KR20070038422A - Ultraviolet-curing resist composition for etching a glass, and method of etching treatment of glass - Google Patents

Abstract

assignment

Provided is a glass etching treatment method capable of processing with high processing precision and deeply, and an ultraviolet curable resist composition preferably used in the method.

Resolution

An ultraviolet curable resist composition for glass etching containing (A) an acid group-containing resin, (B) an unsaturated compound, (C) a photoinitiator, (D) an unsaturated group or an epoxy group, and (E) an inorganic fine powder; And the glass etching process method which performs (1) resist film formation process, (2) exposure process, (3) image development and heating process, (4) glass etching process, and (5) resist film peeling process using this resist composition. .

Description

UV-curable resist composition for glass etching and glass etching processing method {ULTRAVIOLET-CURING RESIST COMPOSITION FOR ETCHING A GLASS, AND METHOD OF ETCHING TREATMENT OF GLASS}

[Patent Document 1] Japanese Unexamined Patent Publication No. 2005-164877

[Patent Document 2] Japanese Unexamined Patent Publication No. 2004-71354

The present invention relates to an ultraviolet curable resist composition for glass etching and a glass etching treatment method.

Conventionally, the glass material which etched the glass base material into various shapes is widely used for an electronic material, an optical material, a measuring instrument, etc.

As a conventional glass processing method, the method of apply | coating a photocurable resist resin composition on a glass substrate, forming a resist film, and carrying out the etching process using fluoric acid is known (refer patent document 1). This photocurable resist resin composition is an acrylic resin having an ethylenically unsaturated double bond in a side chain, a polysilane, a photosensitizer, and a (meth) acrylic monomer having an ethylenically unsaturated double bond as necessary. And / or a composition containing an oligomer, a novolak-type epoxy resin, and fluorine-containing crosslinked resin particles. In addition, this photocurable resist resin composition can be developed by alkaline solution.

As performance required for the alkali developable resist composition used for the fluoric acid etching process, in the development process and the etching process process of a glass substrate, the resist film of an irradiation part is not peeled from a glass base material, and in the peeling process after the etching process process The thing which can peel easily a resist film from a glass substrate, and the thing which can remove the resist film of a non-irradiation part completely in a image development process are mentioned. However, the composition described in patent document 1 does not satisfy all these requirements.

As another glass processing method, the processing method of the glass for organic electroluminescent displays is known, for example (refer patent document 2). This processing method includes a step of forming a resist film having acid resistance and sandblast resistance on a glass substrate, a step of projecting and cutting an abrasive thereon, and a step of dipping and etching in an etchant.

This processing method is excellent in the point which can process the accommodating part (dentation part) of the glass for organic electroluminescent displays to the depth of 300 micrometers. However, there is a problem in that the depth of depression due to sandblasting is limited, and the machining process is cumbersome.

An object of the present invention is to provide a glass etching treatment method capable of processing with high processing precision and deeply, and an ultraviolet curable resist composition preferably used in the method.

Means to solve the problem

The present invention comprises (A) an acid group-containing resin, (B) an unsaturated compound, (C) a photoinitiator, an (D) alkoxysilane compound containing an unsaturated group or an epoxy group, and (E) an inorganic fine powder. It is an ultraviolet curable resist composition for glass etching.

In addition, the present invention,

(1) a resist film forming step of coating the ultraviolet curable resist composition on a surface of a glass substrate to form a resist film,

(2) an exposure step of irradiating ultraviolet rays to the resist film through a mask or directly irradiating ultraviolet rays without passing through the mask so that a desired pattern shape is obtained;

(3) the development and heating step of forming a resist film having a desired pattern by performing the development and heat treatment of the resist film;

(4) a glass etching step of etching the glass substrate in the portion exposed from the resist film having the desired pattern, and

(5) It is a glass etching process method which has a peeling process which peels a resist film which remains | survives after the said glass etching process in this order.

To practice the invention  Best form for

The ultraviolet curable resist composition for glass etching of this invention is an acidic radical containing resin (it may abbreviate as "component A" hereafter.), An unsaturated compound (hereinafter, abbreviate as "component B".), A photoinitiator. (Hereinafter abbreviated as "C component"), an alkoxysilane compound containing an unsaturated group or an epoxy group (hereinafter abbreviated as "D component"), and an inorganic fine powder (hereinafter, " It may abbreviate as "E component".) As an essential component. Each component is demonstrated below.

<Acid-containing resin (A component)>

A component is used in order to remove with the solubility to the alkali developing solution of a resist film, or the peeling solution of a photocuring film. As A component, (meth) acrylic-type resin which has a carboxyl group, polyester-based resin which has a carboxyl group, etc. are mentioned, for example. These resin can be used 1 type or in combination or 2 or more types. In addition, "(meth) acryl" is a generic term of acryl and methacryl.

50-200 KOHmg / g is preferable and, as for the acid value of A component, 60-150KOHmg / g is more preferable. The lower limit of each of these ranges is meaningful from the point of improving the adhesion to a glass base material, the solubility to an alkali developing solution, and improving glass processing precision, for example. In addition, an upper limit is significant from the point which optimizes the solubility to a developing solution, for example, improves glass processing precision, the improvement of storage stability, or the resistance to an etching process liquid.

60 degreeC-100 degreeC is preferable, and, as for the glass transition temperature (measured by a differential scanning calorimeter (DSC)) of A component, 70-95 degreeC is more preferable. The lower limit of each of these ranges is significant in that, for example, the resistance to the etching treatment liquid is maintained to improve the glass processing accuracy. In addition, an upper limit has a meaning from the point which maintains peelability by peeling liquid favorable and improves glass processing precision, for example.

It is preferable that A component has a hydroxyl group. In this case, 1-200 KOHmg / g is preferable and, as for the hydroxyl value of A component, 1-80KOHmg / g is more preferable. When the hydroxyl value is within these ranges, the resistance to the etching treatment liquid is not significantly lowered, the shape of the glass substrate end after the etching treatment is very good, and the peelability to the peeling solution can also be improved.

It is preferable that A component is especially (meth) acrylic-type resin which has a carboxyl group. As this (meth) acrylic-type resin, the radical copolymer of ethylenically unsaturated carboxylic acid, a hydroxyl group containing radically polymerizable unsaturated monomer, and another radically polymerizable unsaturated monomer is mentioned, for example.

Acrylic acid, methacrylic acid, maleic acid, etc. are mentioned as a specific example of ethylenic unsaturated carboxylic acid.

As a specific example of a hydroxyl-containing radically polymerizable unsaturated monomer, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, etc. are mentioned.

As another radically polymerizable unsaturated monomer, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, Alkyl (C1-8) ester of acrylic acid or methacrylic acid, such as butyl methacrylate and hexyl methacrylate; Vinyl aromatic monomers, such as styrene, (alpha) -methylstyrene, and vinyltoluene; Amide compounds of acrylic acid or methacrylic acid and derivatives thereof; Acrylonitrile, methacrylonitrile; Etc. can be mentioned. Among these monomers, in particular, methyl methacrylate and styrene are excellent in resistance to an etching treatment liquid. Therefore, it is preferable to use one or both of these as other radically polymerizable unsaturated monomers.

<Unsaturated Compound (Component B)>

As B component, the ester exchange reaction product of the esterified product of polyhydric alcohol with (meth) acrylic acid, or acrylic acid ester is mentioned, for example. In addition, the unsaturated component used as this B component remove | excludes the above-mentioned D component later.

Specific examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol or polypropylene glycol having a number average molecular weight of 150 to 6000, neopentyl glycol, diethyl propanediol, and ethyl butyl propane. Diol, cyclohexane dimethanol, butylene glycol, pentanediol, hexanediol, hydrogenated bisphenol A, the ethylene glycol adduct of bisphenol A, trimethylol propane, trimethylol ethane, glycerin, pentaerythritol, etc. are mentioned.

Specific examples of the B component include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and 1,3-butyl Lenglycoldi (meth) acrylate, 1,4-butanedioldiacrylate, 1,9-nonanedioldi (meth) acrylate, glycerindi (meth) acrylate, trimethylolpropanedi (meth) acrylate, penta Erythritol di (meth) acrylate, neopentylglycol diacrylate, 1,6-hexanediol diacrylate, kayarad R-167 (manufactured by Nippon Kayaku Co., Ltd., brand name), kayarad R-551 (Nippon Explosives company make, brand name), Kayarard R-604 (Nippon Chemicals Co., Ltd. brand name), Kayarard R-712 (Nippon Chemicals Co., Ltd. brand name), Kayarard HX-220 (Nippon Chemicals Co., Ltd. brand name), Kaya Rad HX-620 (manufactured by Nippon Kayaku Co., Ltd., brand name), polyester di (meth) Di (meth) acrylate compounds, such as a relay agent, the urethane di (meth) acrylate; Glycerine tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropanepropylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, pentaerythritol tree (meth ) (Tri) (meth) acrylate compounds, such as acrylate and aronix M-315 (Toagosei make, brand name); Tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; In addition, dipentaerythritol penta (meth) acrylate, etc. are mentioned. These unsaturated compounds can be used 1 type or in combination or 2 or more types. Among these, a tri (meth) acrylate compound is preferable.

<Photoinitiator (C component)>

Specific examples of the C component include aromatic carbonyl compounds such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzyl xanthone, thioxanthone and anthraquinone; Acetophenes such as acetophenone, propiophenone, α-hydroxyisobutylphenone, α, α'-dichlor-4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylacetophenone and diacetylacetophenone Rice field; Benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylhydroperoxide, di-t-butyldiperoxyisophthalate, 3,3'4,4'-tetra (t-butylperoxy Organic peroxides such as carbonyl) benzophenone; Diphenylhalonium salts such as diphenyl iodide bromide and diphenyl iodonium chloride; Organic halides such as carbon tetrabromide, chloroform and iodine form; Heterocyclic and polycyclic compounds such as 3-phenyl-5-isoxazolone and 2,4,6-tris (trichloromethyl) -1,3,5-triazinebenzanthrone; 2,2'-azo (2,4-dimethylvaleronitrile), 2,2-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'- Azo compounds such as azobis (2-methylbutyronitrile); Aminoalkylphenone compounds such as 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; Titanocene compound; Bisimidazole-based compounds; N-aryl glycidyl compounds; Acridine-based compounds; Combinations of aromatic ketones / aromatic amines; Peroxyketal; Etc. can be mentioned. Among these, aromatic carbonyl compounds and aminoalkylphenone compounds are preferred because they have high activity against crosslinking or polymerization.

As a brand name of the commercial item which can be used as a C component, Irgacure 651 (made by Chiba Specialty Chemicals Co., Ltd., an acetophenone type radical photopolymerization initiator), Irgacure 184 (made by Chiba Specialty Chemicals Co., Ltd.) Acetophenone optical radical polymerization initiator), Irgacure 1850 (made by Chiba Specialty Chemicals Co., Ltd., acetophenone optical radical polymerization initiator), Irgacure 907 (made by Chiba Specialty Chemicals Co., Ltd., aminoalkyl phenone optical radicals) Polymerization initiator), Irgacure 369 (manufactured by Chiba Specialty Chemicals, aminoalkyl phenone photo radical polymerization initiator), Lucirin TPO (manufactured by BASF, 2,4,6-trimethylbenzoyldiphenylphosphine oxide) And Kayacure DETX-S (manufactured by Nippon Chemical Co., Ltd.), CGI-784 (manufactured by Chiba Specialty Chemicals, titanium complex compound), and the like.

These photoinitiators can be used 1 type or in combination or 2 or more types.

<Alkoxysilane Compound (Component D) Containing Unsaturated Group or Epoxy Group>

An unsaturated group containing alkoxysilane compound (component D-1) is a compound containing 2 or more alkoxy silyl groups in 1 molecule, and 1 unsaturated group in 1 molecule, for example. Specific examples of the D-1 component include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, and γ- (meth) And vinyl silanes such as acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropyldimethoxymethylsilane, and 2-steel ethyltrimethoxysilane.

The epoxy group-containing alkoxysilane compound (component D-2) is, for example, a compound containing two or more alkoxysilyl groups in one molecule and one epoxy group in one molecule. Specific examples of the D-2 component include γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

These alkoxysilane compounds can be used 1 type or in combination or 2 or more types.

<Inorganic fine powder (E component)>

Specific examples of the component E include talc, mica, sericite, mica, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, magnesium carbonate, alumina white, and the like. These inorganic fine powders can be used 1 type or in combination of 2 or more types. Among these, flake pigments, such as talc, mica, and sericite, are preferable. In particular, talc is preferable because of its excellent resistance to etching liquid and a great effect of preventing decomposition of the film and deterioration of adhesion due to penetration of the etching treatment liquid into the resist film.

0.01 micrometer-20 micrometers are preferable, and, as for the primary average particle diameter of E component, 0.1 micrometer-10 micrometers are more preferable. The lower limit of each of these ranges is, for example, by lowering the viscosity of the resist composition so that the adhesion (talc property) on the surface of the resist film is appropriate to improve workability, or to reduce the amount of the diluent solvent to paint once. This is significant in that a thick film (for example, 30 µm or more) can be formed. In addition, an upper limit has meaning, for example from a resistance with respect to etching liquid, or a resolution.

<Mixing ratio>

The compounding ratio of the resist composition of this invention is as follows. In addition, the following compounding ratio is a value (solid content conversion value) with respect to 100 mass parts of A components.

B component: Usually, it is 10-100 mass parts, Preferably it is 20-80 mass parts. The lower limit of each of these ranges is meaningful in the glass processing precision improvement by the hardenability of a composition, for example. In addition, an upper limit is significant in the glass processing precision improvement by the solubility to alkaline developing solution, for example.

C component: Usually, it is 0.1-10 mass parts, Preferably it is 0.5-8 mass parts. The lower limit of each of these ranges is meaningful in the glass processing precision improvement by the hardenability of a composition, for example. In addition, an upper limit has significance, for example in the balance of the limit of photocurability improvement, and economical efficiency.

D component: Usually, it is 1-80 mass parts, Preferably it is 1-40 mass parts, More preferably, it is 2-30 mass parts. The lower limit of each of these ranges is meaningful in the glass processing precision improvement by the resistance with respect to etching liquid, for example. In addition, an upper limit has a meaning in the photocurability, for example.

E component: Usually, it is 5-100 mass parts, Preferably it is 10-80 mass parts. The lower limit of each of these ranges is meaningful in the glass processing precision, for example. In addition, an upper limit is significant from the point of glass processing precision improvement by the hardenability and resolution of a composition, for example.

<Others>

The resist composition of this invention can also be used as an organic solvent composition obtained by melt | dissolving or disperse | distributing A-E component in the organic solvent, for example. Specific examples of the organic solvent include ketones, esters, ethers, cellosolves, aromatic hydrocarbons, alcohols, halogenated hydrocarbons, and the like.

Moreover, B-E component can be mix | blended with neutralizing resin which neutralized the acidic radical of A component with a basic compound, and can also be used as an aqueous-based composition disperse | distributed.

30-95 mass% is preferable, and, as for solid content of the resist composition of this invention, 40-90 mass% is more preferable.

<Glass etching processing method>

The glass etching treatment method of the present invention comprises (1) a resist film forming step, (2) exposure step, (3) developing and heating step, (4) glass etching step, and the like using the resist composition of the present invention described above. (5) It is a method of performing the peeling process of a resist film.

In the glass etching treatment method of the present invention, first, the resist composition of the present invention is coated on the surface of a glass substrate to form a resist film. As a coating means, a roller, a roll coater, a spin coater, a curtain roll coater, a spray, brush coating, immersion coating, silk printing, spin coating, etc. are mentioned, for example. Although the coating film thickness is not specifically limited, 10-150 micrometers is preferable and 20-100 micrometers is preferable.

In a resist film formation process, heat processing is performed as needed. This heat processing can be performed on 40 degreeC-120 degreeC, and the conditions for 5 to 60 minutes after setting as needed, for example.

In addition, the resist composition can be coated by dividing it into a plurality of times. As a coating method in that case, wet-on-wet coating, such as a 2-coat 1 bake conventionally known and dry-on-wet coating, such as a 2-coat 2-bake, are possible.

Next, an exposure process is performed so that a desired pattern shape can be obtained. This exposure process may irradiate an ultraviolet-ray with respect to a resist film through a mask, and may irradiate an ultraviolet-ray in a desired pattern without passing through a mask. Sources of ultraviolet radiation are conventionally used, for example, ultra-high pressure, high pressure, medium or low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, solar light Can be mentioned. The irradiation amount is 100-10000J / m <2> normally, Preferably it is 500-7000J / m <2>.

Next, the development and heating process of a resist film are performed. Specifically, an exposure pattern is developed by removing either one of the ultraviolet (irradiated) portion and the unirradiated portion (unexposed portion) of the ultraviolet ray in the exposure step of the resist film, followed by heating to form a resist film having a desired pattern image. do. In particular, the developing treatment is performed by removing the unilluminated portion (unexposed portion) of the resist film under predetermined conditions using an alkaline developer or the like. The heat treatment is performed by, for example, heating the resist film after development under predetermined conditions.

As alkaline developing solution used by image development processing, aqueous solutions, such as a triethylamine, diethanolamine, a triethanolamine, ammonia, a sodium metasilicate, a calcium metasilicate, a sodium carbonate, tetraethylammonium hydroxide, are mentioned, for example. have. The concentration of the alkaline developer is usually 0.5 to 3% by weight, preferably 0.6 to 2% by weight. The developing treatment can be performed under conditions of 20 to 50% and 40 to 120 seconds, for example. The heat treatment can be carried out under conditions of, for example, 100 ° C to 200 ° C, preferably 120 ° C to 180 ° C, 5 minutes to 120 minutes, and preferably 10 minutes to 60 minutes.

Next, a glass etching process is performed. Specifically, the glass substrate of the part exposed from the desired pattern of the resist film formed by the development and heating process is etched. This etching process is performed by immersing a glass base material in an etching process liquid, for example. As an etching process liquid, if it is known conventionally as what can be used for a glass etching process, it can be used without a restriction | limiting in particular. As a specific example of an etching process liquid, hydrofluoric acid type aqueous solutions, such as hydrofluoric acid and hydrofluoric acid, are mentioned. The conventionally known various additives, other strong acids, etc. can also be mix | blended with the fluoric-acid type aqueous solution. An etching process can be performed by immersing for 5 to 100 minutes in the etching process liquid of 5-100 degreeC, for example.

Next, the process of peeling the resist film which remains on the glass base material after an etching process is performed. Peeling of this resist film is performed by swelling or melt | dissolving and wash | cleaning the irradiation part (exposure part) of a residual resist film, for example using alkaline aqueous solution or an organic solvent. As an example of aqueous alkali solution, aqueous solution, such as caustic soda, caustic kali, ammonia, triethanolamine, and triethylamine, is mentioned. Specific examples of the organic solvent include solvents such as 1,1,1-trichloroethane, methyl ethyl ketone, and methylene chloride. Peeling of a resist film can be used by immersing in 20-80 degreeC aqueous alkali solution or the organic solvent for 5 to 30 minutes, for example.

According to this invention, the glass which has a target shape and a pattern can be manufactured by etching a glass base material. Specifically, for example, the production of a sealing glass formed on the surface of a display device using an organic EL (electroluminescent) device, the production of a microlens substrate, the etching of glass, the production of a line & space pattern, or the like In the present invention, the present invention is very useful.

Example

An Example and a comparative example are shown to the following, and this invention is demonstrated in more detail. However, the present invention is not limited to these.

<Example 1>

Acid group-containing resin A-1 (acid value 50KOHmg / g, hydroxyl value 30KOHmg / g, glass transition temperature 80 degreeC, weight average molecular weight 35,000, styrene / n-butylacrylate / methyl methacrylate / methacrylic acid / methacrylic acid 2 -Hydroxyethyl) 100 parts by mass, aronix M-309 (trimethylolpropane triacrylate, manufactured by Toagosei Co., Ltd.), 50 parts by mass, Irgacure 907 (photoinitiator, manufactured by Chiba Specialty Chemicals Co., Ltd.) 1 mass parts of Kaya Cure DETX-S (photoinitiator, manufactured by Nippon Chemistry pharmacist, Ltd., trade name) 1 parts by mass of talc (average particle size about 5㎛, MgO and SiO ₂₎ 40 parts by mass, γ- methacryloyl yl oxy propyl trimethoxy 10 mass parts of oxysilane and 200 mass parts of methyl ethyl ketones were mix | blended, and the resist liquid (UV curable resist composition for glass etching) of Example 1 was prepared.

In order to confirm whether the resist liquid of this Example 1 was suitable for manufacture of the sealing glass formed in the surface of the display device using an organic electroluminescent element, the glass etching process was performed as follows.

First, the resist liquid of Example 1 was coated on a plate-shaped glass substrate (thickness 1 mm, length 200 mm, width 200 mm) using a curtain flow coater so as to have a dry film thickness of 40 μm. Subsequently, preliminary drying was performed at 80 degreeC for 20 minutes. Thereafter, coating and drying were performed again under the same conditions to form a resist film having a film thickness of 80 µm.

Subsequently, on the surface of this resist film, through a mask (a mask manufactured so as to form a concave shape having a length of 10 mm and a width of 30 mm in the center of the glass substrate), at a irradiation condition of 4500 J / m 2 using a mercury lamp. The exposure was performed.

Subsequently, image development was performed on 30 degreeC and 120 second conditions using the 1 weight% sodium-carbonate aqueous solution (alkaline developing solution), and also heat-processed on the conditions of 150 degreeC and 30 minutes, and the pattern of the resist film was formed.

Subsequently, the glass substrate exposed from the pattern of the said resist film was etched on the conditions of the etching resistance test mentioned later, and the recessed part of 10 mm in length and 30 mm in width was formed in the center of the glass substrate. Next, the remaining resist film was peeled off under the conditions of the peelability test of the resist film mentioned later. This obtained the glass base material which has a recessed part.

In Table 1, the outline | summary and the performance test result of the composition of this resist composition are shown.

<Examples 2-9, Comparative Examples 1-3>

Except having changed the composition of the resist composition as shown in Table 1, it carried out similarly to Example 1, the resist composition was prepared, and the glass etching process was performed. Each performance test result is shown in Table 1.

(Note 1) Acid-group-containing resin A-2: Acid value 100KOHmg / g, hydroxyl value 30KOHmg / g, glass transition temperature 80 degreeC, weight average molecular weight 35,000, styrene / n-butylacrylate / methyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate

(Note 2) Acid-group-containing resin A-3: Acid value 170KOHmg / g, hydroxyl value 30KOHmg / g, glass transition temperature 80 degreeC, weight average molecular weight 35,000, styrene / n-butylacrylate / methyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate

(Note 3) Acid-group-containing resin A-4: Acid value 100KOHmg / g, hydroxyl value 0KOHmg / g, glass transition temperature 80 degreeC, weight average molecular weight 35,000, styrene / n-butylacrylate / methyl methacrylate / methacrylic acid

(Note 4) Acid group-containing resin A-5: Acid value 100KOHmg / g, hydroxyl value 60KOHmg / g, glass transition temperature 80 degreeC, weight average molecular weight 35,000, styrene / n-butylacrylate / methyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate

(Note 5) Acid-group-containing resin A-6: Acid value 100KOHmg / g, hydroxyl value 90KOHmg / g, glass transition temperature 80 degreeC, weight average molecular weight 35,000, styrene / n-butylacrylate / methyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylic acid.

Performance test

ㆍ Heat Resistance Test:

The glass substrate after pattern formation of a resist film was immersed in 40 degreeC etching liquid (7 mass% of fluoric acid concentrations, 15 mass% of sulfuric acid concentrations) for 80 minutes (etching depth 300 micrometers), and 100 minutes (etching depth 400 micrometers), respectively. Then, water washing was performed. The state of the resist film after water washing was visually observed, and the following criteria were determined.

"(Double-circle)": There is no lifting and peeling from the glass base material of a resist film, and it is very favorable.

"(Circle)": Although the edge part of a resist film is a little excited from a glass base material, it does not peel and is favorable.

"Δ": There is a portion where the resist film is lifted up from the glass substrate.

"X": The resist film is peeled off from the glass substrate.

Peelability Test of Resist Film:

The glass base material after pattern formation of the resist film was immersed in 40 degreeC etching liquid (7 mass% of fluoric acid concentrations, 15 mass% of sulfuric acid concentrations) for 80 minutes, and it washed with water after that. Subsequently, the glass base material was immersed in 5 weight% of caustic soda aqueous solution (peel solution) at 60 degreeC for 15 minutes. The peeling state of the resist film after immersion was observed visually, and the following references | standards judged.

"◎": The entire surface of the resist film is peeled off the glass substrate.

"(Circle)": Although the resist film is affixed on the glass base material, it peels off by the subsequent water washing.

"Δ": A part of resist film is affixed on the glass base material, and is not peeled off by subsequent water washing.

"X": Most of the resist film is affixed to the glass base material, and is not peeled off by subsequent washing with water.

Glass shape after etching:

The end shape of the glass base material after the peelability test of the said resist film was observed visually, and the following references | standards judged.

"◎": The glass base end is sharp and very favorable.

"O": Although the edge part of a glass base material is slightly round, it is favorable.

"Δ": The glass base end is round.

"X": The glass base end is very round.

In this invention, the following remarkable effect is exhibited especially by combining an acidic radical containing resin, an inorganic fine powder, and the alkoxysilane compound containing an unsaturated group or an epoxy group.

The acid group of an acidic radical containing resin improves the stability with respect to the glass etching process liquid of a resist film, and simultaneously improves the solubility with respect to peeling liquids, such as aqueous solution of caustic soda.

The inorganic fine powder prevents decomposition, deterioration of adhesion, and the like of the resist film due to penetration of the glass etching treatment liquid into the resist film.

The alkoxysilane compound containing an unsaturated group is photoradically copolymerized with another unsaturated compound to form a strong resist film. Moreover, the cured film which has a siloxane bond is formed by the self condensation by an alkoxy silyl group, or reaction with a hydroxyl group. Thereby, stability to the glass etching process liquid of a resist film is improved, and decomposition | disassembly, adhesion deterioration, etc. of a resist film are prevented. Moreover, as a result of hydrolysis by peeling liquids, such as a caustic soda aqueous solution, peeling of the resist film in a peeling process becomes easy.

Since the alkoxysilane compound containing an epoxy group forms a strong resist film by the crosslinking reaction by an alkoxy silyl group, and reaction of an epoxy group and the acid group of an acid group containing resin, it exhibits the above effects.

According to the above effects, the glass etching process can be performed with high processing accuracy and deep processing.

Claims (7)

The ultraviolet curable resist composition for glass etching containing (A) acidic radical containing resin, (B) unsaturated compound, (C) photoinitiator, (D) unsaturated group, or an alkoxysilane compound containing an epoxy group, and (E) inorganic fine powder. The method of claim 1, It contains 10-100 mass parts of B components, 0.1-10 mass parts of C components, 1-80 mass parts of D components, and 5-100 mass parts of E components (all solid content conversion values) with respect to 100 mass parts of A components. UV curable resist composition for glass etching. The method of claim 1, The ultraviolet curable resist composition for glass etching whose acid value of A component is 50-200KOHmg / g. The method of claim 1, The ultraviolet curable resist composition for glass etching which A component further has a hydroxyl group. The method of claim 4, wherein The ultraviolet curable resist composition for glass etching whose hydroxyl value of A component is 1-200 KOHmg / g. (1) a resist film forming step of coating a ultraviolet curable resist composition according to claim 1 on a surface of a glass substrate to form a resist film; (2) an exposure step of irradiating ultraviolet rays to the resist film through a mask or directly irradiating ultraviolet rays without passing through the mask so that a desired pattern shape is obtained; (3) the development and heating step of forming a resist film having a desired pattern by performing the development and heat treatment of the resist film; (4) a glass etching step of etching the glass substrate in the portion exposed from the resist film having the desired pattern, and (5) The glass etching processing method which has a peeling process which peels a resist film which remains | survives after the said glass etching process in this order. The method of claim 6, The glass etching processing method which heat-processes in a resist film formation process.