CN1849355A - Photosensitive resin composition and film having cured coat formed therefrom - Google Patents
Photosensitive resin composition and film having cured coat formed therefrom Download PDFInfo
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- CN1849355A CN1849355A CN 200480026265 CN200480026265A CN1849355A CN 1849355 A CN1849355 A CN 1849355A CN 200480026265 CN200480026265 CN 200480026265 CN 200480026265 A CN200480026265 A CN 200480026265A CN 1849355 A CN1849355 A CN 1849355A
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Abstract
A photosensitive resin composition which cures with a radiation to give a film which is excellent in marring resistance and wearing resistance and has a low refractive index and which, when used as an antireflection film, has a low reflectance. The photosensitive resin composition is characterized by comprising (A) an epoxidized silicon compound obtained by condensing, in the presence of a basic catalyst, an epoxidized alkoxysilicon compound represented by the following general formula (1) ReSi(OR1)3 (1) (wherein Re represents a substituent having epoxy; and R1 represents C1-4 alkyl) with itself or with a fluorinated alkoxysilicon compound represented by the following general formula (2) RfSi(OR2)3 (2) (wherein Rf represents a substituent having 1 to 20 fluorine atoms; and R2 represents C1-4 alkyl) and (B) a cationic photopolymerization initiator and optionally containing (C) a fluorinated polymer, (D) colloidal silica having a primary-particle diameter of 1 to 200 nm, and (E) a polymer having a (poly)siloxane structure in a side chain.
Description
Technical field
The film that the present invention relates to contain the photosensitive polymer combination of epoxy group(ing) silicon compound and have its cured film is specifically related to that scuff resistance is good, low-refraction, the photosensitive polymer combination that reflectivity is low when being used for antireflective film and the film with its cured film.
Background technology
Now, plastics are used in the various industrial fields headed by automobile industry, household electric appliances, the electric and electronic industry in a large number.Plastics except its processibility, the transparency, also are that light weight, cheapness, optical characteristics are good etc. by the reason of so a large amount of uses.Yet, compare with glass etc., there are on soft, the surface shortcomings such as scuffing easily.In order to improve these shortcomings, as general method, at surface-coated hard coat agent (hard coatagent).This hard coat agent uses thermohardening type hard coat agents such as silicon class coating, acrylic coating, melamine class coating.Wherein, particularly owing to hardness height, best in quality, so often use silicon class hard coat agent.Yet set time is long, price is high, is not suitable for being arranged on the hard membrane layer on the film of continuous processing.
In recent years, develop and used photosensitive acrylic acid or the like hard coat agent (with reference to Japanese patent laid-open 9-48934 communique, be patent documentation 1.)。Owing to, solidify to form hard tunicle immediately by the irradiation ultraviolet radiation isoradial, so processing treatment speed is fast, and have good performances such as hardness, scuff resistance, overall cost is low, so the photosensitivity hard coat agent becomes the main flow in dura mater field at present.Be particularly suitable for the continuous processing of films such as polyester.Plastics film has polyester film, polyacrylic acid ester film, acrylate film, polycarbonate film, vinyl chloride film, triacetylcellulose film, polyethersulfone film etc., and polyester film is used owing to various good characteristics the most widely.This polyester film is widely used as the photomask of anti-the disperse film or the automobile of glass, blank surface film, whole kitchen surface soiling film, the functional film of the touch-screen of electronic material aspect, liquid-crystal display, CRT flat panel TV etc.These all apply dura mater in order to prevent its surface tear.
In addition, in the indicating meters such as CRT, LCD that the film that applies hard coat agent is set in recent years,, because being difficult to see clearly the tired easily problem of display picture, eyes, reflection handles owing to having produced so have the dura mater that prevents the surface reflection function according to the purposes needs.The method that prevents surface reflection has: disperse to be coated on the film behind inorganic filler or the organic weighting material in photoresist, form the concavo-convex method (AG processing) that reflects of preventing on the surface; Order by high refractive index layer, low-index layer on film is provided with multilayered structure, the interference of light that utilizes the difference of specific refractory power to produce, thus prevent the method (AR processing) that mirrors, reflect; Perhaps make up method that the AG/AR of above-mentioned two kinds of methods handles etc.(with reference to Japanese patent laid-open 9-145903 communique, be patent documentation 2.)
Yet, AR handle employed low-index layer use by sol-gel method make the silane compound condensation thermohardening type (with reference to Japanese patent laid-open 10-000726 communique, be patent documentation 3.), exist to solidify time-consuming, productivity difference and hard membrane layer and produce problem of cracks because of heat shrink.On the other hand, also developed the radiation-curing type resin that uses (methyl) acrylate with fluorine atom (with reference to Japanese patent laid-open 10-182745 communique, be patent documentation 4.), but exist the scuff resistance deficiency, need be in a vacuum or make under the nitrogen atmosphere that it solidifies, the problem of apparatus expensive for (methyl) acrylate is fully solidified.
Because productivity and add problem such as thermogenesis crack needs the low-refraction dura mater of radiation-curing type.In addition, practical situation are radiation-curing type resin scuff resistance deficiencies at present, for needing to add again equipment in the existing production lines such as nitrogen replacement.
Bibliography:
Patent documentation 1: Japanese patent laid-open 9-48934 communique
Patent documentation 2: Japanese patent laid-open 9-145903 communique
Patent documentation 3: Japanese patent laid-open 10-000726 communique
Patent documentation 4: Japanese patent laid-open 10-182745 communique
The announcement of invention
Problem of the present invention provide without nitrogen replacement etc. also can easily solidify by radioactive rays, scuff resistance is good, the photosensitive polymer combination that reflectivity is low when being used for antireflective film and the film with its cured film.
The inventor finds that the photosensitive polymer combination with specific compound and composition can solve described problem, thereby has finished the present invention for after solving described problem and conscientiously studying.
That is, the present invention relates to following content:
(1) photosensitive polymer combination is characterized in that, contains the silicon compound (A) and the photo-induced cationic polymerization initiator (B) of epoxy group(ing), described compound (A) in the presence of basic catalyst by following general formula (1)
R
eSi(OR
1)
3 (1)
(in the formula, R
eThe substituting group that expression has epoxy group(ing).R
1Expression C
1～C
4Alkyl.) between the represented alkoxy-silicon compound or by described general formula (1) represented alkoxy-silicon compound with epoxy group(ing) and following general formula (2) with epoxy group(ing)
R
fSi(OR
2)
3 (2)
(in the formula, R
fExpression has the substituting group of 1～20 fluorine atom.R
2Expression C
1～C
4Alkyl.) the represented alkoxy-silicon compound condensation with fluorine atom obtains;
(2) as above-mentioned (1) described photosensitive polymer combination, in the compound of general formula (1), R
eBe glycidoxy C
1～C
4Alkyl or had the C of Oxyranyle
5～C
8The C of cycloalkyl substituted
1～C
3Alkyl;
(3) as above-mentioned (1) described photosensitive polymer combination, its feature also is, in the compound of general formula (1), uses R
eBe glycidoxy C
1～C
4The compound and the R of alkyl
eFor being had the C of Oxyranyle
5～C
8The C of cycloalkyl substituted
1～C
3The compound of alkyl;
(4) as each the described photosensitive polymer combination in above-mentioned (1)～(3), its feature also is, contains the macromolecular compound (C) with fluorine atom;
(5) as each the described photosensitive polymer combination in above-mentioned (1)～(4), its feature also is, contains the colloid silica that primary particle diameter is 1～200 nanometer (D);
(6) as each the described photosensitive polymer combination in above-mentioned (1)～(5), its feature also is, contains on side chain the macromolecular compound (E) with (gathering) siloxane structure;
(7) as each the described photosensitive polymer combination in above-mentioned (1)～(6), its feature also is, the macromolecular compound (E) that on side chain, has (gathering) siloxane structure be can be by having terminal double link modified silicone and the comb shape graftomer that obtains of polymerisable monomeric copolymerization, main chain is a silicone for acrylic polymers, a chain portion partly in its structure;
(8) as each the described photosensitive polymer combination in above-mentioned (1)～(7), its feature also is, contains thinner (F);
(9) as each the described photosensitive polymer combination in above-mentioned (1)～(8), its feature also is, the ratio of the compound of the compound of general formula (1) and general formula (2) is that with respect to the compound of 1 mole of general formula (1), the compound of general formula (2) is 0.5～2 mole;
(10) as each the described photosensitive polymer combination in above-mentioned (1)～(9), its feature also is, contains defoamer (G);
(11) antireflection hard coating film obtains applying hard coat agent and specific refractory power each described photosensitive polymer combination in coating above-mentioned (1)～(10) and solidifying on high refractive index hard coat agent more than 1.55 and the hard membrane layer that is solidified to form on the base material film successively;
(12) as above-mentioned (11) described antireflection hard coating film, its feature also is, the high refractive index hard coat agent for contain multifunctional (methyl) acrylate (H), primary particle diameter is the metal oxide (I) of 1～200 nanometer and the photosensitive polymer combination of optical free radical polymerization starter (J);
(13) as above-mentioned (12) described antireflection hard coating film, its feature is that also primary particle diameter is that the metal oxide (I) of 1～200 nanometer is a conductive metal oxide (K).
The best mode that carries out an invention
Below, the present invention is described in detail.
In the photosensitive polymer combination of the present invention, use following general formula (1) separately
R
eSi(OR
1)
3 (1)
(in the formula, R
eThe substituting group that expression has epoxy group(ing).R
1Expression C
1～C
4Alkyl.) the represented alkoxy-silicon compound with epoxy group(ing) or use represented alkoxy-silicon compound with epoxy group(ing) of described general formula (1) and following general formula (2)
R
fSi(OR
2)
3 (2)
(in the formula, R
fExpression has the substituting group of 1～20 fluorine atom.R
2Expression C
1～C
4Alkyl.) the represented alkoxy-silicon compound with fluorine atom.
R in the represented alkoxy-silicon compound of described general formula used in the present invention (1) with epoxy group(ing)
eSo long as have the substituting group of epoxy group(ing), be not particularly limited, can exemplify for example beta epoxide propoxy-ethyl, γ-glycidoxy propyl group, γ-glycidoxy C such as glycidoxy butyl
1～C
4Alkyl, better be glycidoxy C
1～C
3Alkyl, epoxypropyl, β-(3, the 4-epoxycyclohexyl) ethyl, γ-(3, the 4-epoxycyclohexyl) propyl group, β-(3,4-oxirane ring heptyl) ethyl, β-(3, the 4-epoxycyclohexyl) propyl group, β-(3, the 4-epoxycyclohexyl) butyl, β-(3, the 4-epoxycyclohexyl) amyl group etc. have the C of Oxyranyle
5～C
8The C of cycloalkyl substituted
1～C
3Alkyl.
Wherein, better be beta epoxide propoxy-ethyl, γ-glycidoxy propyl group, β-(3, the 4-epoxycyclohexyl) ethyl.Can be as having these substituent R
eThe object lesson of preferred compound of compound of general formula (1) can exemplify beta epoxide propoxy-ethyl trimethoxy silane, beta epoxide propoxy-ethyl triethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane etc.
In the described general formula (1), R
1Expression C
1～C
4Alkyl, from the angle of reaction conditions, R
1Better be methyl, ethyl.
In addition, for the represented alkoxy-silicon compound of employed general formula (2) among the present invention, substituent R with fluorine atom
fGet final product so long as have the substituting group of 1～20 fluorine atom.Object lesson can exemplify for example trifluoro propyl Trimethoxy silane, the trifluoro propyl triethoxyl silane, nine fluorine hexyl Trimethoxy silanes, nine fluorine hexyl triethoxyl silanes, 17 fluorine decyl Trimethoxy silanes, 17 fluorine decyl triethoxyl silanes, 3-Trimethoxy silane base propyl group 15 fluorine octanoates, 3-tri-ethoxy silylpropyl 15 fluorine octanoates, 3-Trimethoxy silane base propyl group 15 fluorine decoylamides, 3-tri-ethoxy silylpropyl 15 fluorine decoylamides, 2-Trimethoxy silane base ethyl 15 fluorine thioethers in the last of the ten Heavenly stems, 2-triethoxysilicane alkyl ethyl 15 fluorine thioethers in the last of the ten Heavenly stems etc., from easy acquisition, and with the intermiscibility of alkoxy-silicon compound with epoxy group(ing), better be the trifluoro propyl Trimethoxy silane.
In the described general formula (2), R
2Expression C
1～C
4Alkyl, from the angle of reaction conditions, R
2Better be methyl, ethyl.
The represented compound of described general formula (2) can be buied from the market.Product sold can exemplify for example KBM-7103, KBM-7803 (Shin-Etsu Chemial Co., Ltd's system) on the market.
Obtain in the described condensation reaction of the employed silicon compound (A) that contains epoxy group(ing) among the present invention, can by in the presence of basic catalyst by obtaining between the alkoxy-silicon compound with epoxy group(ing) of general formula (1) or by (being total to) condensation of the alkoxy-silicon compound with fluorine atom of the alkoxy-silicon compound with epoxy group(ing) of general formula (1) and general formula (2).(being total to) condensation ratio of the compound of the compound of general formula (1) and general formula (2) is from the angle of solidified nature and specific refractory power, and with respect to the compound of 1 mole of general formula (1), the compound of general formula (2) is 0.5～2 mole.In addition, in order to promote (being total to) condensation, can add water as required.With respect to the alkoxyl group of 1 molar reactive mixture integral body, the addition of water is generally 0.05～1.5 mole, is preferably 0.07～1.2 mole.
The catalyzer of above-mentioned condensation reaction so long as alkalescence, be not particularly limited, can use mineral alkalis such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, organic basess such as ammonia, triethylamine, diethylenetriamine, n-Butyl Amine 99, dimethylamino-ethanol, trolamine, tetramethyl ammonium hydroxide.Wherein,, better be mineral alkali or ammonia particularly by the angle of from resultant, removing catalyzer easily.With respect to the alkoxy-silicon compound with epoxy group(ing) (general formula (1)) with have the total amount of the alkoxy-silicon compound (general formula (2)) of fluorine atom, the addition of catalyzer is generally 5 * 10
-4～7.5 weight % better are 1 * 10
-3～5 weight %.
Solvent can not be used in above-mentioned condensation reaction, or carries out in solvent.Solvent when using solvent is not particularly limited so long as dissolving has the alkoxy-silicon compound and the solvent with alkoxy-silicon compound of fluorine atom of epoxy group(ing).Such solvent can exemplify for example non-proton property polar solvents such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), methyl ethyl ketone, methyl iso-butyl ketone (MIBK), and aromatic hydrocarbons such as toluene, dimethylbenzene etc. better are methyl ethyl ketone, methyl iso-butyl ketone (MIBK).
In the photosensitive polymer combination of the present invention, use photo-induced cationic polymerization initiator (B).Photo-induced cationic polymerization initiator (B) is the catalyzer that promotes cationic polymerization under illumination, can use the material by cationic polymerisation catalysts such as generation Lewis acid such as irradiation ultraviolet radiations.Can exemplify for example diazonium salt, sulfonium salt, iodine salt etc.Specifically can exemplify hexafluoro-antimonic acid diazobenzene, phosphofluoric acid diazobenzene, hexafluoro boric acid diazobenzene, hexafluoro-antimonic acid triphenyl sulfonium, phosphofluoric acid triphenyl sulfonium, hexafluoro boric acid triphenyl sulfonium, 4,4 '-two [two (2-hydroxyl-oxethyl phenyl) sulfonium base] diphenyl sulfide two hexafluorophosphates, hexafluoro-antimonic acid diphenyl iodonium, phosphofluoric acid diphenyl iodonium, phosphofluoric acid phenylbenzene-4-sulphur Phenoxyphenyl sulfonium etc. better are iodine salts.They can use separately, also can two or more mixing use.
These photo-induced cationic polymerization initiators (B) can easily be buied from the market.The product of the photo-induced cationic polymerization initiator of selling on the market (B) can exemplify for example UVI-6990 (trade(brand)name) of ユ ニ オ Application カ one バ イ De corporate system, ア デ カ オ プ ト マ one SP-150 of rising sun electrification corporate system, ア デ カ オ プ ト マ one SP-170 (trade(brand)name), the CIT-1370 of Japan Cao Da corporate system, CIT-1682, CIP-1866S, CIP-2048S, CIP-2064S (trade(brand)name), the DPI-101 of body ど り chemical company system, DPI-102, DPI-103, DPI-105, MPI-103, MPI-105, BBI-101, BBI-102, BBI-103, BBI-105, TPS-101, TPS-102, TPS-103, TPS-105, MDS-103, MDS-105, DTS-102, DTS-103 (trade(brand)name).
When the solids component in photosensitive polymer combination was 100 weight parts, the usage quantity of photo-induced cationic polymerization initiator (B) was preferably 0.5～20 weight part, and good especially is 1～15 weight part.
Can also use sensitizing agent simultaneously as required in the photosensitive polymer combination of the present invention.The available sensitizing agent uses the sensitizing agent that promotes photo-induced cationic polymerization.Specifically can exemplify anthracene, 9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 9,10-dipropoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 2-ethyl-9,10-dipropoxy anthracene, 2-ethyl-9,10-two (methoxy ethoxy) anthracene, fluorenes, pyrene, stilbene, 4 '-nitrobenzyl-9,10-dimethoxy anthracene-2-sulphonate, 4 '-nitrobenzyl-9,10-diethoxy anthracene-2-sulphonate, 4 '-nitrobenzyl-9,10-dipropoxy anthracene-2-sulphonate etc., from solvability and with the intermiscibility of photosensitive polymer combination, better be 2-ethyl-9,10-two (methoxy ethoxy) anthracene.Usage quantity when using these sensitizing agents is 1～200 weight part with respect to 100 weight part photo-induced cationic polymerization initiators (B), better is 5～150 weight parts.
Use macromolecular compound (C) in the photosensitive polymer combination of the present invention with fluorine atom.Macromolecular compound (C) with fluorine atom can use various macromolecular compounds with fluorine atom, can exemplify for example tetrafluoroethylene, polyvinylidene difluoride (PVDF), and the independent or two or more polymerizations of the compound with fluorine atom and ethene unsaturated group, the polymkeric substance that the compound that perhaps has fluorine atom and an ethene unsaturated group and the compound polymerization with ethene unsaturated group that does not contain fluorine atom obtain etc., described compound with fluorine atom and ethene unsaturated group has (methyl) vinylformic acid trifluoroethyl ester, (methyl) vinylformic acid tetrafluoro propyl diester, (methyl) vinylformic acid octafluoro amyl group ester, (methyl) vinylformic acid 17 fluorine decyl ester, 1H, 1H, 7H-ten difluoro heptyl (methyl) acrylate, 1H, 1H, 9H-ten hexafluoro nonyl (methyl) acrylate, 2,2,3,4,4,4-hexafluoro butyl (methyl) acrylate, the inferior propyl ester of methacrylic acid hexafluoro, 2-hydroxyl-1H, 1H, 2H, 3H, 3H-nine fluorine heptyl (methyl) acrylate, 2-hydroxyl-1H, 1H, 2H, 3H, 3H-ten trifluoro nonyl (methyl) acrylate, 2-hydroxyl-6-Trifluoromethyl-1 H, 1H, 2H, 3H, 3H-octafluoro heptyl (methyl) acrylate, 2-hydroxyl-8-Trifluoromethyl-1 H, 1H, 2H, 3H, 3H-ten difluoro nonyl (methyl) acrylate etc.
Using primary particle diameter in the photosensitive polymer combination of the present invention is the colloid silica (D) of 1～200 nanometer.Operable colloid silica (D) has the micropowder colloid silica that for example colloid silica is dispersed in the colloidal solution in the solvent or does not contain dispersion solvent.
The dispersion solvent that colloid silica is dispersed in the colloidal solution in the solvent can use for example water, methyl alcohol, ethanol, Virahol, alcohols such as propyl carbinol, ethylene glycol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, polyalcohols and derivatives thereof such as propylene glycol methyl ether acetate, methyl ethyl ketone, mibk, ketones such as pimelinketone, amidess such as N,N-DIMETHYLACETAMIDE, ethyl acetate, ester classes such as n-butyl acetate, toluene, non-polar solvents such as dimethylbenzene, 2-hydroxybutyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, (methyl) esters of acrylic acid and other common organic solvents classes such as 4-hydroxybutyl (methyl) acrylate.The amount of dispersion solvent is 100～900 weight parts with respect to 100 weight part colloid silicas usually.
These colloid silicas can use with the known method manufacturing and on market product sold.For particle diameter, needing to use primary particle diameter is the colloid of 1～200 nanometer, better is that primary particle diameter is 5～500 nanometers, and being more preferably primary particle diameter is 10～80 nanometers.In addition, colloid silica better is to use the colloid of pH=2～6 in the present invention.
In addition, can carry out surface treatment with silane coupling agent etc. to colloid silica.
In addition, can carry out surface treatment with described general formula (1) represented alkoxy-silicon compound with epoxy group(ing) or the represented alkoxy-silicon compound of described general formula (2) to colloid silica with fluorine atom.
Treatment process can be used known method.Specifically, drying process and damp process are arranged, drying process is the method that SiO 2 powder is handled, and disperses the stoste of alkoxy-silicon compound or solution to handle equably to the SiO 2 powder that carries out high-speed stirring by stirrer.In addition, damp process is by silicon-dioxide being dispersed in the solvent etc. and adding the method that alkoxy-silicon compound is handled that stirs in slurried silicon-dioxide.Among the present invention, can use any method.Treatment capacity is so long as by treatment capacity (g)=silica weight (g) * silicon-dioxide specific surface area (m
2/ g)/minimum of alkoxy-silicon compound lining area (m
2/ the amount of g) trying to achieve is following to get final product.
Use the macromolecular compound (E) that on side chain, has (gathering) siloxane structure in the photosensitive polymer combination of the present invention.
This compound (E) be can be by having terminal double link modified silicone and the comb shape graftomer that obtains of polymerisable monomeric copolymerization, main chain is a silicone for acrylic polymers, a chain portion partly in its structure.The method manufacturing that should (E) composition can be put down in writing according to the special fair 7-81113 communique of for example Japanese Patent.(E) ratio of the silicone in the composition in the scope of 10～50 weight parts, better is 20～40 weight parts with respect to 100 weight parts (E) composition, is more preferably 20～30 weight parts.Molecular weight better is 5～100,000.
The product of the macromolecular compound of selling on the market that has (gathering) siloxane structure on side chain (E) can exemplify for example synthetic サ イ マ Star Network US-270 that makes in East Asia, US-350, US-352, US-380 etc.
Can use thinner (F) in the photosensitive polymer combination of the present invention.Operable thinner (F) can exemplify for example lactone such as gamma-butyrolactone, γ-Wu Neizhi, γ-Ji Neizhi, γ-Geng Neizhi, α-ethanoyl-gamma-butyrolactone, 6-caprolactone; Two alkane, 1, ethers such as 2-Methylal(dimethoxymethane), diglyme, diethyl carbitol, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, triglyme, triglycol diethyl ether, tetraethylene glycol dimethyl ether, Tetraglycol 99 diethyl ether; Carbonates such as ethylene carbonate, Texacar PC; Ketones such as methyl ethyl ketone, mibk, pimelinketone, methyl phenyl ketone; Phenol such as phenol, cresols, xylenol; Ester classes such as ethyl acetate, butylacetate, ethyl cellosolve acetate, butyl cellosolve acetate, Trivalin SF acetic ester, acetate of butyl carbitol, propylene glycol methyl ether acetate; Hydro carbons such as toluene, dimethylbenzene, diethylbenzene, hexanaphthene; Halogenated hydrocarbons such as trichloroethane, tetrachloroethane, mono chloro benzene etc., organic solvent classes such as petroleum-type solvents such as sherwood oil, petroleum naphtha etc.They can use separately, also can two or more mixing use.
Can use defoamer (G) in the photosensitive polymer combination of the present invention.Particularly use under the situation of fluorine class material, be easy to generate the problem of whipability, the improvement by interpolation defoamer (G) when applying is very useful.Defoamer (G) can exemplify silicone defoamer, fluorine defoamer, defoaming polymkeric substance, high boiling solvent etc., specifically, better be the BYK-060N of PVC Star Network ケ ミ one corporate system, AF-600, the AF-630 etc. of BYK-066N Shin-Etsu Chemial Co., Ltd system.
They can use separately, also can two or more mixing use.
In addition, in the photosensitive polymer combination of the present invention, can add levelling agent, UV light absorber, photostabilizer etc. as required, give various required functional.Levelling agent can exemplify fluoride compound, silicone compound etc., and UV light absorber can exemplify benzotriazole compound, benzo benzophenone compounds, compound in triazine class etc., and photostabilizer can exemplify hindered amines, benzoate compounds etc.
Photosensitive polymer combination of the present invention can followingly become assign to obtain by mixing in any order: above-mentioned (A) composition and (B) composition, and (C) composition that adds as required, (D) composition and (E) composition, perhaps (F) composition, (G) composition and other composition that adds again as required.In addition, usage quantity is generally (A) composition and accounts for 0.5～50 weight %, (B) composition and account for 0.05～50 weight %, (C) composition and account for 0～30 weight %, (D) composition and account for that 0～39.5 weight %, (E) composition account for 0～15 weight %, (G) composition accounts for 0～5 weight %, for (F) composition, in photosensitive polymer combination, be preferably 0～99.45 weight %, more preferably 50～98 weight %.
The photosensitive polymer combination of the present invention that obtains like this is steady in a long-term.
Antireflection hard coating film of the present invention obtains by in the last order by hard membrane layer, high refractive index hard membrane layer and above-mentioned photosensitive polymer combination layer of base material film (basement membrane) each layer being set.At first, on base material film, be coated with hard coat agent, make dry back thickness reach 1～30 μ m, better be 3～20 μ m that dry back irradiation radioactive rays form cured film.Then, the coating specific refractory power is at the high refractive index hard coat agent more than 1.55 on the hard membrane layer that forms, make dry back thickness reach 0.05～5 μ m, better be that 0.05～3 μ m (better is to set thickness, make to show the peaked wavelength of reflectivity 500～700nm), dry back irradiation radioactive rays form cured film.Then, coating photosensitive polymer combination of the present invention on this high refractive index hard membrane layer, make dry back thickness reach 0.05～0.5 μ m, better be that 0.05～0.3 μ m (better is to set thickness, make show the reflectivity minimum value wavelength at 500～700nm, be preferably 520～650nm), dry back irradiation radioactive rays form cured film.
Base material film can exemplify for example polyester, polypropylene, polyethylene, polyacrylic ester, polycarbonate, triacetyl cellulose, polyethersulfone, cycloolefin polymer etc.Film can be certain thickness sheet.Employed film can be provided with decorative pattern and easy adhesive linkage, or carries out surface treatment such as corona treatment.
The coating process of above-mentioned photosensitive polymer combination for example can exemplify, and the bar type spreader applies, Meyer (Meyer) bar type applies, air knife applies, gravure applies, oppositely gravure applies, miniature gravure applies, mould is coated with device coating, dip-coating coating, spin coating coating etc.
The radioactive rays that shine for curing can exemplify for example ultraviolet ray, electron rays etc.Under the situation by ultraviolet curing, light source uses has the UV irradiation equipment of xenon lamp, high voltage mercury lamp, metal halid lamp etc., adjusts light quantity, configured light sources etc. as required.Use under the situation of high voltage mercury lamp, have 80～120W/cm for one
2The lamp of power better be to be cured with 5～60 meters/minute travelling speed.
The 1st layer of employed hard coat agent of antireflection hard coating film of the present invention can directly use the hard coat agent of selling on the market, also can mix multifunctional (methyl) acrylate (H) and optical free radical polymerization starter (J), thinner (F) use.The object lesson of multifunctional (methyl) acrylate (H) can exemplify for example polyoxyethylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, two (methyl) acrylate of the 6-caprolactone affixture of hydroxyl trimethylacetic acid DOPCP (for example, Nippon Kayaku K. K's system KAYARAD HX-220, HX-620 etc.), two (methyl) acrylate of the EO affixture of dihydroxyphenyl propane, trimethylolpropane tris (methyl) acrylate, TriMethylolPropane(TMP) polyethoxye three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, two TriMethylolPropane(TMP) four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, poly-epoxypropyl compound (bisphenol A type epoxy resin, phenolic resin varnish type epoxy resin, tris-phenol type Resins, epoxy, polyoxyethylene glycol diepoxy propyl ether, glycerol is gathered glycidyl ethers, TriMethylolPropane(TMP) gathers glycidyl ethers etc.) and (methyl) acrylic acid reactant---epoxy (methyl) acrylate, multifunctional (methyl) acrylate (tetramethylolmethane three (methyl) acrylate with hydroxyl, Dipentaerythritol five (methyl) acrylate, tripentaerythritol seven (methyl) acrylate etc.) and polyisocyanate compounds (tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate etc.) reactant---multifunctional urethanum (methyl) acrylate etc.They can use separately, also can two or more mixing use.Better be above (methyl) acrylate of 3 functional groups.
Optical free radical polymerization starter (J) can exemplify for example bitter almond oil camphor classes such as bitter almond oil camphor, benzoin methylether, ethoxybenzoin, bitter almond oil camphor propyl ether, bitter almond oil camphor ethyl isobutyl ether; Methyl phenyl ketone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenyl third-1-ketone, diethoxy acetophenone, 1-hydroxy-cyclohexyl benzophenone, 2-methyl isophthalic acid-[4-(methyl sulphur) phenyl]-acetophenones such as 2-morpholino third-1-ketone; Anthraquinone classes such as 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone; 2, thioxanthene ketones such as 4-diethyl thioxanthone, 2-isopropyl thioxanthone, 2-clopenthixal ketone; Ketals such as methyl phenyl ketone dimethyl ketone acetal, benzyl dimethyl ketone acetal; Benzophenone, 4-benzoyl-4 '-methyldiphenyl sulphur, 4, Benzophenones such as 4 '-dimethylamino benzophenone; 2,4, phosphine oxide classes such as 6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl) benzene phosphine oxide etc.
They can use separately, also can make two or more mixtures uses, can also be used in combination with polymerization promotor etc., tertiary amine such as trolamine, methyldiethanolamine for example, N, N-dimethylaminobenzoic acid ethyl ester, N, benzoic acid derivatives such as N-dimethylaminobenzoic acid isopentyl ester etc.
Employed thinner (F) can use aforesaid thinner (F) in the above-mentioned hard coat agent.
Described hard coat agent employed (H) composition, (J) composition, (F) composition can mix mixing by any order, can add levelling agent, defoamer etc. as required.The usage ratio of each composition accounts for 80～99.5 weight % for (H) composition, (J) composition accounts for 0.5～20 weight %, and (F) composition is 0～90 weight % in the composition of hard coat agent, better is 20～80 weight %.
The 2nd layer of employed high refractive index hard coat agent of antireflection hard coating film of the present invention better is to be the photosensitive polymer combination that the metal oxide (I) of 1～200 nanometer and optical free radical polymerization starter (J) and the thinner (F) that adds as required obtain by multifunctional (methyl) acrylate (H), primary particle diameter so long as specific refractory power is getting final product more than 1.55.
Multifunctional (methyl) acrylate (H) and optical free radical polymerization starter (J), thinner (F) can use aforesaid compound.
Primary particle diameter is that the metal oxide (I) of 1～200 nanometer can exemplify titanium oxide, zirconium white, zinc oxide, stannic oxide, ferric oxide, tin indium oxide (ITO), antimony doped tin oxide (ATO), zinc antimonates, Al-Doped ZnO etc.They can make micropowder or the dispersion liquid that is dispersed in the organic solvent obtains.
The employed organic solvent of dispersion liquid can exemplify for example alcohols such as methyl alcohol, ethanol, Virahol, propyl carbinol, polyalcohols such as ethylene glycol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, ketones such as methyl ethyl ketone, mibk, pimelinketone, ester such as ethyl acetate, butylacetate class, non-polar solvents such as toluene, dimethylbenzene etc.The amount of organic solvent is generally 70～900 weight parts with respect to 100 parts by weight of metal oxide.
In addition, in order to give antireflection hard coating film of the present invention anti-charged function, metal oxide (I) can use conductive metal oxide (K).Conductive metal oxide (K) can exemplify for example stannic oxide, tin indium oxide (ITO), antimony doped tin oxide (ATO), zinc antimonates, Al-Doped ZnO etc.Considering price, stability, dispersiveness etc., better is zinc antimonates.
High refractive index hard coat agent employed (H) composition, (I) composition and (F) composition of (J) composition and interpolation as required can mix mixing by any order, can add levelling agent, defoamer etc. as required.The usage ratio of each composition is, in the composition of high refractive index hard coat agent, usually (H) composition accounts for that 19.5～79.5 weight %, (I) composition account for 20～80 weight %, (J) composition accounts for 0.5～20 weight %, and (F) composition accounts for 0～99 weight %, better is 50～98 weight %.
Embodiment
Below, the present invention will be described in more detail by embodiment, but the present invention is not limited to these embodiment.In addition, unless otherwise specified, part is meant weight part among the embodiment.Each physics value among the embodiment is measured with following method.
(1) epoxy equivalent (weight): use based on the method for JIS K-7236 and measure.
(2) specific refractory power: measure at 25 ℃ with Abbe refractomecer.
Synthesis example 1
(silicon compound synthetic that contains epoxy group(ing))
In reaction vessel, add 47.2 parts of γ-glycidoxypropyltrime,hoxysilane, 43.6 parts of trifluoro propyl Trimethoxy silanes, 90.8 parts of mibks, be warming up to 80 ℃.After the intensification, with the potassium hydroxide aqueous solution that splashed into 21.6 part of 0.1 weight % in 30 minutes continuously.After dripping end, when removing the methyl alcohol of generation, reacted 5 hours down at 80 ℃.After reaction finishes, be washed to washings repeatedly and reach neutral.Then, obtain 65 parts of silicon compounds (A-1) that contain epoxy group(ing) by under reduced pressure, removing to desolvate.The epoxy equivalent (weight) of the compound that obtains is 319g/eq, and specific refractory power is 1.433.In addition, at room temperature through not observing gelation in 1 month yet.
Synthesis example 2
(silicon compound synthetic that contains epoxy group(ing))
In reaction vessel, add 47.2 parts of γ-glycidoxypropyltrime,hoxysilane, 113.7 parts of 1H, 1H, 2H, 2H-17 fluorine decyl Trimethoxy silanes, 160.9 parts of mibks are warming up to 80 ℃.After the intensification, with the potassium hydroxide aqueous solution that splashed into 21.6 part of 0.1 weight % in 30 minutes continuously.After dripping end, when removing the methyl alcohol of generation, reacted 5 hours down at 80 ℃.After reaction finishes, be washed to washings repeatedly and reach neutral.Then, obtain 109 parts of silicon compounds (A-2) that contain epoxy group(ing) of the present invention by under reduced pressure, removing to desolvate.The epoxy equivalent (weight) of the compound that obtains is 679g/eq, and specific refractory power is 1.392.In addition, at room temperature through not observing gelation in 1 month yet.
Synthesis example 3
(silicon compound synthetic that contains epoxy group(ing))
In reaction vessel, add 94.4 parts of γ-glycidoxypropyltrime,hoxysilane, 94.4 parts of mibks, be warming up to 80 ℃.After the intensification, with the potassium hydroxide aqueous solution that splashed into 21.6 part of 0.1 weight % in 30 minutes continuously.After dripping end, when removing the methyl alcohol of generation, reacted 5 hours down at 80 ℃.After reaction finishes, be washed to washings repeatedly and reach neutral.Then, obtain 67 parts of silicon compounds (A-3) that contain epoxy group(ing) by under reduced pressure, removing to desolvate.The epoxy equivalent (weight) of the compound that obtains is 166g/eq.In addition, at room temperature through not observing gelation in 1 month yet.
Production Example 1
Mix 42 parts of dipentaerythritol acrylate (Nippon Kayaku K. K's systems, KAYARAD DPHA), 5 part 1,6-hexanediyl ester (chemical drug サ one ト マ one Co., Ltd.'s system, KS-HDDA), 3 parts of イ Le ガ キ ユ ア 184 (チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ corporate system), 25 parts of methyl ethyl ketones, 25 parts of mibks, make its dissolving.
The hard coat agent that obtains is coated on the PET film (Toyo Boseki K.K's system, A-4300, thickness 188 μ m) with miniature gravure coating machine, makes thickness reach about 5 μ m, after 80 ℃ of following dryings, solidify by ultraviolet radiation device.
Production Example 2
Mix 1.2 parts of dipentaerythritol acrylate (Nippon Kayaku K. K's systems, KAYARAD DPHA), 0.15 part of イ Le ガ キ ユ ア 184 (チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ corporate system), 0.15 part of イ Le ガ キ ユ ア 907 (チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ corporate system), 7.5 parts of セ Le Na Star Network ス CX-Z600M-3F2 (Nissan Chemical Ind Ltd's systems, the methyl alcohol of zinc antimonates disperses colloidal sol, solids component 60%), 31 parts of methyl alcohol, 60 parts of propylene glycol monomethyl ethers, obtain the high refractive index hard coat agent of solids component 6%.
Then, the formation that in Production Example 1, obtains the high refractive index hard membrane layer that obtains with the coating of miniature gravure coating machine on the PET film of hard membrane layer, after 80 ℃ of following dryings, solidify by ultraviolet radiation device.At this moment, adjust thickness, the maximum value that makes reflectivity is at 500～700nm.
Embodiment 1～8 and comparative example 1
Be coated on the photosensitive polymer combination that mixes the material shown in the table 1 on the PET film that is formed up to the high refractive index hard membrane layer that obtains in the Production Example 2 with miniature gravure coating machine, after 80 ℃ of following dryings, solidify by ultraviolet radiation device, obtain antireflection hard coating film.At this moment, adjust thickness, the minimum value that makes reflectivity is at 520～650nm.Unit is " part " in the table 1.
Table 1
| Embodiment | Comparative example | ||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 1 | |
| A-1 A-2 A-3 P12074 BBI-102 KD200 NK-4 NK-8 BYK-060N MEK-ST US-270 DPHA UVI-6990 Irg.184 MFS-10P MEK | 1.5 4.6 0.15 93.75 | 1.5 4.6 0.15 93.75 | 1.5 2.05 3 0.15 93 | 1.5 2.05 3 0.15 93 | 1.4 0.1 2.3 2.3 0.5 93.4 | 1.4 0.1 1.8 2.3 1.0 93.4 | 0.4 0.4 0.1 2.7 0.8 2.8 92.8 | 0.4 0.4 0.1 2.7 2.8 96.6 | 0.85 0.15 20 79 |
(notes)
KD200: Kanto Electrization Industrial Co., Ltd's system, fluorine type polymer (solids component 29.3%)
NK-4: Kanto Electrization Industrial Co., Ltd's system, fluorine type polymer (solids component 42%)
NK-8: Kanto Electrization Industrial Co., Ltd's system, fluorine type polymer (solids component 30%)
BYK-060N: PVC Star Network ケ ミ one system, defoamer (solids component 3%)
MEK-ST: Nissan Chemical Ind Ltd's system, organic silicon dioxide gel MEK-ST (solids component 30%)
US-270: Toagosei Co., Ltd's system has the macromolecular compound (solids component 30%) of (gathering) siloxane structure on side chain
DPHA: Nippon Kayaku K. K's system, KAYARAD DPHA (mixture of dipentaerythritol acrylate and five acrylate, linking agent)
UVI-6990: ユ ニ オ Application カ one バ イ De corporate system, triphenyl sulfonium fluoro phosphoric acid ester
Irg.184: チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ corporate system, イ Le ガ キ ユ ア 184 (1-hydroxy-cyclohexyl benzophenones)
PI2074: ロ one デ イ ア ジ ヤ パ Application Co., Ltd. system, the photo-induced cationic polymerization initiator
BBI-102: body ど り KCC system, photo-induced cationic polymerization initiator
MFS-10P: Nissan Chemical Ind Ltd's system, magnesium fluoride colloidal sol (solids component 10%)
MEK: methyl ethyl ketone
Test example 1
The antireflection hard coating film that obtains in embodiment 1～4, the comparative example 1 is carried out the evaluation of following project, and its result is as shown in table 2.
(pencil hardness)
According to JIS K 5400, use the pencil test machine, measure the pencil hardness of the coated film of above-mentioned composition.Specifically, on polyester film, pencil is applied the load of 1kg with the angles of 45 degree from top, mark about 5mm, confirm situation about scratching with the cured film that will measure.Carrying out 5 times measures.
Estimating in 5/5:5 time 5 times does not all have to scratch
All scratch in 0/5:5 time
(scuff resistance test)
On steel wool #0000, apply 200g/cm
2Load, reciprocal 20 times, judge abrasive situation by range estimation.
Estimate A: do not have scratch
B: produce several scratches
C: to 10 times back and forth till not scratch
Back and forth produce several scratches D:10 time
Back and forth produce significant scratch E:10 time
(adhesivity)
According to JIS K 5400, cut out longitudinal and transverse each 11 seam at film surface with the interval of 1mm with the cured film that will measure, make 100 grids.Express the cellulose film band sticked to its surface after, the unstripped and number that exists when quickly all peeling off.
(reflectivity)
Film-metering device F20 with Off イ Le メ ト リ Network ス corporate system measures.In the mensuration, in order to prevent from the reflection at the film back side, (マ ジ Star Network magic), sticks the vinyl tape of black again at the multi-purpose adhesive of the reverse side painting black of coated side.
The result of above-mentioned evaluation is as shown in table 2.
Table 2
| Pencil hardness | Scuff resistance | Adhesivity | Minimum reflectance | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 comparative examples 1 | 2H(4/5) 2H(3/5) 2H(5/5) 2H(5/5) 2H(0/5) | B C A A E | 100/100 100/100 100/100 100/100 100/100 | 0.6％ 0.5％ 0.8％ 0.7％ 1.0％ |
The antireflection hard coating film of embodiment 1～4 all shows good effect on pencil hardness, scuff resistance, adhesivity, minimum reflectance, the pencil hardness of the antireflection hard coating film of comparative example 1, scuff resistance, minimum reflectance are not good.
Test example 2
The antireflection hard coating film that obtains in embodiment 5～8, the comparative example 1 is carried out the evaluation of following project, and its result is as shown in table 3.
(pencil hardness)
According to JIS K 5400, use the pencil test machine, measure the pencil hardness of filming of above-mentioned composition.Specifically, on polyester film, pencil is applied the load of 1kg with the angles of 45 degree from top, mark about 5mm, in 5 times, do not have the hardness of the pencil of scuffing to represent more than 4 times with the cured film that will measure.
(scuff resistance)
On steel wool #0000, apply 200g/cm
2Load, reciprocal 10 times, judge abrasive situation by range estimation.
Estimate A: do not have scratch
B: produce several scratches
C: produce scratch on the whole
(wearability)
With the wire cloth of selling on the market wiping of exerting oneself, visual observation and lower floor peel off
Estimate A: do not change
B: scratch is arranged, but tone does not change
C: peel off
(defoaming)
Prepare the 5g solids component and be adjusted to 10% solution, pour the clear-glass bottle of 10cc into, fasten lid, the fierce vibration for 10 seconds.Leave standstill, observe the foamy state after 30 minutes.
Estimate A: do not have foam
B: except big foam does not almost have
C: foam is all residual
(adhesivity)
According to JIS K 5400, cut out longitudinal and transverse each 11 seam at film surface with the interval of 1mm with the cured film that will measure, make 100 grids.Express the cellulose film band sticked to its surface after, when peeling off fast unstripped and exist number.
(reflectivity)
Beam split sclerometer UV-3150 with Shimadzu Seisakusho Ltd.'s system measures.In the mensuration, in order to prevent,, stick the vinyl tape of black again at the multi-purpose adhesive of the reverse side painting black of coated side from the reflection at the film back side.
The result of above-mentioned evaluation is as shown in table 3.
Table 3
| Pencil hardness | Scuff resistance | Wearability | Defoaming | Adhesivity | Minimum reflectance | |
| Embodiment 5 embodiment 6 embodiment 7 embodiment 8 comparative examples 1 | 3H 3H 3H 3H 2H | B A A B C | B A A B B | A A B C A | 100/100 100/100 100/100 100/100 100/100 | 0.6％ 0.6％ 0.7％ 0.6％ 1.0％ |
The antireflection hard coating film of embodiment 5～7 all shows good effect on pencil hardness, scuff resistance, wearability, defoaming, adhesivity, minimum reflectance, the antireflection hard coating film of embodiment 8 all shows good effect on pencil hardness, scuff resistance, wearability, adhesivity, minimum reflectance.But the pencil hardness of the antireflection hard coating film of comparative example 1, scuff resistance, minimum reflectance are not good.
The possibility of utilizing on the industry
By take new silicon compound with epoxy radicals and fluorine atom and photo-induced cationic polymerization initator as neccessary composition, marresistance, mar proof, defoaming, the good adhesion of the cured film that the photosensitive polymer combination of the present invention that contain as required in addition macromolecular compound, cataloid with fluorine atom, has the macromolecular compound of (gathering) siloxane structure at side chain obtains, and be suitable for making the low antireflective film of reflectivity by applying to solidify at high refractive index layer. Film of the present invention like this is particularly suitable for the field that plastic optical members, touch-screen, flat-panel monitor, film liquid crystal cell etc. need anti-reflective function.
Claims (13)
1. photosensitive polymer combination is characterized in that, contains the silicon compound (A) and the photo-induced cationic polymerization initiator (B) of epoxy group(ing), described compound (A) in the presence of basic catalyst by following general formula (1)
R
eSi(OR
1)
3 (1)
Between the represented alkoxy-silicon compound or by described general formula (1) represented alkoxy-silicon compound with epoxy group(ing) and following general formula (2) with epoxy group(ing)
R
fSi(OR
2)
3 (2)
The represented alkoxy-silicon compound condensation with fluorine atom obtains, in the formula (1), and R
eThe substituting group that expression has epoxy group(ing), R
1Expression C
1～C
4Alkyl, in the formula (2), R
fExpression has the substituting group of 1～20 fluorine atom, R
2Expression C
1～C
4Alkyl.
2. photosensitive polymer combination as claimed in claim 1, its feature also be, in the compound of general formula (1), and R
eBe glycidoxy C
1～C
4Alkyl or had the C of Oxyranyle
5～C
8The C of cycloalkyl substituted
1～C
3Alkyl.
3. photosensitive polymer combination as claimed in claim 1, its feature also are, in the compound of general formula (1), use R
eBe glycidoxy C
1～C
4The compound and the R of alkyl
eFor being had the C of Oxyranyle
5～C
8The C of cycloalkyl substituted
1～C
3The compound of alkyl.
4. as each the described photosensitive polymer combination in the claim 1～3, its feature also is, contains the macromolecular compound (C) with fluorine atom.
5. as each the described photosensitive polymer combination in the claim 1～4, its feature also is, contains the colloid silica that primary particle diameter is 1～200 nanometer (D).
6. as each the described photosensitive polymer combination in the claim 1～5, its feature also is, contains on side chain the macromolecular compound (E) with (gathering) siloxane structure.
7. as each the described photosensitive polymer combination in the claim 1～6, its feature also is, the macromolecular compound (E) that has (gathering) siloxane structure on side chain is the comb shape graftomer that obtains by modified silicone with terminal double link and polymerisable monomeric copolymerization, and main chain is a silicone for acrylic polymers, a chain portion partly in its structure.
8. as each the described photosensitive polymer combination in the claim 1～7, its feature also is, contains thinner (F).
9. as each the described photosensitive polymer combination in the claim 1～8, its feature also is, the ratio of the compound of the compound of general formula (1) and general formula (2) is that with respect to the compound of 1 mole of general formula (1), the compound of general formula (2) is 0.5～2 mole.
10. as each the described photosensitive polymer combination in the claim 1～9, its feature also is, contains defoamer (G).
11. antireflection hard coating film, it is characterized in that, obtain applying hard coat agent and specific refractory power each described photosensitive polymer combination in the coating claim 1～10 and solidifying on high refractive index hard coat agent more than 1.55 and the hard membrane layer that is solidified to form on the base material film successively.
12. antireflection hard coating film as claimed in claim 11, its feature also is, the high refractive index hard coat agent for contain multifunctional (methyl) acrylate (H), primary particle diameter is the metal oxide (I) of 1～200 nanometer and the photosensitive polymer combination of optical free radical polymerization starter (J).
13. antireflection hard coating film as claimed in claim 12, its feature are that also primary particle diameter is that the metal oxide (I) of 1～200 nanometer is a conductive metal oxide (K).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003364718 | 2003-10-24 | ||
| JP364718/2003 | 2003-10-24 | ||
| JP255541/2004 | 2004-09-02 |
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| Publication Number | Publication Date |
|---|---|
| CN1849355A true CN1849355A (en) | 2006-10-18 |
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ID=37078406
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480026265 Pending CN1849355A (en) | 2003-10-24 | 2004-10-21 | Photosensitive resin composition and film having cured coat formed therefrom |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101377553B (en) * | 2007-08-30 | 2010-06-02 | 株式会社有泽制作所 | Composition for forming antireflection film and image display device |
| CN101688050B (en) * | 2007-07-10 | 2013-05-29 | 爱克工业株式会社 | Composition, transfer sheet, melamine decorative board, and method for producing melamine decorative board |
-
2004
- 2004-10-21 CN CN 200480026265 patent/CN1849355A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101688050B (en) * | 2007-07-10 | 2013-05-29 | 爱克工业株式会社 | Composition, transfer sheet, melamine decorative board, and method for producing melamine decorative board |
| CN101377553B (en) * | 2007-08-30 | 2010-06-02 | 株式会社有泽制作所 | Composition for forming antireflection film and image display device |
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