JP2002214779A - Photosensitive resin laminate for sandblast - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin laminate excellent in sensitivity, resolution and adhesion, capable of forming a fine pattern in a substrate to be worked as a mask material for sandblast in a good yield and less liable to generate scum in a developing step and to provide a surface working method using the laminate. SOLUTION: The photosensitive resin laminate is obtained by stacking a photosensitive resin layer comprising a photosensitive resin composition containing a polyurethane prepolymer, an alkali-soluble polymer, an ethylenically unsaturated addition polymerizable monomer of a specified formula and a photopolymerization initiator and, optionally, a protective layer on a base. Surface working is carried out using the laminate.

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 resin laminate excellent in resolution and adhesion, capable of processing a fine pattern on a substrate to be processed as a mask material for sandblasting with high yield, and generating less scum in a developing process, and a surface processing method using the same About.

[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
No. 34 discloses a photosensitive resin composition comprising a carboxy-modified urethane (meth) acrylate compound, an alkali-soluble polymer compound and a photopolymerization initiator.

Also, a photosensitive resin comprising a urethane compound having an acrylate or methacrylate group at a terminal, an alkali-soluble polymer compound and a photopolymerization initiator disclosed in JP-A-8-305017 and JP-A-9-127692. Composition or polyurethane prepolymer having an ethylenically unsaturated bond at a terminal, alkali-soluble polymer and ethylenically unsaturated addition-polymerizable monomer disclosed in JP-A-10-239840 and JP-A-11-188631 And a photosensitive resin laminate containing a photosensitive resin composition containing a photopolymerization initiator.

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 where a photomask having a desired fine pattern is in close contact with the support or at a distance of tens to hundreds of μm, and (c) the support is peeled off A developing step of dissolving and removing an unexposed portion of the photosensitive resin layer using an alkali developing solution to form a fine resist pattern on the substrate, and (d) spraying a blast material from above the formed resist pattern, A plasma blasting process through a sand blasting process of cutting to a desired depth, and (e) a stripping process of removing a resist pattern from a substrate using an alkali stripping solution. It is possible to form the panel of the partition wall.

[0006]

However, in the case where the conventional photosensitive resin laminate as described above is used, the scum ( (Hereinafter referred to as developing scum), and settled at the bottom of the developing tank, and clogged the spray nozzle for spraying the developing solution. Also, when the proportion of the photosensitive resin composition present in the alkali developer increases, the amount of the development scum also increases accordingly, and adheres to a glass substrate or a low-melting glass substrate, which may lower the production yield of the partition walls. there were.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the use of a photosensitive resin laminate composed of a specific photosensitive resin layer has reduced the occurrence of development scum. Low, excellent in sensitivity, resolution and adhesion,
As a mask material for sandblasting, it has been found that a fine pattern can be processed on a substrate to be processed with high yield.

That is, the present invention provides (1) a support (A) having (i) a polymer or monomer having a hydroxyl group at a terminal, a polyisocyanate, a functional group having active hydrogen, and an ethylenically unsaturated bond in the molecule. A polyurethane prepolymer obtained from the compound, (ii) an alkali-soluble polymer, (iii) a photopolymerization initiator, and (iv) a compound represented by the following chemical formula (I) as an ethylenically unsaturated addition-polymerizable monomer. A photosensitive resin laminate for sandblasting, wherein a photosensitive resin layer (B) made of a photosensitive resin composition is laminated.

[0009]

Embedded image (R ₁ is a hydrogen atom or a methyl group, R ₂ is an ethylene group, R
₃ is a propylene group, R ₄ is an alkylene group having 4 to 6 carbon atoms,
R ₅ represents an alkyl group or a halogen group having 1 to 15 carbon atoms. L, M, and N are integers equal to or greater than 0, and their sum is 2
~ 15. T represents an integer of 0 to 3. )

In the invention of the above (1), as a preferred embodiment, the photosensitive material for sandblasting according to the above (1), further comprising a compound having at least three terminal ethylene groups as an ethylenically unsaturated addition polymerizable monomer. Functional resin laminate. In the invention of the above (1), laminating a protective layer (C) as necessary on the photosensitive resin layer (B) is also one of the embodiments of the present invention.

The present application further provides the following inventions. (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) of the present invention is a film for supporting the photosensitive resin layer of the present invention, and is preferably formed of a transparent base film that transmits active light. As such a substrate film, there is a synthetic resin film such as polyethylene, polypropylene, polycarbonate, polyethylene terephthalate and the like having a thickness of about 10 to 100 μm, but usually polyethylene terephthalate having appropriate flexibility and strength is preferably used.

The polyurethane prepolymer of the component (i) of the present invention has a functional group having an active hydrogen and an ethylenic non-functional 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 can be obtained by reacting a compound having a saturated bond 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 2 × 10 ^-4 to 10 ^-2 mo.
1 / g is preferred. If it is less than 2 × 10 ⁻⁴ mol / g, it will not be sufficiently crosslinked and will cause a significant decrease in sandblast resistance.
If it exceeds 0 ^-2 mol / g, the cured film becomes too hard and the sandblast resistance deteriorates.

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. Here, the number average molecular weight is the number average molecular weight in terms of polystyrene by the GPC method.

The content of the polyurethane prepolymer of the component (i) is 10 to 70% by weight, preferably 20 to 65% by weight, more preferably 2 to 70% by weight based on the total weight of the photosensitive resin composition.
5 to 60% by weight. When the amount is less than 10% by weight, sufficient sandblast resistance cannot be obtained, and when it exceeds 70% by weight, crosslinking is not sufficiently performed, and the sandblast resistance is reduced and the sensitivity is remarkably reduced. The polyurethane prepolymer of the component (i) may be used alone,
Two or more kinds may be used in combination.

Examples of the alkali-soluble polymer of the component (ii) of 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. 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 a compound obtained by vinyl copolymerizing at least one second monomer selected from glycidyl (meth) acrylate.

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. They may be used alone or in combination of two or more. The ratio 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, preferably from 30,000 to 150,000. The weight average molecular weight in this case is GPC
It is the weight average molecular weight in terms of polystyrene by the 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 coating property 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 photo-curing of the photosensitive resin layer becomes insufficient, and the sandblast resistance decreases.

The photopolymerization initiator of the component (iii) of the present invention includes 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, 4-fluorothioxanthone,

2-chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, benzophenone, 4,4'-bis (dimethylamino) benzophenone [Michler's ketone], 4,4'-
Aromatic ketones such as bis (diethylamino) benzophenone and 2,2-dimethoxy-2-phenylacetophenone; biimidazole compounds such as 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer;
Acridines such as phenylacridine, α, α-dimethoxy-α-morpholino-methylthiophenylacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylglycine, N-phenylglycine

Oxime esters such as 1-phenyl-1,2-propanedione-2-o-benzoyl oxime and ethyl 2- (o-benzoylcarbonyl) -oxime 2,3-dioxo-3-phenylpropionate ,
Examples thereof include p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, p-diisopropylaminobenzoic acid, esters of these alcohols, and p-hydroxybenzoic acid esters. Among them, 2- (o
-Chlorophenyl) -4,5-diphenylimidazolyl dimer and Michler's ketone or 4,4 '-(diethylamino) benzophenone are preferred.

The content of the photopolymerization initiator (iii) is 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.

The component (iv) of the present invention is a compound represented by the following chemical formula (I). Ethylene oxide and propylene oxide contained in the structure of the compound;
As long as the total of the repeating units of the alkylene oxide of No. 6 is 2 to 15, it may be in a random manner or may be in a block.

[0032]

Embedded image (R ₁ is a hydrogen atom or a methyl group, R ₂ is an ethylene group, R
₃ is a propylene group, R ₄ is an alkylene group having 4 to 6 carbon atoms,
R ₅ represents an alkyl group or a halogen group having 1 to 15 carbon atoms. L, M, and N are integers equal to or greater than 0, and their sum is 2
~ 15. T represents an integer of 0 to 3. )

The compound (I) is a modified monool obtained by adding ethylene oxide and / or propylene oxide and / or an alkylene oxide having 4 to 6 carbon atoms to an alkyl-substituted, halogen-substituted or unsubstituted phenol by a known method; It can be obtained by an esterification reaction with an acid or methacrylic acid. Examples of such compounds include phenoxytetraethylene glycol (meth) acrylate, 4-normal octylphenoxypentapropylene glycol (meth) acrylate, 4-normal octylphenoxypentaethylene glycol tripropylene glycol (meth) acrylate, and 4-normalonyl. Phenoxytetrapropylene glycol tetraethylene glycol (meth) acrylate,

4-Normalonylphenoxypentapropylene glycol tri (tetramethylene glycol)
(Meth) acrylate, phenoxypentaethylene glycol tetra (tetramethylene glycol) (meth) acrylate, phenoxytetrapropylene glycol di (hexamethylene glycol) (meth) acrylate,
Normal octylphenoxytetraethylene glycol tri (hexamethylene glycol) (meth) acrylate, normal octylphenoxytetraethylene glycol tetrapropylene glycol di (tetramethylene glycol) (meth) acrylate and the like can be mentioned.

Of the compounds (I), those having a repeating unit of ethylene oxide and propylene oxide in the structure thereof are particularly preferred. As long as the total of the repeating units of ethylene oxide and propylene oxide is 2 to 15, the repeating units may be included randomly or as blocks.

Such compounds include normal nonyl phenoxy heptaethylene glycol dipropylene glycol (meth) acrylate, normal nonyl phenoxy nona ethylene glycol tripropylene glycol (meth) acrylate, and normal octyl phenoxy hexaethylene glycol tripropylene glycol (meth) Acrylate, normal nonyl phenoxy pentaethylene glycol pentapropylene glycol (meth)
Acrylate, phenoxytriethylene glycol tripropylene glycol (meth) acrylate and the like can be mentioned.

The content of the component (iv) is 2 to 30% by weight, preferably 5 to 20% by weight based on the total weight of the photosensitive resin composition. If the proportion is less than 2% by weight, the occurrence of scum in the developing step is not sufficiently reduced. If the proportion exceeds 30% by weight, the resolution and the adhesion will decrease.
The compound (I) of the component (iv) may be used alone or in combination of two or more.

The photosensitive resin composition of the present invention may contain an ethylenically unsaturated addition polymerizable monomer other than the component (iv). Such monomers include, for example, 2
-Hydroxy-3-phenoxypropyl 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, polyoxypropyl trimethylol propane tri (meth)
Acrylate, polyoxyethyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (Meth) acrylate,

Diallyl phthalate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bis (triethylene glycol methacrylate) nonapropylene glycol, bis (tetraethylene glycol methacrylate) polypropylene glycol, bis (triethylene glycol methacrylate) Examples include polypropylene glycol, bis (diethylene glycol acrylate) polypropylene glycol, 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.

More preferably, among the ethylenically unsaturated addition-polymerizable monomers other than the component (iv), a compound having at least three terminal ethylene groups is used. Such compounds include glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane tri (meth) acrylate, dipentaerythritol Examples thereof include penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and trimethylolpropane triglycidyl ether tri (meth) acrylate.

The total content of the ethylenically unsaturated addition polymerizable monomer other than the components (iv) and (iv) is 5 to 40% by weight, preferably 1 to 40% by weight based on the total weight of the photosensitive resin composition.
0 to 35% by weight. 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 decreases.

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 concentration of the ethylenically unsaturated bond in the photosensitive resin composition of the present invention is from 5.0 × 10 ^{-4 to} 3.0 × 10 ^-3 mol.
/ G. If this concentration is 5.0 × 10 ⁻⁴ mol / g, sufficient resolution cannot be obtained. In addition, this concentration is 3.
If it exceeds 0 × 10 ⁻³ mol / g, the cured film becomes too hard, and the sandblast resistance decreases. A more preferable range of the concentration of the ethylenically unsaturated bond is 8.0 × 10 ^{−4 to} 2.5 ×.
10 ⁻³ mol / g.

The concentration of the ethylenically unsaturated bond in this case 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.

The 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, a polypropylene film, and a polyester 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, mixed with a solvent that dissolves them to leave a uniform solution,
First, the surface of the support (A) on which a release agent has been previously formed is applied using a bar coater or a roll coater and dried, and the photosensitive resin layer (B) made of a photosensitive resin composition is formed on the support.
Are laminated. Next, a protective layer (C) is formed on the photosensitive resin layer (B).
To form a photosensitive resin laminate.

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 for 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. As shown in FIG. 2, a laminating step in which a protective layer of the photosensitive resin laminate of FIG. 1 is peeled off and adhered to a substrate to be processed using a hot roll laminator, and a photomask having a desired fine pattern is supported on a substrate. An exposure step of exposing the substrate using an actinic light source while in close contact with the substrate, dissolving and removing the unexposed portion of the photosensitive resin layer using an alkaline developer after removing the support, and applying a fine resist pattern on the substrate to be processed. Developing process, sandblasting process of spraying a blast material over the formed resist pattern to cut the substrate to a desired depth, and stripping the resist pattern from the substrate using an alkali stripper By sequentially performing the steps, a fine pattern can be processed on the substrate to be processed.

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.

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. A known blast material is used for the sand blasting process.
Fine particles of about 2 to 100 μm such as C, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, and glass 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.

[0057]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be described below in more detail with reference to examples. Note that the present invention is not limited to these 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,
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) Adhesion to resist line The 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: 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 part and the unexposed part 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 exposed entirely 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. Based on the wear time, the following ranking was performed. Less than 30 seconds: × More than 30 seconds and less than 60 seconds: △ More than 60 seconds: ○

(5) Generation amount of development scum The generation amount of development scum was measured as follows. The obtained photosensitive resin layer was taken out in an amount of 0.2 m ² , added to a 1.0% by weight aqueous solution of sodium carbonate, and stirred at room temperature for 2 hours with a stirrer. The weight of scum remaining on the well-dried backing paper was weighed.
Regarding the evaluation results, the weight of the developing scum of the comparative example was 1.
According to the relative value when it was set to 0, ranking was performed as follows. 0.5 or more and 1.0 or less: × 0.3 or more and less than 0.5: 未 満 less than 0.3: ◎

[0063]

EXAMPLES Examples 1 to 6 and Comparative Example 1 (Preparation of photosensitive resin laminate) A photosensitive resin composition having the composition shown in Table 1 was mixed, and a solution of the photosensitive resin composition having a thickness of 20 was prepared.
The resultant was uniformly coated on a μm polyethylene terephthalate film using a bar coater and dried in a drier at 90 ° C. for 4 minutes to form a photosensitive resin layer having a thickness of 40 μm. 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 types of soda glass having a thickness of 3 mm and soda glass coated with glass paste and 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 glass paste has a thickness of 150 μm after drying. A soda glass dried and coated with a glass paste was prepared.

(Lamination) While peeling off the polyethylene film of the photosensitive resin laminate, the photosensitive resin laminate was laminated on a substrate to be processed at 105 ° C. using a hot roll laminator (“AL-70” manufactured by Asahi Kasei Kogyo). Air pressure is 0.35MP
a 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 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,
% Aqueous sodium carbonate solution was sprayed for a predetermined period of time to dissolve and remove unexposed portions of the photosensitive resin layer.

Table 1 shows the results of Examples and Comparative Examples. The composition abbreviations shown in Table 1 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: methacrylic acid / methyl methacrylate / n-butyl acrylate (weight ratio: 25/65/1)
A 29% methyl ethyl ketone solution of a copolymer having the composition of 0) 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 ',
60.7 parts by weight of α'-tetramethyl-m-xylylene diisocyanate was added, and the mixture was stirred well and the external temperature was raised to 40.
The temperature was raised from 80 ° C. to 80 ° C. and allowed to react for about 5 hours, and then 2-hydroxyethyl methacrylate (molecular weight 130)
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 to 6;

[0074]

Embedded image M-1; p = 2, q + r = 5, _Ra = H,
_{R b = C 8 H 17 M} -2; p = 4, q + r = 4, R a = CH 3,
_Rb = HM-3; p = 7, q + r = 2, _Ra = H,
_{R b = C 9 H 19 M} -4; p = 2, q + r = 2, R a = CH 3,
_{R b = C 8 H 17 M} -5; p = 9, q + r = 3, R a = H,
_{R b = C 9 H 19 M} -6; p = 5, q + r = 5, R a = CH 3,
R _b = C ₉ H ₁₉

M-7: Trimethylolpropane triacrylate M-8: Dipentaerythritol hexaacrylate M-9: Urethane compound of hexamethylene diisocyanate and tripropylene glycol monomethacrylate M-10: Addition of 8 mol of propylene oxide on average Dimethacrylate of glycol obtained by adding 3 mol of ethylene oxide to both ends of polypropylene glycol thus obtained. M-11: 8 mol of propylene oxide and 8 mol of ethylene oxide reacted with bisphenol A, and dimethacrylate M-12 in which methacrylic acid is ester-bonded. : Nonaethylene glycol diacrylate

I-1: Bendidimethylketal I-2: Benzophenone I-3: 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer I-4: 2,4-Diethylthioxanthone I-5: Michler's ketone I-6: ethyl p-dimethylaminobenzoate

D-1: Leuco Crystal Violet D-2: Diamond Green

[0078]

[Table 1]

[0079]

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 scum can be reduced in the developing step.

[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 point glass substrate) 5 actinic ray 6 photomask 7 photosensitive resin layer (photocured portion) a laminating step b exposing step c developing step d Sandblasting process e Stripping process

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 290/06 C08F 290/06 5C040 299/02 299/02 G03F 7/004 511 G03F 7/004 511 512 512 7/038 501 7/038 501 H01J 9/02 H01J 9/02 F 11/02 11/02 B F term (reference) 2H025 AA01 AA02 AA14 AB11 AB20 AC01 AD01 BC13 BC32 BC65 BC66 BC83 BJ10 CA00 CB42 DA19 FA17 FA42 4J011 AC04 CA02 CC10 PA69 PB30 QB15 QB16 QB24 RA03 SA06 SA22 SA25 SA34 SA54 SA64 SA65 SA78 SA83 SA84 UA01 WA01 4J026 AA17 AA21 AA43 AA45 AA46 AA48 AA49 AA50 AA76 AC29 AC36 BA27 BA28 BA50 DB06 DB11 AC04 AG03 AG03 AC03 AG03 AG23 AG24 BA07 BA11 CA03 CB10 CD10 5C027 AA09 5C040 GF19

Claims (3)

[Claims] 1. A polyurethane prepolymer obtained from (i) a polymer or monomer having a hydroxyl group at the terminal, a polyisocyanate, a functional group having active hydrogen and an ethylenically unsaturated bond in the molecule of the support (A). A polymer, (ii) an alkali-soluble polymer, and (iii)
A photopolymerization initiator and (iv) a photosensitive resin layer (B) composed of a photosensitive resin composition containing a compound represented by the following chemical formula (I) as an ethylenically unsaturated addition polymerizable monomer are laminated. A photosensitive resin laminate for sandblasting. Embedded image (R ₁ is a hydrogen atom or a methyl group, R ₂ is an ethylene group, R
₃ is a propylene group, R ₄ is an alkylene group having 4 to 6 carbon atoms,
R ₅ represents an alkyl group or a halogen group having 1 to 15 carbon atoms. L, M, and N are integers equal to or greater than 0, and their sum is 2
~ 15. T represents an integer of 0 to 3. ) 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.