CN103809374A - Light-shielding composition for touch panel and touch panel - Google Patents
Light-shielding composition for touch panel and touch panel Download PDFInfo
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- CN103809374A CN103809374A CN201310530322.2A CN201310530322A CN103809374A CN 103809374 A CN103809374 A CN 103809374A CN 201310530322 A CN201310530322 A CN 201310530322A CN 103809374 A CN103809374 A CN 103809374A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
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- 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
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- 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
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Abstract
The invention provides a light-shielding composition for a touch panel and the touch panel. The light-shielding composition can be used as a light-shielding layer of the touch panel, is excellent in chemical agent resistance, light resistance, and insulation properties, and can form images through photoetching. A cured film thereof is provided. The light-shielding composition for the touch panel is characterized by containing a copolymer (A) and carbon black (B) processed through insulation, the copolymer (A) is provided with a plurality of repetitive units, and is formed by 20-90 mol% of repetitive units expressed in formula (1) and 10-80 mol% of more than one repetitive unit which is from a polymerized unsaturated chemicals and is capable of copolymerizing with the repetitive units expressed in formula (1), the number-average molar mass is in the range of 2000-20,000, and the acid value is in the range of 35-120mgKOH/g. The cured film is formed by the curing of the light-shielding composition.
Description
Technical field
The present invention relates to novel touch panel Lightproof composition and there is its touch panel of cured film.
Background technology
Now, be widely used touch panel as the input media in the display device such as liquid crystal display.As the formation of touch panel, known have variety of way, but the touch panel of condenser type (projection-type) rely on can realize bright picture display, can detect the advantages such as contact, many places simultaneously and enjoy and gaze at.
Capacitive touch panel has the mosaic electrode pattern that is formed as 2 layers by transparent conductive materials such as ITO in picture.2 layers of electrode pattern present respectively along x axially and axially continuous shape of y, are situated between and are connected up and be connected with outside control circuit by the extraction of metal etc.When the picture of finger touches touch panel, electrode pattern generation capacitance variations in its vicinity, detects thereby control circuit sets it as coordinate information the position (for example, with reference to patent documentation 1) that can identify finger.
For such touch panel, when form touch panel circuit on front glass time, proposed by the extraction wiring of metal etc. be hidden in be frame shape be formed at the periphery of picture light shield layer after, cannot see from user's direction like this, improve thus the visuality of display, the technology of designability.Now, owing to forming the etching and processing of extracting wiring, electrode pattern after light shield layer, so as the material of light shield layer, the chemical reagent resistance of the stripper of the etching solution of requirement to metal, resist.In addition, because this light shield layer is positioned at the near surface of display, so as its material requirements high-light-fastness.And in order to prevent interelectrode short circuit, light shield layer must have insulativity, after the thermal treatment of special requirement under the required high temperature of the manufacturing process through touch panel circuit, maintain insulativity.
As light shield layer, can utilize the ink composite of light-proofness, but just attempt recently using a kind of light-proofness photoresist that can form image by photoetching.Because the technique of utilizing photoetching can easily only form the light shield layer thick compared with film at the periphery of picture, so preferably.But, by existing material, for example, when the Lightproof composition that the black matrix of color filter is used is converted to touch panel purposes, there is chemical reagent resistance, the photostability level that cannot meet the demands, and their characteristic and insulativity this class problem that is difficult to get both.
On the other hand, also proposed to aim at the well-designed Lightproof composition of touch panel (for example, with reference to patent documentation 2,3), but the also unrealized sufficient improvement of such composition wishes to occur the more high performance material of one.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2011-186717 communique
Patent documentation 2: TOHKEMY 2012-145699 communique
Patent documentation 3:WO2012/133148 pamphlet
Summary of the invention
The present invention carries out in view of the problem of above-mentioned conventional art, and its object is to provide touch panel Lightproof composition a kind of chemical reagent resistance, photostability and insulativity excellence, can form image by photoetching.
Be studied in order to solve above-mentioned problem, the discoveries such as the result inventor contain to have the multipolymer of specific structure and contain through the Lightproof composition of the carbon black of insulation processing and are applicable to touch panel purposes, thereby have completed the present invention.
; the present invention relates to touch panel Lightproof composition; it is characterized in that; contain multipolymer (A) and the carbon black (B) through insulation processing; described multipolymer (A) is the multipolymer with multiple repetitives; the repetitive being represented by 20～90 % by mole of following general formulas (1) and 10～80 % by mole can be above with a kind of repetitive copolymerization that general formula (1) represents the repetitive from polymerizable unsaturated compound form, number-average molecular weight be 2,000～20,000 and acid number be 35～120mgKOH/g.
(wherein, R
1and R
2represent independently of one another hydrogen atom or methyl.）
At this, preferably A composition is only made up of the repetitive group that does not contain aromatic rings.
In addition, the invention still further relates to the touch panel of the cured film with above-mentioned touch panel Lightproof composition.
Embodiment
Below, the present invention is described in detail.
Lightproof composition of the present invention contains multipolymer (A), repetitive that it is represented by 20～90 % by mole of general formulas (1) and 10～80 % by mole can be above with a kind of repetitive copolymerization that general formula (1) represents the repetitive from polymerizable unsaturated compound form, number-average molecular weight be 2,000～20,000 and acid number be 35～120mgKOH/g.Preferably A composition is to utilize conventional method that the polymerizable unsaturated compound take (methyl) acrylic acid derivative as representative is carried out to polymkeric substance that free radical polymerization obtains or multipolymer as basic framework.At this, (methyl) acrylic acid refers to acrylic or methacrylic acid (below too).While carrying out free radical polymerization, can use the known radical polymerization initiator such as azo-compound, superoxide.In addition, can utilize known chain-transferring agent, polymerization inhibitor etc. to control the degree of polymerization.Should illustrate, contain the ratio that repetitive that 20～90 % by mole of general formulas (1) represent represents to form the number of repeat unit of the general formula (1) in total number of repeat unit of multipolymer (A).Below, by repetitive also referred to as unit.
When the unit that general formula (1) is represented imports A composition, also have 1,3-bis-(methyl) acrylic acid glyceride directly carries out free radical polymerization method as raw material, but for the gelation that prevents that cross-linking reaction from causing, preferably adopt and make to have from polymkeric substance or multipolymer and (methyl) glycidyl acrylate addition of (methyl) acrylic acid unit or make to there are the polymkeric substance of unit or the 2 step synthetic methods of multipolymer and the addition of (methyl) acrylic acid from (methyl) glycidyl acrylate.Described addition reaction can utilize conventional method to carry out, and also can use tertiary amine, quaternary ammonium salt, tertiary phosphine, season
the known catalysts such as salt.
As mentioned above, multipolymer (A) has the repetitive of 20～90 % by mole of general formulas (1) expression and a kind of above repetitive from polymerizable unsaturated compound of 10～80 % by mole of repetitive copolymerization that can represent with this general formula (1).; can copolymerization general formula (1) any unit in addition in this A composition, for example can import the unit from (methyl) acrylic acid, (methyl) acrylate, (methyl) acrylamide, Styrene and its derivatives, maleic anhydride and derivant thereof, vinyl ethers, olefines etc.Consider preferably do not there is absorption in ultraviolet light region from sunproof angle as far as possible, therefore as A composition, preferably only formed by the unit group that does not contain aromatic rings.
As the alcohol (R that forms above-mentioned (methyl) acrylate
3oH) amine (R of composition or formation (methyl) acrylamide
4r
5nH) composition, can utilize known material with no particular limitation.As R
3, R
4and R
5concrete example, can enumerate methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl, the tert-butyl group, amyl group, isopentyl, neopentyl, tertiary pentyl, hexyl, heptyl, octyl group, 2-ethylhexyl, nonyl, decyl, dodecyl, myristyl, cetyl, octadecyl, eicosyl, cyclopropyl, cyclopentyl, cyclopentyl ethyl, cyclohexyl, cyclohexyl methyl, 4-methylcyclohexyl, adamantyl, isobornyl, dicyclo pentyl, double cyclopentenyl, vinyl, allyl, ethinyl, phenyl, tolyl,
saturated or the undersaturated monovalence alkyl such as base, naphthyl, anthryl, phenanthryl, benzyl, 2-phenylethyl, 2-phenyl vinyl, saturated or undersaturated monovalence heterocyclic radical such as pyridine radicals, piperidyl, piperidino, pyrrole radicals, pyrrolidinyl, imidazole radicals, imidazolidinyl, furyl, tetrahydrofuran base, thienyl, tetrahydro-thienyl, morpholinyl, morpholino base (4-position base), quinolyl etc.In addition; also can enumerate the structure that imports the optional position of above-mentioned alkyl and heterocyclic radical etc. using following radicals as substituting group, described group is halogen atom, hydroxyl, sulfenyl (ス Le Off ァ ニ Le base), carbonyl, thiocarbonyl, carboxyl, thiocarboxyl group, dithiocarboxyl, formoxyl, cyano group, nitro, nitroso-, sulfo group, amino, imino group, silicyl, ether, thioether group, ester group, thioester substrate, dithioesters base, amide group, thioamides base, urethane groups, sulfo-urethane groups, urea groups, ghiourea group etc.Such univalent perssad is suitably selected according to the structure of the A composition as target, consider the saturated or undersaturated monovalence alkyl of preferred carbon number 1～20 from the angle of performance and economy, more preferably saturated the or undersaturated monovalence alkyl of carbon number 1～6.In addition, R
4and R
5can be hydrogen atom, R
4and R
5also can in conjunction with and form ring.
Except above-mentioned, also preferred following unit is as copolymer composition, , there is the unit of epoxy radicals (for example, from (methyl) glycidyl acrylate, (methyl) acrylic acid 4-(glycidyl oxygen base) and butyl ］ ester, (methyl) acrylic acid ［ (3, 4-epoxycyclohexyl) methyl ］ ester, 4-(glycidyl oxygen ylmethyl) unit of styrene etc.), there is unit (for example from (methyl) acrylic acid ［ 3-(trimethoxysilyl) propyl group of alkoxysilyl ］ ester, (methyl) acrylic acid 3-(triethoxysilyl) and propyl group ］ ester, 4-(trimethoxysilyl) unit of styrene etc.).
In addition,, as cinnamic derivant, also can use α-methyl styrene, to the compound that has imported alkyl, halogen atom, hydroxyl etc. in cinnamic aromatic rings.In addition, as the derivant of maleic anhydride, can use the monoesters of maleic anhydride and alcohol or acid amides or the sub-acid amides etc. of diester, maleic anhydride and amine.As vinyl ethers, can illustrate alkyl vinyl ether etc., as olefines, the structure that the hydrogen atom that can illustrate ethene, propylene, butadiene and these compounds is replaced by halogen atom, cyano group etc.In addition, also can utilize alkyl vinyl ketone, vinyl acetate etc.
Should illustrate, in epimere, said alkyl represents the saturated or undersaturated alkyl of carbon number 1～20, and described alkyl can have branched structure, ring structure, can be replaced by substituting group arbitrarily.
A composition need contain the unit that 20～90 % by mole of general formulas (1) represent, more preferably contains 30～90 % by mole, particularly preferably contains 30～60 % by mole.The unit that general formula (1) represents is when fewer than above-mentioned scope, the chemical reagent resistance of Lightproof composition, insulativity deficiency.On the other hand, general formula (1), though how the unit representing can not cause the problem in function, if its ratio is excessive, is difficult to take into account by acid number control within the limits prescribed.The upper limit of the unit that therefore, general formula (1) represents is required to be 90 % by mole.
In addition, the number-average molecular weight of A composition need be in 2,000～20,000 scope, more preferably in 5,000～10,000 5 thousand scope.Number-average molecular weight is than the chemical reagent resistance of above-mentioned scope hour Lightproof composition, insulativity deficiency, is difficult to form image by photoetching when large on the contrary.The weight-average molecular weight of A composition is not particularly limited, preferably the scope of dispersion degree (weight-average molecular weight ÷ number-average molecular weight) 1～4.The value of these molecular weight can be utilized GPC(SEC) measure and try to achieve.
In addition, the acid number of A composition is required to be 35～120mgKOH/g, more preferably 50～80mgKOH/g.When acid number departs from this scope, lose the deliquescent balance in alkaline-based developer and be difficult to form image by photoetching.Give acid number to A composition, typical case can carry out with the mol ratio copolymerization of regulation from (methyl) acrylic acid unit by making, but also preferably imports the unit of general formula (2) expression as described below.The unit that general formula (2) represents can synthesize by unit and dicarboxylic anhydride addition that general formula (1) is represented.
(wherein, R
1and R
2represent independently of one another hydrogen atom or methyl, Z represents the divalent residue of dicarboxylic anhydride.）
As dicarboxylic anhydride, can utilize with no particular limitation known material, for example, can enumerate succinic anhydride (Z=ethylidene), maleic anhydride (Z=ethenylidene), cyclohexane-1, 2-dicarboxylic anhydride (Z=cyclohexane-1, 2-bis-bases), cyclohexene-1, 2-dicarboxylic anhydride (Z=cyclohexene-1, 2-bis-bases), cyclohexene-4, 5-dicarboxylic anhydride (Z=cyclohexene-4, 5-bis-bases), norbornane-2, 3-dicarboxylic anhydride (Z=norbornane-2, 3-bis-bases), phthalic anhydride (Z=1, 2-phenylene), benzene-1, 2, 4-tricarboxylic acids-1, 2-acid anhydride (Z=4-carboxyl-1, 2-phenylene), cyclohexane-1, 2, 4-tricarboxylic acids-1, 2-acid anhydride (Z=4-carboxyl cyclohexane-1, 2-bis-bases) etc.
Except said units, also can utilize from make (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 4-hydroxy butyl ester etc. there is the unit of (methyl) acrylate of hydroxyl and the structure of dicarboxylic anhydride addition, from unit of maleic anhydride and derivant thereof etc.
The reason of the Lightproof composition that the applicable touch panel of A composition is used is not yet completely clear and definite, but supposition is because the unit that general formula (1) represents has polymerism unsaturated link at its end, so can utilize fine and close cross-linked structure to form the cured film of chemical reagent resistance, photostability and insulativity excellence.In addition, the use capable of being combined of A composition forms different multipolymers of more than two kinds.
Lightproof composition of the present invention contains the carbon black (B) through insulation processing.For the insulation processing of carbon black, the method (for example Japanese kokai publication hei 9-95625 communique) that known useful resin covers, for example, by the method (Japanese kokai publication hei 11-181326 communique) of oxygenant oxidation processes, utilization has the method (for example Japanese kokai publication hei 9-265006 communique) of the macromolecular compound grafting of reactive group, for example, by the method (Japanese Unexamined Patent Application Publication 2008-517330 communique) of organic group chemical modification, and the method (for example TOHKEMY 2002-249678 communique) covering with graft reaction with resin, the method (such as WO2013/129555 pamphlet) covering with pigment etc., as B composition, can adopt either method.As the index of insulativity, preferably the surface resistivity of the cured film of Lightproof composition shows 10
10more than Ω/sq, preferably can realize the insulation processing of this resistivity.While using the carbon black that does not pass through insulation processing, the surface resistivity of the cured film of Lightproof composition is generally less than 10
8Ω/sq, therefore the necessity of the insulation processing of B composition is clear and definite.B composition can be used in combination two or more.
Lightproof composition of the present invention preferably contains respectively 20～70 % by weight A compositions and B composition in solid constituent, further preferably contains respectively 30～50 % by weight.Composition (about solvent aftermentioned) beyond this solid constituent refers to the contained solvent of Lightproof composition.When the amount of A composition is fewer than above-mentioned scope, chemical reagent resistance, photostability and insulativity deficiency, the design of Lightproof composition of contrary many times becomes difficulty.In addition, light-proofness deficiency when the amount of B composition is fewer than above-mentioned scope, forms image by photoetching when many and becomes difficulty on the contrary.Should illustrate, as the index of light-proofness, preferably the optical density of the cured film of Lightproof composition is more than 2.0/ μ m.
For the object of performance of controlling curability, photoetching, can make Lightproof composition of the present invention contain the compound with polymerism unsaturated link (C) beyond A composition.As C composition, can use with no particular limitation photosensitive composite known compound used in the past, for example, can preferably use diethylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, (methyl) acrylate derivatives such as dipentaerythritol six (methyl) acrylate, bisphenol type epoxy two (methyl) acrylate, Bisphenol F type epoxy two (methyl) acrylate, bisphenol fluorene type epoxy two (methyl) acrylate, phenol phenolic varnish type epoxy gathers (methyl) acrylate, (methyl) acrylic acid epoxy ester derivants such as poly-(methyl) acrylate of cresols phenolic varnish type epoxy etc.In addition, also preferably in above-mentioned (methyl) acrylic acid derivative and structure, there is the resultant of reaction of the compound of (being preferably multiple) isocyanate group, anhydride group etc. etc.Should illustrate, except (methyl) acrylic acid derivative, can also enumerate maleic acid derivatives, maleimide derivatives, crotonic acid derivant, derivatives from itaconic acid, cinnamic acid derivative, ethenyl derivatives, vinyl alcohol derivatives, vinyl ketone derivant, vinyl aromatic derivant etc.These compounds with polymerism unsaturated link can further have alkali-soluble functional group such as functional group, carboxyl of the heat reactivities such as epoxy radicals etc. and Complex Function.The use level of C composition is not particularly limited, and is preferably 1～30 % by weight, more preferably 5～20 % by weight in the solid constituent of Lightproof composition.C composition can only use a kind of compound, also can be used in combination multiple.
For improving the object of photo-curable, can make to contain in Lightproof composition of the present invention Photoepolymerizationinitiater initiater and/or dye-sensitized dose (D).As D composition, can use with no particular limitation photosensitive composite known compound used in the past, for example, can enumerate acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, the acetophenone compounds such as benzyl dimethyl ketal, benzophenone, 2, 4, 6-tri-methyl benzophenone, 4, 4 '-bis-(N, N-diethylamino) benzophenone cpd such as benzophenone, benzoin ethyl ether, the benzoin ether compounds such as the tertiary butyl ether of benzoin, 2-methyl isophthalic acid-and 4-(methyl mercapto) phenyl ］-2-morpholino propane-1-ketone, 2-benzyl-2-(N, N-dimethylamino)-1-(4-morpholino phenyl) the alpha-aminoalkyl benzophenone compound such as butane-1-ketone, thioxanthone, 2, the thioxanthone compounds such as 4-diethyl thioxanthone, 3, 3 ', 4, the organic peroxides such as 4 '-tetra-(t-butyl peroxy carbonyl) benzophenone, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetraphenyl-1, the diimidazole compounds such as 2-diimidazole, two (η
5-cyclopentadienyl group) two ［ 2, the fluoro-3-(1-pyrrole radicals of 6-bis-) phenyl ］ two cyclopentadiene titanium compounds such as titanium, 2, 4, 6-tri-(trichloromethyl)-1, 3, 5-triazine, 2-［ 3, 4-(methylene dioxy base) phenyl ］-4, two (trichloromethyl)-1 of 6-, 3, the triaizine compounds such as 5-triazine, (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, two (2, 4, 6-trimethylbenzoyl) the acylphosphine oxide compound such as phenyl phosphine oxide, the naphtoquinone compounds such as camphorquinone, 1-4-(thiophenyl) and phenyl ］ octane-1, 2-diketone=2-O-benzoyl oxime, 1-9-ethyl-6-(2-methyl benzoyl) and carbazole-3-yl ］ ethyl ketone=O-acetyl oxime, oxime ester compounds such as (9-ethyl-6-nitrocarbazole-3-yl) ［ 4-(2-methoxyl-1-methyl ethoxy)-2-aminomethyl phenyl ］ ketone=O-acetyl oxime etc.In these, from improving the angle of sensitivity of Lightproof composition, particularly preferably oxime ester compound, further preferably has the oxime ester compound of carbazole skeleton as chromophoric group.The use level of D composition is not particularly limited, and is preferably 0.1～20 % by weight, more preferably 1～10 % by weight in the solid constituent of Lightproof composition.D composition can only use a kind of compound, also can be used in combination multiple.
For the object that further improves chemical reagent resistance, can make to contain in Lightproof composition of the present invention epoxy compound (E).As E composition, can be used as with no particular limitation the commercially available known compounds such as epoxy resin, for example, can enumerate bisphenol type epoxy compound, Bisphenol F type epoxy compound, bisphenol fluorene type epoxy compound, phenol phenolic varnish type epoxy compound, cresols phenolic varnish type epoxy compound, the glycidol ether of polyvalent alcohol, the ethylene oxidic ester of polybasic carboxylic acid, for thering is polymkeric substance or the multipolymer of epoxy radicals and not being the compound of A composition, with 3, 4-7-oxa-bicyclo[4.1.0 carboxylic acid (3, 4-epoxycyclohexyl) the methyl esters alicyclic epoxy compound that is representative, 2, 1 of two (the methylol)-n-butyl alcohols of 2-, 2-epoxy-4-(2-epoxy ethyl) cyclohexane addition product (for example DAICEL company system " EHPE3150 "), epoxidized polybutadiene (for example Japanese Cao Da society's system " NISSO-PBJP-100 "), there is the epoxy compound of silicone skeleton etc.As these compositions, preferably epoxide equivalent is that 100～300g/eq and number-average molecular weight are 100～5,000 compound.The use level of E composition is not particularly limited, and is preferably 1～20 % by weight, more preferably 2～10 % by weight in the solid constituent of Lightproof composition.E composition can only use a kind of compound, also can use multiple.
For making B stable components be dispersed in the object in Lightproof composition, can make to contain in Lightproof composition of the present invention spreading agent (F).As F composition, can use with no particular limitation the known compound used of Pigments in the past (with spreading agent, disperse wetting agent, disperse the commercially available compound of the titles such as promoter etc.), for example, can enumerate cationic macromolecular spreading agent, anionic property macromolecular spreading agent, nonionic macromolecular spreading agent, pigment derivative type spreading agent (dispersing aid) etc.Particularly preferably following cationic macromolecular spreading agent, its functional group with cationic such as imidazole radicals, pyrrole radicals, pyridine radicals, primary, secondary or tertiary amino is as the adsorption site to pigment, amine value is 1～100mgKOH/g, and number-average molecular weight is in 1,000～100,000 scope.The example of such cationic macromolecular spreading agent is disclosed in Japanese kokai publication hei 9-169821 communique.The use level of F composition is not particularly limited, and is preferably 1～25 % by weight, more preferably 2～15 % by weight in the solid constituent of Lightproof composition.F composition can only use a kind of compound, also can use multiple.Should illustrate also there is the effect that makes stably dispersing as the such high-viscosity material of resene, disperse to promote that the material of performance is not used as spreading agent but do not have.But, do not limit the object for making stably dispersing.
Can make to contain in Lightproof composition of the present invention solvent (G).As G composition, known compound can be utilized, for example, ester series solvent (butyl acetate, cyclohexyl acetate etc.), ketone series solvent (methyl isobutyl ketone, cyclohexanone etc.), ether series solvent (diethylene glycol dimethyl ether, diethylene glycol B ether etc.), alcohol series solvent (3-methoxybutanol, the tertiary butyl ether of ethylene glycol list etc.), aromatic series series solvent (toluene, dimethylbenzene etc.), aliphatics series solvent, amine series solvent, acid amides series solvent etc. can be used with no particular limitation.From the angle of security, preferably use the solvent that ester is, ether is with propylene glycol skeleton, such as propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene-glycol diacetate etc.In addition, also preferably the acetic acid 3-methoxyl butyl ester of similar structures, acetic acid 3-methoxyl-3-methyl butyl ester, oxalic acid 1,3-BDO ester etc.Solid component concentration about Lightproof composition is not particularly limited, and as touch panel Lightproof composition, generally solid component concentration is adjusted to the scope of 10～30 % by weight.In addition, in order to improve the coating of Lightproof composition, preferably and to be less than boiling point under the solvent of 150 ℃ and 10～70 % by weight normal pressures with boiling point under 30～90 % by weight normal pressures be 150 ℃ of solvents above, control the drying property of Lightproof composition.
Lightproof composition of the present invention can contain other any composition as required, for example, can contain painted material, filler, resin, adjuvant etc.At this, as painted material, can enumerate dyestuff, organic pigment, inorganic pigment etc., as filler, silicon dioxide, talcum etc. can be enumerated, as resin, vinylite, vibrin, polyamide, polyimide resin, urethane resin, polyether resin, melamine resin etc. can be enumerated, as adjuvant, can enumerate crosslinking chemical, surfactant, silane coupling agent, viscosity modifier, wetting agent, defoamer, antioxidant, ultraviolet light absorber etc.As these compositions arbitrarily, can use with no particular limitation known compound.As touch panel Lightproof composition, (fluorine is surfactant to use surfactant, silicon-type surfactant etc.), silane coupling agent (3-(glycidyl oxygen base) propyl trimethoxy silicane, 3-isocyano propyl-triethoxysilicane, 3-urea propyl-triethoxysilicane, 3-aminopropyl triethoxysilane, 3-(phenyl amino) propyl trimethoxy silicane, 3-((methyl) acryloxy) propyl trimethoxy silicane etc.) be favourable, the total of its amount in the solid constituent of Lightproof composition preferably take 10 % by weight as the upper limit.In addition, the compound with (being preferably more than 2) sulfenyl also has the effect of the performance that improves photoetching, is therefore useful.
The method for making of Lightproof composition of the present invention is not particularly limited, can illustrate and previously preparedly make carbon black (B) (preferably using spreading agent (F)) through insulation processing be scattered in the dispersion liquid that solvent (G) etc. forms, coordinate wherein multipolymer (A), Photoepolymerizationinitiater initiater and/or dye-sensitized dose (D) etc. to make the method for Lightproof compositions.In addition, also have the carbon black through insulation processing (B) is scattered in multipolymer (A) etc. is dissolved in to solvent (G) and composition in method.The making of dispersion liquid can be used the method for known Pigments, for example, can enumerate the processing that utilizes three rollers, kneader, ball mill etc.
Can be upper by Lightproof composition of the present invention being coated on to substrate etc., fire etc. and to make it curing and obtain cured film with irradiation, heating.As the method for coating Lightproof composition, can utilize known method, for example can enumerate the coating that utilizes spin coater, excellent coating machine, slit type coater etc.In addition, after coating, preferably use hot plate, pressure Reduction Dryer etc., carry out the dry of Lightproof composition.Wherein, coating and dry method are not particularly limited.
Also known method can be utilized by the method that irradiation is curing, for example, the UV-irradiation take xenon lamp, Halogen lamp LED, tungsten lamp, ultrahigh pressure mercury lamp, high-pressure sodium lamp, medium pressure mercury lamp, low pressure mercury lamp etc. as light source can be enumerated.While carrying out described irradiation, can use photomask etc. to carry out image exposure, further use developer solution processing, on substrate, form thus image.As developer solution, as long as the developer solution that dissolves unexposed portion, do not dissolve exposed portion is just not particularly limited, preferably contain the alkaline aqueous solution of various adjuvants.At this, as the alkaline components of developer solution, for example, can enumerate the oxyhydroxide of alkali-metal carbonate, alkali-metal oxyhydroxide, quaternary ammonium salt etc., as adjuvant, for example, can enumerate organic solvent, surfactant, defoamer, mildewproof agent etc.Developing method also can utilize known method, for example, can enumerate immersion development, spray development, magnetic brush development, ultrasound wave development etc.The method of irradiation and development is also not particularly limited.
In order further to improve and to solidify film strength, preferably after irradiation, heat and fire.The method that heating is fired also can be utilized known method, for example, can enumerate the processing that utilizes hot plate, hot-air oven etc., is not particularly limited.
Condition of cure about Lightproof composition is not particularly limited, and for photocuring, preferably carries out 10～1000mJ/cm
2uV-irradiation, for heat curing, the heating of preferably carrying out at 200～250 ℃ 20～60 minutes is fired.
Should illustrate, as using the cured film of Lightproof composition of the present invention to make the method for touch panel, can utilize known method.
Invention effect
Touch panel of the present invention can form the cured film of chemical reagent resistance, photostability and insulativity excellence with Lightproof composition, therefore exceedingly useful.Particularly can form image by photoetching, so preferred on excellent this aspect of throughput rate of touch panel.
Below, by embodiment, the present invention is described in more detail, but the invention is not restricted to these embodiment.
［ embodiment 1 ］
(making of Lightproof composition)
Coordinate by the composition shown in table 1, be at room temperature uniformly mixed 3 hours solid constituent is dissolved or dispersed in solvent, make Lightproof composition.The numerical value of composition is weight portion, records in the mode that adds up to 100 weight portions of solid constituent.In solid constituent, also have at the beginning and be dissolved in composition synthetic under the state of solvent (propylene glycol methyl ether acetate), now the numeric representation of composition is as the weight portion of solid constituent, and the solvent part of bringing into is documented in the weight portion of solvent.In addition, use and utilize in advance spreading agent to make the dispersion liquid (composition: carbon black 25.0 % by weight, cationic macromolecular spreading agent 4.0 % by weight, copper phthalocyanine derivative thing type spreading agent 1.0 % by weight, propylene glycol methyl ether acetate 70.0 % by weight that are insulated processing by covering resin) forming in solvent through the carbon black dispersion of insulation processing.The composition using in the cooperation of embodiment is below shown.
A-1: by the unit from methacrylic acid { 14 }-from the R of the unit { 30 } of methyl methacrylate-represent from unit { the 20 }-general formula (1) of cyclohexyl methacrylate
1, R
2be the multipolymer (number-average molecular weight 10,000, acid number 50mgKOH/g) of unit { 36 } formation of methyl
(be mol ratio in braces { }, below too)
A-2: by the unit from methacrylic acid { 30 }-from the R of the unit { 22 } of methyl methacrylate-represent from unit { the 28 }-general formula (1) of cyclohexyl methacrylate
1, R
2be the multipolymer (number-average molecular weight 10,000, acid number 120mgKOH/g) of unit { 20 } formation of methyl
A-3: by the unit from methacrylic acid { 10 }-from the R of the unit { 40 } of methyl methacrylate-represent from unit { the 10 }-general formula (1) of acrylic acid dicyclo pentane ester
1, R
2be the multipolymer (number-average molecular weight 5,000, acid number 35mgKOH/g) of unit { 40 } formation of methyl
A-4: by the R of the unit from methacrylic acid { 20 }-represent from unit { the 30 }-general formula (1) of methyl methacrylate
1, R
2be the multipolymer (number-average molecular weight 10,000 5 thousand, acid number 70mgKOH/g) of unit { 50 } formation of methyl
B-1: the carbon black that is insulated processing by covering resin
Represent respectively and A of the present invention, composition that B composition is suitable at this " A-" " B-".
C-1: dipentaerythritol acrylate
D-1:(9-ethyl-6-nitrocarbazole-3-yl) and 4-(2-methoxyl-1-methyl ethoxy)-2-aminomethyl phenyl ］ ketone=O-acetyl oxime
D-2:1-9-ethyl-6-(2-methyl benzoyl) and carbazole-3-yl ］ ethyl ketone=O-acetyl oxime
E-1: phenol phenolic varnish type epoxy compound (society of Mitsubishi Chemical system " jER154 ")
E-2:2,1 of two (the methylol)-n-butyl alcohols of 2-, 2-epoxy-4-(2-epoxy ethyl) cyclohexane addition product (DAICEL company system " EHPE3150 ")
F-1: cationic macromolecular spreading agent
F-2: copper phthalocyanine derivative thing type spreading agent
G-1: propylene glycol methyl ether acetate
G-2: cyclohexanone
Represent respectively the composition suitable with C～G composition of the present invention at this " C-" " D-" " E-" " F-" " G-".
S-1:3-isocyano propyl-triethoxysilicane
S-2: fluorine is surfactant (DIC company system " MEGAFACE F-556 ")
Other that use as required in this " S-" expression composition arbitrarily.
[table 1]
(evaluation of Lightproof composition: chemical reagent resistance)
Use spin coater that above-mentioned Lightproof composition is coated on alkali-free glass substrate, with dry 2 minutes making test films of the hot plates of 90 ℃.Now, regulate coating condition (rotation rotating speed) in the mode of the cured film that obtains thickness 1.5 μ m.Next, be situated between by the photomask of pattern of frame shape with touch panel picture, use illumination 30mW/cm
2ultra high pressure mercury light irradiation 100mJ/cm
2ultraviolet ray (numerical value is take i ray as benchmark) test film is carried out to image exposure., with the alkaline-based developers of 25 ℃ (Nippon Steel live 10 times dilutions of aurification society system " V-2401ID ") test film processed 1 minute, further wash and make image developing thereafter.Finally with the hot-air oven of 230 ℃, test film is fired 30 minutes, obtained the cured film of Lightproof composition.
In 60 ℃ of strippers (30% 2-ethylaminoethanol and the mixed liquor of 70% diethylene glycol monobutyl ether) that the test film of cured film that is formed with Lightproof composition are immersed in to resist 10 minutes, after washing, being dried, the thickness of measuring cured film, carries out 3 grade evaluations by following benchmark.Zero (well): the Thickness Variation impregnated in before and after stripper is below 2%, ▲ (slightly bad): be greater than 2% and be below 5%, × (bad): be greater than 5%.
(evaluation of Lightproof composition: photostability)
Similarly make the test film of the cured film that is formed with Lightproof composition with above-mentioned chemical reagent resistance evaluation.From glass surface, test film was irradiated 500 hours with the xenon lamp of 2.5kW, cured film is easily torn to cloth rubber belt disbonded test, carry out 3 grade evaluations by following benchmark.Zero: without peeling off, ▲: see on a small quantity and peel off, ×: see much and peel off.
(evaluation of Lightproof composition: insulativity)
Similarly make the test film of the cured film that is formed with Lightproof composition with above-mentioned chemical reagent resistance evaluation.Further test film is fired after 180 minutes with the hot-air ovens of 230 ℃, by the surface resistivity of 10V voltage determination cured film, carried out 3 grade evaluations by following benchmark.Zero: surface resistivity is 10
10more than Ω/sq, ▲: be 10
8Ω/sq is above and be less than 10
10Ω/sq, ×: be less than 10
8Ω/sq.
(evaluation of Lightproof composition: processability)
Similarly make the test film of the cured film that is formed with Lightproof composition with above-mentioned chemical reagent resistance evaluation.The image forming with observation by light microscope, carries out 3 grade evaluations by following benchmark.Zero: do not find picture pattern shortcoming, develop residual, ▲: find a little shortcoming, develop residual, ×: find shortcoming, develop residual.
The evaluation result of the Lightproof composition of embodiment 1 is shown in to table 2.The Lightproof composition of embodiment 1 all meets the desired chemical reagent resistance of touch panel purposes, photostability and insulativity, and the processability of photoetching is also excellent.In addition, the optical density of the cured film of Lightproof composition is 3.1/ μ m.
[table 2]
［ embodiment 2～8 ］
Change respectively as shown in table 1 the composition of embodiment 1, other carry out making and the evaluation of the Lightproof composition of embodiment 2～8 similarly to Example 1.Evaluation result is shown in to table 2.The Lightproof composition of embodiment 2～8 all meets the desired chemical reagent resistance of touch panel purposes, photostability and insulativity, and the processability of photoetching is also excellent.In addition, about the optical density of the cured film of Lightproof composition, in embodiment 2～4, be 3.1/ μ m, in embodiment 5～8, be 2.4/ μ m.
［ comparative example 1～4 ］
Change respectively as shown in table 3 the composition of embodiment 1, other compare making and the evaluation of the Lightproof composition of example 1～4 similarly to Example 1.The composition that the cooperation of comparative example is used is below shown.
AX-1: by the unit from methacrylic acid { 16 }-from the multipolymer (number-average molecular weight 10,000, acid number 60mgKOH/g) of the unit { 16 } of methyl methacrylate-form from the unit { 68 } of benzyl methacrylate
AX-2: by the unit from methacrylic acid { 18 }-from the R of the unit { 50 } of methyl methacrylate-represent from unit { the 20 }-general formula (1) of cyclohexyl methacrylate
1, R
2be the multipolymer (number-average molecular weight 10,000, acid number 80mgKOH/g) of unit { 12 } formation of methyl
AX-3: the alkali-developable photosensitive resin (solid constituent of aurification society system " V-259ME " is lived by Nippon Steel) with bisphenol fluorene skeleton
BX-1: the carbon black that does not pass through insulation processing
At this, " AX-" " BX-" represents respectively the composition of the scope that departs from A of the present invention, B composition.
[table 3]
The evaluation result of the Lightproof composition of comparative example 1～4 is shown in to table 4.The Lightproof composition of comparative example 1～4 cannot meet the desired each characteristic of touch panel purposes.
[table 4]
Utilizability in industry
Lightproof composition of the present invention is not only applicable to forming the light shield layer of touch panel, can also be preferred for forming black matrix, the light-proofness soldering-resistance layer of color filter.In addition, think that also can be used as being coloured to of coating, printing-ink, stationery ink, plastics etc. assigns to utilize, or be applied in the purposes such as optical filter as light absorption material.
Claims (3)
1. a touch panel Lightproof composition, is characterized in that, contains copolymer A and the black B through insulation processing,
Described copolymer A has multiple repetitives, 1 kind of above repetitive from polymerizable unsaturated compound of the repetitive being represented by 20～90 % by mole of following general formulas (1) and 10～80 % by mole of repetitive copolymerization that can represent with described general formula (1) forms, number-average molecular weight be 2,000～20,000 and acid number be 35～120mgKOH/g
Wherein, R
1and R
2represent independently of one another hydrogen atom or methyl.
2. touch panel Lightproof composition according to claim 1, wherein, A composition is only made up of the repetitive group that does not contain aromatic rings.
3. a touch panel, has the cured film of the touch panel Lightproof composition described in claim 1 or 2.
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| JP2012-242525 | 2012-11-02 | ||
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| JP2013-213571 | 2013-10-11 | ||
| JP2013213571A JP6529213B2 (en) | 2012-11-02 | 2013-10-11 | Shading composition for touch panel and touch panel |
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| CN103809374B CN103809374B (en) | 2019-11-05 |
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| KR102138381B1 (en) | 2020-07-27 |
| CN103809374B (en) | 2019-11-05 |
| KR20140057172A (en) | 2014-05-12 |
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