JP2019172971A - Etching resist composition - Google Patents

Abstract

To provide an etching resist composition having excellent adhesiveness to a substrate and showing excellent chemical resistance to immersion for a long time in hydrofluoric acid, an alkali aqueous solution containing a strong base such as sodium hydrochloride, or an etching solution containing a strong acid such as nitric acid, sulfuric acid and hydrochloric acid.SOLUTION: An etching resist composition is obtained, which comprises at least one of (A1) asphalt, (A2) chlorinated polypropylene and (A3) chlorinated rubber, (B) a cyclized rubber, and (C) an organic solvent.SELECTED DRAWING: None

Description

  The present invention relates to a heat-drying etching resist composition, and more particularly to a heat-drying etching composition used for glass etching.

  Touch panel type input devices (hereinafter also referred to simply as “touch panels”), optical materials, measuring instruments, and other glass used in the operation sections of various electronic devices such as mobile phones, personal digital assistants, car navigation systems, etc. In the processing of the substrate, not only the formation of relatively shallow grooves on the surface of the glass substrate, step engraving, etc., but also drilling for forming holes or through holes, and so-called counterbore that corrodes up to about 50% of the glass thickness. There is a demand for processing.

  Conventionally, counterboring has been performed by machining using a drill or the like. In recent years, along with the miniaturization of touch panels, etc., there has been a demand to reduce the hole diameter to be processed, and in machining, there is a limit in reducing burrs in the processed hole and reducing the drill diameter. Pointed out that they are becoming unable to withstand these demands. For this reason, counterbore processing has been demanded by etching that can be applied even when the hole diameter becomes fine.

  As an etching resist capable of glass etching, many proposals have been made so far. However, hydrofluoric acid used as an etching solution and a mixture of hydrofluoric acid and strong acid also have a strong permeability to the resist. In many cases, a resist having a film thickness obtained by ordinary screen printing cannot provide sufficient etching resistance.

  On the other hand, in order to improve etching resistance, the invention regarding the etching resist composition containing asphalt, a silica powder, and the organic solvent is proposed (refer patent document 1).

  According to the etching resist composition according to such a proposal, the etching resistance can surely be improved.

JP 2006-17021 A

  However, when deep erosion is performed on the glass thickness as in the above-described counterbore processing, the glass covered with the resist is immersed in an etching solution such as highly permeable hydrofluoric acid for more than 60 minutes for a long time. Therefore, there is a new concern that the etchant may permeate or sink into the resist, possibly causing problems such as resist peeling.

  Therefore, the object of the present invention is excellent in adhesion of the etching resist to a substrate such as a glass substrate even when deep erosion is performed on the glass thickness as in counterbore processing, and a strong base such as hydrofluoric acid or sodium hydroxide is used. An object of the present invention is to provide an etching resist composition that can withstand long-time immersion in an alkaline aqueous solution or an etching solution containing a strong acid such as nitric acid, sulfuric acid, and hydrochloric acid and that provides excellent chemical resistance.

As a result of diligent research, the present inventors have found that the object of the present invention is at least one of (A1) asphalt, (A2) chlorinated polypropylene, and (A3) chlorinated rubber,
(B) a cyclized rubber;
(C) an organic solvent;
The present invention has been found to be achieved by an etching resist composition characterized by comprising:

  The etching resist composition of the present invention comprises (B) a cyclized rubber from 15 to a total amount of 100 parts by mass of at least one of (A1) asphalt, (A2) chlorinated polypropylene, and (A3) chlorinated rubber. It is preferable to include 50 parts by mass.

  Furthermore, the etching resist composition of the present invention preferably contains (D) an inorganic filler.

  The etching resist composition of the present invention is preferably used for glass etching.

  The etching resist composition of the present invention comprises (A1) asphalt, (A2) chlorinated polypropylene, and (A3) at least one of chlorinated rubber, (B) cyclized rubber, and (C) an organic solvent. Containing excellent adhesion to the substrate, long-term resistance to chemicals containing alkaline solutions containing strong bases such as hydrofluoric acid and sodium hydroxide, or etchants containing strong acids such as nitric acid, sulfuric acid and hydrochloric acid (chemical resistance) ).

  Hereinafter, embodiments of the present invention will be described in detail.

  The etching resist composition of the present invention (hereinafter also referred to as resist composition) is a composition for protecting a substrate from etching processing, and includes (A1) asphalt, (A2) chlorinated polypropylene, and (A3) chlorinated rubber. And (B) a cyclized rubber and (C) an organic solvent, and are dried by heat (thermal drying type) to form a resist.

  That is, the etching resist composition of the present invention is screen-printed in a predetermined pattern on a predetermined substrate (processing target), for example, glass such as soda glass (soda lime glass), crystal glass, borosilicate glass, etc. Is applied. Thereafter, the substrate coated with the etching resist on the pattern is heated for a predetermined time. Thus, the heat-dried etching resist becomes a protective film (resist) for the substrate during the etching process.

  The etching resist composition of the present invention has printability such as screen printing, has high adhesion to the substrate, and has excellent chemical resistance, so it is used under severe conditions required for drilling and counterboring. Also in the etching, the possibility that the etching solution permeates between the base material and the resist or into the resist is suppressed, and partial or total peeling of the resist from the base material hardly occurs.

  Thereby, since the etching process of the base material is performed with high accuracy and faithful to the resist pattern, the base material obtained using the etching resist of the present invention has extremely excellent resolution.

  Hereinafter, the components of the etching resist composition of the present invention will be described.

[At least one of (A1) asphalt, (A2) chlorinated polypropylene, and (A3) chlorinated rubber]
The etching resist composition of the present invention contains at least one of (A1) asphalt, (A2) chlorinated polypropylene, and (A3) chlorinated rubber. That is, as the component (A), one type of (A1) asphalt, (A2) chlorinated polypropylene, and (A3) chlorinated rubber can be used, or a mixture of two or more of these can be used.

  As (A1) asphalt used in the present invention, petroleum asphalt such as slate asphalt or blown asphalt, natural asphalt such as lake asphalt, rock asphalt, oil sand asphalt, and modified asphalt added such as polymer, emulsified or powdered. Any asphalt, i.e. any known asphalt, can be used.

  Among the above, blown asphalt and slate asphalt are preferable, and blown asphalt is particularly preferably used.

  Asphalt (A1) used in the present invention has a penetration (according to JIS K2207 (1996)) of 20 or less, preferably 10 or less, and a softening point (according to JIS K2207 (1996)) of 55 ° C. In addition, those having a temperature of 95 ° C or higher, particularly 110 ° C or higher are preferably used.

  (A1) When the penetration of asphalt is 20 or less, the resist coating obtained from the resist composition containing the asphalt does not become too soft, is formed as a resist having a predetermined hardness, and the resist is scratched. Such a problem that a defect such as the above occurs or an unnecessary portion is etched through a scratch on the resist is avoided.

  Further, when the softening point is 55 ° C. or higher, resist softening and damage by the etching solution can be avoided, and a resist having resistance to etching at high temperature can be formed.

  The blown asphalt is excellent in balance between penetration and softening point, and is particularly preferably used as the (A1) asphalt of the present invention.

  In the present invention, (A2) asphalt can be used singly or as a combination of a plurality of types, and by using a combination of two or more types of asphalt, as a mixture in which the penetration and softening point are adjusted, A1) It can also be asphalt.

  Since (A1) asphalt is generally solid at room temperature, it is preferable to use it by dissolving it in an organic solvent. Thereby, manufacture of a resist composition, application | coating with respect to a to-be-processed base material, and resist removal (peeling) can each be performed smoothly.

  The example of the organic solvent used for the dissolution of (A1) asphalt of the present invention is the same as the example of the organic solvent (C) described later, and two or more kinds of mixed solvents can be used.

  The solvent for dissolving asphalt and the organic solvent (C) may be the same or different as long as they do not adversely affect the resist composition.

[(A2) chlorinated polypropylene]
In the etching resist composition of the present invention, (A2) chlorinated polypropylene is used instead of (A1) or in addition to (A1) asphalt.

  In the present invention, as the chlorinated polypropylene (A2), any of chlorinated products of polypropylene (homopolymer) and chlorinated products of polypropylene and lower olefin can be used. Chlorides of (especially chain compounds) are preferably used.

  Various methods for producing chlorinated polypropylene have been proposed, but the chlorinated polypropylene used in the present invention may be obtained by any production method as long as it has desired characteristics. Good.

  For example, (A2) chlorinated polypropylene used in the present invention is a method of chlorinating in a solid phase, or dissolving polypropylene in a chlorinated solvent (for example, chloroform), an aqueous solvent (for example, water), or a mixture of both. It can be produced by a method of chlorination in a liquid phase such as a method of suspending and chlorinating.

  The weight average molecular weight of the (A2) chlorinated polypropylene used in the present invention is 10,000 to 120,000, preferably 30,000 to 80,000 by GPC analysis (polystyrene standard). (A2) If the weight average molecular weight of the chlorinated polypropylene is 10,000 or more, stickiness of the resist composition after drying is suppressed. Further, when the weight average molecular weight is 120,000 or less, the compatibility with the cyclized rubber contained in the resist composition is improved.

  Further, the chlorination rate of (A2) chlorinated polypropylene is preferably in the range of 30% by mass to 70% by mass with respect to the total mass of the chlorinated polypropylene. By using chlorinated polypropylene having a chlorination rate of 30% by mass or more, the chemical resistance of the resulting etching resist composition is particularly improved. On the other hand, when the chlorination rate is 70% by mass or less, the solubility of chlorinated polypropylene in the organic solvent (C) described later is good, and a homogeneous resist composition can be obtained.

  Furthermore, the softening point of (A2) chlorinated polypropylene used in the present invention is preferably in the range of 60 to 250 ° C, particularly 80 to 200 ° C. When (A2) chlorinated polypropylene having a softening point of 60 ° C. or higher is used, stickiness of the resist composition after drying is suppressed. When the softening point is 250 ° C. or less, the compatibility with the cyclized rubber becomes good.

  As specific examples of (A2) chlorinated polypropylene, Super Clone 814HS, Super Clone 390S, Super Clone HP-215 (all manufactured by Nippon Paper Industries Co., Ltd.), HARDREN 526P, HARDREN 523P (all manufactured by Toyobo Co., Ltd.) are listed. be able to.

[(A3) Chlorinated rubber]
Chlorinated rubber is a resin obtained by chlorinating natural rubber and synthetic rubber (polyisoprene). It is chemically stable, resistant to acids and alkalis, and has excellent weather resistance. Aromatic solvents such as toluene, esters and ketones Easily soluble in organic solvents. For this reason, it is used in paints, inks and adhesives, especially in heavy anticorrosion paints, and has been industrially manufactured for a long time.

  In order to manufacture chlorinated rubber industrially, raw materials such as natural rubber and synthetic rubber are dissolved in carbon tetrachloride, which is a chlorine-based inert solvent, and this solution is chlorinated through chlorine gas. Although the method “method” is known, the chlorinated rubber used in the present invention is not limited to the present production method as long as desired characteristics are obtained.

  The weight average molecular weight of the (A3) chlorinated rubber used in the present invention is 10,000 to 120,000, preferably 30,000 to 80,000 by GPC analysis (polystyrene standard). (A3) When the weight average molecular weight of the chlorinated rubber is 10,000 or more, stickiness of the resist composition after drying is suppressed. Further, when the weight average molecular weight is 120,000 or less, the compatibility with the cyclized rubber contained in the resist composition is improved.

The chlorination rate of the (A3) chlorinated rubber used in the present invention is preferably in the range of 30% by mass to 80% by mass with respect to the total mass of the chlorinated rubber. By using a chlorinated rubber having a chlorination rate of 30% by mass or more, the chemical resistance of the resulting etching resist composition is particularly improved. On the other hand, when the chlorination rate is 80% by mass or less, the solubility of (A3) chlorinated rubber in (C) organic solvent described later is good, and a homogeneous resist composition is obtained.
Furthermore, the softening point of the (A3) chlorinated rubber used in the present invention is preferably in the range of 50 to 250 ° C, particularly 60 to 150 ° C. When (A3) chlorinated rubber having a softening point of 60 ° C. or higher is used, stickiness of the resist composition after drying is suppressed. When the softening point is 250 ° C. or less, the compatibility with the cyclized rubber becomes good.

  (A3) Specific examples of the chlorinated rubber include YURON CR-10 and CR-20 (both manufactured by FENHUA YURON CHEMICAL INDUSTRY).

  (A1) Similarly to asphalt, (A2) chlorinated polypropylene and (A3) chlorinated rubber can be used as a single kind or a combination of plural kinds, respectively.

[(B) cyclized rubber]
The etching resist composition of the present invention contains (B) a cyclized rubber.
(B) The cyclized rubber is not particularly limited as long as it is a cyclized product of a conjugated diene rubber or a derivative thereof. (B) The conjugated diene rubber used as a raw material for the cyclized rubber may be a polymer of only a conjugated diene monomer or a copolymer rubber of a conjugated diene monomer and another monomer. . The copolymer rubber may be either a random copolymer rubber or a block copolymer rubber.

  Examples of the conjugated diene monomer constituting the copolymer rubber include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1, Examples include 3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene.

Examples of the above-mentioned “other monomers” include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, 2-methyl-1,4-dichlorostyrene, 2,4- Aromatic vinyl monomers such as dibromostyrene and vinylnaphthalene;
Chain olefin monomers such as ethylene, propylene, 1-butene;
Cyclic olefin monomers such as cyclopentene and 2-norbornene;
Non-conjugated diene monomers such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene;
(Meth) acrylic acid esters such as methyl (meth) acrylate and ethyl (meth) acrylate;
(Meth) acrylonitrile, (meth) acrylamide, etc. are mentioned. The conjugated diene monomer and other monomers may be used alone or in combination of two or more.

  By treating natural rubber or synthetic rubber with an acid, a part of chain molecules in the rubber molecule is cyclized. Various production methods have been proposed, but the (B) cyclized rubber in the present invention is not limited to any one of them.

  Specifically, it is obtained by acid treatment of natural rubber or synthetic rubber. For example, organic sulfonic acids such as concentrated sulfuric acid and p-toluenesulfonic acid, chlorosulfonic acid, etc., or Lewis acid such as TiCl4 is directly used. It is produced by a method in which a double bond is reduced by cyclizing a part of chain molecules in a rubber molecule by acting on a rubber component such as natural rubber or synthetic rubber, or by acting on a rubber solution.

  The molecular weight of the (B) cyclized rubber used is a weight average molecular weight of 5,000 to 50,000, preferably 10,000 to 30,000 by GPC analysis (polystyrene standard).

  By using the (B) cyclized rubber having a weight average molecular weight of 5000, chemical resistance of the etching composition is improved. By using (B) cyclized rubber having a weight average molecular weight of 50000 or less, any of (B) cyclized rubber, (A1) asphalt, (A2) chlorinated polypropylene, and (A3) chlorinated rubber (( Compatibility with all of A1) to (A3) used is considered good.

  The cyclized rubber used in the present invention has a softening point of 60 to 200 ° C, preferably 100 to 150 ° C. (B) When the cyclized rubber has a softening point of 60 ° C. or higher, the dryness to the touch becomes good and the working efficiency is improved. Further, when the softening point of (B) the cyclized rubber is 150 ° C. or lower, the compatibility with (A1) asphalt becomes good, which contributes to the homogenization of the resist composition.

  Specific examples of the cyclized rubber include Alpex CK-514, Alpex CK-450, etc. (all manufactured by Nippon Cytex Industries, Ltd.).

  (B) The compounding quantity of cyclized rubber is 3-60 mass parts with respect to 100 mass parts of the sum total of (A1) asphalt, (A2) chlorinated polypropylene, and / or (A3) chlorinated rubber, Preferably it is 15- 50 parts by mass, particularly preferably 20 to 40 parts by mass. (B) When the compounding amount of the cyclized rubber is 3 parts by mass or more, the adhesiveness of the etching composition to the substrate becomes sufficient, and when it is 15 parts by mass or more, for example, the composition is homogenized. In addition, the printability of the resist composition on the substrate is improved. In addition, when the ratio of (B) cyclized rubber is 60 parts by mass or less, particularly 40% or less, (A1) good compatibility with asphalt, and leveling and defoaming properties of the printed coating film are also good. can get.

  The mass ratio of (A1) asphalt to (A2) chlorinated polypropylene or (A3) chlorinated rubber is (65:35) to (55:45), and (B) cyclized rubber having the above blending amount is used. Thus, the etching resistance of the resist can be improved.

[(C) Organic solvent]
The organic solvent (C) used in the present invention is not particularly limited as long as it can dissolve asphalt and other components. Examples thereof include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

  Petroleum solvents such as solvent naphtha, aromatic hydrocarbon solvents, or mixed solvents thereof can be suitably used. By using these, (A1) good asphalt solubility can be obtained.

  In the present invention, it is particularly preferable to use an aromatic solvent, and more preferably an aromatic solvent having a boiling point of 150 ° C. or higher.

  As an aromatic solvent having a boiling point of 150 ° C. or higher, Swazol (registered trademark) 1000, 1500, 1800 (manufactured by Maruzen Petrochemical Co., Ltd.), T-Sol (registered trademark) 100, 150, 200 (manufactured by ExxonMobil) Cactus Fine SF01, SF-02 (manufactured by JXTG Energy Co., Ltd.) and the like. When an aromatic solvent having a boiling point of 150 ° C. or higher is used, a printed matter having particularly good resin solubility and printability and excellent surface condition can be obtained. In addition, since the flash point is high, there is an advantage of high safety in handling.

  In the present invention, an aromatic solvent having a boiling point of 150 ° C. or higher is used alone, or a solvent mixture containing an aromatic solvent having a boiling point of 150 ° C. or higher, that is, highly compatible with the aromatic solvent. Highly soluble (A1) asphalt, (A2) chlorinated polypropylene, and (B) cyclized rubber can be used in combination, such as those containing solvents (for example, ketone solvents such as methyl isobutyl ketone and cyclohexanone).

  (C) The organic solvent can be used alone or as a mixture of two or more. In addition, the amount of (C) the organic solvent can be set to an arbitrary amount depending on the purpose, but 20% by mass to 80% by mass, particularly 30% to 50% in the resist composition of the present invention. Is preferred.

[Other ingredients]
In addition to the resist composition of the present invention, an inorganic filler, a thickener, a fluidity modifier, a surface tension modifier, an adhesion promoter or a coupling agent, a surfactant, a colorant, Silicone-based, fluorine-based, polymer-based antifoaming and leveling agents, matting agents, polyester resins for adjusting film properties, vinyl resins, acrylic resins, rubber resins, and waxes Can be further blended. The said component is used by adjusting the amount of use suitably in the range from which the desired effect by addition is acquired, without impairing the performance of each component (A)-(C).

  As specific examples of the filler, inorganic fillers such as barium sulfate, barium titanate, talc, clay, aluminum oxide, aluminum hydroxide, silicon nitride, and aluminum nitride can be used. Preferably, barium sulfate or talc is used. It is used alone or in combination of two or more. These inorganic fillers play a role of appropriately adjusting the viscosity at the time of adjusting the resist composition, suppressing curing shrinkage during heat drying, and improving the adhesion to the substrate. Of these, barium sulfate is particularly preferably used in order to improve the adhesion to the substrate.

  The average primary particle size of the inorganic filler is preferably 15 μm or less, more preferably 10 μm or less. The average primary particle size (D50) can be measured by a laser diffraction / scattering method.

  Although the compounding quantity of a filler is not specifically limited, It is preferable to use in the ratio of 8 mass%-100 mass% with respect to the etching resist composition whole quantity (a solvent is included), especially 20-60 mass%. If the content is 8% by mass, particularly 20% by mass or more, the thixotropy of the composition is increased, and the printing accuracy is improved.

  Examples of usable antifoaming agents include silicone antifoaming agents, fluorine antifoaming agents, and acrylic antifoaming agents. Examples of silicone-based antifoaming agents include BYK (registered trademark) -063, -065, -066N, -081, -141, and -323 manufactured by Big Chemie Japan, and KS-66 and KS manufactured by Shin-Etsu Chemical Co., Ltd. -69, X-50-1105G, etc., as fluoric defoamers, MegaFac RS, F-554, F-557, etc. manufactured by DIC Corporation, and acrylic defoamers, Disparon OX, manufactured by Enomoto Kasei Co., Ltd. -880EF, OX-70 and the like.

In addition, as colorants, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black,
As the thickener, a known and commonly used thickener containing bentonite and fine silica,
Examples of the silane coupling agent include halogen-containing silane coupling agents such as γ-chloropropylmethoxysilane, vinyl ethoxysilane, vinylmethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltrichlorosilane, and other vinyl. Group-containing silane coupling agent, (meth) acryloyl-containing silane coupling agent such as (meth) acryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β -Glycidyl group-containing silane coupling agents such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mercapto-containing silane coupling agents such as γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxy Examples include amino group-containing silane coupling agents such as silane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane.

  Silane coupling that can prevent deterioration of surface smoothness and interlayer insulation due to voids and pinholes, especially by adding an antifoaming agent and / or leveling agent among the above additives. By blending the agent, the adhesion to the substrate surface can be improved.

  The viscosity at 25 ° C. of the resist composition of the present invention is preferably in the range of 1 to 1500 dPa · s, particularly in the range of 10 to 1000 dPa · s. When the viscosity of the etching resist composition is 1 dPa · s or more, the resist composition becomes a coating film with a film thickness capable of satisfactorily protecting the substrate as an etching resist by heat drying. On the other hand, when the viscosity of the etching resist composition is 1500 dPa · s or less, the composition is easy to handle and suitable for printing by screen printing or the like, and the resist stripping treatment after etching is performed easily and economically.

  In addition, although the etching resist composition of this invention is mainly used suitably for a heat-drying type | mold, it may contain a thermosetting material, for example, an epoxy compound, a hardening | curing agent, etc. as needed.

  Moreover, in the manufacturing method of the board | substrate using the etching resist composition of this invention, after adjusting the above-mentioned etching resist composition as a uniform solution or dispersion liquid, it is 5 by screen printing etc. with respect to board | substrates, such as a glass substrate. The film is printed in a desired pattern with a film thickness of ˜100 μm, preferably 30 to 90 μm, more preferably 45 to 85 μm. Further, the patterned etching resist composition is dried by evaporating the organic solvent by heating in a drying furnace or the like, for example, at 50 to 200 ° C., preferably 80 to 150 ° C. for 5 to 90 minutes, preferably 20 to 60 minutes. And a dry coating film can be formed. The film thickness of the dried coating film is preferably in the range of 3 to 70 μm, particularly 30 to 60 μm, depending on the properties of the etching solution. An etching resist having a film thickness in this range is effective from the viewpoint of protecting the substrate in the etching process because it has sufficient resistance to the etching solution. However, the resist composition of the present invention may have a film thickness exceeding 70 μm as long as the drying temperature and the drying time are satisfied. The film thickness is obtained by general printing conditions.

  Here, the resist composition of the present invention can be applied not only to a screen printing method but also to a printing method such as a gravure method or a gravure offset method. The resist composition can also be applied in a plurality of times. As a coating method at that time, conventionally known wet-on-wet printing such as 2-coat 1-bake or dry-on-wet printing such as 2-coat 2-bake is possible.

  Thereafter, the substrate coated with the resist dried in a desired pattern is subjected to an etching process with an etching solution. By the etching process, the portion of the substrate not covered with the resist is etched. Thereby, a glass molded product having a predetermined pattern can be obtained.

  As the etchant, either hydrofluoric acid alone or an etchant containing hydrofluoric acid (for example, a mixture of hydrofluoric acid and mineral acid (nitric acid, phosphoric acid, etc.), or a weak acid such as acetic acid in some cases 1 type or more).

  Since the resist obtained from the resist composition of the present invention has excellent resistance to the etching solution after the above-mentioned heat drying, the substrate is etched with high accuracy without peeling from the substrate during the etching process. Can be processed.

  If the etching resist composition of the present invention is thermally dried by heating, it forms a resist that adheres well to the substrate without photocuring or thermosetting, and protects the substrate from the etching solution. Furthermore, highly accurate etching is possible, and after completion of etching, it can be easily removed in a short time using a solvent such as ketones, esters, aromatic hydrocarbons or petroleum solvents. For removing the etching resist, it is particularly preferable to use a petroleum solvent from the viewpoints of solubility and economy.

  The etching resist composition of the present invention is very useful not only in etching with hydrofluoric acid etching solution but also in etching with various etching solutions of strong acid, weak acid, strong alkali, weak alkali, and corrosive substances. Excellent resistance and excellent adhesion to the substrate.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited only to these Examples. In the following description, “part” means part by mass unless otherwise specified.

[Examples 1 to 11 and Comparative Examples 1 to 4]
I. Preparation of Etching Resist Composition Ingredients shown in Table 1 were blended in the stated ratios (unit: part), premixed with a stirrer, dispersed and kneaded with a three-roll mill, and Examples 1 to 11 ( The etching resist compositions of the composition of the present invention and Comparative Examples 1 to 4 (Comparative composition) were obtained.

II. Etching resist production [Production conditions 1]
Etching resist is printed on a 1.8mm thick soda lime glass plate (substrate) as follows using a screen printing plate prepared by applying a predetermined photosensitive emulsion to an 80 mesh polyester plate at a film thickness of 80μm. did.

  The soda lime glass is washed with alcohol in advance, and the surface is dried. Then, each of the resist compositions of Examples 1 to 11 and Comparative Examples 1 to 4 is formed into a pattern having a side of 20 mm by the above screen printing plate. Printed as a 5 mm wide square.

  The printed resist composition is heated for 30 minutes at a drying temperature of 120 ° C. with a hot air circulation dryer (DF-610, manufactured by Yamato Kagaku Co., Ltd.) to evaporate and dry the solvent. A test piece of production condition 1) was obtained.

[Production conditions 2]
The same printing and drying based on the manufacturing condition 1 were performed again on the etching resist printed and dried on the same condition as the manufacturing condition 1. The dry thickness of the obtained etching resist (test piece of production condition 2) was 80 μm.

III. Etch resistance test The test piece (film thickness 50 μm) of production condition 1 and the test piece of production condition 2 (film thickness 80 μm) were subjected to an immersion treatment under the following etching conditions 1 to 6.

Etching conditions
Condition 1: 10% hydrofluoric acid, liquid temperature 30 ° C., immersion time 60 minutes Condition 2: 10% hydrofluoric acid, liquid temperature 30 ° C., immersion time 90 minutes Condition 3: 10% hydrofluoric acid, liquid temperature 30 ° C., immersion time 120 minutes Condition 4: 15% hydrofluoric acid, liquid temperature 30 ° C., immersion time 60 minutes Condition 5: 15% hydrofluoric acid, liquid temperature 30 ° C., immersion time 90 minutes Condition 6: 15% Hydrofluoric acid, liquid temperature 30 ° C, immersion time 120 minutes

  After the immersion time, the test piece was taken out from the etching solution, washed with water, dried, and visually evaluated.

  The evaluation criteria are as follows.

○: No appearance abnormality (no peeling at all)
Δ: At least part of the etching solution permeates into the coating film ×: Defilming

  The evaluation results are shown in Table 1.

  The details of the materials in the table are as follows.

KB-2: Asphalt pitch, manufactured by Kuju Electric Co., Ltd. (blown asphalt type: penetration 6-10, softening point 110 ° C.)
Super Clone HP-215: Chlorinated polypropylene, manufactured by Nippon Paper Industries Co., Ltd. (weight average molecular weight about 80,000, chlorination rate 68%, softening point 200 ° C.)
Super Clone 814HS: Chlorinated polypropylene, manufactured by Nippon Paper Industries Co., Ltd. (weight average molecular weight approximately 40,000, chlorination rate 41%, softening point 80 ° C.)
YURON CR-20 Chlorinated rubber (FENGHUA YURON CHEMICAL INDUSTRY) (chlorination rate 68%, softening point 200 ° C)
ALPEX (registered trademark) CK-450: cyclized rubber (weight average molecular weight of about 23,000, softening point of about 130 ° C.)
IPZOL 150: aromatic hydrocarbon (carbon number 10) mixed solvent, manufactured by Idemitsu Kosan Co., Ltd. KS66: dimethylpolysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd. MA-100: carbon black, manufactured by Mitsubishi Chemical Corporation,
Orben M: bentonite, manufactured by Shiraishi Kogyo Co., Ltd. KBM-403: silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd., precipitated barium sulfate 110: barium sulfate, manufactured by Sakai Chemical Industry Co., Ltd.

  From the results of the examples, the etching resist resist composition of the present invention comprises (A1) at least one of asphalt (A2) chlorinated polypropylene and (A3) chlorinated rubber, (B) cyclized rubber, (C) By using in combination with an organic solvent, it exhibits excellent resistance to etching for a long time exceeding 60 minutes in an etching solution with hydrofluoric acid, and forms a relatively deep opening or through hole in the substrate. It turns out that it is used suitably for such an etching process.

  The present invention is not limited to the configurations and examples of the above-described embodiment, and various modifications are possible within the scope of the gist of the invention.

  For example, in the above-described embodiments, etching of a glass substrate has been mainly described. However, the resist composition of the present invention can also be used for etching of a plastic substrate including a metal substrate and synthetic rubber.

  As described above, the etching resist composition of the present invention is excellent in glass etching resistance, storage stability, and resist removability, and is applied to etching of glass casings (substrates) such as touch panels, optical materials, and measuring instruments. .

  According to the resist composition of the present invention and a production method using the same, by applying to a glass substrate by screen printing, drawing a circuit / wiring diagram, forming a through hole, a concave hole, etc. without obtaining complicated processing steps Therefore, it is effective in terms of both operation and economy.

  In addition, because of the high adhesion to the base material of the resist composition of the present invention, highly accurate etching is performed according to the desired resist pattern drawn on the base material. It is also useful for application.

Claims (4)

At least one of (A1) asphalt, (A2) chlorinated polypropylene and (A3) chlorinated rubber;
(B) a cyclized rubber;
(C) an organic solvent;
An etching resist composition comprising:   The (B) cyclized rubber contains 15 to 50 parts by mass with respect to 100 parts by mass of the total amount of at least one of the (A1) asphalt, (A2) chlorinated polypropylene, and (A3) chlorinated rubber, The etch resist composition according to claim 1.   Furthermore, (D) an inorganic filler is included, The etching resist composition of Claim 1 or 2 characterized by the above-mentioned.   The etching resist composition according to claim 1, wherein the etching resist composition is used for etching glass.