CN102471425B - 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 PDF

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CN102471425B
CN102471425B CN201080031455.XA CN201080031455A CN102471425B CN 102471425 B CN102471425 B CN 102471425B CN 201080031455 A CN201080031455 A CN 201080031455A CN 102471425 B CN102471425 B CN 102471425B
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methyl
film
photosensitive polymer
polymer combination
acrylate
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CN102471425A (en
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矢作悦幸
狩野浩和
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Nippon Kayaku Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • 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
    • 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

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  • 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

Photosensitive polymer combination, the antireflection film employing this photosensitive polymer combination and antireflective hard film
Technical field
The present invention relates to photosensitive polymer combination, there is antireflection film and the antireflective hard film of the solidification tunicle of said composition.In more detail, relate to that scuff resistance, wear resistant, stain resistance, the transparency are excellent, low-refraction and for the low photosensitive polymer combination of reflectivity when antireflection film and antireflective hard film and antireflection film and the antireflective hard film with its solidification tunicle.
Background technology
At present, plastics use in a large number in the various industrial circles being representative with automotive field, field of household appliances, electric and electronic field.So a large amount of reason of plastics that uses is: its processibility, the transparency are excellent, and lightweight, cost is low, optical characteristics is also excellent etc.But plastics, than softnesses such as glass, therefore have the shortcomings such as the easy scuffing in surface.In order to improve these shortcomings, be coated with hard paint at frosting as general method.For this hard paint, the hard paint of the thermohardening types such as silicone-based coating, Acrylic coatings, melamine series coating can be used.Wherein, the particularly hard paint of silicone-based, because hardness is high, excellent quality and being often used.But the set time of the hard paint of silicone-based is long, price is high, is not suitable for the hard coat arranged on the film of Continuous maching.
In recent years, develop and make use of the hard paint of photosensitive acrylic acid series (see patent documentation 1).The hard paint of photosensitivity is solidified to form the tunicle of hard immediately by irradiation ultraviolet radiation isoreactivity energy-ray, and therefore have the performance that processing treatment speed is fast and hardness, scuff resistance etc. are excellent, total cost is low, therefore becomes the main flow in hard coat film field at present.Be particularly suitable for the Continuous maching of the film of polyester etc.As the film of plastics, there are 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., polyester film, tri acetyl cellulose membrane have the characteristic of various excellence, thus use the most extensive.Polyester film is widely used as the functional membrane of touch-screen, CRT panel TV set, plasma display panel (PDP) etc. of the photomask of anti-disperse film or the automobile of glass, blank surface film, whole kitchen surface soiling film, electronic material aspect.Tri acetyl cellulose membrane is used as in the polaroid of necessary material of liquid crystal display.As mentioned above, these purposes are all coated with hard paint to make surface not produce scuffing.
In addition, in the indicating meter such as the PDP (plasma display) being provided with the film being coated with hard paint, LCD (liquid crystal panel), CRT (braun tube) in recent years, be difficult to see display picture clearly owing to creating because of reflection, eyes hold fatigable problem, thus according to purposes, effects on surface is needed to carry out having the dura mater process of anti-reflective function.As the method for surperficial antireflection, there is following methods: in hard coat film photosensitive polymer combination after dispersed inorganic filler or organic filler, be applied on film, form the concavo-convex method (AG: non-glare treated) preventing reflecting on surface; Film arranges the layer that multiple specific refractory power is different, and the interference of the light utilizing specific refractivity to produce prevents the method (AR: antireflection process) mirrored; Or combine the method for the AG/AR process of above-mentioned two kinds of methods; Etc. (see patent documentation 2).
Herein, low-index layer used in AR process uses the compound (see patent documentation 3) being made the thermohardening type of silane compound condensation by sol-gel method, but exist solidification time-consuming, produce the problem that rate variance and hard coat crack because of heat shrink.
On the other hand, further developed the active energy ray curable resin (see patent documentation 4) using and there is (methyl) acrylate of fluorine atom, but there is the problem of scuff resistance deficiency, chemical proofing deficiency.
Due to problems such as above-mentioned productivity and heating crack, require that low-refraction dura mater uses 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 Unexamined Patent Publication 9-48934 publication
Patent documentation 2: Japanese Unexamined Patent Publication 9-145903 publication
Patent documentation 3: Japanese Patent No. 3776978 publication
Patent documentation 4: Japanese Patent No. 3724144 publication
Summary of the invention
The object of the present invention is to provide the photosensitive polymer combination of the excellent low-index layer for antireflection film of stain resistance, the transparencys etc. such as easy solidification, high rigidity, scuff resistance, wear resistant, chemical proofing, the magic ink property wiped or the fingerprint property wiped and employ antireflection film and the antireflective hard film of this photosensitive polymer combination.
The present inventor conducts in-depth research to solve above-mentioned problem, found that the photosensitive polymer combination containing specific compound, this completes the present invention.
That is, the present invention relates to:
(1) photosensitive polymer combination, it contains multifunctional (methyl) acrylate (A) in molecule with more than at least 3 (methyl) acryls, the median size with nano-pore structure is the colloidal silica (B) of 1 ~ 200 nanometer, the polysiloxane (C) with (methyl) acryl and optical free radical polymerization starter (D);
(2) photosensitive polymer combination as described in above-mentioned (1), the polysiloxane (C) wherein, with (methyl) acryl is the compound in molecule with 1 ~ 8 (methyl) acryl;
(3) photosensitive polymer combination as described in above-mentioned (1) or (2), it is also containing thinner (E);
(4) antireflection film, wherein, on base material film, is configured at outermost layer using the cured layer of the photosensitive polymer combination described in any one of claims 1 to 3 as low-index layer;
(5) an antireflective hard film, it has the cured layer of the cured layer of hard paint and the photosensitive polymer combination described in any one of above-mentioned (1) to (3) successively on base material film;
(6) the antireflective hard film as described in above-mentioned (5), wherein, hard paint be containing having multifunctional (methyl) acrylate (A) of more than at least 3 (methyl) acryls in molecule, median size is the metal oxide (F) of 1 ~ 200 nanometer and the photosensitive polymer combination of optical free radical polymerization starter (D);
(7) the antireflective hard film as described in above-mentioned (6), wherein, median size is that the metal oxide (F) of 1 ~ 200 nanometer is for being doped with the stannic oxide of phosphorus.
According to the present invention, can provide a kind of photosensitive polymer combination containing specific compound, it is easily solidified by active energy beam; Hardness is high; The 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; The low low-index layer of reflectivity can be formed for when antireflection film or antireflective hard film.
Embodiment
Below, the present invention is described in detail.
Photosensitive polymer combination of the present invention contains multifunctional (methyl) acrylate (A) in molecule with more than at least 3 (methyl) acryls, the median size with nano-pore structure is the colloidal silica (B) of 1 ~ 200 nanometer, the polysiloxane (C) with (methyl) acryl and optical free radical polymerization starter (D).
As multifunctional (methyl) acrylate (A) in molecule with more than at least 3 (methyl) acryls, preferably there is multifunctional (methyl) acrylate of 3 ~ 15 (methyl) acryls in molecule, such as, multifunctional urethane (methyl) esters of acrylic acid of the reactant as multifunctional (methyl) acrylic compound and polyisocyanate compound with hydroxyl can be enumerated, trimethylolpropane tris (methyl) acrylate, TriMethylolPropane(TMP) polyethoxye three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, ditrimethylolpropane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, the polyester acrylate classes such as tripentaerythritol eight (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid ester etc.It should be noted that, they may be used alone, can also be two or more kinds in combination.
As this, there is multifunctional (methyl) acrylic compound of hydroxyl, such as, the Pentaerythritols such as tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, Dipentaerythritol two (methyl) acrylate can be enumerated; The methylol classes such as TriMethylolPropane(TMP) two (methyl) acrylate; Epoxy (methyl) esters of acrylic acids such as bisphenol A diglycidyl (methyl) acrylate.Wherein preferably can enumerate pentaerythritol triacrylate, Dipentaerythritol Pentaacrylate.These multifunctional (methyl) acrylic compound with hydroxyl may be used alone, can also be two or more kinds in combination.
As this polyisocyanate compound, can enumerate using chain stable hydrocarbon, cyclic saturated hydrocarbon (ester ring type), aromatic hydrocarbons as the polyisocyanate compound of basic comprising.As such polyisocyanate compound, such as, the chain stable hydrocarbon polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanates can be enumerated; Cyclic saturated hydrocarbon (ester ring type) polyisocyanates such as isophorone diisocyanate, dicyclohexyl methane diisocyanate, methylene-bis (4-cyclohexyl isocyanate), hydrogenated diphenyl methane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tolylene diisocyanate; 2,4 toluene diisocyanate, 1,3-Xylene Diisocyanate, PPDI, 3, the aromatic polyisocyanates such as 3 '-dimethyl-4,4 '-biphenyl diisocyanate, 6-sec.-propyl-1,3-phenyl diisocyanate, 1,5-naphthalene diisocyanate.As preferred example, tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate can be enumerated.These polyisocyanate compounds may be used alone, can also be two or more kinds in combination.
This multifunctional urethane (methyl) acrylic compound by make above-mentioned there is hydroxyl multifunctional (methyl) acrylic compound and the reaction of above-mentioned polyisocyanate compound obtain.Relative to hydroxyl 1 equivalent in multifunctional (methyl) acrylic compound, the polyisocyanate compound used is worked as gauge with isocyanate group and is generally the scope of 0.1 ~ 50 equivalent, is preferably the scope of 0.1 ~ 10 equivalent.
Temperature of reaction is generally 30 ~ 150 DEG C, is preferably the scope of 50 ~ 100 DEG C.
About the terminal of reaction, react by making remaining isocyanic ester and excessive n-Butyl Amine 99 and utilize the method for the unreacted n-Butyl Amine 99 of 1N hydrochloric acid back titration to calculate remaining amount of isocyanate, polyisocyanate compound being reached the moment of less than 0.5 % by weight as terminal.
In order to Reaction time shorten, catalyzer can be added.As this catalyzer, use any one of basic catalyst or an acidic catalyst.As basic catalyst, such as, the amines such as pyridine, pyrroles, triethylamine, diethylamine, dibutylamine can be enumerated; Ammonia; The phosphine such as tributylphosphine or triphenylphosphine class.In addition, as an acidic catalyst, such as, the metal alkoxide classes such as copper naphthenate, cobalt naphthenate, zinc naphthenate, aluminium butoxide, four butoxy Tritanium/Trititaniums, tetrabutyl zirconate can be enumerated; Louis's acids such as aluminum chloride; The tin compounds such as 2-ethyl hexane tin, trilauryl tin octylate, dibutyl tin laurate, octyltin diacetate.Relative to polyisocyanates 100 % by weight, the addition of these catalyzer is generally more than 0.1 % by weight and less than 1 % by weight.
In addition, in order to prevent the polymerization in reaction during reaction, preferred use stopper (such as, MEHQ, quinhydrones, toluhydroquinone, thiodiphenylamine etc.), the consumption of this stopper is more than 0.01 % by weight relative to reaction mixture and less than 1 % by weight, is preferably more than 0.05 % by weight and less than 0.5 % by weight.
In photosensitive polymer combination of the present invention, when the solids component of this photosensitive polymer combination is set to 100 % by weight, the content of above-mentioned (A) composition is generally 5 ~ 90 % by weight, is preferably 10 ~ 70 % by weight.In the present invention, when composition contains thinner, solvent, whole compositions that solids component remains after referring to and remove these materials from composition.
As the colloidal silica (B) that the median size with nano-pore structure contained in photosensitive polymer combination of the present invention is 1 ~ 200 nanometer, porous silica, hollow silica can be enumerated.About refractive index n=1.45 of common silica dioxide granule, on the other hand, 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.The layer of low-refraction can be formed thus suitably by photosensitive polymer combination of the present invention.
Colloidal silica (B) comprises makes colloidal silica disperse in a solvent and the colloidal solution obtained or the colloidal silica micropowder not containing dispersion solvent.As making colloidal silica disperse the colloidal solution obtained in a solvent, ELCOM series that Catalysts & Chem Ind Co manufactures, THRULYA can be enumerated serial etc.
As making colloidal silica disperse the dispersion solvent of the colloidal solution obtained in a solvent, such as, the alcohols such as water, methyl alcohol, ethanol, Virahol, propyl carbinol can be used; Polyalcohols and the derivatives thereof such as ethylene glycol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate; The ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, N,N-DIMETHYLACETAMIDE; The ester such as ethyl acetate, butylacetate class; The non-polar solvent such as toluene, dimethylbenzene; (methyl) esters of acrylic acid or other ordinary organic solvents classes such as (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester.Relative to colloidal silica 100 % by weight, the amount of dispersion solvent is generally 100 ~ 900 % by weight.
In the present invention, median size refers to the minimum particle diameter that when breaking cohesion, this particle has, and it can by mensuration such as BET method, dynamic light scattering method, electron microscope observations.As colloidal silica (B), the median size needing use to utilize 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 preferably median size is the colloidal silica of 1 ~ 80 nanometer further.
In photosensitive polymer combination of the present invention, when the solids component of this photosensitive polymer combination is set to 100 % by weight, the content of (B) composition is generally 5 % by weight ~ 90 % by weight, is preferably 10 % by weight ~ 80 % by weight, more preferably 20 % by weight ~ 70 % by weight.
In addition, silane coupling agent etc. can also be utilized to carry out surface treatment to the surface of colloidal silica, thus improve dispersed.
As long as surface treatment method utilizes known method process, there are drying process and damp process.Drying process is the method processed SiO 2 powder, wherein, the stoste of silane coupling agent or dissolution homogeneity is distributed to and utilizes stirrer to carry out processing in the SiO 2 powder of high-speed stirring.Damp process is following method: dispersed silicon dioxide in solvent etc., and slurried after, add silane coupling agent wherein and stir processing.Any one method can be used in the present invention.As long as the consumption (g) of silane coupling agent is at the specific surface area (m by silica weight (g) × silicon-dioxide 2/ g) the minimum coated area (m of/silane coupling agent 2/ g) amount of trying to achieve is below.
The polysiloxane (C) with (methyl) acryl contained in photosensitive polymer combination of the present invention is also sometimes referred to as organic silicon acrylic ester, organically-modified organosilicon, organic modified polyorganosiloxane, the organically-modified organic silicon acrylic ester of reaction bonded type etc.; such as, can enumerate and a part for straight chain type dimethyl siloxane is undertaken organically-modified by alkyl or polyether-based etc. and gives (methyl) acrylate-based and material of obtaining to its modification portion end.By increasing the length of siloxane main chain, the sliding, release property, resistance to adhesive, anti-finger printing, the magic ink property wiped, the fingerprint property wiped etc. on surface can be given.In addition, by improving organically-modified rate, consistency, again coating (recoatability), printing can be improved.
Be preferably the compound introducing (methyl) acryl at organically-modified portion end; polyreaction can be carried out by introducing (methyl) acryl; reduce the transitivity of polysiloxane to interface; and to the transfer to the film back side when transfer of roller and winding when can reduce production, and then chemical proofing (basic solution, organic solvent etc.) can be improved.
There is as these polysiloxane (C) of (methyl) acryl, can commercially available product be used, such as, BYK-UV3500, BYK-UV3570 (being Bi Ke chemistry society to manufacture) can be enumerated; TEGO Rad2100,2200N, 2250,2500,2600,2700 (are Degussa society manufacture); 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 to manufacture) etc.
In addition, above-mentioned (C) composition also can contain fluorine atom.
Above-mentioned (C) composition preferably has 1 ~ 8 (methyl) acryl in molecule, and the number of preferred (methyl) acryl is 2 ~ 6.
In photosensitive polymer combination of the present invention, when the solids component of this photosensitive polymer combination is set to 100 % by weight, the content of above-mentioned (C) composition is generally 0.1 % by weight ~ 50 % by weight, is preferably 1 % by weight ~ 20 % by weight.
As the optical free radical polymerization starter (D) contained in photosensitive polymer combination of the present invention, such as, the bitter almond oil camphor classes such as bitter almond oil camphor, benzoin methylether, ethoxybenzoin, bitter almond oil camphor propyl ether, benzoin isobutyl ether can be enumerated; Methyl phenyl ketone, 2, the acetophenones such as 2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenyl-propane-1-ketone, diethoxy acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone; The Anthraquinones such as 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone; The thioxanthene ketones such as 2,4-diethyl thioxanthone, ITX, CTX; The ketal classes such as methyl phenyl ketone dimethyl ketal, benzoin dimethylether; Benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 4, the benzophenones such as 4 '-bis-methylamino benzophenone; The phosphinoxidess etc. such as TMDPO, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide.In addition; the Lucirin TPO (2 of Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), the Irgacure 907 (2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-(4-morpholinyl) propane-1-ketone) of Ciba Specialty Chemicals Inc. manufacture, the manufacture of BASF society easily can be obtained from market; 4,6-trimethyl benzoyl diphenyl base phosphine oxide) etc.In addition, they may be used alone, or two or more kinds can also be mixed.
In photosensitive polymer combination of the present invention, when the solids component of this photosensitive polymer combination is set to 100 % by weight, the content of (D) composition is generally 0.1 % by weight ~ 30 % by weight, is preferably 1 % by weight ~ 15 % by weight.
As required, sensitizing agent can also be share in photosensitive polymer combination of the present invention.
As operable sensitizing agent, such as, anthracene can be enumerated, 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-bis-(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., consider in solvability and the consistency photosensitive polymer combination, particularly preferably 2-ethyl-9, 10-bis-(methoxy ethoxy) anthracene.
When using these sensitizing agents, its consumption is 1 % by weight ~ 200 % by weight relative to optical free radical polymerization starter (D) 100 % by weight, is preferably 5 % by weight ~ 150 % by weight.
Thinner (E) can be used in photosensitive polymer combination of the present invention.As this thinner (E), such as, gamma-butyrolactone, γ-valerolactone, γ-hexalactone, γ-heptalactone, α-ethanoyl-lactone such as gamma-butyrolactone, 6-caprolactone can be enumerated; The ethers such as dioxane, 1,2-Methylal(dimethoxymethane), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, triethylene glycol dimethyl ether, triethylene glycol Anaesthetie Ether, TEG dimethyl ether, TEG Anaesthetie Ether; The carbonates such as NSC 11801, propylene carbonate; The ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, methyl phenyl ketone; The phenols such as phenol, cresols, xylenol; The ester classes such as ethyl acetate, butylacetate, ethyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, acetate of butyl carbitol, propylene glycol methyl ether acetate; The hydro carbons such as toluene, dimethylbenzene, diethylbenzene, hexanaphthene; The organic solvent classes such as petroleum solvents such as the halogenated hydrocarbons such as trichloroethane, tetrachloroethane, monochloro-benzene, sherwood oil, petroleum naphtha; The fluorine system alcohols such as 2,2,3,3-C3-Fluoroalcohol; The hydrogen fluorine ethers etc. such as perfluoro butyl methyl ether, perfluoro butyl ether.They may be used alone, or two or more kinds can also be mixed.
In photosensitive polymer combination of the present invention, the content of above-mentioned (E) composition is 0 ~ 99 % by weight in photosensitive polymer combination of the present invention.
In addition, flow agent, UV light absorber, photostabilizer, defoamer etc. can also be added in photosensitive polymer combination of the present invention as required, give each target functionality.
As flow agent, fluorine based compound, silicone compound, acrylic compounds etc. can be enumerated, as UV light absorber, benzotriazole based compound, benzophenone based compound, triazine based compound etc. can be enumerated, as photostabilizer, hindered amine based compound, benzoic ether based compound etc. can be enumerated.
Photosensitive polymer combination of the present invention can obtain by mixing above-mentioned (A) composition, (B) composition, (C) composition, (D) composition and (E) composition as required and other compositions in any order.
The photosensitive polymer combination of the present invention obtained like this through time stable.
Antireflection film of the present invention by arranging the cured layer of above-mentioned photosensitive polymer combination and obtaining on base material film (basement membrane).Base material film is coated with photosensitive polymer combination of the present invention in the mode that thickness after drying is 0.05 ~ 0.5 μm, be preferably 0.05 ~ 0.3 μm (preferably to illustrate that the wavelength of the minimum value of reflectivity is 500 ~ 700nm, the mode being preferably 520 ~ 650nm set thickness) and after drying, irradiate active energy beam and form solidification tunicle, thus antireflection film of the present invention can be obtained.
In addition, between base material film (basement membrane) and the cured layer of photosensitive polymer combination of the present invention, printed layers can also be set, for improving the layers such as the anchor coat of adaptation, the high refractive index layer with the specific refractory power higher than the specific refractory power of base material film (basement membrane).
When high refractive index layer is set, high refractive index coating agent is coated with also dry in the mode that dried thickness is 0.05 ~ 5 μm, be preferably 0.05 ~ 3 μm (preferably to illustrate that the wavelength of the maximum value of reflectivity is that 500 ~ 700nm, the preferably mode of 520 ~ 650nm set thickness), then irradiate active energy beam, form solidification tunicle.
Antireflective hard film of the present invention obtains by setting gradually hard coat and photosensitive polymer combination layer of the present invention on base material film (basement membrane).First, base material film is coated with hard paint in the mode that thickness after drying is 1 ~ 30 μm, be preferably 3 ~ 20 μm, irradiates active energy beam after dry and form solidification tunicle.Next, on formed hard coat with drying after thickness be 0.05 ~ 0.5 μm, the mode of 0.05 ~ 0.3 μm (preferably to illustrate that the wavelength of the minimum value of reflectivity is 500 ~ 700nm, the mode being preferably 520 ~ 650nm set thickness) that is preferably is coated with photosensitive polymer combination of the present invention, irradiate active energy beam after dry and form solidification tunicle, thus antireflective hard film of the present invention can be obtained.
In addition, also can the high refractive index layer with the specific refractory power higher than the specific refractory power of hard coat be set between hard coat and the cured layer of photosensitive polymer combination of the present invention.Now, with thickness after drying be 0.05 ~ 5 μm, the mode of 0.05 ~ 3 μm (preferably to illustrate that the wavelength of the maximum value of reflectivity is 500 ~ 700nm, the mode being preferably 520 ~ 650nm set thickness) that is preferably is coated with high refractive index coating agent, irradiate active energy beam after dry and form solidification tunicle.
As base material film, as mentioned above, such as, polyester, polypropylene, polyethylene, polyacrylic ester, polycarbonate, triacetyl cellulose, polyethersulfone, cyclic olefine polymkeric substance etc. can be enumerated.Film also can be the film of thicker sheet to a certain degree.The film used can for painted film, be provided with easy adhesive linkage film, carried out the surface-treated films such as corona treatment.
As the coating process of above-mentioned photosensitive polymer combination, such as, bar coater coating, the coating of Meyer rod, airblade coating, photogravure coating, reverse photogravure coating, the coating of nick version, oppositely nick version coating, the coating of mould painting machine, vacuum mold coating, dip coated, spin application etc. can be enumerated.
As the active energy beam irradiated for solidifying, such as, ultraviolet, electron rays etc. can be enumerated.When utilizing ultraviolet to make it solidify, use and there is the UV irradiation equipment as light source such as xenon lamp, high voltage mercury lamp, metal halide lamp, adjust the configuration etc. of light quantity, light source as required.When using high voltage mercury lamp, relative to the lamp of energy with 80 ~ 240W/cm, be preferably cured with transfer rate 5 ~ 60m/ minute.
In addition, more preferably under the environment carrying out inert gas replacement, irradiate active energy beam, be cured.As oxygen concn, be preferably 1 below volume %, be more preferably 0.5 below volume %.As this rare gas element, preferably use nitrogen.
As the hard paint of the 1st layer for antireflective hard film of the present invention; directly can use commercially available hard paint, also can use the photosensitive polymer combination of above-mentioned multifunctional (methyl) acrylate (A) with more than 3 (methyl) acryls and optical free radical polymerization starter (D), thinner (E) as required and other additive mixtures.
In addition, in order to improve the specific refractory power of hard coat and give static resistance to hard coat, preferably use median size is the metal oxide (F) of 1 ~ 200 nanometer.As this metal oxide (F), the metal oxide that specific refractory power is improved can be enumerated, such as titanium dioxide, zirconium white, zinc oxide, stannic oxide, ferric oxide, 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 stannic oxide etc., wherein preferably as the stannic oxide of the metal oxide of imparting static resistance, tin indium oxide (ITO), antimony-doped tin oxide (ATO), zinc antimonates, aluminium-doped zinc oxide, phosphorus doping stannic oxide etc., from price, stability, set out in the aspects such as dispersiveness, particularly preferably zinc antimonates, phosphorus doping stannic oxide, from the aspect of the transparency, particularly preferably phosphorus doping stannic oxide.
They can obtain as micropowder or the dispersion liquid be distributed in organic solvent.
As the organic solvent that can be used for dispersion liquid, such as, the alcohols such as methyl alcohol, ethanol, Virahol, propyl carbinol, ethylene glycol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether can be enumerated; The ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone; The ester such as ethyl acetate, butylacetate class; The non-polar solvent such as toluene, dimethylbenzene etc.Relative to metal oxide 100 % by weight, the amount of organic solvent is generally 70 ~ 900 % by weight.
It should be noted that, median size refers to the minimum particle diameter that when breaking cohesion, this particle has, and can be measured the median size of metal oxide (F) by BET method, dynamic light scattering method, electron microscope observation etc.
In these hard paints, when the solids component of hard paint is set to 100 % by weight, the content of (F) composition is generally 5 % by weight ~ 90 % by weight, is preferably 10 % by weight ~ 80 % by weight.
In addition, in order to improve the hardness of hard coat, median size can be added and be more than 1nm and the colloidal silica of below 200nm (G).The median size used for more than 1nm and the colloidal silica of below 200nm (G) can use with the colloid solution form making colloidal silica be distributed to obtain in solvent or use with the form of the colloidal silica micropowder not containing dispersion solvent.
As the dispersion solvent of colloidal silica (G), such as, the alcohols such as water, methyl alcohol, ethanol, Virahol, propyl carbinol, Pyranton can be used; The polyalcohols such as ethylene glycol and derivative thereof; The ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone; The ester such as ethyl acetate, n-butyl acetate class; The non-polar solvent such as toluene, dimethylbenzene; The esters of acrylic acids such as vinylformic acid-2-hydroxyl ethyl ester; N,N-DIMETHYLACETAMIDE or other ordinary organic solvents classes.Relative to colloidal silica 100 % by weight, the amount of dispersion solvent is generally more than 100 % by weight and less than 900 % by weight.
These colloidal silicas (G) can utilize known method manufacture, also can use commercially available material.Such as, the organic silicon sol MEK-ST etc. that Nissan Chemical Ind Ltd manufactures can be enumerated.Need to use median size for more than 1nm and the colloidal silica of below 200nm, be preferably more than 5nm and below 100nm, be more preferably more than 10nm and below 50nm.For more than 1nm and below 100nm time, can the transparency be guaranteed, for more than 1nm and below 50nm time, the transparency, mist degree all obtains enough good result.
It should be noted that, median size refers to the minimum particle diameter that when breaking cohesion, this particle has, and can be measured the median size of colloidal silica (G) by BET method, dynamic light scattering method, electron microscope observation etc.
Time in these hard paints containing (G) composition, the solids component of hard paint is set to 100 % by weight, the content of (G) composition is generally 10 % by weight ~ 70 % by weight, is preferably 20 % by weight ~ 50 % by weight.
For (A) composition, (D) composition, (E) composition, (F) composition, (G) composition mixture in any order/mix of above-mentioned hard paint, flow agent, defoamer etc. or other additives can also be added as required.
About high refractive index coating agent when arranging the layers such as the high refractive index layer with the specific refractory power higher than the specific refractory power of base material film (basement membrane) between base material film (basement membrane) and the cured layer of photosensitive polymer combination of the present invention, and hard coat on base material film and the high refractive index coating agent when high refractive index layer with the specific refractory power higher than the specific refractory power of hard coat is set between the cured layer of photosensitive polymer combination of the present invention, can by above-mentioned (A) composition, (D) composition, (E) composition as required, (F) composition and other additive mixtures use.
Embodiment
Below, by embodiment, the present invention will be described in more detail, but the present invention is not limited to these embodiments.In addition, in embodiment, only otherwise special declaration, then part represents % by weight.
Production Example 1
By the mixture of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate, (Nippon Kayaku K. K manufactures, KAYARAD DPHA) 37.5 parts, (Osaka organic chemistry Co., Ltd. manufactures vinylformic acid tetrahydro furfuryl ester, Biscoat #150) 2.5 parts, Irgacure 184 (manufacture of Ciba Specialty Chemicals society) 1.5 parts, Irgacure907 (manufacture of Ciba Specialty Chemicals society) 1 part, (Nissan Chemical Ind Ltd manufactures CELNAX CX-Z603M-F2, the methyl alcohol dispersion sol of zinc antimonates, solids component 60%, median size 15 ~ 20nm) 12.5 parts, methyl alcohol 8 parts, propylene glycol monomethyl ether 7.5 parts, diacetone alcohol 2.5 parts, methyl ethyl ketone 27 parts mixing, obtain the hard paint that solids component is 50%.
Obtained hard paint is applied to triacetyl cellulose (TAC) film (the Konica Minolta Opto that saponification thickness before treatment is 80 μm, Inc. manufacture) on, thickness is made to be about 5 μm, at 80 DEG C after drying, ultraviolet irradiation 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, solidification is 89%, and mist degree is 0.7%, and pencil hardness (load 500g) is 3H, and the adaptation of cured film is also good.
Production Example 2
By the mixture of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate, (Nippon Kayaku K. K manufactures, KAYARAD DPHA) 24 parts, (Osaka organic chemistry Co., Ltd. manufactures vinylformic acid tetrahydro furfuryl ester, Biscoat #150) 3 parts, Irgacure 184 (manufacture of Ciba Specialty Chemicals society) 1.8 parts, Irgacure907 (manufacture of Ciba Specialty Chemicals society) 1.2 parts, (Nissan Chemical Ind Ltd manufactures CELNAX CX-S505M, the methyl alcohol dispersion sol of stannic oxide, solids component 50%, median size 10 ~ 40nm) 40 parts, 1-propyl alcohol 25 parts, diacetone alcohol 5 parts mixing, obtain the hard paint that solids component is 50%.
Obtained hard paint is applied to triacetyl cellulose (TAC) film (the Konica Minolta Opto that saponification thickness before treatment is 80 μm, Inc. manufacture) on, thickness is made to be about 5 μm, at 80 DEG C after drying, ultraviolet irradiation 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, solidification 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
Preparation mixture has the photosensitive polymer combination of the material shown in table 1.
[table 1] mixture table (unit representation " part ")
(note)
DPHA: Nippon Kayaku K. K manufactures, KAYARAD DPHA (mixture of Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate) ((A) composition)
ELCOM: Hui Catalysts & Chem Ind Co manufactures, the MIBK dispersion liquid of nanoporous silica (solids component is 20%, median size: 40 ~ 60 nanometers) ((B) composition)
TEGO:Degussa society manufactures, TEGO Rad 2600 (acrylate-functional groups number: 6) ((C) composition)
X-22: Shin-Etsu Chemial Co., Ltd manufactures, X-22-2445 (acrylate-functional groups number: 2) ((C) composition)
US270: Toagosei Co., Ltd manufacture, polysiloxane grafted polymer (solids component 30%) (for (C) comparison of ingredients)
ST103PA: Dong Li DOW CORNING Co., Ltd. manufacture, polysiloxane (for (C) comparison of ingredients)
Initiator 1:1-hydroxycyclohexyl 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 the TAC film being formed with hard coat obtained in Production Example 1 obtains in coating Examples 1, at 80 DEG C after drying, ultraviolet irradiation machine uses high voltage mercury lamp, be cured with the illuminate condition of the energy of 160W/cm, transfer rate 5m/ minute, obtain antireflective hard film.Now, thickness is adjusted to the wavelength region may of minimum value at 520 ~ 650nm that about 0.1 μm makes reflectivity.
Embodiment 4
The photosensitive polymer combination of the present invention that the TAC film being formed with hard coat obtained in Production Example 2 obtains in coating Examples 1, at 80 DEG C after drying, ultraviolet irradiation machine uses high voltage mercury lamp, be cured with the illuminate condition of the energy of 160W/cm, transfer rate 5m/ minute, obtain antireflective hard film.Now, thickness is adjusted to the wavelength region may of minimum value at 520 ~ 650nm that about 0.1 μm makes reflectivity.
Embodiment 5
The photosensitive polymer combination of the present invention that the TAC film being formed with hard coat obtained in Production Example 2 obtains in coating Examples 1, at 80 DEG C after drying, be under the nitrogen atmosphere of 0.1 volume % at oxygen concn, ultraviolet irradiation machine uses high voltage mercury lamp, be cured with the illuminate condition of the energy of 160W/cm, transfer rate 5m/ minute, obtain antireflective hard film.Now, thickness is adjusted to the wavelength region may of minimum value at 520 ~ 650nm that about 0.1 μm makes reflectivity.
Embodiment 6
The photosensitive polymer combination of the present invention that the TAC film being formed with hard coat obtained in Production Example 2 obtains in coating Examples 2, at 80 DEG C after drying, ultraviolet irradiation machine uses high voltage mercury lamp, be cured with the illuminate condition of the energy of 160W/cm, transfer rate 5m/ minute, obtain antireflective hard film.Now, thickness is adjusted to the wavelength region may of minimum value at 520 ~ 650nm that about 0.1 μm makes reflectivity.
Comparative example 3
The TAC film being formed with hard coat obtained in Production Example 2 is coated with in comparative example 1 photosensitive polymer combination of the present invention obtained, at 80 DEG C after drying, ultraviolet irradiation machine uses high voltage mercury lamp, be cured with the illuminate condition of the energy of 160W/cm, transfer rate 5m/ minute, obtain antireflective hard film.Now, thickness is adjusted to the wavelength region may of minimum value at 520 ~ 650nm that about 0.1 μm makes reflectivity.
Comparative example 4
The TAC film being formed with hard coat obtained in Production Example 2 is coated with in comparative example 2 photosensitive polymer combination of the present invention obtained, at 80 DEG C after drying, ultraviolet irradiation machine uses high voltage mercury lamp, be cured with the illuminate condition of the energy of 160W/cm, transfer rate 5m/ minute, obtain antireflective hard film.Now, thickness is adjusted to the wavelength region may of minimum value at 520 ~ 650nm that about 0.1 μm makes reflectivity.
About the antireflective hard film obtained in embodiment 3 ~ 6, comparative example 3 and 4, evaluate following project, it the results are shown 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.In detail, on the film with measured solidification tunicle, make pencil be the angle of 45 degree from top with the load of 500g scraping about 5mm, represent with more than the 4 times hardness without the pencil scratched among 5 times.
(scuff resistance)
Steel Wool #0000 applies 500g/cm 2load and reciprocal 10 times, by the abrasive situation of visual judgement.
Evaluate 5 grades: without scratch
4 grades: the scratch occurring 1 ~ 10
3 grades: the scratch occurring 10 ~ 30
2 grades: the scratch occurring more than 30
1 grade: whole there is scratch or peels off
(adaptation)
According to JIS K5600, cut longitudinal and transverse 6 otch on the surface of the film with measured solidification tunicle with 2mm interval, make 25 checkers.After its surface mount cellophane tape, peel off without a break, the number of now unstripped and remaining grid is shown.
(minimum reflectivity)
Use UV, visible light infrared spectrophotometer Shimadzu Scisakusho Ltd to manufacture UV-3150 to measure.
(the magic ink property wiped)
Use black/red magic ink, writing words on coated face, then wipe, by the visual judgement property wiped with low dirt cleansing tissue (Kimwipes).
Evaluate A: more than 10 times can be wiped in same area
B: 5 ~ 9 times can be wiped in same area
C: 1 ~ 4 time can be wiped in same area
(total light penetration)
Use haze meter Tokyo electricity Se Co., Ltd. manufactures, TC-H3DPK measures.(unit: %)
(mist degree)
Use haze meter Tokyo electricity Se Co., Ltd. manufactures, TC-H3DPK measures.(unit: %)
(surface resistivity)
Use resistrivity meter Mitsubishi chemical Co., Ltd manufactures, HIRESTA IP measures.(unit: Ω/)
(alkali resistance)
Make 1% and the 3%NaOH aqueous solution.Drip liquid to film coated surface, observe the film coated surface state of placement after 30 minutes.
Evaluate A: unchanged
B: produce variable color
C: film is peeled off
Above-mentioned evaluation result lists in table 2.
[table 2]
As shown in Table 2, the pencil hardness of the antireflective hard film of embodiment 3 ~ 6, scuff resistance, adaptation, the magic ink property wiped and alkali resistance demonstrate good result.(C) composition is changed to the graftomer of polysiloxane by comparative example 3, and result forms that scuff resistance reduces, the result of the magic ink property wiped and alkali resistance difference.(C) composition changes to not containing the polysiloxane of acryl by comparative example 4, and result formation scuff resistance reduces, the result of the transparency, the magic ink property wiped and alkali resistance difference.
Industrial applicibility
The stain resistances such as the hardness of the solidification tunicle obtained by photosensitive polymer combination of the present invention, scuff resistance, the transparency, chemical proofing and the magic ink property wiped are excellent.In addition, be adapted to pass through and be applied on hard coat and solidification thus manufacture the low antireflective hard film of reflectivity.Antireflection film, plastic optical members, touch-screen, mobile telephone, film liquid crystal cell etc. that antireflective hard film of the present invention is like this suitable for the flat-panel monitors such as LCD, PDP need the field of anti-reflective function.

Claims (7)

1. a photosensitive polymer combination, it contains multifunctional (methyl) acrylate (A) in molecule with 3 to 15 (methyl) acryls, and this multifunctional (methyl) acrylate (A) is made up of the one kind or two or more compound be selected from multifunctional urethane (methyl) esters of acrylic acid, polyester acrylate class or three (acryloyl-oxyethyl) isocyanuric acid ester; The median size with nano-pore structure is 1 ~ 200 nanometer and specific refractory power is n=1.2 ~ 1.45 colloidal silica (B); There is polysiloxane (C) and the optical free radical polymerization starter (D) of (methyl) acryl; wherein; the content of B component is 10 % by weight ~ 80 % by weight of described resin combination, and described photosensitive polymer combination is not containing the fluoropolymer containing ethene unsaturated group.
2. photosensitive polymer combination as claimed in claim 1, the polysiloxane (C) wherein, with (methyl) acryl is the compound in molecule with 1 ~ 8 (methyl) acryl.
3. photosensitive polymer combination as claimed in claim 1 or 2, it is also containing thinner (E).
4. an antireflection film, wherein, on base material film, is configured at outermost layer using the cured layer of the photosensitive polymer combination described in any one of claims 1 to 3 as low-index layer.
5. an antireflective hard film, it has the cured layer of the cured layer of hard paint and the photosensitive polymer combination described in any one of claims 1 to 3 successively on base material film.
6. antireflective hard film as claimed in claim 5; wherein, hard paint be containing having multifunctional (methyl) acrylate (A) of more than at least 3 (methyl) acryls in molecule, median size is the metal oxide (F) of 1 ~ 200 nanometer and the photosensitive polymer combination of optical free radical polymerization starter (D).
7. antireflective hard film as claimed in claim 6, wherein, median size is that the metal oxide (F) of 1 ~ 200 nanometer is for being doped with the stannic oxide of phosphorus.
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JP5767583B2 (en) 2015-08-19
TW201120566A (en) 2011-06-16
KR20120044286A (en) 2012-05-07

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