JPH10239840A - Photosensitive resin composition for sandblast and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a material excellent in sensitivity, resolution, developability and adhesion and capable of forming a fine pattern on a substrate to be worked as a mask material for sandblast in a high yield by incorporating a specified urethane prepolymer. SOLUTION: This photosensitive resin compsn. contains a polymer having hydroxyl groups at terminals, a polyurethane prepolymer obtd. from a polyisocyanate represented by the formula (where each of R1-R4 is H or alkyl) and a compd. having an active hydrogen-contg. functional group and an ethylenic unsatd. bond, an alkali-soluble high molecular compd., an ethylenic unsatd. addition polymerizable monomer and a photopolymn. initiator. A photosensitive resin layer 2 made of this photosensitive resin compsn. is formed on a substrate 1 to obtain a photosensitive resin laminated body for sandblast. A protective layer 3 may be formed on the layer 2 if necessary.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition for sand blasting, and more particularly, to a sensitivity when applied to a substrate to be processed such as glass, low melting point glass and ceramic.
A photosensitive resin composition having excellent resolution, developability, and adhesion, and capable of processing a fine pattern on a substrate to be processed with good yield as a mask material for sandblasting, and a photosensitive resin laminate using the same, and using the same. Related to the surface processing method used.

[0002]

2. Description of the Related Art Conventionally, a photosensitive resin composition has been used as a mask material when processing an uneven pattern on the surface of a substrate to be processed such as glass, ceramic, ceramics, stone, synthetic resin, metal, and leather by sandblasting. Have been. Examples of the photosensitive resin composition used as a mask material for such sandblasting include, for example, JP-A-55-10355.
Patent Document 4 discloses a photosensitive resin composition comprising an unsaturated polyester, an unsaturated monomer and a photopolymerization initiator, and a acrylate group or a methacrylate group at the terminal disclosed in JP-A-60-20861. A photosensitive resin composition comprising a urethane prepolymer having an unsaturated monomer and a photopolymerization initiator; a photosensitive resin composition comprising polyvinyl alcohol and a diazo resin disclosed in JP-A-2-69754; JP-A No. 161097 and JP-A-6-161098 discloses a photosensitive composition containing a urethane oligomer having a terminal ethylenically unsaturated double bond, a cellulose derivative or a compound containing an ethylenically unsaturated double bond, and a photopolymerization initiator. Resin compositions, carboxy-modified urethanes disclosed in JP-A-8-54734 (T) an acrylate compound, a photosensitive resin composition comprising an alkali-soluble polymer compound and a photopolymerization initiator, and a urethane compound having an acrylate or methacrylate group at a terminal disclosed in JP-A-8-305017 and an alkali-soluble compound Examples thereof include a photosensitive resin composition comprising a molecular compound and a photopolymerization initiator.

In recent years, with the progress of photolithography technology and sandblasting technology, it has become possible to process glass and ceramic into fine patterns with a pitch of 300 μm or less. For example, Japanese Patent Publication No. Hei 7-22893 discloses a method of forming a fine pattern of a low-melting glass using a sand blast apparatus. The performance required of a photosensitive resin composition as a mask material in such fine pattern processing by sandblasting has also become diverse and sophisticated.

That is, the performance required of a photosensitive resin composition as a mask material for sandblasting is 300
High sensitivity and high resolution so that resist patterns with a pitch of μm or less can be formed with a low exposure dose, excellent adhesion so that the resist pattern does not peel off from the substrate to be processed during development, damage by abrasives during sandblasting It is required to have sand blast resistance so that a substrate to be processed can be processed into a fine pattern without being subjected to such a process. When the substrate to be processed is glass or low-melting glass, in order to reduce damage by alkali as much as possible,
It is required that development time and stripping time be as short as possible.

However, the above-described conventional photosensitive resin composition has low sensitivity, requires a large amount of exposure for forming a resist pattern, and has poor developability, making it difficult to resolve a fine resist pattern. Or a long development time is required for resolution, the resist pattern is peeled off due to low adhesion to the substrate during development, or the resist line is chipped or worn during sandblasting. There was a problem such as peeling off due to the occurrence of. In particular, as the pattern pitch to be processed on the substrate to be processed becomes narrower, the above problem becomes remarkable, and the photosensitive resin composition which satisfies the above required performance and can process the substrate to be processed into a fine pattern with good yield. Things were desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to improve sensitivity, resolution, developability, and the like when applied to a substrate to be processed such as glass, low melting point glass, and ceramic.
Provided is a photosensitive resin composition having excellent adhesion and capable of processing a fine pattern on a substrate to be processed with good yield as a mask material for sandblasting, a photosensitive resin laminate using the same, and a surface processing method using the same. Is to do.

[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, have found that a photosensitive resin composition containing a specific urethane prepolymer and a photosensitive resin laminate using the same. It has been found that the above problem can be solved by using. That is, the first invention of the present application is:
(I) a polymer having a hydroxyl group at a terminal, a polyisocyanate represented by the following general formula (I),

[0008]

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(Wherein R1 to R4 are hydrogen or alkyl groups) and a polyurethane prepolymer obtained from a compound having an active hydrogen-containing functional group and an ethylenically unsaturated bond simultaneously, (ii) an alkali-soluble polymer compound, i
ii) an ethylenically unsaturated addition polymerizable monomer, and (i)
v) A photosensitive resin composition for sandblasting, comprising a photopolymerization initiator.

A second invention of the present application is a photosensitive resin laminate for sand blast having a photosensitive resin layer (B) made of the photosensitive resin composition for sand blast of the first invention on a support (A). Further, in this photosensitive resin laminate,
If necessary, a protective layer (C) can be provided on the photosensitive resin layer (B).

A third invention of the present application is to form a photosensitive resin layer comprising the photosensitive resin composition for sandblasting of the first invention on a substrate to be processed, and form a resist pattern by an exposure step and a development step. This is a surface processing method characterized by performing sandblasting. A fourth invention of the present application is to form a photosensitive resin layer on the substrate to be processed by using the photosensitive resin laminate for sand blasting of the second invention, form a resist pattern by an exposure step and a development step, and then perform a sand blast treatment. Surface processing method characterized by performing.

A fifth invention of the present application is the surface processing method according to the third invention or the fourth invention, wherein the substrate to be processed is a plasma display panel. Hereinafter, the present invention will be described in detail. The polyurethane prepolymer of the component (i) of the present invention has a functional group having an active hydrogen and an ethylenically unsaturated bond at the same time as the terminal isocyanate group of a polyurethane having a hydroxyl group at the terminal and a polyisocyanate. It is obtained by reacting a compound.

As the polymer having a hydroxyl group at the terminal,
Examples include 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, and the like. . Used in the present invention,
The polyisocyanate is a compound represented by the general formula (I). R1 to R4 in the formula are hydrogen or an alkyl group. Examples of such polyisocyanates include O-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, α-methyl-
O-xylylene diisocyanate, α-methyl-m-xylylene diisocyanate, α-methyl-p-xylylene diisocyanate, α, α′-dimethyl-O-xylylene diisocyanate, α, α′-dimethyl-m-xylylene diisocyanate Isocyanate, 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.

Examples of the compound having an active hydrogen-containing functional group and an ethylenically unsaturated bond at the same time include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polyethylene glycol monoester. (Meth) acrylate, polypropylene glycol mono (meth) acrylate and the like.

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 from 1,500 to 50,000.
0 is preferred. 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 (i) is 10 to 70% by weight, preferably 20 to 65% by weight, and more preferably 2 to 70% by weight based on the total weight of the photosensitive resin composition.
5 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 compound 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)
At least one selected from acrylates, (meth) acrylamides and compounds in which hydrogen on the nitrogen has been replaced with alkyl or alkoxy groups, styrene and styrene derivatives, (meth) acrylonitrile, and glycidyl (meth) acrylate; A compound obtained by copolymerizing two monomers with vinyl.

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 6
It is 0 to 85% by weight, preferably 65 to 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 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 as the component (ii) is 10 to 70% by weight, preferably 20 to 65% by weight based on the total weight of the photosensitive resin composition.
%, More preferably 25 to 60% by weight. 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. This amount is 7
If the content exceeds 0% by weight, the photo-curing of the photosensitive resin layer becomes insufficient, and the sandblast resistance decreases.

As the ethylenically unsaturated addition-polymerizable monomer of the component (iii) of the present invention, known types of compounds can be used. 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) propanedi (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropanetri (meth) acrylate, polyoxypropyltrimethylolpropanetri (meth) acrylate, polyoxyethyltrimethylolpropanetri (meth) acrylate, Pentaerythritol 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, 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-normal octylphenoxypentaethylene glycol tri Examples include propylene 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. Also, a urethane compound of a polyvalent isocyanate compound such as hexamethylene diisocyanate and toluylene diisocyanate with a hydroxy acrylate compound such as 2-hydroxypropyl (meth) acrylate can 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 as 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) of 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, 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, and further 1-phenyl-1,2-propanedione-2- Oxime esters such as o-benzoyl oxime, ethyl 2,3-dioxo-3-phenylpropionate-2- (o-benzoylcarbonyl) -oxime, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid and p-diisopropyl Examples thereof include aminobenzoic acid and esters thereof with alcohols, p-hydroxybenzoic acid esters, and the like. Among them, 2- (o-chlorophenyl) -4,
A combination of 5-diphenylimidazolyl dimer and Michler's ketone or 4,4 '-(diethylamino) benzophenone is preferred.

The content of the photopolymerization initiator (iv) is 0.01 to 20% by weight based on the total weight of the photosensitive resin composition.
Preferably, it is contained in an amount of 1 to 10% by weight. This amount is 0.01
%, The sensitivity is not sufficient. On the other hand, if the amount is more than 20% 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. Examples of such a radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2,6-di-t-butyl-p-cresol, 2,2
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 thereof include triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, and polypropylene glycol.

The photosensitive resin composition of the present invention may be applied to a substrate to be processed in a liquid state using a bar coater, a roll coater, a spin coater or the like to form a photosensitive resin layer, depending on the purpose of use. After a photosensitive resin layer (B) comprising the photosensitive resin composition of the present invention and a protective layer (C) are laminated in this order on the support (A), a photosensitive resin laminate is formed. It can be used by laminating on a processing substrate.

The support (A) of the photosensitive resin laminate is a film for supporting the photosensitive resin layer composed of the photosensitive resin composition of the present invention, and is made of a transparent material that transmits active light. preferable. 10 ~ 100 for such material
There are synthetic resin films of polyethylene, polypropylene, polycarbonate, polyethylene terephthalate and the like having a thickness of about μm, but usually polyethylene terephthalate having appropriate flexibility and strength is preferably used.

A protective layer (C) is laminated on the photosensitive resin laminate as required. The property required for the protective layer is that the adhesive force between the photosensitive resin layer and the protective layer in the adhesive force between the photosensitive resin layer (B) and the support is sufficiently smaller than the adhesive force between the photosensitive resin layer and the support. Thus, the protective layer can be easily peeled off. Examples of the film used for such a protective layer 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 (B) is mixed with a solvent for dissolving them to form a uniform solution, and is first coated on the support (A) using a bar coater or a roll coater. And dried, and the photosensitive resin layer (B) is laminated on the support. Next, the photosensitive resin layer (B)
By laminating the protective layer (C) thereon, a photosensitive resin laminate can be prepared.

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 ray 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. As the alkali developing solution used in the developing step, an aqueous solution of sodium carbonate or an aqueous solution of a surfactant is usually used.

As the blast material used in the sand blasting process, known materials are used, for example, SiC, SiO
₂ , fine particles of about ₂ to 100 μm such as Al ₂ O ₃ , ZrO, and glass are used. As the stripping solution used in the stripping step, an aqueous solution of sodium hydroxide or potassium hydroxide or the like 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.

The photosensitive resin composition and the photosensitive resin laminate of the present invention are suitable for producing an electronic display, particularly a plasma display panel.

[0037]

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

(2) Resist Line Adhesion The resist line was exposed 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: を More than 50 μm and 70 μm or less: ○ More than 70 μm and 100 μm or less: Δ More than 100 μm: × (3) 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 and an abrasive application pressure of 3 kg / cm ² , 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: ○

[0039]

Examples 1 to 20, Comparative Examples 1 to 30 (Preparation of Photosensitive Resin Laminate) Photosensitive resin compositions having the compositions shown in Tables 1 to 5 were mixed, and the thickness of the solution of the photosensitive resin composition was adjusted to a thickness. A 20 μm polyethylene terephthalate film was uniformly coated using a bar coater and dried in a drier at 90 ° C. for 4 minutes to form a 40 μm thick photosensitive resin composition layer. 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 used for sandblasting, two types of soda glass and soda glass coated with glass paste and prepared by the following method were used. A glass paste for plasma display (PLS-3150 manufactured by Nippon Electric Glass Co., Ltd.) is applied on soda glass using a screen printing method so that the thickness after drying of the glass paste becomes 150 μm, and the glass paste is dried. A paste-coated soda glass 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 3.5kg /
cm ² gauge, lamination speed 1.0m / min
And

(Exposure) No photomask on photosensitive resin layer
Or, through a photo mask required for evaluation,
15 with a silver lamp (HMW-801 manufactured by Oak Manufacturing Co., Ltd.)
0mJ / cm ^TwoExposure. (Development) Peel off the polyethylene terephthalate film
After that, a 1% aqueous solution of sodium carbonate at 30 ° C is
By playing, unexposed portions of the photosensitive resin layer were dissolved and removed.

Tables 1 to 5 show the compositions and results of the examples and comparative examples. The composition abbreviations shown in Tables 1 to 5 are as follows. P-1: 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-2: methacrylic acid / methyl methacrylate / styrene / acrylonitrile (weight ratio: 30/25)
/ 25/20) and a 35% methyl ethyl ketone solution of a copolymer having a weight average molecular weight of 80,000. 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: methacrylic acid / methyl methacrylate / n-butyl acrylate (weight ratio: 20/40/4)
A 29% methyl ethyl ketone solution of a copolymer having the composition of 0) and having a weight average molecular weight of 100,000. O-1: Urethane prepolymer A (Production of urethane prepolymer A) poly (ethylene glycol adipate) diol (hydroxyl value 56.1) 20
0 parts by weight and dibutyltin dilaurate (hereinafter referred to as B)
0.01 g (abbreviated as TL) was placed in a reaction vessel and mixed well. There, m-xylylene diisocyanate (hereinafter m
23.0 parts by weight of XDI) were added, and the mixture was stirred well, the external temperature was raised from 40 ° C. to 80 ° C., and the mixture was reacted for about 5 hours, and then 2-hydroxyethyl acrylate (molecular weight 116) was added. 5.8 parts by weight were added and 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 15,000.

O-2: Urethane prepolymer B (Production of urethane prepolymer B) α, α, α ', α'
A urethane prepolymer B was obtained in the same manner as in the reaction of the urethane prepolymer A, except that 30.0 parts by weight of -tetramethyl-m-xylylene diisocyanate (hereinafter abbreviated as mTMXDI) was used. The number average molecular weight of urethane prepolymer B was 15,000.

O-3: Urethane prepolymer C (Production of urethane prepolymer C) Reaction was carried out in the same manner as urethane prepolymer A except that 27.3 parts by weight of isophorone diisocyanate (hereinafter abbreviated as IPDI) was used. Prepolymer C was obtained. The number average molecular weight of urethane prepolymer C was 15,000.

O-4: Urethane prepolymer D (Production of urethane prepolymer D) The same reaction as in urethane prepolymer A, except that 20.5 parts by weight of hexamethylene diisocyanate (hereinafter abbreviated as HMDI) was used. Urethane prepolymer D was obtained. The number average molecular weight of urethane prepolymer D was 15,000.

O-5: Urethane prepolymer E (Production of urethane prepolymer E) Tolylene diisocyanate (2,4-form / 2,6-form molar ratio 4/1, hereinafter T
The reaction was carried out in the same manner as the urethane prepolymer A, except that 21.3 parts by weight (abbreviated as DI) was used, to obtain a urethane prepolymer E. The number average molecular weight of the urethane prepolymer E was 15,000.

O-6: Urethane prepolymer F (Production of urethane prepolymer F) Poly (1,4-butanediol adipate) diol (having a hydroxyl value of 44.9)
100 parts by weight of polyoxyethylene (EO) -oxypropylene (PO) block copolymer diol (EO / P
100 parts by weight of an O mole ratio, 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 mXDI was added thereto, and the mixture was stirred well, the external temperature was raised from 40 ° C. to 80 ° C., and the mixture was reacted for about 5 hours. Parts by weight were added and stirred well.
When the reaction was completed for about 2 hours, the reaction was stopped to obtain a urethane prepolymer F. The number average molecular weight of urethane prepolymer F was 21,000.

O-7: Urethane prepolymer G (Production of urethane prepolymer G) mTMXDI
Except that 2 parts by weight were used, the reaction was carried out in the same manner as the urethane prepolymer F to obtain a urethane prepolymer G. The number average molecular weight of urethane prepolymer G was 21,000.

O-8: Urethane prepolymer H (Production of urethane prepolymer H) A urethane prepolymer H was obtained in the same manner as in the reaction of urethane prepolymer F except that 21.1 parts by weight of IPDI was used. The number average molecular weight of urethane prepolymer H was 21,000.

O-9: Urethane prepolymer I (Production of urethane prepolymer I) Except that 15.9 parts by weight of HMDI was used, the same reaction as in urethane prepolymer F was carried out to obtain urethane prepolymer I. The number average molecular weight of urethane prepolymer I was 21,000.

O-10: Urethane prepolymer J (Production of urethane prepolymer J) A urethane prepolymer J was obtained by reacting in the same manner as urethane prepolymer F, except that 16.4 parts by weight of TDI was used. The number average molecular weight of urethane prepolymer J was 21,000.

O-11: Urethane prepolymer K (Production of urethane prepolymer K) 200 parts by weight of polypropylene glycol (having a hydroxyl value of 74.8) and 0.01 g of BTL as a catalyst were put in a reaction vessel and mixed well. 31.3 parts by weight of mXDI was added thereto, and 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. Parts by weight were added and stirred well. When the reaction was completed for about 2 hours, the reaction was stopped to obtain a urethane prepolymer K. The number average molecular weight of urethane prepolymer K is 1
It was 0000.

O-12: Urethane prepolymer L (Production of urethane prepolymer L) mTMXDI
A urethane prepolymer L was obtained by reacting in the same manner as the urethane prepolymer K, except that 0 parts by weight was used. The number average molecular weight of the urethane prepolymer L was 10,000.

O-13: Urethane prepolymer M (production of urethane prepolymer M) Except for using 37.2 parts by weight of IPDI,
The urethane prepolymer M was reacted in the same manner as the urethane prepolymer K to obtain a urethane prepolymer M. The number average molecular weight of the urethane prepolymer M was 10,000.

O-14: Urethane prepolymer N (Production of urethane prepolymer N) Except that 27.9 parts by weight of HMDI was used, the same reaction as in urethane prepolymer K was carried out to obtain urethane prepolymer N. The number average molecular weight of the urethane prepolymer N was 10,000.

O-15: Urethane prepolymer O (Production of urethane prepolymer O) A urethane prepolymer O was obtained in the same manner as in the reaction of urethane prepolymer K except that 28.9 parts by weight of TDI was used. The number average molecular weight of the urethane prepolymer O was 10,000.

O-16: Urethane prepolymer P (Production of urethane prepolymer P) 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 and 0.01 g of BTL as a catalyst were placed in a reaction vessel and mixed well. 46.0 parts by weight of mXDI was added thereto, and the mixture was stirred well, the external temperature was raised from 40 ° C. to 80 ° C., and the mixture was reacted for about 5 hours, and then 2-hydroxyethyl methacrylate (mol. Parts by weight were added and stirred well. When the reaction was completed for about 2 hours, the reaction was stopped to obtain a urethane prepolymer P. The number average molecular weight of the urethane prepolymer P was 5,000.

O-17: Urethane prepolymer Q (Production of urethane prepolymer Q) mTMXDI60.
A urethane prepolymer Q was obtained in the same manner as in the reaction with the urethane prepolymer P except that 7 parts by weight was used. The number average molecular weight of the urethane prepolymer Q was 5,000.

O-18: Urethane prepolymer R (Production of urethane prepolymer R) Except that 54.9 parts by weight of IPDI was used, a reaction was carried out in the same manner as urethane prepolymer P to obtain urethane prepolymer R. The number average molecular weight of the urethane prepolymer R was 5,000.

O-19: Urethane prepolymer S (Production of urethane prepolymer S) A urethane prepolymer S was obtained in the same manner as the urethane prepolymer P, except that 41.0 parts by weight of HMDI was used. The number average molecular weight of the urethane prepolymer S was 5,000.

O-20: Urethane prepolymer T (Production of urethane prepolymer T) Except that 42.5 parts by weight of TDI was used, a reaction was carried out in the same manner as urethane prepolymer P to obtain urethane prepolymer T. The number average molecular weight of the urethane prepolymer T was 5,000.

M-1: Nonaethylene glycol diacrylate M-2: Urethane compound of hexamethylene diisocyanate and tripropylene glycol monomethacrylate M-3: Trimethylolpropane triacrylate M-4: Phenoxyhexaethylene glycol acrylate M -5: Dimethacrylate of glycol in which ethylene oxide is further added to both ends of polypropylene glycol having an average of 8 moles added to propylene oxide on an average of 3 moles I-1: benzophenone I-2: benzyldimethyl ketal I-3: Michler's ketone I- 4: 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer I-5: 2,4-diethylthioxanthone I-6: ethyl p-dimethylaminobenzoate D-1: leuco Squirrel barrel Violet D-2: Diamond Green

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

[0071]

The photosensitive resin composition for sandblasting of the present invention and the photosensitive resin laminate using the same can be applied to a substrate to be processed such as glass, low-melting glass, ceramics, etc. It is excellent in developability and adhesion, and has an effect that a fine pattern can be processed on a substrate to be processed with good yield as a mask material for sandblasting.

[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 using the photosensitive resin laminate of the present invention.

[Explanation of symbols]

 1: support 2: photosensitive resin layer 3: release film (protective layer) 4: substrate to be processed 5: actinic ray 6: photomask 7: photosensitive resin layer (photocured portion)

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/004 512 G03F 7/004 512 H01J 9/02 H01J 9 / 02F // B24C 1/04 B24C 1/04 C

Claims (5)

[Claims] (1) a polymer having a hydroxyl group at a terminal,
A polyisocyanate represented by the following general formula (I): (Wherein, R1 to R4 are hydrogen or alkyl groups) and a polyurethane prepolymer obtained from a compound having an active hydrogen-containing functional group and an ethylenically unsaturated bond simultaneously, (i
A photosensitive resin composition for sandblasting comprising: (i) an alkali-soluble polymer compound, (iii) an ethylenically unsaturated addition-polymerizable monomer, and (iv) a photopolymerization initiator. 2. A photosensitive resin laminate for sandblast, comprising a photosensitive resin layer (B) comprising the photosensitive resin composition for sandblast according to claim 1 on a support (A). 3. A photosensitive resin layer comprising the photosensitive resin composition for sandblasting according to claim 1 is formed on a substrate to be processed, and after a resist pattern is formed by an exposure step and a development step, sandblasting is performed. A surface processing method, characterized in that: 4. A photosensitive resin layer is formed on the substrate to be processed by using the photosensitive resin laminate for sand blasting according to claim 2, and a resist pattern is formed by an exposure step and a development step. A surface processing method characterized by performing. 5. The surface processing method according to claim 3, wherein the substrate to be processed is a plasma display panel.