CN101108944A - Coating agent for antireflection film and antireflection film - Google Patents
Coating agent for antireflection film and antireflection film Download PDFInfo
- Publication number
- CN101108944A CN101108944A CNA200610173284XA CN200610173284A CN101108944A CN 101108944 A CN101108944 A CN 101108944A CN A200610173284X A CNA200610173284X A CN A200610173284XA CN 200610173284 A CN200610173284 A CN 200610173284A CN 101108944 A CN101108944 A CN 101108944A
- Authority
- CN
- China
- Prior art keywords
- antireflection film
- layer
- coating
- forming agent
- methyl
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/006—Anti-reflective coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
To provide an antireflection film having high adhesion of layers constituting the antireflection film, having high abrasion resistance, and less liable to warp, and a coating agent for an antireflection film used in the production of the antireflection film. The antireflection film 1 comprises (A) a transparent base layer 3, (B) a first layer 5 formed using the coating agent for an antireflection film containing a triazine ring-containing (meth)acrylate prepolymer, and (C) a second layer 7 formed of a material having a lower refractive index than the first layer, and has a laminated structure with the order of (A)/(B)/(C).
Description
Technical field
In recent years, in televisor or Personal Computer, replace existing Braun tube, bring into use PDP (plasma display) or liquid-crystal display to realize big picture thin typeization. because aforementioned display device is a high image quality, therefore light or object can bring tremendous influence to the outward appearance of image at the reflection of its picture portion, must give antireflection property.
The display material of mobile apparatus such as the mobile phone of use liquid crystal or organic EL display modes such as (electroluminescent), PDA (personal digital assistant), Electronic Paper is owing to use without, therefore the reflection of light or object is big to the influence of image, also must give antireflection property.
As one of method of antireflection, beginning is at the surface-mounted antireflection film (referring to patent documentation 1) of display frame. this antireflection film a side surface of transparent substrate lamination successively the specific refractory power that is made of acrylic resin etc. high the 1st layer is arranged and the specific refractory power that is made of silicone based resin or fluorine-type resin etc. is low the 2nd layer. the 2nd layer thickness according to the visible light that incides on the antireflection film in, the opposite setting of catoptrical phase place of reflecting at the catoptrical phase place of the 2nd laminar surface reflection and boundary in layers 1 and 2. thus, the reflected light that antireflection film will reflect on the 2nd laminar surface with cancel out each other at the reflected light of the boundary of layers 1 and 2 reflection, thereby can prevent reflection.
[patent documentation 1] Japanese kokai publication hei 09-193327 communique
Summary of the invention
But there be the 1st layer of low, the 2nd layer of problem of easily peeling off of the adaptation with the 2nd layer in existing antireflection film. in addition, also there is the insufficient problem of scuff resistance of antireflection film, causes the problem of antireflection film warpage because of the 1st layer cure shrinkage.
The present invention finishes in view of above problem, and purpose is to provide a kind of adaptation height, scuff resistance height that constitutes the layer of antireflection film, is difficult for the antireflection film of warpage, and the coating-forming agent that is used for antireflection film that uses in its preparation.
(1) invention of claim 1 relates to a kind of coating-forming agent that is used for antireflection film, it is characterized by, and this coating-forming agent contains (methyl) acrylic ester prepolymer of triazine ring.
Use the coating-forming agent that is used for antireflection film of the present invention, for example can form the layer (for example on transparent substrate layer, form the 1st layer) of antireflection film. at this moment, the adaptation increase of layer that forms and the layer that is adjacent (for example be formed on the 1st layer of upside the 2nd layer), the peeling off of interlayer becomes and is difficult to take place. in addition, the layer that uses the coating-forming agent that is used for antireflection film of the present invention to form can suppress cure shrinkage, so antireflection film is difficult to warpage.
(methyl) acrylic ester prepolymer that contains triazine ring of the present invention is that molecular-weight average that following Chemical formula 1 is represented for example is (methyl) acrylic ester prepolymer that contains triazine ring of 200～8000.
[Chemical formula 1]
The functional group a kind or 2 kind or more of n=1～10.R1 for selecting 1 valency represented from following Chemical formula 2 or the polyvalent functional group in the Chemical formula 1.
[Chemical formula 2]
In Chemical formula 1, the Chemical formula 2, R2～R5, R8, R9 are from-CH
2-,-CH
2OCH
2The functional group of selecting in the divalent functional group of-expression and the hydrogen more than a kind or 2 kinds, wherein ,-CH
2OCH
2-be used for making triazine ring each other the .R6 of functional group, the R7 of bonding be from hydroxyl and comprise the 1 valency functional group that the functional group with ethene unsaturated link(age) of following chemical formula 3 is selected, as end group be bonded among R2～R5, R8, the R9 not with other triazine ring bondings-CH
2-on.
[chemical formula 3]
Wherein, have the functional group of 1 chemical formula 3 at least in molecule, its R10 reaches-CH from hydrogen
3The middle functional group of selecting.
Particularly, as (methyl) acrylic ester prepolymer that contains triazine ring, the group of following chemical formula 4～6 expressions is for example arranged. wherein, the example of chemical formula 4～5 expression n=1, the example of chemical formula 6 expression n=3.
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
(methyl) acrylic ester prepolymer that contains triazine ring of the present invention for example can be dissolved in aminotriazine compound and Paraformaldehyde 96 in (methyl) vinylformic acid 2-hydroxy methacrylate, reacts as 1 individual system to be prepared.
(methyl) vinylformic acid 2-hydroxy methacrylate that uses in this reaction is the phraseology that comprises vinylformic acid 2-hydroxy methacrylate and 2-hydroxyethyl methacrylate, among the present invention, and not only expression is together used both, the implication of using is separately respectively also arranged. below, " (methyl) " has identical implication, except (methyl) vinylformic acid 2-hydroxy methacrylate, as required, can add compound with the ethene unsaturated link(age) that contains at least 1 hydroxyl, (methyl) vinylformic acid 2-hydroxy propyl ester for example, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, TriMethylolPropane(TMP) list (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, vinyl carbinol, the ethylene glycol allyl ethers, glycerine is (single, two) allyl ethers, the mixture of N-methylol (methyl) acrylamide etc. or above-mentioned substance. need to prove, above-mentioned " (single; two) " is allylin, the two phraseology of glycerine diallyl ether. this technical terms also represents that not only both use simultaneously, also the implication used separately respectively of expression.
Can be used for the synthetic aminotriazine compound that contains (methyl) acrylic ester prepolymer of triazine ring and be meant that structure is by C
3N
3On 3 carbon atoms of the triazine ring that constitutes respectively bonding amino compound is arranged, the aminotriazine compound is meant aminotriazine itself or amino-triazine.
As aminotriazine itself, can enumerate trimeric cyanamide, as amino-triazine, can enumerate benzoguanamine, acetylguanamine, hexanaphthene phosphinylidyne guanamines (cyclohexanecarboguanamine), tetrahydrobenzene phosphinylidyne guanamines (cyclohexene carboguanamine), norbornane phosphinylidyne guanamines, norbornylene phosphinylidyne guanamines etc.
Synthesize when containing (methyl) acrylic ester prepolymer of triazine ring, can use any aminotriazine compound separately or also can use their mixture. in addition, based on reasons such as desired characteristic, costs, also can allow to other compounds (for example urea class, ketone, phenol etc.) with formaldehyde reaction in the system identical and formaldehyde reaction with the reaction system of aminotriazine compound.
In addition, can be used for the synthetic Paraformaldehyde 96 that contains (methyl) acrylic ester prepolymer of triazine ring for example is to be solid, the material that is used as formaldehyde source under the normal temperature. because Paraformaldehyde 96 can together be dissolved in (methyl) vinylformic acid 2-hydroxy methacrylate with the aminotriazine compound and use, therefore do not need dehydration, desolventizing operation basically. in addition, in the building-up reactions of prepolymer, unreacted Paraformaldehyde 96 is with the form gasification of formaldehyde, break away from reactant, Gu this need not recycle unreacted Paraformaldehyde 96 especially.
(methyl) acrylic ester prepolymer that adopts the aforesaid method synthetic to contain triazine ring can be understood as the dehydrating condensation etherificate by the reaction that is directed into the hydroxyl in methylol and (methyl) vinylformic acid 2-hydroxy methacrylate in the aminotriazine compound by Paraformaldehyde 96 material or by the aminotriazine compound with the reaction of (methyl) vinylformic acid 2-hydroxy methacrylate～formaldehyde hemiacetal the material of dehydrating condensation etherificate.
In this prepolymer building-up reactions, even do not use solvent, also because (methyl) vinylformic acid 2-hydroxy methacrylate is liquid at normal temperatures, therefore only aminotriazine compound and Paraformaldehyde 96 are dissolved in wherein and can in 1 individual system, carry out the reaction of 1 operation efficiently. just under different situations, in order to reduce viscosity or reactions such as easy and moisture generation azeotropic, also can add toluene, alcohol, alcohol formalin etc. in right amount and react.
Aminotriazine compound when synthetic, Paraformaldehyde 96, and the interpolation mol ratio of (methyl) vinylformic acid 2-hydroxy methacrylate different and different according to the desired rerum natura of kind, the target cured article of raw material, as the aminotriazine compound, use representational trimeric cyanamide, when under solvent-free, reacting, preferred trimeric cyanamide: Paraformaldehyde 96=more than 1: 2, in addition, preferred trimeric cyanamide: (methyl) vinylformic acid 2-hydroxy methacrylate=more than 1: 2.
When Paraformaldehyde 96 is low with respect to the ratio of trimeric cyanamide or (methyl) vinylformic acid 2-hydroxy methacrylate when low with respect to the ratio of trimeric cyanamide, the gelation that causes from condensation owing to trimeric cyanamide takes place in the solvability variation of trimeric cyanamide easily.
The prepolymer building-up reactions is undertaken by condensation reaction. and the progress of this reaction uses the amount of moisture that spins off from condensation reaction to represent. therefore, only need to observe this amount of moisture, can make condensation reaction stop at the required stage at the time point stopped reaction that distills out required amount of moisture. need to prove, and the distillation speed of moisture is consolidated the influence difference of temperature of reaction, stirring efficiency, catalyzer, the air amount of being blown into, solvent etc.
The building-up reactions of prepolymer also can be carried out under the condition of catalyst-free, in order to promote solvability and/or etherification reaction as raw-material aminotriazine compound, can when adding, use organic-inorganic alkali such as sodium hydroxide, yellow soda ash, ammoniacal liquor, triethylamine or when packing into or reaction use mineral acid organic acids such as tosic acid as common catalyst for etherification, hydrochloric acid midway.
Need to prove and have the ethene unsaturated link(age) in this reaction system usually. therefore, in prepolymer synthetic, may consolidate this ethene unsaturated link(age) generation addition polymerization and cause gelation. in order to prevent gelation, can add phenol, the polymerization of amine ethene unsaturated link(age) prevents agent, maybe will have the oxygen of forbidding polymerization is blown into reaction system and carries out building-up reactions. certainly, also can use polymerization to prevent agent and oxygen simultaneously. the oxygen that is blown in reaction system is particularly preferably in industrial also easy-to-use air. and, being blown into moisture that gas can promote condensation reaction to produce is distilled and removes, make balance generate side shifting, so preferred to ehter bond.
In order to prevent that gelation from promoting reaction to carry out, preferred temperature of reaction is about 50～150 ℃, is preferably especially about 70～130 ℃, and the preferred reaction times is about 0.5～10 hour. for the distillation that promotes moisture removes out, also can under reduced pressure react.
The molecular-weight average that synthetic contains triazine ring (methyl) acrylic ester prepolymer can be limited in 200～8000 the scope by the control reaction process. during less than 200, can't obtain the abundant performance used as the coating-forming agent that is used for antireflection film, if surpass 8000, then viscosity is too high, is difficult to use.
(methyl) acrylic ester prepolymer that contains triazine ring that adopts method for preparing is the compound that contains (methyl) acrylate-based and alkylether radicals and/or methylol and/or amino and/or methylene radical in triazine ring. above-claimed cpd makes with water white thick liquid form usually, may not need to make with extra care, also can make with extra care by methods such as washings according to application target.
As constituting the solvent that is used for the coating-forming agent of antireflection film of the present invention, for example can use ketones solvents such as methyl ethyl ketone as organic solvent, methyl iso-butyl ketone (MIBK), acetone, hexanaphthene, the fragrant same clan such as dimethylbenzene, esters solvent such as ethyl acetate, butylacetate, ethylene glycol monoethyl ether acetate, methyl proxitol acetate, ethyl-glycol ether ester kind solvents such as 3-ethoxy-c acid esters, tetrahydrochysene blow mutter, ether solvent such as dioxane, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, furfural etc., methyl alcohol, ethanol, Virahol etc.
At the coating-forming agent that is used for antireflection film of the present invention, the use level that contains (methyl) acrylic ester prepolymer of triazine ring divides 100 weight parts preferably in the scope of 1～90 weight part, more preferably in the scope of 30～70 weight parts with respect to the solid formation of the coating-forming agent that is used for antireflection film.
As the binder constituents that is used for the coating-forming agent of antireflection film of the present invention; for example can use multifunctional polymerization monomer. have more than at least 2 in the preferred molecule of this multifunctional polymerization monomer and be selected from (methyl) acryl; the monomer of functional group more than a kind in vinyl and the allyl group. the monomeric free radical reaction that wherein has (methyl) acryl is very high; has the rigid and high rigidity of speed; so it is preferred. particularly, can enumerate six (methyl) vinylformic acid dipentaerythritol ester; five (methyl) vinylformic acid dipentaerythritol ester; four (methyl) vinylformic acid dipentaerythritol ester; three (methyl) vinylformic acid dipentaerythritol ester; four (methyl) vinylformic acid pentaerythritol ester; three (methyl) vinylformic acid pentaerythritol ester; trimethylolpropane tris (methyl) acrylate; trimethylolethane trimethacrylate (methyl) acrylate; two (methyl) vinylformic acid hexylene glycol ester; multifunctional (methyl) acrylate such as two (methyl) vinylformic acid glycol ether ester. above-mentioned monomer can be used alone or as a mixture.
The coating-forming agent that is used for antireflection film of the present invention, can add acrylic resin as required, the styrene butadiene resin, chloroprene resin, urethane resin, ethylene vinyl acetate resin, vinyl acetate resin, rosin based, the rosin derivative class, the terpine resin class, natural tack imparting agents such as terpene derivatives class, tree oil lipid, styrene resin lipid, the coumarone-indene resin class, the resol class, the synthetic resin viscosity imparting agent of xylene resin class, aqueous nitrile rubber, rubber constituents such as silicon rubber, hydrated barta, magnesium hydroxide, aluminium hydroxide, silicon oxide, titanium oxide, calcium sulfate, barium sulfate, lime carbonate, alkaline carbonic acid zinc, basic lead white, silica sand, clay, talcum, silicon dioxide compound, titanium dioxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, inorganic filling agent such as antimony pentaoxide, in addition, can also add coupling agents such as silicane or metatitanic acid salt, sterilant, sanitas, softening agent, flowing regulator, tackifier, the pH regulator agent, tensio-active agent, the homogenizing conditioning agent, defoamer, tinting pigment, compounding ingredients such as rust-stabilising pigment. in addition, in order to improve photostabilization, also can add antioxidant or UV light absorber.
As other compounding ingredients, can add antistatic agent, ionic liquid, electroconductive polymer, metal oxide etc. and give electrostatic-proof function.
As antistatic agent, can enumerate nonionic class Voranol EP 2001, polyxyethylated phenol, polyoxyethylene alkyl amine, polyoxyethylene alkylamide, fatty acid polyglycol ester, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerin fatty acid ester, alkyl polyethylene imine etc. in addition, as the cationic antistatic agent, can enumerate alkylamine salt, alkyl quaternary ammonium salts, alkyl imidazoline derivatives etc. also can use the ionic conduction type antistatic agent of metal ions such as the acrylic compound that has oxyethane in the mixed matrix or lithium ion.
As ionic liquid, can be from the BF of the fragrant same clan, aliphatic quaternary ammonium salts etc. such as the imidazole salt of cation constituent side, pyridine salt and anionic component side
4 -, PF
6 -Deng in the mineral ion class and CF
3SO
2 -, (CF
3SO
2)
2N
-Used etc. freely selecting in the combination of fluorine-containing organic anion class.
As electroconductive polymer, can use polyaniline, polypyrrole, Polythiophene, gather 3, the derivative of 4-Ethylenedioxy Thiophene and above-mentioned substance.
As metal oxide, also can use antimony dopant type stannic oxide (ATO), doped tin type Indium sesquioxide (ITO), adulterated al type zinc oxide, the secondary oxide compound of antimony etc.
The viscosity that is used for the coating-forming agent of antireflection film is considered and can be used in 1～50000mPas/20 ℃ scope from aspects such as coating, equal voltinism and coating processes, except the selection of above-mentioned compounding ingredient and cooperate the ratio, can also adjust the viscosity of coating fluids by suitable interpolation solvent or the various additives that do not influence polyreaction.
As the solvent that is used for above-mentioned purpose, for example can enumerate toluene, dimethylbenzene, acetone, MEK, MIBK, ethyl acetate, butylacetate, methyl alcohol, ethanol, Virahol etc.
(2) invention of claim 2 relates to the described coating-forming agent that is used for antireflection film of claim 1, it is characterized by, and this coating-forming agent contains metal oxide.
The coating-forming agent that is used for antireflection film of the present invention when forming the layer of antireflection film, has better interlayer adaptation, scuff resistance by containing metal oxide. as metal oxide, can enumerate SiO
2, TiO
2, ZrO
2, HfO
2, ZnO, Sb
2O
3, Sb
2O
5Deng. in order to improve the affinity of above-mentioned metal oxide and resin, also can carry out surface treatment with the type siloxane organism. wherein, preferably make the particle surface residual hydroxyl of above-mentioned metal oxide.
(3) invention of claim 3 relates to a kind of coating-forming agent that is used for antireflection film, it is characterized by, and described metal oxide is for being selected from SiO
2, TiO
2, ZrO
2More than a kind.
The metal oxide that is used for the coating-forming agent of antireflection film of the present invention is from SiO
2, TiO
2, ZrO
2More than a kind of middle selection, interlayer adaptation, scuff resistance when forming the layer of antireflection film are better.
(4) invention of claim 4 relates to claim 2 or the 3 described coating-forming agents that are used for antireflection film, it is characterized by, and divides 100 weight parts with respect to the above-mentioned solid formation that is used for the coating-forming agent of antireflection film, and the use level of above-mentioned metal oxide is 0.01～70 weight part.
The coating-forming agent that is used for antireflection film of the present invention divides 100 weight parts with respect to the solid formation of the coating-forming agent that is used for antireflection film, and the use level of metal oxide is 0.01～70 weight part, and interlayer adaptation, scuff resistance when forming the layer of antireflection film are better.
(5) invention of claim 5 relates to a kind of antireflection film, it is characterized by, possess (A) transparent substrate layer, (B) and contain the 2nd layer that the 1st layer of (methyl) acrylic ester prepolymer of triazine ring, (C) are made of above-mentioned the 1st layer of low material of refractive index ratio, laminar structure with (A)/(B)/(C) order.
The 1st layer of (methyl) acrylic ester prepolymer that contains triazine ring of reflectance coating of the present invention, improved thus the 1st layer with the 2nd layer adaptation, the splitting of layers 1 and 2 be difficult for to take place. by suppressing the 1st layer cure shrinkage, if can suppress the warpage of antireflection film. particularly reduce the cross-linking density of (methyl) acrylic ester prepolymer that contains triazine ring that contains in the 1st layer, the effect of warpage that then suppresses antireflection film is more remarkable. and, even the surface of scratching reflectance coating of the present invention, also be difficult to it is caused damage. its former surface that is promptly to use the 2nd layer of foreign object scratching admittedly, owing to the 1st layer of adaptation height with the 2nd layer, Gu this 2nd layer also is difficult to peel off from the 1st layer, the result does not form scuffing.
The transparent substrate layer of using among the present invention is not particularly limited; can be that commercially available thickness more than 90% is suitably to select to use the known overlay of 10 μ m～5mm from total light transmittance. as above-mentioned transparent substrate layer; for example can be with saturated polyester resin; polycarbonate resin; the polyacrylic ester resinoid; the ester ring type polyolefin resin; polystyrene resins; polyvinyl chloride resin; resin treatment such as polyvinyl acetate base esters resin become membranaceous or laminar and use. more specifically, can enumerate polyester film; polyethylene film; polypropylene screen; glassine paper; the diacetyl cellulose film; the tri acetyl cellulose film; ethanoyl cellulose butylate film; polychloroethylene film; polyvinylidene chlorida film; polyvinyl alcohol film; the ethylene-vinyl alcohol film; Polystyrene Film; polycarbonate membrane; the polymethylpentene film; polysulfone membrane; the polyether-ether-ketone film; poly (ether sulfone) film; polyetherimde films; polyimide film; fluororesin film; nylon membrane; acrylic film etc.
As being processed into the membranaceous or laminar method that is applicable to transparent substrate layer, can enumerate extrusion molding, calendaring molding, compression molding, injection molded, make method that above-mentioned resin dissolves pours into a mould etc. in solvent. need to prove, also can in the resin that constitutes transparent substrate layer, add antioxidant, fire retardant, heat-resisting agent, UV light absorber, the easy additives such as lubrication prescription, antistatic agent of preventing.
Forming method of the present invention the 1st layer and be not particularly limited, can adopt print processes such as coating method such as known spraying method, rolling method, metal pattern coating method, airblade coating method, scraper coating method, spin-coating method, counter-rotating coating method, intaglio plate coating method, merchant bar mill or intaglio printing, silk screen printing, offset printing, ink jet printing to form. the specific refractory power that the preferred 1 μ m of the 1st layer thickness～10 μ m. is the 1st layer is preferably in 1.50～1.80 scope.
In order to form the 1st layer, for example after the surface coated of transparent substrate layer is used for the coating-forming agent of antireflection film or after carrying out heat drying again, use has known light sources such as electrod lamp, electrodeless lamp, according to wavelength with irradiation ultraviolet radiations such as high pressure mercury vapour lamps, metal halide lamp, thereby make the 1st layer of photocuring. can be the metal halide lamp of 80～240W/cm and easily being cured for example by distance 5cm irradiation several seconds output rating.
When forming the 1st layer, after for example coating is used for the coating-forming agent of antireflection film, can make its curing by means such as radical polymerization, photopolymerization, electron rays polymerization or X ray, alpha-ray, β ray, the polymerizations of gamma-rays isoradial. in the above-mentioned curing means, utilize photopolymerisable curing to realize fast setting, so preferred with easy equipment.
When forming the 1st layer, in order to make its thermofixation or photocuring, preferably cooperate polymerization starter at the coating-forming agent that is used for antireflection film, use level with respect to (methyl) acrylic ester prepolymer 100 weight parts that contain triazine ring in the scope of 1～10 weight part. as thermal polymerization, can enumerate superoxide, azo two compounds etc., as superoxide, for example can enumerate peroxidation dibutyl, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide etc.; As azo two compounds, for example can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two-2-methylbutyronitrile, 2,2 '-azo two-2,4-methyl pentane nitrile, 2,2 '-azo two (2-methyl-propyl amidine) dihydrochloride etc.
As Photoepolymerizationinitiater initiater, for example can use methyl phenyl ketone, 2,2-diethoxy acetophenone, to dimethyl acetophenone, to carbonyl compound such as dimethylaminophenyl ethyl ketone (p-dimethylaminopropiophenon), benzophenone, 2-chloro benzophenone, benzyl compounds, bitter almond oil camphor, benzoin methyl ether, bitter almond oil camphor ethyl ether, bitter almond oil camphor isopropyl ethers, thioxanthone, 2-clopenthixal ketone, 2-methyl thioxanthone, tetramethyl-thiuram disulfide sulfides etc.
The electron rays polymerization can not use polymerization starter to carry out polymerization, have no polymerization starter residual, can make advantage such as its curing at normal temperatures, therefore can adopt under the situation of poor, thin at base material film, easy thermal distortion the resistibility of heat.
Material of the present invention the 2nd layer is not particularly limited, for example can enumerate the interpolation silicone resin, fluorine-type resin, it is resin below 1.50 etc. that inorganic particulate such as porous silica or magnesium fluoride makes specific refractory power. wherein, preferably be the silicone resin of main skeleton with the type siloxane condenses. the 2nd layer thickness is preferably according in inciding the visible light of antireflection film, catoptrical phase place that on the 2nd layer surface, reflects and opposite setting of catoptrical phase place of reflecting at the layers 1 and 2 boundary. thus, the reflected light that reflects on the 2nd layer surface and the reflected light in the boundary reflection of layers 1 and 2 are cancelled out each other, preventing reflection effectively. the 2nd layer concrete thickness for example is preferably 50～150nm. as the method that forms the 2nd layer, can use and the identical method of method that forms the 1st layer. the specific refractory power after the 2nd layer of curing is preferably in 1.35～1.45 scope. and need to prove, it is solidified in nitrogen atmosphere the resin that is hindered by oxygen easily.
In the antireflection film of the present invention, can on transparent substrate layer, directly form the 1st layer, also can between transparent substrate layer and the 1st layer, form the layer that specific refractory power is the intermediate value of layers 1 and 2. the material as this layer can be used acrylic resin etc., thickness is preferably in the scope of 1～10 μ m. and in addition, specific refractory power is preferably in 1.45～1.60 scope.
(6) invention of claim 6 relates to the described antireflection film of claim 5, it is characterized by, and above-mentioned the 1st layer contains metal oxide.
Antireflection film of the present invention contains metal oxide in the 1st layer, thereby can have adaptation and scuff resistance between the better layers 1 and 2.
As metal oxide, for example can enumerate SiO
2, TiO
2, ZrO
2, HO
2, ZnO, Sb
2O
3, Sb
2O
5Deng. the use level of metal oxide with respect to the 1st layer of 100 weight part preferably in the scope of 0.01～70 weight part.
(7) invention of claim 7 relates to claim 5 or 6 described antireflection films, it is characterized by, and above-mentioned the 1st layer of each described coating-forming agent that is used for antireflection film of coating claim 1～4 forms.
Antireflection film of the present invention can easily prepare by using each described coating-forming agent that is used for antireflection film of claim 1～4.
And, also can on the above-mentioned antireflection film bonding coat be set. bonding coat so long as the layer that constitutes by the tackiness agent of the surperficial driving fit that can when keeping the transparency of antireflection film, make antireflection film and indicating meter etc. or binding agent get final product, for example can use by acrylic acid or the like, polyurethanes, epoxies, tackiness agents such as polyester, the thermoplastics type, heat curing-type, the layer that binding agents such as UV curing constitute. from the optical characteristics aspect, photostabilization, weathering resistance, thermotolerance, transparency aspect is considered, preferred especially acrylic resin. constitute the monomer of acrylic resin, can enumerate for example ethyl propenoate, butyl acrylate, the vinylformic acid pentyl ester, 2-EHA, Octyl acrylate, cyclohexyl acrylate, alkyl acrylates such as vinylformic acid benzyl ester, or butyl methacrylate, methacrylic acid 2-(ethyl hexyl) ester, cyclohexyl methacrylate, alkyl methacrylates such as methacrylic acid benzyl ester, Jia Jibingxisuanyizhi, can also be on above-claimed cpd the copolymerization vinyl-acetic ester, propionate, vinyl ether, vinylbenzene, vinyl cyanide, methacrylonitriles etc. contain the compound of vinyl. and, in order to improve the driving fit endurance quality of bonding coat, suppress venting, the host that can make tackiness agent is acrylic resin, and weight-average molecular weight is more than 500,000, and polydispersity is below 5.
In the bonding coat, can cooperate linking agent as required, catalyzer, antioxidant, tinting pigment, granulated glass sphere, weighting agent, fire retardant, antiseptic-germicide, photostabilizer, tinting material, fluidity amendment, lubricant, anticlogging agent, antistatic agent, crosslinking coagent etc. above-mentioned substance can use separately, also two or more kinds may be used. as linking agent, so long as do not influence the material that requires characteristic, just can use without particular limitation. for example can enumerate polymeric polyisocyanate, inner complex, Resins, epoxy, melamine resin, amide resins etc. in addition, also can adopt and in bonding coat, add near infrared absorbent, infrared absorbent, the neon absorption agent, UV absorption agents etc. may produce the composition that dysgenic harmful light cuts off to human body.
Bonding coat can be formed on the 1st layer and the 2nd layer of opposite transparent substrate layer on. the method that forms bonding coat on transparent substrate is not particularly limited, can enumerate and adopt silk rod (Meyerbar), material feeder, hairbrush, shower nozzle, roller, the intaglio plate coating machine, the metal pattern coating machine, the lip coating type coating device coating machine, comma scraper coating machine (comma coater), knife coater, the counter-rotating coating machine, rotary coating, the nozzle coating machine, dip coated, rod is coated with, the coating process of scraper coating etc. drying means is not particularly limited, can utilize warm air drying, the drying means of infrared rays or decompression method. drying conditions also depends on the curing form of bonding coat, thickness or selected solvent can be about 60～180 ℃.
The thickness of bonding coat is not particularly limited, preferred 0.1 μ m～50 μ m, preferred especially 10 μ m～50 μ m.
On bonding coat; can also fit and be used to protect the mold release film of bonding coat. mold release film can be used polyethylene terephthalate, polyethylene, polyvinyl chloride, polycarbonate, polymethyl acrylate, paper, cloth, glass, pottery, metal sheet, acrylic panel, olefin resin, PPS resin, TAC film, acrylic resin film or above-mentioned materials be implemented the demoulding handle the film that obtains etc. and the thickness of mold release film is not particularly limited; preferred less than 500 μ m; more preferably 1 μ m～100 μ m are preferably 10 μ m～50 μ m. especially
(8) invention of claim 8 relates to each described antireflection film of claim 5～7, it is characterized by, above-mentioned the 1st layer and above-mentioned the 2nd layer by the chemical reaction combination.
Among the present invention, because layers 1 and 2 is by the chemical reaction combination, so the adaptation of layers 1 and 2 is higher. in addition, because the adaptation height, so the scuff resistance of antireflection film is higher.
As the chemical reaction among the present invention, for example can enumerate in the 1st layer the reactions such as dehydration reaction, transesterification reaction of the silicone resin that contains in the hydroxyl that exists and the 2nd layer.
(9) invention of claim 9 relates to the described antireflection film of claim 8, it is characterized by, above-mentioned the 2nd layer is that the silicone resin of main skeleton and/or the fluoro-resin that (b) has hydroxyl constitute by (a) with the type siloxane condenses, and above-mentioned chemical reaction is the hydroxyl of existence in above-mentioned the 1st layer and the dehydration reaction of above-mentioned (a) or resin (b).
Among the present invention, the hydroxyl that exists during layers 1 and 2 is passed through the 1st layer combines with the silicone resin of the 2nd layer of formation or the dehydration reaction of fluoro-resin, therefore the adaptation of layers 1 and 2 is higher. in addition, because the adaptation height, so the scuff resistance of antireflection film is higher.
As above-mentioned silicone resin, can enumerate silicoorganic compound and/or its hydrolysate of following general formula (I) expression.
General formula (I): R1
aR2
bSi (OR3)
4-a-b
Wherein, R1, R2 be respectively alkyl, alkenyl, aryl or have the alkyl of halogen atom, epoxy group(ing), glycidoxy, amino, sulfydryl, methacryloxy or cyano group, R3 is that carbonatoms is 1～8 alkyl, alkoxyalkyl, acyl group, aryl, a and b be 0 or 1 and a+b be 0～2.
As silicoorganic compound and/or its hydrolysate, methyltrimethoxy silane is for example arranged, alkoxyl silicone alkanes such as Union carbide A-162, hexichol TMOS class or two acyloxy silane classes or its hydrolysate etc. above-mentioned silicoorganic compound can add more than a kind or 2 kinds. in addition, in order to realize lower specific refractory power, for example can use the fluorine modified organic silicone resin of putting down in writing in the TOHKEMY 2003-25510 communique. as above-mentioned fluoro-resin, for example, can enumerate the resin that the following fluorochemical monomer of polymerization obtains. as fluorochemical monomer, fluorine can be positioned at main chain during polymerization, also can be positioned at side chain, preferred main chain partly has fluorine. as the example of fluorochemical monomer, can enumerate fluoroolefin class (vinyl fluoride for example, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, R 1216 etc.), (methyl) acrylate moiety or fully by fluorinated alkyl ester derivative class (for example BISCOAT 6FM (trade(brand)name Osaka organise length of schooling) or M-2020 (trade(brand)name Da Jin system) etc.), fluorizated vinyl ethers (perfluoro propyl vinyl ether for example wholly or in part, 1H, 1H-nine fluorine pentyloxy ethyl vinyl ethers etc.), fluorine-containing epoxides (3-perfluor decyl-1, the 2-propylene oxide, 3-(perfluor-9-methyl decyl)-1,2-propylene oxide etc.) etc., preferred perfluoroolefine class, from specific refractory power, solvability, the transparency, aspect such as acquired is considered, preferred especially R 1216. two or more kinds may be used for above-mentioned monomer.
In addition, as fluoro-resin, for example can use the fluoro-resin of putting down in writing in the TOHKEMY 2004-307524 communique.
Description of drawings
Fig. 1 is the sectional view of expression anti-reflection film structure.
Drawing reference numeral
1... antireflection film
3...PET film
5... the 1st layer
7... the 2nd layer
Embodiment
Use embodiment that the present invention is described below.
[embodiment 1]
(1) the synthetic acrylic ester prepolymer that contains triazine ring
Possess whipping appts, thermometer, gas introduction tube, cut derive with the separable flask of the 2L of prolong, reflux condensing tube in adding vinylformic acid 2-hydroxy methacrylate 696g (6 moles), trimeric cyanamide 126g (1 mole), 95 weight % Paraformaldehyde 96 189g (formaldehyde is 6 moles), tosic acid 3.0g, Hydroquinone monomethylether 0.2g, the limit is blown into the air limit and heats up. under 80～100 ℃, after making trimeric cyanamide and Paraformaldehyde 96 be dissolved in the vinylformic acid 2-hydroxy methacrylate, interior temperature is remained on 105～115 ℃, react to the quantity of distillate of moisture be 108g (6 moles).
(2) preparation silicone resin solution
Mix hydroxypropyl Trimethoxy silane (50% methanol solution, eastern レ ダ ウ コ one ニ Application グ (strain)) 4g, Union carbide A-162 (eastern レ ダ ウ コ one ニ Application グ (strain)) 10g, be cooled to 20 ℃. then, with the hydrochloric acid 4g that slowly added 1N in 1 hour, 20～30 ℃ of one nights of following slaking, be hydrolyzed. add acetate 7g, IPA 25g, MEK 70g in this solution, the solid formation of preparation is divided into 10% silicone resin solution.
(3) preparation is used for the coating-forming agent of antireflection film
The acrylic ester prepolymer 14g that contains triazine ring, silica slurry (MEK-ST, NV30%, MEK dispersion, daily output chemical industry (strain)) 20g, methyl ethyl ketone (MEK) 16g that mix preparation in above-mentioned (1), again will be as the Irgacure184 of UV initiator (チ バ ス ペ ジ ャ Le テ イ Network ミ カ Le ズ (strain) system, trade(brand)name) being that the ratio of 5 weight parts is added obtain solution (antireflection film coating-forming agent) with respect to acrylic ester prepolymer 100 weight parts that contain triazine ring.
(4) preparation antireflection film
Prepare antireflection film shown in Figure 1 1. as described below at first, at solution thickness 100 μ m, that prepare in the coating above-mentioned (3) on as the PET film of transparent substrate layer (polyethylene terephthalate: Japan twist flax fibers and weave (strain) コ ス モ シ ャ イ Application (trade(brand)name)) 3, making the thickness after the curing is 3 μ m, use the uviolizing machine, with 1500mW/cm
2Exposure intensity to carry out amount of work be 300mJ/cm
2UV treatment, obtain the 1st layer 5 (specific refractory power 1.54). then, be coated with silicone resin solution of preparation in above-mentioned (2), making the thickness after the curing is 0.1 μ m, makes its curing under 140 ℃, forms the 2nd layer 7.
[embodiment 2]
(1) preparation is used for the coating-forming agent of antireflection film
Mix the acrylic ester prepolymer 14g that contain triazine ring, titanium dioxide slurries (NV40%, median size 30nm, MEK dispersion, テ イ カ (strain)) 15g, the MEK 21g same with the foregoing description 1, with Irgacure184 being that the ratio of 5 weight parts is added obtain solution (coating-forming agent that is used for antireflection film) with respect to acrylic ester prepolymer 100 weight parts that contain triazine ring.
(2) preparation antireflection film
Prepare antireflection film shown in Figure 1 1. as described below at first, with the same PET film 3 of the foregoing description 1 on the solution of preparation in the coating above-mentioned (1), making the thickness after the curing is 3 μ m, use uviolizing machine is with 1500mW/cm
2Exposure intensity, carrying out amount of work is 300mJ/cm
2UV treatment, obtain the 1st layer 5 (specific refractory power 1.63). then, the silicone resin solution that coating is same with the foregoing description 1, making the thickness after the curing is 0.1 μ m, makes its curing under 140 ℃, forms the 2nd layer 7.
[embodiment 3]
(1) preparation is used for the coating-forming agent of antireflection film
Mix the acrylic ester prepolymer 14g that contain triazine ring, zirconium white slurries (NV15%, median size 20nm, MEK dispersion, シ one ア イ change into (the strain)) 40g same with the foregoing description 1, again with Irgacure184 being that the ratio of 5 weight parts is added obtain solution (coating-forming agent that is used for antireflection film) with respect to acrylic ester prepolymer 100 weight parts that contain triazine ring.
(2) preparation antireflection film
Prepare antireflection film shown in Figure 1 1. as described below at first, with the same PET film 3 of the foregoing description 1 on the solution of preparation in the coating above-mentioned (1), making the thickness after the curing is 5 μ m, use uviolizing machine is with 1500mW/cm
2Exposure intensity, carrying out amount of work is 300mJ/cm
2UV treatment, obtain the 1st layer 5 (specific refractory power 1.61). then, the silicone resin solution that coating is identical with the foregoing description 1, making the thickness after the curing is 0.1 μ m, makes its curing under 140 ℃, forms the 2nd layer 7.
[embodiment 4]
(1) preparation is used for the coating-forming agent of antireflection film
Mix the acrylic ester prepolymer 19.8g that contain triazine ring, silica slurry 0.6g, the MEK 29.6g same with the foregoing description 1, again with lrgacure184 being that the ratio of 5 weight parts is added obtain solution (coating-forming agent that is used for antireflection film) with respect to acrylic ester prepolymer 100 weight parts that contain triazine ring.
(2) preparation antireflection film
Prepare antireflection film shown in Figure 1 1. as described below at first, with the same PET film 3 of the foregoing description 1 on the solution of preparation in the coating above-mentioned (1), making the thickness after the curing is 3 μ m, use uviolizing machine is with 1500mW/cm
2Exposure intensity, carrying out amount of work is 300mJ/cm
2UV treatment, obtain the 1st layer 5 (specific refractory power 1.55). then, the silicone resin solution that coating is same with the foregoing description 1, making the thickness after the curing is 0.1 μ m, makes its curing under 140 ℃, forms the 2nd layer 7.
[embodiment 5]
(1) preparation is used for the coating-forming agent of antireflection film
Mix the acrylic ester prepolymer 6g that contain triazine ring, the silica slurry 46.6g same with the foregoing description 1, again with Irgacure184 being that the ratio of 5 weight parts is added obtain solution (coating-forming agent that is used for antireflection film) with respect to acrylic ester prepolymer 100 weight parts that contain triazine ring.
(2) preparation antireflection film
Prepare antireflection film shown in Figure 1 1. as described below at first, with the same PET film 3 of the foregoing description 1 on the solution of preparation in the coating above-mentioned (1), making the thickness after the curing is 3 μ m, use uviolizing machine is with 1500mW/cm
2Exposure intensity, carrying out amount of work is 300mJ/cm
2UV treatment, obtain the 1st layer 5 (specific refractory power 1.51). then, the silicone resin solution that coating is same with the foregoing description 1, making the thickness after the curing is 0.1 μ m, makes its curing under 140 ℃, forms the 2nd layer 7.
[embodiment 6]
(1) preparation is used for the coating-forming agent of antireflection film
Mix the acrylic ester prepolymer 14g that contain triazine ring, silica slurry 20g, the MEK 16g same with the foregoing description 1, again with Irgacure184 being that the ratio of 5 weight parts is added obtain solution (antireflection film coating-forming agent) with respect to resin 100 weight parts.
(2) preparation antireflection film
Prepare antireflection film shown in Figure 1 1. as described below at first, with the same PET film 3 of the foregoing description 1 on the solution of preparation in the coating above-mentioned (1), making the thickness after the curing is 3 μ m, use uviolizing machine is with 1500mW/cm
2Exposure intensity, carrying out amount of work is 300mJ/cm
2UV treatment, obtain the 1st layer 5 (specific refractory power 1.54). then, magnesium fluoride slurries (NV15%, MIBK dispersion, シ one ア イ change into (strain)) are added 10 weight parts with respect to silicone resin solution 100 weight parts of preparation in the foregoing description 1. being coated with solution after this interpolation, to make the thickness after the curing be 0.1 μ m, under 140 ℃, make its curing, form the 2nd layer 7.
[embodiment 7]
(1) the synthetic methacrylate prepolymers that contains triazine ring
Basic according to the synthetic method in (1) of the foregoing description 1, use 2-hydroxyethyl methacrylate 780g to replace vinylformic acid 2-hydroxy methacrylate 696g, the synthetic methacrylate prepolymers that contains triazine ring.
(2) preparation is used for the coating-forming agent of antireflection film
Synthetic contains the methacrylate prepolymers 7g of triazine ring in (1) of mixing present embodiment 7, (1) middle synthetic of the foregoing description 1 contains acrylic ester prepolymer 7g, silica slurry 20g, the MEK 16g of triazine ring, again with Irgacure184 being that the ratio of 5 weight parts is added obtain solution (coating-forming agent that is used for antireflection film) with respect to resin 100 weight parts.
(3) preparation antireflection film
Use the solution of preparing in (2) of present embodiment 7, the same method in (2) of employing and the foregoing description 6 prepares antireflection film.
[embodiment 8]
(1) preparation is used for the coating-forming agent of antireflection film
Mix the acrylic ester prepolymer 7g that contain triazine ring, six vinylformic acid dipentaerythritol ester (NK ester A-DPH, Xin Zhong village chemical industry (strain)) 7g, silica slurry 20g, the MEK 16g same with the foregoing description 1, again with lrgacure184 being that the ratio of 5 weight parts is added obtain solution (coating-forming agent that is used for antireflection film) with respect to resin 100 weight parts.
(2) preparation antireflection film
Prepare antireflection film shown in Figure 1 1. as described below at first, with the same PET film 3 of the foregoing description 1 on the solution of preparation in the coating above-mentioned (1), making the thickness after the curing is 3 μ m, use uviolizing machine is with 1500mW/cm
2Exposure intensity, carrying out amount of work is 300mJ/cm
2UV treatment, obtain the 1st layer 5 (specific refractory power 1.53). then, the silicone resin solution that coating is same with the foregoing description 1, making the thickness after the curing is 0.1 μ m, makes its curing under 140 ℃, forms the 2nd layer 7.
[embodiment 9]
(1) preparation is used for the coating-forming agent of antireflection film
Mix the acrylic ester prepolymer 20g, the MEK30g that contain triazine ring same with the foregoing description 1, again with Irgacure184 being that the ratio of 5 weight parts is added obtain solution (coating-forming agent that is used for antireflection film) with respect to acrylic ester prepolymer 100 weight parts that contain triazine ring.
(2) preparation antireflection film
Prepare antireflection film shown in Figure 1 1. as described below at first, with the same PET film 3 of the foregoing description 1 on the solution of preparation in the coating above-mentioned (1), making the thickness after the curing is 3 μ m, use uviolizing machine is with 1500mW/cm
2Exposure intensity, carrying out amount of work is 300mJ/cm
2UV treatment, obtain the 1st layer 5 (specific refractory power 1.55). then, the silicone resin solution that coating is same with the foregoing description 1, making the thickness after the curing is 0.1 μ m, makes its curing under 140 ℃, forms the 2nd layer 7.
(comparative example 1)
(1) preparation is used for the coating-forming agent of antireflection film
Mix A-DPH (six vinylformic acid dipentaerythritol ester) 20g, MEK 30g, with Irgacure184 being that the ratio of 5 weight parts is added obtain solution (coating-forming agent that is used for antireflection film) with respect to A-DPH 100 weight parts.
(2) preparation antireflection film
Prepare antireflection film shown in Figure 1 1. as described below at first, with the same PET film 3 of the foregoing description 1 on the solution of preparation in the coating above-mentioned (1), making the thickness after the curing is 3 μ m, use uviolizing machine is with 1500mW/cm
2Exposure intensity, carrying out amount of work is 300mJ/cm
2UV treatment, obtain the 1st layer 5 (specific refractory power 1.53). then, the silicone resin solution that coating is same with the foregoing description 1, making the thickness after the curing is 0.1 μ m, makes its curing under 140 ℃, forms the 2nd layer 7.
(comparative example 2)
(1) preparation is used for the coating-forming agent of antireflection film
Mix A-DPH14g, silica slurry 20g, MEK 16g, again with Irgacure184 being that the ratio of 5 weight parts is added obtain solution (coating-forming agent that is used for antireflection film) with respect to A-DPH 100 weight parts.
(2) preparation antireflection film
Prepare antireflection film shown in Figure 1 1. as described below at first, with the same PET film 3 of the foregoing description 1 on the solution of preparation in the coating above-mentioned (1), making the thickness after the curing is 3 μ m, use uviolizing machine is with 1500mW/cm
2Exposure intensity, carrying out amount of work is 300mJ/cm
2UV treatment, obtain the 1st layer 5 (specific refractory power 1.52). then, the silicone resin solution that coating is same with the foregoing description 1, making the thickness after the curing is 0.1 μ m, makes its curing under 140 ℃, forms the 2nd layer 7.
(comparative example 3)
(1) preparation is used for the coating-forming agent of antireflection film
Mix A-DPH 14g, titanium dioxide slurries 15g, MEK 21g, again with lrgacure184 being that the ratio of 5 weight parts is added obtain solution (coating-forming agent that is used for antireflection film) with respect to the A-DPH100 weight part.
(2) preparation antireflection film
Prepare antireflection film shown in Figure 1 1. as described below at first, with the same PET film 3 of the foregoing description 1 on the solution of preparation in the coating above-mentioned (1), making the thickness after the curing is 3 μ m, use uviolizing machine is with 1500mW/cm
2Exposure intensity, carrying out amount of work is 300mJ/cm
2UV treatment, obtain the 1st layer 5 (specific refractory power 1.61). then, the silicone resin solution that coating is same with the foregoing description 1, making the thickness after the curing is 0.1 μ m, makes its curing under 140 ℃, forms the 2nd layer 7.
(comparative example 4)
(1) preparation is used for the coating-forming agent of antireflection film
Mix A-DPH 14g, zirconium white slurries 40g, again with as the Irgacure184 of UV initiator being that the ratio of 5 weight parts is added obtain solution (coating-forming agent that is used for antireflection film) with respect to A-DPH 100 weight parts.
(2) preparation antireflection film
Prepare antireflection film shown in Figure 1 1. as described below at first, with the same PET film 3 of the foregoing description 1 on the solution of preparation in the coating above-mentioned (1), making the thickness after the curing is 3 μ m, use uviolizing machine is with 1500mW/cm
2Exposure intensity, carrying out amount of work is 300mJ/cm
2UV treatment, obtain the 1st layer 5 (specific refractory power 1.59). then, the silicone resin solution that coating is same with the foregoing description 1, making the thickness after the curing is 0.1 μ m, makes its curing under 140 ℃, forms the 2nd layer 7.
(evaluation test of antireflection film)
Be used for confirming test as described below in the performance of the antireflection film of embodiment 1～9 and comparative example 1～4 preparation.
(1) test evaluation method
(i) mensuration of total light transmittance
Regulation based on JIS K 7361-1 (version in 2000) 3.2 is measured. and as determinator, use the smart mechanism of (strain) Japan to make the Haze-gard II. that is produced
The (ii) mensuration of mist value
Regulation based on JS K 7136 (version in 2000) is carried out. particularly, in the incident parallel rays, according to forward scattering, mensuration departs from the percentage of the above transmitted light of incident light 0.044rad (2.5 °). and as determinator, use the smart mechanism of (strain) Japan to make the Haze-gard II. that is produced
The (iii) mensuration of minimum reflectance
Antireflection film is ground equably with sand paper, the black of making of mark is coated with full sample, use 5 ° ,-5 ° beam split reflection spectrums of ultraviolet-visible pectrophotometer (Japanese beam split (strain) system) mensuration 350～800nm, read minimum reflectance by reflectance spectrum. when amplitude is arranged with its center as minimum reflectance.
The (iv) mensuration of pencil hardness
Regulation based on JIS K 5600-5-4 (version in 1999) is carried out. and as determinator, use the smart mechanism of (strain) Japan to make the pencil scratch hardness of film trier of being produced (form P).
(the v) mensuration of scuff resistance
The surface of antireflection film is rubbed with the ス チ one Le ウ one Le #0000 (Japanese ス チ one Le ウ, one Le (strain) system) that has applied the 200g load, and whether visual assessment causes scuffing. do not have to scratch and be labeled as zero, have scuffing be labeled as *.
(vi) fitness test
Carry out based on JIS K 5600-5-6 (version in 1999). particularly, surface at antireflection film makes 10 * 10 chessboard trellis square opening, sticking glass paper tape on this square opening, stretch up and confirm to peel off situation. the hole count that counting is not stripped from, calculate " residual/whole hole counts (100) ".
(vii) specific refractory power
Use the multi-wavelength Abbe refractometer (DR-M2) of (strain) ア go system to measure.
(viii) measure the warpage of antireflection film
Will as the square PET film of 10cm in processing (heating, UV irradiation) under the condition identical of blank (Japan twist flax fibers and weave (strain) コ ス モ シ ャ イ Application thickness 100 μ m) with antireflection film with rest on faceup on the smooth glass plate as the square antireflection film separate application of the 10cm of sample, measure the perk situation (mm) of 4 ends after 10 seconds. calculate the mean value of blank and sample, the calculating formula of substitution " sample mean "-" blank mean value " and obtaining.
(2) test-results is shown in table 1, table 2.
[table 1]
| |
Embodiment 2 | |
Embodiment 4 | |
Embodiment 6 | Embodiment 7 | ||
| The 1st coating layer | Resin | The acrylic ester prepolymer that contains triazine ring | The acrylic ester prepolymer that contains triazine ring contains the methacrylate prepolymers of triazine ring (1: 1) | |||||
| The kind of inorganic particulate | SiO 2 | TiO 2 | ZrO 2 | SiO 2 | SiO 2 | SiO 2 | SiO 2 | |
| The inorganic particulate addition | 30％ | 30％ | 30％ | 1％ | 70％ | 30％ | 30％ | |
| Specific refractory power | 1.54 | 1.63 | 1.61 | 1.55 | 1.52 | 1.54 | 1.54 | |
| The 2nd coating layer | Resin | Organosilicon | ||||||
| Inorganic particulate | - | - | - | - | - | MgF2 | MgF2 | |
| Evaluation result | Total light transmittance | 92.5％ | 93.0％ | 92.6％ | 94.2％ | 92.0％ | 93.8％ | 93.1％ |
| The mist value | 0.8％ | 0.8％ | 0.8％ | 0.7％ | 0.9％ | 0.8％ | 0.8％ | |
| Minimum reflectance | 2.0％ | 1.3％ | 1.4％ | 1.7％ | 2.1％ | 1.9％ | 1.9％ | |
| The minimum reflectance wavelength | 620nm | 600nm | 610nm | 610nm | 600nm | 610nm | 600nm | |
| Pencil hardness | 2H | 2H | 2H | H | 3H | 3H | 3H | |
| Scuff resistance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Adaptation | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 | |
| Warpage | ＜0.1mm | ＜0.1mm | ＜0.1mm | 0.8mm | ＜0.1mm | ＜0.1mm | ＜0.1mm | |
[table 2]
| Embodiment 8 | Embodiment 9 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | ||
| The 1st coating layer | Resin | Acrylic ester prepolymer/the A-DPH that contains triazine ring | The acrylic ester prepolymer that contains triazine ring | A-DPH | |||
| The kind of inorganic particulate | SiO 2 | - | - | SiO 2 | TiO 2 | ZiO 2 | |
| The inorganic particulate addition | 30％ | - | - | 30％ | 30％ | 30％ | |
| Specific refractory power | 1.53 | 1.55 | 1.53 | 1.52 | 1.61 | 1.59 | |
| The 2nd coating layer | Resin | Organosilicon | |||||
| Inorganic particulate | - | - | - | - | - | - | |
| Evaluation result | Total light transmittance | 92.8％ | 93.3％ | 93.3％ | 92.8％ | 92.2％ | 92.3％ |
| The mist value | 0.8％ | 0.8％ | 0.8％ | 0.8％ | 1.0％ | 0.9％ | |
| Minimum reflectance | 2.0％ | 1.7％ | 2.0％ | 2.1％ | 1.5％ | 1.6％ | |
| The minimum reflectance wavelength | 600nm | 600nm | 610nm | 600nm | 600nm | 610nm | |
| Pencil hardness | 2H | H | 2B | HB | B | B | |
| Scuff resistance | ○ | ○ | × | × | × | × | |
| Adaptation | 100/100 | 100/100 | 0/100 | 98/100 | 40/100 | 20/100 | |
| Warpage | ＜0.1mm | ＜0.1mm | 32.0mm | 25.8mm | 28.1mm | 29.7mm | |
Shown in table 1, table 2, among the embodiment 1～9 warp value of antireflection film of preparation less than 0.1mm, very good. in addition, total light transmittance, mist value, minimum reflectance, pencil hardness, scuff resistance, adaptation are all good.
Particularly be combined with metal oxide (SiO in the 1st layer
2, TiO
2, ZrO
2) pencil hardness, scuff resistance, the adaptation of embodiment 1～8 better.
Need to prove that the present invention is not limited to the foregoing description, in not departing from the scope of the present invention, can implement the present invention in every way.
Claims (9)
1. a coating-forming agent that is used for antireflection film is characterized by, and this coating-forming agent contains (methyl) acrylic ester prepolymer of triazine ring.
2. the coating-forming agent that is used for antireflection film as claimed in claim 1 is characterized by, and this coating-forming agent contains metal oxide.
3. a coating-forming agent that is used for antireflection film is characterized by, and described metal oxide is from SiO
2, TiO
2, ZrO
2More than a kind of middle selection.
4. as claim 2 or the 3 described coating-forming agents that are used for antireflection film, it is characterized by, divide 100 weight parts with respect to the described solid formation that is used for the coating-forming agent of antireflection film, the use level of described metal oxide is 0.01～70 weight part.
5. an antireflection film is characterized by, and described antireflection film possesses:
(A) transparent substrate layer,
(B) contain the 1st layer of (methyl) acrylic ester prepolymer of triazine ring,
(C) constitute by described the 1st layer of low material of refractive index ratio the 2nd layer;
Laminar structure with (A)/(B)/(C) order.
6. antireflection film as claimed in claim 5 is characterized by, and described the 1st layer contains metal oxide.
7. as claim 5 or 6 described antireflection films, it is characterized by, described the 1st layer of each described coating-forming agent that is used for antireflection film of coating claim 1～4 forms.
8. as each described antireflection film of claim 5～7, it is characterized by, described the 1st layer and described the 2nd layer combines by chemical reaction.
9. antireflection film as claimed in claim 8, it is characterized by, described the 2nd layer is that the silicone resin of main skeleton and/or the fluoro-resin that (b) has hydroxyl constitute by (a) with the type siloxane condenses, and described chemical reaction is the hydroxyl of existence in described the 1st layer and the dehydration reaction of described (a) or resin (b) simultaneously.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006199444 | 2006-07-21 | ||
| JP2006199444A JP2007052409A (en) | 2005-07-21 | 2006-07-21 | Coating agent for antireflection film and antireflection film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101108944A true CN101108944A (en) | 2008-01-23 |
Family
ID=39041214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200610173284XA Pending CN101108944A (en) | 2006-07-21 | 2006-12-15 | Coating agent for antireflection film and antireflection film |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20080008930A (en) |
| CN (1) | CN101108944A (en) |
| TW (1) | TW200806763A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130020657A (en) * | 2010-02-16 | 2013-02-27 | 티에프케이 가부시키가이샤 | Preventive and/or ameliorative agent for diseases, stamina enhancement agent, anti-fatigue agent, and pharmaceutical and food and drink using them |
| CN104284913A (en) * | 2012-03-08 | 2015-01-14 | 日产化学工业株式会社 | Resin coating agent |
| CN105295082A (en) * | 2014-07-25 | 2016-02-03 | 大日本印刷株式会社 | Multi-layer base material and image display device |
| CN105482609A (en) * | 2015-12-30 | 2016-04-13 | 芜湖奕辰模具科技有限公司 | Pretreatment agent used for spray coating of inner wall of automobile radiator |
| CN110612471A (en) * | 2019-06-19 | 2019-12-24 | 深圳盈天下视觉科技有限公司 | Aerial imaging system and aerial imaging method for increasing visual range |
| CN113031121A (en) * | 2019-12-09 | 2021-06-25 | 现代自动车株式会社 | Infrared anti-reflection lens |
| CN116023831A (en) * | 2023-03-30 | 2023-04-28 | 宁波长阳科技股份有限公司 | Antibacterial coating liquid, preparation method and application thereof in reflective film |
-
2006
- 2006-10-31 TW TW095140189A patent/TW200806763A/en unknown
- 2006-11-27 KR KR1020060117471A patent/KR20080008930A/en not_active Withdrawn
- 2006-12-15 CN CNA200610173284XA patent/CN101108944A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130020657A (en) * | 2010-02-16 | 2013-02-27 | 티에프케이 가부시키가이샤 | Preventive and/or ameliorative agent for diseases, stamina enhancement agent, anti-fatigue agent, and pharmaceutical and food and drink using them |
| KR101718577B1 (en) * | 2010-02-16 | 2017-03-21 | 티에프케이 가부시키가이샤 | Preventive and/or ameliorative agent for diseases, stamina enhancement agent, anti-fatigue agent, and pharmaceutical and food and drink using them |
| CN104284913A (en) * | 2012-03-08 | 2015-01-14 | 日产化学工业株式会社 | Resin coating agent |
| CN105295082A (en) * | 2014-07-25 | 2016-02-03 | 大日本印刷株式会社 | Multi-layer base material and image display device |
| CN105295082B (en) * | 2014-07-25 | 2018-10-02 | 大日本印刷株式会社 | multi-layer substrate and image display device |
| CN105482609A (en) * | 2015-12-30 | 2016-04-13 | 芜湖奕辰模具科技有限公司 | Pretreatment agent used for spray coating of inner wall of automobile radiator |
| CN110612471A (en) * | 2019-06-19 | 2019-12-24 | 深圳盈天下视觉科技有限公司 | Aerial imaging system and aerial imaging method for increasing visual range |
| CN113031121A (en) * | 2019-12-09 | 2021-06-25 | 现代自动车株式会社 | Infrared anti-reflection lens |
| CN113031121B (en) * | 2019-12-09 | 2024-04-05 | 现代自动车株式会社 | Anti-reflection lens for infrared ray |
| CN116023831A (en) * | 2023-03-30 | 2023-04-28 | 宁波长阳科技股份有限公司 | Antibacterial coating liquid, preparation method and application thereof in reflective film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080008930A (en) | 2008-01-24 |
| TW200806763A (en) | 2008-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101108944A (en) | Coating agent for antireflection film and antireflection film | |
| CN102702753B (en) | Curable resin composition, cured product thereof, and various articles derived from those | |
| CN102459378B (en) | Antifouling composition, antifouling film, antifouling laminated film, transfer film, resin laminate, and method for producing resin laminate | |
| JP5213984B2 (en) | Transfer material using resin composition and method for producing molded product | |
| EP2535184B1 (en) | Sheet for forming hard coating | |
| JP6928002B2 (en) | Transparent resin substrate | |
| KR20190079611A (en) | Transparent Substrate Having Antistatic Property and Antireflection Property and Method of Manufacturing the Same | |
| JP2008184514A (en) | Ultraviolet curable resin composition, the cured product, and various articles derived therefrom | |
| CN104937059A (en) | Transparent double-sided adhesive sheet, laminate obtained using same for constituting image display device, process for producing said laminate, and image display device obtained using said laminate | |
| CN102245662A (en) | Curable composition comprising inorganic oxide microparticles that are surface-modified with maleimide groups | |
| CN102532426A (en) | Photocurable resin composition, method of fabricating optical film using the same, and optical film including the same | |
| TW201428066A (en) | Composition for hard coating and formed article having a hard coating layer | |
| CN109456711A (en) | Thermal finalization protective film for camber display screen | |
| KR20190053544A (en) | Photocurable composition and coating layer comprising cured product of the same | |
| CN104781300A (en) | Aqueous composition and hard coat layer | |
| CN100350001C (en) | Resin composition capable of solidifying, production method for lamina of said composition, transcribe material and production method thereof | |
| JP5616036B2 (en) | Laminate formed by laminating a substrate, an intermediate film, and a fine relief structure film | |
| CN109971411A (en) | Sticker, adhesive sheet and display body | |
| US20180009985A1 (en) | Curable organopolysiloxane composition, cured product thereof, and method of forming cured film | |
| CN107735465A (en) | Heat-resisting quantity with raising uV curable and can infrared light ink composition for ink jet | |
| CN105229497A (en) | Near infrared ray absorbing composition, the near infrared ray cut-off filter using it and manufacture method thereof and camera module | |
| JPWO2013146651A1 (en) | Cyclic ether group-containing (meth) acrylate | |
| JP2022110332A (en) | Antireflection substrate | |
| JP6894835B2 (en) | Active energy ray-curable composition and cured product | |
| KR102740686B1 (en) | Composition for forming hard coating layer having 3D shape and protective film using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20080123 |