CN100476458C - Reflection preventive film - Google Patents
Reflection preventive film Download PDFInfo
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- CN100476458C CN100476458C CNB2005800460983A CN200580046098A CN100476458C CN 100476458 C CN100476458 C CN 100476458C CN B2005800460983 A CNB2005800460983 A CN B2005800460983A CN 200580046098 A CN200580046098 A CN 200580046098A CN 100476458 C CN100476458 C CN 100476458C
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- 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
-
- 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
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- 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
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
- G02B1/116—Multilayers including electrically conducting layers
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- 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
Abstract
A reflection preventive film which comprises a base film and, formed on at least one surface thereof in the following order, (A) a hard coat layer having a thickness of 1 to 20 m and containing a resin cured by the irradiation of an active energy ray and 2 to 25 wt % of an antistatic agent and (B) a low refractive index layer having a thickness of 0.05 to 0.3 m and containing a resin cured by the irradiation of an active energy ray and 30 to 80 wt % of porous silica particles and which has a surface resistivity of 5 X 10<SUP>12 </SUP>O/ or less. The above reflection preventive film has the characteristic that it has one reflection preventive layer which can effectively prevent the reflection of a light by the surface of an image display element, is excellent in the durability of the antistatic effect for inhibiting the attachment of dust, motes or the like and the resistance to marring and further exhibits excellent resistance to a solvent.
Description
Technical field
The present invention relates to antireflective film, more particularly, relating to anti-reflection layer is the antireflective film of 1 layer of type, it can effectively prevent the light reflection on plasma scope (PDP), cathode ray tube (CRT), LCD image-displaying member surfaces such as (LCD), and the continuation and the excellent scratch resistance that suppress the anti-charged effect that dust and dust etc. adhere to, and also excellence of solvent resistance.
Background technology
In displays such as PDP, CRT, LCD, to the picture irradiation light, can take place that this light produces reflection and the situation that can't see display image especially in recent years, is accompanied by the maximization of display from the outside, address the above problem to become more and more important problem.
In order to solve such problem, up to now, various displays are carried out various antireflections handle and non-glare treated.As a kind of method wherein, on various displays, use antireflective film.
This antireflective film uses by dry process methods such as evaporation or sputters at present, thus on base film with the material (MgF of low-refraction
2) method of filming or the material that refractive index is high [ITO (indium oxide of doped tin), TiO
2Deng] and the low material (MgF of refractive index
2, SiO
2Deng) preparations such as method of lamination alternately.Yet, can't avoid the high problem of manufacturing cost by the antireflective film existence of such dry process method preparation.
Therefore, in recent years, attempted by the wet processed method, promptly rubbing method prepares antireflective film.Yet, in this antireflective film, to compare with above-mentioned antireflective film by the preparation of dry process method by the preparation of wet processed method, the mar resistance that produces the surface worsens such problem.
Therefore, in order to solve the problems referred to above in the wet processed method, use the ionizing radiation curable resin composition to form cured layer (hard conating).For example disclose on base film, (1) stacks gradually (A) to contain the cured resin and the thickness that form by ionizing radiation is the hard conating of 2～20 μ m; (B) at least 2 kinds of metal oxides, refractive index that contain the cured resin that forms by ionizing radiation and comprise the tin oxide of antimony dopant in 1.65～1.80 scope, thickness be the high refractive index layer of 60～160nm and (C) contain type siloxane polymkeric substance, refractive index in 1.37～1.47 scope, thickness is the film for optical use (referring to for example patent documentation 1) that the low-index layer of 80～180nm forms; (2) stack gradually (A) contain metal oxide and by solidfied material, thickness that heat or ionizing radiation form be the hard conating of 2～20 μ m and (B) contain porous silica and polysiloxane base polymer, refractive index in 1.30～1.45 scope, thickness is the film for optical use (referring to for example patent documentation 2) that forms of the low-index layer of 40～200nm etc.
These film for optical use effectively prevent the surface light reflection of image-displaying member, are the good antireflective film of mar resistance simultaneously.
On the other hand, in antireflective film,, require the charging preventive property of continuation excellence in order to prevent the adhesion of dust and dust etc.In order in above-mentioned film for optical use, to give the charging preventive property of continuation excellence, for example, can be in the film for optical use of (1), metal oxide as (B) high refractive index layer uses the metal oxide with anti-charging property, or in the film for optical use of (2), use metal oxide as the metal oxide of (A) high refractive index layer with anti-charging property.
Yet present situation is only on hard conating in 1 of stacked low-index layer layer of type, does not also begin to use on low-index layer the antireflective film with charging preventive property beyond the silicone compounds up to now.
Patent documentation 1: TOHKEMY 2002-341103 communique
Patent documentation 2: TOHKEMY 2003-139908 communique
Summary of the invention
The present invention is in view of such fact, purpose provides a kind of light reflection that can effectively prevent image-displaying member surfaces such as PDP, CRT, LCD, the continuation and the excellent scratch resistance that suppress the anti-charged effect that dust and dust etc. adhere to simultaneously, and the also excellent anti-reflection layer of solvent resistance is the antireflective film of 1 layer of type.
The present inventor is in order to develop the antireflective film with above-mentioned excellent properties, carried out deep research, found that the hard conating by on base film, stacking gradually the anti-live agent that contains the cured resin that forms by active energy ray irradiation and specified quantitative and contain the cured resin that forms by the active energy ray irradiation and the low-index layer of the porous silica particle of specified quantitative, can realize this purpose, finish the present invention based on this understanding.
That is, the invention provides:
(1) a kind of antireflective film is characterized in that on the one side at least of base film, has the hard conating that (A) contains the anti-live agent of the cured resin that forms by active energy ray irradiation and 2～25 weight % successively, and thickness is 1～20 μ m; And the low-index layer that (B) contains the porous silica particle of the cured resin that forms by active energy ray irradiation and 30～80 weight %, thickness is 0.05～0.3 μ m, and this antireflective film surface resistivity is 5 * 10
12Below Ω/,
(2) as above-mentioned (1) described antireflective film, (A) anti-live agent in the layer be in molecule, have 1 above quaternary ammonium salt base the cationic anti-live agent and
(3) as above-mentioned (1) or (2) described antireflective film, (B) the porous silica particle proportion in the layer is 1.7～1.9, refractive index be 1.25～1.36 and mean grain size be 20～100nm.
Embodiment
Antireflective film of the present invention has by the wet processed method, stacks gradually (A) hard conating and (B) structure of low-index layer on the one side at least of base film.
Base film in the antireflective film of the present invention is had no particular limits, can be from suitably selecting the known plastic sheeting to use as the base material that has antireflective film now.As such plastic sheeting, can enumerate for example polyethylene terephthalate; polybutylene terephthalate; poly-to mylars such as naphthalenedicarboxylic acid second diester; polyethylene film; polypropylene film; cellophane; the diacetyl cellulose film; the tri acetyl cellulose film; acetyl group cellulose butylate film; polyvinyl chloride film; the Vingon film; polyvinyl alcohol film; the vinyl-vinyl acetate copolymer film; plasticon; polycarbonate film; poly-methyl pentene film; polysulphone film; poly (ether ether ketone) film; the polyethersulfone film; the polyetherimide film; Kapton; fluorine resin film; polyamide film; the acryl resin film; the norbornene resin film; cyclic olefin resins film etc.
These base films can be transparent, translucent any, perhaps can be painted, also can be non-coloring, can suitably select according to purposes.For example, under the situation that protection is used as liquid crystal display, preferred water white film.
Thickness to these base films has no particular limits, and can suitably select, usually at 15～250 μ m, preferably in the scope of 30～200 μ m.In addition, this base film according to expectation, carries out surface treatment by oxidizing process or concavo-convexization method etc. in order to improve the cohesive with the layer that is provided with from the teeth outwards on one or both sides.As above-mentioned oxidizing process, can enumerate Corona discharge Treatment, chromic acid processing (wet type), flame treatment, hot blast processing, ozone ultraviolet ray treatment with irradiation etc.In addition, as concavo-convexization method, can enumerate for example sand-blast, solvent treatment method etc.These surface preparations can suitably be selected according to the kind of base film, usually, from aspects such as effect and operability, preferably use the Corona discharge Treatment method.In addition, can use and on one or both sides, carry out undercoat and handle.
In antireflective film of the present invention, on the one side at least of above-mentioned base film, (A) at first is set comprises by the cured resin of active energy ray irradiation formation and the hard conating of anti-live agent.
This hard conating that comprises the cured resin that forms by active energy ray irradiation and anti-live agent for example can will contain active energy ray-curable compound, above-mentioned anti-live agent and form with coating fluid coating on the one side at least of base film according to the hard conating that expectation contains Photoepolymerizationinitiater initiater etc., formation is filmed, the irradiation active energy ray is filmed to solidify this, thereby forms.
Wherein, so-called active energy ray-curable compound is meant the ray that has the quanta of energy in electromagnetic wave or the charged particle line by being radiated at, i.e. irradiation ultraviolet radiation or electronics line etc., thereby the compound of crosslinking curing.
As such active energy ray-curable compound, can enumerate for example optical polymerism prepolymer and/or photopolymerization monomer.In above-mentioned optical polymerism prepolymer, comprise radical polymerization mould assembly and cationic polymerization type, as the optical polymerism prepolymer of radical polymerization mould assembly, can enumerate for example polyester acrylate class, epoxy acrylate class, urethane acrylate class, polyalcohol acrylate class etc.Wherein, as polyester acrylate class prepolymer, for example can be by the hydroxyl of polyester oligomer that has hydroxyl at two ends that obtains by polybasic carboxylic acid and polyol condensating by (methyl) acroleic acid esterification, or the hydroxyl of the end of the oligomer by the acquisition of addition epoxy alkyl in polybasic carboxylic acid obtains by (methyl) acroleic acid esterification.
Propylene oxide acids prepolymer for example can obtain by reaction (methyl) acroleic acid esterification in the oxirane ring of the bisphenol-type epoxy resin of lower molecular weight or phenol aldehyde type epoxy resin.The urethane oligomer that urethane acrylate class prepolymer for example can obtain polyether glycol or polyester polyol and polyisocyanate reaction obtains by (methyl) acroleic acid esterification.In addition, polyalcohol acrylate class prepolymer can obtain the hydroxyl of polyether glycol by (methyl) acroleic acid esterification.These optical polymerism prepolymers can use a kind, also can will be used in combination more than 2 kinds.
On the other hand, as cationic polymerization type photo-polymerization type prepolymer, use epikote usually.As this epikote, for example can enumerate polyatomic phenols such as bisphenol resin or phenolics by chloropropylene oxide etc. and epoxidised compound, compound that straight chain shape olefin(e) compound or cyclic olefin compound are obtained by peroxide oxidation etc.
As the optical polymerism polymkeric substance, for example can enumerate 1,4-butylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, neopentyl alcohol hexane diacid two (methyl) acrylate, hydroxyl trimethylace tonitric neopentyl glycol two (methyl) acrylate, dicyclopentenyl two (methyl) acrylate, dicyclopentenyl two (methyl) acrylate of caprolactone modification, the di(2-ethylhexyl)phosphate of oxirane modification (methyl) acrylate, allylation cyclohexyl two (methyl) acrylate, chlorinated isocyanurates two (methyl) acrylate, trimethyl propane three (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol three (methyl) acrylate of propionic acid modification, pentaerythrite three (methyl) acrylate, trimethyl propane three (methyl) acrylate of epoxy pronane modification, three (propenyloxy group ethyl) chlorinated isocyanurates, dipentaerythritol five (methyl) acrylate of propionic acid modification, dipentaerythritol six (methyl) acrylate, multi-functional acrylates such as dipentaerythritol six (methyl) acrylate of caprolactone modification.These photopolymerization monomers can use a kind, also can will be used in combination more than 2 kinds, in addition, can also coupling optical polymerism prepolymer.
As the Photoepolymerizationinitiater initiater that uses according to expectation, optical polymerism prepolymer or photopolymerization monomer for the radical polymerization mould assembly, can enumerate for example benzoin, benzoin methyl ether, the benzoin ethylether, the benzoin isopropyl ether, the benzoin n-butyl ether, the benzoin isobutyl ether, acetophenone, the dimethylamino benzoylformaldoxime, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone, the 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholine-third-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2-(hydroxyl-2-propyl group) ketone, benzophenone, to the phenyl benzophenone, 4,4 '-diethylamino benzophenone, two chloro benzophenones, 2-methylanthraquinone, the 2-EAQ, 2-tert-butyl group anthraquinone, the 2-amino anthraquinones, 2-methyl thioxanthones, 2-ethyl thioxanthones, the 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2, the 4-diethyl thioxanthone, benzyl dimethyl ketal, the acetophenone dimethyl ketal, to dimethyl amine benzoic ether etc.In addition, as the Photoepolymerizationinitiater initiater of cationic polymerization type optical polymerism prepolymer, can enumerate and for example comprise aromatic series sulphion, aromatic series oxo sulphion, aromatic series iodide ion etc. and anionic compounds such as tetrafluoroborate, hexafluorophosphate, hexafluoro antimonate, hexafluoro arsenate.These materials can use a kind, also can will be used in combination more than 2 kinds, and in addition, its combined amount is selected in the scope of 0.2～10 weight portion usually with respect to above-mentioned optical polymerism prepolymer of 100 weight portions and/or photopolymerization monomer.
On the other hand, anti-live agent contained in the hard conating is had no particular limits, can use at least a kind that is selected from present known nonionic class, anionic species, cationic, the both sexes class anti-live agent.In these materials,, preferably in molecule, has the cationic anti-live agent of 1 above quaternary ammonium salt base from effect with to the uniformly dispersed viewpoint of hard conating.
Cationic anti-live agent with quaternary ammonium salt base can use any of low molecule-type and polymer electrolyte, from the lasting type of effect and the viewpoints such as preventing property of leakage or gas generation, preferred polymer electrolyte cationic anti-live agent.
As above-mentioned polymer electrolyte cationic anti-live agent, can use in the present known material, suitably selecting arbitrarily, material uses.Specifically, can preferably be set forth in the high molecular polymer that has formula (I) expression in the molecule with quaternary ammonium salt base.
(in the formula, R
1And R
2Represent that respectively identical or different carbon number is 1～10 alkyl, R
3The expression carbon number is that 1～10 alkyl or carbon number are 7～10 aralkyl, X
N-The negative ion of expression n valency, n represents 1～4 integer.)
In above-mentioned formula (I), as R
1And R
2The alkyl and the R of expression
3In alkyl, be preferably carbon number and be 1～6 alkyl, especially carbon number and be 1～4 alkyl, in addition, as R
3In aralkyl, preferred benzyl.As carbon number is 1～4 alkyl, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group.
On the other hand, X
N-Can be any of inorganic anion, organic anion,, can enumerate F as its example
-, Cl
-, Br
-, I
-Halide anion, NO
3 -, ClO
4 -, BF
4 -, CO
3 2-, SO
4 2-Deng inorganic anion, CH
3OSO
3 -, C
2H
5OSO
3 -, and the organic anion that comprises organic acid residues such as acetate, propionic acid, succinic acid, maleic acid, fumaric acid, p-toluenesulfonic acid, trifluoroacetic acid.
As such polymer electrolyte quaternary ammonium salt anti-live agent, can enumerate compound for example shown below, that is, tygon benzylic type [(a)], poly-(methyl) acrylic ester type [(b)], styrene-(methyl) acrylate copolymer type [(c)], styrene-maleimide copolymer type [(d)], methacrylate-metering system imide copolymer type [(e)] etc.In addition, in (c), (d) and copolymer type (e), can also be any of atactic copolymer type and segmented copolymer type.
(wherein, R represents H or CH
3)
(wherein, R represents H or CH
3)
(wherein, in above-mentioned (a)-(e), x, y, w represent the degree of polymerization (3-30))
In the present invention, this polymer electrolyte cationic anti-live agent can use a kind, also can will be used in combination more than 2 kinds.
On the other hand, as low molecule-type cationic anti-live agent, can preferably enumerate for example compound with quaternary ammonium salt base of formula (II) expression.
(in the formula, A represents that carbon number is 10～30 alkyl, R
4And R
5Represent that respectively identical or different carbon number is 10 alkyl, R
6The expression carbon number is that 1～10 alkyl or carbon number are 7～10 aralkyl, Y
M-The negative ion of expression m valency, m represents 1～4 integer.)
As the example of A in above-mentioned (II), can enumerate octadecyls such as cetyls such as myristyls such as dodecyl, myristyl, palmityl, stearyl, eicosyl, docosyls etc. such as lauryl.
In addition, R
4, R
5, R
6, Y
M-With m respectively with formula (I) in R
1, R
2, R
3, X
N-Identical with n.
In the present invention, this low molecule-type cationic anti-live agent can use a kind, also can will be used in combination more than 2 kinds.
In addition, in the present invention,, can also use the reactive cationic anti-live agent that in molecule, has 1 above quaternary ammonium salt base and 1 above polymerism unsaturated group as anti-live agent.
By using so reactive cationic anti-live agent, when the irradiation active energy ray, can with the copolymerization of above-mentioned active energy ray-curable compound, sneak in the macromolecular chain of formation, so the continuation of the charging preventive property of gained antireflective film is improved.
As this reactivity cationic anti-live agent, can enumerate the reactive quaternary ammonium compound of for example formula (III) expression etc.
(in the formula, R represents hydrogen atom or methyl.)
In the present invention, this reactivity cationic anti-live agent can use a kind, also can will be used in combination more than 2 kinds.In addition, can appropriate combination use above-mentioned polymer electrolyte cationic anti-live agent, low molecule-type cationic anti-live agent and reactive cationic anti-live agent.
In the present invention, select in the scope of 2～25 weight % as the content of above-mentioned anti-live agent in the hard conating of (A) layer.As long as the content of this anti-live agent is in above-mentioned scope, then antireflective film can be brought into play good charging preventive property, and can not produce bad influence to other performance.This content is preferably at 3～25 weight %, more preferably in the scope of 5～20 weight %.
This hard conating that uses among the present invention forms uses coating fluid, as required can be by in appropriate solvent, ratio according to the rules adds above-mentioned active energy ray-curable compound and anti-live agent respectively, above-mentioned Photoepolymerizationinitiater initiater and various adjuvant according to the expectation use, for example antioxidant, ultraviolet light absorber, light stabilizer, levelling agent, defoamer etc. are with dissolving or disperse and prepare.
As the solvent that use this moment, for example can enumerate cellosolve kind solvents such as esters such as ketone such as alcohol, acetone, MEK, 2 pentanone, methyl isobutyl ketone, isophorone, ethyl acetate, butyl acetate, ethyl cellosolve such as halogenated hydrocarbons such as aromatic hydrocarbons such as aliphatic hydrocarbons such as hexane, heptane, cyclohexane, toluene, dimethylbenzene, methylene chloride, ethylene dichloride, methyl alcohol, ethanol, propyl alcohol, butanols, 1-methoxyl-2-propyl alcohol etc.
As concentration, the viscosity of coating fluid of preparation thus, so long as the concentration that can be coated with, viscosity get final product, have no particular limits, can suitably select according to situation.
Then, on the one side at least of base film, use present known method, for example rod is coated with method, cutter is coated with method, rolling method, scraping blade rubbing method, mould rubbing method, photogravure rubbing method etc., be coated with above-mentioned coating fluid and form and film, after the drying, shine active energy ray therein and film, thereby form hard conating to solidify this.
As active energy ray, can enumerate for example ultraviolet ray or electronics line.Acquisitions such as above-mentioned ultraviolet ray high-pressure mercury-vapor lamp, fusion H lamp, xenon lamp.On the other hand, the electronics line is by acquisitions such as electronics line accelerators.In this active energy ray, preferred especially ultraviolet ray.In addition, under the situation of using the electronics line, can need not to add polymerization initiator and obtain cured film.
In the present invention, (A) hard conating thickness in the scope of 1～20 μ m.This thickness less than 1 μ m probably can't give full play to the mar resistance of the antireflective film of gained, in addition, if surpass 20 μ m, then can produce the crack on hard conating.The preferred thickness of this hard conating is in the scope of 2～15 μ m.
In film for optical use of the present invention, the refractive index of being somebody's turn to do (A) hard conating is usually 1.45～1.60, preferably in 1.49～1.55 scope.
In antireflective film of the present invention, (B) is set in above-mentioned hard conating comprises by the cured resin of active energy ray irradiation formation and the low-index layer of porous silica particle.
The low-index layer that comprises the cured resin that forms by the irradiation of this active energy ray and porous silica particle for example can be on (A) hard conating be filmed by comprising active energy ray-curable compound, above-mentioned porous silica particle and forming to form with the coating fluid coating according to the low-index layer of the Photoepolymerizationinitiater initiater of expectation, the irradiation active energy ray makes this curing of coating, and forms.
For above-mentioned active energy ray-curable compound and the Photoepolymerizationinitiater initiater that uses according to expectation, as shown in the explanation of above-mentioned (A) hard conating.
As the porous silica particle that this (B) layer comprises, preferably using proportion is 1.7～1.9, refractive index be 1.25～1.36 and mean grain size in the scope of 20～100nm.By the porous silica particle that use has this proterties, can obtain the antireflective film of 1 layer of type of antireflection property excellence.
In the present invention, the content that is somebody's turn to do the porous silica particle in (B) layer is selected in the scope of 30～80 weight %.As long as the content of this porous silica particle in above-mentioned scope, should (B) layer be the layer with expectation low-refraction then, the antireflection excellence of gained antireflective film.The preferred content of this porous silica particle is 50～80 weight %, in the scope particularly preferably in 60～75 weight %.
The thickness that is somebody's turn to do (B) layer is 0.05～0.3 μ m, and refractive index is usually in 1.30～1.42 scope.As long as the thickness of this (B) layer and refractive index then can obtain the antireflective film of antireflection property, charging preventive property and excellent scratch resistance in above-mentioned scope.(B) Ceng thickness is preferably 0.07～0.13 μ m, and refractive index is preferably in 1.35～1.40 scope.
This low-index layer that uses among the present invention forms with coating fluid as required, can be by in appropriate solvent, the above-mentioned Photoepolymerizationinitiater initiater and the various adjuvant that add above-mentioned active energy ray-curable compound, porous silica particle, use according to expectation of ratio according to the rules respectively, for example antioxidant, ultraviolet light absorber, light stabilizer, levelling agent, defoamer etc. are with dissolving or disperse and prepare.
For the solvent that uses this moment, as forming with as shown in the explanation of coating fluid at above-mentioned hard conating.
As concentration, the viscosity of coating fluid of preparation thus, so long as the concentration that can be coated with, viscosity get final product, have no particular limits, can suitably select according to situation.
On (A) hard conating, use present known method, for example rod is coated with method, cutter is coated with method, rolling method, scraping blade rubbing method, mould rubbing method, photogravure rubbing method etc., be coated with this coating fluid and form and film, after the drying, shine active energy ray therein and film, thereby form (B) low-index layer to solidify this.
For active energy ray, as shown in the explanation of above-mentioned hard conating.
In the present invention, above-mentioned (A) hard conating and (B) formation of low-index layer are favourable according to method shown below.
At first, the formation of coating hard conating forms with coating fluid and films on the one side of base film, and the irradiation active energy ray is to be cured to semi-cured state.At this moment, under the situation of irradiation ultraviolet radiation, light quantity is generally 50～150mJ/cm
2About.Then, on the cured layer of the semi-cured state that forms thus, the formation of coating low-index layer forms with coating fluid films, and fully shines active energy ray, with the cured layer full solidification of above-mentioned semi-cured state.At this moment, under the situation of irradiation ultraviolet radiation, light quantity is generally 200～1000mJ/cm
2About.
Thus, on base film, form (A) layer and (A) hard conating of (B) interlaminar adhesion excellence and (B) low-index layer successively.
In the antireflective film of the present invention of preparation thus, surface resistivity is 5 * 10
12Below Ω/.As long as this surface resistivity is 5 * 10
12Below Ω/, then charging preventive property be can bring into play, in this antireflective film, dust and dust are difficult to adhere to.Lower limit to surface resistivity has no particular limits, and is generally 1 * 10
8About Ω/.In addition, the average reflectance of antireflective film luminous ray of the present invention is below 3%.
In addition, because the low-index layer that (B) comprises the cured resin that forms by the active energy ray irradiation is set on (A) hard conating, so the continuation excellence of charging preventive property, and have solvent resistance, can suppress because the reduction of the charging preventive property that solvent causes.
In addition, being determined at of surface resistivity is described later.
Thus, can obtain effectively to prevent the surface light reflection of various image-displaying members, and the continuation and the excellent scratch resistance that suppress the anti-charged effect that dust and dust adhere to, and solvent resistance also the anti-reflection layer of excellence be the antireflective film of 1 layer of type.
In antireflective film of the present invention, be provided with on the one side of base film under the situation of hard conating, can with the face of this hard conating opposition side on be formed for attaching the adhesive phase of adherends such as liquid crystal display.As the bonding agent that constitutes this adhesive phase, the material that preferably uses optical applications to use, for example acrylate adhesive, polyurethane binding, polysiloxane-based bonding agent.The thickness of this adhesive phase is usually at 5～100 μ m, preferably in the scope of 10～60 μ m.
In addition, can on this adhesive phase, stripping film be set.As this stripping film, can enumerate for example film of remover such as silicone coated resin on paper such as glassine, art paper, laminated paper and various plastic sheeting.Thickness to this stripping film has no particular limits, and is generally about 20～150 μ m.
Embodiment
Below, the present invention will be described in detail by embodiment, but the present invention does not carry out any qualification by these examples.
In addition, the rerum natura of the antireflective film that obtains in each example is measured according to method shown below.
(1) reflectivity among wavelength 500nm, 600nm and the 700nm
By spectrophotometer [(strain) Shimadzu Seisakusho Ltd. system " UV-3101PC "], measure the reflectivity among wavelength 500nm, 600nm and the 700nm.
(2) surface resistivity
According to JIS K 6911, use is measured with the parallel pole that the digital electrometer that (strain) ア De バ Application テ ス ト company produces is connected.In addition, the surface resistivity after the ethanol wiping is by following mensuration.
With the gauze that the infiltrates ethanol surface 5 times of wiping low-index layer back and forth, again with the gauze of doing back and forth after the wiping 5 times, under 23 ℃, the environment of relative humidity 50%, placed 30 minutes, carry out equally with the mensuration of above-mentioned surface resistivity then.
(3) mar resistance
Use stainless steel wool #0000, at load 9.8 * 10
-3N/mm
2After the following wiping back and forth 5 times, visualization is estimated by following criterion.
Zero: not scratch
*: produce scratch
Embodiment 1
(1) preparation of A liquid (hard conating forms and uses coating fluid)
Will be by of pentaerythritol triacrylate [East Asia synthetic (strain) manufacturing of 45 weight portions as 3 functional acrylate's monomers, trade name " ア ロ ニ Star Network ス M-305 ", solid component concentration 100%], 0.9 weight portion is as 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholine-third-1-ketone [チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ company production of Photoepolymerizationinitiater initiater, trade name " イ Le ガ キ ユ ア 907 ", solid component concentration 100%] and 90 weight portions [コ Le コ-ト company produces as the cationic anti-live agent with polymer electrolyte of quaternary ammonium salt base, trade name " コ Le コ-ト NR-121X-9IPA ", solid component concentration 9.5 weight %] potpourri that constitutes is with 1-methoxyl-2-propyl alcohol dilution, thus the A liquid of preparation solid component concentration 35 weight % (hard conating forms and uses coating fluid).
(2) preparation of B liquid (low-index layer forms and uses coating fluid)
Will be by of pentaerythritol triacrylate [East Asia synthetic (strain) manufacturing of 10 weight portions as 3 functional acrylate's monomers, trade name " ア ロ ニ Star Network ス M-305 ", solid component concentration 100%], [catalyst changes into industry (strain) manufacturing to methyl isobutyl ketone (MIBK) dispersion of 142 weight portion porous silica particles, trade name " ELCOM RT-1002SIV ", solid component concentration 21 weight %, porous silica particle: proportion 1.8, refractive index 1.30, mean grain size 60nm], 0.5 weight portion is as 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholine-third-1-ketone [チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ company production of Photoepolymerizationinitiater initiater, trade name " イ Le ガ キ ユ ア 907 ", solid component concentration 100%] and 0.005 weight portion [eastern レ ダ ウ コ-ニ Application グ シ リ コ-Application (strain) is made as the modified dimethyl polysiloxane of levelling agent, trade name " SH28PA ", solid component concentration 100%] potpourri that constitutes is with MIBK/1-methoxyl-2-propyl alcohol mixed solvent (weight ratio 1/1) dilution, thus the B liquid of preparation solid component concentration 2.5 weight % (low-index layer forms and uses coating fluid).
(3) preparation of antireflective film
[Fuji's description Off イ Le system (strain) is made at the tri acetyl cellulose film as the thickness 80 μ m of base film; trade name " T-80UZ "] the surface on; with the A liquid that obtains in マ イ ヤ-バ-No.8 coating above-mentioned (1), make that the thickness after solidifying is 3 μ m.Then, after under 90 ℃ dry 1 minute, with light quantity 80mJ/cm
2Irradiation ultraviolet radiation is cured to semi-cured state.
Then, on this semi-solid preparation face,, make that the thickness after solidifying is 0.1 μ m with the B liquid that obtains in マ イ ヤ-バ-No.4 coating above-mentioned (2).Then, after under 80 ℃ dry 1 minute, with light quantity 350mJ/cm
2Irradiation ultraviolet radiation, full solidification forms the hard conating of refractive index 1.50 and the low-index layer of refractive index 1.36 successively on the tri acetyl cellulose film, thus the preparation antireflective film.
The rerum natura of Zhi Bei antireflective film is shown in the table 1 thus.
In addition, " MCPD-2000 " that the thickness of each coating is made by Da mound electronics (strain) measures, the ア Star ベ refractometer that refractive index is produced by (strain) ア go (Na light source, wavelength: about 590nm) measure.(following identical)
Embodiment 2
Except the use amount of anti-live agent " コ Le コ-ト NR-121X-9IPA " among the embodiment 1 (1) being changed into 60 weight portions, carry out preparation antireflective film, the refractive index of hard conating: 1.49 similarly to Example 1
The rerum natura of Zhi Bei antireflective film is shown in the table 1 thus.
Embodiment 3
Except the use amount of the MIBK dispersion " ELCOM RT-1002SIV " of porous silica particle among the embodiment 1 (2) being changed into 120 weight portions, carry out preparation antireflective film, the refractive index of low-index layer: 1.40 similarly to Example 1
The rerum natura of Zhi Bei antireflective film is shown in the table 1 thus.
Comparative example 1
In the preparation except A liquid in embodiment 1 (1), do not use beyond the anti-live agent, carry out similarly to Example 1, preparation antireflective film, the refractive index of hard conating: 1.49
The rerum natura of Zhi Bei antireflective film is shown in the table 1 thus.
Comparative example 2
Except will be in embodiment 1 (1) in the preparation of A liquid, the use amount of Photoepolymerizationinitiater initiater " イ Le ガ キ ユ ア 907 " is changed into beyond 1.8 weight portions, and be same with embodiment 1 (1), and the preparation hard conating forms uses coating fluid.
Then, on surface, be coated with above-mentioned hard conating with マ イ ヤ-バ-No.8 and form and use coating fluid, make that the thickness after the curing is 3 μ m as the tri acetyl cellulose film " T80UZ " (aforementioned) of the thickness 80 μ m of base film.Then, after under 90 ℃ dry 1 minute, with light quantity 350mJ/cm
2Irradiation ultraviolet radiation prepares hardcoat film with full solidification.
The rerum natura of Zhi Bei hardcoat film is shown in the table 1 thus.
Table 1
By table 1 as seen, the antireflection of antireflective film of the present invention (embodiment 1～3) is all excellent, and simultaneously, the surface resistance after initial stage and the ethanol wiping is lower, has good anti-charging property and solvent resistance, and mar resistance is also excellent.
On the contrary, comparative example 1 is not owing to comprise anti-live agent in hard conating, so the surface resistivity after initial stage and the ethanol wiping is higher, and anti-charging property is bad.In addition, comparative example 2 is not owing to be provided with low-index layer, so antireflection is bad, and the surface resistivity after the ethanol wiping is higher, and solvent resistance is bad.
Industrial utilizability
Antireflective film of the present invention can effectively prevent the light reflection on image-displaying member surface, And suppress continuation and the excellent scratch resistance of the anti-charged effect that dust and dust adhere to, and Solvent resistance is also excellent, can be applicable in the displays such as PDP, CRT, LCD.
Claims (2)
1. antireflective film, it is characterized in that on the one side at least of base film, have the hard conating that has the cationic anti-live agent of 1 above quaternary ammonium salt base in the molecule that contains the cured resin that forms by active energy ray irradiation and 2～25 weight % successively from above-mentioned base film side, thickness is 1～20 μ m; And the low-index layer that contains the porous silica particle of the cured resin that forms by active energy ray irradiation and 30～80 weight %, thickness is 0.05～0.3 μ m, and this antireflective film surface resistivity is 5 * 10
12Below the Ω.
2. as the described antireflective film of above-mentioned claim 1, the porous silica particle proportion in the above-mentioned low-index layer is 1.7～1.9, refractive index be 1.25～1.36 and mean grain size be 20～100nm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP002822/2005 | 2005-01-07 | ||
| JP2005002822A JP4390717B2 (en) | 2005-01-07 | 2005-01-07 | Antireflection film |
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| Publication Number | Publication Date |
|---|---|
| CN101099093A CN101099093A (en) | 2008-01-02 |
| CN100476458C true CN100476458C (en) | 2009-04-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800460983A Active CN100476458C (en) | 2005-01-07 | 2005-12-28 | Reflection preventive film |
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| Country | Link |
|---|---|
| JP (1) | JP4390717B2 (en) |
| KR (1) | KR101314407B1 (en) |
| CN (1) | CN100476458C (en) |
| TW (1) | TWI389798B (en) |
| WO (1) | WO2006073139A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008242076A (en) * | 2007-03-27 | 2008-10-09 | Nippon Shokubai Co Ltd | Antistatic hard coat composition and optical article |
| US20090075074A1 (en) * | 2007-09-12 | 2009-03-19 | Dai Nippon Printing Co., Ltd. | Optical layered body, method of producing the same, polarizer, and image display device |
| JP2010170089A (en) * | 2008-12-22 | 2010-08-05 | Nof Corp | Reflection preventing film |
| JP2011008155A (en) * | 2009-06-29 | 2011-01-13 | Toppan Printing Co Ltd | Antistatic antireflection film, polarizing plate having the same, and display |
| JP2012072275A (en) * | 2010-09-28 | 2012-04-12 | Fujifilm Corp | Hard coat layer-forming composition, optical film, production method for optical film, polarizing plate and image display device |
| KR101900985B1 (en) * | 2011-03-28 | 2018-09-20 | 도판 인사츠 가부시키가이샤 | Antireflection film and method for producing same |
| JP5937394B2 (en) * | 2012-03-23 | 2016-06-22 | リケンテクノス株式会社 | Active energy ray-curable resin composition |
| CN111057261B (en) * | 2019-12-20 | 2022-05-03 | 合肥乐凯科技产业有限公司 | Anti-dazzle hardened film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4014133B2 (en) | 2001-10-23 | 2007-11-28 | 日東電工株式会社 | Antireflection film, optical element and image display device |
| JP3980423B2 (en) * | 2002-07-01 | 2007-09-26 | 日東電工株式会社 | HARD COAT FILM, ITS MANUFACTURING METHOD, OPTICAL ELEMENT AND IMAGE DISPLAY DEVICE |
| JP4404337B2 (en) * | 2003-02-20 | 2010-01-27 | 大日本印刷株式会社 | Anti-reflection laminate |
-
2005
- 2005-01-07 JP JP2005002822A patent/JP4390717B2/en active Active
- 2005-12-28 WO PCT/JP2005/024273 patent/WO2006073139A1/en not_active Application Discontinuation
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| Publication number | Publication date |
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| TW200631775A (en) | 2006-09-16 |
| JP4390717B2 (en) | 2009-12-24 |
| JP2006188016A (en) | 2006-07-20 |
| TWI389798B (en) | 2013-03-21 |
| CN101099093A (en) | 2008-01-02 |
| WO2006073139A1 (en) | 2006-07-13 |
| KR20070095386A (en) | 2007-09-28 |
| KR101314407B1 (en) | 2013-10-04 |
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