JP2007128052A - Ultraviolet-curing resist composition for glass etching and glass etching processing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass etching processing method which ensures high processing accuracy and allows deep processing, and an ultraviolet-curing resist composition suitable for use in the method. <P>SOLUTION: The ultraviolet-curing resist composition for glass etching contains (A) an acid group-containing resin, (B) an unsaturated compound, (C) a photoinitiator, (D) an alkoxysilane compound containing an unsaturated group or an epoxy group, and (D) inorganic fine powder. The glass etching method comprises (1) a resist film forming process using the resist composition, (2) an exposure step, (3) a developing and heating step, (4) a glass etching process and (5) a resist film stripping process. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  Conventionally, glass materials obtained by etching glass substrates into various shapes have been widely used for electronic materials, optical materials, measuring instruments, and the like.

  As a conventional glass processing method, for example, a method is known in which a photocurable resist resin composition is applied on a glass substrate to form a resist film, and etching is performed using hydrofluoric acid (Patent Document 1). reference). This photocurable resist resin composition has an acrylic resin having an ethylenically unsaturated double bond in the side chain, polysilane, a photosensitizer, and, if necessary, an ethylenically unsaturated double bond. It is a composition containing (meth) acrylic monomer and / or oligomer, novolac type epoxy resin, and fluorine-containing crosslinked resin particles. Moreover, this photocurable resist resin composition can be developed with an alkaline solution.

  The performance required for the alkali-developable resist composition used in hydrofluoric acid etching is that the resist film in the irradiated area does not peel from the glass substrate in the development process and the etching process of the glass substrate, and the etching process. The resist film can be easily peeled from the glass substrate in the peeling step after the process, and the resist film in the unirradiated portion can be completely removed in the development process. However, the composition described in Patent Document 1 does not satisfy all of these requirements.

  As another glass processing method, for example, a processing method of glass for an organic EL display is known (see 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 on the glass substrate, and a step of etching by immersion in an etching solution. It consists of a process.

This processing method is excellent in that the storage part (digging part) of the glass for organic EL display can be processed to a depth of 300 μm. However, there is a limit to the digging depth by sandblasting, and there is a problem that the machining process is complicated.
JP 2005-164877 A JP 2004-71354 A

  An object of the present invention is to provide a glass etching treatment method having high processing accuracy and capable of deep processing, and an ultraviolet curable resist composition suitably used for the method.

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

Furthermore, the present invention provides
(1) A resist film forming step of forming a resist film by coating the ultraviolet curable resist composition on the surface of a glass substrate;
(2) An exposure step of irradiating the resist film with ultraviolet rays through a mask or directly irradiating ultraviolet rays without using a mask so as to obtain a desired pattern shape;
(3) A development and heating step of performing a development treatment and a heat treatment of the resist film to form a resist film having a desired pattern;
(4) a glass etching step of etching a portion of the glass substrate exposed from the resist film having the desired pattern; and
(5) A peeling step for peeling off the remaining resist film after the glass etching step,
In this order.

  In the present invention, the following remarkable effects are exhibited particularly by combining an acid group-containing resin, an inorganic fine powder, and an alkoxysilane compound containing an unsaturated group or an epoxy group.

  The acid group of the acid group-containing resin improves the stability of the resist film with respect to the glass etching solution, and at the same time improves the solubility of the resist film in a stripping solution such as an aqueous caustic soda solution.

  The inorganic fine powder prevents the resist film from being decomposed or deteriorated due to penetration of the glass etching solution into the resist film.

  An alkoxysilane compound containing an unsaturated group forms a tough resist film by photoradical copolymerization with other unsaturated compounds. Furthermore, a cured film having a siloxane bond is formed by self-condensation with an alkoxysilyl group or reaction with a hydroxyl group. As a result, the stability of the resist film with respect to the glass etching treatment liquid is improved, and the resist film is prevented from being decomposed or deteriorated. Further, as a result of hydrolysis with a stripping solution such as an aqueous caustic soda solution, the resist film can be easily stripped in the stripping step.

  Since the alkoxysilane compound containing an epoxy group forms a tough resist film by a crosslinking reaction with an alkoxysilyl group and a reaction between the epoxy group and the acid group of the acid group-containing resin, the same effect as described above is exhibited.

  Due to the above-described effects, a glass etching process with high processing accuracy and capable of deep processing can be performed.

  The UV-curable resist composition for glass etching of the present invention comprises an acid group-containing resin (hereinafter sometimes abbreviated as “A component”) and an unsaturated compound (hereinafter sometimes abbreviated as “B component”). , A photoinitiator (hereinafter sometimes abbreviated as “C component”), an alkoxysilane compound containing an unsaturated group or an epoxy group (hereinafter sometimes abbreviated as “D component”), and inorganic fine particles. Contains powder (hereinafter sometimes abbreviated as “E component”) as an essential component. Each component will be described below.

<Acid group-containing resin (component A)>
The component A is used for the solubility of the resist film in an alkaline developer and the removal of the photocured film with a stripping solution. Examples of the component A include (meth) acrylic resins having a carboxyl group, polyester resins having a carboxyl group, and the like. These resins can be used alone or in combination of two or more. “(Meth) acryl” is a general term for acrylic and methacrylic.

  The acid value of the component A is preferably 50 to 200 KOH mg / g, and more preferably 60 to 150 KOH mg / g. The lower limits of these ranges are significant in terms of improving glass processing accuracy by, for example, improving adhesion to glass substrates and optimizing solubility in alkaline developers. The upper limit value is significant in terms of, for example, optimizing solubility in a developing solution to improve glass processing accuracy, improving storage stability, and improving resistance to an etching treatment solution.

  The glass transition temperature of the component A (measured with a differential scanning calorimeter (DSC)) is preferably 60 ° C to 100 ° C, more preferably 70 to 95 ° C. The lower limits of these ranges are significant, for example, in that the resistance to the etching treatment liquid is maintained and the glass processing accuracy is improved. Moreover, an upper limit is significant at the point which maintains the peelability by stripping solution favorably and improves glass processing precision, for example.

  The component A preferably has a hydroxyl group. In this case, the hydroxyl value of the component A is preferably 1 to 200 KOHmg / g, more preferably 1 to 80 KOHmg / g. If the hydroxyl value is within these ranges, the resistance to the etching treatment solution is not greatly reduced, the shape of the edge of the glass substrate after the etching treatment becomes very good, and the peelability to the peeling solution is improved. be able to.

  The component A is particularly preferably a (meth) acrylic resin having a carboxyl group. Examples of the (meth) acrylic resin include radical copolymers of an ethylenically unsaturated carboxylic acid, a hydroxyl group-containing radical polymerizable unsaturated monomer, and other radical polymerizable unsaturated monomers. It is done.

  Specific examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid and the like.

  Specific examples of the hydroxyl group-containing radically polymerizable unsaturated monomer include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and 3-hydroxypropyl methacrylate.

  Other radical polymerizable unsaturated monomers include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid. Alkyl (C1-8) esters of acrylic acid or methacrylic acid such as isopropyl acid, butyl methacrylate, hexyl methacrylate; vinyl aromatic monomers such as styrene, α-methylstyrene, vinyltoluene; amide compounds of acrylic acid or methacrylic acid And derivatives thereof; acrylonitrile, methacrylonitrile; and the like. Of these monomers, methyl methacrylate and styrene are particularly excellent in resistance to the etching treatment solution. Therefore, it is preferable to use one or both of these as other radical polymerizable unsaturated monomers.

<Unsaturated compound (component B)>
Examples of the component B include an esterified product of a polyhydric alcohol and (meth) acrylic acid or a transesterification product of an acrylic ester. The unsaturated compound used as this B component excludes the D component described in detail 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, diethylpropanediol, ethylbutylpropanediol. , Cyclohexanedimethanol, butylene glycol, pentanediol, hexanediol, hydrogenated bisphenol A, ethylene glycol adduct of bisphenol A, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol and the like.

  Specific examples of the component B include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and 1,3-butylene glycol di (meth). ) Acrylate, 1,4-butanediol diacrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, neopentyl Glycol diacrylate, 1,6-hexanediol diacrylate, Kayrad R-167 (Nippon Kayaku Co., Ltd., trade name), Kayarad R-551 (Nippon Kayaku Co., Ltd., trade name), Kayarad R-604 (Nihon Kasei) Product made by Yakuhin Name), Kayrad R-712 (product name) manufactured by Nippon Kayaku Co., Ltd., Kayrad HX-220 (product name manufactured by Nippon Kayaku Co., Ltd.), Kayrad HX-620 (product name manufactured by Nippon Kayaku Co., Ltd.), Polyester Di Di (meth) acrylate compounds such as (meth) acrylate and urethane di (meth) acrylate; glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane Tri (meth) acrylate compounds such as ethylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Aronix M-315 (trade name, manufactured by Toagosei Co., Ltd.); tetra (meth) acrylate such as pentaerythritol tetra (meth) acrylate Meta) Acrylate compounds; Other, dipentaerythritol penta (meth) acrylate. These unsaturated compounds can be used alone or in combination of two or more. Among these, tri (meth) acrylate compounds are preferable.

<Photoinitiator (C component)>
Specific examples of the component C include aromatic carbonyl compounds such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzylxanthone, thioxanthone, and anthraquinone; acetophenone, propiophenone, α-hydroxyisobutylphenone, α, α'-dichloro- Acetophenones such as 4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylacetophenone, diacetylacetophenone; benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butyl hydroperoxide, di-t-butyl Organic peroxides such as diperoxyisophthalate, 3,3′4,4′-tetra (t-butylperoxycarbonyl) benzophenone; diphenyliodobromide, diphenyliodine Diphenylhalonium salts such as donium chloride; organic halides such as carbon tetrabromide, chloroform, iodoform; 3-phenyl-5-isoxazolone, 2,4,6-tris (trichloromethyl) -1,3,5 -Heterocyclic and polycyclic compounds such as triazine benzanthrone; 2,2'-azo (2,4-dimethylvaleronitrile), 2,2-azobisisobutyronitrile, 1,1'-azobis (cyclohexane -1-carbonitrile), azo compounds such as 2,2′-azobis (2-methylbutyronitrile); 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc. Aminoalkylphenone compounds; titanocene compounds; bisimidazole compounds; N-aryl glycidyl compounds; acridine compounds; Ton / aromatic amine combinations; peroxyketals; and the like. Among these, aromatic carbonyl compounds and aminoalkylphenone compounds are preferable because of their high activity for crosslinking or polymerization.

  Examples of commercially available product names that can be used as component C include Irgacure 651 (Ciba Specialty Chemicals, acetophenone photoradical polymerization initiator), Irgacure 184 (Ciba Specialty Chemicals, acetophenone photoradical). Polymerization initiator), Irgacure 1850 (manufactured by Ciba Specialty Chemicals, acetophenone photoradical polymerization initiator), Irgacure 907 (manufactured by Ciba Specialty Chemicals, aminoalkylphenone photoradical polymerization initiator), Irgacure 369 ( Ciba Specialty Chemicals, aminoalkylphenone photoradical polymerization initiator), Lucyrin TPO (BASF 2,4,6-trimethylbenzoyldiphenylphosphine oxide), Kayacure ETX-S (manufactured by Nippon Kayaku Co., Ltd.), CGI-784 (manufactured by Ciba Specialty Chemicals, titanium complex compound), and the like.

  These photoinitiators can be used alone or in combination of two or more.

<Alkoxysilane compound containing unsaturated group or epoxy group (component D)>
The unsaturated group-containing alkoxysilane compound (D-1 component) is, for example, a compound containing two or more alkoxysilyl groups in one molecule and one unsaturated group in one molecule. Specific examples of component D-1 include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane. And vinyl silanes such as γ- (meth) acryloyloxypropyldimethoxymethylsilane and 2-styrylethyltrimethoxysilane.

  The epoxy group-containing alkoxysilane compound (D-2 component) 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 alone or in combination of two or more.

<Inorganic fine powder (E component)>
Specific examples of the E component include talc, mica, sericite, mica, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, magnesium carbonate, and alumina white. These inorganic fine powders can be used alone or in combination of two or more. Among these, flake pigments such as talc, mica and sericite are preferable. In particular, talc is preferable because it has excellent resistance to an etching solution and has a large effect of preventing the decomposition and adhesion deterioration of the film due to the etching treatment solution penetrating into the resist film.

  The primary average particle size of the E component is preferably 0.01 μm to 20 μm, and more preferably 0.1 μm to 10 μm. The lower limit of each of these ranges is, for example, by keeping the viscosity of the resist composition low, thereby improving the workability by making the resist film surface tacky (tackiness) appropriate, and reducing the amount of dilution solvent. This is significant in that a thick film (for example, 30 μm or more) can be formed by one coating. The upper limit is significant in terms of resistance to the etching solution and resolution, for example.

<Combination ratio>
The mixing ratio of the resist composition of the present invention is as follows. In addition, the following mixture ratio is a value (solid content conversion value) with respect to 100 mass parts of A component.

  B component: It is 10-100 mass parts normally, Preferably it is 20-80 mass parts. The lower limits of these ranges are significant, for example, in terms of improving glass processing accuracy due to the curability of the composition. The upper limit is significant in terms of improving glass processing accuracy due to, for example, solubility in an alkali developer.

  Component C: Usually 0.1 to 10 parts by mass, preferably 0.5 to 8 parts by mass. The lower limits of these ranges are significant, for example, in terms of improving glass processing accuracy due to the curability of the composition. The upper limit is significant in terms of, for example, the balance between improvement in photocurability and economic efficiency.

  D component: It is 1-80 mass parts normally, Preferably it is 1-40 mass parts, More preferably, it is 2-30 mass parts. The lower limits of these ranges are significant in terms of improving the glass processing accuracy due to, for example, resistance to the etching solution. The upper limit is significant in terms of photocurability, for example.

  E component: It is 5-100 mass parts normally, Preferably it is 10-80 mass parts. The lower limits of these ranges are significant in terms of glass processing accuracy, for example. The upper limit value is significant in terms of improving glass processing accuracy due to, for example, the curability and resolution of the composition.

<Others>
The resist composition of the present invention can also be used, for example, as an organic solvent composition obtained by dissolving or dispersing components A to E in an organic solvent. Specific examples of the organic solvent include ketones, esters, ethers, cellosolves, aromatic hydrocarbons, alcohols, halogenated hydrocarbons and the like.

  Moreover, it can also be used as the aqueous composition which mix | blended BE components with the neutralization resin which neutralized the acid group of A component with the basic compound, and was water-dispersed.

  The solid content of the resist composition of the present invention is preferably 30 to 95% by mass, and more preferably 40 to 90% by mass.

<Glass etching treatment method>
The glass etching treatment method of the present invention uses (1) a resist film forming step, (2) an exposure step, (3) a development and heating step, (4) a glass etching step, and the above-described resist composition of the present invention. (5) A method of performing a resist film peeling step.

  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. Examples of the coating means include a roller, a roll coater, a spin coater, a curtain roll coater, spray, brush coating, dip coating, silk printing, and spin coating. The coating film thickness is not particularly limited, but is preferably 10 to 150 μm, and more preferably 20 to 100 μm.

  In the resist film forming step, heat treatment is performed as necessary. This heat treatment can be performed, for example, under conditions of 40 ° C. to 120 ° C. for 5 to 60 minutes after setting as necessary.

  Further, the resist composition can be applied in a plurality of times. As a coating method at that time, conventionally known wet-on-wet coating such as 2-coat 1-bake or dry-on-wet coating such as 2-coat 2-bake is possible.

Next, an exposure step is performed so that a desired pattern shape is obtained. In this exposure step, the resist film may be irradiated with ultraviolet rays through a mask, or may be irradiated with ultraviolet rays in a desired pattern without passing through the mask. Ultraviolet radiation sources are conventionally used, for example, ultra-high pressure, high pressure, medium pressure, or low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, sunlight And the like. Its dose is usually 100~10000J / m ^2, preferably 500~7000J / m ^2.

  Next, a resist film is developed and heated. Specifically, the exposure pattern is developed by removing one of the ultraviolet irradiation part (exposure part) and the non-irradiation part (unexposed part) in the exposure step of the resist film, and then heated to obtain a desired film A resist film having a pattern shape is formed. In particular, the development treatment is performed, for example, by removing an unirradiated portion (unexposed portion) of the resist film under a predetermined condition using an alkaline developer or the like. The heat treatment is performed, for example, by heating the developed resist film under predetermined conditions.

  Examples of the alkaline developer used in the development treatment include aqueous solutions such as triethylamine, diethanolamine, triethanolamine, ammonia, sodium metasilicate, potassium metasilicate, sodium carbonate, and tetraethylammonium hydroxide. The concentration of the alkaline developer is usually from 0.5 to 3% by weight, preferably from 0.6 to 2% by weight. The development processing can be performed, for example, under conditions of 20 to 50 ° C. and 40 to 120 seconds. The heat treatment can be performed, for example, under conditions of 100 ° C. to 200 ° C., preferably 120 ° C. to 180 ° C., 5 minutes to 120 minutes, preferably 10 minutes to 60 minutes.

  Next, a glass etching process is performed. Specifically, the glass substrate in a portion exposed from a desired pattern of the resist film formed by the development and heating processes is etched. This etching process is performed, for example, by immersing the glass substrate in an etching process liquid. Any etching solution can be used without particular limitation as long as it is conventionally known as being usable for glass etching. Specific examples of the etching treatment liquid include hydrofluoric acid aqueous solutions such as hydrofluoric acid and silicohydrofluoric acid. Various kinds of conventionally known additives and other strong acids can be added to the hydrofluoric acid aqueous solution. The etching treatment can be performed, for example, by immersing in an etching treatment solution at 5 to 100 ° C. for 5 to 100 minutes.

  Next, a step of removing the resist film remaining on the glass substrate after the etching treatment is performed. For example, the resist film is peeled off by swelling or dissolving the irradiated portion (exposed portion) of the remaining resist film using an alkaline aqueous solution or an organic solvent. Specific examples of the alkaline aqueous solution include aqueous solutions of caustic soda, caustic potash, ammonia, triethanolamine, triethylamine and the like. Specific examples of the organic solvent include solvents such as 1,1,1-trichloroethane, methyl ethyl ketone, and methylene chloride. The resist film can be peeled off by, for example, immersing in an alkaline aqueous solution or organic solvent at 20 to 80 ° C. for 5 to 30 minutes.

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

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these.

<Example 1>
Acid group-containing resin A-1 (acid value 50 KOH mg / g, hydroxyl value 30 KOH mg / g, glass transition temperature 80 ° C., weight average molecular weight 35,000, styrene / n-butyl acrylate / methyl methacrylate / methacrylic acid / methacrylic acid 2 -Hydroxyethyl) 100 parts by mass, Aronix M-309 (trimethylolpropane triacrylate, manufactured by Toagosei Co., Ltd., trade name), 50 parts by mass, Irgacure 907 (photoinitiator, manufactured by Ciba Specialty Chemicals, trade name) 1 Part by mass, Kayacure DETX-S (photoinitiator, Nippon Kayaku Co., Ltd., trade name) 1 part by mass, talc (average particle size of about 5 μm, MgO · SiO ₂ ) 40 parts by mass, γ-methacryloyloxypropyltrimethoxysilane 10 parts by mass and 200 parts by mass of methyl ethyl ketone were blended to obtain a cash register of Example 1. Preparative liquid (glass etching ultraviolet-curable resist composition) was prepared.

  In order to confirm whether or not the resist solution of Example 1 is suitable for producing a sealing glass provided on the surface of a display device using an organic EL element, a glass etching treatment was performed as follows.

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

Next, 4500 J / m using a mercury lamp through a mask (a mask prepared so that a concave shape having a size of 10 mm in length and 30 mm in width can be formed in the center of the glass substrate) on the surface of the resist film. Exposure was performed under the irradiation conditions of ² .

  Next, using a 1% by weight aqueous sodium carbonate solution (alkaline developer), development is performed at 30 ° C. for 120 seconds, followed by heat treatment at 150 ° C. for 30 minutes to form a resist film pattern. did.

  Next, the glass substrate exposed from the resist film pattern was etched under the conditions of an etching resistance test described later to form a concave digging portion having a length of 10 mm and a width of 30 mm in the center of the glass substrate. . Next, the remaining resist film was peeled off under the conditions of a resist film peelability test described later. Thereby, the glass base material which has a digging part was obtained.

  Table 1 shows an outline of the composition and performance test results of the resist composition.

<Examples 2-9, Comparative Examples 1-3>
A resist composition was prepared in the same manner as in Example 1 except that the composition of the resist composition was changed as shown in Table 1, and glass etching treatment was performed. Table 1 shows the results of each performance test.

（注１）酸基含有樹脂Ａ−２：酸価１００ＫＯＨｍｇ／ｇ、水酸基価３０ＫＯＨｍｇ/ｇ、ガラス転移温度８０℃、重量平均分子量３５,０００、スチレン／ｎ−ブチルアクリレート／メタクリル酸メチル／メタクリル酸／メタクリル酸２−ヒドロキシエチル
（注２）酸基含有樹脂Ａ−３：酸価１７０ＫＯＨｍｇ／ｇ、水酸基価３０ＫＯＨｍｇ/ｇ、ガラス転移温度８０℃、重量平均分子量３５,０００、スチレン／ｎ−ブチルアクリレート／メタクリル酸メチル／メタクリル酸／メタクリル酸２−ヒドロキシエチル
（注３）酸基含有樹脂Ａ−４：酸価１００ＫＯＨｍｇ／ｇ、水酸基価０ＫＯＨｍｇ/ｇ、ガラス転移温度８０℃、重量平均分子量３５,０００、スチレン／ｎ−ブチルアクリレート／メタクリル酸メチル／メタクリル酸
（注４）酸基含有樹脂Ａ−５：酸価１００ＫＯＨｍｇ／ｇ、水酸基価６０ＫＯＨｍｇ/ｇ、ガラス転移温度８０℃、重量平均分子量３５,０００、スチレン／ｎ−ブチルアクリレート／メタクリル酸メチル／メタクリル酸／メタクリル酸２−ヒドロキシエチル
（注５）酸基含有樹脂Ａ−６：酸価１００ＫＯＨｍｇ／ｇ、水酸基価９０ＫＯＨｍｇ/ｇ、ガラス転移温度８０℃、重量平均分子量３５,０００、スチレン／ｎ−ブチルアクリレート／メタクリル酸メチル／メタクリル酸／メタクリル酸２−ヒドロキシエチル。

(Note 1) Acid group-containing resin A-2: acid value 100 KOH mg / g, hydroxyl value 30 KOH mg / g, glass transition temperature 80 ° C., weight average molecular weight 35,000, styrene / n-butyl acrylate / methyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate (Note 2) Acid group-containing resin A-3: acid value 170 KOH mg / g, hydroxyl value 30 KOH mg / g, glass transition temperature 80 ° C., weight average molecular weight 35,000, styrene / n-butyl acrylate / Methyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate (Note 3) Acid group-containing resin A-4: acid value 100 KOH mg / g, hydroxyl value 0 KOH mg / g, glass transition temperature 80 ° C., weight average molecular weight 35,000 Styrene / n-butyl acrylate / methyl methacrylate / methacrylic acid (Note 4) Resin A-5: Acid value 100 KOH mg / g, hydroxyl value 60 KOH mg / g, glass transition temperature 80 ° C., weight average molecular weight 35,000, styrene / n-butyl acrylate / methyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate (Note 5) Acid group-containing resin A-6: acid value 100 KOH mg / g, hydroxyl value 90 KOH mg / g, glass transition temperature 80 ° C., weight average molecular weight 35,000, styrene / n-butyl acrylate / methyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate.

Performance test and etching resistance test:
The glass substrate after pattern formation of the resist film is subjected to an etching treatment liquid (hydrofluoric acid concentration 7 mass%, sulfuric acid concentration 15 mass%) at 40 ° C. for 80 minutes (etching depth 300 μm) and 100 minutes (etching depth). 400 μm) soaking, followed by washing with water. The state of the resist film after washing with water was visually observed and judged according to the following criteria.
“◎”: The resist film is very good without any lifting or peeling from the glass substrate.
“◯”: The end of the resist film is slightly lifted from the glass substrate, but it is satisfactory without peeling.
“Δ”: There is a portion where the resist film is floating from the glass substrate.
“X”: The resist film is peeled off from the glass substrate.
-Resist film peelability test:
The glass substrate after pattern formation of the resist film was immersed in an etching solution at 40 ° C. (hydrofluoric acid concentration 7 mass%, sulfuric acid concentration 15 mass%) for 80 minutes, and then washed with water. Next, the glass substrate was immersed in a 5% by weight aqueous caustic soda solution (stripping solution) at 60 ° C. for 15 minutes. The peeled state of the resist film after immersion was visually observed and judged according to the following criteria.
“◎”: The entire resist film is peeled off from the glass substrate.
“◯”: The resist film adheres to the glass substrate, but all peel off by subsequent washing with water.
“Δ”: A part of the resist film adheres to the glass substrate and cannot be peeled off even by subsequent water washing.
“X”: Most of the resist film adheres to the glass substrate and cannot be peeled off by subsequent water washing.
-Glass shape after etching:
The edge part shape of the glass base material after the said peelability test of the said resist film was observed visually, and the following references | standards determined.
“◎”: The edge of the glass substrate is sharp and very good.
“◯”: Good although there is a slight roundness at the edge of the glass substrate.
“Δ”: The glass substrate has a round end.
"X": The glass base material edge is large and rounded.

Claims (7)

  (A) Acid group-containing resin, (B) unsaturated compound, (C) photoinitiator, (D) alkoxysilane compound containing unsaturated group or epoxy group, and (E) glass containing inorganic fine powder An ultraviolet curable resist composition for etching.   10 to 100 parts by weight of B component, 0.1 to 10 parts by weight of C component, 1 to 80 parts by weight of D component, and 5 to 100 parts by weight of E component (all solid content) The ultraviolet curable resist composition for glass etching according to claim 1, which is contained in a conversion value.   The ultraviolet curable resist composition for glass etching according to claim 1, wherein the acid value of the component A is 50 to 200 KOHmg / g.   The ultraviolet curable resist composition for glass etching according to claim 1, wherein the component A further has a hydroxyl group.   The ultraviolet curable resist composition for glass etching according to claim 4, wherein the hydroxyl value of the component A is 1 to 200 KOHmg / g. (1) A resist film forming step of forming a resist film by coating the surface of the glass substrate with the ultraviolet curable resist composition according to claim 1;
(2) An exposure step of irradiating the resist film with ultraviolet rays through a mask or directly irradiating ultraviolet rays without using a mask so as to obtain a desired pattern shape;
(3) A development and heating step of performing a development treatment and a heat treatment of the resist film to form a resist film having a desired pattern;
(4) a glass etching step of etching a portion of the glass substrate exposed from the resist film having the desired pattern; and
(5) A peeling step for peeling off the remaining resist film after the glass etching step,
The glass etching processing method which has these in this order.   The glass etching method according to claim 6, wherein heat treatment is performed in the resist film forming step.