a1), R ^{la to} R ^3a each independently represents a monovalent organic group. R ^1a is preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group is preferable because of high radical reactivity. R ^2a and R ^3a are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, or a substituent. An aryl group that may have a group, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable because of high radical reactivity.

X represents an oxygen atom, a sulfur atom, or —N (R ^12a ) —, and R ^12a represents a hydrogen atom or a monovalent organic group. Here, R ^12a includes an alkyl group which may have a substituent, and among them, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

  Here, examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylamino group, an arylamino group, a carboxyl group, an alkoxycarbonyl group, A sulfo group, a nitro group, a cyano group, an amide group, an alkylsulfonyl group, an arylsulfonyl group and the like can be mentioned.

In the general formula (a2), R ^{4a to} R ^8a each independently represents a monovalent organic group. R ^{4a to} R ^8a are preferably a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, An aryl group that may have a substituent, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent. An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent An alkyl group which may have a group and an aryl group which may have a substituent are preferable. Examples of the substituent that can be introduced are the same as those in the general formula (a1).

Y represents an oxygen atom, a sulfur atom, or —N (R ^12a ) —. R ^12a has the same meaning as R ^{12a in} formula (a1), and preferred examples thereof are also the same.

In the general formula (a3), R ^9a is preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group is preferable because of high radical reactivity. . R ^10a and R ^11a are each independently a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl group which may have a substituent. An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, a substituent An arylamino group that may have, an alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, and the like, among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable because of high radical reactivity.

Here, examples of the substituent that can be introduced include those similar to those of the general formula (a1). Z represents an oxygen atom, a sulfur atom, -N (R ^13a )-, or an optionally substituted phenylene group. ^Examples of R ^13a include an alkyl group which may have a substituent. Among them, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

  The polymer binder having the crosslinkable group in the side chain not only functions as a film-forming agent for the photosensitive layer but also needs to be dissolved in a developer, preferably an alkali developer, so that it is soluble or swelled in alkaline water. It is preferable that the organic polymer be an organic polymer. Therefore, the polymer binder preferably has an alkali-soluble group such as a carboxyl group in the side chain in addition to the crosslinkable group.

Examples of the polymer binder include those described in JP-A-59-53836 and JP-A-59-71048, that is, a crosslinkable group such as an allyl group or a (meth) acryloyl group in the side chain. Examples thereof include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, and partially esterified maleic acid copolymer.
Also useful as the polymer binder are those obtained by adding a cyclic acid anhydride to an addition polymer having a crosslinkable group and a carboxyl group in the side chain, a polyurethane, an acidic cellulose derivative, and a hydroxyl group. .

  Among the above, the polymer binder contained in the photosensitive layer is more preferably a polyurethane resin having a crosslinkable group in the side chain and a (meth) acrylic resin having a crosslinkable group in the side chain.

  The polyurethane resin having a crosslinkable group in the side chain particularly preferably used in the present invention includes, for example, (i) a diisocyanate compound, (ii) a diol compound having at least one carboxyl group, and (iii) a diisocyanate compound having a crosslinkable group. If necessary, (iv) a diol compound having no carboxyl group can be obtained by polyaddition reaction.

  As the polymer binder, in addition to the polyurethane resin obtained by introducing a crosslinkable group into the side chain during polyurethane synthesis, a polymer having a carboxyl group as described in JP-A-2003-270775 is used. A polyurethane resin obtained by introducing a crosslinkable group by reaction can also be used. Specific examples of such a polyurethane resin are listed in paragraph Nos. 0050 to 0137 of JP-A-2007-57597, and the polyurethane resin described in the publication is preferably used in the present invention.

  In the present invention, JP-B-7-12004, JP-B-7-120041, JP-B-7-120042, JP-B-8-12424, JP-A-63-287944, JP-A-63-287947. Polyurethane resins described in JP-A-1-271741, JP-A-2001-109139, JP-A-2001-117217, JP-A-2001-312062, and JP-A-2003-131397 are also preferably used.

Next, the (meth) acrylic resin having a crosslinkable group in the side chain will be described in detail.
The (meth) acrylic resin having a crosslinkable group in the side chain used in the present invention is preferably a resin having a repeating unit represented by the following general formula (i) from the viewpoint of developability.
Hereinafter, the resin having the repeating unit represented by the general formula (i) is appropriately referred to as a specific (meth) acrylic resin and will be described in detail.

In the general formula (i), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents one or more selected from the group consisting of a single bond, a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom. Represents a linking group composed of atoms. A represents an oxygen atom or —NR ²³ represents —, and R ²³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. n2 represents an integer of 1 to 5.

R ²¹ in the general formula (i) represents a hydrogen atom or a methyl group, and a methyl group is particularly preferable.

The linking group represented by R ²² in the general formula (i) is composed of one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom. The number of atoms excluding substituents is preferably 2 to 82. Specifically, the number of atoms constituting the main skeleton of the linking group represented by R ²² is preferably 1 to 30, more preferably 3 to 25, and further preferably 4 to 20. Preferably, it is 5-10. The “main skeleton of the linking group” in the present invention refers to an atom or an atomic group used only for linking A and the terminal COOH in the general formula (i), and particularly when there are a plurality of linking paths. Refers to an atom or atomic group that constitutes a path with the smallest number of atoms used. Therefore, when a linking group has a ring structure, the number of atoms to be included differs depending on the linking site (for example, o-, m-, p-, etc.).

More specifically, alkylene, substituted alkylene, arylene, substituted arylene and the like can be mentioned, and a plurality of these divalent groups may be linked by an amide bond or an ester bond.
Examples of the linking group having a chain structure include ethylene and propylene. A structure in which these alkylenes are linked via an ester bond can also be exemplified as a preferable example.

Among these, the linking group represented by R ²² in the general formula (i) is preferably an (n + 1) -valent hydrocarbon group having an aliphatic cyclic structure having 3 to 30 carbon atoms. More specifically, a compound having an aliphatic cyclic structure such as cyclopropane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, dicyclohexyl, tercyclohexyl, norbornane and the like, which may be substituted one or more by any substituent. And (n + 1) valent hydrocarbon groups by removing (n + 1) hydrogen atoms on an arbitrary carbon atom constituting. R ²² preferably has 3 to 30 carbon atoms including a substituent.

One or more arbitrary carbon atoms of the compound constituting the aliphatic cyclic structure may be replaced with a heteroatom selected from a nitrogen atom, an oxygen atom, or a sulfur atom. In terms of printing durability, R ²² represents a condensed polycyclic aliphatic hydrocarbon, a bridged cyclic aliphatic hydrocarbon, a spiro aliphatic hydrocarbon, an aliphatic hydrocarbon ring assembly (a plurality of rings connected by a bond or a linking group). A (n + 1) valent hydrocarbon group having an aliphatic cyclic structure which may have a substituent of 5 to 30 carbon atoms containing two or more rings. . Also in this case, the carbon number includes the carbon atom of the substituent.

As the linking group represented by R ²² , those having 5 to 10 atoms constituting the main skeleton of the linking group are particularly preferable, and are structurally a chain structure, and an ester bond in the structure. And those having a cyclic structure as described above are preferred.

Examples of the substituent that can be introduced into the linking group represented by R ²² include a monovalent non-metallic atomic group other than hydrogen, such as a halogen atom (—F, —Br, —Cl, —I), hydroxyl group Group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N- Diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy Si group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N ′ An arylureido group, an N ′, N′-diarylureido group, an N′-alkyl-N′-arylureido group, an N-alkylureido group, an N-arylureido group, an N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′— Rualkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and its conjugate base group, Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, Alkylsulfini Group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO 3 _H) and its conjugated base group, alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, N- alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N- alkylsulfonylsulfamoyl group _(-SO 2 NH O ₂ (alkyl)) and its conjugated base group, N- aryl sulfonylsulfamoyl group _{(-SO 2 NHSO 2 (aryl)} ) and its conjugated base group, N- alkylsulfonylcarbamoyl group _(-CONHSO 2 _(alkyl)) And its conjugate base group, N-arylsulfonylcarbamoyl group (—CONHSO ₂ (aryl)) and its conjugate base group, alkoxysilyl group (—Si (Oalkyl) ₃ ), aryloxysilyl group (—Si (Oaryl) ₃ ) , Hydroxysilyl group (—Si (OH) ₃ ) and its conjugate base group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group, dialkylphosphono group (—PO ₃ (alkyl) ₂ ), diarylphosphono Group (—PO ₃ (aryl) ₂ ), alkylarylphosphono group (—PO ₃ ( alkyl) (aryl)), monoalkylphosphono group (—PO ₃ H (alkyl)) and its conjugate base group, monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group, phosphonooxy group ( -OPO ₃ H2) and its conjugated base group, a dialkyl phosphono group _{(-OPO 3 (alkyl) 2)} , diaryl phosphono group _{(-OPO 3 (aryl) 2)} , alkylaryl phosphono group (-OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group, monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group , Cyano group, nitro group, dialkylboryl group (—B (alkyl) ₂ ), diarylboryl group (—B ( aryl) ₂ ), alkylarylboryl group (-B (alkyl) (aryl)), dihydroxyboryl group (-B (OH) ₂ ) and its conjugate base group, alkylhydroxyboryl group (-B (alkyl) (OH)) ) And its conjugated base group, arylhydroxyboryl group (-B (aryl) (OH)) and its conjugated base group, aryl group, alkenyl group and alkynyl group.

  In the photomask material used in the present invention, depending on the design of the photosensitive layer, a substituent having a hydrogen atom capable of hydrogen bonding, particularly a substituent having an acid dissociation constant (pKa) smaller than that of a carboxylic acid. Is not preferred because it tends to lower the printing durability. On the other hand, hydrophobic substituents such as halogen atoms, hydrocarbon groups (alkyl groups, aryl groups, alkenyl groups, alkynyl groups), alkoxy groups, aryloxy groups and the like are more preferable because they tend to improve printing durability. When the cyclic structure is a monocyclic aliphatic hydrocarbon having 6 or less members such as cyclopentane or cyclohexane, it preferably has such a hydrophobic substituent. If possible, these substituents may be bonded to each other or with a substituted hydrocarbon group to form a ring, and the substituent may be further substituted.

When A in the general formula (i) is —NR ²³ —, R ²³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ²³ include an alkyl group, an aryl group, an alkenyl group, and an alkynyl group.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, sec-butyl group, 1 carbon number such as tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-norbornyl group Up to 10 linear, branched or cyclic alkyl groups.
Specific examples of the aryl group include carbon having one heteroatom selected from the group consisting of an aryl group having 1 to 10 carbon atoms such as a phenyl group, a naphthyl group, and an indenyl group, a nitrogen atom, an oxygen atom, and a sulfur atom. Examples include heteroaryl groups of 1 to 10, such as furyl, thienyl, pyrrolyl, pyridyl, and quinolyl groups.
Specific examples of the alkenyl group include those having 1 to 10 carbon atoms such as vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group and the like. A linear, branched, or cyclic alkenyl group is mentioned.
Specific examples of the alkynyl group include alkynyl groups having 1 to 10 carbon atoms such as ethynyl group, 1-propynyl group, 1-butynyl group, and 1-octynyl group. Examples of the substituent that R ²³ may have are the same as those described as the substituent that R ²² can introduce. The number of carbon atoms of R ²³ is 1 to 10 including the carbon number of the substituent.

  A in the general formula (i) is preferably an oxygen atom or —NH— because synthesis is easy.

  N2 in the general formula (i) represents an integer of 1 to 5, and is preferably 1 in terms of printing durability.

  Although the preferable specific example of the repeating unit represented by general formula (i) below is shown, this invention is not limited to these.

  The specific (meth) acrylic resin in the present invention is combined with the repeating unit represented by the general formula (i), the repeating unit having a crosslinkable group in the side chain, and, if necessary, other copolymer components. A copolymer is preferred. One type of repeating unit represented by general formula (i) may be contained in the specific (meth) acrylic resin, or two or more types may be contained. The total content of the repeating unit represented by the general formula (i) in the copolymer is appropriately determined depending on the structure, the design of the photopolymerizable composition, and the like, but preferably with respect to the total molar amount of the resin component, 1 to 99 mol%, more preferably 5 to 40 mol%, still more preferably 5 to 20 mol%.

  Examples of the polymer having an ethylenically unsaturated bond which is a crosslinkable group in the side chain include an ester or amide polymer of acrylic acid or methacrylic acid, and an ester or amide residue (R of -COOR or -CONHR ) May have a polymer having an ethylenically unsaturated bond.

Examples of the residue (the R) having an ethylenically unsaturated _{bond, - (CH 2) n CR} 1 = CR 2 R 3, - (CH 2 O) n CH 2 CR 1 = CR 2 R 3, - _{(CH 2 CH 2 O) n} CH 2 CR 1 = CR 2 R 3, - (CH 2) n NH-CO-O-CH 2 CR 1 = CR 2 R 3, - (CH 2) n -O-CO —CR ¹ ═CR ² R ³ and — (CH ₂ CH ₂ O) ₂ —X (wherein R ^{1 to} R ³ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, Represents an alkoxy group or an aryloxy group, and R ¹ and R ² or R ³ may combine with each other to form a ring, n represents an integer of 1 to 10. X represents dicyclopentadienyl. Represents a residue).
Specific examples of the ester _{residue, -CH 2 CH = CH 2,} ( described in JP Kokoku _{7-21633.) - CH 2 CH 2} O-CH 2 CH = CH 2, -CH 2 C _{(CH 3) = CH 2,} -CH 2 CH = CH-C 6 H 5, -CH 2 CH 2 OCOCH = CH-C 6 H 5, -CH 2 CH 2 -NHCOO-CH 2 CH = CH 2 and - CH ₂ CH ₂ O—X (wherein X represents a dicyclopentadienyl residue).
Specific examples of the amide residue include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ —Y (wherein Y represents a cyclohexene residue), —CH ₂ CH ₂ —OCO—CH═CH _2. Is mentioned.

  The binder polymer having crosslinkability, for example, has a free radical (polymerization initiation radical or a growth radical in the polymerization process of the polymerizable compound) added to the crosslinkable functional group, and the polymerization chain of the polymerizable compound is formed directly between the polymers. Through addition polymerization, a cross-link is formed between the polymer molecules and cured. Alternatively, atoms in the polymer (eg, hydrogen atoms on carbon atoms adjacent to the functional bridging group) are abstracted by free radicals to form polymer radicals that are bonded together, thereby causing cross-linking between polymer molecules. Forms and cures.

  The content of the crosslinkable group in the binder polymer (content of the unsaturated double bond capable of radical polymerization by iodine titration) is preferably 0.1 mmol to 10.0 mmol, more preferably 1.0 mmol, per 1 g of the binder polymer. ˜7.0 mmol, most preferably 2.0 mmol to 5.5 mmol. Within this range, better sensitivity and better storage stability can be obtained.

  As other copolymerization components, conventionally known monomers can be used without limitation as long as they are radically polymerizable monomers. Specific examples include monomers described in “Polymer Data Handbook—Basic Edition” (Edition of Polymer Society, Bafukan, 1986). One type of such copolymerization component may be used, or two or more types may be used in combination.

The amount of the polymer binder having a crosslinkable group in the photosensitive layer can be appropriately determined, but is usually 10 to 90% by mass with respect to the total mass of nonvolatile components in the photosensitive layer, preferably Is in the range of 20-80% by weight, more preferably 30-70% by weight.
Moreover, it is preferable to make the polymer binder which has a photopolymerizable ethylenically unsaturated bond containing compound and a crosslinkable group into the range of 1 / 9-9 / 1 by mass ratio. A more preferable range is 2/8 to 8/2, still more preferably 3/7 to 7/3.

As the polymer binder, one or more other resins may be used in combination with the polymer binder having a crosslinkable group.
The resin used in combination is generally 50% by mass or less, preferably 30% by mass or less, based on the mass of the polymer binder having a crosslinkable group.

  The molecular weight of the polymer binder in the present invention is appropriately determined from the viewpoint of image formability and printing durability. A preferred weight average molecular weight is in the range of 2,000 to 1,000,000, more preferably 5,000 to 500,000, and still more preferably 10,000 to 200,000.

  The polymer binder used in the present invention may be used alone or in combination of two or more. Further, one or more other binder polymers having no crosslinkable group may be used in combination as a mixture. As the binder polymer that can be used in combination, conventionally known alkali-soluble or swellable binders can be used without limitation. Specifically, acrylic main chain binders, urethane binders, and the like often used in the industry are preferably used.

  The total amount of the polymer binder in the photosensitive layer and the binder polymer that may be used in combination can be determined as appropriate, but is usually 10 to 90% by mass with respect to the total mass of nonvolatile components in the photosensitive layer. Preferably, it is 20-80 mass%, More preferably, it is the range of 30-70 mass%.

  In addition to the above, an alkali-insoluble polymer such as an epoxy resin or a melamine resin can be added to the photosensitive layer within a range that does not adversely affect developability and the like in order to improve the strength. The solid content in the photosensitive layer solid content of the polymer is preferably 0.2 to 50% by mass, more preferably 1 to 30% by weight. In this range, the effect of improving the cured film strength and the developability become better.

<Ethylenically unsaturated bond-containing compound>
The ethylenically unsaturated bond-containing compound is a compound having at least one ethylenically unsaturated bond, and when the photopolymerizable composition is irradiated with actinic rays, it undergoes addition polymerization by the action of a photopolymerization initiator, Contributes to crosslinking and curing.

  The ethylenically unsaturated bond-containing compound can be arbitrarily selected from, for example, compounds having at least 1, preferably 2 or more, more preferably 2 to 6 terminal ethylenically unsaturated bonds. It has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

Examples of the ethylenically unsaturated bond-containing compound include esters of unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and aliphatic polyhydric alcohol compounds. Examples include amides of saturated carboxylic acids and aliphatic polyvalent amine compounds.
Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrelane , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester Examples include acrylate oligomers.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [ - (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis - [p-(methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,5-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Furthermore, the mixture of the above-mentioned ester monomer can also be mentioned.
Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like.

  As another example, a polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-B-48-41708 contains a hydroxyl group represented by the following general formula (m). Examples thereof include a vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer is added.

_{CH 2 = C (R) COOCH} 2 CH (R ') OH (m)
(However, R and R ′ each independently represent H or CH _3. )

  Also, urethane acrylates as described in JP-A-51-37193 and JP-B-2-32293, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, as described in each publication. Furthermore, Journal of Japan Adhesion Association Vo 1.20, No. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  In addition, content of these ethylenically unsaturated bond containing compounds is 5-80 mass% normally with respect to the total mass of a photosensitive layer, Preferably it is the range of 30-70 mass%.

<Photopolymerization initiation system>
Depending on the wavelength of the light source used, various photoinitiators known in patents, literatures, etc., or sensitizing dyes and initiator compounds are used as the photopolymerization initiator (agent) to be contained in the photosensitive layer of the photomask material. And a combination system (photoinitiation system) can be appropriately selected and used. Hereinafter, the photoinitiating system suitably applied to the present invention will be described in detail, but the present invention is not limited thereto.

-Initiator compound-
The initiator compound applicable to the present invention will be described.
The initiator compound in the present invention refers to a compound that generates radicals, acids, or bases as starting seeds for initiating and advancing the polymerization (crosslinking) reaction of coexisting addition polymerizable compounds by the application of energy. Hereinafter, radicals, acids, and bases generated in this way are simply referred to as active species.
As one embodiment in which the sensitizing dye and the initiator compound are used in combination, these may be used as a single compound by an appropriate chemical method (such as linking the sensitizing dye and the initiator compound by chemical bonding). Is possible. Such a technical idea is disclosed in, for example, Japanese Patent No. 2720195.

  Usually, many of these initiator compounds are considered to generate active species through the following initial chemical processes (1) to (3). (1) Reductive decomposition of the initiator compound based on the electron transfer reaction from the electronically excited state of the sensitizing dye to the initiator compound, (2) Electron transfer from the initiator compound to the electronically excited state of the sensitizing dye (3) decomposition of the initiator compound from the electronically excited state based on energy transfer from the electronically excited state of the sensitizing dye to the initiator compound. Although it is often ambiguous as to which type (1) to (3) each individual initiator compound belongs, the major feature of the specific sensitizing dye in the present invention is any of these types. Even when combined with an initiator compound, the present invention has a very high sensitizing effect.

  Specific initiator compounds known to those skilled in the art can be used without limitation. Specifically, for example, Bruce M. Monroe et al., Chemical Revue, 93, 435 (1993) and RSD Davidson, Journal of Photochemistry and biology A: Chemistry, 73.81 (1993); JPFaussier, "Photoinitiated Polymerization-Theory and Applications ": Rapra Review vol. 9, Report, Rapra Technology (1998); M. Tsunooka et al., Prog. Polym. Sci., 21, 1 (1996). In addition, as other compound groups having the functions (1) and (2), FDSaeva, Topics in Current Chemistry, 156, 59 (1990); GGMaslak, Topics in Current Chemistry, 168, 1 ( 1993); HBShuster et al, JACS, 112, 6329 (1990); IDFEaton et al, JACS, 102, 3298 (1980) etc., resulting in oxidative or reductive bond cleavage Compound groups are also known.

  The following are specific examples of preferred initiator compounds: (a) those that are reduced to cause bond cleavage to produce active species, (b) those that can be oxidized to cause bond cleavage to produce active species, and ( c) Others are classified and explained, but there are many cases where there is no general explanation as to which individual compounds belong to them, and the present invention is not limited to the description of these reaction mechanisms.

(A) Compound that is reduced to generate bond by cleaving an active species Compound having carbon-halogen bond: It is considered that a carbon-halogen bond is reductively cleaved to generate an active species (for example, Polymer Preprints, Jpn., 41 (3) 542 (1992)). As the active species, radicals and acids can be generated. Specifically, for example, in addition to halomethyl-s-triazines, halo which can be easily synthesized by those skilled in the art by the synthesis method described in MPHutt, EFElslager and LMMerbel, Journal of Heterocyclic Chemistry, 7, 511 (1970). Methyl oxadiazoles and the compounds described in German Patent Nos. 2641100, 3333450, 3021590, and 3021599 can be preferably used.

  Compound having nitrogen-nitrogen bond or nitrogen-containing heterocycle-nitrogen-containing heterocycle bond: reductive bond cleavage (for example, described in J.Pys.Chem., 96, 207 (1992)) . Specifically, hexaarylbiimidazoles and the like are preferably used. The active species produced are lophine radicals, which together with hydrogen donors as necessary, initiate radical chain reactions and are also known to form images using oxidation reactions with lophine radicals (J. Imaging Sci., 30 , 215 (1986)).

  Compound having oxygen-oxygen bond: It is considered that an oxygen-oxygen bond is reductively cleaved to generate an active radical (for example, described in Polym. Adv. Technol., 1, 287 (1990)). Specifically, for example, organic peroxides are preferably used. A radical can be generated as an active species.

  Onium compounds: It is considered that carbon-hetero bonds and oxygen-nitrogen bonds are reductively cleaved to generate active species (for example, as described in J. Photopolym. Sci. Technol., 3, 149 (1990)). ) Specifically, for example, iodonium salts described in European Patent No. 104143, US Pat. No. 4,837,124, JP-A-2-150848, JP-A-2-96514, European Patents 370693 and 233567. Sulfonium salts described in U.S. Pat. Nos. 297443, 297442, 279210, 422570, U.S. Pat.Nos. 3,902,144, 4,933,377, 4760013, 4,734,444 and 2,833,827, Diazonium salts (such as benzenediazonium which may have a substituent), diazonium salt resins (formaldehyde resin of diazodiphenylamine), N-alkoxypyridinium salts and the like (for example, US Pat. No. 4,743,528, Kaisho 63-13834 No. 63-142345, JP-A 63-142346, JP-B 46-42363, etc., specifically 1-methoxy-4-phenylpyridinium tetrafluoroborate, etc. Further, compounds described in JP-B Nos. 52-147277, 52-14278, and 52-14279 are preferably used. Generates radicals and acids as active species.

Active esters: nitrobenzyl esters of sulfonic acid or carboxylic acid, esters of sulfonic acid or carboxylic acid with N-hydroxy compounds (N-hydroxyphthalimide, oxime, etc.), sulfonic acid esters of pyrogallol, naphthoquinone diazide-4 -Sulfonates can be reductively decomposed. As the active species, radicals and acids can be generated. Specific examples of sulfonic acid esters include European Patent Nos. 0290750, 046083, 156153, 271851, 0388343, U.S. Pat. Nos. 3,901,710 and 4,181,531, 60-198538, JP-A-53-1333022, nitrobenzester compounds, European Patent No. 0199672, No. 84515, No. 199672, No. 0441115, No. 0101122, U.S. Pat. No. 4,618,564, Nos. 4371605, 4431774, JP-A 64-18143, JP-A-2-245756, JP-A-4-365048, iminosulfonate compounds, JP-B-62-2223, Kosho 63-14340, JP 59-17483 Issue JP-like compounds described are listed, further, include, for example, compounds as shown below. (In the formula, Ar represents an aromatic group or an aliphatic group which may be substituted.)

  Ferrocene and iron arene complexes: An active radical can be reductively generated. Specifically, for example, they are disclosed in JP-A-1-304453 and JP-A-1-152109.

  Moreover, it is also possible to produce | generate a base as an active species, for example, the following compound groups are known. In the formula, R represents an aliphatic group or an aromatic group which may be substituted.

  Disulfones: Reducing S—S bond reductively and generating an acid. For example, diphenyl disulfones as described in JP-A No. 61-166544 are known.

(B) Oxidized to generate an active species by cleaving a bond Alkylate complex: It is considered that a carbon-hetero bond is oxidatively cleaved to generate an active radical (for example, J. Am. Chem. Soc ., 112, 6329 (1990)). Specifically, for example, triarylalkyl borates are preferably used.

  Alkylamine compound: It is considered that the C—X bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical (for example, J. Am. Chem. Soc., 116, 4211 (1994)). be written). X is preferably a hydrogen atom, a carboxyl group, a trimethylsilyl group, a benzyl group or the like. Specific examples include ethanolamines, N-phenylglycines, N-trimethylsilylmethylanilines, and the like.

  Sulfur-containing and tin-containing compounds: Compounds in which the nitrogen atoms of the above-described amines are replaced with sulfur atoms and tin atoms can generate active radicals by the same action. Further, a compound having an SS bond is also known to be sensitized by SS cleavage.

  α-Substituted methylcarbonyl compound: An active radical can be generated by oxidative cleavage of the carbonyl-α carbon bond. Moreover, what converted carbonyl into the oxime ether also shows the same effect | action. Specifically, 2-alkyl-1- [4- (alkylthio) phenyl] -2-morpholinopronone-1 and these and a hydroxylamine were reacted, and then N—OH was etherified. Mention may be made of oxime ethers.

  Sulfinic acid salts: An active radical can be reductively generated. Specific examples include sodium arylsulfinate.

(C) Others Although the sensitization mechanism is not clear, many of them can function as initiator compounds. Examples thereof include organometallic compounds such as titanocene and ferrocene, aromatic ketones, acylphosphine, bisacylphosphine and the like, and active species can generate radicals and acids.

  Hereinafter, among the initiator compounds that can be used in the present invention, preferred compounds particularly excellent in sensitivity and stability are specifically exemplified.

(1) Halomethyltriazines Examples include compounds represented by the following formula [II]. Excellent radical generation and acid generation ability.

In the formula [II], X represents a halogen atom. Y ¹ represents —CX ′ ₃ , —NH ₂ , —NHR ¹ ′, —NR ¹ ′ ₂ , —OR ¹ ′. Here, R ¹ ′ represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. X ′ represents a halogen atom. R ¹ represents —CX ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group.

  Specific examples of such compounds include, for example, compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), such as 2-phenyl-4,6-bis (trichloromethyl)- S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2 -(P-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl)- S- Triazine, 2- (α, α, β- trichloroethyl) -4,6-bis (trichloromethyl) -S- triazine. In addition, compounds described in GB 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine Compounds described in JP-A-53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy- Naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-tri Lormethyl-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (acenaphtho-5-yl) -4,6-bis Examples include compounds described in German Patent No. 3337024, such as -trichloromethyl-S-triazine, and the like.

  Further, compounds described in J. Org. Chem., 29, 1527 (1964) by FC Schaefer et al., For example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris (Tribromomethyl) -S-triazine, 2,4,6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl And -6-trichloromethyl-S-triazine.

  Further, compounds described in JP-A No. 62-58241, for example, the following compounds can be mentioned.

Further, compounds described in JP-A-5-281728, for example, the following compounds can be mentioned.

(2) Titanocenes Any titanocene compound that is particularly preferably used as an initiator compound may be any titanocene compound that can generate an active species when irradiated with light in the presence of the sensitizing dye. Well, for example, JP-A-59-152396, JP-A-61-151197, JP-A-63-41483, JP-A-63-41484, JP-A-2-249, JP-A-2-291, Known compounds described in JP-A-3-27393, JP-A-3-12403, and JP-A-6-41170 can be appropriately selected and used.

  More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5 , 6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2 , 4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- Bis-2, 3, , 6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6- And difluoro-3- (pyr-1-yl) phenyl) titanium.

(3) Borate salt compounds Borate salts represented by the following formula [III] are excellent in radical generating ability.

In the formula [III], R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be the same or different from each other, and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl. A group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group, wherein R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ are bonded to each other to form a cyclic structure. Also good. However, at least one of R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ is a substituted or unsubstituted alkyl group. Z ⁺ represents an alkali metal cation or a quaternary ammonium cation.

The alkyl groups of R ^{51 to} R ⁵⁴ include straight chain, branched, and cyclic groups, and those having 1 to 18 carbon atoms are preferable. Specifically, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like are included. Examples of the substituted alkyl group include the above alkyl groups, halogen atoms (for example, -Cl, -Br, etc.), cyano groups, nitro groups, aryl groups (preferably phenyl groups), hydroxy groups, the following groups,

(Here, R ⁵⁵ and R ⁵⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group), —COOR ⁵⁷ (where R ⁵⁷ is a hydrogen atom, 1 carbon atom) -14 represents an alkyl group or aryl group), -COOR ⁵⁸ or -OR ⁵⁹ (wherein R ⁵⁸ represents an alkyl group having 1 to 14 carbon atoms or an aryl group) as a substituent. included.

Examples of the aryl group of R ^{51 to} R ⁵⁴ include 1 to 3 ring aryl groups such as a phenyl group and a naphthyl group, and examples of the substituted aryl group include the substitution of the above substituted alkyl group with the above aryl group. And those having an alkyl group having 1 to 14 carbon atoms.

Examples of the alkenyl group represented by R ^{51 to} R ⁵⁴ include linear, branched, and cyclic groups having 2 to 18 carbon atoms, and examples of the substituent of the substituted alkenyl group include the substituents of the substituted alkyl group. Is included.

Examples of the alkynyl group of R ^{51 to} R ⁵⁴ include linear or branched groups having 2 to 28 carbon atoms, and examples of the substituent of the substituted alkynyl group include those listed as the substituent of the substituted alkyl group. included.

In addition, examples of the heterocyclic group of R ^{51 to} R ⁵⁴ include a 5- or more-membered heterocyclic group containing at least one of N, S, and O, preferably a 5- to 7-membered heterocyclic group. May contain a condensed ring. Furthermore, you may have what was mentioned as a substituent of the above-mentioned substituted aryl group as a substituent.

  Specific examples of the compound represented by the formula [III] include compounds described in the specifications of U.S. Pat. Nos. 3,567,453 and 4,434,891, European Patent Nos. 109772 and 109773, and those shown below. Can be mentioned.

(4) Hexaarylbiimidazoles Excellent in stability and capable of generating highly sensitive radicals. Specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5 '-Tetraphenylbiimidazole, 2,2'-bis (o-trifluoromethyl Eniru) -4,4 ', 5,5'-tetraphenyl biimidazole.

(5) 15 (5B), 16 (6B), and 17 (7B) group elements of the periodic table of onium salt compounds, specifically, N, P, As, Sb, Bi, O, S, Se, Te, I The onium compound is an initiator compound with excellent sensitivity. Particularly, iodonium salts and sulfonium salts, particularly diaryliodonium and triarylsulfonium salt compounds are extremely excellent in terms of both sensitivity and storage stability. Acids and / or radicals can be generated, and these can be used properly by appropriately selecting the use conditions according to the purpose. Specific examples include the following compounds.

(6) Organic peroxide When an organic peroxide type initiator compound is used, radicals can be generated as active species with very high sensitivity.

The organic peroxide that can be used in the present invention includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples thereof include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3, 3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxide Oxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paraffin hydroperoxide, 2,5-dimethylhexane 2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, bis (t-butylperoxide Oxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, acetyl peroxide , Isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, Meta-toluoyl peroxide, diisopropyl par Xydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, t-butyl Peroxyacetate, t-butylperoxypivalate, t-butylperoxyneodecanoate, t-butylperoxyoctanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t- Butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl maleate, t -Butyl peroxyisopropyl carbonate, 3 , 3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3 ′, 4, 4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t-octylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (cumylperoxy) Carbonyl) benzophenone, 3,3 ′, 4,4′-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogendiphthalate), carbonyldi (t-hexylperoxydihydrogen) Diphthalate).

Among these, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3 , 3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t-octylperoxycarbonyl) benzophenone, 3,3 ′, 4,4 ′ Peroxide esters such as tetra (cumylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthalate are preferred. .
Preferable examples of the initiator compound include titanocene compounds, triazine compounds, and hexaarylbiimidazole compounds, and particularly preferable initiator compounds include hexaarylbiimidazole compounds.

  As with the above-described specific sensitizing dye, the initiator compound described above can be further subjected to various chemical modifications for improving the characteristics of the photosensitive layer. For example, binding with specific sensitizing dyes, addition polymerizable unsaturated compounds and other initiator compound parts, introduction of hydrophilic sites, compatibility improvement, introduction of substituents to suppress crystal precipitation, substitution to improve adhesion Methods such as group introduction and polymerization can be used.

  The usage method of these initiator compounds can be arbitrarily set arbitrarily according to the performance design of the light-sensitive material, as in the case of the sensitizing dye described above. For example, the compatibility with the photosensitive layer can be increased by using two or more kinds in combination.

  The total content of the initiator compound in the photosensitive layer is 0.1 to 50% by mass, preferably 0.5 to 30% by mass, and particularly preferably 1 to 20% by mass in the total solid content constituting the photosensitive layer. It is.

-Suitable sensitizing dye-
One preferred embodiment of the sensitizing dye that can be applied to the present invention is a sensitizing dye represented by the following general formula (B) (hereinafter, referred to as “specific sensitizing dye” as appropriate).

In general formula (B), R ¹ and R ³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group. X represents -N ^(R 6 R ^7). R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵ is aliphatic with R ¹ , R ² , R ³ or R ⁴ . Or they can be joined to form an aromatic ring. Z represents a divalent nonmetallic atomic group necessary for forming an acidic nucleus in cooperation with an adjacent atom.

  One of the characteristics of the specific sensitizing dye is that it has particularly excellent absorption characteristics in the wavelength range of 350 nm to 450 nm. Furthermore, the specific sensitizing dye efficiently causes decomposition of various initiator compounds contained in the photosensitive composition and exhibits very high photosensitivity.

  In general, the sensitization mechanism of a photoinitiating system composed of a sensitizing dye / initiator compound is (a) reductive decomposition of an initiator compound based on an electron transfer reaction from an electronically excited state of the sensitizing dye to the initiator compound, ( b) Oxidative decomposition of initiator compound based on electron transfer from initiator compound to electronically excited state of sensitizing dye, (c) Initiation based on energy transfer from electronically excited state of sensitizing dye to initiator compound Although a route such as decomposition of the agent compound from an electronically excited state is known, the specific sensitizing dye causes any of these types of sensitization reactions with excellent efficiency.

The present inventors have found that the high sensitivity and excellent storage stability exhibited by the photomask material of the present invention are based on the fact that the photosensitive layer contains a specific sensitizing dye as an essential component. . The mechanism of action is not clear, but is presumed as follows.
First, as a factor that the specific sensitizing dye contributes to high sensitivity, the specific sensitizing dye exhibits a high-intensity emission (fluorescence and / or phosphorescence) spectrum. Since the dye-sensitive dye has a relatively long lifetime in the excited state, it is presumed that it acts on the efficiency of the reaction with the initiator compound. As another possibility, the molecular structure of the specific sensitizing dye may contribute to the efficiency of the initial process of the sensitization reaction (electron transfer, etc.) and the efficiency of the subsequent reaction leading to the decomposition of the initiator compound. There is also sex.
Next, as a factor that the specific sensitizing dye contributes to the improvement in storage stability, the specific sensitizing dye has less dye aggregation, association, etc. under natural aging conditions, so that a decrease in sensitizing efficiency is suppressed. It is presumed that the fact that it is a thing has an influence. The sensitizing dye plays an important role in the photoinitiated reaction, and aggregation or association in the photosensitive composition greatly affects the decrease in the amount of radicals generated by exposure (decrease in sensitivity), that is, the decrease in storage stability. Therefore, it is considered that the specific sensitizing dye with little dye aggregation, association, etc. greatly contributes to the improvement of the storage stability of the photomask material.

Hereinafter, the sensitizing dye (specific sensitizing dye) represented by the general formula (B) will be described in detail.
In the general formula (B), Z represents a divalent nonmetallic atomic group necessary for forming an acidic nucleus, and preferably represents a 5-membered or 6-membered ring structure containing a hetero atom.

  Here, “acidic nucleus” means “The Theory of the Photographic Process” edited by James, 4th edition, Macmillan Publishing Co., Ltd., 1977, p. 198. Is defined.

Specific examples of the acidic nucleus in the general formula (B) include a 1,3-dicarbonyl nucleus (for example, 1,3-indandione, 1,3-dioxane-4,6-dione, etc.), a pyrazolinone nucleus (for example, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazolyl) -3-methyl-2-pyrazolin-5-one, etc.), Isoxazolinone nucleus (for example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one), oxindole nucleus (for example, 1-alkyl-2,3- Dihydro-2-oxindole and the like), 2-thio-2,4-thiazolidinedione nucleus (for example, rhodanine and N-substituted derivatives thereof such as 3-methylrhodanine, 3-ethylrhodani 3-phenylrhodanine, 3-allylrhodanine, 3-benzylrhodanine, 3-carboxymethylrhodanine, 3-carboxyethylrhodanine, 3-methoxycarbonylmethylrhodanine, 3-hydroxyethylrhodanine, 3- Morpholinoethyl rhodanine, etc.), 2-thio-2,4-oxazolidinedione nucleus, 1,3-oxazolidine 2,4-dione nucleus (for example, 3-ethyl-1,3-oxazolidine 2,4-dione, etc.) , A thianaphthenone nucleus (for example, 3 (2H) -thianaphthenone, 3 (2H) -thianoftenone-1,1-dioxide, etc.), a 2-thio-2,5-thiazolidinedione nucleus (for example, 3-ethyl-2-thio- 2,5-thiazolidinedione, etc.), 2,4-thiazolidinedione nucleus (for example, 2,4-thiazolidinedione) 3-ethyl-4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, etc.), thiazolidinone nucleus (for example, 4-thiazolidinone, 3-ethyl-4-thiazolidinone, 2-ethylmercapto-4-thiazolidinone, 2- Methylphenylamino-4-thiazolidinone, etc.), 2-imino-2-oxazolin-4-one nucleus (ie pseudohydantoin nucleus), 2,4-imidazolidinedione nucleus (ie hydantoin nucleus such as 2,4- Imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, 1,3-diethyl-2,4-imidazolidinedione, etc.), 2-thio-2,4-imidazolidinedione nucleus (ie, thiohydantoin nucleus) For example, 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-i Imidazolidinedione, 1,3-diethyl-2-thio-2,4-imidazolidinedione, etc.), imidazolin-5-one nucleus (for example, 2-propylmercapto-2-imidazolin-5-one, etc.), furan Examples include a -5-one nucleus, a thioindoxyl nucleus (for example, 5-methylthioindoxyl), a 2-imino-2,4-oxazolidinedione nucleus, and the like.
These acidic nuclei may further have a substituent. Preferable substituents that can be introduced into the acidic nucleus include substituents having unsaturated bonds such as alkenyl groups, aromatic groups, and aromatic heterocyclic residues.

  Preferable acidic nucleus in the general formula (B) includes a 2-thio-2,4-oxazolidinedione nucleus, a 1,3-oxazolidine 2,4-dione nucleus, and a 2-imino-2,4-oxazolidinedione nucleus. More preferred are a 1,3-oxazolidine-2,4-dione nucleus and a 2-imino-2,4-oxazolidinedione nucleus.

In the general formula (B), the monovalent nonmetallic atomic group represented by R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ or R ⁷ is a substituted or unsubstituted alkyl group, substituted or unsubstituted. Of the aryl group and a substituted or unsubstituted alkoxy group.

In the general formula (B), examples of the alkyl group represented by R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ or R ⁷ are linear or branched having 1 to 20 carbon atoms. And a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and an undecyl group. , Dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group , 2-methylhexyl group, cyclohexyl group, cyclopentyl group, and 2-norbornyl group. Among these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

In the general formula (B), when the alkyl group represented by R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ or R ⁷ is a substituted alkyl group, the substituent is a monovalent group other than hydrogen. Examples include groups composed of non-metallic atomic groups. Preferred examples of the substituent that the substituted alkyl group has include a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, and an alkyldithio group. , Aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyl Oxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group , Arylsulfoxy group, acyloxy group, acyl Thio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-aryl Ureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-aryl Ureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-al Luureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonyl Amino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkyl Carbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, Arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N— Dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N - dialkyl sulfamoyl group, N- aryl sulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group, a phosphono group (-PO ₃ H ₂₎ and its conjugate base group (hereinafter, referred to as phosphonato group), dialkylphosphono group (-PO ₃ (alkyl) _2), Ariruhosuhono group (a -PO ₃ (aryl) _2), alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugate base Group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H _2). ) And its conjugated base group (hereinafter referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy Group (—OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its A conjugated base group (hereinafter referred to as an alkylphosphonatoxy group), a monoarylphosphonooxy group (—OPO ₃ H (aryl)) and a conjugated base group (hereinafter referred to as an arylphosphonatoxy group), a cyano group, Examples thereof include a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, and a silyl group. Specific examples of the alkyl group in these substituents include the aforementioned alkyl groups, which may further have a substituent.

In the general formula (B), specific examples of the aryl group that the substituted alkyl group represented by R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ or R ⁷ has as a substituent include a phenyl group and a biphenyl group. , Naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoy Roxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenyl Carbamoy Phenyl group include a phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, a phosphate Hona preparative phenyl group.

In the general formula (B), the substituted aryl group represented by R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ or R ⁷ has a nitrogen, oxygen, or sulfur atom as a heteroaryl group as a substituent. Examples include groups derived from monocyclic or polycyclic aromatic rings containing at least one. Particularly preferred as examples of heteroaryl rings in heteroaryl groups are, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine , Indolizine, isoindolizine, indoir, indazole, purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthroline, phthalazine, phenalazine, phenoxazine, Examples include furazane, phenoxazine, and the like, which may be further benzo-fused and may have a substituent.

In the general formula (B), examples of the alkenyl group which the substituted alkyl group represented by R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ or R ⁷ has as a substituent include a vinyl group and 1-propenyl. Group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like, and examples of the alkynyl group include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. It is done.

In the general formula ^{(B), R 1, R} 2, R 4, R 5, substituted alkyl group represented by ^{R 6} or ^{R 7,} as G ¹ in the acyl group (G ¹ CO-) having as a substituent , Hydrogen, and the above alkyl groups and aryl groups. Among these substituents, even more preferable are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-arylsulfur Amoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatoxy group, an aryl group, an alkenyl group, and an alkylidene group (such as a methylene group).

In the general formula (B), the substituted alkyl group represented by R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ or R ⁷ has an alkylene group as the substituent having 1 to 20 carbon atoms as described above. Examples include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group, preferably a straight chain having 1 to 12 carbon atoms, and 3 to 12 carbon atoms. And a branched alkylene group having from 5 to 10 carbon atoms.

Specific examples of preferred substituted alkyl groups as R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ or R ⁷ obtained by combining the above substituents and alkylene groups include chloromethyl group, bromomethyl group, 2 -Chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, tolylthiomethyl, ethylaminoethyl, diethylaminopropyl, morpholinopropyl, acetyl Oxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxyl Propyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatopropyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl Group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphenol Suphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1 -Phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, A 3-butynyl group etc. can be mentioned.

Specific examples of preferred aryl groups as R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ or R ^{7 in the} general formula (B) include those in which 1 to 3 benzene rings form a condensed ring, A benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group or a naphthyl group is more preferable.

In the general formula (B), specific examples of the preferable substituted aryl group represented by R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ or R ⁷ include substitution on the ring-forming carbon atom of the aryl group. As the group, a group having a monovalent nonmetallic atomic group (other than a hydrogen atom) is used. Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl Methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, Examples include 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

In general formula (B), preferred alkoxy groups for R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ or R ⁷ include C 1-15 alkoxy groups, and specific examples thereof include methoxy Group, ethoxy group and the like.

More preferable examples of R ¹ and R ³ in the general formula (B) include a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkoxy group. More preferable examples of R ¹ and R ³ include an optionally substituted alkyl group having 1 to 15 carbon atoms or an optionally substituted alkoxy group having 1 to 15 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a methoxy group, and an ethoxy group can be mentioned. It is particularly preferable that both R ¹ and R ³ are a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxy group.
A more preferable example of R ⁶ and R ⁷ in the general formula (B) is a substituted or unsubstituted alkyl group, that is, X in the general formula (B) is a dialkylamino group. More preferable examples of R ⁶ and R ⁷ are alkyl groups having 2 to 15 carbon atoms which may have a substituent, and specific examples include an ethyl group and a butyl group.
The reason why these substituents are suitable as R ¹ , R ³ , R ⁶ and R ⁷ in the general formula (B) is not clear, but by having such substituents, electronic excitation caused by light absorption Since the interaction between the state and the initiator compound is particularly large, the efficiency of generating radicals, acids or bases of the initiator compound is improved (sensitivity improving effect), and since there is a substituent at the ortho position of the aromatic ring, It is conceivable that the substituent X has a twisted structure and the sensitizing dyes hardly aggregate with each other and aggregation in the photosensitive layer is suppressed (storage stability improving effect).

Further, as a more preferable examples of R ⁴ in the general formula (B), an alkyl group having carbon atoms of 1 to 15 which may have a substituent, and an alkoxy group having 1 to 15 carbon atoms.

  Among the specific sensitizing dyes, the sensitizing dyes having the structures represented by the following general formulas (B1) to (B7) have a high sensitizing ability and also have excellent storage stability. This is particularly preferable because it gives a product. Among these, as the specific sensitizing dye, the sensitizing dye represented by the general formula (B1) is most preferable.

In general formulas (B1) to (B7), X ^{1 to} X ⁴ and Y each independently represent an oxygen atom, a sulfur atom, or NR ²¹ , and R ¹ and R ³ each independently represent a hydrogen atom or Represents a monovalent nonmetallic atomic group. X represents -N ^(R 6 R ^7). R ² , R ^{4 to} R ²⁰ each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and R ⁵ is aliphatic or aromatic with R ¹ , R ² , R ³ or R ⁴ . Can be linked to form a ring. Here, in the general formulas B1) to (B7), the monovalent nonmetallic atomic group represented by R ^{1 to} R ²⁰ has the same meaning as the monovalent nonmetallic atomic group in the general formula (B), The preferable range is also the same. Further, X ¹ is preferably an oxygen atom. Y is preferably NR ²¹ , R ²¹ represents a hydrogen atom or a monovalent nonmetallic atomic group, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

  Although the preferable specific example (Exemplary compound D-1-Exemplified compound D-32) of a specific sensitizing dye is shown below, this invention is not limited to these.

  A method for synthesizing a specific sensitizing dye will be described. The specific sensitizing dye can be synthesized, for example, by a condensation reaction between an acidic nucleus having an active methylene group and a substituted or unsubstituted aromatic ring or heterocyclic ring. Japanese Patent Publication No. 59-28329 can be referred to for this synthesis method. As one of the methods for synthesizing a specific sensitizing dye, for example, as shown in the following reaction formula (a), a condensation reaction of an acidic nucleus compound and a basic nucleus material having an aldehyde group or a carbonyl group on the heterocycle is performed. Examples of the synthesis method to be used. The condensation reaction is carried out in the presence of a base as necessary. As the base, generally used ones such as amines, pyridines (trialkylamine, dimethylaminopyridine, diazabicycloundecene DBU, etc.), metal amides (lithium diisopropylamide, etc.), metal alkoxides ( Sodium methoxide, potassium-t-butoxide, etc.) and metal hydrides (sodium hydride, potassium hydride, etc.) can be used without limitation.

  Regarding the specific sensitizing dye, various chemical modifications for improving the characteristics of the photosensitive layer can be further performed. For example, a specific sensitizing dye and an addition polymerizable compound structure (for example, acryloyl group or methacryloyl group) are bonded by a method such as a covalent bond, an ionic bond, or a hydrogen bond to thereby form a photosensitive layer (exposure film). It is possible to increase the strength and to suppress unnecessary precipitation of the dye from the photosensitive layer after exposure.

  Further, a partial structure having a radical generating ability in the specific sensitizing dye and the initiator compound described later (for example, reductive decomposable sites such as alkyl halide, onium, peroxide, biimidazole, onium, biimidazole, borate, Oxidation-cleavable sites such as amine, trimethylsilylmethyl, carboxymethyl, carbonyl, imine, etc.) can significantly increase the photosensitivity particularly when the concentration of the starting system is low.

Furthermore, for the purpose of enhancing the processing suitability for alkaline or aqueous developers, the specific sensitizing dye contains a hydrophilic moiety (carboxyl group and ester thereof, sulfonic acid group and ester thereof, ethylene oxide group, etc. It is effective to introduce an acid group or a polar group). In particular, ester-type hydrophilic groups have a relatively hydrophobic structure in the photosensitive layer and thus have excellent compatibility, and in the developer, acid groups are generated by hydrolysis, resulting in increased hydrophilicity. Have
In addition, for example, a substituent can be appropriately introduced into the specific sensitizing dye in order to improve compatibility in the photosensitive layer and to suppress crystal precipitation. For example, in certain types of photosensitive systems, unsaturated bonds such as aryl groups and allyl groups may be very effective in improving compatibility. By introducing an obstacle, crystal precipitation can be remarkably suppressed. Further, by introducing a phosphonic acid group, an epoxy group, a trialkoxysilyl group, or the like, adhesion to an inorganic substance such as a metal or a metal oxide can be improved. In addition, a method such as polymerization of a sensitizing dye can be used depending on the purpose.

When a specific sensitizing dye is used as the sensitizing dye, at least one sensitizing dye represented by the general formula (B) may be used. As long as it is represented by the general formula (B), for example, For details on how to use the dyes, such as those with the modifications described, whether they are used alone or in combination of two or more, and how much is added, see the performance of the final photosensitive material. It can be set appropriately according to the design. For example, the compatibility with the photosensitive layer can be enhanced by using two or more kinds of specific sensitizing dyes in combination.
In selecting a specific sensitizing dye, the molar extinction coefficient at the emission wavelength of the light source used is an important factor in addition to the photosensitivity. By using a dye having a large molar extinction coefficient, the amount of the dye added can be relatively small, which is economical and advantageous from the viewpoint of film properties of the photosensitive layer.
In the present invention, in addition to the specific sensitizing dye, other general-purpose sensitizing dyes can be used in combination as long as the effects of the present invention are not impaired.

Since the photosensitivity and resolution of the photosensitive layer and the physical properties of the exposed film are greatly affected by the absorbance at the light source wavelength, the addition amount of the sensitizing dye is appropriately selected in consideration of these factors. For example, the sensitivity decreases in a low region where the absorbance is 0.1 or less. Also, the resolution becomes low due to the influence of halation. However, for the purpose of curing a thick film of, for example, 5 μm or more, there is a case where such a low absorbance can be increased instead.

  For example, when the photosensitive layer in the photomask material has a relatively thin film thickness, the addition amount of the sensitizing dye is such that the absorbance of the photosensitive layer is in the range of 0.1 to 1.5, preferably 0.25. Is preferably set in a range of 1 to 1. Since the absorbance is determined by the amount of the specific sensitizing dye added and the thickness of the photosensitive layer, the predetermined absorbance can be obtained by controlling both conditions. The absorbance of the photosensitive layer can be measured by a conventional method. As a measuring method, for example, on a transparent or white support, a photosensitive layer having a thickness appropriately determined in a range where the coating amount after drying is necessary as a photomask material is formed, and a transmission type optical densitometer is formed. And a method of measuring a reflection density by forming a photosensitive layer on a reflective support such as aluminum.

  The addition amount of the sensitizing dye is 0.05 to 30 parts by mass, preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the total solid components constituting the photosensitive layer. Part range.

<Other ingredients>
-UV absorber, metal oxide-
For the purpose of increasing the absorbance in the ultraviolet region, a UV absorber, a metal, a metal oxide such as titanium oxide, and the like may be added to the photopolymerizable composition at the same time. As the UV absorber, a compound that exhibits strong absorption in the ultraviolet region by heat treatment as described in JP-A-9-25360 can also be used.

-Thermal polymerization inhibitor-
In addition, a small amount of a thermal polymerization inhibitor is added as an additive to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated bond-containing compound during preparation or storage of the photopolymerizable composition. It is preferable. Furthermore, it is preferable to add a thermal polymerization inhibitor. Examples thereof include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2 , 2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, phenothiazine, N-nitrosophenylhydroxylamine cerium salt, N-nitrosophenylhydroxylamine aluminum salt, and the like.

  The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the total solid content constituting the photosensitive layer. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and unevenly distributed on the surface of the photosensitive layer during the drying process after coating. Good. The addition amount of the higher fatty acid derivative or the like is preferably about 0.5% by mass to about 10% by mass with respect to the total solid content constituting the photosensitive layer.

-Other additives-
Furthermore, a known additive such as a plasticizer and a surfactant can be added to the composition used in the present invention as necessary.

  The film thickness of the photosensitive layer is preferably in the range of 0.3 μm to 7 μm from the viewpoint of film thickness uniformity, resolution, and sensitivity. A particularly preferable film thickness is 0.5 μm to 3 μm.

  The photosensitive layer is a coating liquid for forming a photosensitive layer such as the photopolymerizable composition described above, a spin coater, a slit spin coater, a roll coater, a die coater, or a curtain coater on a transparent substrate. It can be provided by direct application.

(Protective layer)
The photomask material used in the present invention may have a protective layer on the photosensitive layer. The protective layer will be described below.

The protective layer has an oxygen transmission rate at 25 ° C. and 1 atm of 1.0 ml / m ² · day · atm or more and 2000 ml / m ² · day · atm or more, and 2.0 ml / m ² · day · atm or more. 1500 ml / m ² · day · atm or less is preferred, 5.0 ml / m ² · day · atm or more and 1000 ml / m ² · day · atm or less is more preferred, and 10 ml / m ² · day · atm or more and 800 ml / m ² ···. Most preferably, it is not more than day · atm. Oxygen permeability within the above range ensures no unnecessary polymerization reaction during production and raw storage, and no problem of unnecessary fogging or image line weighting during image exposure. Is obtained.

  In addition to the oxygen permeability described above, the properties desired for the protective layer further do not substantially inhibit the transmission of light used for exposure, have excellent adhesion to the photosensitive layer, and in the development step after exposure. It is desirable that it can be easily removed.

  As a material that can be used for the protective layer, for example, a water-soluble polymer compound having relatively excellent crystallinity is preferably used. Specifically, polyvinyl alcohol, vinyl alcohol / vinyl phthalate copolymer, vinyl acetate / vinyl are used. Water-soluble polymers such as alcohol / vinyl phthalate copolymer, vinyl acetate / crotonic acid copolymer, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, polyacrylic acid, polyacrylamide polyester, polyurethane, etc. These can be used alone or in combination. Of these, the use of polyvinyl alcohol as the main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability.

  The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. Specific examples of polyvinyl alcohol include those that are hydrolyzed by 71 to 100 mol% and have a polymerization repeating unit in the range of 300 to 2400. Specifically, PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC made by Kuraray Co., Ltd. , PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA -420, PVA-613, L-8, KL-506, KL-318, KL-118, KM-618, KM-118, C-506, R-2105, R-1130, R-2130, M-205 , MP-203, LM15, LM20, LM25 and the like, and these can be used alone or in combination.

A copolymer containing a repeating unit derived from unsubstituted vinyl alcohol and a repeating unit having a polyoxyalkylene group in the side chain is also preferably used. The polyoxyalkylene group contained in the copolymer is preferably one or more groups selected from the group consisting of a polyoxyethylene group, a polyoxypropylene group, and an oxyethylene-oxypropylene mixed group.
The oxyethylene-oxypropylene mixed group may be a group formed by combining one or more of an oxyethylene group and an oxypropylene group, such as a mixed group of a polyoxyethylene group and a polyoxypropylene group, a polyoxy Examples include a mixed group of an ethylene group and an oxypropylene group, a mixed group of an oxyethylene group and a polyoxypropylene group, and a mixed group of an oxyethylene group and an oxypropylene group.

  In a preferred embodiment, the content of polyvinyl alcohol in the protective layer is 20 to 95% by mass, and more preferably 30 to 90% by mass.

A surfactant can be added to the protective layer.
Examples of the surfactant include polyoxyethylene castor oil ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene Polyoxyethylene alkyl allyl ethers such as ethylene nonylphenyl ether, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioxide Sorbitan alkyl esters such as oleate, sorbitan trioleate, glycerol monostearate, glycerol monooleate, etc. Nonionic surfactants such as noglyceride alkyl esters; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; alkyls such as sodium butyl naphthalene sulfonate, sodium pentyl naphthalene sulfonate, sodium hexyl naphthalene sulfonate, sodium octyl naphthalene sulfonate Anionic surfactants such as naphthalene sulfonates, alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates such as sodium dodecyl sulfonate, sulfosuccinic acid ester salts such as sodium dilauryl sulfosuccinate; lauryl betaine, stearyl betaine, etc. Amphoteric surfactants such as alkylbetaines and amino acids can be used.

A particularly preferred surfactant that can be used in the protective layer is a polyoxyethylene castor oil ether surfactant. Castor oil, which is a main component of polyoxyethylene castor oil ether surfactant, is a vegetable non-drying oil obtained by pressing from castor bean seeds. Contains 35-57% oil based on total seeds. The component contains about 85% of the unsaturated carboxylic acid ricinoleic acid. Ricinoleic acid is a stearic acid derivative having a terminal carboxyl group, a hydroxyl group at the 12-position, and an unsaturated double bond at the 9-position. Polyoxyethylene castor oil ether surfactant is a general term for nonionic surfactants synthesized by adding ethylene oxide to ricinoleic acid, which is the main component of castor oil. In the addition reaction process, a hydroxy group of ricinoleic acid and a carboxylic acid group react with each other depending on conditions to form a polyester, and a surfactant containing a polymer having a molecular weight of 10,000 to 20,000 can also be formed.
Also included are surfactants of the type obtained by adding ethylene oxide to glycerol ricinoleic acid.

  The polyoxyethylene castor oil ether surfactant has HLB = 10.0 to 16.0, preferably 11.0 to 15.0. If the HLB is less than 10.0, the water solubility is low, and turbidity occurs when added to an aqueous solution of polyvinyl alcohol. Moreover, when HLB is larger than 16, hydrophilicity is too high and the hygroscopic property of a protective layer increases. Further, the weight average molecular weight of the polyoxyethylene castor oil ether surfactant is 800 to 5000, preferably 1000 to 3000, from the viewpoint of the friction coefficient and solubility.

  Specific examples of such polyoxyethylene castor oil ether surfactant include PIONEIN D-225, PIONEIN D-240-W, PIONEIN D-230, PIONEIN D-236, PIONEIN D-225 manufactured by Takemoto Yushi Co., Ltd. -K, Kao Corporation Emanon CH-25, Emanon CH-40, Emanon CH-60, etc. can be mentioned.

  When using polyoxyethylene castor oil ether surfactant, the addition amount is 1.0 to 10% by mass, preferably 2.0 to 6.0% by mass in the total solid content of the protective layer. If the amount added is small, the effect of lowering the friction coefficient is reduced, while if the amount added is too large, the coating property of the protective layer is deteriorated, resulting in coating unevenness.

  The content of the surfactant in the protective layer is preferably 0.1 to 2% by mass in the total solid content of the protective layer.

  Further, a filler such as silica gel and mica can be added to the protective layer to adjust the surface properties.

The coating amount of the protective layer is a dry weight typically ^{0.1g / m 2 ~10g / m 2} , and preferably from ^{0.5g / m 2 ~5g / m 2} . Moreover, regarding the application method, there are a method of applying sequentially and a method of applying multiple layers at once, either of which may be used.

(Undercoat layer)
In the photomask material of the present invention, it is preferable to provide an undercoat layer on a transparent substrate. When providing the undercoat layer, the photosensitive layer is provided on the undercoat layer. When preparing the photomask, the undercoat layer enhances the adhesion between the transparent substrate and the photosensitive layer in the exposed area, and easily causes the photosensitive layer to peel from the transparent substrate in the unexposed area. Therefore, developability is improved.

Specific examples of the compound contained in the undercoat layer include 3-aminopropyltrimethoxysilane, octyltrimethoxysilane, 3-cyanopropyltriethoxysilane, and [2- (3,4-epoxycyclohexyl) ethyl] trimethoxy. Silane, phenyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, allyltrimethoxysilane, vinylmethoxysilane, 3- (N, N-diethylamino) propyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, Examples of suitable compounds include p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane.
The coating amount of the undercoat layer is a dry ^weight, preferably from ^{2mg / m 2 ~200mg / m 2} , 5mg / m 2 ~100mg / m 2 is more preferred.

[Manufacture of photomasks]
In the production method of the present invention, the above-described photomask material is imagewise exposed with near ultraviolet light or visible light (exposure process), and then the exposed photomask material is developed using a specific developer. A photomask is obtained by (developing step).

<Exposure process>
The exposure step is preferably performed by exposing the photomask material imagewise through a transparent original image having a line image, a halftone dot image, or the like, or by imagewise exposure by laser light scanning or the like using digital data.
Examples of light sources suitable for exposure include carbon arc lamps, mercury lamps, xeno lamps, metal hydrado lamps, strobes, ultraviolet rays, infrared rays, and laser beams.

In the exposure step, laser exposure is particularly preferable. As the laser, a laser that emits near-ultraviolet light from visible light that can be operated under a white light or a yellow light is preferable. As the wavelength, a laser that emits light of 250 nm to 540 nm is suitable, a laser that emits light of 300 nm to 500 nm is preferable, a laser that emits light of 350 nm to 450 nm is more preferable, and light of 400 nm to 430 nm is emitted. Most preferred is a laser. Examples of such a laser include an ultraviolet semiconductor laser that emits light of 250 to 420 nm, an argon ion laser that emits visible light, and an FD-YAG laser.
More specifically, lasers applicable to the present invention include, but are not limited to, a 405 nm violet laser, a 442 nm HeCd laser, a 488 nm argon laser, and the like.

<Development process>
The development step is performed by developing the exposed photomask material using a specific developer.

  In the development step, examples of the mode in which the specific developer is brought into contact with the photomask material after exposure include manual treatment, immersion treatment, and mechanical treatment.

  Examples of the manual treatment include a mode in which a developing solution is sufficiently contained in sponge or absorbent cotton, the whole is treated while being rubbed, and washed thoroughly with water after the treatment is completed.

  Examples of the immersion treatment include a method in which the exposed photomask material is immersed in a vat or deep tank containing a developer and stirred, and then sufficiently washed with water while rubbing with absorbent cotton or a sponge. The immersion time is preferably about 60 seconds.

  An automatic developing machine can be used for the mechanical processing. When using an automatic developing machine, for example, a method of pumping a developer charged in a developing tank with a pump and spraying it onto a photomask material after exposure from a spray nozzle, a liquid in a tank filled with the developing solution is used. Process by immersing and transporting the exposed photomask material with an intermediate guide roll, etc., and supplying substantially unused developer for each photomask material after exposure for processing Any of the so-called disposable processing methods can be applied. In any system, those having a mechanism such as high-pressure washing, brush or molton are more preferable. In addition, an apparatus in which a laser exposure unit and an automatic processor unit are integrated can be used.

  Moreover, as temperature of the specific developing solution at the time of image development, the range of 20 to 35 degreeC is preferable, and the range of 25 to 30 degreeC is more preferable.

  When a developer composed of an alkaline aqueous solution is used, it is generally preferable to rinse (rinse) with pure water after development.

<Heating process>
In the production method of the present invention, it is possible to increase the film strength by subjecting the photomask material after the development step to a heat treatment, if necessary (heating step). As heating temperature, the range of 120 to 250 degreeC is preferable, and the range of 150 to 250 degreeC is more preferable. Yes. Moreover, as heating time, 15 minutes-90 minutes are preferable and 30 minutes-60 minutes are more preferable. For heating, a known means such as a dry oven or a hot plate can be used.

  Further, after image formation on the photomask material, a protective film such as a thermosetting epoxy resin may be provided on the image. By providing a protective film on the image, the film strength can be further improved.

As described above, a photomask can be obtained by the manufacturing method of the present invention.
If the obtained photomask has a defect, the defect can be corrected as follows.

  Here, in the case of a black portion, the defect of the photomask mainly means a defect that transmits light such as a white portion of the black portion, for example, a pinhole. Moreover, in the case of a white part, for example, it refers to a defect in which light transmittance is reduced due to adhesion of a foreign substance or a photosensitive layer on a transparent substrate in a part that should originally become a white part. When black spots are generated, after applying the photosensitive layer coating solution (photosensitive composition) to the periphery of the defect, for example, exposure and development with a HeCd laser is performed to remove unnecessary photosensitive layers. By doing so, the defect can be corrected. Further, instead of performing exposure and development with a HeCd laser, it is also possible to remove unnecessary portions by ablation with a YAG laser. On the other hand, a defect in a white portion can be removed by ablation with a YAG laser or the like. In this case, unlike the Em mask, there is no organic component such as a photosensitive layer in the white portion, so that no new defect is generated due to laser ablation.

The photomask obtained by the production method of the present invention can be suitably used in a photolithography process in the fields of flat panel displays such as PDP, FED and LCD, shadow mask for CRT, printed wiring board and semiconductor.
When the photomask used in the present invention is used for patterning an ultraviolet photosensitive resist, it is also possible to select an exposure wavelength by incorporating a band pass filter into an ultraviolet exposure machine such as an ultrahigh pressure mercury lamp.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[Examples 1 to 22, Comparative Examples 1 to 10]
1. Production of photomask material [P] (formation of undercoat layer)
Undercoat composition S-1 having the following composition on a glass substrate (10 cm × 10 cm) washed with pure water
Was applied with a spin coater MS-A-100 manufactured by Mikasa Co., Ltd. so that the mass after drying was 20 mg / m ² and dried at 100 ° C. for 1 minute.

<Undercoat composition S-1>
・ 99 parts by mass of propylene glycol monomethyl ether acetate ・ 1 part by mass of 3-methacryloxypropyltrimethoxysilane

(Formation of photosensitive layer)
On the undercoat layer coated as described above, a high-sensitivity photopolymerizable composition P-1 having the following composition was applied so that the dry coating mass was 1.4 g / m ^2, and dried at 100 ° C. for 1 minute. A photosensitive layer was formed.

<Photopolymerizable composition P-1>
-Carbon rack dispersion (30% by mass methyl ethyl ketone solution) 16.0 parts by mass-Ethylenically unsaturated bond-containing compound (A-1) (the following structural compound) 4.2 parts by mass-Linear organic polymer (B -1) (polymer binder having the following structure) 3.6 parts by mass Sensitizer (C-1) (compound having the following structure) 0.21 part by mass Photoinitiator (D-1) (of the following structure) Compound) 0.81 part by mass Chain transfer agent (E-1) (compound having the following structure) 0.3 part by mass ε-phthalocyanine dispersion 0.76 part by mass Fluorine nonionic surfactant 0.05 part by mass・ (Megafuck F780, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 58 parts by mass ・ Propylene glycol monomethyl ether acetate 53 parts by mass

(Formation of protective layer)
On this photosensitive layer, the following protective layer coating solution was applied and dried to form a protective layer to obtain a negative photomask material [P]. The drying conditions for forming the protective layer were 120 ° C. and 1 minute.

<Protective layer coating solution>
・ 87 g of water
・ Polyvinyl alcohol PVA105 (Kuraray Co., Ltd.) 10g
・ Polyvinylpyrrolidone (manufactured by BASF) 2g
・ EMALEX 710 (Nippon Emulsion Co., Ltd., surfactant) 1 g

2. Preparation of developer (preparation of specific developers 1 to 14 and comparative developers C1 to C10)
By dissolving the surfactant and chelating agent shown below in the amount of water shown in the following composition and adjusting to a desired pH with potassium hydroxide, the specific developers 1 to 14 and the comparative developer C1-C10 were prepared.

<Specific Developers 1-14, Composition of Comparative Developers C1-C10>
・ Surfactant Type and amount shown in Table 1 below ・ Chelating agent (Cyrest 400, manufactured by Kirest Co., Ltd.) 0.1 g
・ Water 94.75g
Potassium hydroxide required for pH adjustment

(Preparation of specific developer 15-22)
Specific developers 15 to 22 were prepared by dissolving the surfactant and chelating agent shown below in the amount of water shown in the following composition and adding the alkali agent in the amount shown in Table 2.

<Composition of specific developer 15-22>
・ Surfactant Type and amount shown in Table 2 below ・ Chelating agent (Kyrest 400, manufactured by Kyrest Co., Ltd.) 0.1 g
・ Alkaline agent Type and amount shown in Table 2 below ・ Water Amount to be 100 g in total

3. Photomask preparation The photomask material [P] (10 cm × 10 cm) was exposed at 30% output with VILD (Dainippon Screen Mfg. Co., Ltd.) (laser output 350 mW, light source 405 nm violet laser) as a laser plotter. .
Further, the exposed photomask material [P] was immersed in 1 L of a specific developer 1 at 30 ° C. for 15 seconds, developed, washed with water, and dried. Further, a heat treatment was performed at 180 ° C. for 30 minutes to obtain a photomask of Example 1.
Further, Examples 2 to 22 and Comparative Examples were made in the same manner as the photomask of Example 1 except that the developer was changed from the specific developer 1 to the specific developers 2 to 22 and the comparative developers C1 to C10, respectively. 1 to 10 photomasks were obtained.
The exposure sensitivity was about 6 mJ / cm ² . The absorbance at 365 nm of each photomask after development and heat treatment was about 4.0.

[Evaluation]
1. Evaluation of resolution of photomask By measuring the line / space in each photomask obtained in Examples 1 to 22 and Comparative Examples 1 to 10 with a digital microscope “VHX-100F” manufactured by Keyence, photo Mask resolution was evaluated.
The resolution is evaluated by using the specific developer 1 to 22 and the comparative developers C1 to C10 to process 50 photomask materials [P] after exposure for each developer, and the first and 25th sheets. This was performed on the photomask obtained on the eyes and the 50th sheet.

2. Evaluation of sludge generation state Next, in order to confirm the repeated processing performance of the developing solution, each developing solution is used to process 50 photomask materials [P] after exposure, and then each developing solution is left to stand. Then, the state of sludge generation (presence or absence of precipitation) was visually observed. The state of sludge generation was observed 2 days, 7 days, and 15 days after the development processing. Evaluation was performed based on the following evaluation criteria.
-Evaluation criteria-
○: No sludge △: Slight occurrence of sludge is observed ×: Many sludge is observed

The above evaluation results are shown in Table 1 below for Examples 1-14 and Comparative Examples 1-10, and in Table 2 below for Examples 15-22.

  Details of the surfactants A to C shown in Tables 1 and 2 are as follows.

  As shown in Table 1 or Table 2, each of the photomasks obtained in Examples 1 to 22 is excellent in resolution, and there is little or no change in resolution even when the number of processed sheets increases. It was found that a photomask with a resolution can be obtained stably. In addition, it was found that the specific developers 1 to 22 used in Examples 1 to 22 showed no sludge generation at any time of evaluation, and the generation of sludge was suppressed over a long period of time. .

  On the other hand, in Comparative Examples 3 and 8, as shown in Table 1, the resolution of the photomask was inferior from the first sheet. About Comparative Examples 1 and 6, it deteriorated as the number of processed sheets increased. In Comparative Examples 2, 4, 7, and 9, development could not be performed, and in Comparative Examples 5 and 10, image flow occurred. Also, except for Comparative Examples 5 and 10, sludge accumulation was observed on the bottom of the developing bath in any of the Comparative Examples.

3. Next, the performance of the photomask was evaluated by performing pattern exposure of an ultraviolet photosensitive resist material using the photomask obtained in Examples 1 to 22.
Pattern exposure is performed on a glass plate (a glass plate is washed with 5% KOH alkaline aqueous solution, washed with water, and then surface-treated with hexamethyldisilazane) on a positive resist film (Fuji Film Orin), which is an ultraviolet photosensitive resist material. A positive resist 204LT manufactured by Co., Ltd. is applied to a thickness of 1.5 μm to form a resist film, and a band pass filter having a half-value width of about 15 nm with a center wavelength of 365 nm is formed on the resist film. Then, the photomask was contacted, and exposure was performed under the condition of 250 mJ / cm ² using an aligner having a ² KW ultra-high pressure mercury lamp. The exposed glass plate was immersed and washed with water at room temperature (23 ° C.) for 45 seconds using a tetramethylammonium hydroxide developer (FHD-5 manufactured by FFO) as a developer.
When the obtained positive resist image was evaluated, it was confirmed that a good image reproducing the photomask image was formed.

Claims (5)

  A photomask material containing at least a light-shielding material and having a photosensitive layer capable of forming an image with near-ultraviolet or visible light on a transparent substrate is imagewise exposed with near-ultraviolet or visible light, and then exposed. A developer having a pH of 8 to 13 containing at least one surfactant selected from the group consisting of an anionic surfactant and a nonionic surfactant in a total mass of 1 to 10 mass% A method for producing a photomask, comprising developing using   The anionic surfactant contained in the developer includes an anionic group of sulfonic acid or an anionic group of sulfuric monoester, and an anionic surfactant having at least one aromatic group which may have a substituent. 2. The method for producing a photomask according to claim 1, wherein the photomask is an agent. The nonionic surfactant contained in the developer is at least one surfactant selected from the group consisting of nonionic aromatic ether surfactants represented by the following general formula (1). A method of manufacturing a photomask according to claim 1 or 2.
X-Y-O- (A) _n- (B) _m- H (1)
(In general formula (1), X represents an aromatic group which may have a substituent, Y represents a single bond or an alkylene group having 1 to 10 carbon atoms, and A and B are groups different from each other. And represents either —CH ₂ CH ₂ O— or —CH ₂ CH (CH ₃ ) O—, and n and m each represent 0 or an integer of 1 to 100, provided that n and m are 0 at the same time. And when either n or m is 0, n and m are not 1.)   The photosensitive layer in the photomask material further contains a polymer binder, and the polymer binder is a polyurethane resin having a crosslinkable group in the side chain or a (meth) acrylic resin having a crosslinkable group in the side chain. The method for producing a photomask according to any one of claims 1 to 3, wherein:   5. The method of manufacturing a photomask according to claim 1, wherein the imagewise exposure is performed using a laser that emits light having a wavelength of 250 nm to 540 nm.