JP2002148822A - Method for producing inorganic material microstructure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a good inorganic material microstructure having high dimensional accuracy. SOLUTION: A photosensitive resin composition layer containing an oligomer having a urethane bond is disposed on a substrate, particularly on its top layer, exposed through a pattern mask and developed to form a pattern having ruggedness. An inorganic material is filled into the hollows of the pattern by thermal spraying and then the pattern is removed by firing or with liquid chemicals.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal display, a fluorescent display, a plasma display panel (PDP),
Field Emission Display (FE
D), Plasma Address Lyquid
The present invention relates to a method for manufacturing an inorganic material microstructure having high dimensional accuracy useful for manufacturing processes such as Crystal (PALC) and hybrid integrated circuits.

[0002]

2. Description of the Related Art A screen printing method and a sandblasting method using a photosensitive resin composition are known for forming a fine uneven pattern of an inorganic material on a fine structure of an inorganic material, for example, a substrate. The screen printing method, using a screen printing technology, on a substrate such as glass, ink material obtained by kneading a powder of a material to be melted at a high temperature, a binder resin and a solvent, is applied in a predetermined place, and thereafter, It is a method of forming a structure by removing the resin component by sintering and sintering the inorganic material. However, it is difficult to obtain an accuracy of 100 μm or less in a screen plate used for screen printing, and there is a problem with miniaturization. is there. In addition, in the sandblasting method, a layer is formed on the entire surface of the substrate with a powder of a material that is melted at a high temperature and a binder resin, and a masking pattern is formed thereon with a photosensitive resin composition.
Dry or wet hard powder is sprayed onto the existing layer,
After cutting the unmasked part, the masking layer is removed by firing or chemical solution, and the inorganic material is sintered to form a structure.However, a large amount of expensive inorganic material is removed by cutting. There is a high demand for a new construction method because of its complicated process.

In recent years, an embedding method has been proposed. In this embedding method, using a high aspect pattern of a photosensitive resin as a template, a paste containing an inorganic material is embedded between the patterns, and then the photosensitive resin mold is removed by firing or a chemical solution, and the inorganic material is further sintered. This is a method of forming a structure. Conventionally, the embedding method generally uses a special paste made by kneading a powder of an inorganic material with a binder resin and a solvent. There was a problem in the formation of a fine structure in the above. In order to solve such a problem, attempts have been made to form a fine structure of an inorganic material by a thermal spraying method. For example, in the technology disclosed in JP-A-11-191363, a step of forming a photosensitive coating layer on a substrate, a step of forming an opening having a predetermined pattern in the photosensitive coating layer, and a step of forming the opening by a thermal spraying method. The partition walls of the plasma display panel are manufactured through a step of depositing a partition wall material therein to form a sprayed film, and a polishing step of removing a portion of the sprayed film protruding from the surface of the photosensitive coating layer by polishing. .
It also describes that a dry film resist is used to form a photosensitive coating layer.

[0004]

However, when the above-mentioned method is carried out with a commonly used photosensitive resin composition, the uneven pattern is liable to collapse due to the impact of thermal spraying, the height cannot be maintained, and the sprayed inorganic material is used. If the (sprayed material) adheres to the surface of the photosensitive resin composition layer in the convex portion, there is a possibility that the inorganic material portion sprayed in the concave portion may be shaved when polishing the adhered spraying agent. There is a problem that a fine structure of an inorganic material having a desired size cannot be obtained.

[0005]

Means for Solving the Problems As a result of intensive studies in view of such circumstances, the present inventors have found that a photosensitive resin composition layer containing an oligomer having a urethane bond is preferably formed on a substrate as an uppermost layer. After providing the photosensitive resin composition layer as described above, exposure through a pattern mask, development to form a pattern having irregularities, burying the inorganic material by thermal spraying in the concave portions of the pattern, then firing or patterning the pattern with a chemical solution The present inventors have found that a method for producing an inorganic material microstructure to be removed meets the above object, and have completed the present invention.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, the photosensitive resin composition layer is provided on the substrate so that the uppermost layer becomes a photosensitive resin composition layer containing an oligomer having a urethane bond. The layer has (1) a urethane bond. Even if the photosensitive resin composition layer containing the oligomer is a single layer, or (2) the photosensitive resin composition layer has two or more layers, and the uppermost layer contains the oligomer having a urethane bond. Although the resin composition layer may be used, the oligomer having a urethane bond is usually expensive and requires high-temperature sintering in the subsequent sintering. Therefore, the constitution (2) is practical. Is described.

In the present invention, the photosensitive resin composition layer having a urethane bond provided on the uppermost layer on the substrate comprises a base polymer (a), an oligomer having a urethane bond (b),
(Meth) acrylate compound (c), photopolymerization initiator (d) [hereinafter, each component is simply referred to as (a), (b),
(C) and (d)).

As the (a) of the photosensitive resin composition layer containing an oligomer having a urethane bond, a (meth) acrylic resin, a polyester resin, a polyurethane resin or the like is used. It is preferably used. As the acrylic resin, an acrylic copolymer containing (meth) acrylate as a main component and optionally copolymerizing an ethylenically unsaturated carboxylic acid or another copolymerizable monomer is used. A group-containing acrylic copolymer can also be used.

As the (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth)
Acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth)
Acrylate, glycidyl (meth) acrylate and the like can be mentioned.

The ethylenically unsaturated carboxylic acids include:
Monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid are preferably used, and dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, or anhydrides and half esters thereof can also be used. Of these, acrylic acid and methacrylic acid are particularly preferred. When using the alkali solution developing type, the ethylenically unsaturated carboxylic acid is added in an amount of about 15 to 30% by weight (acid value of 100 to 200%).
(about mgKOH / g).

Other copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, and alkyl vinyl ether.

The oligomer (b) having a urethane bond may be any reaction product of a polyol compound, a polyisocyanate compound and a hydroxyl group-containing acrylate. Particularly, the development after exposure of the photosensitive resin composition through a pattern mask is performed. However, in the case of a dilute alkali developing type, a polyol compound containing a carboxyl group is used.

The polyol compound is not particularly restricted but includes, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,4 -Butanediol, polybutylene glycol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol , Sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin, poly Polyether alcohols having at least one structure of polyhydric alcohols such as lyserin and polytetramethylene glycol, polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block or random copolymer, polyhydric alcohols or polyether polyols Caprolactone-modified polyols such as polyester polyols, caprolactone-modified polytetramethylene polyols, and polyolefins, which are condensates with polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, and isophthalic acid. System polyol,
And polybutadiene-based polyols such as hydrogenated polybutadiene polyol. The carboxyl group-containing polyol compound preferably has a molecular weight of 500 or less. If the molecular weight exceeds 500, the solubility in a reaction solvent is reduced, and the reactivity with an isocyanate is reduced, which is not preferable. Specific examples include 2,2-bis (hydroxymethyl) butyric acid, tartaric acid, 2,4-dihydroxybenzoic acid,
3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, dihydroxymethylacetic acid, bis ( 4-hydroxyphenyl) acetic acid, 4,4-bis (4-
(Hydroxyphenyl) pentanoic acid, homogentisic acid and the like.

As the polyisocyanate compound, a polyisocyanate compound having a molecular weight of 500 or less, preferably 300 or less is used. Specific examples include hexamethylene diisocyanate, heptamethylene diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, octamethylene diisocyanate,
5-dimethylhexane-1,6-diisocyanate,
2,2,4-trimethylpentane-1,5-diisocyanate, nonamethylene diisocyanate, 2,2,4-
Trimethylhexane diisocyanate, decamethylene diisocyanate, undecamethylene diisocyanate,
Dodecamethylene diisocyanate, tridecamethylene diisocyanate, pentadecamethylene diisocyanate, butene diisocyanate, 1,3-butadiene
1,4-diisocyanate, 2-butynylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, isophorone diisocyanate, 1,3-xylylene diisocyanate, 1,4
-Xylylene diisocyanate.

Examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl-2-hydroxypropyl. Examples include phthalate, glycerin di (meth) acrylate, and 2-hydroxy-3-acryloyloxypropyl (meth) acrylate. Preferably, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are used. Can be

The above (b) is, for example, a method in which three components of a polyol compound, a polyisocyanate compound and a hydroxyl group-containing acrylate are mixed and reacted at once, a reaction between the polyol compound and the polyisocyanate compound, and then a hydroxyl group-containing acrylate. How to react,
A method of reacting a reaction product of a polyisocyanate compound and a hydroxyl group-containing acrylate with a polyol compound is exemplified.

The weight average molecular weight of (b) is 2,000
It is preferably from 0 to 40,000, and more preferably from 10,
000 to 27,000. When the weight-average molecular weight is less than 2,000, the pattern convex portion, which is a cured portion of the photosensitive resin composition, lacks flexibility, and the convex portion is cut off at the time of thermal spraying, so that the height may not be maintained. If it exceeds, curing may not proceed sufficiently and pattern formation may be incomplete, which is not preferable.

The above (c) includes ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
1,6-hexane glycol di (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, E
O (ethylene oxide) -modified trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, glycerin tri (meth) acrylate, ethylene oxide-modified glycerin tri (meth) acrylate,
Ethylene oxide-modified bisphenol A diacrylate, glycerin tri (meth) acrylate, propylene-modified glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2,2-bis (4- ( (Meth) acryloxydiethoxyphenyl) propane, 2,2-bis- (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3-
(Meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, 2-acryloyloxyethyl phthalate, diglycidyl ester di (meth) acrylate, glue Polyfunctional monomers such as cerarin triacrylate and glycerin polyglycidyl ether poly (meth) acrylate are mainly used.

An appropriate amount of a monofunctional monomer can be used together with these polyfunctional monomers. Examples of monofunctional monomers include 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, phenoxy polyethylene glycol acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (Meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxy-2
Phthalic acid derivatives such as -hydroxypropyl phthalate and EO (ethylene oxide) -modified phthalate; half (meth) acrylate; and N-methylol (meth) acrylamide.

(D) includes benzoin compounds, benzyl compounds, benzophenone compounds, acetophenone compounds, hexaarylbiimidazole compounds, thioxanthone compounds, sulfone compounds, triazole compounds,
Triazine compounds, acridine compounds, N-phenylglycine, diacetyl, anthraquinone, naphthoquinone,
Pivaloin ethyl ether, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanone, and one or two of these More than one type is used.

Examples of the benzoin compound include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether and benzoin phenyl ether.

Examples of the benzyl compound include diphenyl disulfide, benzyl dimethyl ketal, and dibenzyl.

As the benzophenone compound, 3,3 ′
-Dimethyl-4-methoxybenzophenone, benzophenone, p, p'-bis (dimethylamino) benzophenone, p, p'-bis (diethylamino) benzophenone.

As the acetophenone compound, 1,1-
Dichloroacetophenone, pt-butyldichloroacetophenone, 2,2-diethoxyacetophenone, 2,
2-dimethoxy-2-phenylacetophenone, 2,2
-Dichloro-4-phenoxyacetophenone.

The hexaarylbiimidazole compounds include 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
5'-tetrakis (m-methoxyphenyl) biimidazole, 2,2'-bis (p-carboxyphenyl)-
4,4 ′, 5,5′-tetraphenylbiimidazole,
2,2'-bis (p-chlorophenyl) -4,4 ',
5,5′-tetrakis (p-methoxyphenyl) biimidazole, 2,2′-di-o-tolyl-4,4 ′, 5,5
5'-tetraphenylbiimidazole, 2,2'-di-
p-Tolyl-4,4'-di-o-tolyl-5,5'-diphenylbiimidazole.

As the thioxanthone compound, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4
-Diethylthioxanthone.

Examples of the sulfone compound include tribromophenyl sulfone and tribromomethylphenyl sulfone.

As the triazole compound, 1,2,3
-Benzotriazole, 1-chloro-1,2,3-benzotriazole, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, bis (N-2-ethylhexyl) ) Aminomethylene-1,2,3-benzotriazole, bis (N-
2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl)
Aminomethylene-1,2,3-benzotriazole.

As the triazine compound, 2,4,6-
Tris (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n- Propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-
Chlorophenyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -4'-methoxyphenyl-s-
Triazine, 2- (4-methoxy-naphth-1-yl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
[4- (2-ethoxyethyl) -naphth-1-yl]-
4,6-bis (trichloromethyl) -s-triazine,
2- (4,7-dimethoxy-naphth-1-yl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
(Acenaphth-5-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′, 4′-dichlorophenyl) -4,6-bis (trichloromethyl) -s
-Triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl)
-S-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2-p-methylstyryl-4,6-bis (trichloromethyl) -s-triazine, 2-p-methoxystyryl -4,6-bis (trichloromethyl) -s-triazine.

As the acridine compound, 2-methyl-
[4- (methylthio) phenyl] -2-morpholino-
1-Prolpanone acridine, 9-phenyl acridine.

Regarding the compounding ratio of each component in the photosensitive resin composition containing the oligomer having a urethane bond, the compounding amount of (b) is 5 parts per 100 parts by weight of (a).
It is desirable to select from the range of 0 to 1000 parts by weight, particularly 100 to 1000 parts by weight. If (b) is less than 50 parts by weight, the pattern projections may not be able to withstand the impact during thermal spraying, and if (b) exceeds 1000 parts by weight, poor compatibility and poor developability may result.

The compounding amount of (c) is desirably selected from the range of 10 to 200 parts by weight, particularly 40 to 100 parts by weight, per 100 parts by weight of (a). If (c) is less than 10 parts by weight, poor curing, reduced flexibility, and delayed development speed are caused.
If the amount exceeds 200 parts by weight, undesirably, an increase in tackiness, a cold flow, and a delay in peelability after curing are caused.

The amount of (d) is 1 to 20 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the total of (a) and (c).
It is appropriate to use 10 parts by weight. If (d) is less than 1 part by weight, poor curing results, and if it exceeds 20 parts by weight, poor compatibility and poor developability are not preferred.

Further, a dye, a solvent and the like may be further added to the composition as required. Examples of the dye include photochromic dyes such as leuco crystal violet, leucomalachite green, leuco diamond green, and leucomethylene blue, and it is preferable to include one or more of these dyes. If necessary, one or more base dyes such as malachite green and crystal violet may be added.

Examples of the solvent include methyl ethyl ketone, methyl cellosolve, acetone and the like, and it is preferable to contain one or more of these.

Next, the photosensitive resin composition layer used as a lower layer of the photosensitive resin layer containing a urethane bond, which is the uppermost layer, will be described. Such a photosensitive resin composition layer contains (a), (c), and (d) described above and, if necessary, a dye and a solvent, and each component is described in the above-described uppermost layer. Ingredients are used. Further, a silane compound may be added as an adhesion-imparting agent in order to increase the adhesion to the substrate. Examples of the silane compound include silane compounds having a vinyl group, such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (β-methoxyethoxy) silane.
(3,4 epoxycyclohexyl) -ethyltrimethoxysilane, β- (3,4 epoxycyclohexyl) -ethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- Silane compounds having an epoxy group such as glycidoxypropylmethyldiethoxysilane, γ-
(Meta) such as (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, and γ- (meth) acryloxypropyltriethoxysilane ) A silane compound having an acryloyl group, N-β (aminoethyl) γ-aminopropyltrimethoxysifuran, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyl Methyldimethoxysilane, γ-
Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, silane compounds having an amino group such as N-phenyl-γ-aminopropyltrimethoxysilane, silane compounds having a chloro group such as γ-chloropropyltrimethoxysilane, Examples thereof include silane compounds having a mercapto group such as γ-mercaptopropyltrimethoxysilane, among which silane compounds having an epoxy group or a (meth) acryloyl group are preferably used.

The amount of each component in the photosensitive resin composition layer is from 10 to 200 parts by weight, particularly 40 to 100 parts by weight, per 100 parts by weight of (a). It is desirable to choose. If (c) is less than 10 parts by weight, poor curing, reduced flexibility, and a delay in development speed will be caused. If it exceeds 200 parts by weight, adhesion will increase, cold flow will occur, and peelability will be delayed after curing. It is not preferable. The compounding amount of (d) is 10 (total amount of (a) and (c)).
The amount is suitably 1 to 20 parts by weight, preferably 1 to 10 parts by weight based on 0 parts by weight. If (d) is less than 1 part by weight, poor curing results, and if it exceeds 20 parts by weight, poor compatibility and poor developability are not preferred.

The amount of the silane compound to be added is 0.05 to 5 parts per 100 parts by weight of (a).
It is preferably 1 part by weight, more preferably 1 to 4 parts by weight, particularly preferably 2 to 3 parts by weight. If the content of the silane compound is less than 0.05 part by weight, the effect of improving the adhesion of the photosensitive resin composition layer to the glass substrate is difficult to obtain, and if it exceeds 5 parts by weight, the adhesion is undesirably reduced.

In the present invention, in addition to the above components, a plasticizer, an antioxidant, a thermal polymerization inhibitor, a surface tension modifier, a stabilizer, a chain transfer agent, a defoaming agent may be added to each photosensitive resin composition. In addition, a flame retardant can be appropriately added.

When a photosensitive resin composition layer is formed on a substrate in carrying out the method of the present invention, the photosensitive resin composition layer may be directly coated, but preferably the composition is applied to a base film. The composition layer is laminated on the substrate surface in multiple stages using a dry film which is coated and a protective film is laminated thereon.

As the base film, a polyester film, a polypropylene film, a polystyrene film or the like is used. As the protective film, a polyester film, a polypropylene film, a polystyrene film, a polyvinyl alcohol film or the like is used. The thickness of these films is preferably from 5 to 100 μm, more preferably from 10 to 50 μm.

Next, a method for producing an inorganic material microstructure using the dry film in the method of the present invention will be specifically described.

(Lamination of Photosensitive Resin Composition Layer on Substrate) As the substrate used in the present invention, glass, metal,
Ceramics, plastics and the like can be mentioned. For laminating a dry film on such a substrate surface, for example, there is a method of laminating sequentially using a laminator provided with a hot roll. In the above case, after the protective film of the dry film is peeled off using a laminator provided with a hot roll adjusted to an arbitrary temperature on the substrate surface, the photosensitive resin composition layer is bonded to the substrate surface. This operation is repeated as necessary, and the photosensitive resin composition layer serving as the lower layer is laminated to a desired height. At this time, after removing the base film, the next dry film is laminated. Thereafter, a photosensitive resin composition layer containing an oligomer having a urethane bond is formed on the uppermost layer by the same operation.

The thickness of the entire photosensitive resin composition layer is 1
The thickness is preferably from 300 to 300 µm, and particularly preferably from 5 to 200 µm. The thickness of the lower photosensitive resin composition is 1 to 100 μm.
m is preferable, and 5 to 50 μm is particularly adopted. If the thickness of the lower photosensitive resin composition is less than 1 μm, pinholes may increase and it may not be usable, and if it exceeds 300 μm, the resolution may be reduced, which is not preferable.

The thickness of the uppermost layer is 1 to 100 μm, preferably 1 to 10 μm. If the thickness is less than 1 μm, the effect of protecting the cured portion of the photosensitive resin composition of the pattern during thermal spraying is weak, and if it exceeds 100 μm, it is necessary to increase the firing temperature, which is not preferable. Of course, two or more layers can be provided.

(Exposure) Next, exposure is performed by closely attaching a pattern mask to a base film existing on a photosensitive resin composition layer containing an oligomer having a urethane bond. When the photosensitive resin composition has no tackiness, the base film may be peeled off, and then the pattern mask may be brought into direct contact with the photosensitive resin composition layer for exposure.

Exposure is usually carried out by irradiation with ultraviolet light, and a high-pressure mercury lamp, ultra-high-pressure mercury lamp, carbon arc lamp, xenon lamp, metal halide lamp, chemical lamp or the like is used as a light source at that time. After irradiation with ultraviolet rays, heating can be performed as necessary to complete the curing.

(Development) After exposure, development is performed after the base film is peeled and removed. The development is performed using a dilute aqueous solution of about 0.1 to 2% by weight of an alkali such as sodium carbonate or potassium carbonate, and the cured photosensitive resin composition having a predetermined height is formed on the substrate by partition walls (projections). Get the pattern you want.

(Heat treatment) The obtained pattern was
50 ° C, furthermore 140 to 230 ° C, especially 150 to 20
The heat treatment is preferably performed in a temperature range of 0 ° C. As a result, the volatile matter on the substrate is completely scattered, so that there is no floating of the pattern in the thermal spraying described below, and an excellent effect that thermal spraying can be performed is exhibited. When the temperature of the heat treatment is 10
If the temperature is lower than 0 ° C., there is a possibility that a part of the pattern may be scattered at the time of firing. Further, the heat treatment time is preferably 5 minutes or more, more preferably 5 to 20 minutes, and particularly preferably 10 to 20 minutes.

(Spraying) The concave portions of the pattern are filled with an inorganic material by spraying. Thermal spraying is a technique in which an inorganic material is melted and applied by a heat source such as a gas flame or a plasma flame to form a film on a substrate.The inorganic material used in the present invention includes aluminum, copper, gold, It is a powder such as a metal such as silver, platinum and solder, or a ceramic such as a metal oxide such as silica, alumina and zirconia.

The method of thermal spraying is not particularly limited, and may be plasma thermal spraying, gas thermal spraying, or other thermal spraying. However, plasma thermal spraying is preferable because a wide range of thermal spraying materials can be selected.

When an inorganic material, for example, an inorganic material such as alumina is embedded by plasma spraying, it can be carried out by the following method. An arc discharge is generated by applying a DC voltage to the anode and the cathode of the spray torch of the plasma spray device, and an inert gas or hydrogen is supplied to the spray torch from a gas port. The fed gas is heated and ionized by arc discharge, and is ejected from a nozzle as a plasma jet. Examples of the inert gas include argon, helium, and nitrogen. Alumina is loaded on a carrier gas from a supply port in a powder state and blown into a plasma jet. The supplied alumina powder is heated and melted by the plasma jet, is sprayed toward the substrate surface, and collides at a high speed. As a result, a film is formed, and the material is deposited by repeating this. In order to suppress the thermal influence on the substrate or the pattern due to the thermal spraying, a cooling measure may be taken such as applying a cooling gas to the substrate during thermal spraying or bringing the substrate into close contact with a thermoconductive material at a constant temperature.

(Polishing) The surface of the structure formed by thermal spraying tends to be rough, and when used as a structure, the rough surface is not preferred, or the thickness of the sprayed layer is larger than the intended size. In this case, the surface may be polished with, for example, a wrapping tape. Polishing the surface with a wrapping tape is preferable because the inorganic material remaining on the partially cured photosensitive resin composition layer is also removed in the same step.

(Removal of Cured Resin Composition Component by Firing or Chemical Solution) After forming the inorganic material layer, the cured photosensitive resin composition component is removed by firing or chemical solution. First, the case of removing by firing will be described. The cured photosensitive resin composition component containing an acrylic resin as a main component is usually cured by firing at 500 ° C. or higher in the presence of oxygen.
00% can be removed. In the present invention, the thermal spraying method may be used to fill the inorganic material by the thermal spraying method so that the thermal spraying has a thermal influence on the cured photosensitive resin composition. It has a great feature that can be removed.

When the photosensitive resin composition component cured at a temperature of 480 ° C. or lower is removed by baking, it is not necessary to set the baking temperature rapidly from the start of baking at the time of baking.
It is preferable to bake under a gradual temperature increase condition of about 20 ° C./min, preferably about 5 ° C./min.

In the above calcination, it is preferable to introduce air at a volume of 30% or more, preferably 30 to 120% per minute (at 20 ° C. and 1 atm) with respect to the volume of the calcination furnace used. If the amount of such air is less than 30% per minute, it is difficult to remove black ash, and if it exceeds 120%, the firing temperature cannot be controlled and the temperature becomes high, which is not preferable.

It is also possible to remove the cured resin composition component by a strong alkaline aqueous solution instead of baking. In this case, the resin composition is immersed in an aqueous solution of 1 to 5% by weight of sodium hydroxide. Alternatively, such an aqueous solution may be showered. Thus, according to the method of the present invention, a fine inorganic material fine structure with high accuracy can be formed, and a liquid crystal display device, a fluorescent display device, a plasma display panel (PDP), and a field emission can be formed.
Display (FED), Plasma Addre
It is very useful as a method for forming an inorganic material fine structure in a process of manufacturing ss lysid crystal (PALC), a hybrid integrated circuit, or the like.

Hereinafter, the present invention will be described specifically with reference to examples. In the examples, “parts” and “%” mean weight basis unless otherwise specified.

EXAMPLES Example 1 (Preparation of photosensitive resin composition 1) The following base polymer
(A), (meth) acrylate compound (c), photopolymerization
Mix the initiator (d), silane compound, dye and solvent
Light-sensitive resin composition 1 was obtained.Base polymer (a) A copolymer having a copolymerization ratio of methyl methacrylate / n-butyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid of 35/30/15/20 by weight (acid value 130 mgKOH / g, glass transition point 79 ° C., Weight average molecular weight 68,000) 60.0 parts (Meth) acrylate compound (c) ・ Tetraethylene glycol dimethacrylate 40.0 partsPhotopolymerization initiator (d) 0.1 parts of p, p'-bis (diethylamino) benzophenone 3.0 parts of 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazoleSilane compounds ・ Γ-glycidoxypropyltrimethoxysilane 1.0 part (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) dye ・ Leuco crystal violet 0.8 parts ・ Malachite green 0.06 parts solvent ・ Methyl ethyl ketone 90.0 parts ・ Methyl cellosolve 20.0 parts

(Preparation of Dry Film 1) Next, the obtained photosensitive resin composition 1 was applied on a polyester film having a thickness of 20 μm using an applicator having a gap of 10 mil and left at room temperature for 1 minute and 30 seconds. 60 ° C, 90 ° C, 1
Each was dried in an oven at 10 ° C. for 3 minutes to make the thickness of the photosensitive resin composition layer 50 μm, and then a photosensitive resin composition liquid was applied thereon, and the same treatment was carried out. A dry film 1 having a resin composition layer having a thickness of 150 μm was prepared.

(Preparation of photosensitive resin composition 2)
Spolymer (a), oligomer having urethane bond
(B), (meth) acrylate compound (c), photopolymerization
Photosensitive resin composition by mixing initiator (d), dye and solvent
2 was prepared.Base polymer (a) A copolymer having a copolymerization ratio of methyl methacrylate / n-butyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid of 50/12/15/23 by weight (acid value 150 mgKOH / g, glass transition point 63 ° C., weight) (Average molecular weight: 80,000) 30.0 parts Oligomers (b) having urethane bonds 137 parts of isophorone diisocyanate and 815 parts of a polyol having an average molecular weight of 2,000 (a condensate of ethylene glycol / 1,4-butanediol / adipic acid, "Adecanuease V14-90" manufactured by Asahi Denka Co., Ltd.) are reacted. 50.0 parts of an oligomer having a urethane bond produced by reacting 48.4 parts of 2-hydroxyethyl acrylate [glass transition temperature -39 ° C, weight average molecular weight 20,000] (Meth) acrylate compound (c) ・ Ethylene oxide-modified bisphenol A diacrylate (“New Frontier BPE-10” manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 15.0 parts ・ 2-acryloyloxyethyl phthalate 5.0 parts Photopolymerization initiator (d) ・ 2,4-diethyloxanthon 1.0 part ・ Ethyl-p-dimethylaminobenzoate 5.0 partsdye ・ Leuco Crystal Violet 0.2 parts ・ Malachite Green 0.06 partssolvent ・ Methyl ethyl ketone 90.0 parts ・ Methyl cellosolve 20.0 parts

(Preparation of Dry Film 2) The obtained photosensitive resin composition 2 was coated on a 20 μm-thick polyester film using an applicator having a gap of 2 mil, left at room temperature for 1 minute 30 seconds, 60 ° C, 90 ° C, 11
Each was dried in an oven at 0 ° C. for 2 minutes to prepare a dry film 2 having a photosensitive resin composition layer thickness of 5 μm.

(Lamination of Photosensitive Resin Composition on Substrate) The glass substrate was preheated to 60 ° C. in an oven, and the temperature of the laminating roll was adjusted so that the surface of the photosensitive resin composition layer of the dry film 1 was in contact with the substrate. 100 ° C., laminating roll pressure 3 kg / cm ² , laminating speed 1.5 m / min
Then, the substrate and the dry film 1 were laminated. Next, the laminated polyester film of the dry film 1 was peeled off, and the photosensitive resin composition layer of the dry film 1 and the photosensitive resin composition layer of the dry film 2 were laminated in the same manner as described above.

(Exposure and Development) Lines / lines were formed on the upper surface of the polyester film of the dry film 2 laminated as described above.
2 kW with an exposure machine HMW-532D manufactured by Oak Manufacturing Co., Ltd. by applying a pattern mask of space = 30 μm / 70 μm.
Exposure was performed with an ultra-high pressure mercury lamp at 500 mJ / cm ² . After a hold time of 15 minutes after the exposure, development is performed using a 1% aqueous solution of sodium carbonate at 30 ° C. for 1.5 times the minimum development time, and an opening width of 30 μm and an opening height of 155 μm are formed on the substrate. A pattern having irregularities using the cured resin composition (aspect ratio with respect to the opening of about 5) as a partition was formed.

(Heat Treatment) The above substrate was placed in a hot air circulating dryer previously maintained at 180 ° C., and heat treated for 10 minutes.

(Spraying) Alumina powder (inorganic material) having an average particle size of 7 μm and a purity of 99% or more was sprayed on the entire surface of the substrate so as to fill up the concave portions of the pattern. The spraying conditions were such that argon gas was supplied to the spraying torch at a rate of 40 liters per minute and helium gas at a rate of 20 liters per minute. In a state, speed 750m
Thermal spraying was performed while moving over the entire surface of the substrate at a pitch of 3 mm at m / sec.

(Polishing) A sandpaper having a number of 800 is pasted on a metal plate having a flat surface, and the surface after thermal spraying is polished with the sandpaper to remove excess alumina on the pattern and smooth the thermal sprayed surface. did.

(Firing) Finally, using a baking furnace having a volume of 600 liters, baking was performed by passing the substrate through a substrate while feeding 230 liters of air per minute into a mesh belt furnace set at a temperature of 500 ° C. The inorganic material microstructure was formed by burning off the cured photosensitive resin composition component.

When the shape of the inorganic material fine structure formed above was observed with a scanning electron microscope, the cross-sectional shape of the structure was a good rectangle and no collapse defect was observed. At this time, the upper width of the structure is 28 μm and the height is 13 μm.
The pitch was 8 μm and the pitch was 100 μm.

Example 2 In Example 1, instead of firing, a 3% aqueous solution of sodium hydroxide was removed from the pattern by showering and dried. When the shape of the inorganic material microstructure formed above was observed with a scanning electron microscope, the cross-sectional shape of the structure was
The rectangle was good, and no collapse defect was observed. At this time, the upper width of the structure is 28 μm, the height is 136 μm,
The pitch was 100 μm.

Comparative Example 1 In Example 1, an inorganic material fine structure was similarly formed using only the dry film 1. When the shape of the structure formed above was observed with a scanning electron microscope, the cross-sectional shape of the structure was rectangular and no collapse defect was observed, but the upper width of the structure at this time was 28 μm,
The height was 108 μm and the pitch was 100 μm, and the partition wall height was significantly reduced.

[0071]

According to the method of the present invention, a photosensitive resin composition layer containing an oligomer having a urethane bond is provided on a substrate, particularly on the uppermost layer, and then exposed and developed through a pattern mask to form a pattern having irregularities. Is formed, and the inorganic material is buried in the concave portions of the pattern by thermal spraying, and then the pattern is removed by baking or a chemical solution. Therefore, a fine inorganic material microstructure with high dimensional accuracy can be formed, and a liquid crystal display device, a fluorescent material, Display device, plasma display panel (PDP), Field Emission Disp
lay (FED), Plasma Address L
It is useful for applications such as yquid Crystal (PALC) and hybrid integrated circuits.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) H01J 9/02 H01J 9/02 F 5C027 11/02 11/02 B 5C040 // C08F 2/44 C08F 2/44 C 2 / 46 2/46 F-term (reference) 2H025 AA02 AA03 AB11 AB14 AB17 AC01 AD01 BC13 BC66 CA00 DA13 FA17 FA39 FA47 2H096 AA27 AA28 BA01 EA02 GA08 HA30 KA02 LA02 LA06 4F100 AA00B AA19 AB00B AD00B AG00 E00ABA02EJB JL01 4J011 PA76 PA86 PA88 PA90 PA95 PB30 PB40 PC02 PC08 QA03 QA06 QA13 QA17 QA18 QA22 QA23 QA33 QA34 QA46 QB16 QB24 RA03 RA07 RA10 SA01 SA21 SA31 SA41 SA63 SA64 SA78 SA83 UA01 BA01 BA04 BA02 BA21 BA04 BA28 CA03 CA06 CA10 CC05 CD10 5C027 AA09 5C040 GF18 GF19 KB13 MA24

Claims (2)

[Claims] After a photosensitive resin composition layer containing an oligomer having a urethane bond is provided on a substrate, it is exposed and developed through a pattern mask to form a pattern having irregularities, and is sprayed onto the concave portions of the pattern by thermal spraying. Embedded with inorganic material,
Then, the pattern is removed by firing or a chemical solution. 2. The photosensitive resin composition layer is provided such that the photosensitive resin composition layer has two or more layers, and the uppermost layer is a photosensitive resin composition layer containing an oligomer having a urethane bond. The method for producing an inorganic material microstructure according to claim 1, wherein: