CN114430767A - Composition for forming coating, laminate coated with the composition, touch panel using the laminate, and method for forming cured coating - Google Patents

Composition for forming coating, laminate coated with the composition, touch panel using the laminate, and method for forming cured coating Download PDF

Info

Publication number
CN114430767A
CN114430767A CN202080066096.5A CN202080066096A CN114430767A CN 114430767 A CN114430767 A CN 114430767A CN 202080066096 A CN202080066096 A CN 202080066096A CN 114430767 A CN114430767 A CN 114430767A
Authority
CN
China
Prior art keywords
film
forming
silane compound
coating
composition
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.)
Granted
Application number
CN202080066096.5A
Other languages
Chinese (zh)
Other versions
CN114430767B (en
Inventor
小仓健嗣
池堂圭祐
中野正
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.)
Sakata Inx Corp
Original Assignee
Sakata Inx Corp
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 Sakata Inx Corp filed Critical Sakata Inx Corp
Publication of CN114430767A publication Critical patent/CN114430767A/en
Application granted granted Critical
Publication of CN114430767B publication Critical patent/CN114430767B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Abstract

The invention provides a set for forming a skin membraneThe compound is used in photolithography, and the cured film formed in an exposed portion is difficult to dissolve or corrode by a developing solution and has excellent adhesion with a light-transmitting substrate such as a touch panel, an ITO electrode, and a metal electrode, and the uncured film in an unexposed portion is easy to dissolve and can be quickly removed even with a dilute alkali developing solution, and an insulating film having an appropriate thickness can be formed. The present invention relates to a composition for forming a coating film, which is characterized by comprising a siloxane polymer having a structure represented by the following general formula (A), a photopolymerizable compound having two or more radical polymerizable unsaturated double bonds, a polymerization initiator, and an organic solvent, wherein the ratio of p to q is 1:0.8 to 1: 2.4. Wherein, in the following general formula (A), X has the structure of the following general formula (B), and p and q represent integers; in the following general formula (B), Y is a monovalent substituent having a radical polymerizable double bond, m represents an integer of 1 to 5 inclusive, and n represents an integer of 1 to 1 inclusive;

Description

Composition for forming coating, laminate coated with the composition, touch panel using the laminate, and method for forming cured coating
Technical Field
The present invention relates to a composition for forming a coating film, a laminate formed by applying the composition for forming a coating film, a touch panel formed by using the laminate, and a method for forming a cured coating film.
Background
A touch panel used in a smart phone or a tablet PC is a device that can detect a position and an operation of a finger or the like touching a surface of the panel, and can click an icon or the like displayed at a corresponding position on a display to zoom in or out or scroll a screen. As a method of detecting the position and the motion of a finger or the like on the touch panel, a resistive film method and a capacitive method are currently used in many cases.
Wherein the configuration is as follows: in the resistive type, a voltage variation between electrode layers due to a finger's pressing is converted into an electric signal by using a sensor portion, and in the capacitive type, a capacitance change generated when a finger approaches or touches a panel surface is converted into an electric signal, thereby obtaining information on a position and an operation of the finger.
The sensor portion is formed by a combination of an electrode layer, an insulating layer, and the like.
When an insulating layer used for such a sensor portion is formed by photolithography, a composition for forming a coating film for forming an insulating layer is required to have properties opposite to those of a coating film after curing in an exposed portion and an uncured coating film in an unexposed portion.
That is, it is necessary to have a property that the cured coating does not dissolve but remains when exposed to the developer, and on the other hand, the uncured coating can be quickly dissolved and removed.
In addition, even if the cured film itself is not dissolved, when the chemical adsorption force (adhesion) at the interface between the film and the light-transmissive substrate and the ITO electrode is weak, the film is easily peeled off by the erosion of the developer, and therefore, the adhesion at the interface is also required.
As a composition for forming a coating film, for example, patent document 1 discloses a resist underlayer film forming composition for lithography, which contains a hydrolyzable (hydrolyzable) organosilane, a hydrolysis product thereof, a hydrolysis-condensation product thereof, or a mixture thereof as a silane compound, and which contains a silane compound containing an organic group having an amide bond and a carboxylic acid moiety or a carboxylic acid ester moiety or both a carboxylic acid moiety and a carboxylic acid ester moiety in its molecule.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2011/105368
Disclosure of Invention
Problems to be solved by the invention
In the resist underlayer film forming composition for lithography disclosed in patent document 1, it is difficult to say that the property of not dissolving the cured film but rapidly dissolving and removing the uncured film when exposed to the above-mentioned developer and the adhesion between the light-transmissive substrate and the ITO electrode are sufficient, and it is difficult to dissolve and remove the uncured film when a dilute alkali solution is used as the developer, and therefore there is a technical problem (problem) that usable equipment is limited, and there is room for improvement.
Means for solving the problems
The present inventors have made intensive studies focusing on a silicone polymer contained in a film-forming composition, and as a result, have found that the following means can completely solve the above-mentioned problems, and have completed the present invention. The scheme is as follows: the material constituting the silicone polymer contains a specific silicone polymer, a photopolymerizable compound having two or more radically polymerizable double bonds, a polymerization initiator, and an organic solvent, wherein the specific silicone polymer contains a silane compound (a) containing an organic group having an amide bond and a carboxylic acid moiety described later in the molecule, and a silane compound (B) having a radically polymerizable unsaturated double bond, and the amount of the silane compound (a) and the silane compound (B) are mixed is within a predetermined range.
Namely, a composition for forming a skin film, which is characterized by comprising a siloxane polymer having a structure represented by the following general formula (A), a photopolymerizable compound having two or more radical polymerizable unsaturated double bonds, a polymerization initiator, and an organic solvent, wherein the ratio of p to q is 1:0.8 to 1: 2.4.
Figure BDA0003556065390000031
Wherein, in the general formula (A), X has the following general formula (B) structure, p and q represent integers;
Figure BDA0003556065390000032
in the general formula (B), Y is a monovalent substituent having a radical polymerizable double bond, m represents an integer of 1 to 5 inclusive, and n represents an integer of 1 to 1 inclusive.
In addition, the present invention is preferably: the material constituting the siloxane polymer further includes a silane compound (C) which is at least one selected from the group consisting of tetraalkoxysilanes and bis (trialkoxysilyl) alkanes and/or a silane compound (D) which is at least one selected from the group consisting of alkyltrialkoxysilanes, dialkyldialkoxysilanes, cycloalkyltrialkoxysilanes, vinyltrialkoxysilanes and phenyltrialkoxysilanes.
In addition, the present invention is preferably: the molar ratio of the silane compound (C) to the silane compound (D) [ the silane compound (C): the silane compound (D) ] is 1:0.1 to 1: 10.
In addition, the present invention is preferably: the material constituting the siloxane polymer also includes a silane compound having an epoxy group in the molecule.
The present invention also relates to a laminate having a cured film of the above-described composition for forming a film on a substrate.
The present invention also relates to a touch panel, which is characterized by using a laminate.
The present invention also relates to a method for forming a cured coating, including: a coating step of coating the composition for forming a coating film; an exposure step of irradiating an exposed portion with an active energy ray to form a cured coating film; and a developing step of dissolving and removing the coating liquid in the unexposed portion with a developing solution.
Effects of the invention
The composition for forming a coating film of the present invention is used in a photolithography method, and has high developability because a cured coating film formed in an exposed portion is hardly dissolved or eroded by a developer, and has excellent adhesion to a light-transmitting substrate such as a touch panel, an ITO electrode, and a metal electrode, and an uncured coating film in an unexposed portion can be easily dissolved and quickly removed even with a developer containing a dilute alkali, and an insulating coating film having an appropriate thickness can be formed.
In the present specification, "dilute alkali" means a pH in the range of 10.0 to 12.5.
The coating film-forming composition of the present invention will be described in detail below.
Detailed Description
(siloxane Polymer)
The composition for forming a coating film is characterized by comprising a siloxane polymer having a structure represented by the following general formula (A), a photopolymerizable compound having two or more radical polymerizable unsaturated double bonds, a polymerization initiator, and an organic solvent, wherein the ratio of p to q is 1:0.8 to 1: 2.4.
Figure BDA0003556065390000041
Wherein, in the general formula (A), X has the following general formula (B) structure, p and q represent integers;
Figure BDA0003556065390000042
in the general formula (B), Y is a monovalent substituent having a radical polymerizable double bond, m represents an integer of 1 to 5 inclusive, and n represents an integer of 1 to 1 inclusive.
< silane Compound (A) >)
In the general formula (a), the monomer having the structure X (hereinafter also referred to as silane compound (a)) contains an organic group having an amide bond and a carboxylic acid moiety in the molecule.
The organic group having an amide bond and a carboxylic acid moiety in the molecule means that the organic group has a combination of an amide bond and a carboxylic acid moiety (amic acid structure) in the silane molecule.
As the silane compound (a), a hydrolyzable organosilane disclosed in international publication No. 2011/105368 and a method for producing the same can be appropriately selected and used.
In the general formula (B), m represents an integer of 1 or more and 5 or less, and n represents an integer of 1 or more.
In the method for producing the silane compound (a), it is convenient from the viewpoint of satisfying m and n as appropriate to cause a reaction between a trialkoxysilane having a substituent group having a primary amino group, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, and a dibasic acid anhydride, such as succinic anhydride, maleic anhydride, phthalic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, and the like.
The silane compound (a) is preferably a reaction product obtained by reacting aminopropyltriethoxysilane with succinic anhydride, hexahydrophthalic anhydride, or itaconic acid, and more preferably a reaction product obtained by reacting aminopropyltriethoxysilane with succinic anhydride.
Specifically, the following structure is provided.
Figure BDA0003556065390000051
< silane Compound (B) >)
In the general formula (B), the monomer containing Y (also referred to as silane compound (B)) has a monovalent substituent having a radical polymerizable double bond.
Examples of the silane compound (B) include: 3- (meth) acryloyloxypropylsilane compounds such as 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylethyldiethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane, and allylsilane compounds such as allyltrimethoxysilane and allyltriethoxysilane.
Among them, 3-methacryloxypropyltrimethoxysilane is preferable from the viewpoint of higher hydrolysis reactivity and crosslinking density.
The ratio of p to q (p: q) in the above general formula (A) of the above siloxane polymer is 1:0.8 to 1: 2.4.
From the viewpoint of suitably satisfying the ratio of p to q (p: q), the molar ratio of the silane compound (a) to the silane compound (B) [ the silane compound (a): the silane compound (B) ] is preferably 1:0.8 to 1: 2.4.
When the ratio of p to q (p: q) is 1 (less than 0.8), the cured film cannot be sufficiently provided with adhesion to the light-transmissive substrate and the ITO electrode; when the above ratio is 1 (more than 2.4), the solubility of the uncured coating film in a developer, particularly in a dilute alkali developer, becomes insufficient.
From the viewpoint of more suitably satisfying the ratio of p to q (p: q), the molar ratio of the silane compound (a) to the silane compound (B) [ the silane compound (a): the silane compound (B) ] is preferably 1:1.0 to 1:2.0, and more preferably 1:1.5 to 1: 1.8.
As a material constituting the siloxane polymer, it is preferable that the siloxane polymer further contains a silane compound (C) which is at least one selected from the group consisting of tetraalkoxysilanes and bis (trialkoxysilyl) alkanes and/or a silane compound (D) which is at least one selected from the group consisting of alkyltrialkoxysilanes, dialkyldialkoxysilanes, cycloalkyltrialkoxysilanes, vinyltrialkoxysilanes and phenyltrialkoxysilanes.
The silane compound (C) can impart solubility to an uncured coating film in a developer, and the silane compound (D) can impart resistance to a developer and an etchant to a cured coating film.
By containing the silane compound (C) and/or the silane compound (D), adhesion between the cured film and the light-transmissive substrate and the ITO electrode can be appropriately provided, and solubility of the uncured film in a developer can be provided.
In particular, when the silane compound (C) and the silane compound (D) are contained in a molar ratio as described later, the properties of the silane compound (C) and the silane compound (D) can be suitably satisfied, and thus adhesion between the cured film and the light-transmissive substrate and the ITO electrode can be more suitably provided, and solubility of the uncured film in a developer can also be more suitably provided.
< silane Compound (C) >)
The silane compound (C) is at least one selected from the group consisting of tetraalkoxysilanes and bis (trialkoxysilyl) alkanes.
Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, and methoxytriethoxysilane.
Examples of the bis (trialkoxysilyl) alkane include bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1, 2-bis (trimethoxysilyl) ethane, and 1, 2-bis (triethoxysilyl) ethane.
Among these, preferred are tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, bis (triethoxysilyl) methane, and 1, 2-bis (triethoxysilyl) ethane, and more preferred are tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane, from the viewpoint of general versatility.
The silane compound (D) is at least one selected from the group consisting of alkyltrialkoxysilanes, dialkyldialkoxysilanes, cycloalkyltrialkoxysilanes, vinyltrialkoxysilanes, and phenyltrialkoxysilanes.
The silane-based compound (D) is preferably an alkyltrialkoxysilane as a compound having a saturated hydrocarbon group, and is preferably a phenyltrialkoxysilane as a compound having an unsaturated hydrocarbon group.
Examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltris-n-propoxysilane, methyltriisopropoxysilane, methyltris-n-butoxysilane, methyltriisobutoxysilane, methyltris-sec-butoxysilane, methyltris-tert-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, ethyltriisobutoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltriisopropoxysilane, n-propyltri-n-butoxysilane, n-propyltriisobutoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltri-butoxysilane, and the like, Isopropyl tri-n-propoxysilane, isopropyl triisopropoxysilane, isopropyl tri-n-butoxysilane, isopropyl triisobutoxysilane, isopropyl tri-sec-butoxysilane, and isopropyl tri-tert-butoxysilane.
Examples of the dialkyldialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldiisobutoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-tert-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldiisobutoxysilane, diethyldi-sec-butoxysilane, diethyldi-tert-butoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxysilane, di-n-propyldiisopropoxysilane, di-n-propyldi-n-butoxysilane, di-n-propyldiisobutoxysilane, di-n-propyldiethoxysilane, di-n-butoxysilane, di-n-propoxysilane, di-n-propyldiisopropoxysilane, di-n-propylsilane, di-n-propoxysilane, di-n-propyldiisopropoxysilane, di-n-propylsilane, di-n-propoxysilane, di-n-propylsilane, di-propyldiisopropoxysilane, di-n-propylsilane, di-n-propylsilane, di-n-propylsilane, and, Di-n-propyldi-sec-butoxysilane, di-n-propyldi-tert-butoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldi-n-propoxysilane, diisopropyldiisopropoxysilane, diisopropyldi-n-butoxysilane, diisopropyldiisoisobutoxysilane, diisopropyldi-sec-butoxysilane, diisopropyldi-tert-butoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n-butyldiisopropoxysilane, di-n-butyldi-n-butoxysilane, di-n-butyldi-iso-butoxysilane, di-n-butyldi-sec-butoxysilane, di-n-butyldimethoxysilane, diisobutyldiethoxysilane, diisobutyldi-n-propoxysilane, diisobutyldiisopropoxysilane, diisopropoxysilane, diisopropyldimethylsiloxane, diisopropoxysilane, and the like, Diisobutyl di-n-butoxysilane, diisobutyl di-iso-butoxysilane, diisobutyl di-sec-butoxysilane, diisobutyl di-tert-butoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldi-n-propoxysilane, di-sec-butyldiisopropoxysilane, di-sec-butyldi-n-butoxysilane, di-sec-butyldiisobutoxysilane, di-sec-butyldi-tert-butoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, di-tert-butyldiisopropoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldi-iso-butoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, and the like.
Examples of the cycloalkyltrialkoxysilane include cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltri-n-propoxysilane, cyclopentyltriisopropoxysilane, cyclopentyltri-n-butoxysilane, cyclopentyltriisobutyloxysilane, cyclopentyltris-sec-butoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltri-n-propoxysilane, cyclohexyltriisopropoxysilane, cyclohexyltri-n-butoxysilane, cyclohexyltriisobutoxysilane, cyclohexyltri-sec-butoxysilane, and cyclohexyltri-tert-butoxysilane.
Examples of the vinyltrialkoxysilane include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltri-n-butoxysilane, vinyltriisobutoxysilane, vinyltri-sec-butoxysilane, and vinyltri-tert-butoxysilane.
Examples of the phenyltrialkoxysilane include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, phenyltriisobutoxysilane, phenyltri-sec-butoxysilane, and phenyltri-tert-butoxysilane.
Among them, at least one selected from the group consisting of methyltriethoxysilane, dimethyldimethoxysilane, cyclohexyltriethoxysilane, vinyltriethoxysilane, and phenyltriethoxysilane is preferable, and methyltriethoxysilane and phenyltriethoxysilane are more preferable.
< silane compound having epoxy group in molecule >
If necessary, the siloxane polymer preferably further contains a silane compound having an epoxy group in the molecule.
Examples of the silane-based compound having an epoxy group in the molecule include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethylmethyldimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethylmethyldiethoxysilane.
Among them, 3-glycidoxypropyltrimethoxysilane is preferable from the viewpoint of crosslinking density and high hydrolysis reactivity.
< other silane Compounds >
The siloxane polymer may contain other silane compounds.
Examples of the other silane compounds include silane compounds having a mercapto group, and examples thereof include mercaptoalkyltrialkoxysilane compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 2-mercaptoethyltrimethoxysilane.
< content ratio of silane-based Compound >
From the viewpoint of adhesion between the cured film and the light-transmissive substrate and the ITO electrode and solubility of the uncured film in the developer, the molar ratio of the silane compound (a) to the silane compound (D) [ the silane compound (a): the silane compound (D) ] is preferably 1:0.1 to 1: 5.0.
The above molar ratio [ the above silane-based compound (A): the above silane-based compound (D) ] is more preferably 1:0.8 to 1:3.0, and still more preferably 1:1.0 to 1: 2.5.
From the viewpoint of adhesion between the cured film and the light-transmissive substrate and the ITO electrode and solubility of the uncured film in the developer, the molar ratio of the silane compound (C) to the silane compound (D) [ the silane compound (C): the silane compound (D) ] is preferably 1:0.1 to 1: 10.
The above molar ratio [ the above silane-based compound (C): the above silane-based compound (D) ] is more preferably 1:0.3 to 1:5, and still more preferably 1:0.5 to 1: 2.5.
From the viewpoint of suitably imparting adhesion between the cured film and the light-transmitting substrate and the ITO electrode, the molar ratio of the silane-based compound (a) to the silane-based compound having an epoxy group in the molecule [ the silane-based compound (a): the silane-based compound having an epoxy group in the molecule ] is preferably 1:0.1 to 1:1.0, more preferably 1:0.2 to 1:0.7, and still more preferably 1:0.3 to 1: 0.6.
In addition, from the viewpoint of appropriately imparting adhesion between the cured film and the light-transmitting substrate and the ITO electrode, the molar ratio of the silane compound (a) to the other silane compound [ the silane compound (a): the other silane compound ] is preferably 1:0.1 to 1:1.0, more preferably 1:0.2 to 1:0.7, and still more preferably 1:0.3 to 1: 0.6.
Method for producing siloxane polymer
Next, a method for producing the siloxane polymer will be described.
Examples of the method for producing the siloxane polymer include the following methods: after the silane compound (a) and the silane compound (B) are mixed in an appropriate container, the silane compound (C), the silane compound (D), the silane compound having an epoxy group in the molecule, and the other silane compound are mixed as necessary, water and a polymerization catalyst are added, and a reaction solvent is added as necessary, thereby performing a hydrolytic condensation reaction.
After the condensation reaction, unnecessary by-products other than the siloxane polymer are removed by a method such as extraction, dehydration, or solvent removal, whereby the siloxane polymer can be obtained.
The amount of water is preferably such that the same number of water molecules is obtained with respect to the number of all the hydrolyzable substituents of the silane compound put in the container.
In addition, since the main silane compounds used in the present invention have 3 or 4 hydrolyzable substituents on the average molecule, when a large amount of such silane compounds is contained, the amount of water can be easily adjusted to an amount of about 3 to 4 times (as a molar ratio, the total amount of silane compounds: water: 1:3 to 1:4) the amount of water relative to the total number of molecules of the silane compounds put in the container.
Examples of the polymerization catalyst include acid catalysts such as acetic acid and hydrochloric acid, and base catalysts such as ammonia, triethylamine, cyclohexylamine, and tetramethylammonium hydroxide.
The amount of the polymerization catalyst is preferably about 0.05 to 0.2 times (molar ratio, total amount of silane compounds: polymerization catalyst: 1:0.05 to 1:0.2) the total molecular weight of the silane compounds charged in the container.
The reaction solvent is preferably a lower alcohol (ethanol, n-propanol, isopropanol, etc.), a ketone compound (acetone, methyl ethyl ketone, etc.), an ester compound (ethyl acetate, n-propyl acetate, etc.), and particularly preferably a lower alcohol; from the viewpoint of maintaining an appropriate reaction temperature and facilitating evaporation, ethanol and isopropanol are more preferable.
The reaction temperature is preferably 60 to 80 ℃ and the reaction time is preferably approximately 2 to 24 hours, so that the reaction can progress sufficiently.
< Silicone Polymer >
The silicone polymer preferably has a weight average molecular weight (Mw) of 1000 to 10000. When the weight average molecular weight (Mw) is less than 1000, curability of the film-forming composition may decrease; when the weight average molecular weight (Mw) is more than 10000, the solubility of the coating film-forming composition may be reduced.
The silicone polymer preferably has a weight average molecular weight (Mw) of 1500 to 8000, more preferably 2000 to 6000.
The weight average molecular weight (Mw) can be measured under the following conditions by dissolving the siloxane polymer to prepare a 0.02 mass% solution, passing the solution through a filter (GL Sciences inc., GL Chromatodisc, water system 25A, pore size 0.2 μm), and using an allence (manufactured by wawter co., ltd., japan) composed of a size exclusion chromatography (size exclusion chromatography) and a refractive index detector.
Column: pLgel mixed D (Agilent) x 2 serial connections
A detector: allonce (manufactured by Vout corporation of Japan)
Eluent: THF (tetrahydrofuran)
Flow rate: 1.0ml/min
Injection amount: 100 μ l
(photopolymerizable Compound having two or more radically polymerizable unsaturated double bonds)
The film-forming composition of the present invention contains a photopolymerizable compound having two or more radical polymerizable unsaturated double bonds.
Examples of the photopolymerizable compound having two or more radically polymerizable unsaturated double bonds include ester compounds between two or more hydroxyl group-containing compounds and (meth) acrylic acid, and examples thereof include 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, and mixtures thereof, Bisphenol a di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
In particular, from the viewpoint of being able to increase the crosslinking density and providing excellent hardness to the cured film, for example, compounds having three or more functional reactive groups such as trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are preferable, and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate are more preferable.
(polymerization initiator)
The film-forming composition of the present invention contains a polymerization initiator.
As the polymerization initiator, a photopolymerization initiator which can obtain a sufficient photocuring reaction when a cured film is formed by a photolithography method described later is preferably used.
Examples of such photopolymerization initiators include: benzil, benzoin, benzophenone, camphorquinone, 2-dimethoxy-1, 2-diphenylethan-1-one, 4 ' -bis (dimethylamino) benzophenone, 4 ' -bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-dimethoxy-2-phenylacetophenone, 2-methyl- [4 ' - (methylthio) phenyl ] -2-morpholinyl-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butan-1-one, 2,4, carbonyl compounds such as 6-trimethylbenzoyl-diphenylphosphine oxide and bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide; trihalomethanes such as 1, 3-bis (trichloromethyl) -5- (2' -chlorophenyl) -1,3, 5-triazine and 2- [2- (2-furyl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine; imidazole dimers such as 2,2 '-bis (2-chlorophenyl) 4,5, 4', 5 '-tetraphenyl 1, 2' -biimidazole; thioxanthone compounds such as 2-isopropylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone and 2, 4-dichlorothioxanthone.
These photopolymerization initiators may be used alone or in combination of two or more. In addition, it may be used in combination with any photosensitizer.
(organic solvent)
The film-forming composition of the present invention contains an organic solvent.
As the organic solvent, an organic solvent such as an alcohol, a polyhydric alcohol or a derivative thereof, a ketone organic solvent, or an ester organic solvent can be used.
Examples of the alcohols include lower alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and sec-butanol.
Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, 1, 2-butanediol, 1, 3-butanediol, diethylene glycol, and dipropylene glycol.
Examples of the polyhydric alcohol derivatives include glycol monoethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-isobutyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol isobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol isopropyl ether, dipropylene glycol n-butyl ether, and dipropylene glycol isobutyl ether.
Further, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-isopropyl ether acetate, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-isobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-isopropyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-isobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-isopropyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol mono-isobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol mono-n-propyl ether acetate, dipropylene glycol mono-isopropyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-isopropyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-butyl ether acetate, propylene glycol ether acetate, glycol monoether acylates such as dipropylene glycol mono-n-butyl ether acetate and dipropylene glycol mono-isobutyl ether acetate.
Examples of the ketone organic solvent include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, and cyclohexanone.
Examples of the ester-based organic solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, methyl lactate, ethyl lactate, and n-propyl lactate.
The organic solvents mentioned above may be used alone or in combination of two or more.
From the viewpoint of solubility and coating suitability of the siloxane polymer, a derivative of a polyhydric alcohol or an ester organic solvent is preferable, and propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-isobutyl ether, propylene glycol monomethyl ether acetate, n-propyl acetate, and isopropyl acetate are more preferable.
(other materials)
The following may be added to the composition for forming a coating film of the present invention within a range not to reduce the effect of the present invention: chelates of metals such as aluminum, zirconium, and titanium; crosslinking agents having crosslinkable functional groups such as carbodiimide groups, isocyanate groups, epoxy groups, thiol groups, and the like; surfactants such as silicon and fluorine; photosensitizers such as aromatic hydrocarbons, amino compounds, nitro compounds, quinones, xanthones, and the like; polymerization inhibitors such as hydroquinone, p-methoxyphenol, hindered amines, hindered phenols, di-t-butylhydroquinone, 4-methoxyphenol, 2, 6-di-t-butyl-p-cresol, and nitrosamine salts; inorganic metal oxides, organic fine particles, and the like.
(content of each material in the composition for forming a coating film)
The photopolymerizable compound having two or more radically polymerizable unsaturated double bonds is preferably contained in an amount of 10 to 50 parts by mass based on 100 parts by mass of the silicone polymer.
When the content of the photopolymerizable compound having two or more radical polymerizable unsaturated double bonds is less than 10 parts by mass with respect to 100 parts by mass of the silicone polymer, curability of the cured film and adhesion between the light-transmissive substrate and the ITO electrode may be insufficient; if the amount is more than 50 parts by mass per 100 parts by mass of the siloxane polymer, the solubility of the uncured film in the developer may be insufficient.
The polymerization initiator is preferably contained in an amount of 0.5 to 40 parts by mass, based on 100 parts by mass of the total amount of the silicone polymer and the polymerizable monomer having two or more radically polymerizable unsaturated double bonds.
If the content of the polymerization initiator is less than 0.5 parts by mass, photopolymerization may be reduced and unreacted components may remain in an exposed portion of a photolithography method; if the amount is more than 40 parts by mass, the storage stability of the composition for forming a coating film may be lowered.
The polymerization initiator is more preferably 1 to 20 parts by mass when the total amount of the silicone polymer and the polymerizable monomer having two or more radically polymerizable unsaturated double bonds is set to 100 parts by mass.
(method for producing composition for forming coating)
As a method for producing the film-forming composition of the present invention, the following method can be used: the organic solvent is placed in a suitable container, and the silicone polymer, the photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, the polymerization initiator, and other materials used as needed are placed and mixed while stirring with, for example, a high-speed stirrer or the like.
The method for producing the film-forming composition of the present invention is not limited to the above method, and the order of putting the materials may be arbitrary.
In addition, in the case of a solid material, if it is soluble with respect to an organic solvent, the solid material may be dissolved in advance before being placed; if the dispersion can be made in an organic solvent as it is or by using a dispersant or the like, the solid material may be dispersed in advance before being put in.
(method of Forming cured coating film)
The method for forming a cured film using the film-forming composition of the present invention preferably includes: a coating step of coating the composition for forming a coating film on a substrate; an exposure step of irradiating an exposed portion with an active energy ray to form a cured coating film; and a developing step of dissolving and removing the coating liquid in the unexposed portion with a developing solution.
The method for forming such a cured coating is also an aspect of the present invention.
The coating method in the coating step, the active energy ray irradiated to the exposed portion in the exposure step, the irradiation method thereof, and the developer for removing the coating liquid in the exposed portion can be appropriately selected and used from those used in conventional photolithography.
For example, it is preferable that the coating composition is diluted so that the concentration of nonvolatile components in the coating composition becomes 25%, applied using a spin coater, subjected to a heating (prebaking) treatment at 80 ℃ for 3 minutes, and then subjected to a photolithography (mask aligner) treatment at 100mJ/cm2Printing the test pattern under the irradiation condition ofThe treatment (imprinting) is carried out by immersing the substrate in a developer for 1 minute, and then heating (post-baking) the substrate at 150 ℃ for 30 minutes to obtain a cured coating film.
The pre-baking is carried out at 80 to 100 ℃ for 1 to 3 minutes.
The irradiation condition is preferably 20 to 120mJ/cm2。
The post-baking is preferably carried out at 120 to 180 ℃ for 30 to 60 minutes.
As the substrate, a glass substrate or a plastic substrate which is conventionally known to be used as a touch panel can be suitably used, and a substrate having a transparent electrode formed on the surface thereof can be used.
When the surface has a transparent electrode, a cured film of the film-forming composition of the present invention is preferably formed on the surface on which the transparent electrode is formed.
A laminate is also one aspect of the present invention, and is characterized in that the cured film of the film-forming composition of the present invention is provided on the substrate.
In addition, a touch panel is also one aspect of the present invention, and is configured by using the laminate of the present invention.
As a material constituting the touch panel, conventionally known materials can be suitably used in addition to the laminate of the present invention.
Examples
The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples. In addition, "%" means "% by mass" and "parts" means "parts by mass" unless otherwise specified.
< preparation of silane Compound (A) >
Into a 200ml three-necked flask, 20.00g of aminopropyltriethoxysilane was charged, 9.04g of powdered succinic anhydride was charged while cooling with a water bath, and the mixture was stirred at room temperature for 20 minutes. Then, the obtained crude product was concentrated and used for the synthesis of a siloxane polymer described later.
The following materials were used in the synthesis of the siloxane polymer.
< silane Compound (B) >)
3-Methacryloyloxypropyltrimethoxysilane (Tokyo Kasei Co., Ltd.)
< silane Compound (C) >)
Tetraethoxysilane (manufactured by Tokyo chemical industry Co., Ltd.)
< silane Compound (D) >)
Phenyltrimethoxysilane (Tokyo Kasei Kaisha)
Methyltriethoxysilane (manufactured by Tokyo chemical industry Co., Ltd.)
< silane compound having epoxy group in molecule >
3-glycidyloxypropyltrimethoxysilane (manufactured by Tokyo Kasei Co., Ltd.)
< other silane Compounds >
3-mercaptopropyltrimethoxysilane (manufactured by Tokyo Kasei Co., Ltd.)
(Synthesis of siloxane Polymer)
The crude product of the silane compound (a) and the respective materials in the mixing ratios shown in table 1 were dissolved in acetone in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel to form a uniform solution.
Water and nitric acid were added dropwise thereto, and the mixture was mixed for 60 minutes while refluxing, and then the obtained reaction solution was cooled to room temperature.
Then, 20.00g of propylene glycol monomethyl ether acetate was added to the reaction solution, and ethanol, water and hydrochloric acid as reaction by-products were distilled off under reduced pressure to obtain a hydrolysis condensation product solution.
Then, propylene glycol diethyl ether was added to the hydrolytic condensation product solution to obtain a hydrolytic condensation product solution having a solid content concentration of siloxane polymers 1 to 12 of 25 mass%.
(measurement of weight average molecular weight (Mw) of Silicone Polymer)
The solvent of the hydrolysis-condensation product solution of siloxane polymers 1 to 12 was evaporated under reduced pressure and dissolved in THF to prepare a 0.02 mass% solution.
Subsequently, the solution was passed through a filter (GL Sciences inc., GL Chromatodisc, water system 25A, pore size 0.2 μm), and then measured using an alias (manufactured by wawter co., japan) composed of a size exclusion chromatograph and a refractive index detector under the following conditions.
Column: pLgel mixed D (Agilent) x 2 serial connections
A detector: allonce (manufactured by Vout corporation of Japan)
Eluent: THF (tetrahydrofuran)
Flow rate: 1.0ml/min
Injection amount: 100 μ l
[ Table 1]
Figure BDA0003556065390000181
(preparation of film-Forming compositions of examples 1 to 8 and comparative examples 1 to 5)
The film-forming composition was prepared by adding the hydrolysis-condensation product solutions of siloxane polymers 1 to 12 and the respective materials at the mixing ratios shown in table 2 to a container equipped with a high-speed stirring device and stirring them.
The following materials were used for the preparation of the film-forming compositions of examples and comparative examples.
< photopolymerizable compound having two or more radically polymerizable unsaturated double bonds >
Tris (2-hydroxyethyl) isocyanuric acid triacrylate (THITA, manufactured by Tokyo Kasei Co., Ltd.)
Dipentaerythritol hexaacrylate (DPHA, manufactured by Tokyo chemical industry Co., Ltd.)
Pentaerythritol tetraacrylate (manufactured by Tokyo chemical industry Co., Ltd., PTA)
< photopolymerizable compound having one radical polymerizable unsaturated double bond >
Acrylic acid benzyl ester
< photopolymerization initiator >
Bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819, manufactured by BASF)
< other materials >
4-methoxyphenol (polymerization inhibitor, 4-MeOPh, Tokyo chemical industry Co., Ltd.)
BYK-310 (silicon surfactant, BYK corporation)
< evaluation of solubility, erosion (erosion) and film thickness ratio >
The film-forming compositions of examples 1 to 8 and comparative examples 1 to 5 were each diluted with propylene glycol monomethyl ether acetate so that the nonvolatile content concentration became 25%, and each film-forming composition was applied to a commercially available 50mm square soda glass substrate at 400rpm for 60 seconds using a spin coater (MS-a100, manufactured by MIKASA co., ltd.).
Next, the resultant was subjected to a heating (prebaking) treatment at 80 ℃ for 3 minutes, and then the resultant was processed at 100mJ/cm using a photo-etching machine (PLA-501FA, manufactured by Canon Inc.)2The test pattern was subjected to a printing treatment (imprint) under the irradiation conditions of (1) and a part of the test pattern was immersed in a 0.045 wt% aqueous solution of potassium hydroxide (pH 12) as a developer for 1 minute, and then subjected to a heating (post-baking) treatment at 150 ℃ for 30 minutes to prepare test pieces for evaluation of the solubility, erosion, and film thickness ratio of each film-forming composition.
< evaluation of solubility >
The dissolution state of the unexposed portion of the evaluation test piece when exposed to the developer was visually observed, and the solubility of the film-forming composition was evaluated according to the following evaluation criteria.
< evaluation Standard >
Very good: completely dissolved in less than 1 minute
Good: the solution was not completely dissolved in 1 minute or less, but was completely dissolved in 5 minutes or less
And (delta): substantially dissolved in less than 5 minutes but a residue was generated
X: does not dissolve in 5 min
< evaluation of erosion >
The thinning (thinning) of the line pattern portion of the exposed portion of the evaluation test piece when exposed to the developer was measured as the dissolution rate (nm/s), and the erosion of the film-forming composition was evaluated according to the following evaluation criteria.
< evaluation Standard >
Very good: the dissolution speed is less than 400nm/s
Good: the dissolution rate is more than 400nm/s and less than 600nm/s
And (delta): the dissolution rate is more than 600nm/s and less than 1200nm/s
X: the dissolution rate is over 1200nm/s
< evaluation of film thickness ratio >
The film thickness (T1) of the exposed portion of the evaluation test piece exposed to the developer and the film thickness (T2) of the exposed portion of the evaluation test piece not exposed to the developer were measured using a film thickness measuring apparatus (Alpha-Step IQ profilometer, manufactured by KLM-Tencor), and the film thickness ratio of the film-forming composition was evaluated according to the following evaluation criteria.
< evaluation Standard >
Very good: T1/T2 is 0.75 or more
Good: T1/T2 is 0.55 or more and less than 0.75
And (delta): T1/T2 is 0.35 or more and less than 0.55
X: T1/T2 is less than 0.35
< evaluation of adhesion between cured coating and transparent electrode >
Each of the film-forming compositions of examples 1 to 8 and comparative examples 1 to 5 was diluted with propylene glycol monomethyl ether acetate so that the nonvolatile content concentration became 25%, and applied to the ITO-laminated surface of a glass substrate obtained by laminating ITO in a thin film form on the surface by a sputtering method using a spin coater (MS-a100, manufactured by MIKASA co., ltd.) under coating conditions of 400rpm and 60 seconds.
Next, the resultant was subjected to a heating (prebaking) treatment at 80 ℃ for 3 minutes, and then the resultant was processed at 100mJ/cm using a photo-etching machine (PLA-501FA, manufactured by Canon Inc.)2A test pattern was subjected to a printing treatment (imprint) under the irradiation conditions of (1), a part of the test pattern was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide as a developing solution for 1 minute, and then subjected to a heating (post-baking) treatment at 150 ℃ for 30 minutes, washing with water, and dryingThen, the coating compositions were dried to prepare test pieces for evaluating adhesion between the coating compositions and the transparent electrodes.
A transparent tape (product name: CELLOTAPE (registered trademark)) was attached to the surface of the obtained test piece for evaluation of adhesion, and the state of separation of the cured film from the glass substrate at the time of separation was observed, and the adhesion of the composition for forming a film was evaluated according to the following evaluation criteria.
< evaluation Standard >
Very good: almost no peeling was observed
Good: several peelings were observed
And (delta): about half of the film is peeled off
X: most peeling occurred
Table 2 shows the results of the evaluation of the solubility, erosion, film thickness ratio and adhesion of the film-forming compositions of examples 1 to 8 and comparative examples 1 to 5.
[ Table 2]
Figure BDA0003556065390000211
It can be confirmed that: when the compositions for forming a coating film of the present invention of examples 1 to 8 were used in the photolithography method, the cured coating film formed in the exposed portion was less likely to be dissolved or eroded by the developer, and the uncured coating film in the unexposed portion was easily dissolved in the developer and could be quickly removed, and an insulating coating film having an appropriate film thickness could be formed.
In particular, example 4, which contained the silane compound (a) and the silane compound (B) at a predetermined molar ratio and contained the silane compound (C) and the silane compound (D) at a predetermined molar ratio, was extremely excellent in all of the evaluations of solubility, erosion, film thickness ratio, and adhesion.
On the other hand, the film-forming compositions of comparative examples 1 and 4 had poor solubility in the unexposed area, and were also poor in the evaluation of the film thickness ratio.
In addition, the compositions for forming a coating film of comparative examples 2, 3 and 5 had poor evaluation of erosion at the exposed portions and also poor evaluation of the film thickness ratio. Further, the coating composition of comparative example 2 was slightly poor in adhesion to the ITO-laminated surface of the glass substrate, and the coating composition of comparative example 5 was poor in adhesion to the ITO-laminated surface of the glass substrate.
Industrial applicability
The composition for forming a coating film of the present invention is used in a photolithography method, since a cured coating film formed in an exposed portion is hardly dissolved or eroded by a developer, and has excellent adhesion to a light-transmitting substrate such as a touch panel, an ITO electrode, and a metal electrode, and an uncured coating film in an unexposed portion can be easily dissolved and quickly removed even with a dilute alkali developer, and an insulating coating film having an appropriate thickness can be formed, the composition for forming a coating film of the present invention can be suitably used as an insulating coating film to be applied to a light-transmitting substrate such as a touch panel.

Claims (7)

1. A composition for forming a skin film, characterized in that,
the composition for forming a coating film comprises a siloxane polymer having a structure represented by the general formula (A), a photopolymerizable compound having two or more radical polymerizable unsaturated double bonds, a polymerization initiator, and an organic solvent, wherein the ratio of p to q is 1:0.8 to 1:2.4,
Figure FDA0003556065380000011
wherein, in the general formula (A), X has the following general formula (B) structure, p and q represent integers;
Figure FDA0003556065380000012
in the general formula (B), Y is a monovalent substituent having a radical polymerizable double bond, m represents an integer of 1 to 5 inclusive, and n represents an integer of 1 to 1 inclusive.
2. The film-forming composition according to claim 1, wherein,
the material constituting the siloxane polymer further contains a silane compound (C) which is at least one selected from the group consisting of tetraalkoxysilanes and bis (trialkoxysilyl) alkanes and/or a silane compound (D) which is at least one selected from the group consisting of alkyltrialkoxysilanes, dialkyldialkoxysilanes, cycloalkyltrialkoxysilanes, vinyltrialkoxysilanes and phenyltrialkoxysilanes.
3. The film-forming composition according to claim 1 or 2, wherein,
the molar ratio of the silane compound (C) to the silane compound (D), i.e., the ratio of the silane compound (C) to the silane compound (D), is 1:0.1 to 1: 10.
4. The film-forming composition according to any one of claims 1 to 3, wherein,
the material constituting the siloxane polymer also includes a silane compound having an epoxy group in the molecule.
5. A laminate comprising a substrate and a cured coating film of the coating film-forming composition according to any one of claims 1 to 4.
6. A touch panel comprising the laminate according to claim 5.
7. A method for forming a cured coating, comprising:
a coating step of coating the composition for forming a coating film according to any one of claims 1 to 4 on a substrate;
an exposure step of irradiating an exposed portion with an active energy ray to form a cured coating film; and
and a developing step of dissolving and removing the coating liquid in the unexposed portion with a developing solution.
CN202080066096.5A 2019-09-30 2020-08-11 Composition for forming film, laminate coated with the composition, touch panel using the laminate, and method for forming cured film Active CN114430767B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2019-181018 2019-09-30
JP2019181018A JP7382196B2 (en) 2019-09-30 2019-09-30 Film-forming composition, laminate formed by coating the film-forming composition, touch panel using the laminate, and method for forming a cured film
PCT/JP2020/030574 WO2021065211A1 (en) 2019-09-30 2020-08-11 Coating film-forming composition, laminate obtained by coating said coating film-forming composition, touch panel obtained by using said laminate, and method for forming cured coating film

Publications (2)

Publication Number Publication Date
CN114430767A true CN114430767A (en) 2022-05-03
CN114430767B CN114430767B (en) 2023-04-28

Family

ID=75269925

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202080066096.5A Active CN114430767B (en) 2019-09-30 2020-08-11 Composition for forming film, laminate coated with the composition, touch panel using the laminate, and method for forming cured film

Country Status (5)

Country Link
JP (1) JP7382196B2 (en)
KR (1) KR20220073731A (en)
CN (1) CN114430767B (en)
TW (1) TW202116880A (en)
WO (1) WO2021065211A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009019093A (en) * 2007-07-11 2009-01-29 Asahi Kasei Electronics Co Ltd Polyorganosiloxane
KR20130078559A (en) * 2011-12-30 2013-07-10 주식회사 삼양사 Photoresist composition and insulation layer produced from the same
JP2014118418A (en) * 2012-12-13 2014-06-30 Nagase Chemtex Corp Silsesquioxane derivative and negative photosensitive resin composition using the same
CN104969126A (en) * 2013-02-14 2015-10-07 东丽株式会社 Negative-type photosensitive coloring composition, cured film, light-shielding pattern for touch panel, and touch panel manufacturing method
CN107974101A (en) * 2016-10-25 2018-05-01 东京应化工业株式会社 Colorant dispersion, photosensitive polymer combination and its manufacture method, solidfied material, organic EL element and pattern formation method
US20180181002A1 (en) * 2016-12-28 2018-06-28 Tokyo Ohka Kogyo Co., Ltd. Method of pattern formation and method of producing polysilane resin precursor

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008203613A (en) 2007-02-21 2008-09-04 Asahi Kasei Electronics Co Ltd Polyorganosiloxane composition
WO2011105368A1 (en) 2010-02-25 2011-09-01 日産化学工業株式会社 Silicon-containing resist underlayer-forming composition containing amic acid
US20140193632A1 (en) 2011-08-31 2014-07-10 Asahi Kasei E-Materials Corporation Photosensitive alkali-soluble silicone resin composition
JP2015227387A (en) 2012-09-24 2015-12-17 旭硝子株式会社 Partially hydrolyzed condensate, ink-repelling agent, negative photosensitive resin composition, cured film, partition wall, and optical element
JP2019189803A (en) 2018-04-27 2019-10-31 ナガセケムテックス株式会社 Manufacturing method of amic acid group-containing polysiloxane, organopolysiloxane, amic acid group-containing organic resin composition, cured film, semiconductor device, and manufacturing method of electronic component

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009019093A (en) * 2007-07-11 2009-01-29 Asahi Kasei Electronics Co Ltd Polyorganosiloxane
KR20130078559A (en) * 2011-12-30 2013-07-10 주식회사 삼양사 Photoresist composition and insulation layer produced from the same
JP2014118418A (en) * 2012-12-13 2014-06-30 Nagase Chemtex Corp Silsesquioxane derivative and negative photosensitive resin composition using the same
CN104969126A (en) * 2013-02-14 2015-10-07 东丽株式会社 Negative-type photosensitive coloring composition, cured film, light-shielding pattern for touch panel, and touch panel manufacturing method
CN107974101A (en) * 2016-10-25 2018-05-01 东京应化工业株式会社 Colorant dispersion, photosensitive polymer combination and its manufacture method, solidfied material, organic EL element and pattern formation method
US20180181002A1 (en) * 2016-12-28 2018-06-28 Tokyo Ohka Kogyo Co., Ltd. Method of pattern formation and method of producing polysilane resin precursor

Also Published As

Publication number Publication date
CN114430767B (en) 2023-04-28
JP2021054995A (en) 2021-04-08
JP7382196B2 (en) 2023-11-16
TW202116880A (en) 2021-05-01
WO2021065211A1 (en) 2021-04-08
KR20220073731A (en) 2022-06-03

Similar Documents

Publication Publication Date Title
JP5589387B2 (en) Siloxane resin composition and protective film for touch panel using the same
JP5867083B2 (en) Negative photosensitive resin composition and protective film using the same
JP5423004B2 (en) Negative photosensitive resin composition and touch panel material using the same
JP5459315B2 (en) Silane coupling agent, negative photosensitive resin composition, cured film, and touch panel member
CN112955514B (en) Composition for forming coating film, glass substrate coated with the composition, and touch panel using the glass substrate
JP5587791B2 (en) Silsesquioxane resin
JP2001083710A (en) Material for electronic parts and electronic parts obtained by curing the material
JP2013512994A (en) Stabilization of silsesquioxane resin
JP7069081B2 (en) A photosensitive resin composition containing silica sol and a cured product using the same.
JP5720604B2 (en) Radiation-sensitive composition, cured film and method for forming the same
JP7382196B2 (en) Film-forming composition, laminate formed by coating the film-forming composition, touch panel using the laminate, and method for forming a cured film
JP2008116598A (en) Photosensitive resin composition
JP2023081087A (en) Polysiloxane-based compound, film-forming composition, laminate formed by application of the film-forming composition, touch panel formed by using the laminate, and method for forming cured film
JP2022154563A (en) Film formation composition, laminate coated with film formation composition, fingerprint authentification sensor obtained by using laminate, and method for forming cured film
JP2023168981A (en) Polysiloxane-based compound, film-forming composition, laminate, touch panel, and method for forming cured film
JP2023168982A (en) Polysiloxane-based compound, film-forming composition, laminate, touch panel, and method for forming cured film
JP6458902B1 (en) Photosensitive siloxane resin composition, cured film and touch panel member
WO2023238286A1 (en) Photosensitive resin composition
KR20140083174A (en) Photosensitive organosiloxane compound and photosensitive resin composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant