CN102471425A - Photosensitive resin composition, and antireflection film and antireflective hard coating film which are produced using same - Google Patents
Photosensitive resin composition, and antireflection film and antireflective hard coating film which are produced using same Download PDFInfo
- Publication number
- CN102471425A CN102471425A CN201080031455XA CN201080031455A CN102471425A CN 102471425 A CN102471425 A CN 102471425A CN 201080031455X A CN201080031455X A CN 201080031455XA CN 201080031455 A CN201080031455 A CN 201080031455A CN 102471425 A CN102471425 A CN 102471425A
- Authority
- CN
- China
- Prior art keywords
- methyl
- photosensitive polymer
- polymer combination
- film
- hard
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
- H01L21/0276—Photolithographic processes using an anti-reflective coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Structural Engineering (AREA)
- Power Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Architecture (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Provided is a photosensitive resin composition which can be easily cured by means of active energy rays. The photosensitive composition can provide a cured product which exhibits high hardness, and excellent scratch resistance, adhesion, chemical resistance, stain resistance (such as removability of marker pen ink or fingerprints by rubbing), and transparency, and which has a low refractive index. Further, an antireflection film produced using the photosensitive resin composition exhibits a low reflectivity. Also provided are an antireflection film and an antireflective hard coating film, which have films prepared by curing the resin composition. A photosensitive resin composition which comprises (A) a polyfunctional (meth)acrylate having at least three (meth)acryloyl groups in the molecule, (B) colloidal silica that has a nanoporous structure with a mean particle diameter of 1 to 200 nm, and (C) a (meth)acryloyl-containing polysiloxane, and (D) a photo-radical polymerization initiator.
Description
Technical field
The antireflection film and the antireflective hard that the present invention relates to photosensitive polymer combination, have a curing tunicle of said composition are filmed.In more detail, relate to that scuff resistance, wear resistant, stain resistance, the transparency are excellent, low-refraction and reflectivity is low when being used for antireflection film and antireflective hard and filming photosensitive polymer combination and have its antireflection film and antireflective hard that solidifies tunicle and film.
Background technology
At present, plastics use in the various industrial circles that with automotive field, field of household appliances, electric and electronic field are representative in a large number.Use the reason of plastics to be so in a large number: its processibility, the transparency are excellent, and in light weight, cost is low, also excellence etc. of optical characteristics.But therefore plastics have shortcomings such as the easy scuffing in surface than softnesses such as glass.In order to improve these shortcomings, be to be coated with hard paint at frosting as general method.For this hard paint, can use silicone-based coating, acrylic acid series coating, trimeric cyanamide is the hard paint of thermohardening types such as coating.Wherein, the hard paint of silicone-based particularly is because hardness is high, excellent quality and often being used.But the set time of the hard paint of silicone-based is long, price is high, is not suitable for the hard coat that on the film of processing continuously, is provided with.
In recent years, develop and utilized the hard paint of photosensitive acrylic acid series (referring to patent documentation 1).The hard paint of photosensitivity is solidified to form the tunicle of hard immediately through irradiation ultraviolet radiation isoreactivity energy-ray, therefore has excellent performances such as the fast and hardness of processing treatment speed, scuff resistance, and total cost is low, therefore becomes the main flow in hard coat film field at present.Be particularly suitable for the continuous processing of the film of polyester etc.Film as plastics; Polyester film, polyacrylic ester film, acrylic film, polycarbonate membrane, ethylene chloride film, tri acetyl cellulose membrane, poly (ether sulfone) film, cyclo-olefin-polymer films etc. are arranged; Polyester film, tri acetyl cellulose membrane have the characteristic of various excellences, thereby use the most extensive.Polyester film is widely used as the photomask, blank of anti-the disperse film or the automobile of the glass functional membrane with the touch-screen of surface film, whole kitchen surface soiling film, electronic material aspect, CRT panel TV set, PDP etc.Tri acetyl cellulose membrane is used in the polaroid as the necessary material of liquid crystal display.As stated, these purposes all are coated with hard paint in order to make the surface not produce scuffing.
In addition; In the PDP (plasma display) of the film that is provided with the hard paint of coating in recent years, LCD (liquid crystal panel), the CRT indicating meters such as (braun tubes); Owing to produced the problem that is difficult to see clearly display picture, eyes easy fatigue because of reflection; Thereby, need have the dura mater processing of anti-reflective function to the surface according to purposes.As the method for surperficial antireflection, has following method: after hard coat film disperses mineral filler or organic filler in photosensitive polymer combination, it is applied on the film, forms the concavo-convex method (AG: non-glare treated) that reflects of preventing on the surface; The different layer of a plurality of specific refractory poweres is set on film, and the interference of light that utilizes the difference of specific refractory power to produce prevents the method (AR: antireflection is handled) that mirrors; Perhaps make up the method for the AG/AR processing of above-mentioned two kinds of methods; Or the like (referring to patent documentation 2).
Here, low-index layer used during AR handles uses the compound (referring to patent documentation 3) that makes the thermohardening type of silane compound condensation through sol-gel method, but exist solidify time-consuming, produce the problem that rate variance and hard coat crack because of heat shrink.
On the other hand, also developed and used the active energy ray curable resin (referring to patent documentation 4) of (methyl) propenoate with fluorine atom, scuff resistance is not enough, the insufficient problem of chemical proofing but exist.
Because problems such as above-mentioned productivity and heating crack require the low-refraction dura mater to use the active energy ray curable resin.But practical situation are that the scuff resistance of active energy ray curable resin is not enough, chemical proofing is not enough.
Patent documentation 1: japanese kokai publication hei 9-48934 communique
Patent documentation 2: japanese kokai publication hei 9-145903 communique
Patent documentation 3: No. 3776978 communique of Japanese Patent
Patent documentation 4: No. 3724144 communique of Japanese Patent
Summary of the invention
The object of the present invention is to provide excellences such as stain resistance, the transparency such as easy curing, high firmness, scuff resistance, wear resistant, chemical proofing, the magic ink property wiped or the fingerprint property wiped the low-index layer that is used for antireflection film photosensitive polymer combination and used the antireflection film of this photosensitive polymer combination and antireflective hard to film.
The inventor has carried out deep research in order to solve above-mentioned problem, and the result has found to contain the photosensitive polymer combination of specific compound, has accomplished the present invention thus.
That is, the present invention relates to:
(1) a kind of photosensitive polymer combination, its contain at intramolecularly have multifunctional (methyl) propenoate (A) of (methyl) acryl more than at least 3, the median size with nano-pore structure is the colloidal silica (B) of 1～200 nanometer, the ZGK 5 (C) with (methyl) acryl and optical free radical polymerization starter (D);
(2) like above-mentioned (1) described photosensitive polymer combination, the ZGK 5 (C) that wherein, has (methyl) acryl is for having the compound of 1～8 (methyl) acryl at intramolecularly;
(3) like above-mentioned (1) or (2) described photosensitive polymer combination, it also contains thinner (E);
(4) a kind of antireflection film wherein, on base material film, is disposed at outermost layer with the cured layer of each described photosensitive polymer combination of claim 1 to 3 as low-index layer;
(5) a kind of antireflective hard is filmed, and it has the cured layer of hard paint and the cured layer of above-mentioned (1) to each described photosensitive polymer combination of (3) successively on base material film;
(6) film like above-mentioned (5) described antireflective hard; Wherein, hard paint has multifunctional (methyl) propenoate (A) of (methyl) acryl more than at least 3, MOX (F) that median size is 1～200 nanometer and the photosensitive polymer combination of optical free radical polymerization starter (D) for containing at intramolecularly;
(7) film like above-mentioned (6) described antireflective hard, wherein, median size is the White tin oxide of the MOX (F) of 1～200 nanometer for the phosphorus that mixed.
According to the present invention, a kind of photosensitive polymer combination that contains specific compound can be provided, it solidifies through active energy beam easily; Hardness is high; Excellences such as stain resistance such as scuff resistance, wear resistant, chemical proofing, the transparency, the magic ink property wiped or the fingerprint property wiped; Be used for to form the low low-index layer of reflectivity when antireflection film or antireflective hard are filmed.
Embodiment
Below, specify the present invention.
Photosensitive polymer combination of the present invention contain at intramolecularly have multifunctional (methyl) propenoate (A) of (methyl) acryl more than at least 3, the median size with nano-pore structure is the colloidal silica (B) of 1～200 nanometer, the ZGK 5 (C) with (methyl) acryl and optical free radical polymerization starter (D).
As multifunctional (methyl) propenoate (A) that has (methyl) acryl more than at least 3 at intramolecularly; Multifunctional (methyl) propenoate that preferably has 3～15 (methyl) acryls at intramolecularly; For example, can enumerate polyester acrylate class, three (acryloxy ethyl) isocyanuric acid esters such as multifunctional urethane (methyl) esters of acrylic acid as the reactant of multifunctional (methyl) acryliccompound and polyisocyanate compound, trimethylolpropane tris (methyl) propenoate, TriMethylolPropane(TMP) polyethoxye three (methyl) propenoate, tetramethylolmethane three (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, ditrimethylolpropane four (methyl) propenoate, Dipentaerythritol six (methyl) propenoate, tripentaerythritol eight (methyl) propenoate etc. with hydroxyl.Need to prove that they can use separately, also can mix use more than 2 kinds.
Has multifunctional (methyl) acryliccompound of hydroxyl as this; For example, can enumerate Pentaerythritols such as tetramethylolmethane three (methyl) propenoate, Dipentaerythritol five (methyl) propenoate, Dipentaerythritol four (methyl) propenoate, Dipentaerythritol three (methyl) propenoate, Dipentaerythritol two (methyl) propenoate; Methylol classes such as TriMethylolPropane(TMP) two (methyl) propenoate; Epoxy (methyl) esters of acrylic acids such as dihydroxyphenyl propane diepoxy (methyl) propenoate.Wherein preferably can enumerate pentaerythritol triacrylate, Dipentaerythritol five propenoate.These multifunctional (methyl) acryliccompound with hydroxyl can use separately, also can mix use more than 2 kinds.
As this polyisocyanate compound, can enumerate with chain stable hydrocarbon, cyclic saturated hydrocarbon (ester ring type), aromatic hydrocarbons polyisocyanate compound as basic comprising.As such polyisocyanate compound, for example, can enumerate tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2, chain stable hydrocarbon POLYMETHYLENE POLYPHENYLISOCYANATE such as 4-trimethyl hexamethylene diisocyanate; Cyclic saturated hydrocarbon (ester ring type) POLYMETHYLENE POLYPHENYLISOCYANATE such as isophorone diisocyanate, dicyclohexyl methane diisocyanate, methylene-bis (4-cyclohexyl isocyanate), hydrogenated diphenyl methane diisocyanate, hydrogenated xylene diisocyanate, HTDI; 2,4 toluene diisocyanate, 1,3-XDI, PPDI, 3,3 '-dimethyl--4,4 '-biphenyl diisocyanate, 6-sec.-propyl-1,3-phenyl diisocyanate, 1, aromatic polyisocyanates such as 5-naphthalene diisocyanate.As preferred example, can enumerate tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate.These polyisocyanate compounds can use separately, also can mix use more than 2 kinds.
This multifunctional urethane (methyl) acryliccompound is through above-mentioned multifunctional (methyl) acryliccompound and the reaction of above-mentioned polyisocyanate compound with hydroxyl obtained.With respect to hydroxyl 1 equivalent in multifunctional (methyl) acryliccompound, employed polyisocyanate compound in the NCO equivalent be generally 0.1～50 normal scope, 0.1～10 normal scope that is preferably gets final product.
Temperature of reaction is generally 30～150 ℃, is preferably 50～100 ℃ scope.
Terminal point about reaction; Through making the reaction of remaining isocyanic ester and excessive n-Butyl Amine 99 and utilize the method for the unreacted n-Butyl Amine 99 of 1N hydrochloric acid residual titration to calculate remaining amount of isocyanate, polyisocyanate compound is reached moment below the 0.5 weight % as terminal point.
In order to shorten the reaction times, can add catalyzer.As this catalyzer, use any one of basic catalyst or an acidic catalyst.As basic catalyst, for example, can enumerate amines such as pyridine, pyrroles, triethylamine, diethylamine, dibutylamine; Ammonia; Phosphine such as tributylphosphine or triphenylphosphine class.In addition, as an acidic catalyst, for example, can enumerate metal alkoxide classes such as copper naphthenate, cobalt naphthenate, zinc naphthenate, aluminium butoxide, four butoxy Tritanium/Trititaniums, tetrabutyl zirconate; Louis's acids such as aluminum chloride; Tin compounds such as 2-ethyl hexane tin, three LAURIC ACID 99 MIN tin octylates, dibutyl tin laurate, oxalic acid tin octylate.With respect to POLYMETHYLENE POLYPHENYLISOCYANATE 100 weight %, the addition of these catalyzer is generally more than the 0.1 weight % and below the 1 weight %.
In addition; During reaction for the polymerization in preventing to react; Preferred use stopper (for example; MEHQ, quinhydrones, toluhydroquinone, thiodiphenylamine etc.), the consumption of this stopper is more than the 0.01 weight % and below the 1 weight % with respect to reaction mixture, is preferably more than the 0.05 weight % and below the 0.5 weight %.
In the photosensitive polymer combination of the present invention, when the solids component of this photosensitive polymer combination was made as 100 weight %, the content of above-mentioned (A) composition was generally 5～90 weight %, is preferably 10～70 weight %.Among the present invention, contain at compsn under the situation of thinner, solvent, solids component is meant removes residual whole compositions behind these materials from compsn.
As the median size with nano-pore structure that contains in the photosensitive polymer combination of the present invention is the colloidal silica (B) of 1～200 nanometer, can enumerate porous silica, hollow silica.About the refractive index n of common silica dioxide granule=1.45, relative therewith, inside has the porous silica of the air of refractive index n=1, the specific refractory power of hollow silica is n=1.2～1.45.Can form the layer of low-refraction thus by photosensitive polymer combination of the present invention suitably.
Colloidal silica (B) comprises to be dispersed in the solvent colloidal silica and the colloidal solution that obtains, or not to contain the colloidal silica micropowder of dispersion solvent.The colloidal solution that obtains as colloidal silica is dispersed in the solvent can be enumerated ELCOM series that Catalysts & Chem Ind Co makes, THRULYA series etc.
As colloidal silica is dispersed in the solvent and the dispersion solvent of the colloidal solution that obtains for example, can make alcohols such as water, methyl alcohol, ethanol, Virahol, propyl carbinol; Polyalcohols and verivates thereof such as terepthaloyl moietie, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate; Ketones such as methyl ethyl ketone, MIBK, pimelinketone, N,N-DIMETHYLACETAMIDE; Ester such as ETHYLE ACETATE, butylacetate class; Non-polar solvent such as toluene, YLENE; (methyl) esters of acrylic acid or other OOS classes such as (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester.With respect to colloidal silica 100 weight %, the amount of dispersion solvent is generally 100～900 weight %.
Among the present invention, median size is meant the particle diameter of minimum when breaking cohesion, that this particle had, and it can pass through mensuration such as BET method, dynamic light scattering method, electron microscope observation.As colloidal silica (B); Needing to use the median size of utilizing these assay methods to obtain is the colloidal silica of 1～200 nanometer; Preferred median size is the colloidal silica of 1～100 nanometer, and further preferred median size is the colloidal silica of 1～80 nanometer.
In the photosensitive polymer combination of the present invention; When the solids component of this photosensitive polymer combination was made as 100 weight %, (B) content of composition was generally 5 weight %～90 weight %, is preferably 10 weight %～80 weight %, further is preferably 20 weight %～70 weight %.
In addition, can also utilize silane coupling agent etc. to carrying out surface treatment in the surface of colloidal silica, thereby improve dispersed.
As long as surface treatment method utilizes known method to handle, drying process and damp process are arranged.The method of drying process for SiO 2 powder is handled wherein, evenly spreads to the stoste of silane coupling agent or solution and utilizes stirrer to carry out handling in the SiO 2 powder of high-speed stirring.Damp process is following method: dispersed silicon dioxide in solvent etc., and after the slurryization, to wherein adding silane coupling agent and stirring and handle.Can use any one method among the present invention.The consumption of silane coupling agent (g) is as long as at the specific surface area (m by silica weight (g) * silicon-dioxide
2/ g)/minimum of silane coupling agent coats area (m
2Get final product below/the amount of g) trying to achieve.
The ZGK 5 with (methyl) acryl (C) that contains in the photosensitive polymer combination of the present invention also is called as organic silicon acrylic ester, organically-modified organosilicon, organic modified polyorganosiloxane, the organically-modified organic silicon acrylic ester of reaction bonded type etc. sometimes; For example, can enumerate the part of straight chain type dimethyl siloxane is undertaken organically-modified by alkyl or polyether-based etc. and given (methyl) acrylate-based and material of obtaining to its modification portion end.Through increasing the length of siloxane main chain, can give surperficial sliding, release property, anti-adhesive, anti-finger printing, the magic ink property wiped, the fingerprint property wiped etc.In addition, through improving organically-modified rate, can improve consistency, coating (recoatability), printing again.
Be preferably the compound of having introduced (methyl) acryl at organically-modified end; Can carry out polyreaction through introducing (methyl) acryl; Reduce the transitivity of ZGK 5 to the interface; And can reduce when producing to the transfer of roller and when reeling to the transfer at the film back side, and then can improve chemical proofing (basic soln, organic solvent etc.).
As these ZGK 5 (C) with (methyl) acryl, can use commercially available article, for example, can enumerate BYK-UV3500, BYK-UV3570 (being Bi Ke chemistry society makes); TEGO Rad2100,2200N, 2250,2500,2600,2700 (being Degussa society makes); X-22-2445, X-22-2455, X-22-2457, X-22-2458, X-22-2459, X-22-1602, X-22-1603, X-22-1615, X-22-1616, X-22-1618, X-22-1619, X-22-2404, X-22-2474, X-22-174DX, X-22-8201, X-22-2426, X-22-164A, X-22-164C (being Shin-Etsu Chemial Co., Ltd makes) etc.
In addition, above-mentioned (C) composition also can contain fluorine atom.
Above-mentioned (C) composition preferably has 1～8 (methyl) acryl at intramolecularly, and the number of preferred (methyl) acryl is 2～6.
In the photosensitive polymer combination of the present invention, when the solids component of this photosensitive polymer combination was made as 100 weight %, the content of above-mentioned (C) composition was generally 0.1 weight %～50 weight %, is preferably 1 weight %～20 weight %.
As the optical free radical polymerization starter (D) that contains in the photosensitive polymer combination of the present invention, for example, can enumerate 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-propane-1-ketone, diethoxy acetophenone, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-acetophenones such as 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; Ketal classes such as methyl phenyl ketone dimethyl ketal, benzoin dimethylether; UVNUL MS-40,4-benzoyl--4 '-dimethyl diphenyl sulfide, 4,4 '-benzophenones such as two methylamino UVNUL MS-40; 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl)-phosphinoxidess such as phenyl phosphine oxide etc.In addition; Can easily obtain the Lucirin TPO (2 that Irgacure 184 (1-hydroxy-cyclohexyl phenyl ketone), Irgacure 907 (2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-(4-morpholinyl) propane-1-ketone), BASF society that Ciba Specialty Chemicals Inc. makes make from market; 4,6-trimethylbenzoyl diphenyl phosphine oxide) etc.In addition, they can use separately, perhaps also can mix use more than 2 kinds.
In the photosensitive polymer combination of the present invention, when the solids component of this photosensitive polymer combination was made as 100 weight %, (D) content of composition was generally 0.1 weight %～30 weight %, is preferably 1 weight %～15 weight %.
As required, can also share sensitizing agent in the photosensitive polymer combination of the present invention.
As operable sensitizing agent, for example, can enumerate 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.; Aspect solvability and the consistency photosensitive polymer combination, consider preferred especially 2-ethyl-9,10-two (methoxy ethoxy) anthracene.
When using these sensitizing agents, its consumption is 1 weight %～200 weight %, is preferably 5 weight %～150 weight % with respect to optical free radical polymerization starter (D) 100 weight %.
Can use thinner (E) in the photosensitive polymer combination of the present invention.As this thinner (E), for example, can enumerate lactone such as gamma-butyrolactone, γ-Wu Neizhi, γ-Ji Neizhi, γ-Geng Neizhi, α-ethanoyl-gamma-butyrolactone, 6-caprolactone; Dioxane, 1, ethers such as 2-Methylal(dimethoxymethane), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene Glycol dibutyl ether, propylene glycol monomethyl ether, Ucar 35 list ethyl ether, triethylene glycol dimethyl ether, triethylene glycol Anaesthetie Ether, TEG dimethyl ether, TEG Anaesthetie Ether; Carbonates such as NSC 11801, propylene carbonate; Ketones such as methyl ethyl ketone, MIBK, pimelinketone, methyl phenyl ketone; Phenols such as phenol, cresols, xylenol; Ester classes such as ETHYLE ACETATE, butylacetate, ethyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate, Trivalin SF acetic ester, acetate of butyl carbitol, propylene glycol methyl ether acetate; Hydro carbons such as toluene, YLENE, diethylbenzene, hexanaphthene; Organic solvent classes such as petroleum-type solvent such as halogenated hydrocarbons such as trichloroethane, tetrachloroethane, monochloro-benzene, sherwood oil, petroleum naphtha; 2,2,3, fluorine such as 3-C3-Fluoroalcohol are alcohols; Hydrogen fluorine ethers such as perfluoro butyl methyl ether, perfluoro butyl ether etc.They can use separately, perhaps also can mix use more than 2 kinds.
In the photosensitive polymer combination of the present invention, the content of above-mentioned (E) composition is 0～99 weight % in photosensitive polymer combination of the present invention.
In addition, can also add flow agent, UV light absorber, photostabilizer, skimmer etc. in the photosensitive polymer combination of the present invention as required, give each objective function property.
As flow agent; Can enumerate fluorine based compound, silicone compound, acrylic acid series compound etc.; As UV light absorber; Benzotriazole based compound, UVNUL MS-40 based compound, triazine based compound etc. can be enumerated,, hindered amine based compound, benzoic ether based compound etc. can be enumerated as photostabilizer.
Photosensitive polymer combination of the present invention can obtain with other compositions through mixing above-mentioned (A) composition, (B) composition, (C) composition, (D) composition and (E) composition as required in any order.
The photosensitive polymer combination of the present invention that obtains like this through the time stable.
Antireflection film of the present invention obtains through the cured layer that above-mentioned photosensitive polymer combination is set on base material film (basement membrane).On the base material film with drying after thickness be 0.05～0.5 μ m, after the mode that is preferably 0.05～0.3 μ m (preferably the wavelength with minimum value that reflectivity is shown is 500～700nm, the mode that is preferably 520～650nm sets thickness) is coated with photosensitive polymer combination of the present invention and drying; Shine active energy beam and form the curing tunicle, thereby can obtain antireflection film of the present invention.
In addition, between the cured layer of base material film (basement membrane) and photosensitive polymer combination of the present invention, printed layers can also be set, be used to improve intermediary's coating of adaptation, the layer such as high refractive index layer with specific refractory power higher than the specific refractory power of base material film (basement membrane).
When high refractive index layer is set; With dried thickness be 0.05～5 μ m, be preferably 0.05～3 μ m (preferably with the peaked wavelength that reflectivity is shown be 500～700nm, the mode that is preferably 520～650nm sets thickness) mode be coated with high refractive index coating agent and dry; Shine active energy beam then, form and solidify tunicle.
Antireflective hard of the present invention is filmed through on base material film (basement membrane), setting gradually hard coat and photosensitive polymer combination layer of the present invention obtains.At first, on the base material film with drying after thickness be 1～30 μ m, the mode that is preferably 3～20 μ m is coated with hard paint, dry back irradiation active energy beam and form the curing tunicle.Next; On the formed hard coat with drying after thickness be 0.05～0.5 μ m, the mode that is preferably 0.05～0.3 μ m (preferably the wavelength with minimum value that reflectivity is shown is 500～700nm, the mode that is preferably 520～650nm sets thickness) is coated with photosensitive polymer combination of the present invention; Dry back is shone active energy beam and is formed the curing tunicle, films thereby can obtain antireflective hard of the present invention.
In addition, also the high refractive index layer with specific refractory power higher than the specific refractory power of hard coat can be set between the cured layer of hard coat and photosensitive polymer combination of the present invention.At this moment; With thickness after the drying be 0.05～5 μ m, be preferably 0.05～3 μ m (preferably with the peaked wavelength that reflectivity is shown be 500～700nm, the mode that is preferably 520～650nm sets thickness) mode be coated with the high refractive index coating agent, dry back irradiation active energy beam and form the curing tunicle.
As base material film, as stated, for example, can enumerate polyester, Vestolen PP 7052, Vilaterm, polyacrylic ester, polycarbonate, triacetyl cellulose, polyethersulfone, cyclic olefine polymkeric substance etc.Film also can be a thicker flaky film to a certain degree.Employed film can be for painted film, be provided with the film that is prone to adhesive linkage, carried out surface-treated films such as corona treatment.
Coating process as above-mentioned photosensitive polymer combination; For example, can enumerate rod is coated with machine coating, the coating of Meyer rod, airblade coating, photogravure coating, reverse photogravure coating, the coating of nick version, reverse nick version coating, mould and is coated with machine coating, vacuum mold coating, dip coated, spin application etc.
The active energy beam that shines as being used to solidify for example, can be enumerated ultraviolet ray, electron rays etc.When utilizing ultraviolet ray that it is solidified, use to have the UV irradiation equipment as light source such as xenon lamp, high voltage mercury lamp, metal halide lamp, adjust light quantity, configured light sources etc. as required.When using high voltage mercury lamp, a lamp with respect to the energy with 80～240W/cm preferably was cured with transfer rate 5～60m/ minute.
In addition, more preferably irradiation active energy beam under the environment that has carried out inert gas replacement is cured.As oxygen concn, be preferably below the 1 volume %, more preferably below the 0.5 volume %.As this rare gas element, preferably use nitrogen.
As being used for the 1st layer the hard paint that antireflective hard of the present invention is filmed; Can directly use commercially available hard paint, also can use the photosensitive polymer combination that above-mentioned multifunctional (methyl) propenoate (A) with (methyl) acryl more than 3 and optical free radical polymerization starter (D), as required thinner (E) and other additives are mixed and form.
In addition, give static resistance for the specific refractory power that improves hard coat and to hard coat, preferably using median size is the MOX (F) of 1～200 nanometer.As this MOX (F); Can enumerate MOX that specific refractory power is improved, for example titanium oxide, zirconium white, zinc oxide, White tin oxide, red stone, tin indium oxide (ITO), antimony-doped tin oxide (ATO), zinc antimonates, aluminium-doped zinc oxide, Ga-doped zinc oxide, tin dope zinc antimonates, phosphorus doping White tin oxide etc.; Wherein preferred as the White tin oxide of giving the MOX of static resistance, tin indium oxide (ITO), antimony-doped tin oxide (ATO), zinc antimonates, aluminium-doped zinc oxide, phosphorus doping White tin oxide etc.; From aspects such as price, stability, dispersivenesses; Preferred especially zinc antimonates, phosphorus doping White tin oxide; From the aspect of the transparency, preferred especially phosphorus doping White tin oxide.
They can be used as micropowder or are distributed to the dispersion liquid acquisition in the organic solvent.
As the organic solvent that can be used for dispersion liquid, for example, can enumerate alcohols such as methyl alcohol, ethanol, Virahol, propyl carbinol, terepthaloyl moietie, ethylene glycol monoethyl ether, propylene glycol monomethyl ether; Ketones such as methyl ethyl ketone, MIBK, pimelinketone; Ester such as ETHYLE ACETATE, butylacetate class; Non-polar solvent such as toluene, YLENE etc.With respect to MOX 100 weight %, the amount of organic solvent is generally 70～900 weight %.
Need to prove that median size is meant the particle diameter of minimum when breaking cohesion, that this particle had, can pass through the median size that BET method, dynamic light scattering method, electron microscope observation etc. are measured MOX (F).
In these hard paints, when the solids component of hard paint was made as 100 weight %, (F) content of composition was generally 5 weight %～90 weight %, is preferably 10 weight %～80 weight %.
In addition, in order to improve the hardness of hard coat, can add median size is the above and colloidal silica (G) below the 200nm of 1nm.Employed median size is that the above and colloidal silica (G) below the 200nm of 1nm can be so that colloidal silica be distributed to the colloidal solution form that obtains in the solvent uses, or uses with the form of the colloidal silica micropowder that do not contain dispersion solvent.
As the dispersion solvent of colloidal silica (G), for example, can make alcohols such as water, methyl alcohol, ethanol, Virahol, propyl carbinol, Pyranton; Polyalcohols and verivates thereof such as terepthaloyl moietie; Ketones such as methyl ethyl ketone, MIBK, pimelinketone; Ester such as ETHYLE ACETATE, n-butyl acetate class; Non-polar solvent such as toluene, YLENE; Vinylformic acid-esters of acrylic acids such as 2-hydroxyl ethyl ester; N,N-DIMETHYLACETAMIDE or other OOS classes.With respect to colloidal silica 100 weight %, the amount of dispersion solvent is generally more than the 100 weight % and below the 900 weight %.
These colloidal silicas (G) can utilize the known method manufacturing, also can use commercially available material.For example, can enumerate organic silicon sol MEK-ST that Nissan Chemical Ind Ltd makes etc.Need to use median size to be the colloidal silica more than the 1nm and below the 200nm, be preferably more than the 5nm and below the 100nm, more preferably more than the 10nm and below the 50nm.For more than the 1nm and 100nm when following, can guarantee the transparency, for more than the 1nm and 50nm when following, the transparency, mist degree all obtain enough good result.
Need to prove that median size is meant the particle diameter of minimum when breaking cohesion, that this particle had, can pass through the median size that BET method, dynamic light scattering method, electron microscope observation etc. are measured colloidal silica (G).
When containing (G) composition in these hard paints, the solids component of hard paint is made as 100 weight %, (G) content of composition is generally 10 weight %～70 weight %, is preferably 20 weight %～50 weight %.
(A) composition, (D) composition, (E) composition, (F) composition, (G) composition of being used for above-mentioned hard paint are mixed in any order/mix and get final product, and can also add flow agent, skimmer etc. or other additives as required.
High refractive index coating agent during setting has the specific refractory power higher than the specific refractory power of hard coat between the high refractive index coating agent when the layers such as high refractive index layer with specific refractory power higher than the specific refractory power of base material film (basement membrane) are set between the cured layer of base material film (basement membrane) and photosensitive polymer combination of the present invention and the cured layer of hard coat on base material film and photosensitive polymer combination of the present invention high refractive index layer can be with the use that is mixed of above-mentioned (A) composition, (D) composition, as required (E) composition, (F) composition and other additives.
Embodiment
Below, the present invention will be described in more detail through embodiment, but the present invention is not limited to these embodiment.In addition, among the embodiment, only otherwise special declaration, then part expression weight %.
Make example 1
(the methyl alcohol dispersion colloidal sol of Nissan Chemical Ind Ltd's manufacturing, zinc antimonates, solids component 60%, 15～20nm) 12.5 parts of median sizes, 8 parts of methyl alcohol, 7.5 parts of propylene glycol monomethyl ethers, 2.5 parts of diacetone alcohols, methyl ethyl ketone mix for 27 parts, obtain solids component and be 50% hard paint with 2.5 parts in 37.5 parts in the mixture of dipentaerythritol acrylate and Dipentaerythritol five propenoate (Nippon Kayaku K. K makes, KAYARAD DPHA), vinylformic acid tetrahydro furfuryl ester (organic chemistry Co., Ltd. in Osaka makes, Biscoat #150), 1.5 parts of Irgacure 184 (manufacturings of Ciba Specialty Chemicals society), 1 part of Irgacure907 (manufacturings of Ciba Specialty Chemicals society), CELNAX CX-Z603M-F2.
The thickness that resulting hard paint is applied to before saponification is handled is triacetyl cellulose (TAC) film (the Konica Minolta Opto of 80 μ m; Inc. make) on; Making thickness is about 5 μ m; After 80 ℃ of following dryings, the uviolizing machine uses high voltage mercury lamp, is cured with the illuminate condition of the energy of 160W/cm, transfer rate 5m/ minute.The transmitance of the film after coating, the curing is 89%, and mist degree is 0.7%, and pencil hardness (load 500g) is 3H, and the adaptation of cured film is also good.
Make example 2
(the methyl alcohol dispersion colloidal sol of Nissan Chemical Ind Ltd's manufacturing, White tin oxide, solids component 50%, 10～40nm) 40 parts of median sizes, 25 parts of 1-propyl alcohol, diacetone alcohol mix for 5 parts, obtain solids component and be 50% hard paint with 3 parts in 24 parts in the mixture of dipentaerythritol acrylate and Dipentaerythritol five propenoate (Nippon Kayaku K. K makes, KAYARAD DPHA), vinylformic acid tetrahydro furfuryl ester (organic chemistry Co., Ltd. in Osaka makes, Biscoat #150), 1.8 parts of Irgacure 184 (manufacturings of Ciba Specialty Chemicals society), 1.2 parts of Irgacure907 (manufacturings of Ciba Specialty Chemicals society), CELNAX CX-S505M.
The thickness that resulting hard paint is applied to before saponification is handled is triacetyl cellulose (TAC) film (the Konica Minolta Opto of 80 μ m; Inc. make) on; Making thickness is about 5 μ m; After 80 ℃ of following dryings, the uviolizing machine uses high voltage mercury lamp, is cured with the illuminate condition of the energy of 160W/cm, transfer rate 5m/ minute.The transmitance of coating, the film after solidifying is 91%, and mist degree is 0.5%, pencil hardness (load 500g) is 3H, and the adaptation of cured film is also good.
Embodiment 1～2, comparative example 1～2
The photosensitive polymer combination for preparing the material shown in the table 1 that is mixed.
[table 1] table (unit representation " part ") that is mixed
(notes)
DPHA: Nippon Kayaku K. K makes, KAYARAD DPHA (mixture of Dipentaerythritol five propenoate and dipentaerythritol acrylate) ((A) composition)
ELCOM: wave that Catalysts & Chem Ind Co makes day, (solids component is 20% to the MIBK dispersion liquid of nanoporous silica, median size: 40～60 nanometers) ((B) composition)
TEGO:Degussa society makes, TEGO Rad 2600 (acrylate-functional groups number: 6) ((C) composition)
X-22: Shin-Etsu Chemial Co., Ltd makes, X-22-2445 (acrylate-functional groups number: 2) ((C) composition)
US270: Toagosei Co., Ltd makes, polysiloxane grafted polymer (solids component 30%) (being used for and (C) composition comparison)
ST103PA: eastern beautiful DOW CORNING Co., Ltd. makes, ZGK 5 (be used for (C) composition relatively)
Initiator 1:1-hydroxy-cyclohexyl phenyl ketone ((D) composition)
Initiator 2:2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone ((D) composition)
MEK: methyl ethyl ketone ((E) composition)
DAA: diacetone alcohol ((E) composition)
Embodiment 3
The photosensitive polymer combination of the present invention that obtains among the coating embodiment 1 on the TAC film that is formed with hard coat that in making example 1, obtains; After 80 ℃ of following dryings; The uviolizing machine uses high voltage mercury lamp; Illuminate condition with the energy of 160W/cm, transfer rate 5m/ minute is cured, and obtains antireflective hard and films.At this moment, thickness is adjusted into about 0.1 μ m and makes the wavelength region may of the minimum value of reflectivity at 520～650nm.
Embodiment 4
The photosensitive polymer combination of the present invention that obtains among the coating embodiment 1 on the TAC film that is formed with hard coat that in making example 2, obtains; After 80 ℃ of following dryings; The uviolizing machine uses high voltage mercury lamp; Illuminate condition with the energy of 160W/cm, transfer rate 5m/ minute is cured, and obtains antireflective hard and films.At this moment, thickness is adjusted into about 0.1 μ m and makes the wavelength region may of the minimum value of reflectivity at 520～650nm.
Embodiment 5
The photosensitive polymer combination of the present invention that obtains among the coating embodiment 1 on the TAC film that is formed with hard coat that in making example 2, obtains; After 80 ℃ of following dryings; At oxygen concn is under the nitrogen atmosphere of 0.1 volume %; The uviolizing machine uses high voltage mercury lamp, is cured with the illuminate condition of the energy of 160W/cm, transfer rate 5m/ minute, obtains antireflective hard and films.At this moment, thickness is adjusted into about 0.1 μ m and makes the wavelength region may of the minimum value of reflectivity at 520～650nm.
Embodiment 6
The photosensitive polymer combination of the present invention that obtains among the coating embodiment 2 on the TAC film that is formed with hard coat that in making example 2, obtains; After 80 ℃ of following dryings; The uviolizing machine uses high voltage mercury lamp; Illuminate condition with the energy of 160W/cm, transfer rate 5m/ minute is cured, and obtains antireflective hard and films.At this moment, thickness is adjusted into about 0.1 μ m and makes the wavelength region may of the minimum value of reflectivity at 520～650nm.
Comparative example 3
The photosensitive polymer combination of the present invention that obtains in the coating comparative example 1 on the TAC film that is formed with hard coat that in making example 2, obtains; After 80 ℃ of following dryings; The uviolizing machine uses high voltage mercury lamp; Illuminate condition with the energy of 160W/cm, transfer rate 5m/ minute is cured, and obtains antireflective hard and films.At this moment, thickness is adjusted into about 0.1 μ m and makes the wavelength region may of the minimum value of reflectivity at 520～650nm.
Comparative example 4
The photosensitive polymer combination of the present invention that obtains in the coating comparative example 2 on the TAC film that is formed with hard coat that in making example 2, obtains; After 80 ℃ of following dryings; The uviolizing machine uses high voltage mercury lamp; Illuminate condition with the energy of 160W/cm, transfer rate 5m/ minute is cured, and obtains antireflective hard and films.At this moment, thickness is adjusted into about 0.1 μ m and makes the wavelength region may of the minimum value of reflectivity at 520～650nm.
Antireflective hard about obtaining in embodiment 3～6, the comparative example 3 and 4 is filmed, and estimates following project, and its result lists in table 2.
(pencil hardness)
According to JIS K 5600, use pencil scraping experiment machine, measure the pencil hardness of the coated film of above-mentioned composition.At length say, on the film of the curing tunicle of measuring having, make angle that pencil is 45 degree from the top with the load of 500g scraping 5mm about, represent with the hardness of not having the pencil that scratches among 5 times more than 4 times.
(scuff resistance)
On Steel Wool #0000, apply 500g/cm
2Load and reciprocal 10 times, through the abrasive situation of visual judgement.
Estimate 5 grades: do not have scratch
4 grades: 1～10 scratch takes place
3 grades: 10～30 scratch takes place
2 grades: the scratch more than 30 takes place
1 grade: whole takes place to abrade or peel off
(adaptation)
According to JIS K5600, vertical, horizontal 6 undercut mouths are cut at interval with 2mm in the surface of the film of the curing tunicle of measuring having, and make 25 checkers.After the cellulose film band is pasted on its surface, peel off without a break, the number of unstripped and remaining grid this moment is shown.
(minimum reflectivity)
Using UV, visible light infrared spectrophotometer Shimadzu Scisakusho Ltd to make UV-3150 measures.
(the magic ink property wiped)
Use black/red magic ink, writing words on coated face is wiped with low dirt cleansing tissue (Kimwipes) then, through the visual judgement property wiped.
Estimate A: can wipe more than 10 times in same area
B: can wipe 5～9 times in same area
C: can wipe 1～4 time in same area
(total light penetration)
Use the manufacturing of haze meter Tokyo electricity look Co., Ltd., TC-H3DPK to measure.(unit: %)
(mist degree)
Use the manufacturing of haze meter Tokyo electricity look Co., Ltd., TC-H3DPK to measure.(unit: %)
(surface resistivity)
Use the manufacturing of resistrivity meter Mitsubishi chemical Co., Ltd, HIRESTA IP to measure.(unit: Ω/)
(alkali resistance)
The making 1% and the 3%NaOH aqueous solution.Drip liquid to film coated surface, observe the film coated surface state of placing after 30 minutes.
Estimate A: no change
B: produce variable color
C: film is peeled off
Above-mentioned evaluation result is listed in table 2.
[table 2]
Can know that by table 2 pencil hardness that the antireflective hard of embodiment 3～6 is filmed, scuff resistance, adaptation, the magic ink property wiped and alkali resistance demonstrate good result.Comparative example 3 changes to the graftomer of ZGK 5 with (C) composition, and the result forms that scuff resistance reduces, the result of the magic ink property wiped and alkali resistance difference.Comparative example 4 changes to the ZGK 5 that does not contain acryl with (C) composition, and the result forms that scuff resistance reduces, the result of the transparency, the magic ink property wiped and alkali resistance difference.
Industrial applicibility
The stain resistances such as hardness, scuff resistance, the transparency, chemical proofing and the magic ink property wiped of the curing tunicle that is obtained by photosensitive polymer combination of the present invention are excellent.In addition, thus being adapted to pass through to be applied on the hard coat and to solidify makes the low antireflective hard of reflectivity and films.Film antireflection film that flat-panel monitors such as being suitable for LCD, PDP uses, plastic optical members, touch-screen, mobile telephone, film liquid crystal cell etc. of antireflective hard of the present invention like this needs the field of anti-reflective function.
Claims (7)
1. photosensitive polymer combination, it contains, and to have multifunctional (methyl) propenoate (A) of (methyl) acryl more than at least 3, median size with nano-pore structure at intramolecularly be 1～200 nanometer colloidal silica (B), have the ZGK 5 (C) and the optical free radical polymerization starter (D) of (methyl) acryl.
2. photosensitive polymer combination as claimed in claim 1, the ZGK 5 (C) that wherein, has (methyl) acryl is for having the compound of 1～8 (methyl) acryl at intramolecularly.
3. according to claim 1 or claim 2 photosensitive polymer combination, it also contains thinner (E).
4. antireflection film wherein, on base material film, is disposed at outermost layer with the cured layer of each described photosensitive polymer combination of claim 1 to 3 as low-index layer.
5. an antireflective hard is filmed, and it has the cured layer of each described photosensitive polymer combination of cured layer and the claim 1 to 3 of hard paint successively on base material film.
6. antireflective hard as claimed in claim 5 is filmed; Wherein, hard paint has multifunctional (methyl) propenoate (A) of (methyl) acryl more than at least 3, MOX (F) that median size is 1～200 nanometer and the photosensitive polymer combination of optical free radical polymerization starter (D) for containing at intramolecularly.
7. antireflective hard as claimed in claim 6 is filmed, and wherein, median size is the White tin oxide of the MOX (F) of 1～200 nanometer for the phosphorus that mixed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009176524 | 2009-07-29 | ||
| JP2009-176524 | 2009-07-29 | ||
| PCT/JP2010/062511 WO2011013611A1 (en) | 2009-07-29 | 2010-07-26 | Photosensitive resin composition, and antireflection film and antireflective hard coating film which are produced using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102471425A true CN102471425A (en) | 2012-05-23 |
| CN102471425B CN102471425B (en) | 2015-03-04 |
Family
ID=43529266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080031455.XA Expired - Fee Related CN102471425B (en) | 2009-07-29 | 2010-07-26 | Photosensitive resin composition, and antireflection film and antireflective hard coating film which are produced using same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5767583B2 (en) |
| KR (1) | KR20120044286A (en) |
| CN (1) | CN102471425B (en) |
| TW (1) | TWI494685B (en) |
| WO (1) | WO2011013611A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756383A (en) * | 2013-12-17 | 2014-04-30 | 张家港康得新光电材料有限公司 | Anti-adhesion coating composition used for hard coating and corresponding double-sided hard coating |
| CN109690363A (en) * | 2016-09-08 | 2019-04-26 | 株式会社大赛璐 | Hard conating laminated body and formed body and its manufacturing method |
| US11106134B2 (en) | 2017-12-29 | 2021-08-31 | Industrial Technology Research Institute | Photosensitive composite material and method for forming composite film using the same |
| CN113943504A (en) * | 2020-07-16 | 2022-01-18 | 荒川化学工业株式会社 | Active energy ray-curable coating agent, cured product, and laminate |
| CN114761838A (en) * | 2019-11-19 | 2022-07-15 | 大日本印刷株式会社 | Resin panel and infrared sensor |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5914978B2 (en) * | 2011-03-31 | 2016-05-11 | 大日本印刷株式会社 | Photocurable resin composition |
| TWI625241B (en) * | 2011-08-22 | 2018-06-01 | Mitsubishi Chem Corp | Transparent laminated film |
| KR101941445B1 (en) * | 2011-12-27 | 2019-04-15 | 엘지디스플레이 주식회사 | Position guiding apparatus for needle for ultrasonic operation |
| JP2013173871A (en) * | 2012-02-27 | 2013-09-05 | Mitsubishi Chemicals Corp | Composition, antistatic coating agent, and antistatic laminate |
| JP6080032B2 (en) * | 2012-03-15 | 2017-02-15 | 東レフィルム加工株式会社 | Antireflection film |
| KR101407617B1 (en) | 2012-04-25 | 2014-06-27 | 주식회사 엘지화학 | Thermoset coating composition having self-healing capacity, coating film, and preparation method of coating film |
| KR101379491B1 (en) | 2012-05-31 | 2014-04-01 | 주식회사 엘지화학 | Hard coating film and method of preparing of hard coating film |
| KR101451848B1 (en) | 2012-05-31 | 2014-10-16 | 주식회사 엘지화학 | Method of preparing of hard coating film |
| KR101501686B1 (en) | 2012-05-31 | 2015-03-11 | 주식회사 엘지화학 | Hard coating film |
| KR20150037734A (en) * | 2012-07-24 | 2015-04-08 | 니폰 가야꾸 가부시끼가이샤 | Photosensitive resin composition and antireflection film |
| KR101470465B1 (en) | 2012-08-23 | 2014-12-08 | 주식회사 엘지화학 | Hard coating film |
| KR101807208B1 (en) | 2015-08-18 | 2017-12-08 | 주식회사 엘지화학 | Low refractive layer and anti-reflective film comprising the same |
| JP7161836B2 (en) | 2015-12-18 | 2022-10-27 | デクセリアルズ株式会社 | Antifogging antifouling laminate, article, and method for producing the same |
| KR101973195B1 (en) * | 2016-03-11 | 2019-04-26 | 주식회사 엘지화학 | Anti-reflective film and preparation method of the same |
| WO2017155358A1 (en) * | 2016-03-11 | 2017-09-14 | 주식회사 엘지화학 | Anti-reflective film and method for producing same |
| JP6874312B2 (en) * | 2016-09-28 | 2021-05-19 | 株式会社ニデック | A method for producing a resin composition for hard coating, and a resin composition for hard coating. |
| JP6508559B2 (en) * | 2016-12-01 | 2019-05-08 | Dic株式会社 | Active energy ray curable composition and film using the same |
| KR20180087956A (en) | 2017-01-26 | 2018-08-03 | 동우 화인켐 주식회사 | Hard coating film and display window using the same |
| EP3597710B1 (en) * | 2018-07-18 | 2021-08-18 | Inkron OY | Novel polysiloxane compositions and uses thereof |
| KR102031802B1 (en) | 2019-03-25 | 2019-10-15 | 동우 화인켐 주식회사 | Hard coating film and display window using the same |
| CN114350256B (en) * | 2022-01-04 | 2022-12-06 | 海洋化工研究院有限公司 | High-temperature-resistant high-reflectivity coating component, preparation method thereof, coating and construction method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006109496A1 (en) * | 2005-04-06 | 2006-10-19 | Jsr Corporation | Radiation-curable resin composition and antireflection coating |
| JP2006306008A (en) * | 2005-03-31 | 2006-11-09 | Jsr Corp | Antistatic layered product |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10316860A (en) * | 1997-03-19 | 1998-12-02 | Dow Corning Asia Ltd | Optical polysiloxane resin containing silica |
| JP2001049236A (en) * | 1999-08-10 | 2001-02-20 | Toppan Printing Co Ltd | Stainproofing material and antireflection filter using the same |
| JP2002265866A (en) * | 2001-03-13 | 2002-09-18 | Toppan Printing Co Ltd | Low-refractive index coating material and antireflection film |
| JP2004314468A (en) * | 2003-04-17 | 2004-11-11 | Sumitomo Chem Co Ltd | Transparent substrate with cured coat formed and curable composition for the substrate |
| JP2005089536A (en) * | 2003-09-12 | 2005-04-07 | Jsr Corp | Curable resin composition and antireflection coating |
| JP4726198B2 (en) * | 2005-04-27 | 2011-07-20 | 日本化薬株式会社 | Photosensitive resin composition and film having cured film thereof |
| JP2009160755A (en) * | 2007-12-28 | 2009-07-23 | Jgc Catalysts & Chemicals Ltd | Transparently coated base material |
-
2010
- 2010-07-26 JP JP2011524763A patent/JP5767583B2/en active Active
- 2010-07-26 WO PCT/JP2010/062511 patent/WO2011013611A1/en active Application Filing
- 2010-07-26 KR KR1020117027658A patent/KR20120044286A/en not_active Application Discontinuation
- 2010-07-26 CN CN201080031455.XA patent/CN102471425B/en not_active Expired - Fee Related
- 2010-07-28 TW TW099124975A patent/TWI494685B/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006306008A (en) * | 2005-03-31 | 2006-11-09 | Jsr Corp | Antistatic layered product |
| WO2006109496A1 (en) * | 2005-04-06 | 2006-10-19 | Jsr Corporation | Radiation-curable resin composition and antireflection coating |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756383A (en) * | 2013-12-17 | 2014-04-30 | 张家港康得新光电材料有限公司 | Anti-adhesion coating composition used for hard coating and corresponding double-sided hard coating |
| CN103756383B (en) * | 2013-12-17 | 2016-09-07 | 张家港康得新光电材料有限公司 | Cured film Antiblock coating composition and corresponding two-sided cured film |
| CN109690363A (en) * | 2016-09-08 | 2019-04-26 | 株式会社大赛璐 | Hard conating laminated body and formed body and its manufacturing method |
| CN109690363B (en) * | 2016-09-08 | 2021-07-27 | 株式会社大赛璐 | Hard coat laminate, molded body, and method for producing same |
| US11106134B2 (en) | 2017-12-29 | 2021-08-31 | Industrial Technology Research Institute | Photosensitive composite material and method for forming composite film using the same |
| CN114761838A (en) * | 2019-11-19 | 2022-07-15 | 大日本印刷株式会社 | Resin panel and infrared sensor |
| CN113943504A (en) * | 2020-07-16 | 2022-01-18 | 荒川化学工业株式会社 | Active energy ray-curable coating agent, cured product, and laminate |
| CN113943504B (en) * | 2020-07-16 | 2024-05-10 | 荒川化学工业株式会社 | Active energy ray-curable coating agent, cured product, and laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011013611A1 (en) | 2013-01-07 |
| WO2011013611A1 (en) | 2011-02-03 |
| TWI494685B (en) | 2015-08-01 |
| CN102471425B (en) | 2015-03-04 |
| JP5767583B2 (en) | 2015-08-19 |
| TW201120566A (en) | 2011-06-16 |
| KR20120044286A (en) | 2012-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102471425B (en) | Photosensitive resin composition, and antireflection film and antireflective hard coating film which are produced using same | |
| KR101009821B1 (en) | Coating composition for antireflection, antireflection film and method for preparing the same | |
| KR101273097B1 (en) | Anti-reflection and anti-glare coating composition, anti-reflection and anti-glare film, and method for preparation of the same | |
| CN102040903B (en) | Uv curable resin composition for hard coat, and hard coated film and hard coated moldings using the same | |
| KR101504785B1 (en) | Antireflection film | |
| US20100271699A1 (en) | Coating composition for antireflection and antireflection film prepared by using the same | |
| CN104379620A (en) | Photosensitive resin composition and antireflection film | |
| US20100265580A1 (en) | Coating composition for antireflection, antireflection film and method for preparing the same | |
| KR100917961B1 (en) | Antireflective laminate | |
| WO2008007875A1 (en) | Antireflective coating composition with stain resistance, antireflective coating film using the same, and its manufacturing method | |
| KR101268700B1 (en) | Liquid curable composition, cured film, and antistatic layered product | |
| KR20090049517A (en) | Coating composition for antireflection and antireflection film prepared by using the same | |
| JP2006306008A (en) | Antistatic layered product | |
| KR20070089718A (en) | Antireflective film | |
| CN1965041A (en) | Low refractive index coating composition | |
| KR101082667B1 (en) | Coating composition for antireflection and antireflection film prepared by using the same | |
| KR20090049519A (en) | Coating composition for antireflection and antireflection film prepared by using the same | |
| JP2010013572A (en) | Photosensitive resin composition and antireflection film | |
| JP2010174056A (en) | Photosensitive resin composition and antireflective film | |
| JP4929976B2 (en) | High weather resistance antireflection film | |
| JP4618018B2 (en) | Antistatic laminate | |
| KR101539276B1 (en) | Ceramic polymer composition implemented anti-glare, anti-reflection and anti-fouling and surface-treated article using the same | |
| JP2008129317A (en) | Antireflection film and transparent base material with antireflection film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150304 Termination date: 20180726 |