CN101609256A - Diaphragm forms the formation method with radiation sensitive linear resin composition and diaphragm - Google Patents
Diaphragm forms the formation method with radiation sensitive linear resin composition and diaphragm Download PDFInfo
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- CN101609256A CN101609256A CN 200910149137 CN200910149137A CN101609256A CN 101609256 A CN101609256 A CN 101609256A CN 200910149137 CN200910149137 CN 200910149137 CN 200910149137 A CN200910149137 A CN 200910149137A CN 101609256 A CN101609256 A CN 101609256A
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Abstract
The present invention relates to a kind of diaphragm and forms formation method with radiation sensitive linear resin composition and diaphragm, this resin combination as the transparency height of diaphragm, with intermembranous superior, the high rigidity of stickability of electrically conducting transparent, and rub resistance is superior.A kind of diaphragm of touch panel forms and uses radiation sensitive linear resin composition, and it is characterized in that comprising: (A) alkali soluble resins, (B) have vinyl unsaturated compound, (C) radiation sensitive linear polymerization initiator of 1 carboxyl in 1 molecule.
Description
Technical field
The present invention relates to sense ray resin combination very good in a kind of formation of diaphragm of the nesa coating in touch panel and forming method thereof.
Background technology
Aspect touch panel, resistance membrane type, static capacitive, ultrasonic type, optical profile type, induction etc. are arranged, be to be main flow up to now in price with the resistance membrane type.Yet, have shortcomings such as maloperation is more aspect the resistance membrane type, make the manufacturer that adopts static capacitive that the tendency of increase be arranged.Aspect static capacitive; on substrate, form nesa coating as ITO (Indium Tin Oxide) film; in order to protect this kind nesa coating; must on nesa coating, form and possess wear-resisting wiping, and the diaphragm (with reference to Japanese kokai publication hei 6-195174 communique and TOHKEMY 2009-69984 communique) of good adhesion be arranged with substrate.
In TOHKEMY 2009-69984 communique,, utilize sputtering method or CVD method to form silicon oxide film as diaphragm.In the case, when glass substrate maximizes, will need long film formation time, and the problem that causes reducing production efficiency will be arranged.In addition, utilize the formed diaphragm of this method, because and the stickability extreme difference between the substrate, or the cause of hardness deficiency easily produces scar when conveyance or when carrying, peels off, the problem that exists the reliability as touch panel to reduce.
Since above-mentioned condition and strong expectation develop transparency height as diaphragm, with intermembranous superior, the high rigidity of stickability of electrically conducting transparent, and the diaphragm of the touch panel of wear-resisting wiping excellence forms and uses radiation sensitive linear resin composition.
[patent documentation 1] Japanese kokai publication hei 6-195174 communique
[patent documentation 2] TOHKEMY 2009-69984 communique
Summary of the invention
The present invention is for addressing the above problem, provide a kind of transparency height as diaphragm, with intermembranous superior, the high rigidity of stickability of electrically conducting transparent, and form at the diaphragm of the touch panel of excellence aspect the wear-resisting wiping and to use radiation sensitive linear resin composition.
According to the present invention, above-mentioned purpose of the present invention and advantage are to realize by following several aspects:
The first, a kind of diaphragm of touch panel forms and uses radiation sensitive linear resin composition, and it is characterized in that diaphragm comprises: (A) alkali soluble resins, (B) have compound, (C) radiation sensitive linear polymerization initiator of the ethene unsaturated group of selecting more than 1 from following formula (1) and following formula (2).
(at this, X is selected from alkyl, acryloyl group or the methacryl of hydrogen atom, carbon number 1～6, and at least 1 X is acryloyl group or methacryl.W represent carbon number 1～6 alkylidene, contain alkylidene, phenylene or the cyclohexyl of the carbon number 2～6 of 1 unsaturated link).
The second, the diaphragm of a kind of touch panel of being put down in writing according to technical scheme 1 forms and uses radiation sensitive linear resin composition; it is characterized in that (A) alkali soluble resins is to contain (a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, and the monomer that (a2) contains the unsaturated compound of epoxy radicals carries out copolymerization and the multipolymer that forms.
Three, a kind of diaphragm of touch panel forms and uses radiation sensitive linear resin composition, it is characterized in that containing (D) multifunctional cationically polymerizable compound, still, does not comprise and the identical situation of (A) alkali soluble resins.
Four, the diaphragm of the touch panel of being put down in writing according to technical scheme 3 forms and use radiation sensitive linear resin composition, it is characterized in that containing (E) by heating acidic compound.
Five, a kind of touch panel diaphragm, it is formed by described radiation sensitive linear resin composition.
Six, a kind of formation method of diaphragm, it is to use described radiation sensitive linear resin composition to form overlay film, then carries out the treatment with irradiation and the heat treated of radioactive ray.
Embodiment
In the present invention, as the baseplate material of the substrate with nesa coating glass etc. being arranged, is the ITO film as nesa coating.And the part of this substrate is also formed by silicon dioxide sometimes.
In the present invention, then form diaphragm on the surface of nesa coating, coating is in order to the radiation sensitive linear resin composition that forms diaphragm (below, abbreviate " diaphragm forms and use composition " as), by exposure, developing and heating forms diaphragm.
Diaphragm of the present invention forms and uses composition, contains alkali soluble resins, has the multi-functional acryl monomer and the radiation sensitive linear polymerization initiator of carboxyl.
In the present invention, as alkali soluble resins (below, abbreviate multipolymer (A) as),, be not particularly limited as long as employed alkaline-based developer in the development treatment operation of the radiation sensitive linear resin composition that contains this composition is had solubility.
Also have, the alkali soluble resins among the present invention preferably has reactive functional group,, for example can enumerate epoxy radicals, (methyl) acryloyl group etc. as reactive functional group.When reactive functional group is under the situation of epoxy radicals, can be by will having the free radical polymerization monomer of epoxy radicals, and other free radical polymerization monomer carries out copolymerization and obtains.When reactive functional group is under the situation of (methyl) acryloyl group; can be with after containing the free radical polymerization monomer of hydroxyl and other free radical polymerization monomer and carrying out copolymerization, can make the isocyanate compound that contains (methyl) acryloyl group and the hydroxyl reaction in the polymkeric substance and obtain.
As (a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (below, abbreviate compound (a1) as), for example can enumerate monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, 2-acryloxy ethyl succinate, 2-methacryloxy ethyl succinate, 2-acryloxy hexahydro-phthalic acid ethyl ester, 2-methacryloxy hexahydro-phthalic acid ethyl ester; Dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; The acid anhydrides of described dicarboxylic acid etc.
Among these compounds (a1), from copolymerization, to the dissolubility viewpoint of the alkaline-based developer of the polymkeric substance of gained and multipolymer, be good with acrylic acid, methacrylic acid, 2-acryloxy ethyl succinate, 2-methacryloxy ethyl succinate, maleic anhydride etc.
In multipolymer (A), compound (a1) can separately or mix two or more the use.In multipolymer (A), be good from the containing ratio of the repetitive of compound (a1) with 5～60 quality %, for better, serve as special good with 7～50 quality % with 8～40 quality %.The radiation sensitive linear resin composition that all characteristics such as storage stability that can obtain to have the sensitivity of sense ray, development and radiation sensitive linear resin composition when the containing ratio from the repetitive of compound (a1) is 5～60 mass parts are high level.
As (a2) contain epoxy radicals unsaturated compound (below, abbreviate compound (a2) as), for example can enumerate, glycidyl acrylate, acrylic acid 2-methyl ethylene oxidic ester, acrylic acid 3,4-epoxy butyl ester, acrylic acid 6,7-epoxy heptyl ester, acrylic acid 3,4-epoxy cyclohexyl, acrylic acid 3,4-epoxycyclohexyl methyl esters, acrylic acid 2, acrylic acid epoxy Arrcostabs such as 3-epoxy propyl ester; Glycidyl methacrylate, methacrylic acid 2-methyl ethylene oxidic ester, methacrylic acid 3,4-epoxy butyl ester, methacrylic acid 6,7-epoxy heptyl ester, methacrylic acid 3,4-epoxy cyclohexyl, methacrylic acid 3,4-epoxycyclohexyl methyl esters, methacrylic acid 2, methacrylic acid epoxy alkyl esters such as 3-epoxy propyl ester; α-Yi Jibingxisuan ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, α-Yi Jibingxisuan 6, alpha-alkyl acrylic acid epoxy Arrcostabs such as 7-epoxy heptyl ester;
Adjacent ethylene benzyl glycidol ether, an ethylene benzyl glycidol ether are to glycidol ethers such as ethylene benzyl glycidol ethers etc.
In addition, as other free radical polymerization monomer with epoxy radicals, can enumerate, 3-(acryloyl-oxy ylmethyl) oxetanes, 3-(acryloyl-oxy ylmethyl)-3-ethyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-methyl oxetanes, 3-(acryloxy ethyl) oxetanes, 3-(acryloxy ethyl)-3-ethyl oxetanes, 2-ethyl-3-(acryloxy ethyl) oxetanes etc. have the acrylate of oxa-cyclobutyl etc.In addition, can enumerate 3-(methacryloxy methyl) oxetanes, 3-(methacryloxy methyl)-3-ethyl oxetanes, 3-(methacryloxy methyl)-2-methyl oxetanes, 3-(methacryloxyethyl) oxetanes, 3-(methacryloxyethyl)-3-ethyl oxetanes, 2-ethyl-3-(methacryloxyethyl) oxetanes etc. and have methacrylate of oxa-cyclobutyl etc.
In multipolymer (A), compound (a2) is separately or to mix two or more the use.In multipolymer (A), be good from the containing ratio of the repetitive of compound (a2) with 0.5～70 quality %, for better, serve as special good with 1～60 quality % with 3～50 quality %.When the containing ratio from the repetitive of compound (a2) was 0.5～70 quality %, all characteristics such as storage stability of multipolymer thermotolerance, multipolymer and the radiation sensitive linear resin composition that has obtaining were the radiation sensitive linear resin composition of high level.
The employed compound of multipolymer (A) has above-claimed cpd (a1) and (a2) in addition free-radical polymerised unsaturated compound (below, abbreviate compound (a3) as).
At first, as the concrete example of compound (a3), can be set forth in the unsaturated compound that contains 1 above hydroxyl in 1 molecule.As the unsaturated compound that in 1 molecule, contains 1 above hydroxyl, for example can enumerate acrylic acid 2-hydroxyl ethyl ester, acrylic acid 3-hydroxypropyl acrylate, acrylic acid 4-hydroxy butyl ester, the acrylic acid 4-methylol-such hydroxyalkyl acrylate of cyclohexyl methyl esters; Hydroxyalkyl methacrylate that methacrylic acid 2-hydroxyl ethyl ester, methacrylic acid 3-hydroxypropyl acrylate, methacrylic acid 4-hydroxy butyl ester, methacrylic acid 5-hydroxy pentane ester, the own ester of methacrylic acid 6-hydroxyl, methacrylic acid 4-methylol-cyclohexyl methyl esters are such etc.
These contain the unsaturated compound of 1 above hydroxyl in 1 molecule, after multipolymer generates, can react with the isocyanate compound with (methyl) acryloyl group.
From the reactive viewpoint between copolymerization and the isocyanate compound,, be for good with acrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester etc. as the unsaturated compound that in 1 molecule, contains 1 above hydroxyl.
As with the isocyanate compound of the above-mentioned unsaturated compound reaction that contains hydroxyl, for example can enumerate acrylic acid and methacrylic acid derivatives such as 2-acryloxy ethyl isocyanate, 2-methacrylic acid acyloxy ethyl isocyanate.
In addition, commercially available product as 2-acryloxy ethyl isocyanate, trade name karenz AOI (clear and electrician's (strain) system) can be enumerated,, trade name karenz MOI (clear and electrician's (strain) system) can be enumerated as the commercially available product of 2-methacryloxyethyl isocyanates.
As the concrete example of other compound (a3), can enumerate alkyl acrylates such as methyl acrylate, isopropyl acrylate; Alkyl methacrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, the secondary butyl ester of methacrylic acid, metering system tert-butyl acrylate; Cyclohexyl acrylate, acrylic acid 2-first cyclohexyl, acrylic acid three ring [5.2.1.0
2,6] decane-8-base ester, acrylic acid 2-(three ring [5.2.1.0
2,6] decane-8-base oxygen base) acrylate ring type esters such as ethyl ester, isobornyl acrylate; Cyclohexyl methacrylate, methacrylic acid 2-first cyclohexyl, methacrylic acid three ring [5.2.1.0
2,6] decane-8-base ester, methacrylic acid 2-(three ring [5.2.1.0
2,6] decane-8-base oxygen base) methacrylic acid ester ring type esters such as ethyl ester, isobornyl methacrylate;
Acrylic acid such as phenyl acrylate, benzyl acrylate aryl ester; Aryl methacrylate such as phenyl methacrylate, benzyl methacrylate; Dicarboxylic acid dialkyls such as diethyl maleate, DEF, diethyl itaconate;
Tetrahydrofurfuryl methacrylate, methacrylic acid tetrahydrofuran ester, methacrylic acid oxinane-2-methyl esters etc. comprise unsaturated assorted five and hexatomic ring methacrylate of an oxygen atom;
4-acryloyl-oxy ylmethyl-2-methyl-2-ethyl-1,3-dioxolanes, 4-acryloyl-oxy ylmethyl-2-methyl-2-isobutyl-1,3-dioxolanes, 4-acryloyl-oxy ylmethyl-2-cyclohexyl-1,3-dioxolanes, 4-methacryloxy methyl-2-methyl-2-ethyl-1,3-dioxolanes, 4-methacryloxy methyl-2-methyl-2-isobutyl-1,3-dioxolanes etc. comprises the unsaturated assorted five-membered ring methacrylate of two oxygen atoms;
Styrene, α-Jia Jibenyixi, a methyl styrene, p-methylstyrene, to vinyl aromatic compounds such as methoxy styrene, 4-isopropenyl phenols; N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimide-3-maleimide benzoic ether, N-succinimide-N position-substituted maleimide amine such as 4-maleimide butyric ester;
Except 1,3-butadiene, isoprene, 2, outside 3-dimethyl-1,3-butadiene equiconjugate dienes compound, vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide etc.
Among these other free radical polymerization monomers, good the following is: styrene, 4-isopropenyl phenol, methacrylic acid three ring [5.2.1.0 from the viewpoint of copolymerization, development
2,6] decane-8-base ester (three cyclohexyl methyl decyl acrylates), glycidyl methacrylate, methacrylic acid 2-methyl ethylene oxidic ester, methacrylic acid 3,4-epoxy cyclohexyl, methacrylic acid 2,3-epoxy propyl ester, methacrylic acid 3,4-epoxycyclohexyl methyl esters, 3-methyl-3-methacryloxypropyl methyl oxetanes, 3-ethyl-3-methacryloxypropyl methyl oxetanes, tetrahydrofurfuryl methacrylate, 1, the 3-butadiene, acrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-(6-hydroxyethyl hexylyloxy) ethyl ester, 4-acryloyl-oxy methyl-2-methyl-2-ethyl-1, the 3-dioxolanes, N-cyclohexyl maleimide, N-phenylmaleimide etc.
In multipolymer (A), compound (a3) is separately or to mix two or more the use.In multipolymer (A), be good from the containing ratio of the repetitive of compound (a3) with 1～70 quality %, for better, serve as special good with 3～60 quality % with 5～50 quality %.When the containing ratio from the repetitive of compound (a3) was 1～70 quality %, the radiation sensitive linear resin composition that is obtained had the storage stability etc. of thermotolerance, multipolymer and the radiation sensitive linear resin composition of the multipolymer of high level.
In the present invention the diaphragm of touch panel form with the general expression that is adopted in the composition (1) reach the compound shown in (2) (below; abbreviate (B) composition as) be multifunctional (methyl) acrylate compounds that in molecule, has 1 above carboxyl, can be formed in and improved on the high level more the stickability of the substrate of formed diaphragm and the diaphragm of diaphragm skin hardness.
Multifunctional (methyl) acrylate compounds that in molecule, has 1 above carboxyl; be can make the compound that has the anhydride group more than 1 in the molecule at least a, and in molecule, have hydroxyl and more than 2 multifunctional (methyl) acrylate that contains hydroxyl of (methyl) acryloyl group at least a the reaction and obtain.
As the concrete example of the compound that in molecule, has 1 above anhydride group, can enumerate compounds such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalate anhydride, tetrahydrochysene phthalate anhydride.Wherein, be good with succinic anhydride especially.
In addition; as in molecule, having hydroxyl and the concrete example of multifunctional (methyl) acrylate that contains hydroxyl of (methyl) acryloyl group more than 2; can enumerate trimethylolpropane diacrylate, trimethylolpropane dimethylacrylate, pentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol five acrylate etc.
Multifunctional (methyl) acrylate compounds that in molecule, has 1 above carboxyl as (B) composition, for example can enumerate, mono succinate [3-(the 3-acryloxy-2 that contains 5 functional acrylates of carboxyl, the two acryloyl-oxy ylmethyl-propoxyl group of 2-)-2,2-pair-acryloyl-oxy ylmethyl-propyl group] ester.
Form with in the composition at the diaphragm of touch panel, (B) use amount of composition for respect to multipolymer (A) 100 mass parts with 50～300 mass parts be good, with 60～250 mass parts for better.When the use amount of (B) composition was 50～300 mass parts, the radiation sensitive linear resin composition that is obtained had all characteristics that the stickability of diaphragm and pencil hardness are high level such as higher.
(C) radiation sensitive linear polymerization initiator
In the present invention; the diaphragm of touch panel form with (C) radiation sensitive linear polymerization initiator that is adopted in the composition (below; abbreviate (C) composition as); its composition is by the exposure by visible light, ultraviolet ray, far ultraviolet, charged particle line, X ray isoradial, and the spike of the polymerization that generation can the initiated polymerization unsaturated compound forms.As this radiation sensitive linear polymerization initiator, can enumerate as sense ray radical polymerization initiator.As sense ray radical polymerization initiator, can enumerate as O-acyl group oxime compound, acetophenone compounds, bisglyoxaline compounds, styrax compounds, benzophenone compound etc.
Concrete example as above-mentioned O-acyl group oxime compound; can enumerate; 1; 2-octane diketone; 1-[4-(thiophenyl)-; 2-(O-benzoyl oxime)]; ethyl ketone-1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl)-1-(O-acetyl oxime); 1-(9-ethyl-6-benzoyl-9.H.-carbazole-3-yl)-octane-1-ketoxime-O-acetate; 1-(9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl)-ethane-1-ketoxime-O-benzoic ether; 1-(9-normal-butyl-6-(2-ethylamino benzonitrile acyl group)-9.H.-carbazole-3-yl)-ethane-1-ketoxime-O-benzoic ether; ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-(9-ethyl-6-(2-methyl-4-oxinane benzoyl)-9.H.-carbazole-3-yl)-1-(O-acetyl oxime); ethyl ketone-1-(9-ethyl-6-(2-methyl-5-tetrahydrofuran benzoyl)-9.H.-carbazole-3-yl)-1-(O-acetyl oxime); ethyl ketone-1-(9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-1, the 3-dioxolanyl) the methoxybenzoyl base }-9.H.-carbazole-3-yl)-1-(O-acetyl oxime) etc.
In these; as suitable O-acyl group oxime compound; can enumerate; 1; 2-octane diketone; 1-[4-(thiophenyl)-; 2-(O-benzoyl oxime)], ethyl ketone-1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl)-1-(O-acetyl oxime), ethyl ketone-1-(9-ethyl-6-(2-methyl-4-tetrahydrofuran methoxybenzoyl base)-9.H-carbazole-3-yl)-1-(O-acetyl oxime) or ethyl ketone-1-(9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-1, the 3-dioxolanyl) the methoxybenzoyl base }-9.H.-carbazole-3-yl)-1-(O-acetyl oxime).These O-acyl group oxime compounds can separately or mix two or more the use.
As above-mentioned acetophenone compound, for example can enumerate α-ammonia ketonic compound, α-hydroxyl ketonic compound.
Concrete example as α-ammonia ketonic compound, can enumerate 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-Ding-1-ketone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-Ding-1-ketone, 2-methyl isophthalic acid-(4-methyl thio phenyl)-2-morpholino third-1-ketone etc.
Concrete example as α-hydroxyl ketonic compound, can enumerate 1-phenyl-2-hydroxy-2-methyl third-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxyl hexamethylene benzophenone etc.
Among these acetophenone compounds, with α-ammonia ketonic compound is good, serves as special good with 2-benzyl 2-dimethylamino-1-(4-morpholino phenyl)-Ding-1-ketone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-Ding-1-ketone, 2-methyl isophthalic acid-(4-methyl thio phenyl)-2-morpholino third-1-ketone.
As the concrete example of above-mentioned united imidazole, can enumerate 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl 1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.
In radiation sensitive linear resin composition of the present invention, under the situation of using united imidazole as (C) radiation sensitive linear polymerization initiator, for sensitization can be added aliphatics with dialkylamino or aromatics (below, abbreviate " Ammonia sensitizer " as).
As the Ammonia sensitizer, for example can enumerate, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (lignocaine) benzophenone etc.In these Ammonia sensitizers, especially with 4,4 '-two (lignocaine) benzophenone is good.
Also have, in radiation sensitive linear resin composition of the present invention and under the situation with united imidazole and Ammonia sensitizer,, can add mercaptan compound as the hydroperoxyl radical donor.Though united imidazole sensitization by the Ammonia sensitizer, cracking, generation imidazole radical do not present high polymerization threshold energy in this state, and the situation of the bad shape that the pattern top of rewarding diaphragm becomes big, the pattern bottom diminishes.Yet, in the system for coexistence,, can in imidazole radical, supply with hydroperoxyl radical by mercaptan compound by adding mercaptan compound at united imidazole and Ammonia sensitizer.Its result, imidazole radical is converted into neutral imidazoles, produces the composition with the high sulphur free radical of polymerization threshold energy simultaneously, the shape of diaphragm can be formed better shape thus.
As described mercaptan compound, for example can enumerate 2-mercaptobenzothiazole, 2-mercaptobenzoxazole base, 2-mercaptobenzimidazole base, 2-sulfydryl-aromatic mercaptans compounds such as 5-methoxyl benzo thiazole; The single mercaptan compound of aliphatics such as 3-mercaptopropionic acid, 3-mercapto-propionate; Pentaerythrite four (mercaptoacetate), the above analiphatic sulphur alcoholic compound of pentaerythrite four 2 officials such as (3-mercaptopropionic acid esters) energy.Among these mercaptan compounds, be good with 2-mercaptobenzothiazole especially.
When and situation with united imidazole and Ammonia sensitizer under, the addition of Ammonia sensitizer is to be good with respect to united imidazole 100 mass parts with 0.1～50 mass parts, with 1～20 mass parts for better.When the addition of Ammonia sensitizer was 0.1～50 mass parts, the diaphragm that is obtained was shaped as well.
In addition, when and situation with united imidazole and Ammonia sensitizer and mercaptan compound under, as the addition of mercaptan compound, be good with 0.1～30 mass parts with respect to united imidazole 100 mass parts, with 1～20 mass parts for better.When the addition of mercaptan compound was 0.1～30 mass parts, diaphragm shape, stickability were the best.
(C) the full usage ratio of composition is good with respect to multipolymer (A) 100 mass parts with 0.1～50 mass parts, with 1～30 mass parts for better.When (C) radiation sensitive linear polymerization initiator use amount is 0.1～50 mass parts,, radiation sensitive linear resin composition of the present invention has high rigidity and adhesive diaphragm under the situation of low exposure even also can forming.
As (D) multifunctional cationically polymerizable compound (below, abbreviate (D) composition as), can enumerate following (still, not comprising and the identical situation of (A) alkali soluble resins).
As the compound that in molecule, has 2 above epoxy radicals, for example can enumerate the diglycidyl ether of bisphenol compounds such as bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, bisphenol-S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, A Hydrogenated Bisphenol A F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether; 1, the polyglycidyl ether of polyvalent alcohols such as 6-hexane diol diglycidyl ether, glycerine triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether; By polyglycidyl ether in the polyether polyols of the alkylene oxide gained of aliphatic polyol addition more than a kind or 2 kinds such as ethylene glycol, propylene glycol, glycerine; Phenolic resin varnish type epoxy resin; The cresols phenolic resin varnish type epoxy resin; Polyphenol type epoxy resin; The diglycidyl ester of aliphatic long-chain dibasic acid; The glycidyl esters of higher fatty acid; Epoxidised soybean oil, epoxidized linseed etc.
As the compound commercially available product that in described molecule, has 2 above epoxy radicals, for example, as bisphenol A type epoxy resin, can enumerate EPIKOTE 1001, EPIKOTE 1002, EPIKOTE 1003, EPIKOTE 1004 (more than, Japan Epoxy Resins (strain) system) etc.; As bisphenol f type epoxy resin, can enumerate EPIKOTE 807 (Japan Epoxy Resins (strain) system) etc.;
As phenolic resin varnish type epoxy resin, can enumerate EPIKOTE 152, EPIKOTE 154, EPIKOTE 157S65 (more than, Japan Epoxy Resins (strain) system), EPPN 201, EPPN202 (more than, Japanese chemical drug (strain) system) etc.; As the cresols phenolic resin varnish type epoxy resin, can enumerate EOCN 102, EOCN 103S (more than, Japanese chemical drug (strain) system), EPIKOTE 180S75 (Japan Epoxy Resins (strain) system) etc.; As poly-phenol-type epoxy resin, can enumerate EPIKOTE 1032H60, EPIKOTE XY-4000 (more than, Japan Epoxy Resins (strain) system) etc.; As cyclic aliphatic epoxy resin, can enumerate CY-175, CY-177, CY-179, araldite CY-182, araldite CY-192,184 (more than, Ciba SpecialtyChemicals (strain) system) etc.
As in molecule, containing more than 23, the compound of 4-epoxycyclohexyl, for example can enumerate 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, two (3,4-epoxycyclohexyl methyl) hexane diacid, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) hexane diacid, 3,4-epoxy-6-methylcyclohexyl-3 ', 4 '-epoxy-6 '-methylcyclohexanecarboxylic acid ester, di-2-ethylhexylphosphine oxide (3, the 4-7-oxa-bicyclo[4.1.0) etc.
In these epoxy compounds, be good with phenolic resin varnish type epoxy resin and polyphenol type epoxy resin.
By the acidic compound of heating (below, abbreviate temperature-sensitive acid agent and (E) composition as), can enumerate benzyl sulfonium salt class, benzothiazole salt, ammonium salt class, phosphonium salt class etc. as (E).In the middle of these, because the diaphragm of benzyl sulfonium salt class has higher surface hardness and preferably used.
Object lesson as above-mentioned sulfonium salt class, for example can enumerate 4-acetoxyphenyl group dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, dimethyl-4-(benzyloxy carbonyl oxygen base) phenyl sulfonium hexafluoro antimonate, dimethyl-4-(benzoyloxy) phenyl sulfonium hexafluoro antimonate, dimethyl-4-(benzoyloxy) phenyl sulfonium hexafluoro arsenate, dimethyl-alkyl sulfonium salts such as 3-chloro-4-acetoxyl group phenyl sulfonium hexafluoro antimonate; Benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, benzyl-4-methoxybenzene ylmethyl sulfonium hexafluoro antimonate, benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl-benzyl sulfonium salts such as 3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro arsenate etc.
In the middle of these, 4-acetoxyphenyl group dimethyl sulfonium hexafluoro antimonate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate etc. are preferably used.
By the suitable acid agent commercially available product of using, can enumerate rising sun electrochemical industry (strain) system trade name: ADEKAOPUTON CP-66, CP-77 as the alkyl sulfonium salt as the temperature-sensitive acid agent.In addition, as the benzyl sulfonium salt, can enumerate three new chemical industry (strain) systems trade name: SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L.(E) usage ratio of composition is good with respect to multipolymer (A) 100 mass parts with 0.1～10 mass parts, with 0.5～5 mass parts for better.When the use amount of (E) composition was 0.1～10 mass parts, radiation sensitive linear resin composition of the present invention can form had the very high pencil hardness and the diaphragm of wear-resisting wiping.
(adjuvant arbitrarily)
In radiation sensitive linear resin composition of the present invention; do not decreasing in the scope of desired effect, in mentioned component, also can cooperate multifunctional acryl monomer, (G) adhesive aid, (H) that (F) have ethene unsaturated group more than 2 and a urethane bonds as required to improve adjuvants such as acid anhydrides that thermotolerance is a purpose, (I) surfactant.
(F) have 2 above ethene unsaturated groups and urethane bonds multifunctional acryl monomer (below; abbreviate multifunctional urethanes acrylate as and reach (F) composition) be (α) polyfunctional isocyanate compound; (β) contain (methyl) acrylate compounds of 1 hydroxyl at molecule, and as required and (γ) polyol reaction and the compound that obtains.
(α) polyfunctional isocyanate compound as the constitute of above-mentioned multifunctional urethanes acrylate, can enumerate 2, the 3-toluene diisocyanate, 2, the 4-toluene diisocyanate, 1, the 2-ethylene diisocyanate, 1, the 3-trimethylene diisocyanate, 1,4-butylidene diisocyanate, 1,5-pentylidene diisocyanate, 1, the 6-hexylidene diisocyanate, methyl diphenylene diisocyanate, hydrogenated diphenyl methane diisocyanate, isophorone diisocyanate, 1, the 2-phenylene vulcabond, 1, the 3-phenylene vulcabond, 1, the 4-phenylene vulcabond, Xylene Diisocyanate, cyclohexane diisocyanate etc.
In the middle of these (α) polyfunctional isocyanate compounds, from the multifunctional urethanes acrylate of gained viewpoints such as intermiscibility to radiation sensitive linear resin composition, with 2,3-toluene diisocyanate, isophorone diisocyanate, 1,6-hexylidene diisocyanate, 1,3-phenylene vulcabond etc. is good.These can use separately, also can be also with multiple.
Again, contain (methyl) acrylate compounds of 1 hydroxyl as (β) at molecule, can enumerate acrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester, acrylic acid 3-hydroxypropyl acrylate, methacrylic acid 3-hydroxypropyl acrylate, acrylic acid 4-hydroxy butyl ester, methacrylic acid 4-hydroxy butyl ester, caprolactone modification acrylic acid 2-hydroxyl ethyl ester, polyglycol mono acrylic ester, polypropylene glycol mono acrylic ester etc.
Contain at these (β) molecules in the middle of (methyl) acrylate compounds of 1 hydroxyl, from the polymerism and the deliquescent viewpoint of the multifunctional urethanes acrylate of gained, be good with acrylic acid 2-hydroxyl ethyl ester, acrylic acid 3-hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol five acrylate etc.These can use separately, also can be also with multiple.
Also have,, can enumerate polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol etc. as (γ) polyvalent alcohol that can react as required.In the middle of these polyether polyols, be that polyglycol, polypropylene glycol etc. below 10,000 is good with weight-average molecular weight.
Above-mentioned multifunctional urethanes acrylate is known method to synthesize, its preparation method is in the lump with (α) polyfunctional isocyanate compound of ormal weight, (β) contains 1 above hydroxyl at molecule (methyl) acrylate compounds, and (γ) polyvalent alcohol as required packs into, 60 ℃～100 ℃ heating, be stirred to free isocyanate groups and disappear till.Reaction time is generally 60～240 minutes degree.
In addition, as required, can add hydroquinone monomethyl ether or dibutyl tin dilaurate catalyzer such as (IV) during reaction, also can add in order to prevent to cause the quinhydrones, 1,4-benzoquinone, tert-butyl catechol etc. of gelation because of the dark reaction in the storage.
Commercially available product as above-mentioned multifunctional urethanes acrylate, can enumerate KAYARAD DPHA-40H, UX-2201, KAYARAD UX-2301, UX-3204, KAYARAD UX-3301, UX-4101, KAYARAD UX-6101, UX-7101, KAYARAD UX-8101, UX-0937 (more than, Japan's chemical drug (strain) system), ART-RESINUN-9000PEP, ART-RESIN UN-9200A, ART-RESIN UN-3320HS (more than, industry (strain) system on the root) etc.
As the use amount of (F) composition, be good with respect to multipolymer (A) 100 mass parts with 1～50 mass parts, with 5～30 mass parts for better.When the use amount of (F) compound was 1～50 mass parts, the stickability and the pencil hardness that can obtain at the diaphragm of gained were the radiation sensitive linear resin composition that is able to balance under high all characteristic high levels.
Then, as (G) adhesive aid (below, abbreviate (G) composition as), can use the functional silanes coupling agent that for example has reactive substituents.As above-mentioned reactive substituents, for example can enumerate carboxyl, methacryl, isocyanate group, epoxy radicals etc.
As concrete example, for example can enumerate, trimethoxy silane base benzoic acid, gamma-methyl allyl acyloxypropyl trimethoxysilane, ethene triacetoxysilane, ethene trimethoxy silane, γ-isocyanates propyl group three ethoxy silane, γ-Huan Yangbingyangbingjisanjiayangjiguiwan, γ-epoxypropoxy triethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.
This (G) composition is good with respect to multipolymer (A) 100 mass parts with 0.1～50 mass parts, with 1～40 mass parts for better.When the use amount of (G) adhesive aid was 1～50 mass parts, the stickability of the diaphragm of gained was best.
Resin combination of the present invention for improving the thermotolerance of formed diaphragm, can add (H) to improve the acid anhydrides that thermotolerance is a purpose (below, abbreviate (H) composition as).For example can enumerate itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, three carbanilic acid acid anhydrides, maleic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, the such aliphatic dicarboxylic acid acid anhydride of NA acid anhydrides; 1,2,3,4-butane tetracarboxylic acid dianhydride, the such alicyclic polyvalent carboxylic acid's dianhydride of ring penta tetracarboxylic dianhydride; Phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, the such aromatic series polyvalent carboxylic acid acid anhydride of benzophenone tetracarboxylic anhydride; Ethylene glycol bis trimellitate acid anhydride, glycerine three trimellitate acid anhydrides etc. contain the acid anhydrides of ester group.In the middle of these,,, be good with trimellitic anhydride especially with aromatic series polyvalent carboxylic acid acid anhydride from obtaining the viewpoint of the high cured film of thermotolerance.
This (H) composition is good with respect to multipolymer (A) 100 mass parts with 0.1～50 mass parts, is good with 1～40 mass parts more.When the use amount of (H) composition was 1～50 mass parts, the thermotolerance of the diaphragm of gained was best.
Resin combination of the present invention be to improve the coating performance, can contain (I) surfactant (below, abbreviate (I) composition as) again.
As this (I) composition, for example can enumerate fluorine class surfactant, silicon class surfactant.
As above-mentioned fluorine class surfactant, for example, BM CHEMIE corporate system trade name: BM-1000, BM-1100, big Japanese ink chemical industry (strain) system trade name: MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACEF183, NEOS (strain) make trade name: commercially available products such as TTX-218.
As above-mentioned silicon class surfactant, for example can enumerate eastern beautiful DOW CORNING organosilicon (strain) system trade name: SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190, SHIN-ETSU HANTOTAI's chemical industry (strain) system trade name: commercially available products such as KP341.
These (I) compositions are good with respect to multipolymer (A) 100 mass parts with 0.01～10 mass parts, are good with 0.05～5 mass parts more.When the use amount of (I) composition is 0.01～10 mass parts, can be suppressed at the alligatoring of the film that formation is produced when filming on the substrate.
The diaphragm of touch panel used in the present invention forms use composition, by in solvent, mix and dissolving multipolymer (A), (B) composition and (C) one-tenth grade and form.Among above-mentioned solvent, from the reactive of the dissolubility of each composition and each composition and the viewpoints such as easiness of filming and forming, suitable use for example, alcohol, glycol ether, ethylene glycol alkyl ether acetic acid esters, ester and diethylene glycol.Among these, for example benzyl alcohol, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol diethyl ether, diethylene glycol B ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, methoxypropionic acid methyl esters, ethoxyl ethyl propionate, acetate-3 methoxyl butyl ester can be special preferred the use.
Be all the internal homogeneity of further raising thickness with described solvent one, can and use high boiling solvent.As can and the high boiling solvent of usefulness, for example can enumerate N-Methyl pyrrolidone, benzyl ethylether, isophorone, 1-octanol, 1 nonyl alcohol, acetate benzyl ester, benzoic acid ethyl ester, diethyl oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, carbonic allyl ester etc.Among these, be good with N-Methyl pyrrolidone, gamma-butyrolacton.
-(first) operation-
When utilizing rubbing method to form under the situation of overlay film, behind coating radiation sensitive linear resin composition solution of the present invention on the above-mentioned nesa coating, can form overlay film by coated face being heated (prebake).The solids content concn of the composition solution that in rubbing method, is adopted, with 5～50 quality % be good, with 10～40 quality % be preferable, with 15～35 quality % for better.Coating process as composition solution is not particularly limited, and for example can adopt suitable method such as spraying process, rolling method, method of spin coating (spin-coating method), slit die rubbing method, excellent rubbing method, is good with method of spin coating or slit die rubbing method especially.
Especially radiation sensitive linear resin composition of the present invention is specially adapted to the slit die rubbing method, even the translational speed of slit die is made as under the 150mm/ situation of second, also can not produce the situation of crawling.
Thus formed overlay film is preferably and then carries out baking in advance.Pre-roasting condition should each composition kind, cooperation ratio etc. different, be preferably and carrying out about 1～10 minute under 70～120 ℃.
Thickness after pre-the baking of overlay film is good with 0.5～10.0 μ m, is better with 1.0～5.0 μ m degree.
-(second) operation-
Then, at least a portion of established overlay film is exposed.In the case, the local time of exposure overlay film normally gets involved the photomask with given pattern and exposes.
As employed radioactive ray in the exposure, for example can use visible light, ultraviolet ray, far ultraviolet, electron beam, X ray etc., but be that the radioactive ray of 190～450nm scope are good with wavelength, be good especially to contain the ultraviolet radioactive ray of 365nm.
Exposure is, the value that the intensity of the wavelength 365nm of the radioactive ray that are exposed is measured with illuminometer (OAI model 356 OAI Optical Associates Inc. systems), and with 100～10,000J/m
2For good, with 500～3,000J/m
2For better.
-(third) operation-
Then, by the overlay film after the exposure of developing, remove unwanted part and form predetermined pattern.
As the developer solution that is used in development, be good with alkaline-based developer, can enumerate inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium methyl silicate, ammonia as its example; The aqueous solution of alkali compounds such as quaternary ammonium salt such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide.
In addition, in the aqueous solution of described alkali compounds, can suitably add water-miscible organic solvents such as methyl alcohol, ethanol or surfactant and use.
As developing method, can use any methods such as flow liquid method (puddle), infusion process, spray process, development time is preferable with the degree in 10～180 seconds.
After the development, for example carry out 30～90 seconds clean with flowing water after, by carrying out air-dry operation, and form desired pattern as pressurized air or compressed nitrogen.
Embodiment
Below, disclose synthesis example, embodiment, specify the present invention more, but the present invention only is limited to following embodiment.
The manufacturing of (being total to) polymkeric substance
Synthesis example 1
In the flask that possesses condenser pipe and stirrer, pack 2 earlier into, two (2, the 4-methyl pentane nitrile) 5 mass parts of 2 '-azo and diethylene glycol ethylmethyl ether 200 mass parts.The glycidyl methacrylate of then packing into 40 mass parts, styrene 18 mass parts, methacrylic acid 20 mass parts and N-cyclohexyl maleimide 22 mass parts, carry out beginning to stir lentamente after nitrogen replaces again.Make solution temperature rise to 70 ℃, kept this temperature five hours, obtain to contain the polymer solution of multipolymer (A-1).The solids content concn of resulting polymer solution is 33.1 quality %.The number-average molecular weight of resulting polymkeric substance is 7,000 (number-average molecular weight is to use GPC (gel permeation chromatograph) HLC-8020 (TOSOH (strain) system) and the polystyrene conversion molecular weight of mensuration).In addition, molecular weight distribution (Mw/Mn) is 2.
Synthesis example 2
In the flask that possesses condenser pipe and stirrer, pack 2 earlier into, 2 '-azobis isobutyronitrile, 5 mass parts and diethylene glycol ethylmethyl ether 200 mass parts.Then, glycidyl methacrylate 40 mass parts, the methacrylic acid three ring [5.2.1.0 that pack into
2,6] decane-8-base ester 35 mass parts, methacrylic acid 20 mass parts and 1,3-butadiene 5 mass parts, carry out beginning to stir lentamente after nitrogen replaces again.Make solution temperature rise to 80 ℃, kept this temperature five hours, obtain to contain the polymer solution of multipolymer (A-2).The solids content concn of resulting polymer solution is 33.3 quality %.The number-average molecular weight of resulting polymkeric substance is 6,500.In addition, molecular weight distribution (Mw/Mn) is 2.
Synthesis example 3
In the flask that possesses condenser pipe and stirrer, pack 2 earlier into, two (2, the 4-methyl pentane nitrile) 5 mass parts of 2 '-azo and diethylene glycol ethylmethyl ether 200 mass parts.Then, the 3-that packs into (methylacryoyloxyethyl) oxetanes 40 mass parts, styrene 10 mass parts, methacrylic acid 30 mass parts and cyclohexyl maleimide 20 mass parts carry out beginning to stir lentamente after nitrogen replaces again.Make solution temperature rise to 70 ℃, kept this temperature five hours, obtain to contain the polymer solution of multipolymer (A-3).The solids content concn of resulting polymer solution is 33.1 quality %.The number-average molecular weight of resulting polymkeric substance is 7,300.In addition, molecular weight distribution (Mw/Mn) is 2.
Synthesis example 4
In the flask that possesses condenser pipe and stirrer, pack 2 earlier into, 2 '-azoisobutyronitrile, 5 mass parts and diethylene glycol ethylmethyl ether 200 mass parts.Then, the glycidyl methacrylate of packing into 50 mass parts, styrene 50 mass parts carry out beginning to stir lentamente after nitrogen replaces again.Make solution temperature rise to 80 ℃, kept this temperature five hours, obtain to contain the polymer solution of multipolymer (A-4).The solids content concn of resulting polymer solution is 32.8 quality %.The number-average molecular weight of resulting polymkeric substance is 7,000.In addition, molecular weight distribution (Mw/Mn) is 2.
Synthesis example 5
In the flask that possesses condenser pipe and stirrer, pack 2 earlier into, two (2, the 4-methyl pentane nitrile) 5 mass parts of 2 '-azo and monomethyl ether propylene glycol acetic acid esters 200 mass parts.Then, benzyl methacrylate 30 mass parts of packing into, styrene 10 mass parts, phenyl maleimide 30 mass parts and methacrylic acid 2-hydroxyl ethyl ester 20 mass parts, methacrylic acid 10 mass parts carry out beginning to stir lentamente after nitrogen replaces again.Make solution temperature rise to 70 ℃, kept this temperature five hours, obtain to contain the polymer solution of multipolymer (A-5).The solids content concn of resulting polymer solution is 33.1 quality %.The number-average molecular weight of resulting polymkeric substance is 7,000.In addition, molecular weight distribution (Mw/Mn) is 2.
Synthesis example 6
In the flask that possesses condenser pipe and stirrer, pack 2 earlier into, 2 '-azoisobutyronitrile, 5 mass parts and acetate 3-methoxy butyl ester 250 mass parts, then, methacrylic acid 18 mass parts of packing into, methacrylic acid three ring [5.2.1.0
2,6] decane-8-base ester 25 mass parts, styrene 5 mass parts, methacrylic acid 2-hydroxyl ethyl ester 30 mass parts and benzyl methacrylate 22 mass parts, after carrying out the nitrogen replacement, one side stirs, simultaneously makes solution temperature rise to 80 ℃ slowly, this temperature maintenance is carried out polymerization in five hours, obtain the multipolymer that solids content concn is 28.8 quality % (A-6) solution thus.The number-average molecular weight of the multipolymer of gained (A-6) gained is 7,000.In addition, molecular weight distribution (Mw/Mn) is 2.
Secondly, in described multipolymer (A-6) solution, after adding 14 parts of 2-methylacryoyloxyethyl isocyanates (trade name Karenz MOI, clear and electrician's (strain) system) and 4-mequinol 0.1 mass parts, in 40 ℃, stir one hour, make its reaction to stir two hours in 60 ℃ again.From the carrying out of the hydroxyl reaction of the isocyanate group of 2-methylacryoyloxyethyl isocyanates and multipolymer (A-6), be to confirm by IR (infrared ray absorbing) spectrum.Polymer solution (A-6), 40 ℃ of solution and 60 ℃ of solution that react after two hours down that react down after a hour utilize IR spectrum respectively, confirm the 2270cm from the isocyanate group of 2-methylacryoyloxyethyl isocyanates
-1Near peak value has the situation of minimizing.And the acquisition solids content concn is (A-6) polymer solution of 30.0%.
Synthesis example 7
Possess on the flask of condenser pipe and stirrer, pack 2 into, two (2, the 4-methyl pentane nitrile) 5 mass parts of 2 '-azo are with diethylene glycol ethylmethyl ether 200 mass parts.Then, the methacrylic acid 2 of packing into, 3-glycidyl 25 mass parts, N-cyclohexyl maleimide 10 mass parts, to different propylene phenol 10 mass parts and tetrahydrofurfuryl methacrylate 20 mass parts, 3-ethyl-3-methacryloxypropyl methyl oxetanes 20 mass parts, methacrylic acid 15 mass parts, after carrying out the nitrogen replacement, begin to stir lentamente.Make solution temperature rise to 70 ℃, kept this temperature five hours, obtain to contain the polymer solution of multipolymer (A-7).The solids content concn of the polymer solution of gained is 33.2 quality %.The number-average molecular weight of the polymkeric substance of gained is 8,000.In addition, molecular weight distribution (Mw/Mn) is 2.
Compare synthesis example 1
In the flask that possesses condenser pipe and stirrer, pack 2 earlier into, two (2, the 4-methyl pentane nitrile) 5 mass parts of 2 '-azo and diethylene glycol ethylmethyl ether 200 mass parts.Then, methyl methacrylate 60 mass parts of packing into, styrene 10 mass parts, N-cyclohexyl maleimide 30 mass parts, carry out beginning to stir slowly after nitrogen replaces again.Make solution temperature rise to 70 ℃, kept this temperature five hours, obtain to contain the polymer solution of multipolymer (a-1).The solids content concn of resulting polymer solution is 32.6 quality %.The number-average molecular weight of resulting polymkeric substance is 6,400.In addition, molecular weight distribution (Mw/Mn) is 2.
The modulation of resin combination and evaluation
Embodiment 1
The solution (amount that is equivalent to 100 mass parts multipolymers (A-1) (solids content)) that adds the multipolymer (A-1) that comprises gained in the above-mentioned synthesis example 1, with (B-1) mono succinate-[3-(3-acryloyl-oxy-2,2-pair-acryloyl-oxy methyl-propoxyl group)-2,2-pair-acryloyl-oxy methyl-propyl group] ester 200 mass parts, with (C-1) 2-methyl isophthalic acid-(trade name IRGACURE 907 for (4-methylbenzene sulfenyl)-2-morpholino third-1-ketone, Ciba Specialty Chemicals corporate system) 10 mass parts, (D-1) (Japan Epoxy Resins (strain) makes trade name to phenolic resin varnish type epoxy resin: EPIKOTE152) 30 mass parts, (G-1) γ-glycidoxypropyltrime,hoxysilane 30 mass parts, FTX-218 ((strain) NEOS system) is as (I-1) surfactant 0.2 mass parts, add solvent (S-1) diethylene glycol ethylmethyl ether again, make solids content concn become 22 quality %, utilize the millipore filter of aperture 0.5 μ m to filter afterwards and modulated resin combination.
The evaluation of diaphragm
(1) transparence evaluating
Use spinner that above-mentioned composition is coated on SiO
2After on the dip-coating glass substrate, film with 80 ℃ of pre-roasting formation that carried out two minutes on heating plate, 1000J/m exposes on the overlay film that is obtained
2Afterwards, utilize potassium hydroxide 0.05 quality % aqueous solution, after 25 ℃ of developments, clean one minute with pure water, heated 30 minutes in 230 ℃ baking box, thus, forming thickness is the diaphragm of 2.0 μ m.
At the substrate that has as above-mentioned formed diaphragm, be to use spectrophotometer (150-20 type double beam photometer (double beam) (Hitachi (strain) system)) to measure the transmitance of 400～800nm.The minimum value of the transmitance of 400～800nm is shown in table 1 and table 2.When this value reaches 95% when above, we can say that the transparency of its diaphragm is good.
(2) pencil hardness evaluation
Adopt the method identical to form diaphragm, utilize the 8.4.1 pencil test of JISK-5400-1990 to measure the skin hardness of diaphragm with transparence evaluating.This value is shown in table 1 and table 2.When this value reaches 4H when above, we can say that its skin hardness is good.
(3) small hardness evaluation
Adopt the method identical to form diaphragm with transparence evaluating; use slight compression testing machine (trade name FISCHERSCOPE HC-110, (strain) Fischer Instruments system); with Vickers (Vickers) pressure head load speed and unloading speed all are set at 5mN/ second; and kept 10 seconds behind the load till the load 50mN, measure Martens hardness (Martens hardness) by removing load afterwards.This value is shown in table 1 and table 2.If this value reaches 650N/mm
2More than, we can say that its film hardness is good.
(4) wear-resisting wiping test
Adopt the method identical to form diaphragm, use and learn the vibration shape (Gakushin-Type) abrasion testing machine, on steel wool #0000, apply 200g and load and reciprocal 10 times with transparence evaluating.Estimate abrasive situation with naked eyes according to following criterion.This value is shown in table 1 and table 2.
Criterion
◎: do not have scratch fully
Zero: 1～3 scratches
△: 4～10 scratches
*: 10 above scratches
If be ◎, zero, △, then can say so has good wear-resisting wiping.
(5) viscosity test (substrate that the ITO film is arranged with film forming from the teeth outwards on the glass substrate)
With pure water clean, behind dry 4 inches chip glasses, use spinner to be coated on above-mentioned composition on each substrate after, on heating plate, carry out two minutes pre-roasting and form and film with 80 ℃, 1000J/m exposes on the overlay film that is obtained
2Afterwards,, after 25 ℃ of developments, clean one minute, in 230 ℃ baking box, heated 30 minutes again, thus, form the diaphragm of thickness 2.0 μ m with pure water by potassium hydroxide 0.05 quality % aqueous solution.
At the substrate that has as above-mentioned formed diaphragm, be the stickability of utilizing the 8.5.3 tack gridiron pattern eye winding method evaluation diaphragm of JISK-5400-1990.In 100 gridiron patterns, show remaining tessellated quantity.
Except using glass substrate that film forming from the teeth outwards has an ITO film replacing 4 inches chip glasses, other all carries out identical evaluation with the situation identical with 4 inches chip glasses, estimate with the ITO film on stickability.This value is shown in table 1 and table 2.
Embodiment 2～20 and comparative example 1～3
The kind of each composition of composition and amount are the contents of putting down in writing as table 1 and table 2, are documented in the solids content concn of table 1 and table 2 except using solvent to cooperate, similarly to Example 1 resin composition modulation.
Use the diaphragm formation resin combination of as above modulation, form diaphragm as embodiment 1, and estimate.
Above-mentioned evaluation result is shown in table 1 and table 2.
Table 1
Table 2
In addition, in table 1 and table 2, (B) abbreviation of polyfunctional acrylic ester, (C) radiation sensitive linear polymerization initiator, (D) multifunctional cationically polymerizable compound, (E) temperature-sensitive acid agent, (F) multifunctional urethanes acrylate, (G) adhesive aid, (H) acid anhydrides, (I) surfactant, (S) solvent is expressed as follows respectively.
B-1: mono succinate-[3-(3-acryloxy-2,2-pair-acryloyl-oxy methyl-propoxyl group)-2,2-pair-acryloyl-oxy methyl-propyl group] ester
C-1:2-methyl isophthalic acid-(4-methylbenzene sulfenyl)-2-morpholino third-1-ketone (trade name IRGACURE 907, Ciba Specialty Chemicals corporate system)
C-2: ethyl ketone-1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl)-1-(O-acetyl oxime) (trade name IRGACURE OX02, Ciba Specialty Chemicals corporate system)
D-1: (Japan Epoxy Resins (strain) makes trade name to phenolic resin varnish type epoxy resin: EPIKOTE152)
D-2: (Japan Epoxy Resins (strain) makes trade name to bisphenol-A phenolic varnish type epoxy resin: EPIKOTE157S65)
E-1: benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate (three new chemical industry (strain) system SI-80)
E-2: benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate (three new chemical industry (strain) system SI-110)
E-3:4-acetoxyphenyl group dimethyl sulfonium hexafluoro antimonate (three new chemical industry (strain) system SI-150)
F-1: multifunctional urethanes acrylate (industry (strain) system UN-3320HS on the root)
G-1: γ-glycidoxypropyltrime,hoxysilane
H-1: trimellitic anhydride
I-1: ((strain) NEOS makes trade name to fluorine class surfactant: FTX-218)
S-1: diethylene glycol ethylmethyl ether
S-2: propylene glycol monomethyl ether acetate
B-1: dipentaerythritol acrylate (Japanese chemical drug (strain) system trade name: KAYARAD DPHA)
Claims (6)
1. the diaphragm of a touch panel forms and uses radiation sensitive linear resin composition, it is characterized in that containing:
(A) alkali soluble resins;
(B) has the compound of the ethene unsaturated group of from following formula (1) and following formula (2), selecting more than 1;
(C) radiation sensitive linear polymerization initiator,
At this, X is selected from alkyl, acryloyl group or the methacryl of hydrogen atom, carbon number 1～6, and at least 1 X is acryloyl group or methacryl; W represent carbon number 1～6 alkylidene, comprise alkylidene, phenylene or the cyclohexyl of the carbon number 2～6 of 1 unsaturated link.
2. the diaphragm of the touch panel of putting down in writing according to claim 1 forms and uses radiation sensitive linear resin composition; it is characterized in that (A) alkali soluble resins is a kind of multipolymer; be to comprise (a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, and the monomer that (a2) contains the unsaturated compound of epoxy radicals carry out copolymerization and form.
3. use radiation sensitive linear resin composition according to the diaphragm formation of claim 1 or 2 touch panels of being put down in writing, it is characterized in that containing (D) multifunctional cationically polymerizable compound, still, do not comprise and the identical situation of (A) alkali soluble resins.
4. the diaphragm of the touch panel of putting down in writing according to claim 3 forms and use radiation sensitive linear resin composition, it is characterized in that containing (E) by heating acidic compound.
5. a touch panel diaphragm is characterized in that, is formed by the radiation sensitive linear resin composition of putting down in writing according to claim 1.
6. the formation method of a diaphragm is characterized in that using the radiation sensitive linear resin composition of putting down in writing according to claim 1, overlay film is formed on the substrate of touch panel, then carries out the treatment with irradiation and the heat treated of radioactive ray.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
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| JP2008160383 | 2008-06-19 | ||
| JP2008160383 | 2008-06-19 | ||
| JP2008-160383 | 2008-06-19 | ||
| JP2009-100105 | 2009-04-16 | ||
| JP2009100105A JP5201066B2 (en) | 2008-06-19 | 2009-04-16 | Radiation sensitive resin composition for forming protective film of touch panel and method for forming the same |
| JP2009100105 | 2009-04-16 |
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| CN101609256A true CN101609256A (en) | 2009-12-23 |
| CN101609256B CN101609256B (en) | 2013-12-04 |
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| JP (1) | JP5201066B2 (en) |
| CN (1) | CN101609256B (en) |
| TW (1) | TWI453537B (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201005436A (en) | 2010-02-01 |
| JP2010027033A (en) | 2010-02-04 |
| CN101609256B (en) | 2013-12-04 |
| TWI453537B (en) | 2014-09-21 |
| JP5201066B2 (en) | 2013-06-05 |
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