JPH11188631A - Photosensitive resin composition for sand blast and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition and a photosensitive resin laminate body which have excellent sensitivity, image dissolving property, and close connecting property, when it is applied to a processed base member such as a glass, a low melting point glass, and a ceramics, in which a minute pattern can be processed to the processed base member as the mask member for sand blast, in a good yield. SOLUTION: A polymer having a hydroxyl group at the terminal; a polyisocyanate; a polyurethaneprepolymer obtained from a compound having a functional group with an active hydrogen, and an ethylene type unsatulated bond symultaneously; an alkaline soluble high polymer; and an photo polymerization starting agent; are included, and furthermore, a photosensitive resin composite having a 5.0×10<-4> to 3.0×10<-3> mol/g of ethylene type unsatulated bond density and a supporting body 1; the photosensitive resin composite; and a protective layer 3; are laminated in order, to form the photosensitive resin laminate body.

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 composition for sandblasting, and more particularly, to a photosensitive resin composition having excellent sensitivity, resolution and adhesion when applied to a substrate to be processed such as glass, low melting point glass and ceramic. The present invention also relates to a photosensitive resin composition capable of processing a fine pattern on a substrate to be processed as a mask material for sandblasting with a high yield, and a photosensitive resin laminate using the same.

[0002]

2. Description of the Related Art Conventionally, glass, ceramics, ceramics,
BACKGROUND ART A photosensitive resin composition is used as a mask material when an uneven pattern is formed on a surface of a substrate to be processed such as a stone, a synthetic resin, a metal, and leather by sandblasting.

A photosensitive resin composition used as a mask material for such sandblasting includes, for example, an unsaturated polyester, an unsaturated monomer and a photopolymerization initiator disclosed in JP-A-55-103554. A photosensitive resin composition, a photosensitive resin composition comprising a urethane prepolymer having an acrylate or methacrylate group at a terminal, an unsaturated monomer and a photopolymerization initiator disclosed in JP-A-60-20861; Kaihei 2-
No. 69754 discloses a photosensitive resin composition comprising polyvinyl alcohol and a diazo resin.

Further, urethane oligomers having a terminal ethylenically unsaturated double bond, cellulose derivatives or ethylenically unsaturated double bond-containing compounds disclosed in JP-A-6-161097 and JP-A-6-161098 are disclosed. Photosensitive resin composition containing a compound and a photopolymerization initiator, a photosensitive composition comprising a carboxy-modified urethane (meth) acrylate compound, an alkali-soluble polymer compound and a photopolymerization initiator disclosed in Japanese Patent Application Laid-Open No. 8-54534. Resin composition, JP-A-8-305017, JP-A-9-12
No. 7692 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.

In recent years, with the progress of photolithography technology and sandblasting technology, it has become possible to process glass or ceramic into fine patterns with a pitch of 300 μm or less. For example, Japanese Patent Publication No. 7-2289
No. 3 discloses a method of forming a fine pattern of low melting point glass using a sand blasting device. In such fine pattern processing by sandblasting, the performance required of a photosensitive resin composition as a mask material has also become diverse and sophisticated.

That is, the performance required of a photosensitive resin composition as a mask material for sandblasting is 30
High sensitivity and high resolution so that a resist pattern with a pitch of 0 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 at the time of development, damage caused 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.

However, the conventional photosensitive resin composition described above 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. In addition, the resist pattern is peeled off due to low adhesion to the substrate to be processed at the time of development, and the resist line is chipped, worn or chipped at the time of sandblasting and peeled off. In particular, as the pattern pitch to be processed on the substrate to be processed becomes narrower, the above problem becomes remarkable,
There has been a demand for a photosensitive resin composition that satisfies the above required performance and can process a substrate to be processed into a fine pattern with a high yield.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide glass, low melting point glass,
A photosensitive resin composition having excellent sensitivity, resolution, and adhesion when applied to a substrate to be processed such as ceramics, and capable of processing a fine pattern on a substrate to be processed with good yield as a mask material for sandblasting, and using the same. An object of the present invention is to provide a photosensitive resin laminate.

[0009]

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 above-mentioned problem has been solved by using a specific photosensitive resin composition and a photosensitive resin laminate using the same. We found that we could solve the problem.

That is, the first invention of the present application comprises (i) a polymer having a hydroxyl group at a terminal, a polyisocyanate,
A polyurethane prepolymer obtained from a compound having a functional group having active hydrogen and an ethylenically unsaturated bond simultaneously, (ii) an alkali-soluble polymer compound, and (ii)
i) an ethylenically unsaturated addition polymerizable monomer; and (iv)
In a photosensitive resin composition containing a photopolymerization initiator, the photosensitive resin composition has an ethylenically unsaturated bond concentration of 5.0 × 10 ^{−4 to} 3.0 × 10 ⁻³ mol /. g
Is a photosensitive resin composition for sandblasting.

[0011] The second invention of the present application is to sequentially laminate a support (A), a photosensitive resin layer (B) composed of the photosensitive resin composition of the first invention, and a protective layer (C) if necessary. A photosensitive resin laminate for sandblasting. Among them, a photosensitive resin laminate for sandblasting in which the light transmittance at 365 nm of the photosensitive resin layer (B) is 2 to 30% is more preferable.

A third invention of the present application is to form a photosensitive resin layer on the substrate to be processed using the photosensitive resin composition of the first invention,
A surface processing method characterized by performing a sandblasting process after forming a resist pattern by an exposure step and a development step.

According to a fourth aspect of the present invention, a photosensitive resin layer is formed on a substrate to be processed using the photosensitive resin laminate of the second aspect,
A surface processing method characterized by performing a sandblasting process after forming a resist pattern by an exposure step and a development step. The above surface processing method is suitably used for surface processing of 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. . Examples of the polyisocyanate include toluylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, m-xylylene diisocyanate, α, α, α ', α'-tetramethyl-m-xylylene diisocyanate, and cyclohexane. And diisocyanates.

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 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. 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,
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.

Specific 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. And each may be used alone or in combination of two or more. 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.

Specific examples of the second monomer used in the carboxylic acid-containing vinyl copolymer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and cyclohexyl (meth) acrylate. 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, (meth)
Glycidyl acrylate and the like may be mentioned, and each 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 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) 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) propane di (meth) acrylate, glycerol tri (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane 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, 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-n-octylphenoxypentaethylene glycol tripropylene glycol acrylate, phenoxytetrapropylene glycol tetraethylene glycol acrylate, bisphenol A (meth) acrylate And compounds containing both ethylene oxide chain and a propylene oxide chain and the like in the molecule mer.

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) 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'-bis (diethylamino) benzophenone, 2,2
Aromatic ketones such as -dimethoxy-2-phenylacetophenone, biimidazole compounds such as 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, acridines such as 9-phenylacridine, α, α
-Dimethoxy-α-morpholino-methylthiophenylacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 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 (iv) is 0.01 to 20% by weight based on the total weight of the photosensitive resin composition.
Preferably, the content is 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. 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 thereof include triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, and polypropylene glycol.

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 the concentration is less than 5.0 × 10 ⁻⁴ mol / g, sufficient resolution cannot be obtained. If this 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. The concentration of ethylenically unsaturated bonds can be determined by adding potassium iodide to an unreacted whis reagent and titrating liberated iodine with sodium thiosulfate.

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. A photosensitive resin layer (B) made of the photosensitive resin composition of the present invention and a protective film (C) are laminated on the support (A) in order to form a photosensitive resin laminate. 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 of the present invention, and is preferably a transparent material that transmits active light. Examples of such a material include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate having a thickness of about 10 to 100 μm, and polyethylene terephthalate having appropriate flexibility and strength is preferably used.

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.

A protective layer (C) is laminated on the photosensitive resin laminate as required. 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, mixed with a solvent that dissolves them to leave a uniform solution,
First, the composition is coated on a support (A) using a bar coater or a roll coater and dried, and then a photosensitive resin layer (B) is formed on the support.
Are laminated. Next, a photosensitive resin laminate can be produced by laminating the protective layer (C) on the photosensitive resin layer.

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. (A) 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 (b) a photomask having a desired fine pattern is placed on a support. (C) exposing the support, peeling off the support, dissolving and removing the unexposed portion of the photosensitive resin layer using an alkali developing solution, and forming a fine resist pattern on the substrate. A developing step of forming on the material, (d) a sandblasting step of blowing a blast material from the formed resist pattern to cut the substrate to be processed to a desired depth, and (e) using an alkali stripper to remove the resist pattern. A fine pattern can be processed on the substrate to be processed through the steps (a) to (e) of the peeling step for removing from the substrate to be processed.

Examples of the actinic light source used in the exposure step include 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.

[0050]

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) Concentration of ethylenically unsaturated bond The concentration of ethylenically unsaturated bond is determined by measuring the number of unsaturated bonds contained in the ethylenically unsaturated addition polymerizable monomer and the polyurethane prepolymer in the photosensitive resin composition. It was calculated by dividing by the total mass of the resin composition.

(2) Light transmittance Unexposed laminate in which a photosensitive resin layer having a thickness of 40 μm was formed on a polyethylene terephthalate film having a thickness of 20 μm using a UV-visible spectrophotometer UV240 (manufactured by Shimadzu Corporation) as a measuring device. Was set in the sample side unit of the sample chamber, and the light transmittance at 365 nm was measured. At this time, the same polyethylene terephthalate film as that used for producing the laminate was set in the reference unit of the sample chamber, and the light transmittance derived from the polyethylene terephthalate film was excluded.

(3) Developability A photosensitive resin layer is formed on soda glass, and the
An aqueous solution of sodium carbonate was sprayed, and the minimum development time required for dissolving the unexposed photosensitive resin layer was measured.

(4) Resist Line Adhesion The resist was exposed 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: ×

(5) 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 line was normally formed was defined as the resist line resolution. Based on this resolution, ranking was made as follows. 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: ×

(6) 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 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: ○

[0057]

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 obtained.
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 a substrate to be used for sandblasting, soda glass coated with glass paste and produced by the following method was 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. Paste-coated soda glass was produced.

(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 Corporation). Air pressure is 3.5kg /
cm ² gauge, lamination speed 1.0m / min
And

(Exposure) An ultra-high pressure mercury lamp (HMW-801 manufactured by Oak Manufacturing Co., Ltd.) is used to pass through the photosensitive resin layer without a photomask or through a photomask required for evaluation.
Exposure was performed at mJ / cm ² .

(Development) After peeling off the polyethylene terephthalate film, 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 1 shows the compositions and results of Examples and Comparative Examples.

The composition abbreviations shown in Table 1 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 30/25/25/2)
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-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: Polyurethane prepolymer A (Production of polyurethane prepolymer A) Poly (ethylene glycol adipate) diol (hydroxyl value: 56.1)
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. 23.0 parts by weight of m-xylylene diisocyanate (hereinafter abbreviated as mXDI) was added thereto, and the mixture was stirred well, the external temperature was raised from 40 ° C. to 80 ° C., and the reaction was continued for about 5 hours. 5.8 parts by weight of -hydroxyethyl acrylate (molecular weight: 116) was added and stirred well. When the reaction was completed for about 2 hours, the reaction was stopped to obtain a polyurethane prepolymer A. The number average molecular weight of the polyurethane prepolymer A was 15,000.

O-2: Polyurethane prepolymer B (Production of polyurethane prepolymer B)
Butanediol adipate) diol (hydroxyl value 44.
9) 100 parts by weight of polyoxyethylene (EO) -oxypropylene (PO) block copolymer diol (EO)
/ PO molar ratio: 1/4, hydroxyl value: 44.9) 100 parts by weight and 0.01 g of BTL as a catalyst were put in a reaction vessel and mixed well. Thereto was added 21.1 parts by weight of isophorone diisocyanate, and the mixture was stirred well and the external temperature was raised from 40 ° C to 80
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 polyurethane prepolymer B. The number average molecular weight of the polyurethane prepolymer B was 21,000.

O-3: Polyurethane Prepolymer C (Production of Polyurethane Prepolymer C) 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. About 2
The reaction was stopped when the reaction was carried out for an hour, and a polyurethane prepolymer C was obtained. The number average molecular weight of the polyurethane prepolymer C was 10,000.

O-4: Polyurethane prepolymer D (Production of polyurethane prepolymer D) 150 parts by weight of polyethylene glycol (hydroxyl value: 112.2) and poly (1,6-hexanediol adipate) diol (hydroxyl value: 74.8) 50 parts by weight and BTL 0.0 as a catalyst
1 g was put in a reaction vessel and mixed well. There, α, α,
After adding 60.7 parts by weight of α ′, α′-tetramethyl-m-xylylenediisocyanate, stirring well, the external temperature was raised from 40 ° C. to 80 ° C., and the mixture was reacted for about 5 hours. -Hydroxyethyl methacrylate (molecular weight 1
30) was added and the mixture was stirred well. When the reaction was completed for about 2 hours, the reaction was stopped to obtain a polyurethane prepolymer D. The number average molecular weight of the polyurethane prepolymer D 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 mol of propylene oxide and an average of 3 mol of ethylene oxide is added to both ends of the glycol

I-1: Benzophenone I-2: Benzyldimethylketal I-3: Michler's ketone I-4: 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer I-5: 2,4-diethyl Thioxanthone I-6: ethyl p-dimethylaminobenzoate D-1: leuco crystal violet D-2: diamond green

[0070]

[Table 1]

[0071]

The photosensitive resin composition for sandblasting of the present invention and the photosensitive resin laminate using the same are excellent in sensitivity, resolution and adhesion when applied to substrates to be processed such as glass and ceramics. In addition, there is an effect that a fine pattern can be processed with a high yield on a substrate to be processed 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]

 Reference Signs List 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)

Claims (4)

[Claims] 1. A polyurethane prepolymer obtained from (i) a polymer having a hydroxyl group at a terminal, a polyisocyanate, a compound having an active hydrogen-containing functional group and an ethylenically unsaturated bond at the same time, and (ii) an alkali-soluble polymer. A photosensitive resin composition containing a molecular compound, (iii) an ethylenically unsaturated addition-polymerizable monomer, and (iv) a photopolymerization initiator. Binding concentration of 5.0 × 10 ^-4 or ^less
A photosensitive resin composition for sandblasting having a concentration of 3.0 × 10 ⁻³ mol / g. 2. A support (A), a photosensitive resin layer (B) comprising the photosensitive resin composition according to claim 1, and a protective layer (C), if necessary. A photosensitive resin laminate for sandblasting. 3. A photosensitive resin layer is formed on the substrate to be processed by using the photosensitive resin composition 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. 4. A photosensitive resin layer is formed on a substrate to be processed by using the photosensitive resin laminate according to claim 2, 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.