JP2003156841A - Photosensitive transfer material, photomask material, photomask, and method for producing photomask - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive transfer material and a photomask material with a photosensitive layer having such photosensitivity as to enable pattern formation with light of >=405 nm wavelength as well as high sensitivity, high mechanical strength, high hardness, and good solvent resistance, to provide a method for producing a photomask from the photosensitive transfer material or the photomask material, and to provide a photomask. SOLUTION: The photosensitive transfer material has on a temporary support at least a photosensitive layer comprising i) at least one alkali-soluble resin binder of formula (1) having polymerizable unsaturated bonds, ii) a monomer having at least one polymerizable unsaturated bond, iii) a photopolymerization initiation system having photosensitivity to light in a long wavelength band of >=405 nm, and iv) a colorant. In the formula (1), R is H or methyl; X is the residue of a polycarboxylic acid; and n is an integer of 0-20.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photomask for forming an image mainly by laser exposure, for example,
A flat panel display such as a PDP, FED or LCD, a shadow mask for a CRT, a printed wiring board, a photomask used in a photolithography process in the field of packages or semiconductors, and a manufacturing method thereof.
The present invention relates to a photomask material and a photosensitive transfer material used therein.

[0002]

2. Description of the Related Art As a photomask used in a photolithography process in the fields of flat panel displays, shadow masks for CRTs, printed wiring boards, semiconductors, etc., "Photofabrication" (published by Japan Photofabrication Association, Educational Education Committee) , P. 67-80, June 1992), a Cr mask provided with a metallic chromium layer and an Em mask (emulsion mask) provided with a silver halide emulsion layer are known.

Among these, 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 providing an etching resist (photosensitive layer) on the chromium layer by coating or the like, and a HeCd laser (442 nm). It is manufactured by performing exposure with light, patterning an etching resist by developing with an aqueous alkaline solution, etching chromium, and peeling the etching resist.

Further, the present inventors have previously exposed and developed a photosensitive layer capable of forming an image with near-ultraviolet light or visible light, thereby eliminating the need for a metal film and simply performing defect correction. Japanese Patent Application No. 2 which enables low cost and has a good balance of sensitivity, resolution, etc.
000-163272. This photosensitive layer has a small absorbance in the near-ultraviolet or visible region, which is the light to be exposed during the production of the photomask, while having a property of well absorbing the light in the ultraviolet region, which is the irradiation light when using the photomask. It has a feature.

In any of the methods for producing the above-mentioned photomask, there is a step of exposing and developing the photosensitive layer, but in order to produce a photomask with high resolution and high quality, this photosensitive layer has high sensitivity. Therefore, it is necessary that the mechanical strength and hardness be high and the solvent resistance be good.

Various types of photosensitive materials are known, and for example, in Japanese Patent Application Laid-Open No. 10-20496, high-sensitivity development for producing a color filter used for a liquid crystal display device or a solid-state image pickup device is known. A pigment-dispersed radiation-sensitive coloring composition having a wide latitude and excellent adhesion during development is disclosed, and the binder resin is a copolymer of an allyl (meth) acrylate monomer and a monomer having an acidic group. It is what However, this radiation-sensitive coloring composition is a composition for producing a color filter and does not relate to a photosensitive transfer material for using a photomask. Moreover, since it is not a radiation-sensitive coloring composition capable of forming an image with near-ultraviolet light or visible light, it cannot be drawn with laser light in the near-ultraviolet light or visible light region having high drawing energy.

Further, in JP-A-10-39502, a composition comprising a binder resin, a compound having an ethylenic double bond having a specific structure, a photopolymerization initiator and a pigment is used as a resist material for a black matrix. However, since a non-polymerizable binder resin is added to this resist, there is a problem that the strength of the obtained film is weak and the laser drawing portion swells in the developing step and the resolution is deteriorated. Further, since this composition absorbs near-ultraviolet light or visible light, it cannot be drawn with laser light in the near-ultraviolet light or visible light region as in the case of the above-mentioned publication. JP-A-10-55064 discloses, as a resist material for a color filter, a binder resin having a molecular weight distribution Mw / Mn of 2.0 to 5.0, a compound having an ethylenic double bond having a specific structure, Although a composition comprising a photopolymerization initiator and a pigment is described, this resist material also has the same problems as those described above.

Further, in JP-A-7-98409, by using a resin having an ethylenic double bond and a fluorene ring as a pigment-dispersing resin, it is not necessary to provide a film for blocking oxygen which prevents photopolymerization. Even though a photosensitive coloring composition for producing a color filter having high exposure sensitivity is described, this photosensitive coloring composition has strong adhesive force and is difficult to be formed into a film. Not only cannot be used as a photosensitive transfer material for transferring, but since the sensitivity in the visible region is not sufficient,
For example, it is not possible to draw with laser light in the visible region. Further, an alkali developing photosensitive resin composition using the resin having the fluorene ring is disclosed in JP-A-9-24133.
As disclosed in Japanese Patent Laid-Open No. 9 and JP-A-304929, these photosensitive resin compositions are drawn with light in the ultraviolet region and cannot be drawn with laser light in the visible region.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and its purpose is to provide a photosensitive layer with high sensitivity, high mechanical strength and hardness, and solvent resistance. To provide a photosensitive transfer material and a photomask material having good photosensitivity and capable of writing with light having a wavelength of 405 nm or more. Further, the photosensitive transfer material or the photomask material is used as a photomask. To provide a method and a photomask for manufacturing the same.

[0010]

The above-mentioned problems can be solved by providing the following photosensitive transfer material, photomask material, photomask, and method for manufacturing a photomask. (1) On the temporary support, i) at least one kind of alkali-soluble resin binder represented by the following general formula (1) having a polymerizable unsaturated bond, ii) at least one polymerizable unsaturated bond A photosensitive transfer material comprising at least a monomer having iii), iii) a photopolymerization initiation system having photosensitivity to light in a long wavelength region of 405 nm or more, and iv) a photosensitive layer containing a colorant.

[0011]

[Chemical 4]

In the above general formula (1), R represents a hydrogen atom or a methyl group, and X represents a residue of an aromatic or alicyclic carboxylic acid having 2 to 4 carboxyl groups. n represents an integer of 0 to 20. (2) A photomask material in which the photosensitive transfer material according to claim 1 is laminated on a light-transmissive base material such that the photosensitive layer side of the photosensitive transfer material faces the base material. (3) At least one kind of alkali-soluble resin binder represented by the following general formula (1) having at least i) a polymerizable unsaturated bond on a light-transmissive substrate, and ii) at least one A photomask material in which a photosensitive layer containing a monomer having a polymerizable unsaturated bond, iii) a photopolymerization initiation system having photosensitivity to light in a long wavelength region of 405 nm or more, and iv) a colorant is formed by coating.

[0013]

[Chemical 5]

In the above general formula (1), R represents a hydrogen atom or a methyl group, and X represents a residue of an aromatic or alicyclic carboxylic acid having 2 to 4 carboxyl groups. n represents an integer of 0 to 20. (4) The photomask material as described in (1) or (2) above, further comprising an oxygen barrier layer on the photosensitive layer. (5) The photomask material as described in any one of (2) to (4) above, wherein the coloring material is at least one kind of pigment selected from a blue pigment and a green pigment. (6) In a photomask in which at least a pattern forming layer is provided on a light-transmitting substrate, the pattern forming layer is represented by the following general formula (1) having i) a polymerizable unsaturated bond. At least one alkali-soluble resin binder, ii) a monomer having at least one polymerizable unsaturated bond, iii) a photopolymerization initiation system having photosensitivity to light in a long wavelength region of 405 nm or more, and iv) coloring A photomask, which is a layer obtained by exposing and developing a photosensitive layer containing a material with light in a long wavelength region of 405 nm or more.

[0015]

[Chemical 6]

In the above general formula (1), R represents a hydrogen atom or a methyl group, and X represents a residue of an aromatic or alicyclic carboxylic acid having 2 to 4 carboxyl groups. n represents an integer of 0 to 20. (7) A method for producing a photomask, which comprises at least the step of exposing and developing the photosensitive layer with light having a wavelength of 405 nm or more after peeling the temporary support of the photomask material according to claim 2.

(8) The step of exposing the photosensitive layer from the side of the temporary support of the photomask material described in (2) above with light having a wavelength of 405 nm or more, the step of peeling the temporary support, and the development of the photosensitive layer. A method for manufacturing a photomask, comprising at least a step. (9) A method for producing a photomask, which comprises at least a step of exposing and developing the photosensitive layer of the photomask material according to (3) above with light having a wavelength of 405 nm or more. (10) 120 ° C. to 250 ° C. with respect to the photosensitive layer after the development treatment described in any one of (7) to (9) above.
A method for manufacturing a photomask, characterized in that the heat treatment is performed within the range. (11) The method for producing a photomask according to any one of (7) to (10), wherein the exposure is performed with a laser beam in a wavelength range of 405 nm to a visible wavelength.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive transfer material, photomask material, photomask and method for producing the same according to the present invention will be described in detail below. In this specification, "above" indicating the relative positional relationship between two or more layers does not necessarily mean a state in which two or more layers are in contact with each other, and one layer does not correspond to another layer. It means "above". [Photosensitive Transfer Material] (Photosensitive Layer) The photosensitive layer of the photosensitive transfer material of the present invention is
i) At least one alkali-soluble resin binder represented by the following general formula (1) having a polymerizable unsaturated bond
A seed, ii) a monomer having at least one polymerizable unsaturated bond, iii) a photopolymerization initiation system having photosensitivity to light in a long wavelength region of 405 nm or more, and iv) a colorant. . The photosensitive layer in the invention uses a binder having a specific structural formula represented by the general formula (1) as a binder, and since it has a high sensitivity in the visible region, it uses a laser beam having a wavelength in the visible region where the drawing energy is large. Can be drawn with high speed drawing.
Further, since the photosensitive layer of the present invention has a high hardness after curing and a good solvent resistance, it is highly resistant to cleaning when using a photomask.

I) Alkali-soluble resin binder having a polymerizable unsaturated bond The binder is represented by the general formula (1). In the general formula (1), R represents a hydrogen atom or a methyl group,
X represents a residue of an aromatic or alicyclic carboxylic acid having 2 to 4 carboxyl groups. n represents an integer of 0 to 20. As the divalent to tetravalent aliphatic, aromatic or alicyclic carboxylic acid, maleic acid, succinic acid, itaconic acid,
Phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, diphenyltetracarboxylic acid, etc. The polybasic carboxylic acid and the acid anhydride of these are mentioned. Of these, tetrahydrophthalic acid is preferable. n is 0
An integer of 10 is preferable, and 1 is particularly preferable. Further, the binder represented by the general formula (1) can be used when preparing a pigment dispersion, and this is preferable from the viewpoint of high sensitivity.

In the present invention, in addition to the alkali-soluble resin binder represented by the general formula (1), an alkali-soluble resin binder having a polymerizable unsaturated bond as shown below can be used in combination. By using this alkali-soluble resin binder, the tackiness of the photosensitive layer can be reduced. When both are used in combination, it is preferable that at least 20% by mass of the compound represented by the general formula (1) is contained. This alkali-soluble resin binder having a polymerizable unsaturated bond can be used without particular limitation as long as it is a resin having an unsaturated bond capable of polymerizing with an acid group in the molecule, but it can be polymerized with an acid group-containing monomer. A copolymer composed of a monomer having an unsaturated bond (in addition to the polymerizable unsaturated bond as a monomer),
Alternatively, in addition to the above-mentioned monomers, copolymers with other monomers having no acid group or polymerizable unsaturated bond may be mentioned. Examples of the acid group include a carboxyl group and a phenolic hydroxyl group, and examples of the acid group-containing monomer include acrylic acid, methacrylic acid and hydroxystyrene. Further, as the polymerizable unsaturated bond, an unsaturated bond derived from an allyl group, one derived from a cinnamyl group, one derived from a crotyl group and the like can be mentioned, and as a monomer having these groups, allyl acrylate, allyl methacrylate, Examples thereof include cinnamyl acrylate, cinnamyl methacrylate, crotyl acrylate and crotyl methacrylate. Examples of other monomers include styrene, acrylic acid ester, methacrylic acid ester, and the like.

As the above-mentioned copolymer, the acid group-containing monomer is 2 mol% to 50 mol%, more preferably 15 to 40 mol%, and the monomer having a polymerizable unsaturated bond is 10 mol%.
To 90 mol%, more preferably 30 to 70 mol%, and Mw (weight average molecular weight) of 2000 to 20000.
It is preferably 0, more preferably 4000 to 120,000. The binary copolymer as the copolymer is methacrylic acid / allyl methacrylate copolymer, acrylic acid / allyl methacrylate copolymer, methacrylic acid / allyl acrylate copolymer, acrylic acid / allyl acrylate copolymer, hydroxystyrene. / Allyl methacrylate copolymer, hydroxystyrene / allyl acrylate copolymer, acrylic acid / cinnamyl methacrylate copolymer, methacrylic acid / cinnamyl methacrylate copolymer, acrylic acid / crotyl methacrylate copolymer, methacrylic acid / black Examples thereof include, but are not limited to, tyl methacrylate copolymer and the like.

As the terpolymer, methacrylic acid / benzyl methacrylate / allyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / allyl acrylate copolymer, acrylic acid / benzyl methacrylate / allyl methacrylate copolymer, acrylic Acid / benzyl methacrylate / allyl acrylate copolymer, methacrylic acid / benzyl acrylate / allyl methacrylate copolymer, methacrylic acid / benzyl acrylate / allyl acrylate copolymer, acrylic acid / benzyl acrylate / allyl methacrylate copolymer, acrylic acid / Benzyl acrylate / allyl acrylate copolymer, hydroxystyrene / benzyl methacrylate / allyl methacrylate copolymer, hydroxystyrene / benzyl acrylate Rate / allyl methacrylate copolymer, hydroxystyrene / benzyl methacrylate /
Allyl acrylate copolymer, hydroxystyrene / benzyl acrylate / allyl acrylate copolymer, methacrylic acid / styrene / allyl methacrylate copolymer, methacrylic acid / styrene / allyl arylate copolymer, acrylic acid / styrene / allyl methacrylate copolymer , Acrylic acid / styrene / allyl arylate copolymer, and the like, but are not limited thereto. Further, as an alkali-soluble resin binder having a polymerizable unsaturated bond, further disclosed in JP-A-10-2049
Examples thereof include those described in paragraphs 0015 to 0032 of JP-A-6.

Ii) Monomer having at least one polymerizable unsaturated bond As the monomer having at least one polymerizable unsaturated bond, first, a (meth) alcohol of a monohydric or polyhydric alcohol is used.
Examples thereof include esters of acrylic acid. Examples of the monohydric alcohol in the ester of (meth) acrylic acid of monohydric or polyhydric alcohol include, for example, methanol, ethanol,
Propanol, isopropanol, n-butanol, isobutanol, t-butanol, cyclohexyl alcohol, benzyl alcohol, octyl alcohol, 2-
Ethylhexanol, lauryl alcohol, n-decanol, undecanol, cetyl alcohol, stearyl alcohol, methoxyethyl alcohol, ethoxyethyl alcohol, butoxyethyl alcohol, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, 2-hydroxy-3-chloropropane, dimethyl. Aminoethyl alcohol, diethylaminoethyl alcohol, glycidol, 2-trimethoxysilylethanol, ethylene chlorohydrin, ethylene bromohydrin, 2,3-dibromopropanol, allyl alcohol, oleyl alcohol, epoxystearyl alcohol, phenol, naphthol, etc. Can be mentioned.

Examples of the polyhydric alcohol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, hexanediol, heptanediol and octanediol. , Nonanediol, dodecanediol, neopentyl glycol, 1,10-decanediol, 2-butene-1,4-diol, 2-n-butyl-2-ethylpropanediol, cycloheptanediol, 1,4-cyclohexanediene Methanol, 3-cyclohexene-1,1-diethanol, polyethylene glycol (diethylene glycol, triethylene glycol, etc.), polypropylene glycol (dipropylene glycol, tripropylene glycol, etc.), polystyrene oxide glycol, polytetrahydrofuran glycol , Xylylenediol,
Bis (β-hydroxyethoxy) benzene, 3-chloro-1,2-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2- Diphenyl-1,3-propanediol, decalindiol, 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1,3- Hexanediol, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 3-hexene-2,5-diol, hydroxybenzyl alcohol, 2-methyl-1,4-butanediol, 2
-Methyl-2,4-pentanediol, 1-phenyl-1,2
-Ethanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,3,5,6-tetramethyl-p-xylene-α, α'-diol, 1,1,4, 4-tetraphenyl-2-butyne-1,4-diol, 1,1'-bi-2-naphthol, dihydroxynaphthalene, 1,1'-methylene-di-2-naphthol, biphenol, 2,2-bis ( 4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, pyrogallol, α- (1-aminoethyl) ) -P-Hydroxybenzyl alcohol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 3-amino-1,2-propanedio Le, N
-(3-aminopropyl) -diethanolamine, N, N
-Bis (2-hydroxyethyl) piperazine, 1,3-bis (hydroxymethyl) urea, 1,2-bis (4-pyridyl) -1,2-ethanediol, Nn-butyldiethanolamine, diethanolamine, N- Ethyldiethanolamine, 3-mercapto-1,2-propanediol, 3-piperidine-1,2-propanediol, 2-
(2-pyridyl) -1,3-propanediol, α- (1
-Aminoethyl) -p-hydroxybenzyl alcohol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripetaerythritol, sorbitol, glucose, α-mannitol, butanetriol, 1,2,6
-Trihydroxyhexane, 1,2,4-benzenetriol, triethanolamine, 2,2-bis (hydroxymethyl) -2,2 ', 2 "-nitrilotriethanol and the like can be mentioned.

Among these (meth) acrylic acid esters of monohydric or polyhydric alcohols, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate,
Neopentyl glycol di (meth) acrylate, sorbitol hexa (meth) acrylate, sorbitol penta (meth) acrylate and the like are preferable.

It is also possible to use (meth) acrylamides of monoamines or polyamines. Examples of the monoamine here include ethylamine, butylamine, aminoamine, hexylamine, octylamine, cyclohexylamine, monoalkylamines such as 9-aminodecalin, monoalkenylamines such as allylamine, methallylamine and benzylamine, and aniline and toluidine. , Aromatic amines such as p-aminostyrene. Examples of the polyamine include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, hexamethylenebis (2-aminopropyl) amine, diethyltriamine, triethylenetetraamine, polyethylenepolyamine, tris (2- Aminoethyl) amine, 4,4'-methylenebis (cyclohexylamine), N, N'-bis (2-aminoethyl) -1,3-
Propanediamine, N, N'-bis (3-aminopropyl) -1,4-butanediamine, N, N'-bis (3-aminopropyl) ethylenediamine, N, N'-bis (3-aminopropyl)- 1,3-propanediamine, 1,3-cyclohexanebis (methylamine), phenylenediamine, xylylenediamine, β- (4-aminophenyl) ethylamine, diaminotoluene, diaminoanthracene, diaminonaphthalene, diaminostyrene, methylenedianiline , 2,4-bis (4-aminobenzyl) aniline, aminophenyl ether and the like.

Further, allyl compounds such as formic acid, acetic acid, propionic acid, butyric acid, lauric acid, benzoic acid, chlorobenzoic acid, malonic acid, oxalic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, terephthalic acid, hexa Mono- or polyallyl esters of mono- or polycarboxylic acids such as hydrophthalic acid, chlorendic acid and trimellitic acid, mono- or polyallyl esters of mono- or polysulfonic acids such as benzenedisulfonic acid, naphthalenedisulfonic acid, diallylamine, N, N ' -Diallyl oxalic acid diamide, 1,3-diallyl urea, diallyl ether, triallyl isocyanurate and the like can also be used.

Further, for example, polyvinyl compounds such as divinylbenzene, p-allylstyrene, p-isopropenylstyrene, divinylsulfone, ethylene glycol divinyl ether, glycerol trivinyl ether, divinyl succinate, divinyl phthalate and divinyl terephthalate, 2-hydroxy. An ester compound of (meth) acrylic acid having an ionic group such as -3-methacryloyloxypropyltrimethylammonium chloride and methacryloyloxyphenyltrimethylammonium chloride can also be used. Furthermore, a commercially available polymerizable monomer or oligomer, for example, Aronix M5700, M6100, M8030, M152, M205, M21 manufactured by Toagosei Kagaku Kogyo Co., Ltd.
5, Acrylic monomers such as M315, M325, NK ester ABPE-4, U-4HA, CB-1, C manufactured by Shin Nakamura Chemical Co., Ltd.
BX-1, Nippon Kayaku KAYARAD R604, DPCA-30, DPCA
-60, KAYAMAR PM-1, PM-2, (meth) acrylate monomers such as Sannopco's Photomers 4061, 5007, epoxy acrylates such as Showa Polymer Co., Ltd. Lipoxy VR60, VR90, SP1509, etc., Spyrac E-4000X , U30
A spirane resin having a spiroacetal structure such as 00 and a (meth) acrylic group can also be used.

These monomers can be used alone or as a mixture of two or more kinds, and in the range of 5 to 100% by mass, preferably 10 to 70% by mass based on the solid content of the photosensitive layer of the present invention. Can be added. iii) Photopolymerization initiation system having photosensitivity to light having a wavelength of 405 nm or more: As a photopolymerization initiation system having photosensitivity to light having a wavelength of 405 nm or more, a sensitizing dye that absorbs laser light in this wavelength range and a polymerization initiation are used. Systems containing agents are preferred. Specific examples of the sensitizing dye and the polymerization initiator that absorb the laser light include the sensitizing dyes described in paragraphs [0052] to [0100] of JP-A-8-334897 and the paragraph [0] of the same.
101] to [0104], and radical polymerization initiators comprising the titanocene compound. Further, as an auxiliary agent for improving sensitivity, paragraph [0105] of the same publication.
To [0182] can be further used. In addition, as a compound that increases the photopolymerization rate, paragraph [0016] of JP-A-8-202035.
Alternatively, the oxime ether compounds described in [0080] can be used.

Iv) Colorant As the colorant, a colorant having no large absorption in the wavelength region of 405 nm or more is preferable. Further, when the photosensitive transfer material is used for a photomask, a pigment having a strong absorption for irradiation light used when using the photomask is preferable. As such a colorant, a blue pigment, a green pigment, a yellow pigment, a violet pigment or the like can be used alone, or a blue pigment or a green pigment and a yellow pigment can be used in combination.

As the above-mentioned blue pigment, yellow pigment and green pigment, Victoria Pure Blue BO (C.I.
42595), auramine (C.I. 41000), fat black HB (C.I. 26150), monolight yellow GT (C.I. pigment yellow 12),
Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmin FBB
(C.I. Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 1
9), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Supra (C.I.
I. Pigment Red 81) Monastral First Blue (C.I. Pigment Blue 15), Monolight First Black B (C.I. Pigment Black 1), Carbon, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I.
Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I.
I. Pigment Red 180, C.I. I. Pigment
Red 192, C.I. I. Pigment Red 215,
C. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Blue 15:
1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36 and the like.

The solid content of the colorant in the solid composition of the photosensitive composition is determined in consideration of the concentration of the photomask, the sensitivity at the time of making the photomask, the resolution, etc., and depends on the type of the colorant. Although it is different, it is generally 10 to 50% by mass, and more preferably 15 to 35% by mass.

(Other components) In addition to the above components, in order to improve the strength of the cured film, an alkali-insoluble polymer such as an epoxy resin or a melamine resin may be added within a range that does not adversely affect the developability and the like. . The solid content in the solid content of the photosensitive composition is 0.2 to 50% by mass, more preferably 1 to 30% by mass. If it is less than 0.2% by mass, the effect of improving the strength of the cured film is not recognized, and if it exceeds 50% by mass, the developability deteriorates.

A UV absorber, a metal, a metal oxide such as titanium oxide may be added to the photosensitive composition at the same time for the purpose of increasing the absorbance in the ultraviolet region. As the compound, a compound which exhibits strong absorption in the ultraviolet region by heat treatment as described in JP-A-9-25360 can be used. In addition to these, it is preferable to add a thermal polymerization inhibitor as an additive. 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-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like can be mentioned. Further, known additives such as a plasticizer and a surfactant can be added to the composition used in the present invention, if necessary.

When the photosensitive transfer material of the present invention is used for a photomask, the photosensitive layer of the photosensitive transfer material is a photosensitive layer capable of forming an image with light having a wavelength of 405 nm or more, and after exposure and development. Can increase the absorbance in the wavelength band of light to be shielded (shielded light) so that the photosensitive layer can also serve as the pattern forming layer. Therefore, it is desirable that the photosensitive layer before exposure and development has low absorbance in the wavelength region of the image forming light (exposure light), but as described later, the sensitivity of the image forming light is high and the photosensitive layer is sufficiently exposed to light. The absorbance does not need to be particularly low as long as the polymerization can occur. The absorbance of the photosensitive layer in the wavelength band of the shielded light is preferably 1.05 or more, more preferably 2.5 or more, still more preferably 3 or more. In order to increase the absorbance of the photosensitive layer, a coloring material or the like having the high absorbance is contained. Since the absorbance of the photosensitive layer varies depending on not only the type of colorant but also the content of the colorant in the layer, the film thickness of the layer, etc., consider these factors in order to obtain the required absorbance. It is necessary.

As the shielded light, for example, light from an ultra-high pressure mercury lamp used in an aligner or the like as an exposure device can be mentioned. In this case, the g-line of 435 nm and the h-line of 405 nm are used.
Line and i-line at 365 nm should be a light-sensitive layer having a large absorbance. On the other hand, as the light for forming an image, light having a wavelength of 405 nm or more, particularly laser light is used. For example, an ND-YAG laser (532n) is used.
m), Ar ion laser (488 nm), HeCd laser (442 nm), Kr ion laser (413 nm) and the like, but not limited to these. Further, it is desirable that the photosensitive layer has a small absorbance in the wavelength band of light for forming an image from the viewpoint of efficiently photopolymerizing the entire photosensitive layer. The absorbance is preferably 2.
It is 4 or less, more preferably 2.0 or less, and further preferably less than 1.0. For example, since the 488 nm Ar ion laser and the 532 nm ND-YAG laser have relatively low sensitivity, when this laser light is used, the absorbance of the photosensitive layer is small at least in the wavelength region longer than 480 nm, particularly in 488 nm or 532 nm. Is desirable.

When a photomask is manufactured by using a photomask material having such a photosensitive layer, light having a wavelength of 405 nm or longer, which is exposed at the time of manufacturing the photomask, sufficiently penetrates into the deep portion of the photosensitive layer and has a light energy. There is no need to increase the size or light irradiation for a long time, while the sensitivity is high,
Since the shielded light is well absorbed, it functions sufficiently as a photomask. In addition, since the composition of the photosensitive layer is as described above in addition, the pattern forming layer of this photomask is excellent in film strength and has high sensitivity as a photomask.

In addition, depending on the type of laser light (for example, 413 nm Kr ion laser, 442 nm H
eCd laser), although the absorbance is somewhat large (the absorbance is about 0.3 to 4.0 in the case of the laser light), there are some that can obtain a predetermined sensitivity, and in this case, the absorbance needs to be particularly small. There is no. Therefore, the absorbance of light having a wavelength for forming an image can be appropriately determined in consideration of sensitivity.

Examples of the photosensitive layer include, for example, a photosensitive layer in which the wavelength range in which the absorbance is large is a wavelength range shorter than 405 nm, the wavelength range is a wavelength range shorter than 380 nm, and the photosensitive wavelength range is 440 nm or more. Examples of the photosensitive layer include a photosensitive layer having an absorbance of 3 or more in a wavelength region shorter than 380 nm and an absorbance of 2.4 or less in a photosensitive wavelength region of 480 nm or more. If it is a layer, it can be sufficiently applied as a photosensitive layer which also serves as a light-shielding layer.

In order to obtain a photosensitive layer having the above-mentioned characteristics, the photosensitive layer contains a coloring material having a light-absorbing property that absorbs light having a wavelength of 405 nm or more less than the light-absorbing property in the wavelength band of the shielded light. (However, as described above, depending on the type of the laser light that is the image forming light, the absorbance for the wavelength of the laser light does not have to be particularly small.) Further, the light-shielding light includes ultraviolet rays. In this case, it is possible to increase the absorbance in the ultraviolet region by adding an ultraviolet absorber.

(Temporary support) The base material used for the temporary support of the photosensitive transfer material is Teflon (R), polyethylene terephthalate, polycarbonate, polyethylene,
A thin sheet such as polypropylene or a laminate thereof is preferable. A suitable thickness of this substrate is 5 μm to 300 μm, preferably 20 μm to 150 μm. Further, when exposed through a temporary support, the substrate is light-transmissive (hereinafter sometimes simply referred to as “transparent”).
It is necessary to be.

(Peeling layer, oxygen barrier layer) Further, the temporary support is provided with a peeling layer between the temporary support and the photosensitive layer in order to facilitate the peeling of the temporary support and the colored photosensitive layer. Is preferred. Further, when the temporary support is peeled off, an oxygen barrier layer is provided on the photosensitive layer (between the temporary support and the photosensitive layer) so that the photosensitive layer is not affected by oxygen (polymerization inhibition, etc.). It is preferable that (if a release layer is provided, it is provided between the release layer and the photosensitive layer). Further, the peeling layer can also serve as the oxygen barrier layer. The oxygen barrier layer and the peeling layer contain an alkali-soluble resin or a water-soluble polymer material. As the alkali-soluble resin, a polymer having a carboxylic acid group in the side chain, for example, JP-A-59-44615 and JP-B-54
-34327, Japanese Patent Publication 58-12577, Japanese Patent Publication 5
Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid as described in JP-A-4-25957, JP-A-59-53836 and JP-A-59-71048. Copolymer, maleic acid copolymer,
There are partially esterified maleic acid copolymers and the like, and a cellulose derivative having a carboxylic acid group in the side chain can be mentioned. In addition, a polymer having a hydroxyl group and a cyclic acid anhydride added thereto is also useful. Particularly preferred is a copolymer of benzyl (meth) acrylate and (meth) acrylic acid described in U.S. Pat. No. 4,139,391, or a multicomponent copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers. Examples of the water-soluble polymer material include polyvinyl alcohol and polyvinylpyrrolidone.

Any known release layer or oxygen barrier layer can be applied without limitation. Specifically, for example, the separation layer described in JP-A-4-208940,
JP-A-5-80503 and JP-A-5-1733
For example, the alkali-soluble thermoplastic resin layer described in JP-A No. 20 and the separation layer having slight permeability to oxygen described in JP-A-5-72724 can be used.

[Photomask Material] The photomask material of the present invention comprises a light-transmissive base material on which at least the colored photosensitive layer and a temporary support are provided in this order, or a light-transmissive substrate. The colored photosensitive layer is provided on a material by coating. The temporary support and the colored photosensitive layer are the same as the temporary support and the colored photosensitive layer described in the description of the photosensitive transfer material. (Light-transmissive base material) As the transparent base material of the photomask material, a glass plate such as quartz, soda glass or non-alkali glass, or a transparent plastic film such as polyethylene terephthalate can be used. The thickness of the transparent substrate varies depending on its application, but is generally in the range of 1 to 7 mm.

[Method for Manufacturing Photomask] Next, a method for manufacturing the photomask of the present invention will be described. The photomask can be manufactured using the photomask material or the photosensitive transfer material. In the case of a photomask material having no temporary support, as it is, or in the case of using a photomask material having a temporary support, after peeling the temporary support, the photosensitive layer is exposed to light having a wavelength of 405 nm or more, or visible. It has at least the process of developing after exposing with the light of a wavelength range. Further, in the above-mentioned method for producing a photomask material, a method may be adopted in which the temporary support is not peeled from the photomask material in advance and is exposed from the temporary support side, and then the temporary support is peeled off to develop the photosensitive layer. Good.

Further, in the method of manufacturing a photomask,
When a photosensitive transfer material is used, the photosensitive transfer material as described above is laminated on a light-transmitting substrate so that the photosensitive layer is in contact with the light-transmitting substrate, and then the photosensitive layer is formed on the light-transmitting substrate. It is a method of transferring onto a substrate, peeling off the temporary support, and then exposing and developing the photosensitive layer. Further, in the above-mentioned method for producing a photomask material, a method may be adopted in which the temporary support is not peeled from the photomask material in advance and is exposed from the temporary support side, and then the temporary support is peeled off to develop the photosensitive layer. Good.

For image formation of the photomask material of the present invention, laser exposure is preferably used. Specific examples thereof include a 442 nm HeCd laser, a 488 nm argon laser, and a 532 nm NdYAG laser, but the present invention is not limited thereto. Examples of the developer used in the present invention include aqueous solutions of alkali metal or alkaline earth metal hydroxides or carbonates, hydrogen carbonates, aqueous ammonia, and quaternary ammonium salts. Particularly preferred is an aqueous sodium carbonate solution. Examples of the etching solution for etching the metal film include cerium ammonium nitrate and perchloric acid for chromium, and hydrochloric acid for aluminum.

In the present invention, after forming an image on the photosensitive layer on the transparent substrate, it is also possible to heat the photosensitive layer in the range of 120 ° C. to 250 ° C. to increase the film strength. If the temperature is less than 120 ° C, the heat treatment has no effect
In the above case, the material is decomposed, and on the contrary, it becomes brittle and has a weak film quality, which is not preferable. The treatment time is appropriately 15 to 60 minutes, and a known means such as a dry oven or a hot plate can be used for heating.

[0049]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Example 1 (1) Preparation of Photomask Material Formation of Colored Photosensitive Layer On a soda glass substrate having a thickness of 5 mm, the following colored photosensitive layer coating solution was applied by a spinner to a dry film thickness of 3 μm. did. <Preparation of Coating Solution for Colored Photosensitive Layer> First, a green pigment dispersion and a yellow pigment dispersion were prepared as follows. << Preparation of Green Pigment Dispersion >> The following green pigment composition was applied to a motor mill M-200 (manufactured by Eiger) to have a diameter of 1.0.
Using a zirconia bead of mm, the dispersion was performed at a peripheral speed of 9 m / s for 5 hours to obtain a green pigment dispersion. C. I. Pigment Green 7 63 parts by mass Compound 1 represented by the following structural formula 3.15 parts by mass V259MB (Cardo resin manufactured by Nippon Steel Chemical Co., acid value 100.7 mgKOH / g) 31.5 parts by mass 1-methoxy-2-propylacetate 352.4 parts by mass

[0050]

[Chemical 7]

<< Preparation of Yellow Pigment Dispersion >> The following yellow pigment composition was dispersed in a motor mill M-200 (manufactured by Eiger) using zirconia beads having a diameter of 1.0 mm at a peripheral speed of 9 m / s for 3.5 hours. A yellow pigment dispersion was obtained. C. I. Pigment Yellow 138 54 parts by mass of the above compound 1 2.7 parts by mass V259MB (Cardo resin manufactured by Nippon Steel Chemical Co., Ltd., acid value 100.7 mgKOH / g) 27.0 parts by mass 1-methoxy-2-propylacetate 366.3 Mass part

[0052] << Preparation of coating liquid for colored photosensitive layer >> 36.16 parts by mass of the green pigment dispersion liquid 35.17 parts by mass of the yellow pigment dispersion liquid Methacrylic acid / allyl methacrylate / benzyl methacrylate copolymer (copolymer Combined composition ratio (molar ratio) = 28/48/24) 2.47 parts by mass Dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.)                                                     6.04 parts by mass Compound 2 represented by the following structural formula 0.45 parts by mass Irgacure 784 (Ciba Specialty Chemicals)                                                     1.38 parts by mass Compound 3 1.03 parts by mass represented by the following structural formula Hydroquinone monomethyl ether 0.003 parts by mass F176P (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.)                                                   0.021 parts by mass Methyl ethyl ketone 70.40 parts by mass 1-Methoxy-2-propyl acetate 19.14 parts by mass

[0053]

[Chemical 8]

Formation of Oxygen Barrier Layer The following oxygen barrier layer formulation was formed on the photosensitive layer to a thickness of 1.6 μm to prepare a photomask material. <Oxygen barrier layer prescription> Polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd., saponification rate = 80%) 21.2 parts by mass Polyvinylpyrrolidone (PVP, K-30 manufactured by GAF Corporation) 2.35 parts by mass Methanol 214 parts by mass Distillation Water 262 parts by mass

(2) Preparation of photomask FR7000 manufactured by Dainippon Screen Co., Ltd. as a laser plotter from the oxygen blocking layer side of the photomask material.
(The light source was a 532 nm NdYAG laser) and it exposed. Then, it was immersed in an alkaline developer (10% aqueous solution of TCD manufactured by Fuji Photo Film Co., Ltd.) at 28 ° C. for 90 seconds to perform a development treatment, further washed with ion-exchanged water and dried. Subsequently, heat treatment was performed at 200 ° C. for 30 minutes to obtain a desired photomask. A resolution of line / space = 8 μm / 8 μm was obtained, and the exposure sensitivity was high at about 0.45 mJ / cm ² . Further, it was found that the pencil hardness was 5H to 6H, and the solvent resistance was not scratched even by a wiping test with acetone, and the solvent resistance was sufficient as a photomask.

[Use of Photomask] Next, pattern exposure of an ultraviolet-sensitive resist material was performed using the photomask manufactured here. On a glass plate (glass plate is 5% K
After washing with an OH alkaline aqueous solution and washing with water, surface treatment with hexamethyldisilazane), a positive resist film (positive resist 204LT manufactured by FUJIFILM Ohlin Co., Ltd.), which is a UV-sensitive resist material, to a thickness of 1.5 μm. Formed into
The photomask was brought into contact, and exposed using an aligner equipped with a 2 KW ultra-high pressure mercury lamp under the condition of 250 mJ / cm ² . After exposure, a tetramethylammonium hydroxide-based developer (FH manufactured by FFO) is used as a developer.
D-5) was used for immersion for 45 seconds at room temperature (23 ° C.) and washing with water to evaluate the image of the positive resist. A good image was formed that reproduced the image of the photomask.

Example 2 (1) Preparation of Photosensitive Transfer Material 1) Formation of Release Layer On a temporary PET support having a thickness of 100 μm, a release layer coating solution having the following composition was applied, dried, and dried. Thickness 0.7
A μm release layer was provided. (Release layer coating liquid composition) Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 55/12/5/28, weight average molecular weight = 95000, Tg≈73 ° C.) 7 mass Part Styrene / acrylic acid copolymer (copolymerization molar ratio 63/37, weight average molecular weight = 10 000, Tg≈100 ° C.) 16.33 parts by mass Compound of bisphenol A with 2 equivalents of octaethylene glycol monomethacrylate dehydrated and condensed ( Shin-Nakamura Chemical Co., Ltd. BPE-500 10.89 parts by mass F176P (Dainippon Ink and Chemicals, Inc. fluorine-containing surfactant) 1.96 parts by mass Methyl ethyl ketone 508.1 parts by mass Methanol 13.32 parts by mass Methoxy Propanol 7.44 parts by mass 1-methoxy-2-propylacetate 231.9 parts by mass

2) Formation of Oxygen Barrier Layer Next, an oxygen barrier layer coating solution having the following composition was applied onto the release layer and dried to provide an oxygen barrier layer having a dry film thickness of 1.6 μm. . (Oxygen barrier layer coating liquid composition) Polyvinyl alcohol (Kuraray Co., Ltd. PVA205, saponification rate = 80%) 21.2 parts by mass Polyvinylpyrrolidone (GAF Corporation, PVP K-30 2.35 parts by mass Methanol 214 parts by mass) Distilled water 262 parts by mass

3) Formation of Photosensitive Layer Next, the coating solution for the colored photosensitive layer used in Example 1 was formed on the above oxygen barrier layer to a thickness of 3 μm, and further formed on this layer. A 12 μm polypropylene film was laminated as a protective layer to obtain a colored photosensitive transfer material.

(2) Preparation of Photomask Material After peeling off the polypropylene film of the photosensitive transfer material prepared in the above (1), the photosensitive layer side of the transfer material is
A laminator (MDL601 manufactured by Muromachi Chemical Co., Ltd.) was laminated on the alkali-cleaned soda glass substrate under heating at 130 ° C. to obtain a photomask material. At this time, the alkali cleaning of the glass substrate is performed using Semicoclean SE.
The glass substrate was immersed in 10 (Furuuchi Chemical Co., Ltd.), ultrasonic waves were applied for 15 minutes, washed with ion-exchanged water, and further dried at 110 ° C. for 10 minutes.

(3) Preparation of Photomask The PET temporary support of the photomask material of (2) above was peeled off and exposed with FR7000 (NdYAG laser of 532 nm light source) manufactured by Dainippon Screen Co., Ltd. as a laser plotter. . Next, use an alkaline developer (TCD10% aqueous solution manufactured by Fuji Photo Film Co., Ltd.) at 28 ° C. for 120
It was dipped for a second for development, washed with ion-exchanged water, and dried. Subsequently, heat treatment was performed at 200 ° C. for 30 minutes to obtain a desired photomask. A resolution of line / space = 8 μm / 8 μm is obtained, and the exposure sensitivity is about 0.
It was 8 mJ / cm ² . Further, the pencil hardness was 5H, and the solvent resistance was no problem in the wiping test with acetone.

Comparative Example 1 Instead of the dispersant used in preparing the pigment dispersion liquid (green and yellow pigment) of Example 1, a dispersant containing no polymerizing group (methacrylic acid / benzyl methacrylate copolymer of MW 30000) was used. Polymer, molar ratio 2
8/72), but in the same manner as in Example 1,
A photomask having a line / space of 10 μm / 10 μm was produced. The exposure sensitivity was as low as about 2.3 mJ / cm ² . The pencil hardness was 4H to 5H, and the solvent resistance was poor in that the surface was scratched by an acetone wiping test.

[0063]

Since the photosensitive layer in the photosensitive transfer material or photomask material of the present invention has the composition as described above, the cured film has high mechanical strength and hardness and good solvent resistance. In addition, since the sensitivity in the visible region is high, it is possible to perform writing with laser light having a wavelength in the visible region, which has a large drawing energy.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/40 501 G03F 7/40 501 F term (reference) 2H025 AA01 AA02 AA06 AB11 AB14 AB15 AB17 AB20 AC01 AC08 AD01 BC14 BC42 BC74 BC85 CC11 DA04 FA29 2H095 BA11 BA12 BB08 BB38 BC06 BC08 BC19 2H096 AA26 AA30 BA05 BA06 CA16 EA04 EA23 HA01

Claims (11)

[Claims] 1. On a temporary support, i) at least one alkali-soluble resin binder represented by the following general formula (1) having a polymerizable unsaturated bond, ii) at least one polymerizable unsaturated bond. A monomer having a saturated bond, iii) 40
A photosensitive transfer material comprising at least a photopolymerization initiation system having sensitivity to light in a long wavelength region of 5 nm or more, and iv) a photosensitive layer containing a colorant. [Chemical 1] In the general formula (1), R represents a hydrogen atom or a methyl group, and X represents a residue of an aromatic or alicyclic carboxylic acid having 2 to 4 carboxyl groups. n is 0
Represents an integer of 20. 2. A photomask material in which the photosensitive transfer material according to claim 1 is laminated on a light-transmissive base material such that the photosensitive layer side of the photosensitive transfer material faces the base material. 3. A light-transmissive substrate, at least:
i) At least one alkali-soluble resin binder represented by the following general formula (1) having a polymerizable unsaturated bond
A photosensitive layer containing a seed, ii) a monomer having at least one polymerizable unsaturated bond, iii) a photopolymerization initiation system having sensitivity to light in a long wavelength region of 405 nm or more, and iv) a colorant. Photomask material formed by coating. [Chemical 2] In the general formula (1), R represents a hydrogen atom or a methyl group, and X represents a residue of an aromatic or alicyclic carboxylic acid having 2 to 4 carboxyl groups. n is 0
Represents an integer of 20. 4. The photomask material according to claim 2, further comprising an oxygen barrier layer provided on the photosensitive layer. 5. The photomask material according to claim 2, wherein the coloring material contains at least one pigment selected from a blue pigment and a green pigment. 6. A photomask in which at least a pattern forming layer is provided on a light-transmitting substrate, wherein the pattern forming layer has the following general formula (1) having i) a polymerizable unsaturated bond. At least one alkali-soluble resin binder represented, ii) a monomer having at least one polymerizable unsaturated bond, iii) a photopolymerization initiation system having photosensitivity to light in a long wavelength region of 405 nm or more, and i
v) A photomask, which is a layer obtained by exposing and developing a photosensitive layer containing a coloring material with light in a long wavelength region of 405 nm or more. [Chemical 3] In the general formula (1), R represents a hydrogen atom or a methyl group, and X represents a residue of an aromatic or alicyclic carboxylic acid having 2 to 4 carboxyl groups. n is 0
Represents an integer of 20. 7. A method for producing a photomask, which comprises at least a step of exposing and developing the photosensitive layer with light having a wavelength of 405 nm or more after peeling off the temporary support of the photomask material according to claim 2. 8. A step of exposing the photosensitive layer from the side of the temporary support of the photomask material according to claim 2 with light having a wavelength of 405 nm or more, a step of peeling the temporary support, and a step of developing the photosensitive layer. A method for manufacturing a photomask, which has at least. 9. A method for producing a photomask, which comprises at least a step of exposing and developing the photosensitive layer of the photomask material according to claim 3 with light having a wavelength of 405 nm or more. 10. The method according to any one of claims 7 to 9.
Item 8. A method for producing a photomask, which comprises subjecting the photosensitive layer after the development treatment described in the item 1 to heat treatment within a range of 120 ° C to 250 ° C. 11. The method for manufacturing a photomask according to claim 7, wherein the exposure is performed with laser light in a wavelength range of 405 nm to a visible wavelength.