CN1908700A - Antireflection film, polarizing plate, and image display device - Google Patents
Antireflection film, polarizing plate, and image display device Download PDFInfo
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- CN1908700A CN1908700A CNA2006101084438A CN200610108443A CN1908700A CN 1908700 A CN1908700 A CN 1908700A CN A2006101084438 A CNA2006101084438 A CN A2006101084438A CN 200610108443 A CN200610108443 A CN 200610108443A CN 1908700 A CN1908700 A CN 1908700A
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Abstract
An antireflection film comprising a support and a low refractive index layer prepared by coating a coating composition containing the following components: (A) a fluorine-containing polymer, a principal chain of which is made of only carbon atoms and which contains at least one fluorine-containing vinyl monomer polymerization unit and at least one hydroxyl group-containing vinyl monomer polymerization unit, wherein a content of the hydroxyl group-containing vinyl monomer polymerization unit exceeds 20% by mole, provided that the polymer does not have a polysiloxane structure in the principal chain; (B) a crosslinking agent capable of reacting with a hydroxyl group; and (C) a compound containing two or more (meth)acryloyl groups in one molecule thereof.
Description
Technical field
The present invention relates to a kind of antireflection film, use the Polarizer of this antireflection film and the image display device that this antireflection film or Polarizer is used for the display outermost surface.
Background technology
Usually, in image display such as CRT display (CRT) plasma display, (PDP), electroluminescent display (ELD) and liquid crystal indicator (LCD),, because reducing or image reflection, contrast that outside reflection of light caused antireflection film is placed on the outermost surface of display in order to prevent so that utilize the optical interference theory to reduce reflection.
Usually, such antireflection film can prepare by form low-index layer on stilt, and the refractive index of described low-index layer is lower than the refractive index of stilt and has suitable thickness.In order to realize low-refraction, it is desirable using the material of low-refraction as far as possible for this low-index layer.
In addition, because this antireflection film is used to the outermost surface of display, it must have high scratch-resistant.For in the film of about 100nm, in order to realize this high scratch-resistant, this film must self have intensity and to the adhesion of lower floor at thickness.
In addition, because this antireflection film is used to the outermost surface of display, therefore require it to have good opposing is adhered to the impression of the hand of having assembled various stains in displaying or daily use performance, perhaps or even under the contaminated situation of film, require it to have good stain and remove performance (these two kinds of performances will be called " soil resistance " hereinafter jointly).
In order to reduce the refractive index of material, exist for example (1) to introduce the measure that fluorine atom and (2) reduce density (introducing hole).Yet, in these all measures, film strength or at the interface cohesive be lowered, make that scratch-resistant is tending towards being lowered.Like this, making low-refraction and high scratch-resistant compatible each other is a very difficult problem.
In addition, in order to increase the hardness of film self, it is very important that sclerous reaction is fully carried out.In No. the 3498381st, Jap.P., JP-A-11-189621, JP-A-11-228631, JP-A-2004-307524 and JP-A-2003-26732, proposed a kind of effect and made the hydroxyl of fluoropolymer and the method that rigidizer reacts the low-index layer of the antireflection film that hardens by acid catalyst.
In addition, in order to improve antifouling property, the example of introducing the fluoropolymer of silicon on a kind of main polymer chain has been described in No. the 3498381st, Jap.P., JP-A-11-189621, JP-A-11-228631, JP-A-2004-307524.
On the other hand, JP-A-62-174276, JP-A-1-259071, JP-A-2-173172 and JP-A-2-302477 have proposed to use hardenable compositions or the coating of the amine salt of sulfonic acid as catalyzer.
Summary of the invention
For sclerosis,, use p-toluenesulfonic acid as acid catalyst according to the technology of No. the 3498381st, Jap.P., JP-A-11-189621, JP-A-11-228631, JP-A-2004-307524 and JP-A-2003-26732.Because its sclerosis activity is very high, sclerous reaction has partly taken place when storing, stablizing of coating solution is not enough, to such an extent as to the coating condition is restricted.Like this, wish to make the active stability of sclerosis to reach compatible each other with coating solution.
From improving the viewpoint of antifouling property, the method that silicon is incorporated into main polymer chain described in No. the 3498381st, Jap.P., JP-A-11-189621, JP-A-11-228631, JP-A-2004-307524 may make film not be durable.
In addition, the described technology of JP-A62-174276, JP-A-1-259071, JP-A-2-173172 and JP-A-2-302477 is not applied to antireflection film embodiment, and does not have to show choice criteria for substrate.
An object of the present invention is to provide and have good scratch-resistant and antifouling property, make antireflection film compatible with each other between the storage stability of coating solution and the sclerosis activity simultaneously.In addition, another object of the present invention provides a kind of Polarizer and image display device that uses such antireflection film.
In order to overcome the problem of front, the present inventor has carried out extensive and deep research.The result is, the problem that the formation below having found can solve the front to be achieving the above object, thereby caused of the present invention finishing.
That is to say that the present invention achieves the above object by following formation.
(1) a kind of antireflection film, the low-index layer that it comprises stilt and contains the coating composition preparation of following composition by coating:
(A) fluoropolymer, its main chain is only made by carbon atom and contains at least a fluorine-containing polymerization of vinyl monomer unit and at least a hydroxyl polymerization of vinyl monomer unit, wherein, if do not have polysiloxane structure in this main polymer chain, then the content of hydroxyl polymerization of vinyl monomer unit surpasses 20 moles of %;
(B) can with the crosslinking chemical of hydroxyl reaction; With
(C) in a molecule, contain the compound of two or more (methyl) acryloyl group.
(2) a kind of antireflection film, the low-index layer that it comprises stilt and contains the coating composition preparation of following composition by coating:
(A) fluoropolymer, its main chain is only made by carbon atom and contains at least a fluorine-containing polymerization of vinyl monomer unit and at least a hydroxyl polymerization of vinyl monomer unit, wherein, if do not have polysiloxane structure in this main polymer chain, then the content of hydroxyl polymerization of vinyl monomer unit surpasses 20 moles of %;
(B) can with the crosslinking chemical of hydroxyl reaction; With
(D) organic silane compound or contain the hydrolysate of this organic silane compound and the partial condensate of this organosilane at least a composition.
(3) a kind of antireflection film, it comprises stilt and contains the low-index layer that the coating composition of following composition prepares by coating:
(A) fluoropolymer, its main chain is only made by carbon atom and contains at least a fluorine-containing polymerization of vinyl monomer unit and at least a hydroxyl polymerization of vinyl monomer unit, wherein, if do not have polysiloxane structure in this main polymer chain, then the content of hydroxyl polymerization of vinyl monomer unit surpasses 20 moles of %;
(B) can with the crosslinking chemical of hydroxyl reaction; With
(E) particle diameter is 1nm or bigger and be no more than the inorganic particle of 100nm.
(4) it is 1nm or bigger and be no more than the inorganic particle of 100nm that the antireflection film of being set forth in (1) or (2) as in the above, wherein said coating composition further contain (E) particle diameter.
(5) each antireflection film of setting forth in (1)-(4) as in the above, wherein said fluoropolymer comprise at least one polymerized unit with grafting site that contains the polysiloxane repetitive of following formula (1) expression in its side chain,
Formula (1)
In formula (1), R
1And R
2Can be same or different and represent alkyl or aryl separately; And
pRepresent the integer of 10-500.
(6) each antireflection film of setting forth in (1)-(5) as in the above, wherein said coating composition further comprises the polysiloxane compound that (F) has hydroxyl or can form the functional group of binding with hydroxyl reaction.
(7) each antireflection film of setting forth in (1)-(6) as in the above, wherein said coating composition further comprises at least a salt, and this salt is that organic base and the acid of 5.0-10.5 forms by the pKa of its conjugate acid.
(8) each antireflection film of setting forth in (1)-(6) as in the above, wherein said coating composition further comprises at least a salt, and this salt is 35 ℃ or higher and be no more than 85 ℃ nitrogenous organic base and acid and form by boiling point.
(9) each antireflection film of setting forth in (3)-(8) as in the above, wherein said inorganic particle is the hollow silica particle.
(10) each antireflection film of setting forth in (1)-(9) as in the above, it has the layer that at least one refractive index is higher than the refractive index of low-index layer between stilt and low-index layer, wherein said layer comprise a kind of organic silane compound or contain the hydrolysate of organic silane compound and the partial condensate of organic silane compound at least a composition.
(11) comprise (1)-(10) in the Polarizer of each described antireflection film, wherein said antireflection film is provided as a film in two diaphragms of the light polarizing film that is used for Polarizer.
(12) a kind of image display device, it is included in the Polarizer of being set forth in each described antireflection film in (1)-(10) or superincumbent (11), and wherein said antireflection film or Polarizer are used for the outermost surface of display.
Yet antireflection film of the present invention has enough antireflection properties, and it is all very excellent on scratch-resistant and antifouling property.In addition, because antireflection film of the present invention is that the coating solution compatible each other with the activity of hardening produced by using storge quality, so it has very high production applicability.In addition, have the image display device of antireflection film of the present invention and have the image display device of the Polarizer that uses antireflection film of the present invention, it is lower and sharpness is high to be subjected to outside reflection of light and background reflectance.
Description of drawings
Fig. 1 is the section of outline figure that has schematically shown the optimal technical scheme of film of the present invention.
Fig. 2 is the section of outline figure that has schematically shown the optimal technical scheme of film of the present invention.
Fig. 3 is the section of outline figure that has schematically shown the optimal technical scheme of film of the present invention.
Fig. 4 is the section of outline figure that has schematically shown the optimal technical scheme of film of the present invention.
Fig. 5 is the section of outline figure that has schematically shown the optimal technical scheme of film of the present invention.
Embodiment
Below the present invention will be described in more detail.Carry one in passing, in this instructions, under the situation of numerical value performance physical property value, eigenwert etc., term " from (numerical value 1) to (numerical value 2) " means " (numerical value 1) or more and be no more than (numerical value 2) ".In addition, in this instructions, term " (methyl) acrylate " means " in acrylate and the methacrylate at least a ", and this is suitable for " (methyl) acrylic acid " etc. equally.
1. the formation of antireflection film of the present invention
At first, will describe formation, and for example can and constitute all cpds that uses in the layer at the stilt that constitutes antireflection film of the present invention.
The adhesive ingredients that 1-(1) adds as monomer
But the formation layer of film of the present invention can form by the cross-linking reaction or the polyreaction of ionising radiation hardening resin.That is to say, adhesive phase can by coating on the transparent support thing contain ionising radiation can harden polyfunctional monomer or multifunctional oligomer coating composition and make described polyfunctional monomer or multifunctional oligomer forms through cross-linking reaction or polyreaction.Preferably, the adhesive ingredients that adds as monomer is included in the coating composition of the hard conating that is used to form antireflection film of the present invention and/or low-index layer, will make an explanation to it below
As can the harden functional group of polyfunctional monomer or multifunctional oligomer of ionising radiation, photopolymerization functional group, electron beam polymerizable functional group and radiation polymerizable functional group are preferred, and photopolymerization functional group is particularly preferred.
The example of photopolymerization functional group comprises unsaturated polymerizable functional group, for example (methyl) acryloyl group, vinyl, styryl and allyl, and wherein (methyl) acryloyl group is preferred.Particularly, the following compound that contains two or more (methyl) acryloyl group in a molecule can be used as the constituent (C) of low-index layer among the present invention.
The operable instantiation that contains the photopolymerization polyfunctional monomer of photopolymerization functional group comprises:
(methyl) diester acrylates of aklylene glycol, neopentyl glycol acrylate, 1 for example, 6-hexanediol (methyl) acrylate and propylene glycol two (methyl) acrylate;
(methyl) diester acrylates of polyoxyalkylene glycol, for example triethylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate;
(methyl) diester acrylates of polyvalent alcohol, for example pentaerythrite two (methyl) acrylate; With
(methyl) diester acrylates of oxirane or propylene oxide adduct, for example 2, two { 4-(acryloxy-diethoxy) phenyl } propane and 2 of 2-, 2-two { 4-(acryloxy-poly-propoxyl group) phenyl } propane.
In addition, also preferably use epoxy (methyl) acrylate, urethane (methyl) acrylate and polyester (methyl) acrylate as the photopolymerization polyfunctional monomer.
Especially, polyvalent alcohol and (methyl) acrylic acid ester are preferred; And the polyfunctional monomer that contains three or more (methyl) acryloyl group in a molecule is preferred.Its concrete example comprises trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, 1,2,4-cyclohexane four (methyl) acrylate, five glycerine triacrylates (pentaglycerol triacrylate), pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, (2) pentaerythritol triacrylate, (2) pentaerythrite five acrylate, (2) pentaerythrite four (methyl) acrylate, (2) pentaerythrite six (methyl) acrylate, the tripentaerythritol triacrylate, with tripentaerythritol six triacrylates (tripentaerythritolhexatriacrylate).In this instructions, term " (methyl) acrylate ", " (methyl) acrylic acid " and " (methyl) acryloyl " means " acrylate or methacrylate " respectively, " acrylic or methacrylic acid " and " acryloyl or methacryl ".
In order to control the refractive index of each layer, the monomer that has different refractivity with regard to its polymkeric substance can be used as the monomer as bonding agent.Particularly, the example of high refractive index monomers comprises two (4-methacryl thiophenyl) thioethers, vinyl naphthalene, vinyl benzene thioether and 4-methacryloxy phenyl-4 '-methoxyphenyl thioether.
Can also use dendritic polymer and the monomer that contains the norborene ring as in JP-2005-60425, describing as in JP-A-2005-76005 and JP-A-2005-36105, describing.
Polyfunctional monomer can two or more be used in combination.
The polymerization that contains the ethylenically unsaturated group monomer like this can be by being undertaken by irradiation with ionization radiation or heating in the presence of optical free radical initiating agent or thermal free radical initiator.
For the polyreaction of the polyfunctional monomer of photopolymerization, preferably use photo-induced polymerization initiator.As photo-induced polymerization initiator, optical free radical polymerization initiator and light cationic polymerization initiators are preferred, special preferred light radical polymerization initiator.
The adhesive ingredients that 1-(2) adds as polymkeric substance
In the present invention, can use polymkeric substance or cross-linked polymer as the bonding agent that constitutes layer.Preferred described cross-linked polymer contains anionic group.The crosslinked polymkeric substance that contains anionic group has the structure that the main chain that contains the anionic group polymkeric substance is crosslinked.Preferably the adhesive ingredients that adds as polymkeric substance is included in the coating composition of the hard conating of the antireflection film of the present invention that will explain below being used to form and/or low-index layer.
The example of main polymer chain comprises polyolefin (stable hydrocarbon), polyethers, polycarbamate, polyester, polyamine, polyamide and melamine resin.Wherein, polyolefin backbone, polyether backbone and polyureas main chain are preferred; Polyolefin backbone and polyether backbone are more preferably; And polyolefin backbone is most preferred.
Polyolefin backbone is made of stable hydrocarbon.Polyolefin backbone is that the polyaddition reaction by for example unsaturated polymerizable group obtains.In polyether backbone, its repetitive (O-) connects by ehter bond.Polyether backbone is that the ring-opening polymerization by for example epoxide group obtains.In the polyureas main chain, its repetitive (NH-CO-NH-) connects by the urea key.The polyureas main chain is to obtain by for example isocyanate groups and amino polyreaction.In the polycarbamate main chain, its repetitive (NH-CO-O-) connects by amino-formate bond.The polycarbamate main chain is that the reaction by for example isocyanate groups and hydroxyl (comprising the N-methylol) obtains.In polyester backbone, its repetitive (CO-O-) connects by ester bond.Polyester backbone is to obtain by the reaction between for example carboxyl (comprising acid halide group) and the hydroxyl (comprising the N-methylol).In the polyamine main chain, its repetitive (NH-) connects by the imido key.This polyamine main chain is that the ring-opening polymerization by for example Ethylenimine obtains.In polyamide skeleton, its repetitive (NH-CO-) connects by amido link.Polyamide skeleton is to obtain by the reaction between for example isocyanate groups and the carboxyl (comprising acid halide group).The main chain of melamine resin is to obtain by the reaction between for example triazine group (for example, melamine) and the aldehyde (for example, formaldehyde).By the way, in melamine resin, self has cross-linked structure main chain.
Anionic group directly is attached on the main polymer chain or by linking group to be attached on the main chain.The preferred anionic group is attached on the main chain by linking group as side chain.
The example of anionic group comprises carboxylic acid group's (carboxyl), sulfonic group (sulfo group) and phosphate (phosphono), and wherein sulfonic group and phosphate are preferred.
Anionic group can be in the state of salt.The kation that forms salt with anionic group is alkali metal ion preferably.In addition, the proton of anionic group can be dissociated.
Preferably anionic group is attached to linking group on the main chain and is be selected from-CO-,-divalent group of O-, alkylidene, arlydene and their combination.
Cross-linked structure has the chemical bonding (preferably covalently key) of two or more main chains and preferably has the covalency keyed jointing of three or more main chains.Preferred this cross-linked structure be by be selected from-CO-,-O-,-divalence or the multivalence group of S-, nitrogen-atoms, phosphorus atoms, aliphatic group, aromatic radical and their combination.
The preferred crosslinked polymkeric substance that contains anionic group is the multipolymer that contains the repetitive of anionic group and have the repetitive of cross-linked structure.Contain the ratio of anionic group repetitive in this multipolymer and be preferably 2-96 weight %, more preferably 4-94 weight %, most preferably 6-92 weight %.Described repetitive can contain two or more anionic groups.The ratio of repetitive in described multipolymer with cross-linked structure is preferably 4-98 weight %, more preferably 6-96 weight %, and 8-94 weight % most preferably.
The repetitive of the crosslinked polymkeric substance that contains anionic group can have anionic group and cross-linked structure.In addition, can contain other repetitive (neither having the repetitive that anionic group does not have cross-linked structure yet).
As other repetitive, the repetitive that contains amino or quaternary ammonium group is preferred with the repetitive that contains phenyl ring.Amino or quaternary ammonium group have the function that carrying is similar to the dispersed inorganic particle of anionic group.Carry one in passing, even, also can obtain identical effect when containing the anionic group repetitive or having the time marquis who comprises amino, quaternary ammonium group or phenyl ring in the repetitive of cross-linked structure.
In the repetitive that comprises amino or quaternary ammonium group, amino or quaternary ammonium group are directly to be attached on the main polymer chain or by linking group to be attached on the main chain.Preferred amino or quaternary ammonium group are attached on the main chain by linking group as side chain.Amino or quaternary ammonium group be secondary amino group, uncle's amino or quaternary ammonium group preferably, and is more preferably uncle's amino or quaternary ammonium group.In secondary amino group, uncle's amino or quaternary ammonium group, the group that is attached to nitrogen-atoms is alkyl preferably, is more preferably the alkyl with 1-12 carbon atom, and most preferably is the alkyl with 1-6 carbon atom.The counterion of preferred quaternary ammonium group is the halogen ion.Preferably secondary amino group, uncle's amino or quaternary ammonium group are attached to linking group on the main chain and are be selected from-CO-,-NH-,-divalent group of O-, alkylidene, arlydene and their combination.Comprise under the situation of the repetitive that contains amino or quaternary ammonium group at the crosslinked polymkeric substance that contains anionic group, the ratio of repetitive is preferably 0.06-32 weight %, more preferably 0.08-30 weight %, and 0.1-28 weight % most preferably.
1-(3) fluoro-containing copolymer adhesive [constituent of low-index layer of the present invention (A)]:
In the present invention, in low-index layer, used a kind of polymkeric substance, the main chain of this polymkeric substance is only made by carbon atom and it contains at least a fluorine-containing polymerization of vinyl monomer unit and at least a hydroxyl polymerization of vinyl monomer unit, wherein, if do not have polysiloxane structure in this main polymer chain, then the content of hydroxyl polymerization of vinyl monomer unit surpasses 20 moles of %.
(fluorine-containing polymerization of vinyl monomer unit)
In the present invention, the structure that is included in the fluorine-containing polymerization of vinyl monomer unit in the fluoropolymer that is used for forming low-index layer does not have concrete restriction, and its example comprises the polymerized unit based on Fluorine containing olefine, perfluoroalkyl vinyl ether, the vinyl ether that contains fluoroalkyl or (methyl) acrylate etc.Consider desired performance in production applicability and the low-index layer, for example low-refraction and film strength, this fluoropolymer is the multipolymer of Fluorine containing olefine and vinyl ether preferably, is more preferably the multipolymer of perfluoroolefine and vinyl ether.In addition, in order to reduce refractive index, perfluoroalkyl vinyl ether be can comprise, fluorine-containing alkyl vinyl ether or (methyl) acrylate etc. contained as the copolymerization composition.
As perfluoroolefine, what have 3-7 carbon atom is preferred; From polymerization activity, perfluoropropene and perfluorobuttene are preferred; And perfluoropropene is particularly preferred from the easness that obtains.
The content of perfluoroolefine in this polymkeric substance is 25-75 mole %.In order to realize the low-refraction of material, though it is desirable increasing the introducing rate of perfluoroolefine, but from the introducing amount of the viewpoint 50-70 mole % of polymerization activity is based on the limit the Raolical polymerizable of common solution, and the introducing that surpasses above-mentioned scope is difficult to.In the present invention, above-mentioned content is preferably 30-70 mole %, more preferably 30-60 mole %, further preferred 35-60 mole %, and preferred especially 40-60 mole %.
In addition, in the used in the present invention fluoropolymer, in order to realize low-refraction, can copolymerization contain fluorovinyl ether by what following M1 represented.Described copolymerization composition can be with 0-40 mole %, preferred 0-30 mole %, and the scope of preferred especially 0-20 mole % is incorporated in the polymkeric substance.
In M1, Rf
111Expression has the fluoroalkyl that contains of 1-30 carbon atom, preferably has the fluoroalkyl that contains of 1-20 carbon atom, and especially preferably has the fluoroalkyl that contains of 1-5 carbon atom; Can be linear for example ,-CF
2CF
3,-CH
2(CF
2)
aH and-CH
2CH
2(CF
2)
aF (integer of a:2-12) }; Can be branched structure for example ,-CH (CF
3)
2,-CH
2CF (CF
3)
2,-CH (CH
3) CF
2CF
3With-CH (CH
3) (CF
2)
5CF
2H}; Can have alicyclic structure (preferred 5 yuan of rings or 6 yuan of rings, for example perfluor cyclohexyl, perfluor cyclopentyl and the alkyl that replaced by such group); And can contain ehter bond for example ,-CH
2OCH
2CF
2CF
3,-CH
2CH
2OCH
2(CF
2)
bH ,-CH
2CH
2OCH
2(CF
2)
bF (integer of b:2-12) and-CH
2CH
2OCF
2CF
2OCF
2CF
2H}.By the way, should not be considered as by Rf
111The substituting group of expression only only limits to cited in this article substituting group.
The above-mentioned monomer of being represented by M1 can be synthetic by the following method, for example, by at Macromolecules, Vol.32 (21), p.7122 (1999), described in the JP-A-2-721 etc., in the presence of base catalyst, make for example method of vinyl oxyalkyl sulphonic acid ester and the reaction of vinyl oxyalkyl chloride of fluorine-containing alcohol and the alkyl vinyl ether that is replaced by split-off group; In WO92/05135, describe in the presence of palladium catalyst, make fluorine-containing alcohol and vinyl ether for example butyl vinyl ether mix, thereby the method for carrying out the vinyl exchange; And at US3, make in the presence of the potassium fluoride catalyzer fluorine-containing ketone and ethylene dibromide described in 420,793 react each other then by the method for base catalyst through the engaging vibrating bromize hydrogen reaction.
To provide the preferred embodiment of the constituent of representing by M1 below, but should not be considered as the present invention is limited to these examples.
In fluoropolymer used in the present invention, in order to realize low-refraction, the perfluoroalkyl vinyl ether of can copolymerization representing by following M2.Above-mentioned copolymerization composition can be with 0-40 mole %, preferred 0-30 mole %, and the scope of preferred especially 0-20 mole % is incorporated in this polymkeric substance.
In M2, Rf
112Expression has the fluoroalkyl that contains of 1-30 carbon atom, preferably has the fluoroalkyl that contains of 1-20 carbon atom, especially preferably has the fluoroalkyl that contains of 1-10 carbon atom, and further preferably has the perfluoro alkyl group of 1-10 carbon atom.In addition, above-mentioned fluorine-containing alkyl group can have substituting group.Rf
112Instantiation comprise-CF
3{ M2-(1) } ,-CF
2CF
3{ M2-(2) } ,-CF
2CF
2CF
3{ M2-(3) } and-CF
2CF (OCF
2CF
2CF
3) CF
3{ M3-(4) }.
(hydroxyl polymerization of vinyl monomer unit)
Requirement is used in fluoropolymer of the present invention and comprises hydroxyl polymerization of vinyl monomer unit, and its content in polymkeric substance surpasses 20 moles of %.Because hydroxyl has the function of sclerosis when reacting with crosslinking chemical, is high because can form the content of the preferred oh group of dura mater.Its content is preferably more than 20 moles of % and be no more than 70 moles of %, more preferably more than 20 moles of % but be no more than 60 moles of %, and further preferred 25 moles of % or more and be no more than 55 moles of %.
Can copolymerization as long as contain the fluorine-containing polymerization of vinyl monomer unit of the vinyl monomer of hydroxyl and front, then it can be used and not have specific restriction, and its example comprises vinyl ether, (methyl) acrylate and styrene.For example, be used as under the situation of fluorine-containing vinyl monomer the preferred hydroxyl vinyl ether that uses with good copolymerization at perfluoroolefine (for example, hexafluoropropylene).Its instantiation comprises 2-hydroxyethyl vinyl ether, 4-hydroxy butyl vinyl ether, 6-hydroxyl hexyl vinyl ether, 8-hydroxyl octyl group vinyl ether, diglycol vinyl ether, triethylene glycol vinyl ether and 4-(methylol) cyclohexyl methyl vinyl ether.But, should not be considered as the present invention and be limited to this.
(formation unit) with polysiloxane structure
In order to give antifouling property, the fluoropolymer of Shi Yonging comprises the formation unit with polysiloxane structure also preferred in the present invention.As being fit to be used in the fluoropolymer with polysiloxane structure of the present invention, enumerated and comprised (a) at least a fluorine-containing polymerization of vinyl monomer unit, (b) at least a hydroxyl polymerization of vinyl monomer unit and (c) at least a polymerized unit that on side chain, contains the grafting site of the polysiloxane repetitive of representing by following formula (1), and wherein its main chain is only to be made by carbon atom.
Formula (1)
In formula (1), R
1And R
2Can be identical or different and represent alkyl or aryl separately.Alkyl preferably has 1-4 carbon atom, and its example comprises methyl, trifluoromethyl and ethyl.Aryl preferably has 6-20 carbon atom, and its example comprises phenyl and naphthyl.In these, methyl and phenyl are preferred; And methyl is particularly preferred.P represents the integer of 10-500, preferred 10-350 and preferred especially 10-250.
The polymkeric substance that has the polysiloxane structure of being represented by formula (1) in side chain can synthesize by the following method, wherein for (for example containing reactive group, epoxy radicals, hydroxyl, carboxyl, and anhydride group) polymkeric substance, by for example at J.Appl.Polym.Sci., 78,1995 (2000) and JP-A-56-28219 described in polyreaction, to (for example at one end contain corresponding reactive group, amino for epoxy radicals or anhydride group, sulfydryl, carboxyl and hydroxyl) polysiloxane (for example, SILAPLANE series is produced by Chisso Corporation) introduce; And contain the big monomer methods of silicon of polysiloxane by polymerization, and these two kinds of methods can be by advantageous applications.In the present invention, the method for reaching introducing by the big monomer methods of polymerization silicon is preferred.
As the big monomer of silicon, any big monomer of silicon that can carry out the polymerizable groups of copolymerization with Fluorine containing olefine that contains all is to be fit to use.Structure by any expression in following formula (2)-(5) all is preferred.
Formula (2)
Formula (3)
Formula (4)
Formula (5)
In formula (2)-(5), R
1, R
2With p have with formula (1) in identical implication; And their preferable range is also identical.R
3-R
5That expression independently of one another replaces or unsubstituted unit price organic group or hydrogen atom.Wherein, the alkyl (for example, methyl, the ethyl that have 1-10 carbon atom, and octyl group), the alkoxy (for example, methoxyl, the ethoxy that have 1-10 carbon atom, and propoxyl group), and the aryl (for example, phenyl and naphthyl) with 6-20 carbon atom be preferred; And the alkyl with 1-5 carbon atom is particularly preferred.R
6Expression hydrogen atom or methyl.L
1Expression has any linking group of 1-20 carbon atom; And its example comprises replacement or unsubstituted, linear side chain or alicyclic alkylidene and replacement or unsubstituted arlydene.Wherein, the unsubstituted linear alkylene with 1-20 carbon atom is preferred; And ethylidene and propylidene are particularly preferred.These compounds can be synthetic by the method for describing in JP-A-6-322053 for example.
All compounds by formula (2)-(5) expression can preferably be used among the present invention.Wherein, from the viewpoint of Fluorine containing olefine copolymerization, have by formula (2), the compound of (3) or (4) expression is particularly preferred.Aforementioned polysiloxane position preferably accounts for 0.01-20 weight % in graft copolymer, more preferably account for 0.05-15 weight %, and especially preferably accounts for 0.5-10 weight %.
With respect to the whole fluoropolymer molecular weight of the present invention, contain the amount that polysiloxane structure constitutes the unit and be preferably 0.01-2 mole %, more preferably 0.01-1 mole %, further preferred 0.01-2 mole %, and preferred especially 0.05-2 mole %.
To provide the preferred embodiment of the polymerized unit that is fit to be used in the polymer graft point that in side chain, comprises the polysiloxane position of the present invention below, but should not be considered as the present invention is confined to this.
S-(36) SILAPLANE FM-0711 (producing) by Chisso Corporation
Number-average molecular weight: 1000
S-(37) SILAPLANE FM-0721 (producing) by Chisso Corporation
Number-average molecular weight: 6000
S-(38) SILAPLANE FM-0725 (producing) by Chisso Corporation
Number-average molecular weight: 14000
By introducing polysiloxane structure, not only given film antifouling property and dust removal performance, and given film smooth surface performance.In addition, this also is favourable for mar-proof performance.
(other polymerized unit)
Other copolymerization composition that can form polymerized unit can root from various viewpoints, for example, hardness, suitably select for the cohesive of substrate, the dissolubility and the transparency in the solvent.Their example comprises vinyl ether, for example methyl vinyl ether, ethyl vinyl ether, tert-Butyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether and isopropyl-ethylene base ether; And vinyl esters, for example vinyl acetate, propionate, vinyl butyrate and cyclohexane-carboxylic acid vinyl acetate.The introducing amount of such copolymerization composition is at 0-40 mole %, preferred 0-30 mole %, and in the scope of preferred especially 0-20 mole %.
(configuration of preferred fluoropolymer)
Particularly preferred polymkeric substance configuration is the configuration by following formula (7) expression among the present invention.
Formula (7)
In formula (7), Rf
11Expression has the perfluoroalkyl of 1-5 carbon atom.For by-CF
2CF (Rf
11) position of expression, the front is suitable for about the explanation of as an example perfluoroolefine.In formula (7), Rf
12As above regard to and contain the fluorovinyl ether (Rf in the compound of representing by the formula M2 of front
12) definition identical; And its preferred range also is identical.A
11And B
11Represent hydroxyl polymerization of vinyl monomer unit separately or constitute the unit arbitrarily.A
11As above identical in the face of the definition of hydroxyl polymerization of vinyl monomer unit.Though B
11Be not subjected to concrete restriction, still from the viewpoint of copolymerization, it is preferably vinyl ether or vinyl esters.Particularly, the monomer of having enumerated the monomer (other polymerized unit) enumerated previously here and having represented by the formula M1 of front.
Y
11Expression has the formation unit of polysiloxane structure; And its configuration can be the polymerized unit that comprises the grafting site of the polysiloxane repetitive of being represented by formula (1) on side chain.Its definition is identical with above-described (the formation unit with polysiloxane structure) with preferable range.
A-d represents the mole fraction (%) of each constituent separately; And be to equal 100 (a+b+c+d).Relational expression that their satisfy is: (more preferably 30≤a≤60,30≤a≤70, and further preferred 35≤a≤60), (more preferably 0≤b≤30,0≤b≤40, and further preferred 0≤b≤20), (more preferably 20＜c≤60,20≤c≤70, and 0≤d≤40 (more preferably 0≤d≤30) and further preferred 25≤c≤55).
Y represents to contain polysiloxane and constitutes the weight fraction that the unit accounts for the molecular weight of whole fluoropolymer.They satisfy relational expression: 0.01≤y≤20 (more preferably 0.05≤y≤15, and further preferred 0.5≤y≤10).
In the present invention, the number-average molecular weight that is used for forming the fluoropolymer (preferred, by the fluoropolymer of formula (7) expression shown in top) of low-index layer is preferably 5,000-1,000,000, more preferably 8,000-500,000, and be preferably 10 especially, 000-100,000.
Here, number-average molecular weight is by using TSKgel GMHxL, the gpc analysis instrument of TSKgelG4000HxL and TSKgel G2000HxL (being the trade name of Tosoh Corporation all) post, the mode that detects with differential refractometer in as the THF of solvent is amounted to into the molecular weight of polystyrene.
A kind of in the present invention particularly preferred polymkeric substance has the structure by formula 8 expressions.
Formula 8:
In above-mentioned formula 8, a1, c1 and d1 represent the mole fraction (%) of each constituent separately, and a1+b1+c1=100.The respectively preferred separately relational expression below satisfying: 30≤a1≤70 (more preferably 30≤a1≤60, and more preferably 35≤a1≤60, and most preferably 40≤a1≤55); 20≤c1≤50 (more preferably 20≤c1≤45, and more preferably 25≤c1≤40, and most preferably 30≤c1≤40); And 0≤d1≤30 (more preferably 5≤d1≤30, and more preferably 10≤d1≤25, and most preferably 10≤d1≤20).
In above-mentioned formula 8, Y
12Expression has the structural unit by the polysiloxane structure of aforementioned formula 2 expressions, and preferably has 1000-40000, more preferably 3000-20000, and the more preferably number-average molecular weight of 5000-15000.As Y
12Preferred instantiation, can mention S-(1), S-(2), S-(7), S-(37) or S-(38).In them, S-(1), S-(2), S-(37) or S-(38) are more preferably, and S-(2), and S-(37) or S-(38) are further preferred.
Y1 represents to contain polysiloxane formation unit and accounts for the weight fraction (%) of the whole molecular weight of fluoropolymer, and satisfies relational expression: 0.01≤y1≤20 (more preferably 1≤y1≤15, further preferred 2≤y1≤10, most preferably 3≤y1≤7).
Number-average molecular weight by the fluoropolymer of above-mentioned formula 8 expressions is preferably 5,000-500, and 000, more preferably 6,000-100,000, and preferred especially 7,000-50,000.Remind in passing, this number-average molecular weight is identical with the foregoing value that is converted into polystyrene.
In table 1-5, shown the instantiation of fluoropolymer among the present invention.But should not be considered as the restriction that the present invention is subjected to these polymkeric substance.Table 1-5 has shown the combination of the polymerized unit of fluoropolymer.
Table 1
| Fluoropolymer | P1 | P2 | P3 | P4 | P5 | P6 | P7 | P8 | P9 | P10 | P11 | P12 | |
| Fluoropolymer constituent (mole fraction (%)) | |||||||||||||
| Hexafluoropropylene | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | |
| M1-(2) | |||||||||||||
| M1-(6) | |||||||||||||
| M2-3 | |||||||||||||
| HEVE | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | |
| HBVE | |||||||||||||
| HOVE | |||||||||||||
| DEGVE | |||||||||||||
| HMcHVE | |||||||||||||
| EVE | |||||||||||||
| cHVE | |||||||||||||
| tBuVE | |||||||||||||
| VAc | |||||||||||||
Table 1 (continuing)
| Fluoropolymer | P1 | P2 | P3 | P4 | P5 | P6 | P7 | P8 | P9 | P10 | P11 | P12 | |
| Contain organosilicon constituent (weight %) | |||||||||||||
| S-(1) | 2 | ||||||||||||
| S-(2) | 2.1 | ||||||||||||
| S-(11) | 2 | ||||||||||||
| S-(13) | 2 | ||||||||||||
| S-(16) | 1.8 | ||||||||||||
| S-(21) | 2 | ||||||||||||
| S-(29) | 2 | ||||||||||||
| S-(30) | 1.7 | ||||||||||||
| S-(36) | 2.1 | ||||||||||||
| S-(37) | 2.5 | ||||||||||||
| S-(38) | 1.7 | ||||||||||||
| Molecular weight (* 10,000) | 1.5 | 1.7 | 2.2 | 2.6 | 1.9 | 2.4 | 2.9 | 3.5 | 4.1 | 2.5 | 2.2 | 1.7 | |
Table 2
| Fluoropolymer | P13 | P14 | P15 | P16 | P17 | P18 | P19 | P20 | P21 | P22 | P23 | P24 | |
| Fluoropolymer constituent (mole fraction (%)) | |||||||||||||
| Hexafluoropropylene | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 45 | 50 | 50 | 40 | |
| M1-(2) | 10 | ||||||||||||
| M1-(6) | 10 | ||||||||||||
| M2-3 | 5 | 10 | |||||||||||
| HEVE | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 30 | 20 | 25 | |
| HBVE | |||||||||||||
| HOVE | |||||||||||||
| DEGVE | |||||||||||||
| HMcHVE | |||||||||||||
| EVE | 10 | 10 | 10 | 10 | 10 | 10 | 30 | 25 | |||||
| cHVE | 10 | ||||||||||||
| tBuVE | 20 | ||||||||||||
| VAc | |||||||||||||
Table 2 (continuing)
| Fluoropolymer | P13 | P14 | P15 | P16 | P17 | P18 | P19 | P20 | P21 | P22 | P23 | P24 | |
| Contain organosilicon constituent (weight %) | |||||||||||||
| S-(1) | 2.5 | 1.8 | |||||||||||
| S-(2) | |||||||||||||
| S-(11) | 2.3 | 1.9 | |||||||||||
| S-(13) | |||||||||||||
| S-(16) | |||||||||||||
| S-(30) | 2.5 | ||||||||||||
| S-(36) | |||||||||||||
| S-(37) | 6.6 | 4.2 | 1.7 | ||||||||||
| S-(38) | |||||||||||||
| Molecular weight (* 10,000) | 1.5 | 1.7 | 2.1 | 4.5 | 2.8 | 2.5 | 1.6 | 3.1 | 2.5 | 3.1 | 1.9 | 4.1 | |
Table 3
| Fluoropolymer | P25 | P26 | P27 | P28 | P29 | P30 | P31 | P32 | P33 | P34 | P35 | P36 | |
| Fluoropolymer constituent (mole fraction (%)) | |||||||||||||
| Hexafluoropropylene | 50 | 50 | 50 | 50 | 40 | 50 | 50 | 45 | 50 | 50 | 50 | 50 | |
| M1-(2) | 10 | 5 | |||||||||||
| M1-(6) | 5 | 10 | |||||||||||
| M2-3 | 10 | 5 | |||||||||||
| HEVE | |||||||||||||
| HBVE | 40 | 30 | 40 | 20 | 50 | ||||||||
| HOVE | 40 | 25 | 50 | ||||||||||
| DEGVE | 40 | 40 | |||||||||||
| HMcHVE | 15 | 40 | |||||||||||
| EVE | 10 | 20 | 25 | 10 | 35 | ||||||||
| cHVE | 10 | ||||||||||||
| tBuVE | |||||||||||||
| VAc | 25 | 5 | |||||||||||
Table 3 (continuing)
| Fluoropolymer | P25 | P26 | P27 | P28 | P29 | P30 | P31 | P32 | P33 | P34 | P35 | P36 | |
| Contain organosilicon constituent (weight %) | |||||||||||||
| S-(1) | 2.9 | ||||||||||||
| S-(2) | 3.1 | 1.3 | |||||||||||
| S-(11) | 1.9 | ||||||||||||
| S-(13) | 1.9 | ||||||||||||
| S-(30) | 3.1 | ||||||||||||
| S-(36) | 3.2 | ||||||||||||
| S-(37) | 3.1 | ||||||||||||
| S-(38) | 2.8 | 1.9 | 3.4 | ||||||||||
| Molecular weight (* 10,000) | 3.1 | 2.9 | 1.9 | 2.6 | 4.2 | 2.3 | 3.1 | 3.4 | 2.4 | 2.7 | 2.4 | 3.1 | |
Table 4
| Fluoropolymer | P37 | P38 | P39 | P40 | P41 | P42 | P43 | P44 | P45 | P46 | P47 | P48 | |
| Fluoropolymer constituent (mole fraction) | |||||||||||||
| Hexafluoropropylene | 50 | 50 | 50 | 45 | 45 | 45 | 50 | 45 | 50 | 45 | 45 | 45 | |
| M1-(2) | |||||||||||||
| M1-(6) | |||||||||||||
| M2-3 | 5 | 5 | 5 | 5 | 5 | 5 | |||||||
| HEVE | 30 | 30 | 30 | 30 | 30 | 30 | 25 | 25 | 25 | 25 | 25 | 25 | |
| HBVE | |||||||||||||
| HOVE | |||||||||||||
| DEGVE | |||||||||||||
| HMcHVE | |||||||||||||
| EVE | 20 | 20 | 20 | 20 | 20 | 20 | 25 | 25 | 25 | 25 | 25 | 25 | |
| cHVE | |||||||||||||
| tBuVE | |||||||||||||
| VAc | |||||||||||||
Table 4 (continuing)
| Fluoropolymer | P37 | P38 | P39 | P40 | P41 | P42 | P43 | P44 | P45 | P46 | P47 | P48 | |
| Contain organosilicon constituent (weight %) | |||||||||||||
| S-(1) | |||||||||||||
| S-(2) | |||||||||||||
| S-(11) | |||||||||||||
| S-(13) | |||||||||||||
| S-(16) | |||||||||||||
| S-(30) | |||||||||||||
| S-(36) | |||||||||||||
| S-(37) | 3.8 | 3.8 | 3.8 | 3.8 | |||||||||
| S-(38) | 3.8 | 3.8 | 3.8 | 3.8 | |||||||||
| Molecular weight (* 10,000) | 2.4 | 2.6 | 2.6 | 2.8 | 2.9 | 2.9 | 2.6 | 2.6 | 2.7 | 2.6 | 2.7 | 2.7 | |
Table 5
| Fluoropolymer | P49 | P50 | P51 | P52 | P53 | P54 | P55 | P56 | P57 | P58 | P59 | |
| Fluoropolymer constituent (mole fraction) | ||||||||||||
| Hexafluoropropylene | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | |
| M1-(2) | ||||||||||||
| M1-(6) | ||||||||||||
| M2-3 | ||||||||||||
| HEVE | 30 | 30 | 30 | 32 | 32 | 35 | 35 | 35 | 40 | 40 | 40 | |
| HBVE | ||||||||||||
| HOVE | ||||||||||||
| DEGVE | ||||||||||||
| HMcHVE | ||||||||||||
| EVE | 20 | 20 | 20 | 18 | 18 | 15 | 15 | 15 | 10 | 10 | 10 | |
| cHVE | ||||||||||||
| tBuVE | ||||||||||||
| VAc | ||||||||||||
Table 5 (continuing)
| Fluoropolymer | P49 | P50 | P51 | P52 | P53 | P54 | P55 | P56 | P57 | P58 | P59 | |
| S-(1) | ||||||||||||
| S-(2) | ||||||||||||
| S-(11) | ||||||||||||
| S-(13) | ||||||||||||
| S-(30) | ||||||||||||
| S-(36) | ||||||||||||
| S-(37) | 5.9 | 5.2 | 5.8 | 6.0 | 5.0 | 5.8 | 4.9 | |||||
| S-(38) | 4.8 | 5.5 | 5.2 | 4.5 | ||||||||
| Molecular weight (* 10,000) | 1.1 | 1.3 | 1.2 | 1.0 | 1.3 | 0.9 | 0.8 | 1.4 | 1.0 | 1.1 | 1.5 | |
The fluoropolymer of the present invention that is used for shown in the aforementioned table 1-5 has fluoropolymer composition (fluorine-containing polymerization of vinyl monomer unit and hydroxyl vinyl monomer unit) and contains silicone ingredients (composition with polysiloxane structure).Respectively, the composition of fluoropolymer is represented the mole fraction of each composition (%), has represented that siliceous composition accounts for the quality % of the whole molecular weight of fluoropolymer and contain the organosilicon composition.Composition (containing silicone ingredients) with polysiloxane structure has big molecular weight, thereby makes that the contribution of mole fraction of each unit in fluoropolymer is that 2 moles of % are so little or littler.Therefore, mole fraction has been got rid of and has been contained organic composition silicon calculating.Dummy suffix notation in the table is as follows.
HFP: hexafluoropropylene
HEVE:2-hydroxyethyl vinyl ether
The HBVE:4-hydroxy butyl vinyl ether
HOVE:8-hydroxyl octyl group vinyl ether
DEGVE: diglycol vinyl ether
HMcHVE:4-(methylol) cyclohexyl methyl vinyl ether
EVE: ethyl vinyl ether
CHVE: cyclohexyl vinyl ether
TBuVE: tert-Butyl vinyl ether
Vac: vinyl acetate
In the present invention, the fluoropolymer of representing as P1-P59 by the front, P2, P3, P10-P12, P14, P17, P18, P20, P22-P26, P29, P38, P39, P41, P42, P44, P45 and P49-P59 are preferred, P14, P17, P18, P20, P22-P24, P38, P39, P41, P42, P44, P45 and P49-P59 are more preferably, and P49-P59 is further preferred.
The synthetic of employed aforementioned fluoropolymer can be implemented by multiple polymerization among the present invention, for example, and solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, block polymerization and emulsion polymerization.In addition, this synthetic can being undertaken by known operational example such as batch operation, semicontinuous operation and continued operation.
The example that is used for the method for initiated polymerization comprises the method for using radical initiator and the method for irradiates light or radiation.These polymerizations are described in the method that is used for initiated polymerization, for example, by Nikkan Kogyo Shibun Ltd., the 1971 Teiji Tsuruta that publish, KobunshiGosel Hoho (Polymer Synthesis Methods, revised edition); With by Kagaku-dojinPublishing Company, the Takayuki Otsu andMasayoshi Kinoshita that Inc., 124-125 page or leaf (1972) publish, Kobunshi Gosei no Jikkenho (experimental technique that polymkeric substance is synthetic).
In above-mentioned polymerization, it is particularly preferred using the solution polymerization process of radical initiator.The example that is used in the solvent in the solution polymerization process comprises multiple solvent for example ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, diox, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, acetonitrile, methylene chloride, chloroform, ethylene dichloride, methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol and 1-butanols.Such organic solvent can use separately or use with two or more the potpourri in them, and the mixed solvent that perhaps can be used as with water uses.
Polymerization temperature must be according to the molecular weight of formed polymkeric substance, and the kind of initiating agent waits to be set.Though polymerization can be carried out not being higher than under 0 ℃ or 100 ℃ or the higher temperature, preferably carries out polymerization in 40-100 ℃ temperature range.
Though reaction pressure can be selected suitably, reaction pressure is generally about 0.01-10MPa, preferably about 0.05-5MPa, and more preferably from about 0.1-2Mpa is desirable.Reaction time is about 5-30 hour.
About the polymkeric substance that is obtained, in the light of actual conditions, reaction solution can be used for application of the present invention, and perhaps it can use after precipitation or fluid separation applications are operated purification again.
1-(4) organic silane compound [constituent of the low-index layer of film of the present invention (D)]:
From the viewpoint of scratch-resistant, preferably in the low-index layer of film of the present invention, include the hydrolysate and/or its part thing (solution of reacted constituent is called as " colloidal sol composition " sometimes hereinafter) of organic silane compound or this organic silane compound.
Such compound makes after coating as bonding agent, the material of foregoing hardenable compositions condensation in dry and heating steps formation sclerosis.In addition, under the situation that contains the polyfunctional acrylic ester polymkeric substance, formed bonding agent when shining with three-dimensional structure with radioactive ray.
The compound that above-mentioned organic silane compound is preferably represented by following formula [A].
Formula [A]
(R
10)
m-Si(X)
4-m
In the formula in front [A], R
10Expression that replace or unsubstituted alkyl or replacement or unsubstituted aryl.The example of alkyl comprises methyl, ethyl, propyl group, isopropyl, hexyl, decyl and cetyl.This alkyl preferably has 1-30 carbon atom, more preferably 1-16 carbon atom, and preferred especially 1-6 carbon atom.The example of aryl comprises phenyl and naphthyl.In these, phenyl is preferred.
X represents hydroxyl or hydrolyzable group.Hydrolyzable examples of groups comprises alkoxy (alkoxy that preferably has 1-5 carbon atom, for example methoxyl and ethoxy), halogen atom (for example, Cl, Br, and I), and R
2COO (R wherein
2Hydrogen atom or have the alkyl of 1-5 carbon atom preferably; And its example comprises CH
3COO and C
2H
5COO).In them, alkoxy is preferred; And methoxyl and ethoxy are particularly preferred.
M represents the integer of 1-3, preferred 1 or 2, and preferred especially 1.
When there being a plurality of R
10Or X the time, these a plurality of R
10Or X can be identical or different.
Be included in R
10In substituting group be not particularly limited; and its example comprises that halogen atom (for example; fluorine; chlorine; and bromine); hydroxyl; sulfydryl; carboxyl; epoxy radicals; alkyl (for example; methyl; ethyl; isopropyl; propyl group; and the tert-butyl group); and aryl (for example; phenyl and naphthyl); heteroaromatic group (for example; furyl; pyrazolyl; and pyridine radicals); alkoxy (for example; methoxyl; ethoxy; isopropoxy; with own oxygen base); and aryloxy group (for example thiophenyl); the alkyl sulfenyl (for example; methyl sulfenyl and ethyl sulfenyl); and artyl sulfo (for example; thiophenyl); thiazolinyl (for example; vinyl and 1-propenyl), acyloxy (for example, acetoxyl group; acryloxy; and methacryloxy); alkoxy carbonyl group (for example methoxycarbonyl group and carbethoxyl group); aryloxy carbonyl (for example carbobenzoxy), carbamyl (for example, carbamyl; N-methylamino formoxyl; N; the N-formyl-dimethylamino; with N-methyl-N-octyl group carbamyl), and acylamino-(acetylamino for example; benzamido; acrylamido; and methacrylamido).Such substituting group can further be replaced.
There are a plurality of R
10Situation under, preferably at least a in them is the alkyl that replaces or the aryl of replacement.
In the organic silane compound of being represented by the formula [A] of front, the substituent organic silane compound of being represented by following formula [B] of vinyl polymerizable that contains is preferred.
Formula [B]
In the formula in front [B], R
1Expression hydrogen atom, methyl, methoxyl, alkoxy carbonyl, cyano group, fluorine atom or chlorine atom.The example of alkoxy carbonyl comprises methoxycarbonyl and ethoxy carbonyl.Wherein, hydrogen atom, methyl, methoxyl, methoxycarbonyl, cyano group, fluorine atom and chlorine atom are preferred; Hydrogen atom, methyl, methoxycarbonyl, fluorine atom and chlorine atom are preferred; And hydrogen atom and methyl are particularly preferred.
Y represent singly-bound,
*-COO-
*,
*-CONH-
*, or
*-O-
*In them, singly-bound,
*-COO-
*, and
*-CONH-
*Be preferred; Singly-bound and
*-COO-
*Be more preferably; And
*-COO-
*Be particularly preferred.Here,
*The keyed jointing position of expression and=C (R1); And
*The keyed jointing position of expression and L.
L represents the divalence connection chain.Its concrete example comprises alkylidene replacement or unsubstituted, that replace or unsubstituted arlydene, wherein contain linking group (for example, ether, ester and acid amides) replacement or unsubstituted alkylidene, and the replacement or the unsubstituted arlydene that wherein contain linking group.In them, replace or unsubstituted alkylidene, replacement or unsubstituted arlydene and the alkylidene that contains linking group be preferred; And unsubstituted alkylidene, unsubstituted arlydene and contain ether or the alkylidene of ester linking group is preferred; And unsubstituted alkylidene is particularly preferred with the alkylidene that contains ether or ester linking group.Substituent example comprises halogen, hydroxyl, sulfydryl, carboxyl, epoxy radicals, alkyl and aryl.Such substituting group can further be replaced.
N represents 0 or 1 and preferred 0.
R
10With the R in the formula [A]
10Be synonym, and preferably that replace or unsubstituted alkyl or replacement or unsubstituted aryl, and be more preferably unsubstituted alkyl or unsubstituted aryl.
X in X and the formula [A] is a synonym.Wherein, halogen atom, hydroxyl and unsubstituted alkoxy are preferred; Chlorine atom, hydroxyl and the alkoxy with 1-6 carbon atom are preferred; Hydroxyl is more preferably with the alkoxy with 1-3 carbon atom; And methoxyl is particularly preferred.When having a plurality of X, these a plurality of X can be identical or different.
The compound of formula [A] or formula [B] can be to be used in combination with they two or more.Under the situation that compound uses together, preferred use together contain polymerizable groups for example vinyl polymerizable groups compound and do not contain the compound of polymerizable groups.To provide instantiation below, but should not be considered as the present invention is confined to this by the compound of formula [A] or formula [B] expression.
In these formulas, (M-1), (M-2), (M5) and (M-11) be particularly preferred.At compound is under the situation about using together, and for example, the compound that preferably contains vinyl polymerizable groups for example M-1 uses with compound that does not contain polymerizable groups such as M11.
Then, usually, the hydrolysate of aforementioned organic silane compound and/or its partial condensate are to produce by handle aforementioned organic silane compound in the presence of catalyzer.The example of this catalyzer comprises mineral acid example hydrochloric acid, sulfuric acid and nitric acid; Organic acid such as oxalic acid, acetate, formic acid, methane-sulforic acid and benzene methanesulfonic acid; Inorganic base is NaOH, potassium hydroxide and ammonia for example; Organic base is triethylamine and pyridine for example; Metal alkoxide is three different third oxygen aluminium and four fourth oxygen zirconiums for example; With contain the metal chelate compound of metal (for example, Zr, Ti and A1) as central metal.In the present invention, preferably use metal chelate compound or acid catalyst for example mineral acid and organic acid.Hydrochloric acid and sulfuric acid are preferably as mineral acid; And in water, have acid ionization constant (pKa value (under 25 ℃)) and be no more than 4.5 acid preferably as organic acid.Hydrochloric acid, sulfuric acid and in water acid ionization constant be no more than 3.0 organic acid and be more preferably; Hydrochloric acid, sulfuric acid and in water acid ionization constant to be no more than 2.5 organic acid be further preferred; And to be no more than 2.5 organic acid be particularly preferred to acid ionization constant in water.Particularly, methane-sulforic acid, oxalic acid, phthalandione and malonic acid are preferred, and its mesoxalic acid is particularly preferred.
As metal chelate compound, contain be selected from Zr, Ti and Al metal as central metal, wherein by formula R
3OH (R wherein
3Expression has the alkyl of 1-10 carbon atom) represent pure and mild by formula R
4COCH
2COR
5(R wherein
4Expression has the alkyl of 1-10 carbon atom; And R
5Expression has the alkyl of 1-10 carbon atom or has the alkoxy of 1-10 carbon atom) compound represented can be fit to use as the metal chelate compound of part and not have a specific restriction.Two or more metal chelate compounds can use together in this scope.Being used in metal chelate compound of the present invention is preferably selected from following group: by formula Zr (OR
3)
P1(R
4COCHOR
5)
P2, Ti (OR
3)
Q1(R
4COCHOR
5)
Q2And Al (OR
3)
R1(R
4COCHOR
5)
R2The compound of expression, and be used for quickening the condensation reaction of hydrolysate and/or its partial condensate of aforementioned organic silane compound.
In the aforementioned metal chelate compound, R
3And R
4It can be identical or different and alkyl that represent to have 1-10 carbon atom separately.The instantiation of this alkyl comprises ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl and phenyl.In addition, R
5Expression as hereinbefore the alkyl with 1-10 carbon atom or have the alkoxy of 1-10 carbon atom.The example of alkoxy comprises methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy.In addition, in the described in front metal chelate compound, p1, p2, q1, q2, r1 and r2 represent separately by satisfying relational expression: (p1+p2)=4, and (q1+q2)=4 with the integer of (r1+r2)=3 determining.
The instantiation of such metal chelate compound comprises for example three n-butoxy ethyl acetoacetic ester zirconiums of zirconium chelate compound, two (ethyl acetoacetic ester) zirconiums of two n-butoxies, n-butoxy three (ethyl acetoacetic ester) zirconium, four (n-pro-pyl acetoacetic ester) zirconium, four (acetyl group acetoacetic ester) zirconium and four (ethyl acetoacetic ester) zirconiums; The titanium chelate compound is diisopropoxy-two (ethyl acetoacetic ester) titanium, diisopropyl oxygen-two (acetoacetic ester) titanium and diisopropoxy-two (diacetone) titanium (titaniumdisopropoxy-bis (acetylcetone)) for example; With aluminium chelate compound for example two (ethyl acetoacetic ester) aluminium of diisopropoxy ethyl acetoacetic ester aluminium, diisopropoxy base acetoacetic ester aluminium, isopropoxy, isopropoxy two (diacetone acid esters) aluminium, three (ethyl acetoacetic ester) aluminium, three (diacetone acid esters) aluminium and single acetyl pyruvate-two (ethyl acetoacetic ester) aluminium.
In these metal chelate compounds, three n-butoxy ethyl acetoacetic ester zirconiums, two (diacetone acid esters) titaniums of diisopropoxy, diisopropoxy ethyl acetoacetic ester aluminium and three (ethyl acetoacetic ester) aluminium are preferred.Such metal chelate compound can use separately or use with their two or more potpourri.Also can use the partial hydrolysate of such metallo-chelate.
In addition, in the present invention, preferably beta-diketone compound and/or beta-diketonate compound are further joined in the aforesaid hardenable compositions.This will be further described below.
The compound that is used among the present invention is by formula R
4COCH
2COR
5The beta-diketone compound of expression and/or beta-diketonate compound and as the stability improver of employed hardenable compositions among the present invention.Here, R
4Expression has the alkyl of 1-10 carbon atom; And R
5Expression has the alkyl of 1-10 carbon atom or has the alkoxy of 1-10 carbon atom.That is to say, think in this compound and metallo-chelate metallic atom (for example, zirconium, titanium and/or aluminium compound) coordination the time, it shows the condensation reaction of having quickened hydrolysate and/or its partial condensate of organic silane compound by such metal chelate compound, thereby is used for improving the storage stability of formed composition.Constitute beta-diketone compound and/or beta-diketonate compound R
4And R
5With the R that constitutes the aforementioned metal chelate compound
4And R
5Identical.
The instantiation of this beta-diketone compound and/or beta-diketonate compound comprises diacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate n-propyl, isopropyl acetoacetate, the positive butyl ester of acetoacetate, the secondary butyl ester of acetoacetate, tert-butyl acetoacetate, 2,3-hexane-diketone, 2,4-heptane-diketone, 3,5-heptane-diketone, 2,4-octane-diketone, 2,4-nonane-diketone and uncle's methyl hexane-diketone.In these compounds, ethyl acetoacetate and diacetone are preferred; And diacetone is particularly preferred.Such beta-diketone compound and/or beta-diketonate compound can use separately or use with their two or more potpourri.In the present invention, beta-diketone compound and/or beta-diketonate compound preferably use with 2 moles of every mole metal chelates or amount more, more preferably 3-20 mole.When the amount of beta-diketone compound and/or beta-diketonate compound was less than 2 moles, the storage stability of formed composition may be damaged, thereby this is not preferred.
The blending amount of aforementioned organic silane compound or its hydrolysate and/or its partial condensate is preferably the 0.1-50 weight % of the whole solid of low-index layer, more preferably 0.5-30 weight %, and 1-20 weight % most preferably.
Though aforementioned organic silane compound can (for example directly join hardenable compositions, the coating solution that is used for antiglare layer or low-index layer), but preferred above-mentioned organic silane compound is by pretreated in the presence of catalyzer, with the hydrolysate for preparing aforementioned organic silane compound and/or its partial condensate, and above-mentioned hardenable compositions is by using formed reaction solution (sol solution) preparation.In the present invention, preferred at first preparation contains the hydrolysate of aforementioned organic silane compound and/or the composition of its partial condensate and metallo-chelate, to in said composition, add solution that beta-diketone compound and/or beta-diketonate compound form then and be included in and be used for Bewildering resistance layer or low-index layer at least in the coating solution of one deck, next be coated with.
Can be with (a) and (b) below or the silicon-containing compound of describing (c) further join in the component (D).
(a) alkoxyl silicone
Alkoxyl silicone is by R
mSi (OR ')
nThe compound of expression, wherein R and R ' represent to have the alkyl of 1-10 carbon atom separately, and m and n represent to satisfy relational expression separately: integer (m+n)=4.The example of alkoxyl silicone comprises tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan, four n-butoxy silane, four n-butoxy silane, four sec-butoxy silane, four tert-butoxy silane, 4 penta Ethoxysilanes, 4 penta isopropoxy silane, 4 penta positive propoxy silane, 4 penta n-butoxy silane, 4 penta sec-butoxy silane, 4 penta tert-butoxy silane, methyltrimethoxy silane, methyl triethoxysilane, methyl tripropoxy silane, methyl three butoxy silanes, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethylethoxysilane, the dimethyl methyl TMOS, the dimethyl propylene TMOS, the dimethyl butyrate TMOS, methyl dimethoxysilane, methyldiethoxysilane, with the hexyl trimethoxy silane.
(b) silane coupling agent
The example of silane coupling agent comprises γ-(2-amino-ethyl) TSL 8330, γ-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-An Jibingjisanyiyangjiguiwan, γ-methacryloxypropyl trimethoxy silane, N-β-(N-ethenylphenyl amino-ethyl)-gamma-amino propyl group methoxy silane hydrochloride, γ-glycyl oxygen base propyl trimethoxy silicane, amino silane, methyltrimethoxy silane, vinyltriacetoxy silane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-r-chloropropyl trimethoxyl silane, hexamethyldisilazane, vinyl three ('beta '-methoxy ethoxy) silane, octadecyl dimethyl [3-(trimethoxysilyl) propyl group] ammonium chloride, methyl trichlorosilane, and dimethyldichlorosilane.
(c) the ionising radiation silicon compound that can harden
Ionising radiation can harden the example of silicon compound comprise molecular weight be no more than 5,000 and contain a plurality of can by ionising radiation induce reaction and crosslinked group, as the polymerizable double bond group, organo-silicon compound.Reactive organo-silicon compound like this comprise end-vinyl official energy polysilane, two ends vinyl functional polysilane, an end-vinyl functional polysiloxane and two ends vinyl-functional polysiloxane; With react formed vinyl functional polysilane or vinyl functional polysiloxane by above-claimed cpd.
Other examples for compounds comprises (methyl) acryloyl-oxy base silane, for example 3-(methyl) acryloxy propyl trimethoxy silicane and 3-(methyl) acryloxy propyl group methyl dimethoxysilane.
The following reactive organo-silicon compound that are described among the JP-A-2003-39586 for example can use with the bonding agent of front.But these reactivity organo-silicon compound are to be that the amount of 10-100 weight % is used with the total amount based on ionising radiation hardening resin and reactive organo-silicon compound.Particularly, the ionising radiation of face before use can be hardened under the situation of organo-silicon compound (c), might form conductive layer by only using this compound as resinous principle.
1-(5) initiating agent
The various polymerizations that contain olefinic unsaturated group monomer can be in the presence of optical free radical initiating agent or thermal free radical initiator, by carrying out with ionization radiation or heating.
In the preparation of film of the present invention, light trigger and thermal initiator can use together.
＜light trigger 〉
The example of optical free radical polymerization initiator comprises acetophenone, diphenylhydroxyethanone, benzophenone, phosphine oxide, ketal, anthraquinone, thioxanthones, azo-compound, superoxide (for example, describe those), 2,3-dialkyl group dione compounds, disulfide, fluorine amines, fragrant sulfonium, lophine dipolymer, salt, borate, active ester, active halogen, inorganic complex and cumarin in IP-A-2001-139663.
The example of acetophenone comprises 2,2-dimethoxy-acetophenone, 2,2-diethoxy acetophenone, to dimethyl acetophenone, 1-hydroxyl-3,5-dimethylphenyl ketone, 1-hydroxyl-dimethyl-p-isopropyl phenyl ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-4-methyl mercapto-2-morpholino propiophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butanone, 4-phenoxy group dichloroacetophenone and the 4-tert-butyl group-dichloroacetophenone.
The example of diphenylhydroxyethanone class comprises diphenylhydroxyethanone, diphenylhydroxyethanone methyl ether, diphenylhydroxyethanone ethylether, diphenylhydroxyethanone isopropyl ether, benzyl dimethyl ketal, diphenylhydroxyethanone benzene sulfonate, diphenylhydroxyethanone tosylate, diphenylhydroxyethanone methyl ether, diphenylhydroxyethanone ethylether, diphenylhydroxyethanone isopropyl ether.The example of benzophenone comprises benzophenone, dihydroxy benaophenonel, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 2,4-dichloro benzophenone, 4, the 4-dichloro benzophenone, right-chlorobenzophenone, 4,4 '-dimethylamino benzophenone (Michler ketone) and 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone.
Boratory example comprises and is described in Jap.P. No. 2764769, JP-A-2002-116539 and Kunz and Martin's, Red Tech ' 98, Proceeding, April, 19-22 page or leaf (1998), the organic boronic salt compound among the Chicago.For example, enumerated the compound that [0022] of foregoing JP-A-2002-116539-[0027] section is described here.In addition, the instantiation of other organoboron compound is included in organic boron transition metal coordination complexes of describing among JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-A7-306527 and the JP-A-7-292014.Their instantiation also comprises the ionic complex with dye of positive ion.
The example of phosphine oxide comprises 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide.
The example of active ester class comprises 1,2-octane diketone, 1-[4-(thiophenyl)-2-(O-benzoyl oxime)], sulphonic acid ester and ring-type active ester compound.
Particularly, the compound 1-21 that describes in the embodiment of JP-A-2000-80068 is particularly preferred.
The example of salt comprises aromatic series diazo salt, aromatic series salt compounded of iodine and aromatic series sulfonium salt.
As active halogenide, et al., BullChem.Soc.Japan have specifically been enumerated at Wakabayashi here, Vol.42,2924 (1969), US3,905,815, JP-A-5-27830 and M.P.Hutt, Journal of Heterocyclic Chemistry, Vol.1 (No.3), the compound described in 1970, and particularly have trihalomethyl substituting group De oxazole and s-triaizine compounds on it.More suitably, enumerated that at least one is single-, two-or the methyl group that replaces of three halogen be connected to s-pyrrolotriazine derivatives on the s-triazine ring.As concrete example, exist known s-triazine Huo oxadiazole compound to comprise 2-(p-methoxyphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-methoxyphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-styryl phenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(3-bromo-4-two (ethyl acetate) amino) phenyl)-4, two (the trichloromethyl)-s-triazines of 6-and 2-trihalomethyl-5-(p-methoxyphenyl)-1,3,4 ,-oxadiazoles.Particularly, be described in JP-A-58-15503 14-30 page or leaf and JP-A-55-77742, the compound of 6-10 page or leaf; Be described in JP-B-60-27673, the 287th page compound 1-8/ is described in the compound 1-17 of JP-A-60-239736 443-444 page or leaf, and US4, the compound 1-19 in 701,399.
The example of inorganic complex comprises two (η
5-2,4-cyclopentadiene-1-yl)-two (2,6-two fluoro-3-(1H-pyrroles-1-yl) phenyl) titanium.
The example of cumarin comprises 3-ketone group cumarin.
Such initiating agent can use or mix use separately.
By Technical Information Institute Co., the Saishin UV KokaGijutsu (Latest UV Curing Technologies) that Ltd publishes the 159th (1991) and publish by SogoGijutsu Center, Kiyoshi Kato, 65-148 page or leaf (1998) has described a lot of examples and these examples are suitable for the present invention for Shigaisen Koka Shisutemu (Ultraviolet Ray Curing Systems).
For the optical free radical polymerization initiator that can buy on the market, enumerated Co. by NipponKayaku, the KAYACURE series that Ltd produces (for example, DETX-S, BP-100, BDMK, CTX, BMS, 2-FAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, and MCA), the IRGACURE series of being produced by Ciba Speciality Chemicals (for example, 651,184,500,819,907,369,1173,1870,2959,4265, with 4263), the ESACURE series of being produced by Sartmer Company Inc. (for example, KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, and TZT), and their combination as preferred examples.
With respect to 100 weight portion polyfunctional monomers, Photoepolymerizationinitiater initiater preferably uses with the amount of 0.1-15 weight portion, and preferred scope is the 1-10 weight portion.Particularly, by Photoepolymerizationinitiater initiater being attached in the low-index layer of the present invention, having improved the cohesive at the crosslinked and interface of low-index layer self, thereby can improve scratch-resistant with the 0.1-5 weight portion.
＜photosensitizer 〉
Except Photoepolymerizationinitiater initiater, can use photosensitizer.The instantiation of photosensitizer comprises n-butylamine, triethylamine, tri-n-butyl phosphine, Michler ketone and thioxanthones.
In addition, can in conjunction with and use at least a assistant for example diazo-compounds, thiourea compound and sulfhydryl compound.
For the photosensitizer that can buy on the market, enumerated Nippon KayakuCo. here, the KAYACURE series (for example, DMBI and EPA) that Ltd produces.
＜thermal initiator 〉
The example of operable thermal initiator comprises organic or inorganic peroxide, and organic azo or diazo-compounds.
Particularly, the example of organic peroxide comprises benzoyl peroxide, halobenzene formyl superoxide, lauroyl peroxide, acetyl pexoxide, dibutyl superoxide, cumene hydroperoxide and butyl hydroperoxides; The example of inorganic peroxide comprises hydrogen peroxide, ammonium persulfate and potassium persulfate; The example of azo-compound comprises 2,2 '-azo two (isobutyronotrile), 2,2 '-azo two (propionitrile) and 1,1 '-azo two (cyclohexane nitrile); And the example of diazo-compounds comprises diazo aminobenzene and p-nitrophenyl diazotising thing (p-nitrobenzenediazonium).
1-(6) cross-linking compounds [constituent of low-index layer of the present invention (B)]
[rigidizer]
In the present invention, preferred low-index layer be by use contain the hydroxyl fluoropolymer and can be with the compound (rigidizer) of hydroxyl reaction in the fluoropolymer hardenable compositions, be but that so-called hardenable resin composition forms.This rigidizer preferably contains two or more, and more preferably four or more a plurality of can with the position of hydroxyl reaction.
The structure of rigidizer is not concrete limit if its contain above-mentioned quantity can with the functional group of hydroxyl reaction.Its example comprise the partial condensate of polyisocyanates, isocyanate compound or polymkeric substance, with the addition product of polyvalent alcohol, low molecular weight polyester film etc., by the block reagent poly-polyisocyanate compound of block of the isocyanate groups of phenol, amino plastics and polyprotonic acid or its acid anhydrides block for example.
Wherein, in the present invention, the viewpoint that the stability when storing from making is compatible with activity of cross-linking reaction and from the viewpoint of formed film strength can cause that under acid condition the amino plastics with the cross-linking reaction of hydroxy-containing compounds is preferred.Amino plastics be have can with the amino of hydroxyl reaction in the fluoropolymer, that is, hydroxy alkyl amino or alkoxyalkyl amino perhaps are adjacent on the nitrogen-atoms and the compound of the carbon atom that alkoxy replaces.Its concrete example comprises compound based on melamine, based on the compound of urea with based on the compound of benzoguanamine.
The compound of aforementioned melamine is usually the known compound that nitrogen-atoms is attached to the triazine ring skeleton that has, and its instantiation comprises melamine, alkylation melamine, methylol melamine and oxyalkylated methylmelamine.Wherein, considering storage stability, is preferred with methylolation melamine, oxyalkylated methylmelamine and its derivant that formaldehyde reaction obtains by making melamine under alkali condition; And oxyalkylated methylmelamine and its derivant are particularly preferred.In addition, for methylolation melamine and oxyalkylated methylmelamine, have no particular limits, and for example can use by at Plastic Material Course[8]: the various resins of the method acquisition of describing among the Ureamelamine Resins (publishing) by Nikkan Kogyo Shimbun Ltd..
In addition, as aforementioned urea compound, except urea, as the poly-methylolated urea of its derivant and oxyalkylated methyl urea with have glycol urea groups skeleton or 2-imidazolidinone skeleton also is preferred as the compound of ring-type urea structure.For the amino-compound derivant of foregoing urea for example, can also use the various kinds of resin of describing in the aforementioned Urea melamine Resins document etc.
In the present invention, as the compound that is suitable as crosslinking chemical, consider and the compatibility of fluorinated copolymer that melamine compound or glycol ureas based compound are particularly preferred.Wherein, preferably this crosslinking chemical is to contain nitrogen-atoms and contain the compound of two or more and carbon atoms that alkoxy replace adjacent with nitrogen-atoms at its molecule.Particularly preferred examples for compounds comprises compound with structure of being represented by following H-1 or H-2 and its partial condensate.In following formula, the R representative has the alkyl or the hydroxyl of 1-6 carbon atom.
Based on 100 weight portion multipolymers, the amount that adds amino plastics in fluoropolymer is the 1-50 weight portion, preferred 3-40 weight portion, and more preferably 5-30 weight portion.When the addition of amino plastics is 1 weight portion or marquis when more, may fully show as film persistence, this is a performance characteristic of the present invention.When being no more than 50 weight portions, be used for optical application, might keep low-refraction, this is the performance characteristic of low-index layer of the present invention, therefore, this is preferred.Even from keep the viewpoint of low-refraction by the adding rigidizer, even preferred rigidizer is added into, its amount also is very little with respect to increase of refractive index.According to this viewpoint, in above-claimed cpd, those with skeleton of being represented by H-2 are more preferably.
1-(7) hardening catalyst
In film of the present invention, this film is hardened by the hydroxyl of fluoropolymer and the cross-linking reaction of aforementioned rigidizer in heating.In this system,, be desirable but therefore in this hardenable resin composition, add acidic materials because sclerosis is quickened by acid.Yet, when adding common acid, in coating solution, also carried out cross-linking reaction, caused the generation of defective (for example, out-of-flatness and contraction).Correspondingly, active compatible mutually in the thermmohardening system in order to make storage stability and sclerosis, more preferably adding can be by the acidic compound of heating as hardening catalyst.
Preferred this hardening catalyst is the salt that is made by acid and organic base.The example of acid comprises organic acid for example sulfonic acid, phosphonic acids and carboxylic acid; And mineral acid for example sulfuric acid and phosphoric acid.From with the compatibility viewpoint of polymkeric substance, organic acid is preferred; Sulfonic acid and phosphonic acids are further preferred; And sulfonic acid is most preferred.The preferred embodiment of sulfonic acid comprises p-toluenesulfonic acid (PTS), benzene sulfonic acid (BS), to dodecylbenzene sulfonic acid (DBS), p-chlorobenzenesulfonic acid (CBS), 1,4-naphthalenedisulfonic acid (NDS), methane-sulforic acid (MsOH) and nine fluorine butane-1-sulfonic acid (NFBS).These all compounds can preferably use.(each statement in bracket all is abbreviation.)
Hardening catalyst is according to changing a lot with the alkalescence and the boiling point of the sour organic base that combines.To the preferred in the present invention hardening catalyst that uses be described from each viewpoint below.
Alkalescence about organic base is explained as follows.Organic base acidic effect when heating with low alkalinity is very high, and active viewpoint is preferred from hardening.Yet, marquis when alkalescence is too low, it is not enough that bin stability becomes.Correspondingly, the preferred organic base that uses with suitable alkalescence.When with alkalescence with the pKa of conjugate acid time marquis as exponential representation, the pKa of the organic base that uses in the present invention need be 5.0-10.5, more preferably 6.0-10.0, and further preferred 6.5-10.0.PKa for this organic base, because the value in aqueous solution is described in TheChemical Handbook Basic Edition (revised edition, the 5th edition, edit and by Maruzen Co., Ltd. by The ChemicalSociety of Japan, publish), Vol.2, II, 334-340 page or leaf, therefore, might in them, select to have the organic base of suitable pKa.In addition, might preferably use even without be described in above-mentioned list of references but consider that structure has the compound of suitable pKa.To provide the compound of describing in the above referred-to references in the table 6 below, but should not be considered as the present invention is limited to this with suitable pKa.
Table 5
pKa
| b-1 | N, accelerine | 5.1 |
| b-2 | Benzimidazole | 5.5 |
| b-3 | Pyridine | 5.7 |
| b-4 | The 3-picoline | 5.8 |
| b-5 | 2,9-dimethyl-1, the 10-phenanthroline, | 5.9 |
| b-6 | 4,7-dimethyl-1, the 10-phenanthroline, | 5.9 |
| b-7 | The 2-picoline | 6.1 |
| b-8 | The 4-picoline | 6.1 |
| b-9 | 3-(N, N-dimethylamino) pyridine | 6.5 |
| b-10 | 2, the 6-lutidines | 7.0 |
| b-11 | Imidazoles | 7.0 |
| b-12 | Glyoxal ethyline | 7.6 |
| b-13 | N-ethylmorpholine | 7.7 |
| b-14 | N-methylmorpholine | 7.8 |
| b-15 | Two (2-methoxy ethyl) amine | 8.9 |
| b-16 | 2,2 '-imido grpup diethanol | 9.1 |
| b-17 | N, N-dimethyl-ethylaminoethanol | 9.5 |
| b-18 | Trimethylamine | 9.9 |
| b-19 | Triethylamine | 10.7 |
Boiling point about organic base is explained as follows.It is very high and be preferred from the active viewpoint of hardening to have lower boiling organic base acidic efficient in heating.Correspondingly, the preferred organic base that uses with suitable boiling point.The boiling point of this alkali preferably is not higher than 120 ℃.
To provide the examples for compounds that can be preferably used as organic base of the present invention below, but should not be considered as the restriction that the present invention is subjected to these examples.Each statement in the bracket has all shown boiling point.
B-3: pyridine (115 ℃), b-14:4-methyl morpholine (115 ℃), b-20: diallyl methylamine (111 ℃), b-19: triethylamine (88.8 ℃), b-21: tert-butyl group methylamine (67-69 ℃), b-22: dimethyl isopropylamine (66 ℃), b-23: diethylmethyl amine (63-65 ℃), b-24: dimethylethyl amine (36-38 ℃), b-18: trimethylamine (3-5 ℃).
The boiling point that is used in organic base of the present invention is preferably 35 ℃ or higher and be not higher than 85 ℃ especially.Use has the organic base of particular range boiling point, can obtain the stability of good hardening capacity, scratch-resistant and coating solution.More preferably 45 ℃ or higher and be not higher than 80 ℃ of this boiling points, and most preferably 55 ℃ or higher and be not higher than 75 ℃.
When being used as acid catalyst of the present invention, aforementioned salt that is made by acid and organic salt can be separated and in use.Perhaps, can use by acid mixture and organic salt with form in solution that salt obtains solution.In addition, a kind of in acid and the organic base can be used, and multiple acid and multiple organic base can be mixed and use.When acid with organic base mixes and when using, preferred acid mixture and organic base be so that equivalent proportion is preferably 1/0.9-1/1.5, more preferably 1/0.95-1/1.3, and further preferred 1/1.0-1/1.1.
Based on 100 weight portion fluoropolymers in the aforementioned hardenable resin composition, the ratio of the acid catalyst that use is preferably the 0.01-10 weight portion, more preferably 0.1-5 weight portion, and further preferred 0.2-3 weight portion.
＜photosensitive acid forming agent and optical acid generating agent 〉
In the present invention, except above-mentioned hot acid generates agent, can further add the compound that can light-struck the time, generate acid, promptly photosensitive acid forming agent.Will be described in detail below and to be used in optical acid generating agent of the present invention.
The example of acid forming agent comprises for example light trigger of light cationic polymerization of compound known, the light decolorant of dyestuff, light decolorant and known acid forming agent that is used for microetch etc., and their potpourri.But photosensitive acid generate body be give film that above-mentioned hardenable resin composition constitutes with photosensitivity and can make above-mentioned film with radiation for example the time marquis of optical radiation the material of photo-hardening takes place.Generate body as this photosensitive acid, can enumerate and suitably use (1) various salt, for example salt compounded of iodine, sulfonium salt, phosphonium salt, diazo salt, ammonium salt, imonium salt, arsenic salt, selenium salt and pyridiniujm; (2) sulphones, for example 'beta '-ketoester, β-sulphonyl sulfone and its α-diazo-compounds; (3) sulphonic acid ester, for example alkyl sulfonic ester, alkylhalide group sulphonic acid ester, aromatic yl sulphonate and imido grpup sulphonic acid ester; (4) sulfimine compound; (5) diazomethane compound; With other compound.Wherein, consider the photosensitivity that photopolymerization is caused, the stability of material of compound etc., preferred diazo salt, salt compounded of iodine, sulfonate and imonium salt.For example, enumerated the compound of describing in the section of [0058] of JP-A-2002-29162-[0059].
Photosensitive acid generates that body can use separately or uses with two or more potpourri.This photosensitive acid generation body can also use with the hot acid generation body of front in addition.Based on 100 weight portion fluoropolymers in the hardenable resin composition, the ratio that the photosensitive acid that use generates body is preferably the 0-20 weight portion, more preferably the 0.1-10 weight portion.The ratio that generates body when photosensitive acid is not higher than the time marquis of aforementioned higher limit, and formed cured film has the good intensity and the satisfied transparency, thereby is preferred like this.
Photosensitive acid generates body and also can be used in aforementioned low-index layer other layer in addition, for example, and in the hard conating.But used ratio is based on 100 weight portion hardenable resin composition, is preferably the 0.01-10 weight portion, and more preferably 0.1-5 weight portion.
In addition, the content of for example describing in JP-A-2005-43876 can be used as concrete compound and uses its method to use.
1-(8) translucent particle:
In order to give film of the present invention, particularly antiglare layer or hard conating, can use various translucent particle with anti-dazzle performance (surface scattering performance) or scattering-in performance.
This translucent particle can be organic granular or inorganic particle.Marquis when not having scattering in grain size designs turbidity value easily to such an extent as to the scattering in the scattering property diminishes.The plastics pearl is suitable as this translucent particle.Particularly, the particle that has high transparent and have the numerical value of the aforementioned refractive index that is different from bonding agent is preferred.
1.49), crosslinked poly-(propylene-styrene) copolymer pellet (refractive index: 1.54), melamine resin particle (refractive index: 1.57), polycarbonate pellets (refractive index: 1.57), granules of polystyrene (refractive index: 1.60), crosslinked polystyrene particle (refractive index: 1.61), polyvinyl chloride particles (refractive index: 1.60) and benzoguanamine-melamine formaldehyde (MF) particle (refractive index: 1.68) example of organic granular comprises poly methyl methacrylate particle (refractive index:.
1.44), alumina particle (refractive index: 1.63), zirconia particles, titanium dioxide granule and hollow or porous inorganic particulate the example of inorganic particle comprises silica dioxide granule (refractive index:.
Wherein, preferably use crosslinked granules of polystyrene, crosslinked poly-((methyl) acrylate) particle and crosslinked poly-(propylene-styrene) particle.Make its refractive index that is applicable to each translucent particle of from these particles, selecting by the refractive index of adjusting bonding agent, might obtain interior turbidity of the present invention, surface haze and center line average roughness.
In addition, preferably uses by as the trifunctional of principal ingredient or multifunctional (methyl) acrylate monomer (refractive index after the sclerosis: the bonding agent of 1.50-1.53) forming and gather the bond of the translucent particle that (methyl) acrylate polymer makes by acryloyl group content as 50-100 weight % crosslinked.Bonding agent is with (refractive index: combining of the translucent particle that 1.48-1.54) makes is particularly preferred by crosslinked (styrene-propene acyl) multipolymer.
In the present invention, the refractive index of the bond of bonding agent (semi-transparent resin) and translucent particle is preferably 1.45-1.70, and 1.48-1.65 more preferably.For refractive index is fallen in the top scope, can suitably select the kind and the quantity of bonding agent and translucent particle.How selecting kind and quantity easily to test in advance obtains.
In addition, in the present invention, poor [(refractive index of translucent particle)-(refractive index of bonding agent)] of the refractive index of bonding agent and translucent particle is preferably 0.001-0.030 in its absolute value, more preferably 0.001-0.020, and further preferred 0.001-0.015.When this difference surpasses 0.030 marquis, for example the literal on the film is fuzzy its caused problem to have occurred, has reduced darkroom contrast and surface cloudiness.
Here, the refractive index of bonding agent can quantitatively be determined, and can for example directly measure or compose reflectance spectrum by Abbe refractometer or compose oval photometric measurement and calculate.The refractive index of aforementioned translucent particle is to have in the solvent of different refractivity by the equivalent translucent particle being distributed to by changing two kinds of mixing ratios with solvent of different refractivity, with the refractive index of measuring turbidity and the marquis measures solvent by Abbe refractometer when turbidity becomes minimum.
Under the situation of aforementioned translucent particle, though since translucent particle in bonding agent, also be tending towards the precipitation, can add inorganic filler for example silicon dioxide prevent the precipitation.Carrying one in passing, is that effectively it has influenced the transparency of film unfriendly though increase the amount of inorganic filler for the precipitation that prevents translucent particle.Correspondingly, the inorganic filler that preferable particle size is no more than 0.5 μ m is included in the bonding agent with the amount that is less than 0.1 weight %, so that the transparency of film is not hindered.
This translucent particle preferably has 0.5-10 μ m, and the mean grain size of preferred 2.0-6.0 μ m.When the mean grain size of this translucent particle is less than the time marquis of 0.5 μ m, because distributing, the scattering of light angle is diffused into very wide angle, caused the fuzzy of the literal on the display, thereby this not preferred.On the other hand, marquis when it surpasses 10 μ m is to such an extent as to added the problem that thickness must have been occurred curling by being thickened and cost increases of the layer of translucent particle.
In addition, two or more translucent particle with different-grain diameter can be used together.Might give anti-dazzle performance by translucent particle, and the translucent particle of small particle diameter might reduce the harsh feeling on surface by having more with bigger particle diameter.
The aforementioned translucent particle of blending makes that preferably with the amount of 3-30 weight %, more preferably the amount of 5-20 weight % is involved for it based on the total solid of the layer that translucent particle joined.When the blending amount of translucent particle is less than the time marquis of 3 weight %, additive effect is insufficient, yet marquis when it surpasses 30 weight % has caused for example image blurring, external haze and dizzy problem.
In addition, this translucent particle preferably has 10-1,000mg/m
2, more preferably 100-700mg/m
2Density.
The preparation of＜translucent particle and stage division 〉
The example that is used for the method for production translucent particle of the present invention comprises suspension polymerization, emulsion polymerisation process, emulsifier-free emulsion polymerization method, dispersion polymer process and seeding polymerization method.Translucent particle can be by any production the in these methods.Such production method can be by with reference to (being write and by Kagaku-dojin Publishing Company by Takayuki Otsu and Masayoshi Kinoshita at for example Kobunshi Gosei no Jikkenho (polymkeric substance synthetic test method), Inc. publish), the 130th and the 146-147 page or leaf, Gosei Kobunshi (synthetic polymer), Vol.1, the 146-290 page or leaf, ibid., Vol.3, the 1-108 page or leaf, Jap.P. the 2543503rd, 3508304,2746275,3521560 and No. 3580320, JP-A-10-1561, JP-A-7-2908, the method for describing among JP-A-5-297506 and the JP-A-2002-145919 is carried out.
For the size distribution of translucent particle, consider the control of the uniformity coefficient of turbidity value and diffusivity and coating surface performance, monodispersed particle is preferred.For example, when grain size is defined as marquis when coarse grained greater than 20% or more particles of mean grain size, this coarse grained ratio preferably is no more than 1%, more preferably no more than 0.1%, and further preferably is no more than 0.01%.In order to obtain to have the particle of such size distribution, effective and efficient manner is to carry out classification after preparation or synthetic reaction.Quantity by increasing classification or strengthen its grade might obtain to have the particle of the size distribution of hope.
For classification, the preferred method of using such as air classification method, centrifugal classification method, precipitation fractionation method, filtration stage division and static stage division.
1-(9) inorganic particle
In the present invention, in order to improve for example for example reflectivity and scattering property of hardness and optical property of physical property, can use multiple inorganic particle.
The example of inorganic particle comprises at least a metal oxide that is selected from silicon, zirconium, titanium, aluminium, indium, zinc, tin and antimony.Also comprise the inorganic particle shown in the composition (E).Their instantiation comprises ZrO
2, TiO
2, Al
2O
3, In
2O
3, ZnO, SnO
2, Sb
2O
3, and ITO.In addition, also comprise BaSO
4, CaCO
3, talcum and porcelain earth.
About the particle diameter of inorganic particle used in the present invention, preferred inorganic particle is scattered in the dispersion medium as far as possible carefully.With regard to weight-average molecular weight, the particle diameter of inorganic particle is 1-200nm, preferred 5-150nm, more preferably 10-100nm, and preferred especially 10-80nm.Be no more than 100nm by inorganic particle is subdivided into, might form the film that whole transparency is not all hindered.The particle diameter of inorganic particle can be measured by light scattering method or according to electron micrograph.
Inorganic particle preferably has 10-400m
2/ g, more preferably 20-200m
2/ g, and 30-150m most preferably
2The specific surface area of/g.
Preferably being used in inorganic particle of the present invention is to add with the coating solution that is used to form layer, and it is used as the dispersion in the dispersion medium.
The preferred boiling point that uses is 60-170 ℃ the liquid dispersion medium as inorganic particle.The example of dispersion medium comprises water, alcohol (for example, methyl alcohol, ethanol, isopropyl alcohol, butanols, and benzylalcohol), ketone (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone), the ester class (for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, and butyl formate), aliphatic hydrocrbon (for example, hexane and cyclohexane), halogenated hydrocarbons (for example, methylene chloride, chloroform, and phenixin), aromatic hydrocarbon (for example, benzene, toluene, and dimethylbenzene), acid amides (for example, dimethyl formamide, dimethyl acetamide, with positive methyl pyrrolidone), ethers (for example, Anaesthetie Ether diox, and tetrahydrofuran), with the ether alcohol class (for example, 1-methoxyl-2-propyl alcohol).In these, toluene, dimethylbenzene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanols are particularly preferred.
Most preferred dispersion medium is methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone.
Inorganic particle disperses by using dispersion machine.The example of dispersion machine comprises sand attrition mill (for example, band pin particle grinding machine), high speed rotor grinding machine, bowl mill, roller mill, masher and colloid mill.In these machines, sand attrition mill and high speed rotor grinding machine are particularly preferred.In addition, can carry out preliminary dispersion treatment.The example that is used for the dispersion machine of preliminary dispersion treatment comprises bowl mill, three-high mill, kneader and extruder.
＜high refractive index particle 〉
In order to realize constituting the high index of refraction of layer of the present invention, used the inorganic particle that will have high index of refraction to be dispersed in the hardened material that the composition in the silicon compound of monomer, initiating agent and organic replacement constitutes.
In this case, from the viewpoint of refractive index, ZrO
2And TiO
2Be preferably used as this inorganic particle especially.In order to realize the high index of refraction of hard conating, ZrO
2Be most preferred; And TiO
2Fine grained most preferably is used as the particle of high refractive index layer or middle index layer.
Contain TiO
2As principal ingredient and contain at least a inorganic particle that is selected from the element of cobalt, aluminium and zirconium and be especially suitable for use as aforesaid TiO
2Particle.Alleged here " principal ingredient " means in the composition that constitutes particle to have the highest content (weight %).
In the present invention, by TiO as principal ingredient
2The particle that constitutes preferably has 1.90-2.80, more preferably 2.10-2.80, and the refractive index of 2.20-2.80 most preferably.
By TiO
2The preferred weight-average molecular weight of primary particle of this particle that constitutes as principal ingredient is 1-200nm, more preferably 1-150nm, further preferred 1-100nm, and preferred especially 1-80nm.
About by TiO
2The crystal structure of the particle that constitutes as principal ingredient, preferably this principal ingredient is rutile structure, rutile/anatase mixed-crystal structure, anatase structured or impalpable structure.Wherein, preferred especially this principal ingredient has rutile structure.Alleged here " principal ingredient " means in the composition that constitutes particle to have the highest content (weight %).
Be included in by TiO by element at least a Co of being selected from (cobalt), Al (aluminium) and Zr (zirconium)
2In the particle as the principal ingredient formation, might suppress TiO
2The weatherability of photocatalytic activity that has and raising film of the present invention.
Co (cobalt) is particularly preferred element.In addition, also preferred two or more elements that use.
In the present invention, by TiO
2The particle that constitutes as principal ingredient can have core/shell structure by the surface treatment of describing in JP-A-2001-166104.
The amount that joins the monomer of this layer or inorganic particle is preferably the 10-90 weight % of bonding agent general assembly (TW), and more preferably 20-80 weight %.In this layer, can use two or more inorganic particles.
＜low-refraction particle〉[constituent of low-index layer of the present invention (E)]
Wish that the inorganic particle that is included in low-index layer has low-refraction.Its example comprises the fine grained of magnesium fluoride and silicon dioxide.Consider refractive index, dispersion stabilization and cost, the silicon dioxide fine grained is particularly preferred.
The fine grain mean grain size of silicon dioxide be preferably low-index layer thickness 30% or more and be no more than 150%, more preferably 35% or more and be no more than 80%, and further preferred 40% or more and be no more than 60%.That is to say, when the thickness of low-index layer is 100nm, the fine grain particle diameter of silicon dioxide is preferably 30nm or bigger and be no more than 150nm, more preferably 35nm or bigger and be no more than 80nm, and further preferred 40nm or bigger and be no more than 60nm.
When the fine grain particle diameter of silicon dioxide is too little, improves the effect step-down of mar-proof performance, yet when it is too big, on the surface of low-index layer, has formed for example pitch black and overall reflectivity of thin irregularity thing and outward appearance and be damaged.This silicon dioxide fine grained can be a crystal or unbodied; It can be monodispersed particle; And as long as satisfy the particle diameter of regulation, it can be a flocculated particle.Though it is the fine grain shape of silicon dioxide most preferably is spherical,, also no problem even it is unbodied.
In addition, at least a mean grain size is used with the silicon dioxide fine grained with above-mentioned particle diameter (being called as " big particle diameter silicon dioxide fine grained ") less than the silicon dioxide fine grained (being called " small particle diameter silicon dioxide fine grained ") of low-refraction layer thickness 25%.
Because small particle diameter silicon dioxide fine grained may reside in the gap between the big particle diameter silicon dioxide fine grained, so it can be as the fine grain retention agent of big particle diameter silicon dioxide.
When the thickness of low-index layer is 100nm, the fine grain mean grain size of small particle diameter silicon dioxide is preferably 1nm or bigger and be no more than 20nm, more preferably 5nm or bigger and be no more than 15nm, and preferred especially 10hm or bigger and be no more than 15nm.From the viewpoint of the effect of raw materials cost and retention agent, it is preferred using such silicon dioxide fine grained.
The coating weight of low-refraction particle is preferably 1mg/m
2-100mg/m
2, more preferably 5mg/m
2-80mg/m
2, and further preferred 10mg/m
2-60mg/m
2When the coating weight of low-refraction particle is too low, improves the effect step-down of mar-proof performance, yet when it is too high, on the surface of low-index layer, has formed for example pitch black and overall reflectivity of thin irregularity thing and outward appearance and be damaged.
＜hollow silica particle 〉
In order to reduce refractive index more, preferably use the hollow silica fine grained.
The hollow silica fine grained preferably has 1.15-1.40, more preferably 1.17-1.35, and the refractive index of 1.17-1.30 most preferably.The refractive index of indication is expressed as the refractive index of whole particle in this article, rather than is expressed as just the refractive index of the silicon dioxide that forms the fine grain shell of hollow silica.At this moment, when intragranular radius being defined as " a " and the radius of particle shell is defined as " b ", by the porosity x of following numerical expression (VIII) expression:
Expression formula (VIII)
x＝(4πa3/3)/(4πb3/3)×100
Be preferably 10-60%, more preferably 20-60%, and 30-60% most preferably.When planning to make this hollow silica fine grained have than low-refraction and having than macroporosity, the only thickness attenuation of shell makes the intensity of particle be lowered.Correspondingly, from the viewpoint of scratch-resistant, it is not preferred having the particle that is lower than 1.15 low-refraction.
The method that is used for the production hollow silica is described in for example JP-A-2001-233611 and JP-A-2002-79616.Having the blocked particle of pore on the shell of hole in shell, is particularly preferred.Carry one in passing, the refractive index of such hollow silica particle can be calculated by the method for describing among the JP-A-2002-79616.
The coating weight of hollow silica particle is preferably 1mg/m
2-100mg/m
2, more preferably 5mg/m
2-80mg/m
2, and further preferred 10mg/m
2-60mg/m
2When the coating weight of hollow silicon dioxide is too low, be used to the effect step-down realizing the effect of low-refraction and be used to improve mar-proof performance, and when it is too high, on the surface of low-index layer, formed thin irregularity thing, and outward appearance is for example pitch black and overall reflectivity is damaged.
The mean grain size of hollow silica be preferably low-index layer thickness 30% or more and be no more than 150%, more preferably 35% or more and be no more than 80%, and further preferred 40% or more and be no more than 60%.That is to say, when the thickness of low-index layer is 100nm, the mean grain size of hollow silica is preferably 30nm or bigger and be no more than 150nm, more preferably 35nm or bigger and be no more than 80nm, and further preferred 40nm or bigger and be no more than 65nm.
When the fine grain particle diameter of silicon dioxide is too little, the ratio of hole is lowered, thereby expectability reduces refractive index, yet when it is too big when, has formed on the surface of low-index layer that thin irregularity thing and outward appearance are for example pitch black to be damaged with overall reflectivity.This silicon dioxide fine grained can be crystal or unbodied and its can be monodispersed particle.Though it is the fine grain shape of silicon dioxide most preferably is spherical,, also no problem even it is unbodied.
In addition, for hollow silica, can use two or more to have the hollow silica of different mean grain sizes together.Here, the mean grain size of hollow silica can be measured by electron micrograph.
In the present invention, hollow silica preferably has 20-300m
2/ g, more preferably 30-120m
2/ g, and 40-90m most preferably
2The specific surface area of/g.Surface area can use nitrogen, determines by the BET method.
In the present invention, might use with hollow silica and use the silica dioxide granule that does not have hole.There is not the silicon dioxide of hole preferably to have 30nm or bigger and be no more than 150nm, more preferably 35nm or bigger and be no more than 100nm, and 40nm or bigger and be no more than the particle diameter of 80nm most preferably.
1-(10) conductive particle:
In order to give film of the present invention, can use multiple conductive particle with electric conductivity.
Preferred this conductive particle is formed by metal oxide or nitride.The example of metal oxide or metal nitride comprises tin oxide, indium oxide, zinc paste and titanium nitride.In them, tin oxide and indium oxide are particularly preferred.The electric conductivity inorganic particle comprises such metal oxide or the nitride as principal ingredient, and can further contain other element.Alleged here " principal ingredient " means the composition that has high-load (weight %) in constituting the composition of particle.The example of other element comprises Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and halogen atom.In order to improve the electric conductivity of tin oxide and indium oxide, preferably use Sb, P, B, Nb, In, V or halogen atom.The indium oxide (ITO) that contains the tin oxide (ATO) of Sb and contain Sn is particularly preferred.Sb is preferably 3-20 weight % in the ratio of ATO; And the ratio of Sn in ITO is preferably 5-20 weight %.
The mean grain size of primary particle that is used for the electric conductivity inorganic particle of antistatic layer is preferably 1-150nm, more preferably 5-100nm, and 5-70nm most preferably.The mean grain size of the electric conductivity inorganic particle in the antistatic layer that will form is 1-200nm, preferred 5-150nm, more preferably 10-100nm, and 10-80nm most preferably.The mean grain size of electric conductivity inorganic particle is with the weight of the particle mean grain size as weight, and can measure by light scattering method or by electron micrograph.
The specific surface area of electric conductivity inorganic particle is preferably 10-400m
2/ g, more preferably 20-200m
2/ g, and 30-150m most preferably
2/ g.
This electric conductivity inorganic particle can pass through surface treatment.This surface treatment is undertaken by using mineral compound or organic compound.The example that is used for the surface-treated mineral compound comprises aluminium oxide and silicon dioxide.Silica-treated is particularly preferred.The example that is used for the surface-treated organic compound comprises polyvalent alcohol, alkanolamine, stearic acid, silane coupling agent and titanate coupling agent.In them, silane coupling agent is most preferred.Surface treatment can be by carrying out in conjunction with two or more surface treatments.
The shape of preferred electric conductivity inorganic particle is grain of rice shape, sphere, cube, spindle or amorphous.
In specific layer or film, two or more conductive particles can use together.
The ratio of electric conductivity inorganic particle in antistatic layer is preferably 20-90 weight %, more preferably 25-85 weight %, and further preferred 30-80 weight %.
The electric conductivity inorganic particle can make with the state of dispersion and be used for forming antistatic layer.
1-(11) surface conditioning agent
For design reach dispersion stabilization improve compatibility or with suspending liquid or coating solution in the adhesive property of bonding agent, being used in inorganic particle of the present invention can be through physical surface treatment for example plasma discharge treatment and Corona discharge Treatment, or the chemical treatment of carrying out with surfactant, coupling agent etc.
Surface treatment can be undertaken by using the surface conditioning agent that is made by mineral compound or organic compound.The example that is used for the surface-treated mineral compound comprises and contains cobalt mineral compound (for example, CoO
2, Co
2O
3, and Co
3O
4), contain aluminium mineral compound (for example, Al
2O
3, and Al (OH)
3), contain zirconium mineral compound (ZrO for example
2And Zr (OH)
4), silicon-containing inorganic compound (for example, SiO
2) and iron content mineral compound (for example, Fe
2O
3).
In these compounds, it is particularly preferred containing the cobalt mineral compound, containing the aluminium mineral compound and contain the zirconium mineral compound; And contain cobalt mineral compound, Al (OH)
3And Zr (OH)
4Be most preferred.
The example that is used for the surface-treated organic compound comprises polyvalent alcohol, alkanolamine, stearic acid, silane coupling agent and titanate coupling agent.In them, silane coupling agent is most preferred.It is by using at least a the carrying out in silane coupling agent (for example, organic silane compound) and its partial hydrolysate or the condensation product that special preferred surface is handled.
The example of titanate coupling agent comprises metal alkoxide for example tetramethoxy titanium, purity titanium tetraethoxide and tetraisopropoxy titanium; With PLENACT series (for example, KR-TTS, KR-46B, KR-55 and KR-41B, they all are by Ajinomoto Co., Ind. produces).
As being used for the surface-treated organic compound, polyvalent alcohol and alkanolamine and the organic compound that contains anionic group are preferred; And the organic compound that contains carboxyl, sulfonic group or phosphate is particularly preferred.Can preferably use stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid etc.
Be preferred for the surface-treated organic compound and further contain crosslinked or polymerizable functional group.Example crosslinked or polymerizable functional group comprise can carry out addition reaction or polyreaction by the free radical kind ethylenically unsaturated group (for example; (methyl) acryloyl group, allyl, stearyl and ethyleneoxy), cationic polymerization group (for example, epoxy radicals, oxatanyl base and ethyleneoxy), polycondensation reaction group (for example, hydrolyzable silicyl and N-methylol).In these groups, the group that contains ethylenically unsaturated group is preferred.
Can use two or more such surface treatments.Containing the aluminium mineral compound is particularly preferred with the bond that contains the zirconium mineral compound.
When inorganic particle is silicon dioxide, especially preferably use coupling agent.Preferred alkoxide compound (for example, titanium coupling agent and silane coupling agent) is as this coupling agent.Wherein, the silane coupling agent processing is effective especially.
Aforementioned coupling agent is used to carry out the surface conditioning agent of surface treatment as the inorganic filler in the low-index layer in advance before the preparation coating solution.Preferably when preparation is used for the coating solution of above-mentioned layer, adds to make in this layer and comprise coupling agent by being further used as adjuvant.
In order to reduce the surface-treated burden, preferably before surface treatment, silica dioxide granule is dispersed in the media in advance.
Can be preferred for the surface-treated surface conditioning agent among the present invention and the instantiation of catalyzer and comprise organic silane compound and the catalyzer that for example is described among the WO2004/017105.
1-(12) spreading agent
Multiple spreading agent can be used for disperseing to be used in the particle among the present invention.
Preferred this spreading agent further contains crosslinked or polymerisable functional group.Example crosslinked or polymerizable functional group comprise can carry out addition reaction or polyreaction by the free radical kind ethylenically unsaturated group (for example; (methyl) acryloyl group; allyl, stearyl, and ethyleneoxy); the cationic polymerization group (for example; epoxy radicals, oxatanyl base, and ethyleneoxy); and polycondensation reaction group (for example, hydrolyzable silicyl and N-methylol).In these groups, the group that contains ethylenically unsaturated group is preferred.
In order to disperse inorganic particle, particularly disperse by TiO
2As the inorganic particle that principal ingredient constitutes, the preferred spreading agent that contains anionic group that uses.More preferably this spreading agent contains anion base and crosslinked or polymerizable functional group.Preferred especially described crosslinked or polymerizable functional group is included on the side chain of this spreading agent.
As anionic group, for example carboxyl, sulfonic group (sulfo group), phosphate (phosphono), sulfoamido or their salt are effective to contain the acid proton group.Wherein, carboxyl, sulfonic group, phosphate and their salt are preferred; And carboxyl and phosphate are particularly preferred.About being included in the quantity of each intramolecular anionic group of spreading agent, can in a molecule, comprise a plurality of kinds.2 of the preferred average out to of the quantity of anionic group or more, more preferably 5 or more, and preferred especially 10 or more.In addition, the multiple anionic group that is contained in the spreading agent can be included in the molecule.
Contain in side chain in the spreading agent of anionic group, the composition that contains the negative ion repetitive is 10 of whole repetitives
-4-100 moles of %, preferred 1-50 mole %, and preferred especially 5-20 mole %.
Preferred this spreading agent further contains crosslinked or polymerisable functional group.Example crosslinked or polymerizable functional group comprises ethylenically unsaturated group ((for example, (methyl) acryloyl group, allyl, stearyl and ethyleneoxy), cationic polymerization group (for example, epoxy radicals, oxatanyl base and ethyleneoxy), the polycondensation reaction group (for example, hydrolyzable silicyl and N-methylol) that can carry out addition reaction or polyreaction by the free radical kind.In these groups, the group that comprises ethylenically unsaturated group is preferred.
Be included in the quantity of each intramolecular crosslinked or polymerizable functional group of spreading agent, 2 of preferred average out to or more, more preferably 5 or more, and preferred especially 10 or more.In addition, the multiple crosslinked or polymerizable functional group that will cover in the spreading agent can be included in the molecule.
In being used in crowd's of the present invention preferred dispersing agent, as the repetitive that contains ethylenically unsaturated group at side chain, can utilize connect specific free radical (-COOR or-R among the CONHR) poly--1,2-butadiene or poly--1, the repetitive of 2-isoprene structure or (methyl) acrylate or acid amides.The example of aforementioned specific residue (R yl) comprises-(CH
2)
n-CR
21=CR
22R
23,-(CH
2O)
n-CH
2CR
21=CR
22R
23,-(CH
2CH
2O)
n-CH
2CR
21=CR
22R
23,-(CH
2)
n-NH-CO-O-CH
2CR
21=CR
22R
23,-(CH
2)
n-O-CO-CR
21=CR
22R
23, and-(CH
2CH
2O)
2-X(R wherein
21-R
23Represent hydrogen atom, halogen atom separately, have alkyl, aryl, alkoxy or the aryloxy group of 1-20 carbon atom; R
21And R
22Or R
23Can gather and form ring together;
nThe integer of expression 1-10; And X represents dicyclopentadienyl).The instantiation of the R of ester residue comprises-CH
2CH=CH
2(polymkeric substance of (methyl) allyl acrylate that is equivalent to describe among the JP-A-64-17047) ,-CH
2CH
2O-CH
2CH=CH
2,-CH
2CH
2OCOCH=CH
2,-CH
2CH
2OCOC (CH
3)=CH
2,-CH
2C (CH
3)=CH
2,-CH
2CH=CH-C
6H
5,-CH
2CH
2OCOCH=CH-C
6H
5,-CH
2CH
2-NHCOO-CH
2CH=CH
2, and-CH
2CH
2O-X (wherein X represents the dicyclopentadienyl residue).The instantiation of the R of amide residues comprises-CH
2CH=CH
2,-CH
2CH
2-Y (wherein Y represents 1-cyclohexenyl group residue) ,-CH
2CH
2-OCO-CH=CH
2, and-CH
2CH
2-OCO-C (CH
3)=CH
2
In the aforementioned spreading agent that contains ethylenically unsaturated group, free radical (the polymerization initiating radical of polymerizable compound or the growth base in the polymerization process) is added on this unsaturated group, and between molecule directly or the polymeric chain by polymerizable compound caused addition polymerization, thereby therefore between molecule, formed the crosslinked sclerosis that caused.Alternatively, capture atom in the molecule (for example, being adjacent to the hydrogen atom on the carbon atom of unsaturated linking group) by free radical thus form polymer-matrix, these bases mutually combine then, thereby form the crosslinked sclerosis that caused between molecule.
Though the weight-average molecular weight (Mw) that comprises anionic group and crosslinked or polymerizable functional group and contain the spreading agent of above-mentioned crosslinked or polymerizable functional group on side chain does not have concrete restriction, preferred 1,000 or more.The weight-average molecular weight of this spreading agent (Mw) more preferably 2,000-1,000,000, further preferred 5,000-200,000, and preferred especially 10,000-100,000.
Can constitute all repetitives except that containing the anionic group repetitive though contain the unit of crosslinked or polymerizable functional group, preferred its accounts for the 5-50 mole % of whole crosslinked or repetitive, and preferred especially 5-30 mole %.
This spreading agent can be the multipolymer with proper monomer except the monomer that contains crosslinked or polymerizable functional group and anionic group.Though the copolymerization composition does not have specific restriction, its be from various viewpoints for example dispersion stabilization, select with the compatibility of other monomer component and formed film strength.Its preferred examples comprises (methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate and styrene.
Though the form of spreading agent does not have specific restriction, it is the form of segmented copolymer or random copolymers preferably.From synthetic easily viewpoint, it is random copolymers especially preferably.
The use amount that uses the spreading agent on the inorganic particle is preferably in the scope of 1-50 weight %, more preferably in the scope of 5-30 weight %, and most preferably in the scope of 5-20 weight %.In addition, two or more spreading agents can use together.
1-(13) anti fouling agent
In film of the present invention, particularly in the superiors of this film,, preferably suitably add known based on polysiloxane or based on the anti fouling agent of fluorine and antiseize paste etc. in order to give for example characteristic of antifouling property, water resistance, chemical-resistant and slickness.
When having added such adjuvant, the addition of adjuvant is preferably in the scope of the 0.01-20 of low-index layer solid amount weight %, more preferably in the scope of 0.05-10 weight %, and in the scope particularly preferably in 0.1-5 weight %.
[compound] [constituent of the low-index layer of film of the present invention (F)] with polysiloxane structure
Next, the compound that description is had polysiloxane structure.
In the present invention, for by giving slickness and giving antifouling property and improve scratch-resistant, used compound with polysiloxane structure.The structure of this compound is not specifically limited, and its example comprises that containing a plurality of dimethyl silane oxygen bases unit contains substituent structure as repetitive and on the end of its chemical chain and/or side chain.In addition, in the chemical chain that contains dimethyl silane oxygen base, can contain structural unit except dimethyl silane oxygen base as repetitive.
Be not specifically limited though have the molecular weight of the compound of polysiloxane structure, it preferably is no more than 100,000, especially preferably is no more than 50,000, and most preferably is 3,000-30,000.
From preventing the viewpoint of transfer, preferably comprise hydroxyl or can form the functional group that is connected with hydroxyl reaction.Preferably should formation connection be reflected at heating condition and/or in the presence of catalyzer, carry out fast.Substituent example like this comprises epoxy radicals and carboxyl.To provide the preferred examples of this compound below, but should not be considered as the present invention is confined to this.
(compound that contains hydroxyl)
X-22-160AS, KF-6001, KF-6002, KF-6003, X-22-170DX, X-22-176DX, X-22-176D and X-22-176F (all these is by Shin-EtsuChemical Co., and Ltd. produces); FM-4411, FM-4421, FM-4425, FM-0411, FM-0421, FM-0425, FM-DA 11, FM-DA21 and FM-DA25 (all these is produced by Chisso Corporation); With CMS-626 and CMS-222 (all these is by Gelest, and Inc. makes)
(contain can with the compound of the functional group of hydroxyl reaction)
X-22-162C and KF-105 (all these is by Shin-Etsu Chemical Co., and Ltd. produces); With FM-5511, FM-5521, FM-5525, FM-6611, FM-6621 and FM-6625 (these are all produced by Chisso Corporation)
Except above-mentioned compound, can use other compound together based on polysiloxane based on polysiloxane.Its preferred embodiment comprises that containing a plurality of dimethyl silane oxygen bases unit contains substituent compound as repetitive and on the end of its chemical chain and/or side chain.In addition, in the chemical chain that contains dimethyl silane oxygen base, can contain structural unit except dimethyl silane oxygen base as repetitive.Substituting group can be identical or different, and preferably contains a plurality of substituting groups.Substituent preferred embodiment comprises and contains acryloyl group for example, methacryl, vinyl, aryl, cinnamoyl, oxetanyl base, fluoroalkyl, polyoxy alkylidene, carboxyl or amino group.Though this molecular weight based on the compound of polysiloxane is not specifically limited, it preferably is no more than 100,000, more preferably no more than 50,000, is preferably 3 especially, 000-30, and 000, and most preferably be 10,000-20,000.Though should be not specifically limited based on the silicon atom content of organosilyl compound, it is preferably 18.0 weight % or more, preferred especially 25.0-37.0 weight %, and most preferably be 30.0-37.0 weight %.Should comprise X-22-174DX, X-22-2426, X-22-164B, X-22-164C and X-22-1821 (all these is Shin-Etsu Chemical Co., the trade name of Ltd.) based on the preferred embodiment of organosilyl compound; With FM-0725, FM-7725, FM-6621 and FM-1121 (these all are the trade names of Chisso Corporation); And DMS-U22, RMS-033, RMS-083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, FMS123, FMS131, FMS141 and FMS221 (all these is Gelest, the trade name of Inc.).
As the compound based on fluorine as anti fouling agent, the compound that contains fluoroalkyl is preferred.Above-mentioned fluoroalkyl preferably has 1-20 carbon atom, and more preferably 1-10 carbon atom.This fluoroalkyl can have linear structure (for example ,-CF
2CF
3,-CH
2(CF
2)
4H ,-CH
2(CF
2)
8CF
3, and CH
2CH
2(CF
2)
4H), branched structure (for example, CH (CF
3)
2, CH
2CF (CF
3)
2, CH (CH
3) CF
2CF
3, and CH (CH
3) (CF
2)
5CF
2H) or alicyclic structure (preferred 5 yuan the ring or hexatomic ring; For example perfluor cyclohexyl, perfluor cyclopentyl and the alkyl that replaced by aforementioned group); And can contain ehter bond (for example, CH
2OCH
2CF
2CF
3, CH
2CH
2OCH
2C
4F
8H, CH
2CH
2OCH
2CH
2C
8F
17, and CH
2CH
2OCF
2CF
2OCF
2CF
2H).A plurality of fluoroalkyls can be included in the same molecule.
The compound that is preferably based on fluorine further contains and helps to form and the binding of low-refraction tunic or help the substituting group of the compatibility between them.Above-mentioned substituting group can be identical or different, and preferably contains a plurality of substituting groups.Substituent preferred embodiment comprises acryloyl group, methacryl, vinyl, aryl, cinnamoyl, epoxy radicals, oxetanyl base, hydroxyl, the inferior intact base of polyoxy, carboxyl and amino group.Should can be polymkeric substance or oligomer based on the compound of fluorine with the compound that does not have fluorine atom.Its molecular weight does not have concrete qualification.Though should be not specifically limited based on the fluorine atom content in the compound of fluorine, it is preferably 20 weight % or more, preferred especially 30-70 weight %, and most preferably be 40-70 weight %.Preferred embodiment based on the compound of fluorine comprises R-2020, M-2020, R-3833, and M-3833 (all these is Daikin Industries, the trade name of Ltd.); And MEGAFACF-171, MEGAFAC F-172 and MEGAFAC F-170A, and DEFENSAMCF-300 (all these is Dainippon Ink and Chemical, the trade name of Incorporated).Yet, should not be considered as the present invention and only only limit to this.
In order to give for example characteristic of dust removal performance and antistatic property, can also suitably add dedusting agent or antistatic agent, for example known cationic surfactant and poly (oxyalkylene) based compound.For such dedusting agent or antistatic agent, the part that its structural unit can be used as functional group is included in aforesaid based in organosilyl compound or the compound based on fluorine.When such dedusting agent or antistatic agent are used as adjuvant when adding, preferably it is the 0.01-20 weight % with the total solid of low-index layer, more preferably 0.05-10 weight %, and the amount of preferred especially 0.1-5 weight % adds.The preferred embodiment of dedusting agent or antistatic agent comprises MEGAFACF-1500 (Dainippon Ink and Chemical, the trade name of Incorporated) and SH-3748 (Dow Corning Toray Co., the trade name of Ltd.).Yet, should not be considered as the present invention and be subjected to its restriction.
1-(14) surfactant
Particularly, in order to ensure the homogeneity of the even property of surface property such as crawling, the even property of uneven drying and point defect, preferably in being used to form the coating composition of photic diffusing layer, comprise based on the surfactant of fluorine and any or all of based in the organosilyl surfactant.Particularly, can preferably use the surfactant based on fluorine, this is because it shows the effect of improving surface property defective such as the even property of crawling, the even property of uneven drying and point defect with less addition.By in the inhomogeneity while that has increased surface property, brought high-speed coating adaptability, might increase throughput rate.
The multipolymer (being abbreviated as " based on the polymkeric substance of fluorine " sometimes) that comprises fluorine-containing aliphatic group based on the preferred embodiment of the surfactant of fluorine.As polymkeric substance based on fluorine, be characterised in that and contain corresponding to the repetitive of following monomer (i) or contain, but perhaps be suitable for the multipolymer of copolyethylene monomer corresponding to following the monomer (ii) acryl resin or the methacrylic resin of repetitive.
(i) by the monomer of the fluorine-containing aliphatic group of following formula (a) expression:
Formula (a)
In formula (a), R
11Expression hydrogen atom or methyl; X represent oxygen atom, sulphur atom or-N (R
12)-;
mExpression is more than or equal to 1 and be not more than 6 integer; And
nThe integer of expression 2-4.R
12Expression hydrogen atom or have alkyl, particularly methyl, ethyl, propyl group or the butyl of 1-4 carbon atom, wherein hydrogen atom and methyl are preferred.X is oxygen atom preferably.
(ii) by following formula (b) expression monomer, it can carry out copolymerization with aforesaid (i) monomer:
Formula (b)
In formula (b), R
13Expression hydrogen atom or methyl; Y represent oxygen atom or sulphur atom or-N (R
15)-; R
15Expression hydrogen atom or have alkyl, particularly methyl, ethyl, propyl group or the butyl of 1-4 carbon atom, wherein hydrogen atom and methyl are preferred.Y preferably oxygen atom ,-N (H)-or-N (CH
3)-.
R
14Expression is optional substitutedly to have 4 or more and be no more than linearity, side chain or the cyclic alkyl of 20 carbon atoms.By R
14The substituting group example of the alkyl of expression comprises hydroxyl, alkyl carbonyl, aromatic carbonyl, carboxyl, alkane ether, aryl ether group, halogen atom (for example, fluorine atom, chlorine atom and bromine atoms), nitro, cyano group and amino.Yet, should not be considered as the present invention and be subjected to their restriction.As having 4 or more and be no more than linearity, side chain or the naphthenic base of 20 carbon atoms, be fit to use butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, octadecyl and eicosyl, each in them can be linear or straight chain; Monocyclic cycloalkyl is cyclohexyl and suberyl for example; For example bicycloheptyl, dicyclo decyl, three encircle undecyls, Fourth Ring dodecyl, adamantyl, norborneol alkyl and Fourth Ring decyl with polynary ring naphthenic base.
Being benchmark based on each monomer in the polymkeric substance of fluorine, be used in that the present invention will use based in the polymkeric substance of fluorine by the amount of the monomer of the fluorine-containing aliphatic group of formula (a) expression at 10 moles of % or more, preferred 15-70 mole %, and more preferably in the scope of 20-60 mole %.
Be used in the polymkeric substance based on fluorine of the present invention and preferably have 3,000-100,000, and more preferably 5,000-80,000 weight-average molecular weight.
In addition, coating based solution, the addition that is used in the polymkeric substance based on fluorine of the present invention is preferably in the scope of 0.001-5 weight %, more preferably in the scope of 0.005-3 weight %, and further preferred in the scope of 0.01-1 weight %.When the addition based on the polymkeric substance of fluorine was less than 0.001 weight %, effect was not enough, yet, when it surpasses 5 weight %, the drying of film is not fully carried out, and is subjected to negative effect as the performance (for example, reflection potential and scratch-resistant) of film.
1-(15) thickening agent
In film of the present invention, for the viscosity of adjusting coating solution can be used thickening agent.
Especially, for the hard conating that comprises scattering particles, preferably add thickening agent.By increasing viscosity, the surface treatment of scattering particles and decline rate can be lowered.
Here " thickening agent " of indication means the material that can increase the viscosity of solution by its adding.Be preferably 0.05-50cP (mPas) by the degree that adds thickening agent and increase the viscosity of coating solution, 0.10-20cP (mPas) more preferably, and 0.10-10cP (mPas) most preferably.
To provide the example of such thickening agent below, but should not be considered as the present invention is limited.
Poly--6-caprolactone
Poly--the 6-caprolactone glycol
Poly--the 6-caprolactone triol
Polyvinyl acetate
Poly-(hexane diacid ethylidene ester)
Poly-(hexane diacid 1,4-butylidene ester)
Poly-(glutaric acid 1,4-butylidene ester)
Poly-(succinic acid 1,4-butylidene ester)
Poly-(terephthalic acid (TPA) 1,4-butylidene ester)
Poly-(ethylene glycol terephthalate)
Poly-(hexane diacid 2-methyl isophthalic acid, 3-propylidene ester)
Poly-(glutaric acid 2-methyl isophthalic acid, 3-propylidene ester)
Poly-(NGA neopentyl glycol adipate)
Poly-(decanedioic acid DOPCP)
Poly-(hexane diacid 1,3-propylidene ester)
Poly-(glutaric acid 1,3-propylidene ester)
Polyvinyl butyral
Polyvinyl formal
Polyvinyl acetal
The polyvinyl alcohol (PVA) propionic aldehyde that contracts
The polyvinyl alcohol (PVA) hexanal that contracts
Polyvinyl pyrrolidone
Polyacrylate
Polymethacrylate
Cellulose acetate
Cellulose propionate
Cellulose acetate-butyrate
In addition, also have known viscosity modifier and thixotropic agent, the green stone of for example describing among the JP-A-8-325491, fluorine four silicon micas, bentonitic clay, silicon dioxide, polynite and poly-(PAA); With the ethyl cellulose of describing among the JP-A-10-219136, polyacrylic acid and organic clay.
1-(16) coating solvent:
As the solvent that uses in the coating composition that is used to form each layer of the present invention, can use the multiple solvent of selecting from following viewpoint: each composition can dissolve or disperse within it; Can obtain uniform surface property in application step and drying steps; Can guarantee the keeping quality of liquid; And has suitable saturated vapour pressure.
Can use the potpourri of two or more solvents.Particularly, from the viewpoint of drying load, preferably under atmospheric pressure at room temperature boiling point be not higher than 100 ℃ solvent as principal ingredient, yet in order to adjust rate of drying, comprising a spot of boiling point is 100 ℃ or higher solvent.
The example that boiling point is not higher than 100 ℃ solvent comprises hydro carbons, for example hexane (boiling point: 68.7 ℃), heptane (boiling point: 98.4 ℃), cyclohexane (boiling point: 80.7 ℃) and benzene (boiling point: 80.1 ℃), halogenated hydrocarbon, for example methylene chloride (boiling point: 39.8 ℃), chloroform (boiling point: 61.2 ℃), phenixin (boiling point: 76.8 ℃), 1,2-ethylene dichloride (boiling point: 83.5 ℃), and triclene (boiling point: 87.2 ℃); Ethers, for example Anaesthetie Ether (boiling point: 34.6 ℃), Di Iso Propyl Ether (boiling point: 68.5 ℃), dipropyl ether (boiling point: 90.5 ℃) and tetrahydrofuran (boiling point: 66 ℃); Ester class, for example ethyl formate (boiling point: 54.2 ℃), methyl acetate (boiling point: 57.8 ℃), ethyl acetate (boiling point: 77.1 ℃) and isopropyl acetate (boiling point: 89 ℃); Ketone, for example acetone (boiling point: 56.1 ℃) and 2-butanone (, boiling point: 79.6 ℃ identical) with methyl ethyl ketone; Alcohols, for example methyl alcohol (boiling point: 64.5 ℃), ethanol (boiling point: 78.3 ℃), 2-propyl alcohol (boiling point: 82.4 ℃) and 1-propyl alcohol (boiling point: 97.2 ℃); Cyanogen compound, for example acetonitrile (boiling point: 81.6 ℃) and propionitrile (boiling point: 97.4 ℃); And carbon disulphide (boiling point: 46.2 ℃).In these compounds, ketone and ester class are preferred; And ketone is particularly preferred.In these ketone, the 2-butanols is particularly preferred.
Boiling point is that the example of 100 ℃ or higher solvent comprises octane (boiling point: 125.7 ℃), toluene (boiling point: 110.6 ℃), dimethylbenzene (boiling point: 138 ℃), zellon (boiling point: 121.2 ℃), chlorobenzene (boiling point: 131.7 ℃) diox (boiling point: 101.3 ℃), dibutyl ethers (boiling point: 142.4 ℃), isobutyl acetate (boiling point: 118 ℃), cyclohexanone (boiling point: 155.7 ℃), 2-methyl-4-pentanone is (identical with MIBK, boiling point: 115.9 ℃), 1-butanols (boiling point: 117.7 ℃), N, dinethylformamide (boiling point: 153 ℃), N,N-dimethylacetamide (boiling point: 166 ℃), and dimethyl sulfoxide (boiling point: 189 ℃).In these compounds, cyclohexanone and 2-methyl-4-pentanone are particularly preferred.
1-(17) other:
Except mentioned component, resin, coupling agent, anti-coloring agent, colorant (for example, pigment and dyestuff), defoamer, levelling agent, fire retardant, ultraviolet light absorber, infrared absorbent, viscosity imparting agent, polymerization inhibitor, antioxidant, surface modifier etc. can also be joined in the film of the present invention.
1-(18) stilt
The stilt of film of the present invention does not have concrete restriction, and its example comprises transparent resin film, transparent resin plate, transparent resin sheet and clear glass.The example of transparent resin film comprises cellulose acetate membrane (for example, tri cellulose acetate membrane (refractive index: 1.48), cellulose diacetate film, cellulose acetate-butyrate film and cellulose-acetate propionate film), polyethylene terephthalate film, poly (ether sulfone) film, polyacrylic resin film, polycarbamate basement membrane, polyester film, polycarbonate membrane, polysulfone membrane, polyester film, polymethylpentene film, polyetherketone film and (methyl) acrylonitril membrane.
＜cellulose acetate membrane 〉
Wherein, high transparent, low optical birefraction and the easy cellulose acetate membrane of making and be used as usually the diaphragm of Polarizer are preferred, and the tri acetic acid fiber film is particularly preferred.In addition, the thickness of transparent support thing is generally about 25 μ m-1,000 μ m.
In the present invention, preferably use degree of acetylation as the cellulose acetate of 59.0-61.5% as cellulose acetate membrane.
Here " degree of acetylation " of indication means the quantity of the acetate of combination on every cellulose unit weight.Degree of acetylation is according to ASTM D-817-97 measurements and calculations (method of testings of test cellulose acetate etc.).
This cellulose acetate preferably has 250 or more, and more preferably 290 or more viscosity average polymerization degree (DP).
In addition, preferably be used in cellulose acetate of the present invention and have by what the colloidal sol permeation chromatographic column was measured and approach 1.0 Mw/Mn value (wherein Mw represents weight-average molecular weight, and Mn represents number-average molecular weight), in other words, molecular weight distribution is very narrow.Particularly, the Mw/Mn value is preferably 1.0-1.7, more preferably 1.3-1.65, and 1.4-1.6 most preferably.
Usually, be not that per 1/3 equivalent with total degree of substitution distributes at cellulose acetate 2-, 3-and the locational hydroxyl of 6-, but be tending towards diminishing at the degree of substitution of the locational hydroxyl of 6-.In the present invention, preferably at the degree of substitution of the locational hydroxyl of 6-greater than at 2-or the locational degree of substitution of 3-.
This locational hydroxyl by the ratio of acyl substituted be preferably total degree of substitution 32% or bigger, more preferably 33% or bigger, and preferred especially 34% or bigger.In addition, the degree of substitution at the acyl group of the 6-position of cellulose acetate is 0.88 or more.Except that acetyl group, the hydroxyl of 6-position can be had 3 or the acyl group (for example, propiono, bytyry, valeryl, benzoyl and acryloyl group) of more a plurality of carbon atoms replace.Measurement at each locational degree of substitution can be determined by NMR.
In the present invention, can will pass through at JP-A-11-5851, [0043]-[0044] section [embodiment] [synthetic embodiment 1], the cellulose acetate that the method for describing in [0048]-[0049] section [synthetic example 2] and [0051]-[0052] section [synthetic example 3] obtains is as this cellulose acetate.
＜polyethylene terephthalate film 〉
In the present invention, also preferably use the polyethylene terephthalate film, this is not only because its transparency, physical strength, flatness, chemical-resistant and moisture resistance are all very excellent, but also because it is cheap.
In order to improve overlay and the bond strength that hard conating thereon will be provided more, more preferably make this overlay through bonding processing easily.
As the PET film that has the easy bonding coat of optics that can buy on the market, enumerate Co. here, COSMOSHINE A4100 and A4300 that Ltd. produces by Toyobo.
2. constitute the layer of antireflection film
Antireflection film of the present invention obtains by mixing and be coated with aforementioned each layer constituent on above-mentioned supporting layer.Next, will the layer that constitute antireflection film of the present invention be described.
2-(1) antiglare layer:
Because the surface scattering of definition in the present invention, antiglare layer is in order to give film anti-dazzle performance, and preferably forms for the hard conating performance of the scratch-resistant that improves film.
As the method that forms antiglare film, known seat shape film lamination that passing through among the JP-A-6-16851 will have thin irregularity thing forms antiglare layer on its surface the method that is described in is arranged here; But be described in passing through among the JP-A-2000-206317 according to the difference sclerosis of ionizing radiation dose and the method for contraction ionising radiation hardening resin formation antiglare layer; Be described in and in drying, translucent fine grained and semi-transparent resin solidified when utilizing weight ratio between optimum solvent and the semi-transparent resin to reduce to come gel among the JP-A-2000-338310, thereby on the film surface, form the method for the formation antiglare layer of irregularity thing; And the external pressure of describing in JP-A-2000-275404 of passing through is given the method that the surface irregularity degree forms antiglare film.These known methods can be used.
In can being used in antiglare film of the present invention, preferably comprise the bonding agent that can give the hard conating performance, the translucent particle and the solvent that are used to give anti-dazzle performance are to form by the protrusion of translucent particle self or by assembling a plurality of granuloplastic protrusions as neccessary composition and surperficial irregularity thing.
By the antiglare layer of disperseing unglazed particle (mat particle) to form is to be made by bonding agent and the translucent particle that is scattered in the bonding agent.The antiglare film that preferably has anti-dazzle performance has anti-dazzle performance and hard conating performance.
The instantiation that is fit to the unglazed particle of use comprises inorganic compound particle for example silica dioxide granule and TiO
2Particle; With resin particle for example acrylic resin particle, crosslinked acrylic resin particle, granules of polystyrene, crosslinked styrene resin particle, melamine resin particle and guanidines polyimide resin particle.Crosslinked styrene resin particle is preferred in these particles.
The unglazed coating of particles that can adopt can be sphere or unbodied.
Unglazed particle grain size distribution is measured by the Coulter method of counting, and the distribution of being measured is converted into the granule number distribution.
Make its refractive index consistent by the refractive index of adjusting semi-transparent resin, might obtain internal haze of the present invention and external haze with each translucent particle of in these particles, selecting.Particularly, the combination of following semi-transparent resin and translucent particle is preferred, described semi-transparent resin is by trifunctional or polyfunctional (methyl) acrylate monomer (refractive index after the sclerosis: 1.55-1.70) constitute as principal ingredient, preferably be used in the antiglare layer of describing later of the present invention, described translucent particle is that crosslinked poly-(methyl) methyl acrylate polymer and/or the benzoguanamine particle of 50-100 weight % makes by styrene-content; And (refractive index: the combination of the translucent particle that 1.54-1.59) makes is particularly preferred to aforementioned semi-transparent resin with crosslinked poly-(cinnamic acrylic ester) multipolymer that by styrene-content is 50-100 weight %.
Preferred this translucent particle of blending so that its amount with the 3-30 weight % of formed antiglare layer total solid be included in the formed antiglare layer.The amount of translucent particle is 5-20 weight % more preferably.When the amount of translucent particle is less than 3 weight %, anti-dazzle performance deficiency, yet, when it surpasses 30 weight %, caused the problem of image blurring, external haze and flash of light.
In addition, the density of this translucent particle is preferably 10-1,000mg/m
2, more preferably 100-700mg/m
2
In addition, the absolute value of the difference of the refractive index of the refractive index of semi-transparent resin and translucent particle preferably is no more than 0.04.The absolute value of the difference of the refractive index of semi-transparent resin and the refractive index of translucent particle is 0.001-0.030 more preferably, further preferred 0.001-0.020, preferred especially 0.001-0.015.Marquis when this difference surpasses 0.040 has caused that the literal on the film for example is fuzzy, has reduced the muddy problem of darkroom contrast and surface.
Here, the refractive index of above-mentioned semi-transparent resin can quantitatively be determined, and for example directly measures or compose reflectance spectrum by Abbe refractometer or compose oval photometric measurement and calculate.The refractive index of aforementioned translucent particle is to have in the solvent of different refractivity by the equivalent translucent particle being distributed to by changing two kinds of mixing ratios with solvent of different refractivity, with the refractive index of measuring turbidity and the marquis measures solvent by Abbe refractometer when turbidity becomes minimum.
In addition, two or more the unglazed particles with different-grain diameter can use together.Unglazed particle with greater particle size might be given anti-dazzle performance, and has than the unglazed particle of small particle diameter and might give other optical property.For example, be attached under the situation about having on 133ppi or the higher High Resolution Display, might cause the defective of the image quality that is called as " flash of light " at antireflection film." flash of light " is to make the problem that pixel is extended or dwindle cause by the lip-deep irregularity thing of anti-dazzle antireflection film, to such an extent as to the uniformity coefficient of brightness is lost.By using the unglazed particle that has than small particle diameter and have the refractive index that is different from bonding agent than the unglazed particle that can give anti-dazzle performance together, might improve flash of light widely.
The thickness of antiglare layer is preferably 1-10 μ m, and more preferably 1.2-8 μ m.When antiglare layer is too thin, rigid deficiency, however when it was too thick, curling or fragility degenerated, thereby may reduce the processing applicability.Like this, preferably the thickness of antiglare layer falls in the above-mentioned scope.
On the other hand, the center line average roughness of antiglare layer (Ra) is preferably in the scope of 0.10-0.40 μ m.When the center line average roughness (Ra) of antiglare layer surpasses 0.40 μ m, caused when flash of light or the problem of surperficial albefaction for example when reflecting extraneous light.In addition, the value of the image definition of transmission is preferably 5-60%.
According to pencil hardness test, the intensity of antiglare layer is preferably H or higher, more preferably 2H or higher, and 3H or higher most preferably.
2-(2) hard conating
In order to give the film physical strength, except antiglare layer, can in film of the present invention, provide hard conating.
Preferably, provide low-index layer thereon; And more preferably, index layer and high refractive index layer between hard conating and low-index layer, providing, thus constitute antireflection film.
Hard conating can be by stacked two or more layers of formation.
In the present invention, according to the optical design that is used to obtain antireflection film, the refractive index of this hard conating is preferably 1.48-2.00, more preferably 15.2-1.90, and further preferred 1.55-1.80 scope.In the present invention, owing to there is at least one low-index layer on hard conating, compared with this scope low the time when refractive index, antireflection property is lowered, yet, when it is too high, reflected light tone grow.
From giving the angle of enough persistence of film and resistance to impact, the thickness of hard conating is generally about 0.5 μ m-50 μ m, preferred 1 μ m-20 μ m, more preferably 2 μ m-10 μ m, and 3 μ m-7 μ m most preferably.
In addition, according to pencil hardness test, the intensity of hard conating is preferably H or higher, more preferably 2H or higher, and 3H or higher most preferably.
In addition, preferably in the lappet test according to JIS K5400, the wear extent of before the test and test back sample is as much as possible little.
But preferred this hard conating is to form by the cross-linking reaction of ionising radiation hardening compound or polyreaction.For example, might be coated on the transparent support thing, and make polyfunctional monomer or multifunctional oligomer carry out cross-linking reaction or polyreaction forms this hard conating by containing can the harden coating composition of polyfunctional monomer or multifunctional oligomer of ionising radiation.
As can the harden functional group of polyfunctional monomer or multifunctional oligomer of ionising radiation, photopolymerizable functional group, electron beam polymerizable functional group and radiation polymerizable functional group are preferred, and wherein, photopolymerizable functional group is particularly preferred.
The example of photopolymerizable functional group comprises undersaturated polymerizable functional group for example (methyl) acryloyl group, vinyl, styryl and allyl, and wherein (methyl) propenyl is preferred.
In order to give the scattering-in performance, can contain mean grain size in hard conating is the unglazed particle of 1.0-10.0 μ m and preferred 1.5-7.0 μ m, for example inorganic compound particle or resin particle.
In order to control the refractive index of hard conating, can in the bonding agent of hard conating, add the monomer or the inorganic particle of high index of refraction or add the two simultaneously.Except the effect of control refractive index, inorganic particle also has inhibition sclerosis and because the effect of the contraction that cross-linking reaction caused.In the present invention, comprise the formed polymkeric substance of polymerization by aforementioned polyfunctional monomer and/or high refractive index monomers etc. and form the back at hard conating and disperse the material of inorganic particle within it to be called as bonding agent.
In order to keep image definition, except the irregularity shape of adjusting the surface, preferably adjust the sharpness of transmission image.Limpid antireflection film preferably has 60% or higher transmission image sharpness.The transmission image sharpness normally is used for showing the fringe of the image that transmits and show by film.This value is big more, and the sharpness of the image of seeing by film is good more.The transmission image sharpness is preferably 70% or higher, and more preferably 80% or higher.
2-(3) high refractive index layer and middle index layer
In film of the present invention, antireflection property can be improved by high refractive index layer and middle index layer are provided.
In this manual, high refractive index layer and middle index layer will be called high refractive index layer jointly sometimes.Carry one in passing, in the present invention, the term " height " in high refractive index layer, middle index layer and the low-index layer, " in " represent relative each other big and little relation in these layers with " low ".In addition, as long as considered and the relation of transparent support thing that preferred index satisfies relation [(transparent support thing)＞(low-index layer)], and [(high refractive index layer)＞(clear support layer)].
In addition, in this instructions, high refractive index layer, middle index layer and low-index layer are called as anti-reflection layer jointly sometimes.
Prepare antireflection film in order to constitute low-index layer on high refractive index layer, the refractive index of this high refractive index layer is preferably 1.55-2.40, more preferably 1.60-2.20, further preferred 1.65-2.10, and 1.80-2.00 most preferably.
When providing and being coated with these layers and prepare antireflection film with the order of middle index layer, high refractive index layer and low-index layer on supporting layer, this high refractive index layer preferably has 1.65-2.40 and the more preferably refractive index of 1.70-2.20.The refractive index of index layer in the adjustment makes it have refractive index between the refractive index of the refractive index of low-index layer and high refractive index layer.The refractive index of intermediate-index layer is preferably 1.55-1.80.
Be used in high refractive index layer and the middle index layer, with TiO
2The inorganic particle that constitutes as principal ingredient is that the state with the suspending liquid that is used to form high refractive index layer and middle index layer uses.
In the dispersion of inorganic particle, this inorganic particle is to be distributed in the dispersion medium in the presence of spreading agent.
Be used in that high refractive index layer among the present invention and middle index layer preferably form by following process: in dispersion medium, disperse in the dispersion of inorganic particle, further add for forming the necessary adhesive precursor of matrix (hardenable polyfunctional monomer of for example described in the back ionising radiation and multifunctional oligomer), Photoepolymerizationinitiater initiater etc., thereby preparation is used to form the coating composition of high refractive index layer and is used to form the coating composition of middle index layer, the coating composition that is used to form high refractive index layer is coated on the transparent support thing with the coating composition that is used to form middle index layer, but carry out the cross-linking reaction or the polyreaction of ionising radiation hardening compound (for example, polyfunctional monomer and multifunctional oligomer) then.
In addition, preferably in these layers of coating or afterwards, make bonding agent in the high refractive index layer and the bonding agent in the middle index layer and spreading agent carry out cross-linking reaction or polyreaction.
In the bonding agent in bonding agent in the high refractive index layer that makes like this and the middle index layer, for example, can harden polyfunctional monomer or multifunctional oligomer of above-mentioned preferred dispersing agent and ionising radiation carries out cross-linking reaction or polyreaction, thereby the anionic group of spreading agent is brought in each bonding agent.In addition, in each bonding agent of bonding agent in bonding agent in high refractive index layer and the middle index layer, anionic group has the function of the inorganic particle that keeps disperse state, and the structure of crosslinked or polymerization has been given the ability that bonding agent forms film, thereby has improved the high refractive index layer that contains inorganic particle respectively and physical strength, chemical-resistant and the weatherability of middle index layer.
Based on the solids content of the coating composition of described layer, the bonding agent in the high refractive index layer is that the amount with 5-80 weight % adds.
Based on the weight of high refractive index layer, the content of inorganic particle is preferably 10-90 weight % in the high refractive index layer, more preferably 15-80 weight %, and preferred especially 15-75 weight %.In high refractive index layer, can use two or more inorganic particles together.
Under low-index layer was present in situation on the high refractive index layer, the refractive index of preferred high refractive index layer was higher than the refractive index of transparent support thing.
In high refractive index layer, can also preferably use by bonding agent crosslinked or that polyreaction can obtain, but the ionising radiation hardening compound that for example contains aromatic ring, (for example contain defluorination halogen atom in addition, Br, I and Cl) but the ionising radiation hardening compound, but contain for example ionising radiation hardening compound of S, N and P atom.
The thickness of high refractive index layer can be according to using suitably design.When high refractive index layer was used as optical interference layer described later, its thickness was preferably 30-200nm, more preferably 50-170nm, and preferred especially 60-150nm.
Do not contain at high refractive index layer under the situation of the particle that can give anti-dazzle function, preferably the turbidity of this high refractive index layer is low as much as possible.This turbidity is preferably and is no more than 5%, more preferably no more than 3%, and especially preferably is no more than 1%.
Preferred high refractive index layer is directly to construct or be configured on the aforementioned transparent support thing by other layer.
2-(4) low-index layer
In order to reduce the reflectivity of film of the present invention, need to use low-index layer.
Low-index layer preferably has 1.20-1.46, the more preferably refractive index of 1.25-1.46 and preferred especially 1.30-1.46.
This low-index layer preferably has 50-200nm and the more preferably thickness of 70-100nm.This low-index layer preferably have be no more than 3%, more preferably no more than 2% and be most preferably not exceeding 1% turbidity.Particularly, according to the pencil hardness test of making of the load of 500g, low-index layer preferably has H or higher, more preferably 2H or higher and most preferably 3H or higher intensity.
In addition, in order to improve the antifouling property of blooming, water contact angle from the teeth outwards is preferably 90 ° or bigger, and more preferably 95 ° or bigger, and preferred especially 100 ° or bigger.
Preferred above-mentioned hardenable compositions contains (A) above-mentioned fluoropolymer, (B) inorganic particle and (C) organic silane compound.
In order to disperse and to fix fine grained of the present invention, in low-index layer, used bonding agent.Though the bonding agent of describing in the hard conating can be used as this bonding agent in front, the preferred bonding agent self that uses has the fluoropolymer of low-refraction or the bonding agent of fluorine-containing sol-gel raw material.This fluoropolymer or fluorine-containing sol-gel be preferably by the heating or the raw material of crosslinking by ionizing radiation, and the surface of formed low-index layer have 0.03-0.30 coefficient of static friction and with water be 85-120 ° contact angle.
2-(5) antistatic layer and conductive layer:
In the present invention, preferably go the viewpoint of static that antistatic layer is provided from the film surface.The example that forms the method for antistatic layer comprises known method usually, but for example is coated with the method for the conductive coating paint solution that contains electric conductivity fine grained and reactivity hardening resin and can forms the metal of hyaline membrane or the method for metal oxide etc. by vapor deposition or sputter.This conductive layer can be directly or is formed on the stilt by the prime coat that can strengthen the adhesion between itself and the stilt.In addition, this antistatic layer can be used as the part of antireflection film.In this case, when antistatic layer is used for approaching outermost layer,, also might obtain antistatic property fully even when film is very thin.
This antistatic layer preferably has 0.01-10 μ m, more preferably 0.03-7 μ m and the further thickness of preferred 0.05-5 μ m.This antistatic layer preferably has 10
5-10
12Ω/sq, more preferably 10
5-10
9Ω/sq, and most preferably 10
5-10
8The surface resistance of Ω/sq.Surface resistance can be measured by the four point probe method.
Preferred this antistatic layer is a substantial transparent.Particularly, the turbidity of this antistatic layer preferably is no more than 10%, more preferably no more than 5%, further preferably is no more than 3%, and is most preferably not exceeding 1%.For the light with 550nm wavelength, the transmissivity of this antistatic layer is preferably 50% or more, and more preferably 60% or more, further preferred 65% or more, and most preferably 70% or more.
Antistatic layer good strength of the present invention.Particularly, according to the pencil hardness test of making of the load of 1kg, this antistatic layer preferably has H or higher, more preferably 2H or higher, further preferred 3H or higher, and most preferably 4H or higher intensity.
2-(6) stain-proofing layer:
Might on outermost layer of the present invention, provide stain-proofing layer.This stain-proofing layer has reduced the surface energy of antireflection film, thereby makes hydrophilic or the lipophilicity stain almost can not adhere to.
Stain-proofing layer can form by using fluoropolymer or anti fouling agent.
This stain-proofing layer preferably has 2-100nm and the more preferably thickness of 5-30nm.
2-(7) prevents to interfere the layer of inhomogeneous (spectrum is inhomogeneous):
Between transparent support thing and hard conating or the refractive index between transparent support thing and the antiglare layer have in sizable difference (difference of refractive index is 0.3 or more), producing reflected light between transparent support thing and the hard conating or on the interface between transparent support thing and the antiglare layer.This reflected light might interfere with the reflected light on the antiglare layer, thereby has produced because the faint inhomogeneous caused interference unevenness on hard conating (or antiglare layer) thickness.In order to prevent such interference unevenness, for example, can between transparent support thing and hard conating (or antiglare layer), be provided for preventing to interfere uneven layer, this layer has middle refractive index n
pAnd its thickness d
pSatisfy following expression.
Numerical expression (d
p)
d
p＝(2N-1)×λ/(4n
p)
In above-mentioned expression formula, λ represents that wavelength of visible light and its are the arbitrary values in the 450-600nm scope; And N represents natural number.
In addition, in the time of above the antireflection rete adheres to image display etc., may there be pressure sensitive adhesive layer to be layered in clear support layer not have the situation on that side of stacked antireflection film.In such technical scheme, when there is sizable difference (0.3 or more) in the refractive index between transparent support thing and the pressure sensitive adhesive layer (or adhesive phase), may exist in and produce catoptrical situation between transparent support thing and the pressure sensitive adhesive layer (or adhesive phase), and lip-deep reflected light such as this reflected light and antireflection film are interfered mutually, thereby the situation as the front has produced because the delicate inhomogeneous caused interference unevenness on supporting layer or the hard conating thickness.In order to prevent such interference unevenness, can on stilt, not have that side of superimposed antireflection film provide similar in appearance to above-mentioned be used to prevent to interfere unevenness prevent to interfere uneven layer.
By the way, such being used for prevents to interfere the layer of unevenness to be described in detail in JP-A-2004-345333, and also can prevent to interfere the layer of unevenness to be applied to the present invention being used for of existing in this patent documentation.
2-(8) is bonding coat easily
In film of the present invention, can be coated with and provide easy bonding coat.Here " easily bonding coat " of indication mean, for example can give the layer that the diaphragm that is used for Polarizer is adjacent the function that layer or hard conating be bonded to mutually easily with stilt.
Easily the example of adhesion process comprises the processing that easy bonding coat is provided on overlay by the easy bonding agent that is made by polyester, acrylate, polycarbamate, polyethyleneimine, silane coupling agent or analog.
The example that is preferred for the easy bonding coat in this technology comprises and containing-layer of the polymer compound of COOM base (M represents hydrogen atom or kation).Preferred technical scheme is to provide in the film base side to contain-polymkeric substance of COOM base, and is adjacent to provide in that side of light polarizing film and contains the technical scheme that the hydrophilic polymeric compounds is the layer of principal ingredient.The example of the polymer compound of the containing of indication-COOM base comprises and containing-COOM base styrene-maleic acid copolymer and containing-COOM guanidine-acetic acid vinyl acetate-maleic acid or vinyl acetate-maleic acid-copolymer-maleic anhydride in this article.Preferred especially the use contains-COOM guanidine-acetic acid vinyl acetate-maleic acid.Such polymer compound is to use separately or use with two or more the potpourri in them, and its weight-average molecular weight is preferably about 500-500,000.As containing-the particularly preferred example of polymer compound of COOM base, those that describe in JP-A-6-094915, JP-A-7-333436 are to be fit to use.
In addition, the preferred embodiment of hydrophilic polymer compounds (for example comprises the hydrophilic cellulose derivant, methylcellulose, carboxymethyl cellulose, and hydroxylated cellulose), polyvinyl alcohol derivative (for example, polyvinyl alcohol (PVA), vinyl acetate-ethenol copolymer, Pioloform, polyvinyl acetal, polyvinyl formal, with polyvinyl alcohol (PVA) benzylidene (polyvinyl benzal), natural polymeric compounds (for example, gelatin, casein, and Arabic gum), the hydrophilic polyester derivant (for example, partly sulfonated polyethylene terephthalate), with hydrophilic polyethene radical derivative (for example, poly-N-vinyl pyrrolidone, polyacrylamide, the polyvinyl indazole, with the polyvinyl pyrazoles).Such hydrophilic polymer compounds be use separately or use with two or more the potpourri in them.
Easily bonding coat preferably has the thickness in the 0.05-1.0 mu m range.When the thickness of easy bonding coat is less than 0.05 μ m, be difficult to obtain enough cohesives, yet when it surpassed 1.0 μ m, bonding effect was by saturated.
2-(9) non-curl backing
The film of this technology is handled through anti-curling.Here " anti-curl handle " of indication is meant and gives processing that having carried out the function rolled inwards on the anti-surface of handling of curling.By implementing this processing, to implement some surface treatments on a surface, thereby implemented to have in various degree in the surface treatment with kind for two surfaces to transparent resin film, it has played the effect that the phenomenon that prevents from above-mentioned surface to curl inwards takes place.
Here enumerated, the technical scheme of non-curl backing is provided on substrate one side relative with having that side of antiglare layer or antireflection film; On a surface of transparent resin film, be coated with and provide the technical scheme of easy bonding coat; And the technical scheme of the apparent surface being used the anti-processing of curling.
The anti-instantiation of handling that curls comprises with solvent and coating coating, and the transparent resin layer that is made by solvent and cellulose triacetate, cellulose diacetate, cellulose-acetate propionate etc. is provided.Particularly, the method for the use solvent of indication in this article is to contain by coating can dissolve or the composition of solvent that swelling is used as the cellulose acetate membrane of polarization board protective film here carries out.Correspondingly, as coating solution, contain based on ketone or be preferred based on the solution of the organic solvent of ester with the layer that prevents the function of curling.Preferred embodiment based on the organic solvent of ketone comprises acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl lactate, diacetone, diacetone alcohol, isophorone, ethyl normal-butyl ketone, diisopropyl ketone, metacetone, di ketone, methyl cyclohexanone, methyl n-butyl ketone, methyl n-pro-pyl ketone, methyl n hexyl ketone and methyl n heptyl ketone; And the preferred embodiment based on the organic solvent of ester comprises methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate.Yet, may exist except potpourri by solvent that can dissolve cellulose acylate film wherein and/or solvent composition that can swelling acylated cellulose wherein, also comprise do not dissolve acylated cellulose wherein solvent as the solvent that will use.The anti-processing of curling is according to the amount of crimp of transparent resin film and the kind of coating content resin, is undertaken by the composition that these solvents are obtained with suitable ratio mixing.In addition, also shown the anti-function of curling by using transparent hard processing or antistatic treatment.
2-(10) water accepting layer
Water absorbing agent can be used in the film of the present invention.This water absorbing agent can be selected in having the compound that absorbent function is the center simultaneously with the earth alkali metal.Their example comprises BaO, SrO, CaO, and MgO.This water absorbing agent can also be at metallic element Ti for example in addition, and Mg selects among Ba and the Ca.Such water absorbing agent particle grain size preferably is no more than 100nm, and more preferably no more than 50nm.
The layer that contains such water absorbing agent can perhaps can prepare nano particle by several different methods by use vacuum vapor deposition method preparation as the barrier layer of front.The thickness of this layer is preferably 1-100nm, and 1-10nm more preferably.The layer that contains water absorbing agent can be added between stilt and the lamination (lamination of barrier layer and organic layer), in the superiors of lamination, between the lamination or within the organic layer or barrier layer of a lamination.Under the situation in joining barrier layer, preferably carry out common vapor deposition process.
2-(11) prime coat or inorganic thin film layer
In film of the present invention, can improve gas barrier property by between stilt and lamination, placing known prime coat or inorganic thin film layer.
For prime coat, for example can use acryl resin, epoxy resin, carbamate resins and silicones.Yet in the present invention, the organic/inorganic doped layer is preferably as this prime coat.In addition, inorganic vapor deposition layer or according to the accurate inorganic coating film of colloidal sol-gel method preferably as this inorganic thin film layer.Inorganic vapor deposition layer can be by formation such as vacuum vapor deposition method sputtering methods.
Film the layer configuration
For film of the present invention, can adopt the layer configuration of the above-mentioned layer of known use.To provide their representative instance below.
(a) stilt/hard conating
(b) stilt/hard conating/low-index layer (referring to Fig. 1)
(c) stilt/hard conating/high refractive index layer/low-index layer (referring to Fig. 2)
(d) stilt/hard conating/middle index layer/high refractive index layer/low-index layer (referring to Fig. 3)
(b) (Fig. 1) in, by going up superimposed low-index layer (5) at the hard conating (2) that is coated on the stilt (1), can be with this lamination suitably as antireflection film.Form this low-index layer (5) by going up with thickness, can reduce because the surface reflection that the film interference factor is caused near 1/4 optical wavelength at hard conating (2).
In addition, (c) (Fig. 2) in, by going up superimposed high refractive index layer (4) and low-index layer (5), also this lamination can be used as antireflection film suitably at the hard conating (2) that is coated on the stilt (1).In addition, (d) (Fig. 3) in, by order a layer configuration is set according to stilt (1), hard conating (2), middle index layer (3), high refractive index layer (4) and low-index layer (5), reflectivity is remained is not higher than 1%.
In configuration (a)-(d), hard conating (2) can be made by the antiglare layer with anti-dazzle performance.Anti-dazzle performance can be as shown in Figure 4 by disperseing unglazed particle to provide, perhaps can be as shown in Figure 5 method molded surface by for example embossing provide.By disperseing unglazed granuloplastic antiglare layer is to be made by bonding agent and the translucent particle that is dispersed in this bonding agent.Antiglare layer with anti-dazzle performance preferably has anti-dazzle performance and hard conating performance, and can be by for example two-layer or four layers of structure of a plurality of layers.
In addition, can be provided in transparent support thing and comprise: layer, antistatic layer (exist under the situation of the requirement that reduces sheet resistance value from the display side or lip-deep stain etc. become under the situation of problem), other hard conating (under the hard conating that is only made by individual layer or antiglare layer make the not enough situation of hardness), gas-barrier layer, water accepting layer (moisture barrier), viscosity improving layer and the stain-proofing layer (anti-contamination layer) that prevent to interfere unevenness (spectrum unevenness) at the example of the layer between a layer surperficial side or outermost surface.
The preferred refractive index that constitutes each layer of the anti-dazzle antireflection film with anti-reflection layer of the present invention satisfies relation of plane down.
(refractive index of hard conating)＞(refractive index of transparent support thing)＞(refractive index of low-index layer)
4. production method
Film of the present invention can form with following method, but should not be considered as the present invention is limited to this.
The preparation of 4-(1) coating solution
＜preparation 〉
At first, preparation contains the coating solution of the composition that is used for forming each layer.In the case, by making the volatile quantity minimum of solvent, can suppress the increase of liquid water content in the coating solution.Liquid water content in the coating solution preferably is no more than 5%, and more preferably no more than 2%.The inhibition of solvent evaporates amount reaches by following process, for example, improves tight ness rating when stirring after various raw materials being poured in the groove, and in the air contact area minimum of carrying out making when liquid shifts coating solution.In addition, can be provided in the coating process or before or after coating, be used for reducing the measure of coating solution water cut.
The physical property of＜coating solution 〉
In coating system of the present invention,, therefore be necessary physical property, especially viscosity and the surface tension of control solution when coating because the upper limit speed that may be coated with is subjected to the influence of solution physical property widely.
The viscosity of used low-index layer preferably is no more than 2.0[mPas among the present invention], more preferably no more than 1.5[mPas], and be most preferably not exceeding 1.0[mPas].Because viscosity changes with shear rate according to coating solution, therefore above-mentioned value has shown the viscosity under the shear rate when coating.By in this coating solution, adding thixotropic agent, viscosity when implementing the high shear coating, however viscosity uprises in the drying that coating solution is not applied shearing substantially, to such an extent as in drying, produce unevenness hardly.Therefore, be preferred like this.
In addition, except the physical property of solution, the amount of coating the coating solution on the transparent support thing has also influenced the upper limit speed that may be coated with.The amount that is applied to the coating solution on the transparent support thing is preferably 2.0-5.0[mL/m
2].Coating the amount of the coating solution on the transparent support thing by increase, can improve the upper limit speed of coating, therefore, is preferred like this.Yet being crossed when the amount of coating the coating solution on the transparent support thing increases greatly, implements dry burden and becomes big.Therefore, preferably determine to coat the amount of the coating solution on the transparent support thing by solution formula and process conditions.
Surface tension is preferably at 15-36[mN/m] scope in.Preferably reduce surface tension by adding levelling agent or alternate manner, this is because the unevenness Be Controlled when dry.On the other hand, when surface tension decline was too many, the upper limit speed of coating can reduce.Like this, surface tension is more preferably at 17[mN/m]-32[mN/m] scope in, and further preferably at 19[mN/m]-26[mN/m] scope in.
＜filter
Preferably before coating, the coating solution that is used to be coated with is filtered.For the filtrator that is used to filter, has the filtrator of small-bore as far as possible in the scope of preferably using the composition in coating solution not to be removed.In order to filter, to use the filtrator of absolute filtering accuracy, and preferably use the filtrator of absolute filtering accuracy as 0.1-5 μ m as 0.1-10 μ m.This filtrator preferably has 0.1-10mm, and the more preferably thickness of 0.2-2mm.Under the sort of situation, filter preferably being no more than under the 1.5MPa, more preferably no more than 1.0MPa, and further preferably be no more than and carry out under the filtration pressure of 0.2MPa.
Filter cell does not have specific limited as long as it does not influence coating solution.Particularly, enumerated filtering element with the wet suspending liquid of the identical mineral compound of describing in front here.
In addition, also preferably before coating, the coating solution that ultrasonic dispersion is filtered, thus help froth breaking and dispersion and keep suspending liquid.
Processing before 4-(2) coating:
Preferably before coating, carry out surface treatment to being used in holder of the present invention.Its instantiation comprises Corona discharge Treatment, glow discharge processing, flame treatment, acid treatment, alkali treatment and treatment with uv radiation.In addition, also preferred as described in JP-A-7-333433, utilizing it that undercoat is provided.
In addition, the example of dust collection method that is used as the technology before the coating in dust removal process comprises the dry dust removal method, the method for for example describing among the JP-A-59-150571 that adhesive-bonded fabric, thin slice etc. is pressed onto the film surface; That describes in JP-A-10-309553 at full speed advertises the high cleanliness air, so that by film surface isolation sediment, and comes the sedimental method of isolated at suction by adjacent suction opening; And the ultrasonic vibration pressurized air of describing in JP-A-7-333613 of advertising separates sediment and suction this sedimental method (for example, by Shinko Co., the NEW ULTRASONIC CLEANER of Ltd. production).
In addition, also have adaptable wet dust removal method, for example, film is incorporated into rinse bath and separates sedimental method by ultrasonic vibrator; In film, insert cleaning solution, the method for advertising high-speed air and aspirating as what in JP-B-49-13020, describe; As in JP-A-2001-38306, describe pass through the liquid dampener rub continuously nethike embrane and then with spray liquid to the friction surface to reach the method for cleaning.In these dust collection methods, consider the effect of dedusting, method by ultrasonic dedusting and the method by wet dust removal are particularly preferred.
In addition, considering the efficient that increases dedusting and suppress dust adhesion, is particularly preferred at the static that removes on the striping stilt before the dust collecting process.In order to obtain such neutralizing method, might use the electro-dissociator of corona discharge systems, use up for example electro-dissociator of the radiating system of UV and soft X-ray etc.Before dedusting and coating and after, this film stilt preferably has and is no more than 1,000V more preferably no more than 300V, and especially preferably is no more than the charging voltage of 100V.
From keeping the viewpoint of film flatness, preferably the temperature of acylated cellulose is controlled in these are handled and is not higher than Tg, particularly be no more than 150 ℃.
Film of the present invention is being used as under the situation of polarization board protective film; adhere under the situation on the light polarizing film acidylating cellulose membrane; from with the adhering angle of light polarizing film, especially preferably carry out acid treatment or alkali treatment, promptly acylated cellulose is carried out saponification and handles.
Wait from adhesiveness, cellulose acylate film preferably has 55mN/m or more, and more preferably 60mN/m or more and be no more than the surface energy of 75mN/Md.This surface energy can be adjusted by above-mentioned surface treatment.
4-(3) coating:
Each of film of the present invention layer can form by following coating process, but should not be considered as the restriction that the present invention is subjected to these methods.
The known method that application arranged here for example dip coated method, air is scraped slurry rubbing method, plate washer rubbing method, rolling method, line rod rubbing method, texturing rubbing method and extrusion coated method (cloth mould rubbing method) (referring to United States Patent (USP) the 2nd, 681, No. 294) and miniature carving flower rubbing method.In these methods, miniature carving flower coating process and Bu Mo rubbing method are preferred.
Here indication to be applied to " miniature carving flower coating process " of the present invention be a kind of like this coating process, it is characterized in that: with diameter is 10-100mm, preferred about 20-50mm and below the engraved roll that its whole outer surface is carved the texturing pattern is placed on stilt, and rotate engraved roll in the opposite direction with sender simultaneously with holder, and wipe unnecessary coating solution off from the surface of described engraved roll by scraper, and the coating solution that is at the upper surface of stilt under the state of free state fixed amount is sent on the bottom surface of stilt, thereby finishes coating.Transparent support thing under the as-rolled condition is winded out continuously, and by this miniature carving flower rubbing method, and hard conating and the one deck at least that contains in the low-index layer of basic surplus fluorine coating olefin polymer can be coated on the one side of the stilt that is winded out.
For the coating condition of miniature carving flower rubbing method, the number of lines of the texturing pattern of engraving on engraved roll is preferably per inch 50-800 bar, and per inch 100-300 bar more preferably; The degree of depth of texturing pattern is preferably 1-600 μ m, and more preferably 5-200 μ m; The revolution of engraved roll is preferably 3-800rpm, more preferably 5-200rpm; And the transfer rate of stilt is preferably 0.5-100m/min, and more preferably 1-50m/min.
In order to supply with film of the present invention with high productivity, the extrusion coated method of advantageous applications (cloth mould rubbing method).Particularly, being disclosed in production method among the JP-A-2006-122889 can be applied to have little wet coating weight and (be no more than 20cc/m
2) the zone, as in hard conating and the anti-reflection layer, thereby can improve the homogeneity of film.
4-(4)＜drying 〉
Preferably directly or after coating on the stilt by other layer, film of the present invention is sent to heating to come the zone of dry solvent by heat radiator.
As the method for dry solvent, can use various knowledge.The instantiation of this knowledge is included in JP-A-2001-286817, JP-A-2001-314798, JPA-2003-126768, the method for describing among JP-A-2003-315505 and the JP-A-2004-34002.
The temperature of dry section is preferably 25 ℃-140 ℃; And the temperature in the preferred first partial desiccation district is low relatively, and the temperature in the second partial desiccation district is high relatively.Yet preferably this temperature is not higher than the temperature that composition in addition begins to volatilize that desolventizes in the coating composition that is contained in each layer.For example, but the optical free radical that uses with the ultraviolet ray hardening resin that on market, can buy generate in the agent, there have some optical free radicals to generate agent to be in minutes its tens percent just volatilized in 120 ℃ warm air.In addition, in simple function or difunctional acrylate monomer, has the monomer that volatilization takes place 100 ℃ warm air.In this case, the temperature of preferred dry section is not higher than the temperature that the composition the desolventizing in the coating composition that is included in each layer begins to volatilize.
In addition, about the dry air after the coating composition with each layer is coated on the supporting layer, preferably solids content is 1-50% in coating composition, and in order to prevent the even property of uneven drying, the preferred lip-deep air velocity of coated film is in the scope of 0.1-2m/sec.
In addition, after the coating composition with each layer is coated on the stilt, at dry section, when the temperature difference on the transfer roller that the makes contact stilt surface opposite with coating surface falls into 0 ℃-20 ℃ scope, can prevent that the inhomogeneous uneven drying that causes is even to be taken place because the heat on the transfer roller transmits, thereby, be preferred like this.
4-(5) sclerosis:
After dry solvent, make film process of the present invention heat the section that makes the sclerosis of each layer coated film, thereby coated film is hardened by ionising radiation and/or by heat radiator.
Preferably at 70 ℃ or higher and be not higher than under 130 ℃ the temperature, next by being that the activity of representative can be hardened to it by ray (active energy rays) with the ultraviolet ray to 5 minutes-20 minutes time of film heating of the present invention.
The heat hardening temperature is preferably 70 ℃ or higher but be not higher than 120 ℃, and most preferably 80 ℃ or higher and be not higher than 115 ℃.
In the present invention, the kind of ionising radiation does not have specific restriction, and can suitably select from ultraviolet ray, electron beam, near ultraviolet ray, visible light, near infrared ray, infrared ray and X-ray according to the kind of the hardenable compositions that forms film.Wherein, ultraviolet ray and electron beam are preferred; And from handling simply easily and obtaining high-octane viewpoint easily, ultraviolet ray is particularly preferred.
As the ultraviolet light source that is used for photopolymerization ultraviolet ray reactive compound, as long as it can send ultraviolet ray, any light source all is operable.Can use for example low-pressure mercury vapor lamps, middle pressure mercury vapor light, high-pressure mercury vapor lamp, ultra high pressure mercury vapour lamp, carbon arc lamp, metal halide lamp, xenon lamp etc.In addition, can also use ArF excimer laser, KrF excimer laser, excited quasi-molecular lampbulb, synchrotron radiation device etc.In all these, can preferably use ultra high pressure mercury vapour lamp, high-pressure mercury vapor lamp, low-pressure mercury vapor lamps, carbon arc lamp, xenon arc lamp and metal halide lamp.
In addition, can similarly use electron beam.As electron beam, here can enumerate from different electron-beam accelerators for example Cockcroft-Walton type electron-beam accelerator, van deGraaff type electron-beam accelerator, resonant transformation type electron-beam accelerator, insulating core transformer type electron-beam accelerator, line style electron-beam accelerator, that meter type electron-beam accelerator and the emission of high-frequency type electron-beam accelerator have a 50-1,000keV, and the electron beam of the energy of preferred 100-300keV.
Radiation condition changes according to each lamp.The energy intensity of radiation dose is preferably 10mJ/cm
2Or more, 50mJ/cm more preferably
2-10,000mJ/cm
2, and be preferably 50mJ/cm especially
2-2,000mJ/cm
2In the case, based on center greatest irradiation dosage, on thin plate (web) Width, comprise two ends radiation dose distribute and to be preferably 50-100%, and more preferably 80-100%.
In the present invention, preferably make at least one superimposed layer sclerosis on stilt: be no more than in the atmosphere of 10 volume % in oxygen concentration by following steps, radiation ionization radiation under the state of radiation ionization radiation, and under 60 ℃ or higher film surface temperature, after the radiation of beginning radiation ionization, heated 0.5 second or more time.
Also preferred heating is in the radiation ionization radiation or afterwards, carries out in oxygen concentration is no more than the atmosphere of 3 volume %.
Particularly, preferably harden by the method as low-index layer outermost and that have thin thickness.This sclerous reaction is quickened by heating, has the good physical property and the film of chemical resistance thereby can form.
The time that is used for the radiation ionization radiation is preferably 0.7 second or is more and be no more than 60 seconds, and preferred 0.7 second or more and be no more than 10 seconds.When the time that is used for the radiation ionization radiation is no more than 0.5 second, can not reach sclerosis up hill and dale to such an extent as to can not finish sclerous reaction.In addition, owing to need plant bulk to become big and need the amount of inert gas to increase, therefore, it is not preferred keeping hypoxia condition for a long time.
Preferred film is to be no more than under the atmosphere of 6 volume % in oxygen concentration, but cross-linking reaction by the ionising radiation hardening compound or polyreaction form.Oxygen concentration in this atmosphere especially preferably is no more than 2 volume % more preferably no more than 4 volume %, and is most preferably not exceeding 1 volume %.Surpass necessary concentration for oxygen concentration is eased down to, need for example nitrogen of a large amount of inert gases, therefore, from the viewpoint of production cost, this is not preferred.
As oxygen concentration being controlled to the measure that is no more than 10 volume %, preferably replace air (nitrogen gas concn: about 79 volume %, oxygen concentration: about 21 volume %) with other gas.Especially preferably replace (cleaning) air with nitrogen.
By inert gas being joined the ionising radiation radiation chamber and setting inert gas is blown into radiation chamber thin plate entrance side lightly, not only can discharge and follow the air that transports and carry secretly and reduce concentration of oxygen in the reaction chamber effectively, and can be reduced in effectively owing to oxygen has sizable oxygen concentration on the polar surface (polar surface) of big sclerosis obstacle.The direction of the inert gas flow of the thin plate entrance side of radiation chamber can be controlled by the air supply of adjustment radiation chamber and the balance between the consumption.
The method of the air of carrying secretly about discharge, the preferred employing directly with the method for inert blowing gas at thin sheet surface.
In addition, remove oxygen on the thin sheet surface in advance, might make more effective that sclerosis carries out by being provided at cup before the above-mentioned reaction chamber.In addition, in order to effectively utilize inert gas, constitute the side of thin plate entrance side of ionising radiation reaction chamber or cup and the gap between the thin sheet surface and be preferably 0.2-15mm, more preferably 0.2-10mm, and more preferably 0.2-5mm.Yet,, be necessary to connect and engage this thin plate in order to produce thin plate continuously.In order to connect, widely used method is with stickups such as connecting bands with it.Therefore, when the inlet face and the gap between this thin plate of ionising radiation reaction chamber or cup narrow, then caused for example problem that is stuck of connecting band of Connection Element.Therefore, in order to make this gap turn narrow, at least a portion that preferably makes the inlet face of ionising radiation reaction chamber or cup is transportable, to such an extent as to when link entered, this gap was to be broadened corresponding to the ratio that connects thickness.In order to realize this point, adaptable method has: make the inlet face of ionising radiation reaction chamber or cup on the direction that moves, can move forward and backward and when link passes through, move forward and backward, thus the method that the gap is broadened; And the inlet face that makes ionising radiation reaction chamber or cup can move on perpendicular to the direction of thin sheet surface and when from then on link pass through, move up and down, thus the method that the gap is broadened.
In sclerosis, preferably with 60 ℃ or higher and be no more than 170 ℃ temperature to film surface heating.When heating-up temperature was lower than 60 ℃, it was low to add thermal effect, yet, when it surpasses 170 ℃, caused for example problem of substrate deformation.More preferably 60 ℃-100 ℃ of heating-up temperatures.The temperature on " the film surface " of indication means the film surface of the layer that will be hardened in this article.In addition, after beginning UV irradiation, be used for reaching the needed time of said temperature and be 0.1 second or more and be no more than 300 seconds, and more preferably no more than 10 seconds.Time in the temperature with the film surface remains on the said temperature scope is too short, then can not quicken to form the reaction of the hardenable compositions of film.On the other hand, when it was oversize, the optical property of this film was lowered, and had caused that here equipment becomes big problem aborning.
Though heating means are not specifically limited, and its preferred examples comprises a roller of heating and the method that it is contacted with this film; Advertise the method for heated nitrogen; Method with far infrared or infrared radiation.For example hot water, steam and oil flow into the method that heats in the metallic roll of rotation also can to use the medium of describing in No. the 2523574th, Jap.P. that makes.As the measure of heating, can use dielectric warm-up mill etc.
Use the ultraviolet radiation can be at every turn when each constitutes multilayer a layer is provided or after stacked, carry out.Alternatively, radiation can be by making them in conjunction with carrying out.From the viewpoint of throughput rate, preferred ultraviolet ray is shone after stacked a plurality of layers.
In the present invention, can be by repeatedly make the sclerosis of one deck at least that is layered on the stilt with the ionization radiation irradiation.In this case, preferred ionizing radiation exposure is carried out twice in oxygen concentration is no more than the successive reaction chamber of 3 volume % at least.By in having the reaction chamber of identical low oxygen concentration, carrying out ionization radiation irradiation repeatedly, can guarantee to be used to harden the necessary reaction time effectively.
Particularly, under the situation that increases speed of production for high productivity,, be necessary to carry out ionization radiation irradiation repeatedly in order to ensure the essential ionising radiation energy of sclerous reaction.
In addition, under hardening ratio [100-(residual functional group content)] is situation less than 100% value, provide thereon the layer and by in ionising radiation and/or the heat hardening, when the hardening ratio that provides before the upper strata is provided for the hardening ratio of lower floor, adhesiveness between this lower floor and this upper strata is enhanced, thereby this is preferred.
4-(6) operates (handling):
In order to produce film of the present invention continuously, carried out following steps: transportation is in the step of the support membrane of as-rolled condition continuously; Be used to be coated with step with dry paint solution; The step of coated film is used to harden; With the step of rolling support membrane with hardened layer.
The film stilt is to be transported to the decontamination chamber continuously from the film stilt that is in as-rolled condition; In this decontamination chamber, remove the static of band on the film stilt by destaticing the unit; And next other is removed attached to the material on the film stilt by dust removing units.Next, in the coating parts in being placed on the decontamination chamber coating solution is coated on the film stilt, and will this applied film stilt delivers in the hothouse and carry out drying.
The film stilt that will have dry dope layer from hothouse is transported to the hardening cabinet, and makes monomer polymerization and the sclerosis that is included in the dope layer.In addition, the film stilt that will have hardened layer is delivered to the sclerosis part, thereby finishes sclerosis; And the film stilt that will have complete hardened layer rolls and becomes as-rolled condition.
Abovementioned steps can form carrying out each time of each layer.By a plurality of coated portion/hothouses/sclerosis part is provided, also might carry out the formation of each layer.
In order to prepare film of the present invention, preferably in the microfiltration operation of above-mentioned coating solution, the drying steps that in the air atmosphere of high cleanliness, carries out the application step in coated portion and in hothouse, carry out, and preferably before being coated with, pollutant on the film and dust are all removed fully.Based on the air cleanliness according to Federal Standard No.209E, (0.5 μ m or bigger granule number are no more than 353/m to wish air cleanliness in application step and the drying steps to be 10 grades
3) or higher, and (0.5 μ m or bigger granule number are no more than 35.5/m more to wish to be 1 grade
3) or higher.In addition, also preferably for example transport and roll that air cleanliness is high in the step in the step except coating and drying steps.
4-(7) saponification is handled
In film one or two surface protection film preparation Polarizer of the application of the invention, preferably by making the surface hydrophilic that adheres to that side of light polarizing film improve the adhesion of adhesive surface as light polarizing film.
The method of (a) in alkaline solution, flooding
This method is that film is flooded in alkaline solution, thereby has the measure of active all surface on the whole film of the saponification surface with alkali.Because this method does not need special equipment, is preferred from the cost angle.Sodium hydrate aqueous solution is preferably as this alkaline solution.The concentration of alkaline solution is preferably the 0.5-3 mol, and preferred especially 1-2 mol; And the fluid temperature of alkaline solution is preferably 30-75 ℃, and preferred 40-60 ℃ especially.
Though the combination of above-mentioned saponification condition is the combination of appropriate relatively condition, it can be provided with by the configuration of raw material and film and the contact angle of hope.
After immersing alkaline solution, preferred water cleans up hill and dale this film or preferably this film is immersed in diluted acid, thus in and alkaline components so that alkaline components does not remain in the film.
Handle by saponification, with the surperficial facing surfaces that has dope layer by hydrophilicity-imparting treatment.The diaphragm that is used for Polarizer is to provide use after the hydrophiling surface adhesion of transparent support thing is on light polarizing film making.
The surface of this hydrophiling is effective for the adhesiveness that improves with the adhesive surface that is made as principal ingredient by polyvinyl alcohol (PVA).
Handle about saponification, from the viewpoint of the adhesion of light polarizing film, preferably the contact angle of the surface of the transparent support thing in the side relative with there being that side of dope layer and water is low as far as possible.On the other hand, in dipping method since from the surface that has dope layer to the film the inside, film is subjected to the destruction of alkali simultaneously, therefore uses necessary and minimum condition is very important.When the contact angle of the transparent support thing of opposite flank and water is used as the destructing index that each layer be subjected to alkali, especially when the transparent support thing is triacetyl cellulose, this contact angle is preferably 10 °-50 °, more preferably 30 °-50 °, and more preferably 40 °-50 °.When this contact angle surpasses 50 °, caused and the problem of the adhesion of light polarizing film that therefore, this is not preferred.On the other hand, when it was lower than 10 °, the destruction that film is subjected to was too big, and physical strength is hindered, and therefore, this is not preferred.
(b) method of alkaline solution
As the measure of in above-mentioned dipping method, avoiding each damage layer, preferably adopt the method for following alkaline solution: by only with that side opposite surfaces of the surface that has dope layer on alkaline solution, next heating, water cleans and is dry.By the way, in this case, here " coating " of indication mean alkaline solution etc. only contacted with the surface of carrying out saponification.Except coating, also comprise spraying, contact with the band that contains liquid, perhaps other modes.By adopting such method, be to require separately owing to be used for the device and the step of alkaline solution, consider from the cost aspect that therefore this method is not as dipping method (a).On the other hand, because alkaline solution only contacts with the surface of having used the saponification processing, therefore on the surface of opposition side, can provide and use the not layer of the raw material of alkali resistance solution.For example, in the film of vapor deposition or sol gel film because alkaline solution has caused for example burn into dissolving and peeling off of a lot of influences.Correspondingly, though do not wish to provide such vapor deposition film or sol gel film,, so might use such deposited film or sol gel film and do not bring any problem because this film contact with solution in this method by dipping method.
In all aforementioned method for saponification (a)-(b), because saponification can carry out after the film of as-rolled condition being rolled and form each layer from stilt, so it can be added in the film production stage afterwards and reach continuous operation.In addition, carry out the situation of same operation with a slice a slice and compare,, might prepare Polarizer more efficiently by to pasting step continuously by similarly winding out the Polarizer that stilt makes jointly.
(c) reach the method for saponification by laminated film protection
Method (b) as the front; be not enough to resist under the situation of alkaline solution at dope layer; after forming last one deck; by laminated film being adhered on the last one layer surface of formation and being immersed in the alkaline solution then; might only make with the three acyl group cellulose surface hydrophilings that form opposition side on the last one layer surface, peel off this laminated film then.According to this method, also might be only be enough to not destroy dope layer as the hydrophilicity-imparting treatment of polarization board protective film to using with the three acyl group cellulose surfaces that form opposition side on the last one layer surface.Compare with the method (b) of front, produce as refuse, do not need to be used for the special device of alkaline solution though the advantage that this method comprises is a laminated film.
(d) method of after forming the middle layer, in alkaline solution, flooding:
At lower floor's alkali resistance solution and the upper strata is not enough under the situation of alkali resistance solution, after forming lower floor, can be in alkaline solution with this film immersion, thus make its two surface hydrophilics and form the upper strata then.It is complicated that this production technology becomes.Yet, for example, in the film that constitutes by antiglare layer and the low-index layer that makes by fluorine-containing sol gel film, have under the situation of hydrophilic layer the advantage of having brought the interlayer adhesion force between antiglare layer and low-index layer to be enhanced.
(e) method of formation dope layer on the tri acetyl cellulose membrane film of saponification in advance:
Dope layer can directly or by other layer be formed at by immersing alkaline solution or alternate manner by on the arbitrary surface of tri acetyl cellulose membrane film of saponification in advance.Triacetyl cellulose be by the situation that immerses the alkaline solution saponification under, might destroy with by this saponification by the interlayer adhesion force on the surface of the triacetyl cellulose of hydrophiling.In this case, might solve this problem by after saponification, making the surface that only forms dope layer pass through corona discharge or glow discharge processing or alternate manner, thereby remove by the surface of hydrophiling.In addition, contain at dope layer under the situation of hydrophilic radical, interlayer adhesion force might improve.
The preparation of 4-(8) light polarizing film
By with film of the present invention as light polarizing film be positioned at diaphragm on its one or both sides, film of the present invention can be used as light polarizing film.
When using conventional cellulose acetate membrane as other diaphragm, film of the present invention can be used as diaphragm.Yet, the preferred cellulose acetate membrane of producing by above-mentioned solution film forming method and on Width, stretch that is in as-rolled condition that uses with the draw ratio of 10-100%.
In addition, in Polarizer of the present invention, preferably it surface is made by antireflection film, and other diaphragm is the optical compensation films that is made by liquid-crystal compounds.
The example of light polarizing film comprises the iodo light polarizing film, uses the dye-based light polarizing film and the polyalkenyl light polarizing film of dichroic dyestuff.Iodo light polarizing film and dye-based light polarizing film are normally by using the polyvinyl alcohol (PVA) basement membrane to produce.
The slow axis of the transparent support thing of antireflection film or cellulose acetate membrane and the conveying axis of the light polarizing film layout that almost is parallel to each other.
For the throughput rate of Polarizer, the moisture vapor transmission rate of diaphragm is very important.Light polarizing film adheres to by aqueous binder mutually with diaphragm, and the solvent diffusion of this bonding agent is in diaphragm, thereby has reached drying.When the moisture vapor transmission rate of this diaphragm was high, drying accelerated, and throughput rate is enhanced.Yet, when moisture vapor transmission rate is too high, utilizing the environment (under high humility) of liquid crystal indicator, moisture enters this light polarizing film, thus polarization capacity is lowered.
The moisture vapor transmission rate of diaphragm is to determine by thickness, free volume, water wettability or the hydrophobicity etc. of transparent support thing or polymer film (with the polymerisable liquid crystal compound).
When film of the present invention was used as the diaphragm that is used for Polarizer, moisture vapor transmission rate was preferably 100-1,000g/m
224hrs, and more preferably 300-700g/m
224hrs.
In the formation of film, the thickness of transparent support thing can or compress and adjust by cast gate flowing velocity (lipflow rate) and linear velocity or stretching.Because moisture vapor transmission rate changes according to the primary raw material that will use, therefore might this moisture vapor transmission rate be set in the preferred range by adjusting thickness.
In the formation of film, the free volume of transparent support thing can be adjusted by baking temperature and time.
In this case, because moisture vapor transmission rate also changes according to the primary raw material that will use, therefore moisture vapor transmission rate might be set in the preferred range by regulating free volume.
The water wettability of transparent support thing or hydrophobicity can be regulated by adding adjuvant.By add hydrophilic additive in aforementioned free volume, moisture vapor transmission rate uprises, and by adding hydrophobic additive, moisture vapor transmission rate is reduced.
By controlling above-mentioned moisture vapor transmission rate independently, might produce Polarizer with high productivity cheaply with optical compensation performance.
As light polarizing film, can use known light polarizing film and the light polarizing film that cuts out from the axial light polarizing film of the neither parallel also off plumb of absorption axes with axial direction.The axial light polarizing film of neither parallel with the axial direction also off plumb of absorption axes is to make by following method.
That is to say, this light polarizing film be by when keeping the film two ends with holding unit by the tractive force light polarizing film that the polymer film that provides continuously makes that stretches is provided.This light polarizing film can be produced in following drawing process: at least in the Width of the film ratio stretched film with 1.1: 20.0 times; Between the holding unit at film two ends in the difference of the translational speed of axial direction in 3%; And the moving direction of film curls under the state that keeps the film two ends, thereby the angle between the actual draw direction of the moving direction of film and film is with 20 ° of-70 ° of inclinations in the outlet of the step that keeps the film two ends.Particularly, from the viewpoint of throughput rate, preferably use the light polarizing film of above-mentioned angle with 45 ° of inclinations.
The drawing process of polymer film is described in detail in JP-A-2002-86554, in [0020]-[0030] section.
Also preferred in two diaphragms of polarizer, the film except antireflection film is the optical compensation films with the optical compensating layer that comprises optical anisotropic layer.This optical compensation films (phase shift films) can improve the field-of-view angle performance of LCDs.
Known optical compensation films can be used as this optical compensation films.From the viewpoint of the angle of widening the vision, the optical compensation films of describing in JP-A-2001-100042 is preferred.
5. operational version of the present invention
Film of the present invention is used to image display device for example in liquid crystal indicator (LCD), plasma display panel (PDP), el display device (ELD) and the CRT display (CRT).Can be used in known display for example on the plasma display panel (PDP) according to light filter of the present invention.
5-(1) liquid crystal indicator:
Film of the present invention can advantageously be used in image display device for example on the liquid crystal indicator.Preferably the outermost layer at display uses film of the present invention.
Liquid crystal indicator has liquid crystal cell and is positioned at two Polarizers of its both sides, and this liquid crystal cell supports liquid crystal between two electrode basement.In addition, arrange an optical anisotropic layer between can a Polarizer in liquid crystal cell and Polarizer, two optical anisotropic layers of layout between each that perhaps can be in liquid crystal cell and two Polarizers.
Preferred this liquid crystal cell is TN type, VA type, OCB type, IPS type or ECB type.
＜TN type 〉
In TN type liquid crystal cell, the rod shaped liquid crystal molecule substantial horizontal is arranged and is further arranged with 60 °-120 ° twisted state when not applying voltage.
The colored TFT liquid crystal indicator of the most frequently used work of TN type liquid crystal cell and being described in a lot of lists of references.
＜VA type 〉
In VA type liquid crystal cell, rod shaped liquid crystal molecule perpendicular state is arranged when not applying voltage.
VA type liquid crystal cell comprises, except (1) rod shaped liquid crystal molecule perpendicular state when not applying voltage is arranged, and the sense stricto VA type liquid crystal cell (being described in JP-A-2-176625) that substantial horizontal is arranged when applying voltage in addition, (2) multidomain VA type (MVA type) liquid crystal cell that is used to enlarge the visual angle (is described in SID 97, Digest of Tech.Papers, 28 (1997), the 845th page), (3) rod shaped liquid crystal molecule perpendicular state is arranged when not applying voltage, and the liquid crystal cell that distortion multidomain arrange type (n-ASM type) taken place when applying voltage (is described in Preprints of Forum on Liquid Crystal, 58-59 page or leaf (1998) and (4) SURVIVAL type liquid crystal cell (being published in LCDInternational 98).
＜OCB type 〉
OCB type liquid crystal cell is the liquid crystal cell of arrange type of curling, rod shaped liquid crystal molecule (with the symmetric mode) arranged with substantial reverse in the upper and lower of liquid crystal cell wherein, and be disclosed in United States Patent (USP) the 4th, 583, and 825 and 5,410, in No. 422.The arrange type liquid crystal cell has self optical compensation ability because rod shaped liquid crystal molecule in the upper and lower of liquid crystal cell symmetric offset spread, curls.Therefore, the type of this liquid crystal is named as OCB (optical compensation curls-optiallycompersatory bend) liquid crystal type.Liquid crystal indicator with curling arrange type has for example fast advantage of reaction velocity.
＜IPS type 〉
IPS type liquid crystal cell is by applying the switched system of transverse electric field to nematic crystal, and is described in detail in Proc.IDRC (Asia Display ' 95), 577-580 page or leaf and 707-710 page or leaf.
＜ECB type 〉
In ECB type liquid crystal cell, the rod shaped liquid crystal molecule substantial horizontal is arranged when not applying voltage.The ECB type is to have the liquid crystal display type of the simplest structure and for example be described in detail among the JP-A-5-203946.
The display of 5-(2) except liquid crystal indicator
<PDP>
Plasma display panel (PDP) normally is made of gas, glass substrate, electrode, contact conductor material, thick film screen printing material and fluorescent material.Glass substrate is to be made of front glass substrate and back two of glass substrate.In each sheet of two glass substrates, electrode and insulation course have all been formed.In the glass substrate of back, further formed fluorescent material.Two glass substrates are assembled, and with aeroseal between them.
Plasma display panel (PDP) has appeared on the market.Plasma display panel is described among JP-A-5-205643 and the JP-A-9-306366.
The situation that may have plasma display panel arranged in front header board.Preferred this header board has the sufficient intensity of protection plasma display panel.This header board can use or use by it is directly pasted on the plasma display panel main body at distance plasma display panel one segment distance.
, optical filter directly can be adhered on the display surface for example in the plasma display panel at image display device.In addition, provide in the display front under the situation of header board, also light filter might have been adhered on the front side (outside) or rear side (display side) of header board.
＜touch-screen 〉
Film of the present invention can be applied on the touch-screen as described in JP-A-5-127822 and JP-A-2002-48913.
＜organic EL 〉
Film of the present invention can be used as the substrate (substrate membrane) or the diaphragm of organic EL etc.
Under film of the present invention is used in the situation of organic EL etc., can use the content that is described among JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP-A-2001-192653, JP-A-2001-335776, JP-A-2001-247859, JP-A-2001-181616, JP-A-2001-181617, JP-A-2002-181816, JP-A-2002-181617 and the JP-A-2002-056976.In addition, preferred combination is used JP-A-2001-148291, the content of describing among JP-A-2001-221916 and the JP-A-2001-231443.
6. various eigenwerts:
To show various method of testing of the present invention and preferable feature value below.
6-(1) reflectivity:
Measurement about specular reflectance and tone (color taste), by using inside the spectrophotometer " V-550 " of adapter " ARV-474 " (being made by JASCO Corporation) has been installed, to have measured incident angle be 5 ° and output angle is-5 ° specular reflectance in the wavelength region may of 380-780nm, and calculated the average reflectance of 450-650nm, thereby estimated antireflection property.
For anti-dazzle antireflection film of the present invention, specular reflectance be no more than 2.0% and transmissivity be 90% or mostly be preferred, this is because can suppress outside reflection of light and can improve visibility.Specular reflectance especially preferably is no more than 1.5%.Most preferably be no more than 1.0% by adopting the layer configuration of in 3-(d), describing that this reflectivity is controlled to.
6-(2) tone:
About the Polarizer with antireflection ability of the present invention, can estimate that incident angle is the conventional catoptrical tone of 5 ° incident light in wavelength is the zone of CIE standard light source D65 of 380-780nm, promptly by definite CIE1976L
*, a
*And b
*The L of color space
*, a
*And b
*The tone of value.
Preferred L
*, a
*And b
*Value satisfies relational expression (3≤L respectively
*≤ 20), (7≤a
*≤ 7), (10≤b
*≤ 10).By making these values fall into above-mentioned scope, the reddish violet that is considered to problem up to now is lowered to the catoptrical tone of bluish violet.In addition, work as L
*, a
*And b
*Value satisfies relational expression (3≤L respectively
*≤ 10), (0≤a
*≤ 5), (7≤b
*≤ 0) time, above-mentioned FAQs is greatly diminished, thereby be used at Polarizer under the situation of liquid crystal indicator, though exterior light have high brightness, for example in the room, reflected slightly by the light of fluorescent light emission in, to such an extent as to tone is neutral can not arousing attention.Specifically, at (a
*≤ 7) under the situation, it is too strong that redness does not become, and at (a
*〉=7) under the situation, it is too strong that cyan does not become, and therefore, this is preferred.In addition, at (b
*〉=7) under the situation, it is too strong that blueness does not become, and at (b
*≤ 0) under the situation, it is too strong that yellow does not become, and therefore, this is preferred.
In addition, catoptrical uniform hue degree can be from L
*a
*b
*A on the chromatic diagram
*And b
*Obtain, they are the catoptrical reflectance spectrums according to 380nm-680nm, determine according to the tone conversion ratio of following numeral expression formula (21).
Numeral expression formula (21)
[(a
*) the tone conversion ratio]=[(a
* Max-a
* Min)/a
* Av] * 100
[(b
*) the tone conversion ratio]=[(b
* Max-b
* Min)/b
* Av] * 100
A here
* MaxAnd a
* MinRepresent a respectively
*The maximal value and the minimum value of value; b
* MaxAnd b
* MinRepresent b respectively
*The maximal value and the minimum value of value; a
* AvAnd b
* AvRepresent a respectively
*The mean value and the b of value
*The mean value of value.The conversion ratio of color preferably is no more than 30% separately, more preferably no more than 20%, and is most preferably not exceeding 8%.
In addition, film of the present invention preferably have be no more than 15, more preferably no more than 10 and be most preferably not exceeding 5 before the weatherability test and tone reversal Δ E afterwards
WAs Δ E
WWhen falling into this scope, might obtain the reduction of low reflectivity and reflected light tone.Correspondingly, for example, be applied at film of the present invention under the outermost situation of image display device, even when the light of being launched by fluorescent light in the room is reflected slightly, tone is neutral and quality display image improves, and therefore, this is preferred.
Aforesaid tonal variation Δ E
WCan determine according to following numeral expression formula (22).
Numeral expression formula (22)
ΔE
W＝[(ΔL
W)
2+(Δa
W)
2+(Δb
W)
2]
1/2
Here, Δ L
W, Δ a
WWith Δ b
WRepresent weather resistance test front and back L respectively
*Variable quantity, a of value
*The variable quantity and the b of value
*The variable quantity of value.
6-(3) transmission image sharpness
The transmission image sharpness can be by by Suga Test Instruments Co., the image definition instrument (MICM-2D type) that Ltd. produces, measures according to JIS K7105 by using gap width to comb as the light of 0.5mm.
Film of the present invention preferably has the transmission image sharpness of 15-100%.The transmission image sharpness normally shows the index of the fringe of the image that sees through film and be projected.This value is big more, and then the sharpness of the image of seeing by film is good more.When film of the present invention was antiglare film, the transmission image sharpness of this film was preferably 15%-40%, and this is because can obtain enough anti-dazzle performances like this and image blurring and reduce the improvement of darkroom contrast.
6-(4) surfaceness:
The measurement of center line average roughness (Ra) can be carried out according to JIS B0601.
Design antireflection film of the present invention, thereby for the surface imperfection shape, center line average roughness Ra is in the scope of 0.08-0.3 μ m; 10 mean roughness Rz are no more than 10 times of Ra; Average top/root distance is 1-100 μ m from Sm; From the irregularity deepest part the standard deviation of height of projection be no more than 0.5 μ m; Based on center line on average push up/root distance is no more than 20 μ m from the standard deviation of Sm; And incident angle is that 0-5 ° face accounts for 10% or more, and this is because obtained enough anti-dazzle performances and visual even roughness sense.When Ra is less than 0.08 μ m, can not obtain enough anti-dazzle performances, yet when it surpasses 0.30 μ m, cause the problem of for example flash of light and when reflection exterior light surface albefaction.
6-(5) turbidity
The turbidity of film of the present invention is the turbidity value that defines in JIS K7105, and it is to use the Co. by Nippon Denshoku Industries, Ltd. the nephelometer of Sheng Chaning " NDH-1001DP " is measured as " turbidity=[(scattered light)/(all transmitted lights)] * 100 (%) " automatically according to the method for testing that defines in JIS K7361-1.
Carry one in passing, surface haze and inner turbidity can be measured by following procedure.
(1) total turbidity value (H) of film is measured according to JIS K7136.
(2) several silicone oil are added on the front surface of film of that side of low-index layer place and on its rear surface; By two thickness is in the middle of the thick glass plate of 1mm (MICRO SLIDEGLASS Product No.S9111, by Matsunami Glass Ind., Ltd. produces) the past rear side is added in this film, thereby this film is closely contacted with these two glass plates fully; Under the state of cancellation surface haze, measure turbidity; And will be by cutting by only silicone oil being placed on the inside turbidity (Hi) that the value of measuring separately in two glass plates that turbidity obtained is calculated as film.
(3) value that will obtain by the inside turbidity (Hi) that cuts calculating in superincumbent (2) from top (1) in total turbidity (H) of measuring is calculated as surface haze (Hs).
6-(7) scratch-resistant
＜estimate scratch-resistant by steel wire 〉
By using frictional testing machine to carry out friction testing, can provide the index of scratch-resistant under the condition below.
The environmental baseline of-evaluation: 25 ℃, 60%RH
-friction material: steel wire (by Nippon Steel Wool Co., the GradeNo.0000 that Ltd. produces).This steel wire is wound into the tip member (1cm * 1cm) go up and with belt it is fixed that this testing machine will contact with sample.
-displacement (direction): 13cm
-friction velocity: 13cm/sec
-load: 500g/cm
2And 200g/cm
2
The contact area of-tip member: 1cm * 1cm
-friction number: 10 back and forth
The oiliness black ink is coated onto by the rear side of friction sample, and by reflected light range estimation or by from from by the difference assessment of the catoptrical amount of the other parts beyond the friction position by the cut of friction portion.
＜estimate scratch-resistant by the remover friction 〉
Under the condition below, carry out friction testing, the index of scratch-resistant might be provided by using frictional testing machine.
The environmental baseline of-evaluation: 25 ℃, 60%RH
-friction material: plastics remover (MONO, by Tombow Pencil Co., Ltd. produces).This plastics remover is fixed on the tip member of this testing machine that will contact with sample (in the 1cm * 1cm).
-displacement (direction): 4cm
-friction velocity: 2cm/sec
-load: 500g/cm
2
The contact area of-tip member: 1cm * 1cm
-friction number: 100 back and forth
The oiliness black ink is coated onto by the rear side of friction sample, and by reflected light range estimation or by from from by the difference assessment of the catoptrical amount of the other parts beyond the friction position by the cut of friction portion.
＜deflection test 〉
Scratch-resistant can be estimated from the wear extent of this test front and back sample according to the taber test of JIS K5400.
Preferred this wear extent is low as much as possible.
6-(8) hardness
＜pencil hardness 〉
The hardness of film of the present invention can be estimated according to the pencil hardness test of JIS K5400.
This pencil hardness is preferably H or higher, more preferably 2H or higher, and 3H or higher most preferably.
＜surface elastic modulus 〉
In the present invention, surface elastic modulus is the value by using little skin hardness testing machine (Fischer Scope H100VP-HCU is produced by Fischer Instruments K.K.) to determine.Particularly, surface elastic modulus is by using the four limit conical indenters (end face angle: 136 °) that made by adamas and making depth of cup be no more than the elastic modulus of measuring depth of cup, determining from the change of load and displacement under the suitable test load in the scope of 1 μ m when eliminating load.
In addition, also can skin hardness be defined as universal hardness by using above-mentioned little skin hardness testing machine.This universal hardness is to remove the value of this test load acquisition by measuring the depth of cup of four limit conical indenters and be used in the surface area that the geometry computations from this impression of the impression that produces under the aforementioned test load goes out under test load.Known between above-mentioned surface elastic modulus and universal hardness and had positive correlation.
The universal hardness of Ding Yi cross-linked polymer is by by using miniature hardness tester H100 according to following test procedure in the present invention, is the definite universal hardness (N/mm of cross-linked polymer film of 20-30 μ m to the thickness that hardens on glass plate and form
2) expression.
By selecting suitable metering bar coater, will be except containing cross-linked polymer, also contain the catalyzer, crosslinking chemical and the polymerization initiator that are necessary and solid content and be about 25% coating solution and be coated on Co. by Toshinriko, Ltd. the polishing wave carrier piece of Sheng Chaning is (on 26mm * 76mm * 1.2mm), so that thickness is about 20 μ m-30 μ m after sclerosis.Cross-linked polymer be can the situation of thermmohardening under, determine the thermmohardening condition (for example, following 10 minutes) that film is hardened fully in advance at 125 ℃; And at cross-linked polymer is can ionising radiation under the situation of sclerosis, determines curing condition (for example, oxygen concentration: 12ppm, the UV radiation dose: 75mJ/cm that film is hardened fully in advance
2).For each film, load is increased continuously 4mN from 0; 1/10 thickness that does not influence in the hardness that makes the substrate glasses plate is the peaked while, makes taper diamond head impression; And from the area of indentation A (mm under each load F
2) the average measurement value computer general hardness of N=6 of the F/A that determines.
In addition, skin hardness can be determined by the nano impress that is described among the JP-A-2004-354828.In this case, preferred hardness is 2GPa-4GPa, and the nano impress elastic modulus is 10GPa-30GPa.
The antifouling test of 6-(9)
＜marking ink is removed performance 〉
By bonding agent film is fixed on the glass surface; Under the condition of 25 ℃ and 60RH%, write down the circle three times that diameter is 5mm by the nib (carefully) of black marking pen " McKee Ultra-fine (Zebra Co., the trade name of Ltd.) "; After 5 seconds, use by the 10 stacked BEMCOT that close (trade name of Asahi Kasei Corporation) bundle, under the load of the degree that makes this BEMCOT bundle impression, carry out 20 of wipings back and forth.Under these conditions by repeat above-mentioned write with wiping till making that by wiping marking ink seal does not disappear, might estimate antifouling property according to wiping number that may wiping.
The wiping number that does not disappear up to the marking ink seal is preferably 5 or more, and preferred 10 or more.
About black marking ink, by using MAGIC INK No.700 (M700-T1 Black) Ultral-fine on sample, to draw diameter, with BEMCOT (producing) this circle of wiping by Asahi Kasei Corporation as the circle of 1cm and with its painted (painted) and kept 24 hours.Then, whether be wiped free of by marking ink and can estimate wiping properties.
6-(10) contact angle
Use contact angle meter (" CA-X " type contact angle meter, by Kyowa Interface ScienceCo., Ltd. produce), by using pure water in the needle tubing tip under the drying regime (20 ℃ and 65%RH), to prepare the drop of diameter, make it contact the drop for preparing on this film then with the surface of film as 1.0mm as liquid.The position of the point that is in contact with one another at film and liquid is defined as contact angle between the tangent line of liquid surface and film surface and containing the angle that side of liquid forms.
The contact angle of film of the present invention is preferably 94 ° or bigger, and more preferably 97 ° or bigger, and most preferably 101 ° or bigger.
6-(11) surface free energy
Surface energy can be determined by the absorption process that contact horn cupping, the method that is used for measuring wetting heat, the Foundationand Application of Wetting that published on Dec 10th, 1989 by RealizeAdvanced Technology Limited describe.Under the situation of film of the present invention, the preferred contact horn cupping that adopts.
Particularly, two kinds of solvents with known surface energy are dripped on the acetylation of cellulose film; On the point of crossing on drop surface and film surface, be used in the angle that forms between the tangent line drawn on the drop and the film surface and define the angle of containing that side of drop; And by calculating the surface energy that can calculate membrane.
The surface free energy of the film of the present invention of indication (γ s here
v: unit mN/m) means by being expressed as γ s
dWith γ s
hThe value γ s of summation
v(=γ s
d+ γ s
h) surface tension of antireflection film of definition, wherein γ s
dWith γ s
hBe referring to D.K.Owens, J.Appl.Polym.Sci. is in the time of 13,1974 (1969), by following simultaneous equations (a) with (b) respectively from being positioned at the pure water H on the antireflection film
2O and diiodomethane CH
2I
2Contact angle θ
H2OAnd θ
CH2I2, test is determined.As this γ s
vWhen little and surface free energy was low, the exclusion of this film was high and antifouling property is good usually.
Equation (a)
Equation (b)
The measurement of contact angle is under 25 ℃ and 60% condition film to be carried out 1 hour or the humidity control of longer time, the drop of 2 μ L is dripped on the film, by using by Kyowa InterfaceScience Co., Ltd. the automatic contact angle meter of Sheng Chaning, CA-V150 type and after 30 seconds are determined contact angle.
The surface free energy of film of the present invention preferably is no more than 25mN/m, and especially preferably is no more than 20mN/m.
6-(12) curls:
The measurement of curling is undertaken by the model that curls that uses the method A that is used to measure in JIS K7619-1988 " Determination of thecurl of photographic film ".
Measurement be 25 ℃ and relative humidity be 60% and 10 hours condition of controlled humidity under carry out.
In film of the present invention, curl preferably have by following numerical expression represent in-15 to+15 scopes, more preferably in-1 to+12 scope and the further preferred value in-10 to+10 scope.Be the situation of thin plate state under in coating this time, and the direction of measurement that curls in the sample is the carriage direction of substrate.
Numerical expression
Curl=1/R (R: radius-of-curvature (m))
This be used for preventing at film production, processing and on market operation the key character that crack or film separate takes place.Preferred crimp values falls into above-mentioned scope and is little.
Here, curling is to curl inwards on the occasion of the coated side that means film, is that negative value means that the membrane coat side direction is curling outward and curl.
In addition, in film of the present invention, according to aforementioned curling measuring method, when only relative humidity being changed to 80% and 10%, the absolute value of the difference of the crimp values between them is preferably 24-0 when respectively, more preferably 15-0, and 8-0 most preferably.This is under different damp conditions in the adhesive film, with operating performance, separate the feature relevant with the crack.
The fusible evaluation of 6-(13)
Film the layer between or the cohesive between stilt and the dope layer can be by following method evaluation.
By using paperknife, make on the film surface that has that side of dope layer through in 11 lines on the length and the cross cutting of 11 lines on width with the interval of 1mm, be total up to 100 squares thereby provide; Make the polyester pressure sensitive adhesive tape (No.31B) and their face contacts produced by Nitto Denko Corporation; And after stopping 24 hours, peel off test, thereby the existence that range estimation is peeled off or do not exist at identical position triplicate.
Preferred observed peeling off in 10 in 100 squares; And more preferably observed peeling off in 2 in 100 squares.
6-(14) fragility test (anti-crack property)
Anti-crack property is to be used for preventing at processing and cutting, the coating adhesive of handling for example coating, film and to adhere to the key character that the crack takes place on various materials.
Surface crack can be of a size of 35mm * 140mm by the film sample is cut into, and making it is to keep 2 hours under 60% the condition 25 ℃ and relative humidity, and it is rolled into cylindrical, begins to take place the curvature diameter in crack thereby measure.
For the anti-crack performance of film of the present invention, when being rolled, film make its coated side be positioned at outside time, and the curvature diameter that the crack takes place preferably is no more than 50mm, more preferably no more than 40mm, and is most preferably not exceeding 30mm.For the crack of marginal portion, the length that crack or crack preferably do not take place is on average less than 1mm.
6-(15) dust removal performance
Dust removal performance can be by adhering to film of the present invention on the monitor, dust (for example, the batting of futon or fiber) is sprayed onto on the monitor surface and by this dust of cleaning cloth wiping estimates.
Preferred this dust can be removed fully by six wipings; And more preferably this dust can be removed with interior wiping fully by three times.
The performance of 6-(16) liquid crystal indicator
To be described in method of evaluating performance and preferred state when being used in film of the present invention on the display device below.
To use TN type liquid crystal cell (TH-15TA2, by Matsushita Electric IndustrialCo., Ltd. the Polarizer of visual field side is peeled off in liquid crystal indicator production), and to its replacement, by bonding agent film of the present invention or Polarizer are adhered to, make coating surface be positioned at visual field side and make the axis of homology of Polarizer consistent with the Polarizer on sticking to this product.Various performances below can visually estimating by the various field-of-view angles in bright room, black simultaneously this liquid crystal indicator that shows.
The evaluation of＜image unevenness and tone 〉
By using the liquid crystal indicator of preparation, in the time of black demonstration (L1), the variation of unevenness and tone is visually estimated by a plurality of observers.
When 10 observers judge, the tonal variation and the white blur that preferably are no more than variation that 3 observers can recognize unevenness, left and right sides tone, change by temperature and humidity; And more preferably nobody can recognize them.
In addition, for outside reflection of light, can be by using fluorescent light from visually relatively estimating the variation of reflection.
＜black the light leak that shows 〉
From the polar angle orientation measurement of the preceding 45 ° azimuth direction of liquid crystal indicator and 70 ° the light leak rate of black demonstration.The light leak rate preferably is no more than 0.4%, and more preferably no more than 0.1%.
＜contrast and field-of-view angle 〉
For contrast and visual angle, can detect contrast rating on the left and right directions (with the orthogonal directions of the frictional direction of element) and visual angle (contrast rating be 10 or the scope of more perspective) by operational analysis instrument (EZ-Contrast 160D, by ELDIM produce).
Embodiment
Describe the present invention in detail with reference to embodiment below, but should not be considered as the present invention only limits to these embodiment.Among embodiment below and the synthetic embodiment, except as otherwise noted, term " % " is weight %.
[embodiment 1]
The preparation of＜antireflection film 〉
[synthesizing of fluoropolymer]
Synthetic embodiment 1: fluoropolymer P1's is synthetic
Internal capacity be 100mL the installation of making by stainless steel in the autoclave of stirrer; pour 40mL vinyl acetate, 14.7g hydroxyethyl vinyl ether (HEVE) and 0.55g two bay acyl peroxides into, and get rid of the air of this system inside and clean with nitrogen.In addition, (HFP) joins in the autoclave with the 25g hexafluoropropylene, and temperature is elevated to 65 ℃.Temperature in autoclave reaches in 65 ℃, and pressure is 5.4kg/cm
2Make reaction continue 8 hours when the temperature in keeping autoclave is 65 ℃, and reach 3.2kg/cm at pressure
2The time, stop heating, next make its cooling.
When internal temperature drops to room temperature, get rid of unreacted monomer, and open autoclave, and reaction solution is taken out.The reaction solution that is obtained is had high input in the big excessive hexane, remove by decant and desolvate, and the potpourri of precipitation is taken out.In addition, this polymer dissolution is precipitated twice again in amount of ethyl acetate and with hexane, thereby remove residual monomer fully.After drying, the mol ratio that has obtained the HFP of 28g and HEVE is 1/1 copolymer p 1.The polymkeric substance that is obtained has 15,000 number-average molecular weight.
Synthetic embodiment 2-5
If raw material is changed over table those shown in 1-5, with above-mentioned synthetic embodiment 1 in the synthetic substantially the same mode of P1 synthesize fluoropolymer P18, P37, P39 and P45.The number-average molecular weight of each fluoropolymer that is obtained all is shown in above-mentioned table 1 and 2.
Synthetic embodiment 6: fluoropolymer P49's is synthetic
Be 2dm3 and installed in the autoclave of stainless steel stirrer at internal capacity, pour the Syraplane FM-0721 of ethyl vinyl ether (EVE), 15.0g of hydroxyethyl vinyl ether (HEVE), the 28.8g of 2-propyl alcohol, the 52.9g of 2-butanone, the 33.0g of 133.0g and 3.9g V-65 into (by Wako Pure Chemical Co., Ltd. the polymerization initiator of Sheng Chaning), use the inside of nitrogen replacement system then.After in autoclave, further adding 184.1g hexafluoropropylene (HFP), temperature is elevated to 60 ℃.Temperature in autoclave reaches in 60 ℃, and pressure is 0.93MPa.Temperature in keeping autoclave is under 60 ℃, makes reaction continue 8hr.After this temperature of autoclave is brought up to 80 ℃ and make reaction continue other 1 hour.Become stage of 0.44Mpa at pressure, stop heating, and make this system cools.When internal temperature drops to room temperature, clean unreacted monomer.Opening autoclave then takes out reaction solution.The output of the polymkeric substance of Huo Deing is 217g like this.The number-average molecular weight of this polymkeric substance is 11,000.
Synthetic embodiment 7
With with above-described synthetic embodiment in the synthetic fluoropolymer P54 of synthetic essentially identical mode of P49.The number-average molecular weight of formed polymkeric substance is shown in the table 5.
Synthetic embodiment 8: tosilate synthetic
3.0g diethyl methylamine is dissolved in 30cm
3The 2-butanone in, when stirring, add 5.7g p-toluenesulfonic acid monohydrate to it gradually then.Make again to stir to continue for an hour, and distilling off solvent in a vacuum.Thereby with acetone to the solid that obtains again crystallization obtain the diethyl methylamine salt of p-toluenesulfonic acid.
(preparation of sol solution (a))
In the reactor that stirrer and reflux condenser have been installed, add 120 parts of methyl ethyl ketones, 100 parts of acryloyl-oxy propyl trimethoxy silicane (KBM-5103, by Shin-EtsuChemical CO., Ltd. produces) and 3 parts of oacetic acid diisopropoxy aluminium and make their mixing.After adding 30 parts of ion exchange waters, this potpourri was reacted 4 hours, next cool to room temperature down at 60 ℃.Reaction product has 1,600 weight-average molecular weight, and in the composition that comprises oligomer or component of polymer, molecular weight is 1,000-20, and 000 composition accounts for 100%.In addition, gas chromatographic analysis shows that initial acryloyl-oxy propyl trimethoxy silicane has not existed fully.With methyl ethyl ketone conditioned reaction solution so that it has 29% solid content, thereby prepared sol solution (a).
(preparation of sol solution (b))
In the reactor that stirrer and reflux condenser have been installed, add and mix 80 parts of acryloyl-oxy propyl trimethoxy silicanes, 20 parts of methyltrimethoxy silane (KBM-13, by Shin-Etsu Chemical CO., Ltd. produces) and 3 parts of oacetic acid diisopropoxy aluminium.After adding 30 parts of ion exchange waters, this potpourri was reacted 60 minutes down at 40 ℃.Reaction product has 800 weight-average molecular weight, and in the composition that comprises oligomer or component of polymer, molecular weight is 1,000-20, and 000 composition accounts for 30%.In addition, gas chromatographic analysis shows that the initial acryloyl-oxy propyl trimethoxy silicane and the residual rate of methyltrimethoxy silane are no more than 10%
(preparation of hollow silica dispersion A)
(shell is thick for isopropyl alcohol silicon dioxide gel, mean grain size: 40nm: 6nm, silica concentration: 20 weight %, the refractive index of silica dioxide granule: 1.30 to 500 parts of hollow silica fine grained colloidal sols; According to the preparation embodiment 4 of JP-A-2002-79616 by changing the particle diameter preparation) in add and mix 30 parts of acryloyl-oxy propyl trimethoxy silicane (KBM-5103, by Shin-Etsu Chemical CO., Ltd. produces), 2 parts of trimethyl methoxy silane and 1.5 parts of oacetic acid diisopropoxy aluminium.After adding 9 parts of ion exchange waters, this potpourri was reacted 8 hours down at 60 ℃.After cool to room temperature, add 1.8 parts of diacetones.
Adding cyclohexanone so that when the content of silicon dioxide is constant in this dispersion of 500g, is to carry out solvent exchange by distillation under the vacuum of 20kPa at pressure.This dispersion does not produce other material.When solid content being adjusted into 26 weight %, find that the viscosity under 25 ℃ is 10mPas with cyclohexanone.Residual quantity by gas chromatographic analysis isopropyl alcohol in the suspending liquid A that is obtained.The result is to find that it is 1.0%.
[preparation of antireflection film]
[being used for the preparation of the coating solution (LLL-1 to LLL-53) of low-index layer]
Mix and be dissolved in that to prepare solid content among the MEK be 8% the coating solution that is used for low-index layer being shown in various compositions in the table 7.Numeric representation in the bracket in the table 7 weight portion of solid of every kind of composition.
Table 7
| Coating solution No. | Fluoropolymer | Rigidizer | Hardening catalyst | |||
| No. | (use amount) | Kind | (use amount) | Kind | (use amount) | |
| LLL-1 LLL-2 LLL-3 LLL-4 LLL-5 LLL-6 | P1 P1 P1 P1 P1 P1 | (85) (73.5) (59.5) (48.0) (48.0) (48.0) | CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 | (15) (13.0) (10.5) (8.5) (8.5) (8.5) | PTS PTS PTS PTS PTS PTS | (1.0) (1.0) (1.0) (1.0) (1.0) (1.0) |
| LLL-7 LLL-8 LLL-9 LLL-10 LLL-11 LLL-12 | P37 P37 P37 P37 P37 P37 | (85) (73.5) (59.5) (48.0) (48.0) (48.0) | CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 | (15) (13.0) (10.5) (8.5) (8.5) (8.5) | PTS PTS PTS PTS PTS PTS | (1.0) (1.0) (1.0) (1.0) (1.0) (1.0) |
| LLL-13 | P39 | (85) | CYMEL 303 | (15) | PTS | (1.0) |
| LLL-14 LLL-15 LLL-16 LLL-17 LLL-18 LLL-19 | P39 P39 P39 P39 P39 P39 | (73.5) (59.5) (48.0) (48.0) (48.0) (48.0) | CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 | (13.0) (10.5) (8.5) (8.5) (8.5) (8.5) | PTS PTS PTS PTS PTS PTS | (1.0) (1.0) (1.0) (1.0) (1.0) (1.0) |
| LLL-20 LLL-21 LLL-22 LLL-23 | P18 P18 P45 P45 | (48.0) (48.0) (48.0) (48.0) | CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 | (8.5) (8.5) (8.5) (8.5) | PTS PTS PTS PTS | (1.0) (1.0) (1.0) (1.0) |
| LLL-24 LLL-25 LLL-26 LLL-27 LLL-28 | P1 P37 P18 P39 P45 | (48.0) (48.0) (48.0) (48.0) (48.0) | H-a/H-b( *2) H-a/H-b( *2) H-a/H-b( *2) H-a/H-b( *2) H-a/H-b( *2) | (8.5) (8.5) (8.5) (8.5) (8.5) | PTS PTS PTS PTS PTS | (1.0) (1.0) (1.0) (1.0) (1.0) |
| LLL-29 | P39 | (50.8) | CYMEL 303 | (5.7) | PTS | (1.0) |
| LLL-30 LLL-32 LLL-32 | P39 P39 P39 | (45.2) (42.3) (48.0) | CYMEL 303 CYMEL 303 TAKANATE D110 | (11.3) (14.2) (8.5) | PTS PTS - | (1.0) (1.0) - |
| LLL-33 LLL-34 LLL-35 | P37 P37 P37 | (48.0) (48.0) (44.6) | CYMEL 303 CYMEL 303 CYMEL 303 | (8.5) (8.5) (7.9) | PTS PTS PTS | (1.0) (1.0) (1.0) |
| LLL-36 LLL-37 LLL-38 | P39 P39 P39 | (48.0) (48.0) (44.6) | CYMEL 303 CYMEL 303 CYMEL 303 | (8.5) (8.5) (7.9) | PTS PTS PTS | (1.0) (1.0) (1.0) |
| LLL-39 LLL-40 LLL-41 LLL-42 LLL-43 LLL-44 | PR1 PR1 PR1 PR1 PR1 PR1 | (85) (73.5) (59.5) (48.0) (48.0) (48.0) | CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 | (15) (13.0) (10.5) (8.5) (8.5) (8.5) | PTS PTS PTS PTS PTS PTS | (1.0) (1.0) (1.0) (1.0) (1.0) (1.0) |
| LLL-45 LLL-46 LLL-47 | P49 P49 P49 | (80) (69.2) (56.0) | CYMEL 303 CYMEL 303 CYMEL 303 | (20) (17.3) (14.0) | PTS PTS PTS | (1.0) (1.0) (1.0) |
| LLL-48 LLL-49 LLL-50 LLL-51 LLL-52 LLL-53 | P49 P49 P49 P49 P54 P54 | (45.2) (45.2) (42.5) (42.5) (42.4) (42.4) | CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 | (11.3) (11.3) (11.3) (11.3) (14.1) (14.1) | PTS PTS PTS PTS PTS PTS | (1.0) (1.0) (1.0) (1.0) (1.0) (1.0) |
Table 7 (continuing)
| Coating solution No. | Multi-functional acrylate or colloidal sol | Colloidal silica | Polysiloxane | Remarks | |||
| Kind | (use amount) | Kind | (use amount) | Kind | (use amount) | ||
| LLL-1 LLL-2 LLL-3 | -sol solution (a)- | - (13.5) - | - - MEK-ST-L | - - (30) | FM-4425 FM-4425 FM-4425 | (3.0) (3.0) (3.0) | Contrast of the present invention |
| LLL-4 LLL-5 LLL-6 | Sol solution (a) sol solution (a) sol solution (a)/DPHA ( *1) | (13.5) (13.5) (13.5) | MEK-ST-L MEK-ST-L MEK-ST-L | (30) (30) (30) | FM-4425 X-22-160AS FM-4425 | (3.0) (3.0) (3.0) | The present invention of the present invention |
| LLL-7 LLL-8 LLL-9 LLL-10 LLL-11 LLL-12 | -sol solution, (a)-sol solution, (a) sol solution, (a) sol solution, (a)/DPHA, ( *1) | - (13.5) - (13.5) (13.5) (13.5) | - - MEK-ST-L MEK-ST-L MEK-ST-L MEK-ST-L | - - (30) (30) (30) (30) | FM-4425 FM-4425 FM-4425 FM-4425 X-22-160AS FM-4425 | (3.0) (3.0) (3.0) (3.0) (3.0) (3.0) | Contrast the present invention of the present invention |
| LLL-13 LLL-14 LLL-15 LLL-16 LLL-17 | -sol solution (a)-sol solution (a) sol solution (a) | - (13.5) - (13.5) (13.5) | - - MEK-ST-L MEK-ST-L MEK-ST-L | - - (30) (30) (30) | - - - - FM-4425 | - - - - (1.0) | Contrast of the present invention |
| LLL-18 LLL-19 | Sol solution (a) sol solution (a)/DPHA ( *1) | (13.5) (13.5) | MEK-ST-L MEK-ST-L | (30) (30) | X-22-160AS FM-4425 | (1.0) (1.0) | Of the present invention |
| LLL-20 LLL-21 LLL-22 LLL-23 | Sol solution (a) sol solution (a) sol solution (a) sol solution (a) | (13.5) (13.5) (13.5) (13.5) | MEK-ST-L MEK-ST-L MEK-ST-L MEK-ST-L | (30) (30) (30) (30) | - FM-4425 - FM-4425 | - (1.0) - (1.0) | Of the present invention |
| LLL-24 LLL-25 LLL-26 LLL-27 LLL-28 | Sol solution (a) sol solution (a) sol solution (a) sol solution (a) sol solution (a) | (13.5) (13.5) (13.5) (13.5) (13.5) | MEK-ST-L MEK-ST-L MEK-ST-L MEK-ST-L MEK-ST-L | (30) (30) (30) (30) (30) | X-22-160AS X-22-160AS - - - | (3.0) (3.0) - - - | The present invention of the present invention |
| LLL-29 LLL-30 LLL-31 LLL-32 | Sol solution (a) sol solution (a) sol solution (a) sol solution (a) | (13.5) (13.5) (13.5) (13.5) | MEK-ST-L MEK-ST-L MEK-ST-L MEK-ST-L | (30) (30) (30) (30) | - - - - | - - - - | Of the present invention |
| LLL-33 LLL-34 LLL-35 | Sol solution (a) sol solution (a) sol solution (a) | (13.5) (4.5) (4.5) | MEK-ST-L/MEK-ST( *3) hollow silica hollow silica/MEK-ST-L ( *4) | (30) (30) (39) | FM-4425 FM-4425 FM-4425 | (3.0) (3.0) (3.0) | The present invention of the present invention |
| LLL-36 LLL-37 LLL-38 | Sol solution (a) sol solution (a) sol solution (a) | (13.5) (4.5) (4.5) | MEK-ST-L/MEK-ST( *3) hollow silica hollow silica/MEK-ST-L ( *4) | (30) (39) (48) | - - - | - - - | The present invention of the present invention |
| LLL-39 LLL-40 LLL-41 LLL-42 LLL-43 LLL-44 | -sol solution, (a)-sol solution, (a) sol solution, (a) sol solution, (a)/DPHA, ( *1) | - (13.5) - (13.5) (13.5) (13.5) | - - MEK-ST-L MEK-ST-L MEK-ST-L MEK-ST-L | (30) (30) (30) (30) | FM-4425 FM-4425 FM-4425 FM-4425 X-22-160AS FM-4425 | (3.0) (3.0) (3.0) (3.0) (3.0) (3.0) | Contrast contrast contrast contrast contrast contrast |
| LLL-45 | - | - | - | - | - | - | Contrast |
| LLL-46 LLL-47 | Sol solution (a)- | (13.5) - | - MEK-ST-L | - (30) | - - | - - | Of the present invention |
| LLL-48 LLL-49 LLL-50 LLL-51 LLL-52 LLL-53 | Sol solution (a) sol solution (a) sol solution (a) sol solution (a)/DPHA ( *1) sol solution (a) sol solution (a) | (13.5) (4.5) (13.5) (13.5) (13.5) (13.5) | MEK-ST-L hollow silica MEK-ST-L MEK-ST-L MEK-ST-L MEK-ST-L | (30) (39) (30) (30) (30) (30) | - - FM-4425 FM-4425 - FM-4425 | - - (1.0) (1.0) - (1.0) | Of the present invention of the present invention |
(
*1) potpourri (1/1) (weight ratio) of sol solution (a) and DPHA
(
*2) potpourri of MEK-ST-L and MEK-ST (3/7) (weight ratio)
(
*3) potpourri of hollow silica and MEK-ST-L (39/9) (weight ratio)
In addition, title material in the table and name of product are as follows.
MEK-ST: by Nissan Chemical Industries, the colloidal silica that Ltd. produces, mean grain size: 10-15nm
MEK-ST-L: by Nissan Chemical Industries, the colloidal silica that Ltd. produces, mean grain size: about 50nm
Hollow silica: foregoing hollow silica dispersion A.Solids content in aforementioned table has been represented the total amount of silicon dioxide and surface conditioning agent.
CYMEL 303: methylolated melamine, produce by Nihon Cytec Industries Inc.
TAKENATE D110:, produce by TakedaPharmaceutical Industries Limited based on the rigidizer of isocyanates
But the DPHA:UV hardening resin, by Nippon Kayaku Co., Ltd produces
PTS: p-toluenesulfonic acid monohydrate
H-a and H-b are the compounds with following structure.
Fluoropolymer PR1 in table 7 be have following structure and with the described identical condition of following patent documentation under synthetic compound.
PR1: the multipolymer of the embodiment 2 that in No. the 3498481st, Jap.P., describes
Numeral the mole fraction of every kind of monomer.
[being used for the preparation of the coating solution (HCL-1) of antiglare layer]
PET-30： 50.0g
IRGACURE 184： 2.0g
SX-350(30％)： 1.5g
Crosslinked acrylic acid-styrene particle (30%) 13.9g
Sol solution (b): 10.0g
Toluene 38.5g
With the aperture is that the filtrator that is made by polypropylene of 30 μ m filters above-mentioned mixed solution, thereby preparation is used for the coating solution (HCL-1) of hard conating.
Employed here compound is as follows.
PET-30: the potpourri of pentaerythritol acrylate and tetramethylol methane tetraacrylate (by Nippon Kayaku Co., Ltd produces)
IRGACURE 184: polymerization initiator (being produced by Ciba Speciality Chemicals)
SX-350: mean grain size be 3.5 μ m crosslinked granules of polystyrene (refractive index: 1.60, by Soken Chemical ﹠amp; Engineering Co., Ltd. produces; By the Polytron dispersion machine with 10,000rpm disperses the 30% toluene dispersion used after 20 minutes)
[preparation of antireflection film sample 101]
The thick tri acetyl cellulose membrane " TAC-TD80U " (by Fuji Photo Film Co., Ltd produces) of 80 μ m that will be in as-rolled condition winds out; By using per inch to have the texturing pattern of 180 lines and the 40 μ m degree of depth and diameter little engraved roll and scraper as 50mm, revolution at engraved roll is that 30rpm and transfer rate are under the condition of 30m/min, and the above-mentioned coating solution (HCL-1) that is used for hard conating directly is coated on this above film; After dry 150 seconds, being under the nitrogen purge of 0.1 volume % with oxygen concentration by using 160W/cm air cool metal halide lamp (by Eyegraphics Co., Ltd. produces) under 60 ℃, is 400Mw/cm in radiant light illumination
2And radiation dose is 100mJ/cm
2Ultraviolet radiation hardened the time this dope layer that hardens, be the layer of 6 μ m thereby form thickness, next it is rolled.Preparation and the antiglare layer (HC-1) that obtains have surfaceness, 12% surface haze and 29% the inside turbidity of Ra=0.18 μ m and Rz=1.40 μ m like this.
On the antiglare layer that obtains like this, be coated with the above-mentioned coating solution (LLL-1) that is used for low-index layer, make low-index layer have the thickness of 95nm, thereby prepared antireflection film sample 101.For coating solution, various compositions are mixed coating then in 2 hours; For drying condition, low-index layer is following dry 10 minutes at 110 ℃, for UV cured condition, ultraviolet ray is that air cool metal halide lamp by using 240W/cm is (by EyegraphicsCo., Ltd. produce) in the atmosphere that is no more than 0.01 volume % with oxygen concentration with under the nitrogen purge, be 120mW/cm in radiant light illumination
2And radiation energy intensity is 240mJ/cm
2Irradiation.
[preparation of antireflection film 102-153]
Except with each replaces being used for the coating solution (LLL-1) of low-index layer in the coating solution (LLL-2)-(LLL-53), prepare antireflection film 102-153 in the mode identical with antireflection film 101 in preparation antireflection film 101.
[saponification of antireflection film is handled]
Handle under the saponification standard conditions below and dry each antireflection film that is obtained.
Alkali groove: 1.5 moles/dm under 55 ℃
3Sodium hydrate aqueous solution 120 seconds
First rinsing bowl: tap water 60 seconds
Neutralization chamber: 0.05 mole/dm under 30 ℃
3Sulfuric acid 20 seconds
Second rinsing bowl: tap water 60 seconds
Dry: 120 ℃, 60 seconds
[evaluation of antireflection film]
Estimate the antireflection film of each saponification that obtains so in the following manner.
The measurement of (estimating 1) average reflectance
By the method for in this instructions, describing, adopted average reflectance at 450-650nm.About being processed to the sample of Polarizer, used the sample that is in the Polarizer state; And at film self or be under the situation of display device of the state that does not use Polarizer, light absorption is carried out with black ink then through bulk processing in the back side of this antireflection film handle (in the transmissivity of 380-780nm: be less than 10%), next on black desk, measure.
The scratch-resistant evaluation that (estimating 2) undertaken by steel wire
Test is to carry out according to the method for describing in the instructions, the oiliness black ink is coated in by the rear side of friction sample, and estimates by the cut of friction portion and according to following criterion calculation by reflected light.Load is set at 500g/cm
2
A:, also do not find cut fully even by examining
AB:, found light cut a little by very careful observation
B: observe light cut
BC: observe moderate cut
C: just observe cut for first
(estimating 3) is by the evaluation of eraser to scratch-resistant
Test is to carry out according to the method for describing in the instructions, and the oiliness black ink is coated in the rear side that is wiped free of sample, and estimates by the cut of friction portion and according to following criterion calculation by reflected light.Load is set at 500g/cm
2
A:, also do not find cut fully even by examining
AB:, found light cut a little by very careful observation
B: observe light cut
BC: observe moderate cut
C: just observe cut for first
CC: the whole surface of film is all by cut
(estimating 4) marking ink wiping properties:
This test is to carry out according to the method for describing in the instructions, and determines the wiping number when marking ink disappears.Preferably the wiping number that disappears up to marking ink is 5 or more; And more preferably the wiping number that disappears up to marking ink is 10 or more.
(estimating 5) dust removal performance
This test is to carry out according to the method for describing in the instructions, and determines the number of wiping when dust is removed fully.Preferably by 6 wipings, dust can be removed fully; And more preferably can be removed fully with interior wiping dust by 3 times.
Evaluation result is shown in the table 8.
Table 8
| Antireflection film No. | The coating solution No that is used for low-index layer | Reflectivity (%) | Anti-SW | The performance of anti-eraser friction | The marking ink wiping properties | Dust removal performance | Remarks |
| 101 102 103 104 105 106 | LLL-1 LLL-2 LLL-3 LLL-4 LLL-5 LLL-6 | 1.90 1.90 1.92 1.92 1.92 1.92 | C AB AB A A A | A A A A A A | 2 6 5 7 7 7 | 8 6 6 5 5 5 | Contrast the present invention of the present invention |
| 107 108 109 110 111 112 | LLL-7 LLL-8 LLL-9 LLL-10 LLL-11 LLL-12 | 1.88 1.88 1.90 1.90 1.90 1.90 | C A AB A A A | A A A A A A | 2 6 5 8 8 8 | 8 6 6 5 5 5 | Contrast the present invention of the present invention |
| 113 114 115 116 117 118 119 | LLL-13 LLL-14 LLL-15 LLL-16 LLL-17 LLL-18 LLL-19 | 1.88 1.88 1.90 1.90 1.90 1.90 1.90 | C A AB A A A A | AB A A A A A A | 3 6 6 11 15 15 15 | 7 5 5 4 3 3 3 | Contrast of the present invention of the present invention |
| 120 121 122 123 | LLL-20 LLL-21 LLL-22 LLL-23 | 1.91 1.91 1.89 1.89 | A A A A | A A A A | 10 13 12 15 | 4 3 3 3 | Of the present invention |
| 124 125 126 127 128 | LLL-24 LLL-25 LLL-26 LLL-27 LLL-28 | 1.92 1.90 1.91 1.90 1.89 | A A A A A | A A A A A | 7 8 11 13 15 | 6 6 4 4 4 | The present invention of the present invention |
| 129 130 131 132 | LLL-29 LLL-30 LLL-31 LLL-32 | 1.89 1.90 1.91 1.90 | AB A A A | AB A A A | 10 11 11 11 | 4 4 4 4 | Of the present invention |
| 133 134 135 | LLL-33 LLL-34 LLL-35 | 1.90 1.42 1.42 | A A A | AB AB A | 7 6 8 | 6 6 6 | The present invention of the present invention |
| 136 137 138 | LLL-36 LLL-37 LLL-38 | 1.90 1.42 1.42 | A A A | AB A A | 10 9 12 | 5 5 5 | The present invention of the present invention |
| 139 140 141 142 143 144 | LLL-39 LLL-40 LLL-41 LLL-42 LLL-43 LLL-44 | 1.88 1.88 1.90 1.90 1.90 1.90 | C C BC BC BC BC | CC CC C BC BC BC | 1 1 1 2 2 2 | 9 9 9 8 8 8 | Contrast contrast contrast contrast contrast contrast |
| 145 146 147 | LLL-45 LLL-46 LLL-47 | 1.90 1.90 1.92 | C A AB | A A A | 4 8 8 | 4 3 3 | Contrast of the present invention |
| 148 149 150 151 152 153 | LLL-48 LLL-49 LLL-50 LLL-51 LLL-52 LLL-53 | 1.92 1.45 1.92 1.92 1.94 1.94 | A A A A A A | A A A A A A | 13 11 18 18 14 18 | 3 3 2 2 2 2 | Of the present invention of the present invention |
As from clear demonstration the these embodiment, notice that use surpasses 20% and contain the antireflection film of the polymers copolymers of constituent of the present invention according to hydroxyl composition of the present invention, excellent and excellent on antifouling property on anti-SW frictional behaviour and anti-eraser frictional behaviour.
Improvement on the various performances of bringing by the key element of hydroxy radical content in fluoropolymer is to show by the contrast between antireflection film 101-112 and the antireflection film 139-144.
In addition, notice that the marking ink wiping properties is improved (contrast antireflection film 107-112 and 113-119) widely by making polysiloxane structure as the polymer graft chain.
And, notice that reflectivity is greatly diminished (referring to antireflection film 134,135,137,138 and 149) by using hollow silica
[embodiment 2]
[preparation of antireflection film]
[being used for the preparation of the coating solution (LLL-54 to LLL-63) of low-index layer]
Except such kind that changes hardening catalyst as shown in table 8, prepare coating solution LLL-54 to LLL-58 and LLL-59 to LLL-63 to be used for the identical mode of the coating solution (LLL-17 and LLL-38) of low-index layer with preparation.In changing hardening catalyst, use with the equivalent molar weight to such an extent as to made change acid.Alkali is to use with equivalent (1/1) with respect to acid.
(being used for the preparation of the coating solution (HCL-2) of hard conating)
In 90 weight portion MEK, add 10 weight portion cyclohexanone, 85 weight portions by the partially modified polyfunctional acrylic ester (DPCA-20 of caprolactone, by Nippon Kayaku Co., Ltd. production), 10 weight portion KBM-5103 are (by Shin-Etsu Chemical CO., the silane coupling agent of Sheng Chaning) and 5 weight portion Photoepolymerizationinitiater initiaters (IRGACURE 184, produced by CibaSpeciality Chemicals) and stirring Ltd..By the aperture is that the filtrator that is made by polypropylene of 0.4 μ m filters this potpourri, thereby preparation is used for the coating solution (HCL-2) of hard conating.
[preparation and the evaluation of antireflection film sample 201-212]
The thick tri acetyl cellulose membrane " TAC-TD80U " (by Fuji Photo Film Co., Ltd produces) of 80 μ m that will be in as-rolled condition winds out; By using per inch to have the texturing pattern of 180 lines and the degree of depth is 40 μ m and diameter little engraved roll and the scraper as 50mm, revolution at engraved roll is that 30rpm and transfer rate are under the condition of 30m/min, and the above-mentioned coating solution (HCL-2) that is used for hard conating directly is coated with in the above; After dry 150 seconds, being under the nitrogen purge of 0.1 volume % with oxygen concentration by the air cool metal halide lamp (by EyegraphicsCo., Ltd. produces) that uses 160W/cm under 60 ℃, is 400nW/cm in radiant light illumination
2And radiation energy intensity is 100mJ/cm
2Ultraviolet radiation the time this dope layer that hardens, be the layer of 7 μ m thereby form thickness, next it is rolled.The antiglare layer (HC-2) of preparation and acquisition has the surfaceness of Ra=0.005 μ m and Rz=0.01 μ m like this.
In the mode identical with embodiment 1 with above-mentioned low-index layer coating and be provided on the hard conating HC-2, thereby prepared antireflection film 201-212.About the time from the preparation low-index layer to coating, standard conditions were set to 2 hours.In addition, prepare simultaneously under 110 ℃ and to be shortened to 5 minutes sample the thermmohardening time, make it under the condition identical, handle and estimate anti-eraser frictional behaviour through saponification with embodiment 1.
In addition, the coating solution that will be used for low-index layer stores one month respectively and three months at 30 ℃ under shading and under the air-proof condition, is coated with then.The oiliness black ink is coated on the back side of coated film, and on the area of A4 size according to following standard evaluation surface property.
A:, also do not find defective fully even by examining
AB:, found defective (1-3/A4) a little by very careful observation
B: observe little defective (4-10/A4)
C: just observe defective (11 or more/A4) for first
Evaluation result is shown in the table 9.
Table 9
| Antireflection film No. | Coating solution No. | Rigidizer | Hardening catalyst | ||||
| Kind | (use amount) | Acid | Alkali | ||||
| Kind | pKa | Boiling point | |||||
| 201 | LLL-17 | CYMEL 303 | (8.5) | PTS | - | - | - |
| 202 203 204 205 206 | LLL-54 LLL-55 LLL-56 LLL-57 LLL-58 | CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 | (8.5) (8.5) (8.5) (8.5) (8.5) | PTS PTS PTS PTS DBS | b-1 b-14 b-19 b-23 b-23 | 5.1 7.8 10.7 10.5 10.5 | 64 115 88.5 64 64 |
| 207 | LLL-38 | CYMEL 303 | (7.9) | PTS | - | - | - |
| 208 209 210 211 212 | LLL-59 LLL-60 LLL-61 LLL-62 LLL-63 | CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 CYMEL 303 | (7.9) (7.9) (7.9) (7.9) (7.9) | PTS PTS PTS PTS DBS | b-1 b-14 b-19 b-23 b-23 | 5.1 7.8 10.7 10.5 10.5 | 64 115 88.5 64 64 |
Table 9 (continuing)
| Antireflection film No. | The frictional property of anti-the eraser | Month later coating surface performance in the past | Coating surface performance after three months in the past | Remarks | |
| Solidified 10 minutes at 110 ℃ | Solidified 5 minutes at 110 ℃ | ||||
| 201 | A | A | C | CC | The present invention |
| 202 203 204 205 206 | A A A A A | A A AB A A | A A A A A | AB A A A A | The present invention of the present invention |
| 207 | A | A | C | CC | The present invention |
| 208 209 210 211 212 | A A A A A | A A AB A A | A A A A A | AB A A A A | The present invention of the present invention |
As from clear demonstration the these embodiment, notice by using the acid that is used in combination with alkali of the present invention as hardening catalyst, can obtain the antireflection film of the storage stability excellence and the scratch-resistant excellence of coating solution.
[embodiment 3]
Prepared the multi anti reflection coating that describes below.
Following composition put in the mixing channel and stir prepare the coating solution that is used for hard conating.
To 750.0 weight portion trimethylolpropane triacrylate (TMPTA, by NipponKayaku Co., Ltd. produce) in, adding 270.0 weight portion weight-average molecular weight is 15,000 poly-(glycidyl acrylate), 730.0 weight portion methyl ethyl ketones, 500.0 weight portion cyclohexanone, 25.0 weight portion light cationic polymerization initiators (RHODORSIL 2074) and 50.0 weight portion Photoepolymerizationinitiater initiaters (IRGACURE 184, produced by Ciba Speciality Chemicals) and stirring.
By the aperture is making filtrator by polypropylene and filtering this potpourri of 0.4 μ m, thereby preparation is used for the coating solution (HCL-3) of hard conating.
(preparation of titania fine grained dispersion)
Use contains cobalt and (MPT-129C, by Ishihara Sangyo Kaisha, Ltd. produces, TiO through aluminium hydroxide and zirconium hydroxide surface-treated titania fine grained
2/ Co
3O
4/ Al
2O
3/ ZrO
3=90.5/3.0/4.0/0.5 (weight ratio)) as the titania fine grained.
In this particle of 257.1 weight portions, add the following spreading agent and the 701.8 weight portion cyclohexanone of 41.1 weight portions, and disperse this potpourri, thereby the preparation weight average particle diameter is the titanium dioxide dispersion of 70nm by Dyno-Mill.
(being used for the preparation of the coating solution of index layer)
In the above-mentioned titanium dioxide dispersion of 99.1 weight portions, add 68.0 weight portions by potpourri (DPHA), the 3.6 weight portion Photoepolymerizationinitiater initiaters (IRGACURE 907) of five acrylic acid dipentaerythritol ester and six acrylic acid dipentaerythritol ester, (KAYACUREDETX is by Nippon Kayaku CO. for 1.2 weight portion photosensitizers, Ltd. production), 279.6 weight portion methyl ethyl ketones and 1,049.0 weight portion cyclohexanone and stirring.After fully stirring, be that the filtrator that is made by polypropylene of 0.4 μ m filters this potpourri by the aperture, thereby preparation is used for the coating solution of index layer.
(being used for the preparation of the coating solution of high refractive index layer)
In the above-mentioned titanium dioxide dispersion of 469.8 weight portions, add 40.0 weight portions by the potpourri (DPHA) of five acrylic acid dipentaerythritol ester and six acrylic acid dipentaerythritol ester, (IRGACURE 907 for 3.3 weight portion Photoepolymerizationinitiater initiaters, by Ciba Speciality Chemicals), 1.1 weight portion photosensitizers (KAYACURE DETX by Nippon Kayaku CO., Ltd. produce), 526.2 weight portion methyl ethyl ketones and 459.6 weight portion cyclohexanone and stirrings.After fully stirring, be that the filtrator that is made by polypropylene of 0.4 μ m filters this potpourri by the aperture, thereby preparation is used for the coating solution of high refractive index layer.
(preparation of antireflection film sample (301))
By using the texturing spreader that the above-mentioned coating solution that is used for hard conating is coated on the thick tri acetyl cellulose membrane of 80 μ m (TAC-TD80U, by Fuji Photo Film Co., Ltd produces).After 100 ℃ of following dryings, be under the nitrogen purge of 1.0 volume % with oxygen concentration by the air cool metal halide lamp (by Eyegraphics Co., Ltd. produces) that uses 160W/cm, be 400mW/cm in radiant light illumination
2And radiation energy intensity is 300mJ/cm
2Ultraviolet radiation this dope layer that hardens, be the hard conating of 8 μ m thereby form thickness.
On hard conating, the texturing coating machine that has three coating stations by use continuously coating be used for index layer coating solution, be used for the coating solution of high refractive index layer and be used for the coating solution (LLL-1) of low-index layer.
About drying condition, middle index layer is following dry 30 seconds at 90 ℃; And about UV cured condition, ultraviolet ray is by using 180W/cm air cool metal halide lamp (by Eyegraphics Co., Ltd. produce) be no more than in the atmosphere of 0.1 volume % with under the nitrogen purge in oxygen concentration, be 400mW/cm in radiant light illumination
2And radiation energy intensity is 400mJ/cm
2Following irradiation.Should in index layer after sclerosis, have 1.630 refractive index and the thickness of 67nm.
About drying condition, high refractive index layer is following dry 30 seconds at 90 ℃; About UV cured condition, ultraviolet ray is by using 240W/cm air cool metal halide lamp (by Eyegraphics Co., Ltd. produces) to be no more than in the atmosphere of 0.1 volume % with under the nitrogen purge in oxygen concentration, is 600mW/cm in radiant light illumination
2And radiation energy intensity is 400mJ/cm
2Following irradiation.
This high refractive index layer has 1.905 refractive index and the thickness of 107nm after sclerosis.
About drying condition, low-index layer is following dry 10 minutes at 110 ℃; About UV cured condition, ultraviolet ray is by using 240W/cm air cool metal halide lamp (by Eyegraphics Co., Ltd. produce) be no more than in the atmosphere of 0.01 volume % with under the nitrogen purge in oxygen concentration, be 120mW/cm in radiant light illumination
2And radiation energy intensity is 480mJ/cm
2Following irradiation.
This low-index layer has 1.45 refractive index and the thickness of 85nm after sclerosis.
Except the coating solution that will be used for low-index layer respectively changes over (LLL-2) to (LLL-53), prepare sample 302-352 in the mode identical with obtaining sample 301.The result who handles as saponification and according to the evaluation of embodiment 1, by index layer in providing and high refractive index layer, reflectivity all has been greatly diminished in all samples.Notice and obtained to have antiradar reflectivity according to the present invention and had the excellent marking ink wiping properties and the reflectance coating of mar-proof performance.
In addition, by total solid, add KBM-5103 (by Shin-Etsu Chemical CO., the silane coupling agent that Ltd. produces) with the amount of 5 weight % and prepare sample and this sample is estimated based on high refractive index layer.The result is under the situation of using hydroxy radical content above the fluoropolymer of 20 moles of %, to have improved steel wall crocking resistance especially.
[embodiment 4]
(being used for the preparation of the solution (HCL-4) of hard conating)
With 100 weight portion DeSolite Z7404 (comprising the fine grain hard coating composition solution of zirconia), 31 weight portion DPHA by what JSR Corporation produced (by Nippon KayakuCo., but the UV hardening resin that Ltd produces), 10 weight portion KBM-5103 are (by Shin-EtsuChemical CO., Ltd. the silane coupling agent of Sheng Chaning), 8.9 weight portion KE-P150 (by NipponShokubai Co., the 1.5 μ m silica dioxide granules that Ltd. produces), 3.4 weight portion MXS-300 are (by Soken Chemical ﹠amp; The 3 μ m crosslinked PMMA particles that Engineering Co., Ltd. produce), 29 weight portion MEK and 13 weight portion MIBK put in the mixing channel and stir, thereby preparation is used for the coating solution of hard conating.
(preparation of antireflection film)
As stilt, the tri acetyl cellulose membrane (TD80U, by FujiPhoto Film Co., Ltd produces) that will be in as-rolled condition winds out; By using per inch to have the texturing pattern of 135 lines and the degree of depth is 60 μ m and diameter little engraved roll and the scraper as 50mm, is under the condition of 10m/min in transfer rate, and directly coating is in the above with the above-mentioned coating solution that is used for hard conating; Under 60 ℃, after dry 150 seconds, under nitrogen purge, be 400Mw/cm in radiant light illumination by using 160W/cm air cool metal halide lamp (by Eyegraphics Co., Ltd. produces)
2And radiation energy intensity is 100mJ/cm
2Ultraviolet radiation hardened the time this dope layer that hardens, thereby form hard conating, next it is rolled.Prepare hard conating 401 so that coating back hard conating has the thickness of 4.0 μ m by the revolution of adjusting engraved roll.The hard conating of Huo Deing has the surfaceness (Ra (center line average roughness), RMS (square mean surfaceness) and Rz (n point mean roughness) measure by the scan-probe microscopic system SPI3800 that is produced by Seiko Instruments Inc.) of Ra=0.02 μ m, PMS=0.03 μ m and Rz=0.25 μ m like this.
On hard conating 401, be coated with and provide the low-index layer of embodiment 1, and formed antireflection film handled through saponification and according to embodiment 1 to its evaluation.The result is to notice according to this invention to have obtained to have antiradar reflectivity and had the excellent scratch-resistant and the antireflection film of marking ink wiping properties.
[embodiment 5]
(being used for the preparation of the coating solution (HCL-5) of hard conating)
The cyclohexanone that under agitation in 40 mass parts MEK, adds 15 mass parts, 28 mass parts are by the potpourri (PET-30 of pentaerythritol triacrylate and pentaerythritol tetracrylate, Nippon Kayaku Co., the product of Ltd), 12 mass parts are by the potpourri (DPHA of five acrylic acid dipentaerythritol ester and six acrylic acid dipentaerythritol ester, Nippon Kayaku Co., the product of Ltd), (secondary is assembled diameter: 1.5 μ m to assemble silicon dioxide with 5 mass parts, primary particle size: tens nm, Nihon Silica Co., Ltd. product), (IRGACURE 184 for 1 mass parts Photoepolymerizationinitiater initiater, the product of Ciba Speciality Chemicals), 0.2 mass parts Photoepolymerizationinitiater initiater (IRGACURE 907, the product of Ciba Speciality Chemicals), prepare the coating solution (HCL-5) that is used for hard conating with 0.08 mass parts based on the surface modifier (SP-13) of fluorine.
Surface modifier FP-13 based on fluorine:
(coating of hard conating 501)
The thick tri acetyl cellulose membrane " TAC-TD80U " (by Fuji Photo Film Co., Ltd produces) of 80 μ m that will be in as-rolled condition winds out; In transfer rate is under the condition of 30m/min, the coating machine of the throttling mould being installed by use extrude direct with above-mentioned coating solution (HCL-5) coating that is used for hard conating in the above.30 ℃ dry 15 seconds down, next at 90 ℃ down after dry 20 seconds, with under the nitrogen purge, be 90mJ/cm by using 160W/cm air cool metal halide lamp (by Eyegraphics Co., Ltd. produces) with radiation dose
2Ultraviolet radiation hardened the time this dope layer that hardens, have anti-dazzle performance and thickness is the antiglare layer of 2.5 μ m thereby form.Obtained hard conating 501 by rolling this film.The surface haze of this hard conating 501 is 6, and inner turbidity is 1.
Add the coating solution that 0.5 mass parts PM980M (Photoepolymerizationinitiater initiater, the product of Wako Pure Chemical) preparation is used for low-index layer by coating solution LLL-51 and the LLL-53 that in embodiment 1, is used for low-index layer.On hard conating 501, be coated with the coating solution that these are used for low-index layer.The product of coating is estimated uniformity coefficient through the saponification processing and with the method among the embodiment 1.The result is, obtained to show antiradar reflectivity, good scratch-resistant and the antireflection film of marking ink wiping properties once more.
[embodiment 6]
＜have a preparation of the Polarizer of antireflection film 〉
Iodine absorbed on the stretching polyethylene alcohol film prepare light polarizing film.By using the antireflection film of the saponification of embodiment 1 being handled based on the bonding agent of polyvinyl alcohol (PVA) to adhere on the side of this light polarizing film, make stilt (triacetyl cellulose) side of antireflection film to the light polarizing film side.Make the visual angle with optical compensating layer increase film, " WIDE VIEW FILM SA12B " (by Fuji Photo Film Co., Ltd. produces) handled through saponification and adhered on the opposite side of this light polarizing film by the bonding agent of use based on polyvinyl alcohol (PVA).So just prepared Polarizer.Estimate according to 1 pair of this Polarizer of embodiment.The result is to use low-index layer of the present invention to obtain identical effect.
[embodiment 7]
Can affirm that sharpness, scratch-resistant and the antifouling property of TN type transmissive liquid crystal display device that the Polarizer of the present invention that makes so wherein has been installed is good.
[embodiment 8]
Adhere on the glass plate on organic EL display surface by the antireflection film sample of bonding agent embodiment 2.The result is that the reflection of glass surface is suppressed, thereby has obtained to have the display device of high definition.
This application is based on the Japanese patent application JP2006-112368 of Japanese patent application JP2005-225478 that submitted on August 3rd, 2005 and submission on April 14th, 2006, be incorporated herein by reference at this full content, just as it is elaborated these two patented claims.
Claims (27)
1, a kind of antireflection film, the low-index layer that it comprises stilt and contains the coating composition preparation of following composition by coating:
(A) fluoropolymer, its main chain is only made by carbon atom and it contains at least a fluorine-containing polymerization of vinyl monomer unit and at least a hydroxyl polymerization of vinyl monomer unit, wherein, if do not have polysiloxane structure in this main polymer chain, then the content of hydroxyl polymerization of vinyl monomer unit surpasses 20 moles of %;
(B) can with the crosslinking chemical of hydroxyl reaction; With
(C) in a molecule, contain the compound of two or more (methyl) acryloyl group.
2, a kind of antireflection film, the low-index layer that it comprises stilt and contains the coating composition preparation of following composition by coating:
(A) fluoropolymer, its main chain is only made by carbon atom and contains at least a fluorine-containing polymerization of vinyl monomer unit and at least a hydroxyl polymerization of vinyl monomer unit, wherein, if do not have polysiloxane structure in this main polymer chain, then the content of hydroxyl polymerization of vinyl monomer unit surpasses 20 moles of %;
(B) can with the crosslinking chemical of hydroxyl reaction; With
(D) organic silane compound or contain the hydrolysate of this organic silane compound and the partial condensate of this organosilane at least a composition.
3, a kind of antireflection film, it comprises stilt and contains the low-index layer that the coating composition of following composition prepares by coating:
(A) fluoropolymer, its main chain is only made by carbon atom and contains at least a fluorine-containing polymerization of vinyl monomer unit and at least a hydroxyl polymerization of vinyl monomer unit, wherein, if do not have polysiloxane structure in this main polymer chain, then the content of hydroxyl polymerization of vinyl monomer unit surpasses 20 moles of %;
(B) can with the crosslinking chemical of hydroxyl reaction; With
(E) particle diameter is 1nm or bigger and be no more than the inorganic particle of 100nm.
4, it is 1nm or bigger and be no more than the inorganic particle of 100nm that the antireflection film of claim 1, wherein said coating composition further contain (E) particle diameter.
5, it is 1nm or bigger and be no more than the inorganic particle of 100nm that the antireflection film of claim 2, wherein said coating composition further contain (E) particle diameter.
6, the antireflection film of claim 1, wherein said fluoropolymer comprise at least one polymerized unit with grafting site that contains the polysiloxane repetitive of following formula (1) expression in its side chain,
Formula (1)
Wherein, R
1And R
2Can be same or different and represent alkyl or aryl separately; And p represents the integer of 10-500.
7, the antireflection film of claim 2, wherein said fluoropolymer comprise at least one polymerized unit with grafting site that contains the polysiloxane repetitive of following formula (1) expression in its side chain,
Formula (1)
Wherein, R
1And R
2Can be same or different and represent alkyl or aryl separately; And p represents the integer of 10-500.
8, the antireflection film of claim 1, wherein said fluoropolymer comprise at least one polymerized unit with grafting site that contains the polysiloxane repetitive of following formula (13) expression in its side chain:
Formula (1)
Wherein, R
1And R
2Can be same or different and represent alkyl or aryl separately; And p represents the integer of 10-500.
9, the antireflection film of claim 1, wherein said coating composition further comprise the polysiloxane compound that (F) has hydroxyl or can form the functional group of binding with hydroxyl reaction.
10, the antireflection film of claim 2, wherein said coating composition further comprise the polysiloxane compound that (F) has hydroxyl or can form the functional group of binding with hydroxyl reaction.
11, the antireflection film of claim 3, wherein said coating composition further comprise the polysiloxane compound that (F) has hydroxyl or can form the functional group of binding with hydroxyl reaction.
12, the antireflection film of claim 1, wherein said coating composition further comprises at least a salt, and this salt is organic base and sour formation of 5.0-10.5 by the pKa of its conjugate acid.
13, the antireflection film of claim 2, wherein said coating composition further comprises at least a salt, and this salt is organic base and sour formation of 5.0-10.5 by the pKa of its conjugate acid.
14, the wherein said coating composition of the antireflection film of claim 3 further comprises at least a salt, and this salt is organic base and sour formation of 5.0-10.5 by the pKa of its conjugate acid.
15, the antireflection film of claim 1, wherein said coating composition further comprises at least a salt, this salt by boiling point be 35 ℃ or higher and be no more than 85 ℃ nitrogenous organic base and acid form.
16, the antireflection film of claim 2, wherein said coating composition further comprises at least a salt, this salt by boiling point be 35 ℃ or higher and be no more than 85 ℃ nitrogenous organic base and acid form.
17, the antireflection film of claim 3, wherein said coating composition further comprises at least a salt, this salt by boiling point be 35 ℃ or higher and be no more than 85 ℃ nitrogenous organic base and acid form.
18, the antireflection film of claim 3, wherein said inorganic particle are the hollow silica particles.
19, the antireflection film of claim 1, it comprises further that between stilt and low-index layer refractive index is higher than at least one layer of described low-index layer refractive index, wherein said at least one layer include organic silane compound or contain the hydrolysate of organic silane compound and the partial condensate of organic silane compound at least a composition.
20, the antireflection film of claim 2, it comprises further that between stilt and low-index layer refractive index is higher than at least one layer of described low-index layer refractive index, wherein said at least one layer include organic silane compound or contain the hydrolysate of organic silane compound and the partial condensate of organic silane compound at least a composition.
21, the antireflection film of claim 3, it comprises further that between stilt and low-index layer refractive index is higher than at least one layer of low-index layer refractive index, wherein said at least one layer include organic silane compound or contain the hydrolysate of organic silane compound and the partial condensate of organic silane compound at least a composition.
22, a kind of Polarizer, it comprises the antireflection film of light polarizing film and claim 1, wherein said antireflection film is to provide as a film in two diaphragms that are used for the Polarizer light polarizing film.
23, a kind of Polarizer, it comprises the antireflection film of light polarizing film and claim 2, wherein said antireflection film is to provide as a film in two diaphragms that are used for the Polarizer light polarizing film.
24, a kind of Polarizer, it comprises the antireflection film of light polarizing film and claim 3, wherein said antireflection film is to provide as a film in two diaphragms that are used for the Polarizer light polarizing film.
25, a kind of image display device, it comprises the antireflection film of claim 1, wherein said antireflection film is provided at the outermost surface of display.
26, a kind of image display device, it comprises the antireflection film of claim 2, wherein said antireflection film is provided at the outermost surface of display.
27, a kind of image display device, it comprises the antireflection film of claim 3, wherein said antireflection film is provided at the outermost surface of display.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005225478 | 2005-08-03 | ||
| JP225478/2005 | 2005-08-03 | ||
| JP112368/2006 | 2006-04-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1908700A true CN1908700A (en) | 2007-02-07 |
| CN100552475C CN100552475C (en) | 2009-10-21 |
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ID=37699865
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|---|---|---|---|
| CNB2006101084438A Expired - Fee Related CN100552475C (en) | 2005-08-03 | 2006-08-02 | Antireflection film, Polarizer and image display device |
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| CN (1) | CN100552475C (en) |
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