JP2002062645A - Photosensitive resin laminate for sandblasting - Google Patents

Abstract

(57) [Abstract] (with correction) [PROBLEMS] A mask for sandblasting, which is excellent in sensitivity, resolution and adhesion when applied to a substrate to be processed such as glass, low melting point glass, ceramic, etc., in particular, a plasma display panel. A photosensitive resin laminate capable of processing a fine pattern on a substrate to be processed as a material with a high yield, and capable of easily peeling a support from a photosensitive resin layer when a support peeling device is used, and a surface using the same. Provide a processing method. SOLUTION: A photosensitive resin composition containing a polyurethane prepolymer, an alkali-soluble polymer, an ethylenically unsaturated addition-polymerizable monomer, and a photopolymerization initiator on a support comprising a base film having a release agent formed on the surface thereof. A photosensitive resin layer made up of, and a protective layer as required, are sequentially laminated, and surface processing is performed using the laminated layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive resin laminate for sandblasting, and more particularly, to a sensitivity, when applied to a substrate to be processed such as glass, low melting point glass, and ceramic, particularly to a plasma display panel. A photosensitive material that has excellent resolution and adhesiveness, can process fine patterns on the substrate to be processed with good yield as a mask material for sandblasting, and can easily peel the support from the photosensitive resin layer when a support peeling device is used. TECHNICAL FIELD The present invention relates to a conductive resin laminate and a surface processing method using the same.

[0002]

2. Description of the Related Art In recent years, with the progress of photolithography technology and sandblasting technology, glass, low melting point glass,
It has become possible to process ceramics into fine patterns. In particular, in the production of a plasma display panel that requires forming a partition in a lattice, stripe, or waffle shape by processing glass or low-melting glass by sandblasting, recently, with the narrowing of the pixel pitch, the recent 1
Pattern formation at a pitch of 50 μm or less has been required.

In order to produce such a fine partition pattern with good yield, a photosensitive resin laminate in which a photosensitive resin layer is laminated on a film serving as a support, and a protective layer is further laminated as necessary is often used. ing. For example, JP-A-8-547
JP-A-8-305017, JP-A-9-127692, a photosensitive resin composition comprising a carboxy-modified urethane (meth) acrylate compound, an alkali-soluble polymer compound and a photopolymerization initiator disclosed in JP-A-34 JP-A-10-239840, JP-A-11-18863, which discloses a photosensitive resin composition comprising a urethane compound having an acrylate or methacrylate group at a terminal, an alkali-soluble polymer compound and a photopolymerization initiator.
No. 1, disclosed a polyurethane prepolymer having a terminal ethylenically unsaturated bond, a photosensitive resin composition containing an alkali-soluble polymer, an ethylenically unsaturated addition-polymerizable monomer, and a photopolymerization initiator, And the like.

A method of forming a partition of a plasma display panel using a photosensitive resin laminate will be described with reference to FIG. (A) a laminating step in which a protective layer of the photosensitive resin laminate of FIG. 1 is peeled off and closely adhered to a glass substrate or a low-melting glass substrate (hereinafter simply referred to as a substrate) using a hot roll laminator; An exposure step of performing exposure using an actinic ray source in a state in which a photomask having a desired fine pattern is in close contact with the support or separated by several tens to several hundreds of μm, and (c) peeling the support After that, the unexposed portion of the photosensitive resin layer is dissolved and removed using an alkali developing solution to form a fine resist pattern on the substrate. (D) A blast material is sprayed on the formed resist pattern, Through a sand blasting step of cutting the substrate to a desired depth, and (e) a stripping step of removing the resist pattern from the substrate using an alkali stripping solution. It can be formed Ipaneru of the partition wall.

In the step (c), as a means for peeling the support, a manual or automatic support peeling device as exemplified below is used. For example,
Japanese Patent No. 1819952 and Japanese Patent Application Laid-Open No. 62-180371 disclose a method in which an end portion of a cover film is floated by a needle-like projection pressing member, and the cover film is peeled off by spraying a fluid on the floated portion. A part of the cover film is raised using a brush composed of a plurality of hard needles such as resin and steel on the outer peripheral portion of the rotating body described in Japanese Patent No. 1800966 and Japanese Patent Laid-Open No. 62-56243. A method of spraying a fluid between the raised cover film and the substrate to peel off the cover film;
A cover film is raised by using a sticky member provided with a sticky substance on a cylindrical rotating body described in 51556, and a fluid is sprayed between the raised cover film and the substrate. And a method of peeling the cover film by raising a part of the cover film by pressing a plurality of raised linear blades against the edge of the cover film described in JP-A-63-250190. Also, as described in JP-A-62-83974, the cover wheel is peeled by blowing an air jet to the front end portion of the film after pressing and moving the pressure wheel along the front end of the cover film to loosen the front end portion of the film. And a method described in Japanese Patent Application Laid-Open No. 7-101623, in which a member provided with a plurality of small projections at the tip is intermittently provided at a plurality of locations along the film edge. And the like method and pressed multiple times, to peel off the cover film by blowing gas jets towards the film edge at the pushed area.

[0006]

However, when the conventional photosensitive resin laminate as described above is used, a projection pressing member, a brush, an adhesive member, a trigger line, and the like used in the above-described support peeling device are used. Even if a support stripping member such as a blade, a pressure wheel, or a member having small projections is used, a part of the support cannot be sufficiently caused, so that the support cannot be reliably separated. there were. In addition, when an excessive force is applied to the support or the force is applied many times by using the above-described support peeling triggering member to cause a part of the support, the support may be torn or exposed. There is a problem that the conductive resin layer and the substrate are damaged. In addition, when a low-melting glass substrate is used, when the support is forcibly peeled off, the adhesion between the photosensitive resin layer and the low-melting glass substrate is small. There was a problem that peeling occurred at the interface of the glass substrate. Especially after laminating the photosensitive resin laminate on the low melting glass substrate, if left for a long time under high humidity, because the adhesion between the support and the photosensitive resin layer increases,
The above problem was more remarkably recognized.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a support comprising a film having a release agent formed on the surface thereof and a photosensitive material comprising a specific photosensitive resin layer. By using a resin laminate, a part of the support can be sufficiently caused without damaging the support, the photosensitive resin layer, and the substrate, and the support can be easily pulled by a manual or automatic support peeling device. It has been found that it can be peeled off.

That is, the present invention provides (1) a support (A) comprising a base film having a release agent formed on its surface,
(I) a polymer or monomer having a hydroxyl group at a terminal, a polyisocyanate, a polyurethane prepolymer obtained from a compound having a functional group having an active hydrogen and an ethylenically unsaturated bond in the molecule, and (ii) a high alkali solubility. A photosensitive resin layer (B) comprising a molecule, (iii) an ethylenically unsaturated addition-polymerizable monomer, and (iv) a photosensitive resin composition containing a photopolymerization initiator. It is a photosensitive resin laminate for sandblasting.

In the above invention (1), the following aspects are preferred embodiments. (A) The photosensitive resin laminate for sandblasting according to the above (1), wherein the release agent is a release agent containing silicone or an alkyd resin. (B) The photosensitive resin laminate for sandblasting as described in (1) above, wherein the release agent is an alkyd-modified silicone. In the above invention (1), the photosensitive resin layer (B)
Laminating a protective layer (C) as necessary on the layer is also one of the embodiments of the present invention.

Further, the present application also provides the following invention. (2) Forming a photosensitive resin layer on the substrate to be processed using the photosensitive resin laminate according to the above (1), forming a resist pattern by an exposure step and a development step, and then performing a sandblast treatment. Characteristic surface processing method. (3) The surface processing method according to the above (2), wherein the substrate to be processed is a plasma display panel.

Hereinafter, the present invention will be described in detail. The support (A) used in the present invention is a film for supporting the photosensitive resin layer of the present invention, and a release agent is applied to one or both surfaces of a transparent base film that transmits active light. It is formed. As such a base film, there is a synthetic resin film of polyethylene, polypropylene, polycarbonate, polyethylene terephthalate or the like having a thickness of about 10 to 100 μm, but usually polyethylene terephthalate having appropriate flexibility and strength is preferably used.

The release agent referred to here is a compound having the property of easily releasing the base film from the photosensitive resin layer, and known compounds can be used. Alkyd resins are preferred. Examples of the silicone-containing release agent include condensation reaction type silicone obtained by reacting polydimethylsiloxane with silanol at both ends with polymethylhydrogensiloxane or polymethylmethoxysiloxane, dimethylsiloxane / methylvinylsiloxane copolymer or dimethylsiloxane / methylhexenyl An addition reaction type silicone obtained by reacting a siloxane copolymer with polymethyl hydrogen siloxane,
UV-curable or electron beam-curable silicone obtained by curing acrylic silicone or epoxy group-containing silicone with ultraviolet rays or electron beams, epoxy-modified silicone (silicone epoxy), polyester-modified silicone (silicone polyester), acryl-modified silicone (silicone acrylic) ), Phenol-modified silicone (silicone phenol), alkyd-modified silicone (silicone alkyd), and melamine-modified silicone (silicone melamine).

[0013] A silicone-containing release agent formed on a polyethylene terephthalate film includes:
For example, release film # 2 manufactured by Teijin DuPont Films
4, # 31, # 34, # 35, # 36, # 43, # 7
0, # 71, # 75, # 50, # 51, # 52, # 5
3, # 54, # 63, Diafoil MRF type, MRA type, MRX type manufactured by Mitsubishi Chemical Polyester, 19E-0010CH manufactured by Fujimori Kogyo, PET38GS, PET25GS, PET381 manufactured by Lintec
1, PET2511, PET25X, PET38X, P
ET50X, PETL25X, PETL38X, PET
L50X, PET25SK-1 and PET38SK-1 and the like.

The alkyd resin formed on a polyethylene terephthalate film includes, for example, PET25AL-5 manufactured by Lintec Corporation. It is particularly preferable that the release agent is an alkyd-modified silicone, because the release agent does not easily fall off the substrate film even when the photosensitive resin laminate of the present invention is stored for a long period of time.
Examples of the alkyd-modified silicone formed on a polyethylene terephthalate film include PET25X, PET38X, PET50X, and PE50X manufactured by Lintec Corporation.
TL25X, PETL38X, PETL50X, PET
25SK-1 and PET38SK-1.

The release agent may be used alone, or a plurality of release agents may be used in combination. The release agent may contain an additive or the like for the purpose of controlling the releasability. The thickness of the release agent applied on the base film is 0.01 to 10 μm, preferably 0.05 to 2 μm.
μm. The polyurethane prepolymer of the component (i) used in the present invention has a functional group having an active hydrogen and an ethylenically unsaturated group with respect to a terminal isocyanate group of a polyurethane derived from a polymer or a monomer having a terminal hydroxyl group and a polyisocyanate. It is obtained by reacting a compound having a bond together in the molecule.

As the polymer having a hydroxyl group at the terminal,
Polyols such as polyester polyols and polyether polyols, 1,4-polybutadiene having a terminal hydroxyl group, hydrogenated or non-hydrogenated 1,2-polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, hydroxyl group at the terminal Examples of the monomer having the above include glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, and triethylene glycol, and diols having a carboxyl group in a molecule such as dimethylolpropionic acid.

Examples of the polyisocyanate include toluylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, O-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, α, α ' -Dimethyl-O-xylylene diisocyanate, α, α′-dimethyl-m-xylylene diisocyanate, α, α′-dimethyl-p-xylylene diisocyanate, α, α, α′-trimethyl-O-xylylene diisocyanate, α, α, α′-trimethyl-m-xylylene diisocyanate, α, α,
α'-trimethyl-p-xylylene diisocyanate,
α, α, α ′, α′-tetramethyl-O-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-
m-xylylene diisocyanate, α, α, α ′, α ′
-Tetramethyl-p-xylylene diisocyanate, cyclohexane diisocyanate and the like.

Compounds having both a functional group having active hydrogen and an ethylenically unsaturated bond in the molecule include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Examples include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. The concentration of ethylenically unsaturated bonds in the polyurethane prepolymer (i) is
It is preferably 2 × 10 ⁻⁴ to 10 ⁻² mol / g. 2 × 10 ^-4
If it is less than 10 mol / g, it will not be sufficiently crosslinked and the sandblast resistance will be remarkably reduced. If it exceeds 10 ^-2 mol / g, the cured film will be too hard and the sandblast resistance will be deteriorated.

The number average molecular weight of the polyurethane prepolymer (i) is preferably from 1,500 to 50,000. If the number average molecular weight is less than 1,500, the sandblast resistance is reduced, and if it is more than 50,000, the developability after exposure is significantly reduced. A number average molecular weight of 2,000 to 30,000 is more preferred from the viewpoint of sandblast resistance and developability. The number average molecular weight here is GP
It is the number average molecular weight in terms of polystyrene by the C method.

The content of the polyurethane prepolymer (i) is from 10 to 70, based on the total weight of the photosensitive resin composition.
%, Preferably 20 to 65% by weight, more preferably 25 to 60% by weight. If the amount is less than 10% by weight, sufficient sandblast resistance cannot be obtained, and if it exceeds 70% by weight, crosslinking is not sufficiently performed, so that the sandblast resistance is reduced and the sensitivity is significantly reduced. The polyurethane prepolymer of the component (i) may be used alone or in combination of two or more.

Examples of the alkali-soluble polymer of the component (ii) used in the present invention include a carboxylic acid-containing vinyl copolymer and a carboxylic acid-containing cellulose. The carboxylic acid-containing vinyl copolymer refers to at least one first monomer selected from α, β-unsaturated carboxylic acids, an alkyl (meth) acrylate, a hydroxyalkyl (meth) acrylate, and a (meth) acrylate. At least one second monomer selected from acrylamide and a compound in which hydrogen on the nitrogen is substituted with an alkyl group or an alkoxy group, styrene and a styrene derivative, (meth) acrylonitrile, and glycidyl (meth) acrylate It is a compound obtained by vinyl copolymerization. Examples of the first monomer used in the carboxylic acid-containing vinyl copolymer include acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, and maleic acid half ester, each of which is used alone. Or two or more of them may be combined. The proportion of the first monomer in the carboxylic acid-containing vinyl copolymer is 15 to 40% by weight, preferably 20 to 35% by weight. If the proportion is less than 15% by weight, development with an alkaline aqueous solution becomes difficult. If the proportion exceeds 40% by weight, it becomes insoluble in the solvent during the polymerization, so that the synthesis becomes difficult.

As the second monomer used in the carboxylic acid-containing vinyl copolymer, methyl (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, cyclohexyl (meth) acrylate, n
-Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate,
Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate,
(Meth) acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, styrene, α
-Methylstyrene, p-methylstyrene, p-chlorostyrene, (meth) acrylonitrile, glycidyl (meth) acrylate, etc., may be used alone or in combination of two or more.

The proportion of the second monomer in the carboxylic acid-containing vinyl copolymer is 60 to 85% by weight, preferably 65 to 85% by weight.
~ 80% by weight. The weight average molecular weight of the carboxylic acid-containing vinyl copolymer ranges from 20,000 to 300,000, and preferably from 30,000 to 150,000. In this case, the weight average molecular weight is a weight average molecular weight in terms of polystyrene by a GPC method. If the weight average molecular weight is less than 20,000, the strength of the cured film will be low. When the weight average molecular weight exceeds 300,000, the viscosity of the photosensitive resin composition becomes too high, and the coatability is lowered.

Examples of the carboxylic acid-containing cellulose include cellulose acetate phthalate and hydroxyethyl carboxymethyl cellulose. The content of the alkali-soluble polymer is 10 to 70% by weight, preferably 20 to 65% by weight, more preferably 25 to 60% by weight based on the total weight of the photosensitive resin composition. If this amount is less than 10% by weight, the dispersibility in an alkali developing solution is reduced, and the developing time is significantly increased. If this amount exceeds 70% by weight, the photocuring of the photosensitive resin layer becomes insufficient, and the sandblast resistance decreases.

As the ethylenically unsaturated addition-polymerizable monomer of the component (iii) used in the present invention, known types of compounds can be used. Such materials include, for example, 2-hydroxy-3-phenoxypropyl acrylate, phenoxytetraethylene glycol acrylate, β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate, 1,4-tetramethylene glycol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, octapropylene glycol di (meth) acrylate, glycerol (meth) acrylate, 2-di (p-hydroxyphenyl) ) Propane di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polio Siethyl trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) A acrylate, diallyl phthalate, polyethylene glycol di (meth) acrylate,
Polypropylene glycol di (meth) acrylate, 4
-Normal octylphenoxypentapropylene glycol acrylate, bis (triethylene glycol methacrylate) nonapropylene glycol, bis (tetraethylene glycol methacrylate) polypropylene glycol, bis (triethylene glycol methacrylate) polypropylene glycol, bis (diethylene glycol acrylate) polypropylene glycol, 4-
Examples include normal octylphenoxypentaethylene glycol tripropylene glycol acrylate, phenoxytetrapropylene glycol tetraethylene glycol acrylate, and compounds containing both an ethylene oxide chain and a propylene oxide chain in the molecule of a bisphenol A (meth) acrylate monomer.

Hexamethylene diisocyanate,
A urethane compound of a polyvalent isocyanate compound such as toluylene diisocyanate and a hydroxy acrylate compound such as 2-hydroxypropyl (meth) acrylate can also be used. The urethane compound in this case has a number average molecular weight of less than 1,500 in terms of polystyrene by GPC. These ethylenically unsaturated addition-polymerizable monomers may be used alone or in combination of two or more.

The content of the ethylenically unsaturated addition-polymerizable monomer of the component (iii) is 5 to 40% by weight, preferably 10 to 35% by weight based on the total weight of the photosensitive resin composition. If the proportion is less than 5% by weight, the composition is not sufficiently crosslinked, and the sandblast resistance is reduced. If the proportion exceeds 40% by weight, the cured film becomes too hard and the sandblast resistance is reduced.

As the photopolymerization initiator of the component (iv) used in the present invention, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl dipropyl ketal, benzyl diphenyl ketal, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, Benzoin phenyl ether, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone,
4-isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-fluorothioxanthone,
-Fluorothioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, benzophenone, 4,4'-bis (dimethylamino) benzophenone [Michler's ketone], 4,4'-bis (diethylamino) benzophenone Aromatic ketones such as 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl)-
Biimidazole compounds such as 4,5-diphenylimidazolyl dimer, acridines such as 9-phenylacridine, α, α-dimethoxy-α-morpholino-methylthiophenylacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Phenylglycine, N-phenylglycine and 1-phenyl-1,2
-Propanedione-2-o-benzoyl oxime, 2,
Ethyl 3-dioxo-3-phenylpropionate-2-
Oxime esters such as (o-benzoylcarbonyl) -oxime, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid and p-diisopropylaminobenzoic acid, and their esterified products with alcohols, p-hydroxybenzoic acid esters, etc. No. Among them, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and Michler's ketone or 4,
A combination of 4 '-(diethylamino) benzophenone is preferred.

The content of the photopolymerization initiator (iv) is as follows:
It is contained in an amount of 0.01 to 20% by weight, preferably 1 to 10% by weight based on the total weight of the photosensitive resin composition. If this amount is 0.
If it is less than 01%, the sensitivity is not sufficient. This amount is 2
If the content is more than 0% by weight, the ultraviolet ray absorption rate becomes high, and the curing at the bottom of the photosensitive resin layer becomes insufficient. It is preferable that the photosensitive resin composition of the present invention contains a radical polymerization inhibitor in order to improve the thermal stability and storage stability of the photosensitive resin composition. Such radical polymerization inhibitors include:
For example, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2,6-di-t-butyl-p-cresol,
2,2′-methylenebis (4-ethyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6
-T-butylphenol) and the like.

The photosensitive resin composition of the present invention may contain coloring substances such as dyes and pigments. Examples of such coloring substances include fuchsin, phthalocyanine green, auramine base, chalcoxide green S, paramagenta, crystal violet, methyl orange,
Nile Blue 2B, Victoria Blue, Malachite Green, Basic Blue 20, Diamond Green and the like.

Further, the photosensitive resin composition of the present invention may contain a coloring dye which develops a color upon irradiation with light. As such a coloring dye, a combination of a leuco dye and a halogen compound is well known. Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green] and the like. On the other hand, as the halogen compound, amyl bromide, isoamyl bromide,
Isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris (2,3-dibromopropyl) phosphate, trichloroacetamide,
Examples thereof include amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, and hexachloroethane.

Further, the photosensitive resin composition of the present invention may contain additives such as a plasticizer, if necessary. Examples of such additives include phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide,
p-toluenesulfonic acid amide, tributyl citrate,
Examples include triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.

The photosensitive resin composition of the present invention has an ethylenically unsaturated bond concentration of 5.0 × 10 ^{−4 to} 3.0 × 10 ⁻³ mol.
/ G. If the concentration is less than 5.0 × 10 ⁻⁴ mol / g, sufficient resolution cannot be obtained. If the concentration exceeds 3.0 × 10 ⁻³ mol / g, the cured film becomes too hard, and the sandblast resistance is reduced. A more preferable range of the concentration of the ethylenically unsaturated bond is 8.0 × 10 ⁻⁴ to 2.
It is 5 × 10 ⁻³ mol / g.

In this case, the concentration of the ethylenically unsaturated bond is
It can be calculated by dividing the number of unsaturated bonds contained in the ethylenically unsaturated addition polymerizable monomer and the polyurethane prepolymer in the photosensitive resin composition by the total mass of the photosensitive resin composition. The ethylenically unsaturated bond concentration can also be determined by the following method. That is, the photosensitive resin composition is dissolved in a solvent, and an excess of a Wiis reagent is added to brominate the ethylenically unsaturated bond. By adding potassium iodide to the unreacted whis reagent and titrating the liberated iodine with sodium thiosulfate, the concentration of ethylenically unsaturated bonds can be determined.

A protective layer (C) is laminated on the photosensitive resin laminate of the present invention, if necessary. In the adhesive strength between the photosensitive resin layer and the photosensitive resin layer, it is a necessary property for the protective layer that the adhesive strength between the photosensitive resin layer and the protective layer be sufficiently smaller than the adhesive strength between the photosensitive resin layer and the support. The protective layer can be easily peeled off. Examples of such a film include a polyethylene film and a polypropylene film. A method of preparing a photosensitive resin laminate by sequentially laminating the support (A), the photosensitive resin layer (B), and the protective layer (C) can be performed by a conventionally known method. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent for dissolving the same to form a uniform solution. First, a bar coater or a roll coater is formed on the surface of the support (A) on which a release agent has been formed in advance. Is applied and dried, and a photosensitive resin layer composed of a photosensitive resin composition is laminated on a support. Next, by laminating the protective layer (C) on the photosensitive resin layer, a photosensitive resin laminate can be prepared.

The light transmittance at 365 nm of the photosensitive resin layer (B) of the photosensitive resin laminate is preferably 2 to 30%. If the light transmittance is less than 2%, the curing at the bottom of the photosensitive resin layer becomes insufficient, and the adhesiveness decreases. When the light transmittance exceeds 30%, the resolution is reduced. A more preferable range of the light transmittance is 3 to 25%.
The light transmittance can be controlled by blending a compound having an absorption wavelength at 365 nm, for example, a photopolymerization initiator, a dye, a pigment, a pigment, an ultraviolet absorber, and the like, and changing the blending amount. Light transmittance can be easily measured using a visible ultraviolet spectrophotometer.

Next, an example of a method of processing a fine pattern on a substrate to be processed using the photosensitive resin laminate of the present invention will be described with reference to FIG. A laminating step in which a protective layer of the photosensitive resin laminate of FIG. 1 is peeled off while being adhered to a substrate to be processed using a hot roll laminator, a photomask having a desired fine pattern is adhered to a support, and an actinic ray source is activated. An exposure step of performing exposure using a developing step of dissolving and removing an unexposed portion of the photosensitive resin layer using an alkaline developer after peeling off the support, and forming a fine resist pattern on the substrate to be processed. Through a sand blasting process of spraying a blast material over the resist pattern and cutting the substrate to a desired depth, and a stripping process of removing the resist pattern from the substrate using an alkali stripping liquid. A fine pattern can be processed thereon.

The actinic light source used in the exposure step includes a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, a xenon lamp and the like. In order to obtain a finer resist pattern, it is more preferable to use a parallel light source. When it is desired to minimize the influence of dust or foreign matter, exposure (proximity exposure) may be performed with the photomask floating above the support by several tens to several hundreds of micrometers.

In the developing step, when the support is peeled from the photosensitive resin layer, the release agent formed on the surface of the support may or may not remain on the photosensitive resin layer. As the alkali developing solution used in the developing step, an aqueous solution of sodium carbonate, an aqueous solution of a surfactant or the like is usually used. As the blast material used in the sand blasting process, known materials are used, for example, SiC, SiO
2, 2- such as Al2O3, CaCO3, ZrO, glass, etc.
Fine particles of about 100 μm are used.

As the stripping solution used in the stripping step, an aqueous solution of sodium hydroxide or potassium hydroxide is usually used. Note that a step of burning off the resist pattern at a high temperature may be provided instead of the peeling step.

[0041]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. The evaluation in Examples and Comparative Examples was performed by the following method. (1) Minimum development time A photosensitive resin layer is formed on soda glass, and 30% of 1%
An aqueous solution of sodium carbonate was sprayed, and the time required for the unexposed photosensitive resin layer to dissolve was measured, and this was defined as the minimum development time.

(2) Resist Line Adhesion Exposure was performed through a line pattern in which the width of the exposed portion and the unexposed portion during exposure was 1: 100. Developing was performed for a developing time 1.5 times the minimum developing time, and the minimum mask width at which the cured resist line was normally formed was defined as the resist line adhesion value. The following ranking was made based on the adhesion. 50 μm or less: ◎ More than 50 μm and 70 μm or less: ○ More than 70 μm and 100 μm or less: Δ More than 100 μm: ×

(3) Resolution of resist line Exposure was performed through a line pattern in which the width of the exposed portion and the unexposed portion at the time of exposure was 1: 1. 1.5 of minimum development time
The development was performed for twice the developing time, and the minimum mask width at which the cured resist lines were normally formed was defined as the resist line adhesion value. The following ranking was made based on the adhesion. 50 μm or less: ◎ More than 50 μm and 70 μm or less: ○ More than 70 μm and 100 μm or less: Δ More than 100 μm: ×

(4) Sandblast resistance The photosensitive resin layer was entirely exposed without a photomask.
Next, the distance between the blast material discharge nozzle and the sample was set to 100.
mm, abrasive application pressure 0.3MPa, abrasive injection amount 50
g / min, and sand blasting was performed using glass beads # 200 as a blast material. The time until the resin layer was worn to form a through hole (wear time) was measured. The wear time was used to rank the following. Less than 30 seconds: × More than 30 seconds and less than 60 seconds: △ More than 60 seconds: ○

(5) Peelability of support by automatic peeling device for support A support layer and a photosensitive resin layer were laminated on soda glass or soda glass coated with glass paste.
Using a cover film peeling device PSX-3000II (manufactured by Tokuyama Corporation), a metal pressure wheel (knurl) is moved along the tip of the support while pressing it to loosen the tip of the support. The support was peeled off by blowing an air jet into the tip. The pressure to press the pressure wheel is 0.3 ~
0.5MPa, the moving speed of the pressure wheel is 0.5m / sec,
One reciprocation was performed. The pressure of the air jet was 0.3 MPa. The support was peeled using 10 substrates per Example or Comparative Example, and the number of substrates from which the support was completely peeled was divided by the number of tested substrates to calculate the peel probability. The ranking was as follows. Support peeling probability 100%: ◎ Support peeling probability 80% or more and less than 100%: ○ Support peeling probability less than 80%: △ When the support is peeled, the support, the photosensitive resin layer or the substrate is removed. Damaged: ×

(6) Adhesive strength between support and photosensitive resin layer,
Adhesive strength between photosensitive resin layer and soda glass coated with glass paste After laminating the support layer and the photosensitive resin layer on soda glass coated with glass paste, it was left at 23 ° C. and 75% high humidity for 48 hours. did. A cut is made in a width of 1 inch from above the support, and the adhesive strength (180 degree peel strength, peeling speed of 10 when peeling the support from the photosensitive resin layer) is obtained.
0 mm / min, hereafter referred to as adhesive strength 1) and the adhesive strength when peeling the photosensitive resin layer from the glass paste-coated soda glass (180 degree peel strength, peeling speed 1)
00 mm / min, hereinafter referred to as adhesive strength 2).

[0047]

Examples 1 to 12 and Comparative Examples 1 and 2 (Preparation of photosensitive resin laminate) A photosensitive resin composition having the composition shown in Table 1 was mixed.
The solution of the photosensitive resin composition was evenly applied to the surface of the support described in Table 2 on which the release agent was previously formed using a bar coater, and dried in a drier at 90 ° C. for 4 minutes to 40 μm.
A photosensitive resin layer having a thickness was formed. Next, a 30 μm-thick polyethylene film was laminated on the surface of the photosensitive resin layer to obtain a photosensitive resin laminate.

(Substrate to be processed) As the substrate to be processed, two kinds of soda glass having a thickness of 3 mm and soda glass coated with glass paste prepared by the following method were used. A glass paste for plasma display (PLS-3553, manufactured by Nippon Electric Glass Co., Ltd.) is applied on soda glass having a thickness of 3 mm using a screen printing method so that the dried thickness of the glass paste becomes 150 μm. A soda glass dried and coated with a glass paste was prepared. (Lamination) While peeling off the polyethylene film of the photosensitive resin laminate, lamination was performed at 105 ° C. on a substrate to be processed using a hot roll laminator (“AL-70” manufactured by Asahi Kasei Kogyo). The air pressure was 0.35 MPa, and the laminating speed was 1.0 m / min.

(Exposure) An ultra-high pressure mercury lamp (HMW-80 manufactured by Oak Manufacturing Co., Ltd.) was passed through a support without a photomask on the photosensitive resin layer or through a photomask required for evaluation.
Exposure was performed at 150 mJ / cm ^{2 according} to 1). (Development) After the support was peeled off, a 1% aqueous solution of sodium carbonate at 30 ° C. was sprayed for a predetermined time to dissolve and remove unexposed portions of the photosensitive resin layer.

Table 2 shows the results of Examples and Comparative Examples. The abbreviations of the compositions and supports shown in Tables 1 and 2 are as follows. P-1: methacrylic acid / methyl methacrylate / styrene / acrylonitrile (weight ratio is 30/25/25/2)
A 35% methyl ethyl ketone solution of a copolymer having the composition of 0) and having a weight average molecular weight of 80,000. P-2: 35% methyl ethyl ketone solution of a copolymer having a composition of methacrylic acid / methyl methacrylate / acrylonitrile (weight ratio 23/52/25) and having a weight average molecular weight of 130,000. P-3: 29% methyl ethyl ketone solution of a copolymer having a composition of methacrylic acid / methyl methacrylate / n-butyl acrylate (weight ratio: 25/65/10) and having a weight average molecular weight of 80,000. P-4: 29% methyl ethyl ketone solution of a copolymer having a composition of methacrylic acid / methyl methacrylate / n-butyl acrylate (weight ratio: 20/40/40) and having a weight average molecular weight of 100,000.

O-1: Urethane prepolymer A (Production of urethane prepolymer A) 200 parts by weight of polypropylene glycol (hydroxyl value: 74.8) and 0.01 g of BTL as a catalyst were put in a reaction vessel and mixed well. Thereto, 27.9 parts by weight of hexamethylene diisocyanate was added, the mixture was stirred well, the external temperature was raised from 40 ° C. to 80 ° C., and the mixture was allowed to react for about 5 hours, and then 2-hydroxyethyl acrylate (molecular weight 116) was added. 8.5 parts by weight were added and the mixture was stirred well. When the reaction was completed for about 2 hours, the reaction was stopped to obtain a urethane prepolymer A. The number average molecular weight of urethane prepolymer A was 10,000.

O-2: Urethane prepolymer B (Production of urethane prepolymer B) Poly (1,4-butanediol adipate) diol (having a hydroxyl value of 112.
2) 200 parts by weight and 0.01 g of dibutyltin dilaurate (hereinafter abbreviated as BTL) as a catalyst were put in a reaction vessel and mixed well. There isophorone diisocyanate 5
After adding 1.4 parts by weight and stirring well, the external temperature was raised to 40 ° C.
The temperature was raised to 80 ° C and the reaction was continued for about 5 hours.
8.3 parts by weight of -hydroxyethyl acrylate (molecular weight 116) was added, and the mixture was stirred well. When the reaction was completed for about 2 hours, the reaction was stopped to obtain a urethane prepolymer B.
The number average molecular weight of urethane prepolymer B is 15,000.
Met.

O-3: Urethane prepolymer C (Production of urethane prepolymer C) 150 parts by weight of polyethylene glycol (having a hydroxyl value of 112.2) and poly (1,1)
50 parts by weight of 6-hexanediol adipate) diol (hydroxyl value 74.8) and 0.01 g of BTL as a catalyst were put in a reaction vessel and mixed well. There, α, α, α ',
After adding 60.7 parts by weight of α'-tetramethyl-m-xylylene diisocyanate, stirring well,
The temperature was raised from 80 ° C. to 80 ° C. and allowed to react for about 5 hours.
Was added and the mixture was stirred well. When the reaction was completed for about 2 hours, the reaction was stopped to obtain a urethane prepolymer C. The number average molecular weight of the urethane prepolymer C is 5,000
It was 0.

O-4: Urethane prepolymer D (Production of urethane prepolymer D) Poly (propylene glycol adipate) diol (hydroxyl value 44.9) 1
00 parts by weight and a polyoxyethylene (EO) -oxypropylene (PO) block copolymer diol (EO / PO).
100 parts by weight of a molar ratio of 1/4, a hydroxyl value of 44.9) and 0.01 g of BTL as a catalyst were put in a reaction vessel and mixed well. 17.8 parts by weight of m-xylylene diisocyanate was added thereto, and the mixture was stirred well and the external temperature was raised from 40 ° C to 80 ° C.
After the temperature was raised to ° C. and the reaction was allowed to proceed for about 5 hours, 3.9 parts by weight of 2-hydroxyethyl acrylate (molecular weight 116) was added, and the mixture was stirred well. When the reaction was completed for about 2 hours, the reaction was stopped to obtain a urethane prepolymer D. The number average molecular weight of urethane prepolymer D was 21,000.

M-1: Trimethylolpropane triacrylate M-2: Phenoxyhexaethylene glycol acrylate M-3: Dipentaerythritol hexaacrylate M-4: Urethane compound of hexamethylene diisocyanate and tripropylene glycol monomethacrylate M-5 : Dimethacrylate of glycol in which ethylene oxide is further added to polypropylene glycol having an average of 8 moles of propylene oxide and 3 moles of ethylene oxide are added to both ends. M-6: After reacting 8 moles of propylene oxide and 8 moles of ethylene oxide with bisphenol A, methacrylic acid M-7: Nonaethylene glycol diacrylate I-1: Bendidimethyl ketal I-2: Benzophenone I-3: 2- ( - chlorophenyl) -4,5-diphenyl imidazolyl dimer I-4: 2,4-diethyl thioxanthone I-5: Michler's ketone I-6: p-dimethylaminobenzoic acid ethyl

D-1: Leuco Crystal Violet D-2: Diamond Green S-1: Diafoil MRF 25 micron thickness (Mitsubishi Chemical Polyester) S-2: PET25SK-1 25 micron thickness (Lintec) S- 3: PETL25X 25 micron thickness (manufactured by Lintec) S-4: Teijin release film # 54 25 micron thickness (manufactured by Teijin DuPont Films) S-5: 19E-0010CH 20 micron thickness (manufactured by Fujimori Industries) S-6 : Teijin release film # 53 25 micron thickness (manufactured by Teijin DuPont Films) S-7: Polyethylene terephthalate film Diafoil 20 micron thickness (manufactured by Mitsubishi Chemical Polyester)

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

The photosensitive resin laminate for sandblasting of the present invention is excellent in sensitivity, resolution and adhesion when applied to a substrate to be processed such as glass, low melting point glass, ceramic, etc., in particular, a plasma display panel. As a mask material for sandblasting, there is an effect that a fine pattern can be processed on a substrate to be processed with good yield, and the support can be easily separated from the photosensitive resin layer when a support release device is used.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing one example of a photosensitive resin laminate of the present invention.

FIG. 2 is a cross-sectional view showing one example of a method for processing a fine pattern on a substrate to be processed (glass substrate, low-melting glass substrate) using the photosensitive resin laminate of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 support 2 photosensitive resin layer 3 protective layer 4 substrate to be processed (glass substrate, low melting glass substrate) 5 actinic ray 6 photomask 7 photosensitive resin layer (photocured portion)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/40 521 G03F 7/40 521 5C027 H01J 9/02 H01J 9/02 F 5C040 11/02 11/02 B // C08F 2/44 C08F 2/44 C 2/50 2/50 290/06 290/06 299/06 299/06 F term (reference) 2H025 AA01 AA02 AA13 AA14 AA16 AB11 AB20 AC01 AD01 BC13 BC42 BC66 BC83 CA00 CB43 DA19 DA33 EA08 FA42 2H096 AA30 BA05 CA02 HA23 4F100 AK01B AK03B AK04 AK12 AK24B AK24K AK25B AK27 AK51B AL05B AR00C AT00A BA02 BA03 Q07 PC10 BA10A BA10C CA30B EJ91C18 JBB J04B90 QA46 QB16 QB19 QB20 RA03 SA14 SA16 SA20 SA22 SA25 SA28 SA34 SA54 SA58 SA64 SA77 SA78 SA82 SA83 SA84 SA88 UA01 VA01 WA01 4J027 AC04 AE02 AG03 AG04 AG05 A G13 AG14 AG23 AG24 AG27 AG33 BA07 BA08 BA19 BA21 BA23 BA24 BA26 CA03 CB10 5C027 AA09 5C040 FA01 FA02 GF02 GF03 GF19 JA17 MA23 MA26

Claims (3)

[Claims] 1. A support (A) comprising a base film having a release agent formed on its surface, (i) a polymer or monomer having a hydroxyl group at a terminal, a polyisocyanate, a functional group having an active hydrogen and ethylene. A polyurethane prepolymer obtained from a compound having an unsaturated unsaturated bond in the molecule, (ii) an alkali-soluble polymer, (iii) an ethylenically unsaturated addition-polymerizable monomer, and (iv) a photopolymerization initiator. A photosensitive resin laminate for sandblasting, wherein a photosensitive resin layer (B) made of a photosensitive resin composition is laminated. 2. A photosensitive resin layer is formed on a substrate to be processed by using the photosensitive resin laminate according to claim 1, a resist pattern is formed by an exposure step and a development step, and then sandblasting is performed. A surface processing method characterized by the above-mentioned. 3. The surface processing method according to claim 2, wherein the substrate to be processed is a plasma display panel.