CN113227010A - Hydrofluoric acid-resistant resist composition and substrate processed product obtained using same - Google Patents

Hydrofluoric acid-resistant resist composition and substrate processed product obtained using same Download PDF

Info

Publication number
CN113227010A
CN113227010A CN201980083175.4A CN201980083175A CN113227010A CN 113227010 A CN113227010 A CN 113227010A CN 201980083175 A CN201980083175 A CN 201980083175A CN 113227010 A CN113227010 A CN 113227010A
Authority
CN
China
Prior art keywords
resist composition
hydrofluoric acid
meth
carboxyl group
etching
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201980083175.4A
Other languages
Chinese (zh)
Inventor
高桥元范
西尾一则
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiyo Holdings Co Ltd
Original Assignee
Taiyo Ink Mfg Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyo Ink Mfg Co Ltd filed Critical Taiyo Ink Mfg Co Ltd
Publication of CN113227010A publication Critical patent/CN113227010A/en
Pending legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/06—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/0275—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with dithiol or polysulfide compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials For Photolithography (AREA)

Abstract

Providing: a resist composition having excellent adhesion, hydrofluoric acid resistance and stripping properties, and a substrate processed product using the same. A hydrofluoric acid-resistant resist composition and a substrate processed article obtained by etching using the same are obtained, the hydrofluoric acid-resistant resist composition being characterized by comprising: (A) a carboxyl group-containing resin, (B) a polyfunctional (meth) acrylate monomer, (C) a polyfunctional thiol compound, (D) a photopolymerization initiator, and (E) 20 to 100 parts by mass of talc per 100 parts by mass of the carboxyl group-containing resin (A).

Description

Hydrofluoric acid-resistant resist composition and substrate processed product obtained using same
Technical Field
The present invention relates to a resist composition having excellent resistance to hydrofluoric acid.
Background
A glass substrate is generally used for a touch panel type input device (hereinafter, also simply referred to as "touch panel"), an optical material, a measuring instrument, and the like used in operation sections of various electronic devices, such as a mobile phone, a portable information terminal, and a car navigation system. Such a glass substrate has been conventionally manufactured by cutting out the glass substrate by machining or laser cutting.
However, if the cutting and punching are performed by a mechanical processing or a laser cutting technique, burrs and cracks may be generated on the glass end surface and the hole, particularly in the cutting and punching of the tempered glass. Further, with the reduction in thickness and size of touch panels and the like, etching processing capable of fine processing has been increasingly demanded.
As a resist composition capable of etching glass, a large number of resist compositions have been proposed so far, and as an example thereof, a resist composition containing a silane coupling agent has been proposed in order to improve adhesion to a glass substrate (see patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2007-128052
Disclosure of Invention
Problems to be solved by the invention
However, the resist composition of patent document 1 is still insufficient in adhesion to a glass substrate, and is not completely satisfactory in hydrofluoric acid resistance and peeling resistance.
In recent years, hydrofluoric acid has been used for processing silicon wafers as substrates other than glass, substrates containing titanium, metal oxides, and the like, but there has been no report on a resist composition having excellent adhesion to these substrates, hydrofluoric acid resistance, and releasability.
Accordingly, an object of the present invention is to provide: the resist composition has excellent adhesion to substrates such as glass, silicon wafers, titanium, and metal oxides, sufficient resistance to an etching solution containing hydrofluoric acid, and improved stripping properties after etching.
Further, an object of the present invention is to obtain a processed substrate product obtained by etching a substrate using the resist composition.
Means for solving the problems
As a result of intensive studies, the present inventors have found that the above object of the present invention is achieved by a hydrofluoric acid resistant resist composition comprising:
(A) a carboxyl group-containing resin,
(B) A polyfunctional (meth) acrylate monomer,
(C) A polyfunctional thiol compound,
(D) A photopolymerization initiator, and
(E) 20 to 100 parts by mass of talc per 100 parts by mass of the carboxyl group-containing resin (A).
The hydrofluoric acid resistant resist composition of the present invention is preferably that the (C) polyfunctional thiol compound is a compound containing 2 to 6 mercapto groups per molecule.
In addition, the hydrofluoric acid resistant resist composition of the present invention preferably contains a compound having a thermosetting group as the (a) carboxyl group-containing resin.
Further, the hydrofluoric acid resistant resist composition of the present invention preferably contains a half ester of a polybasic acid anhydride and a hydroxyalkyl (meth) acrylate monomer as the carboxyl group-containing resin (a).
In addition, the hydrofluoric acid resistant resist composition of the present invention preferably does not contain a silane coupling agent.
Further, the above object is achieved by a substrate processed article obtained by etching using the hydrofluoric acid resistant resist composition of the present invention.
ADVANTAGEOUS EFFECTS OF INVENTION
The hydrofluoric acid resistant resist composition of the present invention comprises:
(A) a carboxyl group-containing resin,
(B) A polyfunctional (meth) acrylate monomer,
(C) A polyfunctional thiol compound,
(D) A photopolymerization initiator, and
(E) the talc is 20 to 100 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin (a), and thus has excellent adhesion to a glass substrate, a silicon wafer as a base material other than glass, a base material containing titanium, a metal oxide, or the like, sufficient resistance to an etching solution containing hydrofluoric acid, improved peelability after etching, and excellent resolution.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
The hydrofluoric acid resistant resist composition (hereinafter, also referred to as a resist composition) of the present invention is a composition for protecting a substrate from etching processing, and contains: (A) a carboxyl group-containing resin, (B) a polyfunctional (meth) acrylate monomer, (C) a polyfunctional thiol compound, (D) a photopolymerization initiator, and (E) 20 to 100 parts by mass of talc per 100 parts by mass of the carboxyl group-containing resin (A). When the resist composition of the present invention is used as an alkali-developable resist composition, a resist is formed by the following steps: a coating step of coating the composition on a glass substrate to form a coating film, an exposure step of selectively exposing the obtained coating film to active energy rays through a photomask having a desired pattern to cure the coating film, and a development step of developing the unexposed portion with a dilute aqueous alkali solution (for example, a 0.3 to 3 mass% aqueous sodium carbonate solution) to form a pattern of a cured product. When the resist composition of the present invention is used as an ultraviolet-curable resist composition, the resist composition of the present invention is printed on a glass substrate in a desired pattern by screen printing or the like, and cured by irradiation with UV light (ultraviolet rays), thereby forming a resist layer.
That is, the hydrofluoric acid resistant resist composition of the present invention is formed in a predetermined pattern on a predetermined substrate (processing target), for example, particularly, on glass such as soda glass (soda lime glass), glass ceramics, or borosilicate glass. The resist layer formed in the predetermined pattern serves as a protective film (resist) of the substrate during etching.
The hydrofluoric acid resistant resist composition of the present invention has high adhesion to a substrate and excellent chemical resistance, and therefore has sufficient resistance to an etching solution containing a strong acid such as hydrofluoric acid, nitric acid, sulfuric acid, or hydrochloric acid, and thus maintains adhesion even in an etching step. In the present invention, since the etching of the substrate is performed with high accuracy in accordance with the pattern of the resist, the substrate obtained using the hydrofluoric acid resistant resist composition of the present invention is also excellent in resolution. Therefore, the glass substrate is etched with high accuracy, and the possibility of generation of burrs and cracks is suppressed to be extremely low. Further, the stripping property when the hydrofluoric acid resistant resist composition is stripped from the substrate after completion of etching is also extremely good.
The components of the hydrofluoric acid resistant resist composition of the present invention will be described below.
[ (A) carboxyl group-containing resin ]
As the (a) carboxyl group-containing resin contained in the hydrofluoric acid resistant resist composition of the present invention, a resin having a carboxyl group, specifically, a carboxyl group-containing photosensitive resin itself having an ethylenically unsaturated double bond and a carboxyl group-containing resin not having an ethylenically unsaturated double bond may be used. Among them, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is particularly preferable as a photosensitive composition to be subjected to alkali development from the viewpoint of etching resistance, sensitivity, and resolution. Furthermore, the unsaturated double bond is preferably derived from acrylic acid or methacrylic acid, or derivatives thereof.
Specific examples of the carboxyl group-containing resin (a) include the following compounds (both oligomers and polymers).
(1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α -methylstyrene, a lower alkyl (meth) acrylate, or isobutylene.
(2) A carboxyl group-containing polyurethane resin obtained by addition polymerization of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate, a carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutyric acid, a diol compound such as a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol a-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, or a compound having 1 alcoholic hydroxyl group as required.
(3) The carboxyl group-containing photosensitive polyurethane resin is obtained by addition polymerization of a diisocyanate, a (meth) acrylate ester or a partial acid anhydride modified product thereof with a 2-functional epoxy resin such as a bisphenol a epoxy resin, a hydrogenated bisphenol a epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a biphenol epoxy resin, or the like, a carboxyl group-containing diol compound, and a diol compound.
(4) The carboxyl group-containing photosensitive polyurethane resin having a terminal (meth) acryloyl group by adding a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule, such as hydroxyalkyl (meth) acrylate, to the synthesis of the resin of (2) or (3).
(5) The carboxyl group-containing photosensitive polyurethane resin having a terminal (meth) acrylated by adding a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, to the synthesis of the resin of (2) or (3).
(6) A carboxyl group-containing photosensitive resin obtained by reacting a 2-functional or higher polyfunctional epoxy resin with (meth) acrylic acid to add a dibasic acid anhydride to a hydroxyl group present in a side chain. Here, the epoxy resin is preferably solid.
(7) A carboxyl group-containing photosensitive resin is obtained by reacting a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a 2-functional epoxy resin with epichlorohydrin with (meth) acrylic acid and adding a dibasic acid anhydride to the resulting hydroxyl group.
(8) A carboxyl group-containing polyester resin obtained by reacting a 2-functional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid to add a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to the primary hydroxyl group formed.
(9) A carboxyl group-containing photosensitive resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule, such as bisphenol a, bisphenol F, bisphenol S, novolak-type phenol resins, polyparahydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the obtained reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the obtained reaction product with a polybasic acid anhydride.
(10) A carboxyl group-containing photosensitive resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate to obtain a reaction product, reacting the obtained reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the obtained reaction product with a polybasic acid anhydride.
(11) A carboxyl group-containing photosensitive resin obtained by reacting an epoxy compound having a plurality of epoxy groups in 1 molecule, a compound having at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in 1 molecule such as p-hydroxyphenylethanol, and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting the alcoholic hydroxyl group of the obtained reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic anhydride.
(12) A carboxyl group-containing photosensitive resin obtained by further adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in 1 molecule, such as glycidyl (meth) acrylate or α -methylglycidyl (meth) acrylate, to the resins (1) to (11).
Among the carboxyl group-containing resins (a) exemplified in the above (1) to (12), the above (7) is particularly preferable, and when a bisphenol structure (bisphenol a, bisphenol F, etc.) is further contained, the use is particularly preferable.
When the resist composition of the present invention is used to etch a substrate, various etching solutions can be used as described later, but when hydrofluoric acid is used as the etching solution, it is preferable to use (a) a carboxyl group-containing resin other than the above-described (2) to (5).
In the hydrofluoric acid resistant resist composition of the present invention, (a) the carboxyl group-containing resin functions to improve the developability, sensitivity, and resolution. In addition, since the carboxyl group-containing resin (a) has a large number of carboxyl groups in the main chain/side chain of the polymer, development with an alkaline aqueous solution can be achieved by using the same.
The acid value of the carboxyl group-containing resin (A) is preferably in the range of 20 to 200mgKOH/g, more preferably 40 to 150 mgKOH/g. When the acid value of the carboxyl group-containing resin is 20mgKOH/g or more, the adhesion of the coating film becomes good, and the alkali developability becomes good. On the other hand, when the acid value is 200mgKOH/g or less, the dissolution of the exposed portion by the developer can be favorably suppressed, and therefore, the line becomes thinner than necessary, or, in some cases, the exposed portion and the unexposed portion are suppressed from being dissolved and peeled in the developer without distinction, and a patterned resist can be favorably drawn.
The weight average molecular weight of the carboxyl group-containing resin (a) varies depending on the resin skeleton, and is preferably in the range of 2000 to 150000, and more preferably 5000 to 100000. When the weight average molecular weight is 2000 or more, the non-sticking property is good, the moisture resistance of the coating film after exposure is good, and the film loss at the time of development can be suppressed, and the decrease in resolution can be suppressed. On the other hand, when the weight average molecular weight is 150000 or less, the developability is good and the storage stability is excellent.
(A) The carboxyl group-containing resin may be used alone in 1 kind, or in combination of 2 or more kinds. When the etching resist composition of the present invention contains 2 or more kinds of carboxyl group-containing resins, for example, 1 or more kinds of the above carboxyl group-containing photosensitive resins are preferably contained.
When the carboxyl group-containing resin (a) of the present invention contains a thermosetting group (epoxy group, amino group, or the like), the etching resistance of the resist composition for etching is improved, which is preferable. In this case, if a silane coupling agent is added, there may be a problem such as deterioration of developability and deterioration of releasability (that is, development and releasability become slow and separation becomes impossible). Therefore, in the case where the (a) carboxyl group-containing resin contains a thermosetting group, it is preferable not to contain a silane coupling agent.
(A) The amount of the carboxyl group-containing resin is in the range of 35 to 65 mass%, preferably 40 to 60 mass%, based on the total mass of the resist composition. (A) When the amount of the carboxyl group-containing resin is in the above-mentioned ratio in the resist composition, the adhesion to a substrate such as glass is favorably obtained, and the resolution of glass etching becomes favorable. Further, when the amount of the carboxyl group-containing resin (a) is less than the above range, the resist strength obtained by drying the resist composition cannot be sufficiently obtained, and when the amount exceeds the above range, the viscosity of the composition increases, and the coatability and film-forming properties may decrease.
(half ester of polybasic acid anhydride and hydroxyalkyl (meth) acrylate monomer)
When the hydrofluoric acid resistant resist composition of the present invention is used as an ultraviolet-curable resist composition, the carboxyl group-containing resin (a) preferably contains a half ester (hereinafter, also simply referred to as a half ester) of a polybasic acid anhydride and a hydroxyalkyl (meth) acrylate monomer. The half ester is excellent in adhesion to most substrates such as glass and metal, and is also easy to dissolve in an aqueous alkali solution.
As the half ester of the polybasic acid anhydride and the hydroxyalkyl (meth) acrylate monomer, a conventionally known one which can be used in a resist composition can be used. The half ester is typically synthesized by using 1 mole of the (meth) acrylate monomer per 1 mole of the polybasic acid anhydride, and the (meth) acrylate monomer may be used in an excess amount. Examples of the polybasic acid anhydride include: phthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, maleic anhydride, succinic anhydride, dodecylsuccinic anhydride, humic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Examples of the hydroxyalkyl (meth) acrylate monomer include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1, 4-butanediol mono (meth) acrylate, 1, 6-hexanediol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, and the like. The half ester can be used alone in 1 kind, also can be combined with 2 or more kinds and use.
The half ester may be a half ester having a structure obtained by a general esterification reaction of a polybasic acid anhydride and a hydroxyalkyl (meth) acrylate monomer, and may be, for example, a half ester obtained by using a polybasic acid instead of a polybasic acid anhydride.
When the half ester is used as the carboxyl group-containing resin (A), the viscosity thereof is in the range of 2000 to 10000 mPas, preferably 3000 to 7000 mPas, at 25 ℃.
The amount of the half-ester is 10 to 60 mass%, more preferably 15 to 50 mass% based on the total mass of the hydrofluoric acid resistant resist composition of the present invention. When the amount is 10% by mass or more, the curability is good, and the penetration of the plating solution into the coating film is suppressed. When the amount is 60% by mass or less, the solubility at the time of peeling is more excellent, or the stickiness of the cured coating film is suppressed, and the workability is good. When the half ester is used in combination with another carboxyl group-containing resin, the ratio of the half ester: the other carboxyl group-containing resins were 9: 1-1: 9. preferably, 7: 3-3: and 7, the smoothness of the coating film is improved by using the components in combination.
[ (B) polyfunctional (meth) acrylate monomer ]
The resist composition of the present invention comprises: (B) a polyfunctional (meth) acrylate (a (meth) acrylate monomer having 2 or more (meth) acryloyl groups). In the present specification and claims, "(meth) acrylate" means a term collectively referring to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions. The polyfunctional (meth) acrylate compound is photo-cured by irradiation with active energy rays, particularly ultraviolet rays, to insolubilize the resin component in an aqueous alkali solution or to contribute to insolubilization. As such a compound, commonly known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and the like can be used. The reason why the multifunctional (meth) acrylate monomer is used is that photoreactivity is improved and resolution is excellent, compared to the case where the number of (meth) acryloyl functional groups is 1.
Examples of the polyfunctional (meth) acrylate monomer include commonly known polyester (meth) acrylates, polyether (meth) acrylates, urethane (meth) acrylates, carbonate (meth) acrylates, epoxy (meth) acrylates, and the like. Specifically, it is possible to use: diacrylates of glycols such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, and propylene glycol; polyhydric alcohols such as pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and trishydroxyethyl isocyanurate, and polyvalent acrylates such as ethylene oxide adducts, propylene oxide adducts, and epsilon-caprolactone adducts thereof; polyhydric acrylates such as bisphenol a diacrylate and ethylene oxide adducts and propylene oxide adducts of phenols thereof; polyacrylates of glycidyl ethers such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and diglycidyl isocyanurate; acrylic esters and melamine acrylates obtained by direct acrylation of polyols such as polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, and polyester polyol, or urethane acrylation with the aid of diisocyanate, and 1 or more of the respective methacrylic esters corresponding to the above acrylates, or a combination of two or more thereof are used.
In the present invention, a polyfunctional (meth) acrylate, preferably 2 or more and less than 3 functional (meth) acrylates obtained by reacting a polyester polyol, preferably a polyester polyol with (meth) acrylic acid, is preferably used. By less than 3 functional groups is meant herein that the total amount of acryloyl and methacryloyl groups per molecule is on average less than 3 functional groups. The molecular weight of the (B) polyfunctional (meth) acrylate monomer is in the range of 200 to 5000, preferably 400 to 3000.
In the present invention, for example, for the purpose of adjusting the viscosity of the etching composition, the above-mentioned polyfunctional (meth) acrylate monomer, and hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, and N, N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; a monofunctional acrylate comprising phenoxy acrylate.
In addition, a monofunctional or polyfunctional (meth) acrylate oligomer may be added to the polyfunctional (meth) acrylate monomer within a range not to impair the object of the present invention.
(B) The amount of the polyfunctional (meth) acrylate monomer is suitably 10 to 60 parts by mass, preferably 20 to 40 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (a). By setting the amount of the compound to 10 parts by mass or more, photocurability is ensured, and the formation of lines of a conductive pattern is favorable by alkali development after irradiation with an active energy ray. On the other hand, by setting the amount to 600 parts by mass or less, the solubility in an alkaline aqueous solution is secured, and a tough conductive pattern film can be obtained.
[ (C) polyfunctional thiol Compound ]
The resist composition of the present invention comprises (C) a polyfunctional thiol compound. (C) The polyfunctional thiol compound is preferably a compound containing 2 to 6 mercapto groups (also referred to as thiol groups) per molecule.
Further, the (C) polyfunctional thiol compound is preferably a compound containing 1 or more of each of a mercapto group (-SH) and a carboxylate group (-RCOO- (R is a C1-C4 alkyl group), and it is preferable to use a compound containing 2 to 6, particularly 2 to 4, mercaptopropionyloxy groups per molecule, for example
Figure BDA0003116554300000101
(i.e., 3-mercaptopropionyloxy), mercaptobutanoyloxy, e.g.
Figure BDA0003116554300000102
(i.e., 3-mercaptobutanoyloxy), or a combination thereof. (C) The polyfunctional thiol compound is preferably a compound having a molecular weight of 1000 or less, preferably 300 to 800, more preferably 400 to 600 or so, containing an aliphatic hydrocarbon, an alicyclic hydrocarbon, or a non-aromatic heterocyclic moiety, and having, for example, 2 to 6, particularly 2 to 4 mercaptopropionyloxy groups or mercaptobutyryloxy groups.
Specific examples thereof include mercaptopropionyloxy-containing compounds such as trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and dipentaerythritol hexa (3-mercaptopropionate), and mercaptobutyryloxy-containing compounds such as 1, 4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), and 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione.
Examples of commercially available products of the above-mentioned compounds include Karenz MT (registered trademark) PE1, Karenz MT (registered trademark) BD1, and Karenz MT (registered trademark) NR1 (available from Showa Denko K.K.).
(C) Among the above, 3-functional or higher Karenz MT (registered trademark) PE1 and Karenz MT (registered trademark) NR1 are preferable because the polyfunctional thiol compound is excellent not only in hydrofluoric acid resistance but also in other properties such as adhesion and peeling properties.
(C) The amount of the polyfunctional thiol compound to be blended is suitably 1 to 10 parts by mass, preferably 2 to 5 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A).
The glass etching composition of the present invention containing (C) a polyfunctional thiol compound has excellent adhesion to a glass substrate and excellent peelability, and therefore, hydrofluoric acid resistance during glass etching is improved. As a result, the glass substrate can be etched with excellent resolution.
[ (D) photopolymerization initiator ]
The photopolymerization initiator (D) is not particularly limited as long as it can polymerize the (meth) acrylate by irradiation with an energy ray.
(D) The photopolymerization initiator may be any compound that generates radicals by light, laser, electron beam, or the like to initiate radical polymerization. Examples of the photopolymerization initiator (D) include: benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc.; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone and 1, 1-dichloroacetophenone; aminoacetophenones such as 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and N, N-dimethylaminoacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone and 2, 4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; 2,4, 5-triarylimidazole dimer; riboflavin tetrabutyrate; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole; organic halogen compounds such as 2,4, 6-tris (chloromethyl) -s-triazine, 2,2, 2-tribromoethanol, tribromomethylphenylsulfone and the like; benzophenones such as benzophenone and 4, 4' -bisdiethylaminobenzophenone or xanthenone; phosphine oxides such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide; alkylphenones such as alpha-hydroxyalkylphenone.
(D) The photopolymerization initiator may be used alone or in combination of two or more. In addition to these, a photoinitiator aid such as a tertiary amine, e.g., ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, pentyl-4-dimethylurethane benzoate, triethylamine, or triethanolamine, may be used. Further, a titanocene compound such as CGI-784 (manufactured by BASF Japan) which absorbs in the visible light region may be added to the photopolymerization initiator (D) to promote the photoreaction. The component to be added to the photopolymerization initiator (D) is not limited to these, and a plurality of components may be used alone or in combination as long as they absorb light in the ultraviolet light or visible light region and cause radical polymerization of an unsaturated group such as a (meth) acryloyl group.
Examples of the product names of products commercially available as photopolymerization initiators include alkylbenzene series such as Omnirad907, Omnirad127 and Omnirad369 (both manufactured by IGM Resins Co.), and phosphine oxide series such as Omnirad TPO H (manufactured by IGM Resins Co.). (D) The photopolymerization initiator is not particularly limited, and any of the above can be used, and an alkyl ketone system is preferably used.
When the resist composition of the present invention is used as an ultraviolet-curable resist composition, the photopolymerization initiator (D) is preferably a benzil ketal, for example, Omnirad651 (manufactured by IGM Resins).
(D) The amount of the photopolymerization initiator is 0.5 to 35 parts by mass, more preferably 0.5 to 20 parts by mass, and still more preferably 1 to 10 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A) in the resist composition.
By setting the amount of the photopolymerization initiator to 0.5 parts by mass or more, the photocurability is sufficient, and therefore, the adhesion between the resist composition and the substrate is improved. On the other hand, by setting the amount to 35 parts by mass or less, the tendency that light absorption at the surface of the resist composition becomes excessively severe is suppressed, and deep curability can be ensured.
[ (E) Talc ]
The etching resist composition of the present invention contains (E) talc as an inorganic filler. The type of talc (E) used is not particularly limited, and commercially available products include LMS-100, LMS-200, LMS-300, LMS-3500, LMS-400, LMP-100, PKP-53, PKP-80, PKP-81, and Microace K-1 (manufactured by Fuji Talcum Industrial Co., Ltd.); fine talc powder such as P-2, P-3, P-4, P-6, P-8, SG-95 (specific surface area based on BET method 7.5-15.0 m)2(g), fine talc powder having plate body shape (specific surface area by BET method of 18 to 24 m), such as NANOACE D-600, NANOACE D-800, NANOACE D-1000, etc2Ultrafine talc powder (having a BET specific surface area of 30 to 40 m), such as SG-2000, SG-200N152(each of which is manufactured by Japan Talc Co., Ltd.). In the present invention, ultrafine talc powder is preferably used.
In order to improve the resolution of the resist composition, (E) the average particle diameter of talc (measured by light scattering) is preferably 6 μm or less, particularly preferably 3 μm or less, and preferably 0.1 μm or more from the viewpoint of preventing aggregation. (E) Talc may be used alone or in combination of plural kinds.
In the present invention, by using the talc (E) in the above-mentioned compounding amount of 20 to 100 parts by mass per 100 parts by mass of the carboxyl group-containing resin (a), the resist composition can be held on a glass substrate in a film shape, and adhesion between the resist composition and glass and resistance to hydrofluoric acid can be obtained.
[ other ingredients ]
In addition, the resist composition of the present invention may further contain, as necessary: at least 1 kind selected from thickening agent, fluidity modifier, surface tension regulator, adhesion endowing agent, surfactant, colorant, ultraviolet absorbent, defoaming agent and leveling agent of organosilicon series, fluorine series, macromolecule series, etc., delustering agent, polyester series resin for adjusting film physical property, vinyl series resin, acrylic resin, rubber series resin, and wax series. The above components may be used in amounts appropriately adjusted within a range in which desired effects by the addition are obtained without impairing the performance of each of the components (a) to (E).
Since it is difficult to peel off the formed resist layer, it is preferable not to blend an epoxy resin or an elastomer.
Examples of usable defoaming agents include silicone defoaming agents, fluorine defoaming agents, and acrylic defoaming agents. Examples of the silicone defoaming agent include BYK (registered trademark) -063, -065, -066N, -081, -141, -323, manufactured by Ltd, KS-66, KS-69, and X-50-1105G, manufactured by shin-Etsu chemical Co., Ltd, examples of the fluorine defoaming agent include MegaFace RS, F-554, and F-557, manufactured by DIC Co., Ltd, and examples of the acrylic defoaming agent include ISPARLON OX-EF 880, OX-70, manufactured by NAKAI chemical Co., Ltd.
Examples of the colorant include phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, microcrystalline violet, titanium oxide, carbon black, and naphthalene black, and examples of the thickener include known and commonly used thickeners containing bentonite and fine silica powder.
Among the above additives, particularly, by blending an antifoaming agent and/or a leveling agent, deterioration of surface smoothness can be prevented, and deterioration of interlayer insulation due to voids and pinholes can be prevented.
The resist composition of the present invention has a viscosity at 25 ℃ preferably in the range of 1 to 1500 dPas, and particularly preferably in the range of 10 to 1000 dPas. When the viscosity of the etching resist composition is 1 dPas or more, the etching resist composition is dried by heating to form a coating film having a thickness capable of satisfactorily protecting a substrate as an etching resist. On the other hand, if the viscosity of the etching resist composition is 1500 dpas or less, the composition is easy to handle, is suitable for printing by screen printing or the like, and can be used for simply and economically performing a resist stripping treatment after etching.
The hydrofluoric acid resistant resist composition of the present invention is suitable mainly for use in an alkali development type resist composition and an ultraviolet ray curing type resist composition.
< method for producing glass substrate of the present invention >
Next, the method for producing a glass substrate of the present invention using the hydrofluoric acid resistant resist composition (also referred to as a resist composition) as an alkali development type resist composition will be described in further detail for each step.
[ (1) coating film Forming Process ]
When the resist composition of the present invention is used as an alkali-developable resist composition, a desired coating film can be formed by applying a solution of the resist composition of the present invention onto a glass substrate and heating to remove the solvent. As a coating method on the glass substrate, a spin coating method, a slit coating method, a roll coating method, a screen printing method, and an applicator method can be applied, and as a coating method in this case, wet-on-wet coating such as 2-coat 1-bake, and dry-on-wet coating such as 2-coat 2-bake, which have been conventionally known, can be used. The drying conditions of the coating film of the resist composition of the present invention vary depending on the kind of each component in the composition, the blending ratio, the thickness of the coating film, and the like, and are usually about 3 to 15 minutes at 60 to 160 ℃, preferably 80 to 150 ℃. If the drying time is too short, the adhesion state during development is deteriorated, and if it is too long, resolution may be reduced by thermal atomization. The resist composition may be applied in a single step (1 layer).
As described above, the film thickness of the uncured resist composition applied in a pattern on the substrate can be suitably adjusted within a range of preferably 3 to 70 μm, particularly preferably 30 to 60 μm, depending on the properties of the etching solution. A resist composition having a film thickness in this range is effective from the viewpoint of protecting a substrate during etching because it has sufficient resistance to an etching solution. However, the resist composition of the present invention can be formed to a film thickness of more than 70 μm as long as it satisfies the requirements of drying temperature and drying time. The film thickness can be obtained by ordinary printing conditions.
[ (2) Exposure Process ]
The exposed portion can be cured by irradiating the obtained coating film with a radiation such as ultraviolet or visible light having a wavelength of 300 to 500nm through a photomask having a desired pattern or by using a direct exposure machine. The radiation rays here mean ultraviolet rays, visible rays, far ultraviolet rays, X-rays, electron beams, and the like, and as the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon laser, and the like can be used. The amount of radiation varies depending on the kind and amount of each component in the composition, the thickness of the coating film, etc., and is, for example, 100 to 1500mJ/cm in the case of using a high-pressure mercury lamp2The range of (1).
[ (3) developing Process ]
As a developing method after irradiation with radiation, an alkaline aqueous solution is used as a developing solution, and unnecessary unexposed portions are dissolved and removed to leave only exposed portions, thereby obtaining a cured film of a desired pattern. Examples of the developer include aqueous solutions of bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1, 8-diazabicyclo [5.4.0] -7-undecene, and 1, 5-diazabicyclo [4.3.0] -5-nonane.
The resist composition of the present invention can be used without a developing step by directly printing the composition in an image form by a printing method such as screen printing, gravure printing, or gravure offset printing.
[ (4) etching Process ]
By following the above-described steps, the substrate covered with the resist layer photocured in a desired pattern is then supplied to an etching process using an etching liquid. By the etching treatment, the substrate portion not covered with the resist (the portion other than the pattern of the resist) is etched. Thus, a glass molded article having a predetermined pattern can be obtained.
When the resist composition of the present invention is used as an ultraviolet-curable resist composition, the resist composition of the present invention is printed on a glass substrate by screen printing or the like to form a desired pattern with a film thickness of 15 to 80 μm, preferably 20 to 50 μm, and irradiated with UV light (ultraviolet light) of 500 to 2000mJ/cm2Preferably 1000 to 1500mJ/cm2After the resist layer is formed by curing, the substrate portion not covered with the resist layer (the portion other than the pattern of the resist layer) is etched by the etching step.
The etching solution may be hydrofluoric acid alone or a mixture of hydrofluoric acid and an inorganic acid (e.g., nitric acid, phosphoric acid, etc.).
Since the resist film obtained from the resist composition of the present invention has excellent resistance to an etching solution, peeling from the substrate does not occur during etching, and the substrate can be etched with high accuracy.
The resist composition of the present invention constitutes a resist layer that adheres well to the substrate through the above-described steps, and the substrate is well protected from the etching solution. Further, etching can be performed with high accuracy, and after completion of etching, the etching can be easily removed in a short time by using a solvent such as a ketone, an ester, an aromatic hydrocarbon, or a petroleum solvent. For the removal of the etching resist, a petroleum solvent is preferably used particularly from the viewpoint of solubility and economy.
The resist composition of the present invention has very excellent resistance and excellent adhesion to a substrate not only in a hydrofluoric acid-based etching solution but also in etching using various types of strong acid-based etching solutions.
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, "part" means part by mass unless otherwise specified.
Examples
Examples 1 to 5 and comparative examples 1 to 6
Preparation of I-I alkali developable resist composition
The components shown in table 1 were mixed at the ratios (unit: part) described above, premixed in a mixer, and then dispersed and kneaded by a three-roll mill to obtain alkali-developable resist compositions of examples 1 to 5 (inventive compositions) and comparative examples 1 to 6 (comparative compositions).
I-ii. evaluation substrate 1: manufacture of etch resist
Soda-lime glass having a film thickness of 1.8mm was washed with alcohol in advance, and the surface was dried. For this, the alkali-developable resist compositions of examples 1 to 5 and comparative examples 1 to 6 were each printed on the entire surface to a film thickness of 80 μm using a screen printing plate having a predetermined photosensitive emulsion on an 80-mesh polyester plate to a film thickness of 80 μm. The thus-coated alkali-developable resist composition was heated at a drying temperature of 100 ℃ for 30 minutes by means of a hot air circulation dryer (DF-610 manufactured by Yamato Scientific co., Ltd), and the solvent was evaporated and dried to obtain an etching resist having a film thickness of 50 μm (evaluation substrate 1).
I-III. Adhesion
Glass adhesion test the evaluation substrate 1 was subjected to a cross-cut tape peeling test in accordance with JIS K5600-5-6. That is, cuts crossing at 1mm intervals in the longitudinal and transverse directions were introduced into the etching resist layer of the evaluation substrate 1, a large number of grids (lattices) were formed by the cuts, and 100 grids were peeled off by attaching a tape by the method described in JIS K5600-5-6, and the number of lattices where peeling/breakage from the glass substrate occurred was observed and evaluated as follows. The evaluation results are shown in table 1.
None of the 100 lattices peeled off/broken
Good quality all 100 lattices had no peeling, but less than 10 lattices had one end broken
Partial or complete peeling was observed in the cells having a Delta of less than 90
Partial or complete peeling was observed in the grid of 90 or more
I-iv. evaluation substrate 2: production of etching resist layer (cured film)
A photomask having a predetermined pattern was placed on a hydrofluoric acid resistance test evaluation substrate 1, and irradiated with ultraviolet light having a wavelength of 300 to 450nm at 300mJ/cm2The exposed portion is cured, thereby producing the evaluation substrate 2.
The evaluation substrates 2 of the examples and comparative examples were immersed in 10 vol% hydrofluoric acid to etch a depth of 100 μm. Then, with respect to the evaluation substrate 2, the degree of etching (degree of immersion) in the horizontal direction by immersion of the etching solution was observed in a portion (portion to be protected from etching) of the glass substrate directly below the etching resist layer according to the following criteria. The evaluation results are shown in table 1.
Very good immersion 100 μm
O immersion in excess of 100 μm and below 150 μm
A Δ dip of 150 μm or more and less than 250 μm
Dipping in a solution of 250 to 500 μm
I-V. Peel Property
Each evaluation substrate 2 was immersed in a 3 mass% aqueous solution (50 ℃ C.) of sodium hydroxide in a beaker. The state of the resist layer with time was visually observed according to the following evaluation criteria. The evaluation results are shown in table 1.
Very good peeling within 5 minutes
Good quality, peeling within more than 5 minutes and 30 minutes
The delta is not peeled off within 30 minutes, and then peeled off by spraying, ultrasonic treatment, or immersion in an aqueous solution of sodium hydroxide at a temperature of 70 ℃ or higher for 180 minutes
X peeling by immersion for 10 hours or more
I-VI resolution test
The state of etching of each evaluation substrate 2 after the hydrofluoric acid resistance test was observed by SEM (scanning electron microscope) and evaluated according to the following criteria. The results are set forth in Table 1.
No undercut occurred, the end face of the glass substrate after etching was smooth, and etching according to the pattern was performed
Good without undercut, but with notches in the end faces of the etched glass substrates
Acute halo, and basal cut
Halation and undercut were observed, and further, residues were generated on the bottom surface of the etched portion
[ Table 1]
Figure BDA0003116554300000181
1 Kayarad ZFR-1401H, manufactured by Nippon Kabushiki Kaisha, carboxyl group-containing resin (acid-modified polyfunctional bisphenol F type epoxy acrylate, average number of functional groups of 5, and acid value of 100mg KOH/g in terms of solid content), carboxyl group-containing resin corresponding to the above (7)
2 DPHA, manufactured by Nippon Kabushiki Kaisha, dipentaerythritol hexaacrylate, and,
4-functional thiol Compound manufactured by Showa Denko K.K. 3Karenz MT (registered trademark) PE1
(pentaerythritol tetrakis (3-mercaptobutyrate)
4 Karenz MT (registered trademark) BD1, 2-functional thiol Compound (1, 4-bis (3-mercaptobutyryloxy) butane, available from Showa Denko K.K.)
5 Karenz MT (registered trademark) NR1, product of Showa Denko K.K., 3-functional thiol Compound
(1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione)
6 KBM-503 Methylacryloylsilane coupling agent, product of shin-Etsu chemical Co., Ltd
7 KBM-403 epoxy silane coupling agent, product of shin-Etsu chemical Co., Ltd
8 KBM-603 aminosilane coupling agent manufactured by shin-Etsu chemical Co., Ltd
9 Omnirad369, product of IGM Resins, alpha-aminoalkylbenzophenone photopolymerization initiator
10 SG-2000, a product of Japan talc Co., Ltd., ultrafine talc powder
11 BaiRIACE (registered trademark) B-30 made by Sakai chemical industry Co., Ltd., barium sulfate
12 KS-66, dimethylpolysiloxane, an Oil compound type defoaming agent available from shin-Etsu chemical Co., Ltd
13 Fastgen Green S phthalocyanine Green pigment manufactured by DIC Co., Ltd
From the results of the examples, it is understood that the alkali-developable resist composition of the present invention is excellent in all of glass adhesion, resistance to an etching solution, releasability, and resolution. A processed product of a substrate such as glass obtained by using the resist composition can be etched with good precision.
Further, the present invention will be specifically described with reference to examples and comparative examples showing ultraviolet-curable resist compositions, but the present invention is not limited to the following examples.
Examples 7 to 10 and comparative examples 7 to 8
II-I. preparation of ultraviolet-curable resist composition
The components shown in table 2 were mixed at the ratios (unit: part) described above and mixed by stirring. Then, the mixture was kneaded 2 times with a three-roll mill to obtain each of the ultraviolet-curable resist compositions of examples 6 to 10 (inventive compositions) and comparative examples 7 to 8 (comparative compositions).
II-II. evaluation substrate 3: production of etching resist layer (cured film)
Each of the UV-curable resist compositions of examples 6 to 10 and comparative examples 7 to 8 was printed on a copper-clad laminate which had been polished and polished after acid treatment, using a 200-mesh polyester bias screen. The thickness of the coating film at this time was 25 μm. Using a UV irradiator using a metal halide lamp as a light source at 1000mJ/cm2The coating film was cured by the light quantity of (1) to prepare an evaluation substrate 3.
II-III finger Dry
The evaluation substrate 3 was cooled to room temperature, the coating films were bonded to each other, a load of 1kg was applied, and the degree of adhesion after leaving for 6 hours was confirmed. The evaluation results are shown in table 2.
The evaluation method comprises the following steps:
good: even if separated, no abnormality is found on the coating film
And (delta): when separated, the coating film remains
X: at the time of separation, the coating film is peeled off
II-IV. printability
The width of bleeding at the position of the resolution line width of 100 μm of each evaluation substrate 3 was measured. The evaluation results are shown in table 2.
Very good: less than 30 percent
Good: the exudation range is 30-50%
X: the exudation range is more than 50 percent
II-V. glass adhesion
For each of the above-mentioned evaluation substrates 3, a cross-cut tape peeling test was carried out in accordance with JIS K5600-5-6. That is, cuts crossing at 1mm intervals in the longitudinal and transverse directions were introduced into the etching resist layer of the evaluation substrate 1, a large number of grids (lattices) were formed by the cuts, and 100 grids were peeled off by attaching a tape by the method described in JIS K5600-5-6, and the number of lattices where peeling/breakage from the glass substrate occurred was observed and evaluated as follows. The evaluation results are shown in table 2.
Excellent all 100 lattices did not peel off/break
Good quality all 100 lattices have no peeling, but less than 10 lattices have edge breakage
Partial or complete exfoliation was observed in less than 90 lattices
X partial or complete peeling was observed in 90 or more cells
II-VI hydrofluoric acid resistance
The evaluation substrate 3 of each of the examples and comparative examples was immersed in 10 vol% hydrofluoric acid to perform etching to a depth of 50 μm. Then, with respect to the evaluation substrate 3, the degree of etching (degree of immersion) in the horizontal direction by immersion of the etching solution was observed in a portion (portion to be protected from etching) of the glass substrate directly below the etching resist layer according to the following criteria. The evaluation results are shown in table 2.
Very good immersion 50 μm
O immersion in excess of 50 μm and less than 100 μm
A Δ dip of 100 μm or more and less than 250 μm
Dipping in a solution of 250 to 500 μm
II-VII. Peel off Property
Each evaluation substrate 3 was immersed in a 3 mass% aqueous solution (50 ℃ C.) of sodium hydroxide in a beaker. The state of the resist layer with time was visually observed according to the following evaluation criteria. The evaluation results are shown in table 2.
Good quality within 1 minute
X is not peeled off within 1 minute
[ Table 2]
Figure BDA0003116554300000221
*1: half ester, half ester of a polybasic acid anhydride and a hydroxyalkyl (meth) acrylate (HOA-MPL, Kyoeisha chemical Co., Ltd.)
*2: JONCRYL 67, styrene-acrylic copolymer resin (weight average molecular weight 12500, acid value 213mgKOH/g, manufactured by BASF corporation)
*3: aronix M-350, a photoreactive monomer, trimethylolpropane EO-modified triacrylate, available from Toyo Synthesis Co., Ltd
*4: LIGHT ESTER HO-250, Kyoeisha chemical Co., Ltd., photoreactive monomer, 2-hydroxyethyl methacrylate
*5: 3Karenz MT (registered trademark) PE1, product of Showa Denko K.K., 4-functional thiol Compound (pentaerythritol Tetrakis (3-mercaptobutyrate))
*6: karenz MT (registered trademark) BD1, 2-functional thiol Compound (1, 4-bis (3-mercaptobutyryloxy) butane, manufactured by Showa Denko K.K.)
*7: karenz MT (registered trademark) NR1, Showa Denko K.K., 3-functional thiol Compound (1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione)
*8: KS-66, dimethylpolysiloxane, manufactured by shin-Etsu chemical Co., Ltd
*9: phthalocyanine blue and blue colorant
*10: nonirad 651, product of IGM, benzil ketal type photopolymerization initiator
*11: aerosil #200, thixotropic agent, fine powder silica manufactured by Nippon Aerosil Co., Ltd
*12: micro ace K-1, Talc, manufactured by Fuji Talcum Industrial Co Ltd
From the results of the examples, it is understood that the ultraviolet-curable resist composition of the present invention is excellent in all of the properties of dry-to-touch property, printability, glass adhesion, resistance to an etching solution, and releasability. A processed product of a substrate such as glass obtained by using the resist composition can be etched with good accuracy.
The present invention is not limited to the configurations and examples of the above embodiments, and various modifications can be made within the scope of the gist of the invention.
Industrial applicability
As described above, the resist composition of the present invention is excellent in glass adhesion, resistance to an etching solution, stripping property, and resolution, and can be used for etching a glass body (substrate) such as a touch panel, an optical material, and a measuring instrument. Further, a silicon wafer, which is a base material other than glass, or a base material containing titanium, metal oxide, or the like is also excellent in adhesion and hydrofluoric acid resistance, and can be used for etching these base materials.
The resist composition of the present invention has high adhesion to a substrate, and can be used for highly accurate etching of a desired resist pattern drawn on the substrate, and is therefore useful for products with design emphasis such as mobile phones.

Claims (6)

1. A hydrofluoric acid resistant resist composition comprising:
(A) a carboxyl group-containing resin,
(B) A polyfunctional (meth) acrylate monomer,
(C) A polyfunctional thiol compound,
(D) A photopolymerization initiator, and
(E) 20 to 100 parts by mass of talc per 100 parts by mass of the carboxyl group-containing resin (A).
2. The hydrofluoric acid resistant resist composition of claim 1 wherein the (C) polyfunctional thiol compound is a compound containing 2 to 6 mercapto groups per molecule.
3. The hydrofluoric acid resistant resist composition according to claim 1 or 2, wherein a compound having a thermosetting group is contained as the (a) carboxyl group containing resin.
4. The hydrofluoric acid resistant resist composition according to any one of claims 1 to 3, comprising a half ester of a polybasic acid anhydride and a hydroxyalkyl (meth) acrylate monomer as said (A) carboxyl group containing resin.
5. The hydrofluoric acid resistant resist composition of claim 4, free of silane coupling agents.
6. A processed substrate, which is obtained by etching using the hydrofluoric acid resistant resist composition according to any one of claims 1 to 5.
CN201980083175.4A 2018-12-21 2019-12-23 Hydrofluoric acid-resistant resist composition and substrate processed product obtained using same Pending CN113227010A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2018239153 2018-12-21
JP2018-239153 2018-12-21
PCT/JP2019/050256 WO2020130155A1 (en) 2018-12-21 2019-12-23 Hydrofluoric acid-resistant resist composition, and processed substrate product produced using same

Publications (1)

Publication Number Publication Date
CN113227010A true CN113227010A (en) 2021-08-06

Family

ID=71101415

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201980083175.4A Pending CN113227010A (en) 2018-12-21 2019-12-23 Hydrofluoric acid-resistant resist composition and substrate processed product obtained using same

Country Status (4)

Country Link
JP (1) JP7462573B2 (en)
KR (1) KR20210104754A (en)
CN (1) CN113227010A (en)
WO (1) WO2020130155A1 (en)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4689568B2 (en) 2005-10-05 2011-05-25 関西ペイント株式会社 UV curable resist composition for glass etching and glass etching treatment method
JP2009263404A (en) * 2008-04-22 2009-11-12 Toray Ind Inc Paste composition and resin composition using the same
JP5466522B2 (en) * 2010-02-08 2014-04-09 太陽ホールディングス株式会社 Photocurable resin composition, dry film and cured product thereof, and printed wiring board using them
JP5890337B2 (en) * 2013-02-13 2016-03-22 東京応化工業株式会社 Radiation-sensitive resin composition, insulating film, and display device
JP5660692B2 (en) * 2013-12-02 2015-01-28 太陽ホールディングス株式会社 Photosensitive dry film and laminated structure using the same
JP2014078045A (en) * 2014-01-24 2014-05-01 Taiyo Holdings Co Ltd Photocurable resin composition, dry film and cured product of the composition, and printed wiring board using the same
JP6697222B2 (en) * 2015-03-04 2020-05-20 太陽インキ製造株式会社 Etching resist composition and dry film

Also Published As

Publication number Publication date
JP7462573B2 (en) 2024-04-05
KR20210104754A (en) 2021-08-25
WO2020130155A1 (en) 2020-06-25
JPWO2020130155A1 (en) 2021-11-04

Similar Documents

Publication Publication Date Title
EP0323563B1 (en) Photosensitive thermosetting resin composition and method of forming solder resist pattern by use thereof
CN101393394B (en) Photo-cured and heat-cured resin composition and pcondensate thereof
JP4584839B2 (en) Photosensitive resin composition and cured product thereof
KR101169618B1 (en) Photosensitive resin composition and cured product thereof
JP7053345B2 (en) Curable resin composition, dry film, cured product and printed wiring board
JP6852234B2 (en) Photoresist composition and its cured product
KR20170113347A (en) Curable resin composition, dry film, cured product and printed wiring board
KR20050109476A (en) Photosensitive resin composition and curing product thereof
KR20200139632A (en) Curable resin composition, dry film, cured product and printed wiring board
JP2003122001A (en) Photosensitive resin, photosensitive resin composition using the same, and its hardened product
JP2981218B1 (en) Solder photoresist ink composition
KR102444761B1 (en) The photosensitive resin composition, the soldering resist film using this photosensitive resin composition, a flexible printed wiring board, and an image display apparatus
JP2002014466A (en) Photosensitive resin composition
JP2003155320A (en) Photosensitive resin composition and its cured product
JP4257780B2 (en) Photosensitive resin composition, cured product thereof, and use thereof
JP2002338652A (en) Aqueous alkaline solution-soluble urethane forming epoxycarboxylate compound, photosensitive resin composition using the same and its hardened material
CN113227010A (en) Hydrofluoric acid-resistant resist composition and substrate processed product obtained using same
JP4057721B2 (en) Photosensitive resin composition and circuit board solder photoresist ink composition
TW202231671A (en) &lt;b&gt;SOLDER RESIST COMPOSITION, DRY FILM, PRINTED WIRING BOARD AND METHOD FOR PRODUCING THEM&lt;/b&gt;
JP2003280189A (en) Photosetting and thermosetting resin composition
JP2005115187A (en) Photosensitive resin composition and method for manufacturing its hardened product
WO2002094904A1 (en) Photosensitive resin, photosensitive resin compositions containing the same and cured articles of the compositions
JPH10282665A (en) Solder photoresist ink composition
JP2003280191A (en) Photosetting and thermosetting resin composition
JP4408401B2 (en) Alkaline aqueous solution-soluble resin, composition containing the same and cured product thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20210806

WD01 Invention patent application deemed withdrawn after publication