CN101294003A - Process of curable coating composition, antireflection film, polarizing plate and image display device using thereof - Google Patents

Process of curable coating composition, antireflection film, polarizing plate and image display device using thereof Download PDF

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CN101294003A
CN101294003A CNA200810093065XA CN200810093065A CN101294003A CN 101294003 A CN101294003 A CN 101294003A CN A200810093065X A CNA200810093065X A CN A200810093065XA CN 200810093065 A CN200810093065 A CN 200810093065A CN 101294003 A CN101294003 A CN 101294003A
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film
refractive index
compound
high refractive
group
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CN101294003B (en
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加藤荣一
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Fujifilm Corp
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Fujifilm Corp
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  • Surface Treatment Of Optical Elements (AREA)
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Abstract

A high refractive index layer excellent in weatherability or optical properties and durability, an antireflection film having the layer, a polarizing plate having the antireflection film, and an image display device using thereof are provided, each of which is a high refractive index layer or film which contains specific fine particles of a high refractive index composite oxide containing a titanium element or a bismuth element; a production process of a curable coating composition which contains specific fine particles of a high refractive index composite oxide containing a bismuth element; an antireflection film using thereof; a polarizing plate and an image display device using thereof.

Description

Their image display device of the preparation method of curable coating composition, antireflective film, polaroid and use
The application is that the application number submitted on March 5th, 2004 is dividing an application of 200480005907.1 Chinese invention patent application.
Technical field
The present invention relates to high refractive index layer, use antireflective film, polaroid and the image display device of this high refractive index layer, and relate to preparation method, the cured film of curable coating composition, the antireflective film that uses this cured film, polaroid and image display device.
Background technology
For example provide protective film (antireflective film) to be used for lens or image display device on glass or the plastics substrate in residuite so far with antireflection ability.Particularly, this antireflective film is installed in is used for for example surface of the indicating meter of liquid-crystal display (LCD), plasma display panel (PDP), electroluminescent display (ELD) and cathode-ray tube display (CRT) of various image display devices, in case because the reflection of exterior light or external image causes contrast gradient to reduce.Therefore, require this antireflective film to have high physical strength (for example, scratch resistance), chemical resistance and weathering resistance (for example, humidity resistance and photostabilization).In addition, as the antireflective film that pictorial display is used, the high refractive index layer that also requires antireflective film to have the specific refractory power higher than the specific refractory power of the antireflective film that is used for synthetic resin lens, and this high refractive index layer is colourless and transparent.
In recent years, liquid-crystal display (LCD) maximizes day by day, is equipped with the quantity of the liquid-crystal display of antireflective film also increasing.
Equally, in liquid-crystal display (LCD), be absolutely necessary element and have the structure of polarization film usually of polaroid by the protection of two protective films.The ability of giving these protective film antireflections can reduce production costs and the thickness of indicating meter greatly.
Antireflective film is formed by the multiwalled film usually, and described multiwalled film is contained the transparent of metal oxide and thin layer for example high refractive index layer, intermediate-index layer and low-index layer are laminated each other and formed by what a plurality of specific refractory poweres differed from one another.The transparent film of this metal oxide forms by chemical vapor deposition (CVD) method, physical vapor deposition (PVD) method or the VVD vaccum vapor deposition method that belongs to the physical vapor deposition method.Perhaps, also propose by use for example metal alkoxide formation colloidal metal oxide particle film of metallic compound according to sol-gel process, then by aftertreatment (uviolizing: referring to JP-A-9-157855; Cement Composite Treated by Plasma: referring to JP-A-2000-9908) forms this film.
Yet the productivity of the method for the transparent film of the described metal oxide of above-mentioned formation is low, is not suitable for producing in enormous quantities.Therefore, expectation can obtain to have large-duty this film formation method by coating process.
Under situation, use adhesive resin to form film as matrix by coating preparation antireflective film.This adhesive resin has the specific refractory power of 1.45-1.55 usually, therefore by selecting to be used for the kind of inorganic particle wherein and the specific refractory power that quantity is suitably adjusted each layer.Specifically, with regard to high refractive index layer, need the high fine inorganic particle of specific refractory power, and the fine inorganic particle that described specific refractory power is high evenly and not to be distributed in the matrix with enough film strengths be extremely important with assembling.
As the high fine inorganic particle of specific refractory power, known specific refractory power is arranged is 1.7 or particulate (for example, the JP-A-8-110401 and the JP-A-8-122504 of bigger transparent single metal (for example, Ti, Zn, Sb, Sn, Zr, Ce, Ta, La or In) oxide compound; Term used herein " JP-A " is meant " not examining open Japanese patent application ").Also proposed by height is reflected fine inorganic particle join in a large number the fine dispersion state that keeps this height refraction fine inorganic particle in the film simultaneously with form high refractive index layer (referring to, for example, JP-A-11-153703 and JP-A-2001-166104).Wherein, titanium dioxide is the compound with high specific refractory power, and this compound is added extremely effectively (for example, JP-A-2000-9908 and JP-A-2001-310423) as particulate.Yet titanium dioxide has photo-catalysis capability and has extremely poor weathering resistance.Therefore, when long-time use high refractive index film (antireflective film) under sunlight, titanium dioxide decomposes the physical strength and the optical property of organic compound contained in this high refractive index film and badly damaged this film, and therefore this film has problems aspect the wearing quality of film.Be head it off, proposed a kind of technology, it is with other metallic compound capping oxidation titanium particulate surface, thereby the particulate of laminate structures is provided, to improve weathering resistance (for example, JP-A-2001-166104 and JP-A-2000-204301).
On the other hand, many various complex metal oxidess (double oxide) (for example, JP-A-8-234001 JP-A-10-306258 and JP-A-11-140207) that are selected from the element of aforementioned metal element, Si, Al, Fe, W etc. have also been proposed to comprise.Specifically, the high refractive index film that contains titaniferous height composite oxides is wherein disclosed.For example, the complex metal oxides for example composite oxides (JP-A-8-113760) of the complex metal oxides of titanium oxide-cerium oxide-silicon oxide (JP-A-2000-204301), titanium oxide-Zirconium oxide-tin oxide and the composite oxides (JP-A-10-306258) of stannic oxide-titanium oxide have been proposed.
In addition, proposed when composite oxides contain Si, Al etc. and the refrangible metallic element of above-mentioned height to improve particulate dispersiveness and film performance technology (referring to, for example, JP-A-9-21901, JP-A-11-140207 and JP-A-2002-30250).
Yet this titanium-containing composite oxide makes photostabilization reduce, although they can keep specific refractory power in higher level ground when increasing the content of the titanium oxide with high refractive index.In addition, above-mentioned technology uses the matrix of q.s still to be not enough to design high refraction film to keep sufficient film strength and anti-embrittlement.
Therefore, need the excellent high refractive index film of preparation weathering resistance (particularly, photostabilization excellence) and film strength (for example, anti-embrittlement, hardness and binding property).Yet above-mentioned requirements is also failed satisfied fully.On the other hand, the composite oxides of titanium oxide and bismuth oxide have been proposed as the luminous efficiency (JP-A-7-281023) of coating of metal oxides with the reinforcement incandescent-lamp bulb.Yet whether also unexposed these composite oxides can be as the colorless and transparent films of application type antireflective film.
Summary of the invention
An object of the present invention is to provide the high refractive index layer of weathering resistance excellence.
Another purpose of the present invention provides the antireflective film of the weathering resistance excellence of marked down ground scale operation.
Another object of the present invention provides the preparation method of the curable coating composition of optical characteristics and wearing quality excellence.
Another purpose of the present invention provides the cured film of optical characteristics and weathering resistance excellence.
Another purpose of the present invention provides the antireflective film of the optical characteristics and the wearing quality excellence of the scale operation of marked down ground.
A further object of the present invention provides polaroid and the image display device that stands to give the processing of antireflection property by suitable mode.
The problems referred to above can solve by the present invention of following formation.
1, high refractive index layer, it comprises the particulate of matrix and high refractive index composite oxides,
The particulate of wherein said high refractive index composite oxides is the particulates that contain the composite oxides of titanium elements and at least a metallic element, the oxide compound of wherein said at least a metallic element have 1.95 or bigger specific refractory power and
Described composite oxides and at least a Co ion, Zr ion and the Al ionic metal ion mixing of being selected from.
2, as the 1st described high refractive index layer, the particulate of wherein said high refractive index composite oxides carries out surface treatment with at least a compound that is selected from mineral compound and organic compound.
3, as the 1st or 2 described high refractive index layer, wherein said matrix contains at least a cured product that is selected from the material of organic binder bond, organometallic compound and their partial hydrolysate.
4, as each described high refractive index layer of 1-3 item, it has the specific refractory power of 1.75-2.4.
5, as each described high refractive index layer of 1-4 item; it is by passing through the use dispersion agent composition that described high refractive index composite oxide particle disperses to obtain to be formed, and wherein said dispersion agent is to have at least a compound that is selected from the anionic group of carboxyl, sulfo group, phosphono and phosphine oxide acyl group.
6, as the 5th described high refractive index layer, wherein said dispersion agent is the compound that contains crosslinkable or polymerisable functional group.
7, antireflective film, it comprises successively: transparent carrier; As each described high refractive index layer of 1-6 item; With specific refractory power less than 1.55 low-index layer.
8, antireflective film, it comprises transparent carrier successively; Two-layer specific refractory power differing from each other as each described high refractive index layer of 1-6 item; With specific refractory power less than 1.55 low-index layer.
9, as the 7th or 8 described antireflective film, it also comprises hard coat between described transparent carrier and described high refractive index layer.
10, polaroid comprises polarization film and protective film thereof, and wherein said protective film is as each described antireflective film of 7-9 item.
11, polaroid comprises polarization film and protective film thereof, and one of them protective film is as each described antireflective film of 7-9 item, and another protective film is to have optically anisotropic optical compensating film.
12, as the 11st described polaroid, wherein said optical compensating film comprises transparent carrier and comprises the optical compensating layer of optical anisotropic layer, described optical anisotropic layer contains and has the unitary compound of disk-shaped structure, the relative transparent carrier face tilt of the unitary dish face of wherein said disk-shaped structure, and the angle between described dish face and the transparent carrier face changes at the thickness direction of described optical anisotropic layer.
13, image display device, it comprises on the display plotter surface as each described antireflective film of 7-9 item or as each described polaroid of 10-12 item.
14, the preparation method of curable coating composition, described curable coating composition comprises the particulate of film forming curable compound and high refractive index composite oxides, the particulate of wherein said high refractive index composite oxides contains: bismuth element and at least a metallic element, the oxide compound of wherein said at least a metallic element has 1.95 or bigger specific refractory power
Wherein said method comprises uses medium wet disperse high refractive index composite oxide particle and the dispersion agent of median size less than 1mm, makes median size thus and be the particulate of 150nm or littler high refractive index composite oxides.
15, as the 14th described method, wherein said dispersion agent is the polymeric dispersant with polar group.
16, as the 15th described method, wherein said polar group is at least a anionic group that is selected from carboxyl, sulfo group, phosphono and phosphine oxide acyl group.
17, as the 15th or 16 described method, wherein said dispersion agent is the compound with crosslinkable or polymerisable functional group.
18, as each described method of 14-17 item, wherein said film forming curable compound is at least a in curable organic binder bond, organometallic compound and their partial hydrolysate.
19, cured film, it has the specific refractory power of 1.85-2.5 and is formed by curable coating composition, described curable coating composition contains the particulate that film forming curable compound and median size are 100nm or littler high refractive index composite oxides, the particulate of described high refractive index composite oxides comprises: bismuth element and at least a metallic element, the oxide compound of wherein said at least a metallic element have 1.95 or bigger specific refractory power.
20, antireflective film, it comprises successively: transparent carrier; As the 19th described cured film; With specific refractory power less than 1.55 low-index layer.
21, antireflective film, it comprises successively: transparent carrier; Two-layer specific refractory power differing from each other as the 19th described cured film; With specific refractory power less than 1.55 low-index layer.
22, as the 20th or 21 described antireflective film, it also comprises hard coat between described transparent carrier and described cured film.
23, polaroid comprises polarization film and protective film thereof, and wherein said protective film is as each described antireflective film of 20-22 item.
24, polaroid comprises polarization film and protective film thereof, and one of them protective film is as each described antireflective film of 20-22 item, and another protective film is to have optically anisotropic optical compensating film.
25, as the 24th described polaroid, wherein said optical compensating film comprises transparent carrier and comprises the optical compensating layer of optical anisotropic layer, described optical anisotropic layer comprises and has the unitary compound of disk-shaped structure, the described relatively transparent carrier face tilt of the unitary dish face of wherein said disk-shaped structure, and the angle between this dish face and the transparent carrier face changes at the thickness direction of described optical anisotropic layer.
26, image display device, it comprises on the display plotter surface as each described antireflective film of 20-22 item or as each described polaroid of 23-25 item.
27, image display device, comprise as each described antireflective film of 20-22 item or as each described polaroid of 23-25 item, wherein said polaroid is the polaroid on the indicating meter side of two polaroids of the both sides that are installed in liquid crystal cell, and described antireflective film is installed on the face relative with liquid crystal cell.
28, as the 26th or 27 described image display device, it is transmission-type, reflection-type or semi-transmission type liquid crystal display device, these indicating meters each TN-, STN-, IPS-, VA-or OCB-pattern naturally.
Embodiment
Be described in more detail below the present invention.
At first, be described in more detail below high refractive index layer of the present invention.
[high refractive index layer]
High refractive index layer of the present invention contains the particulate and the matrix of the composite oxides of titanium and at least a metallic element, and wherein, the oxide compound of described at least a metallic element has 1.95 or bigger specific refractory power.
High refractive index layer of the present invention has preferred 1.75-2.40, more preferably 1.80-2.40, even the more preferably specific refractory power of 1.85-2.30.
(particulates of high refractive index composite oxides)
The high refractive index particulate of composite oxides among the present invention is described below.
The particulate of composite oxides of the present invention is particles of the composite oxides of titanium elements and at least a metallic element (this paper is abbreviated as the back " Met "), described at least a metallic element is selected from its oxide compound and has 1.95 or the metallic element of bigger specific refractory power, and this is composite oxides doped at least a Co of being selected from ion, Zr ion and Al ionic metal ion.Have 1.95 or the metallic element of bigger specific refractory power as its oxide compound, preferred Ta, Zr, IN, Nd, Sb, Sn and Bi, wherein preferred especially Ta, Zr, Sn and Bi.
With titanium dioxide (TiO 2) meter, the ratio of Ti element 0.6-0.99 weight ratio preferably in the complex oxide fine particle, more preferably 0.7-0.95 weight ratio, even more preferably 0.75-0.90 weight ratio.
The particulate of these composite oxides preferably has crystalline structure for example rutile structure, rutile/anatase mixed-crystal structure, anatase structured or amorphous structure.The particulate main component particularly belongs to rutile structure.
This composite oxide particle is the composite oxide particle that is doped with at least a Co of being selected from ion, Zr ion and Al ionic metal ion.As adulterated metal ion, preferred Co ion and Zr ion, wherein preferred especially Co ion.
In view of the level that keeps specific refractory power, based on the amount of all metals [Ti+Met] of constituting composite oxides, the content of adulterated metal ion is preferably in the scope that is no more than 25 weight % in the composite oxides.This content is more preferably 0.05-10 weight %, even more preferably 0.1-5 weight %, most preferably 0.3-3 weight %.
Adulterated ion can metal ion and arbitrary form of atoms metal exist, the surface that is present in composite oxides suitably is to its inside.The preferable alloy ion not only is present in the surface of composite oxides but also be present in its inside.
When with the amount doped metal ion of above-mentioned scope, the high refractive index particulate of gained composite oxides can obtain good transparency and the high refractive index in the 380nm-600nm scope, and wherein undesirable photocatalytic activity is significantly suppressed or removes.These particulate specific refractory poweres can be adjusted in the scope of 1.98-2.60, preferably specific refractory power are adjusted in the scope of 2.00-2.55.
The weight average particle diameter of the primary particle of the high refractive index particulate of composite oxides preferably in the scope of 1-200nm, is more preferably 3-150nm, even more preferably 5-100nm, especially preferably 10-80nm.
The particle diameter of particulate can be measured according to light scattering method or by electron micrograph.The specific surface area of particulate is 15-400m preferably 2/ g, more preferably 20-200m 2/ g.
According to final purpose and in the scope of not losing specific refractory power and transparency, high refractive index complex oxide fine particle of the present invention can also contain other element.Described other element can be used as impurity and is contained in wherein, therefore has no particular limits.The example of described other element comprises Li, Be, B, Na, Mg, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb etc.For example, add Si formation ternary compound oxides and be used to make the thinner and raising particulate dispersiveness of particle.
The high refractive index composite oxides can be synthetic according to the known sintering process of routine, sol-gel method, sputtering method or CVD method.For example, can be referring to by editor's such as KozoTabe Kinzoku Sankabutsu To Fukugo Sankabutsu(publishing in 1978) by Kabushikikaisha Kodansha; Jpn.J.Appl.Phys.The 32nd volume 4158-4162 page or leaf (1993); JP-A-11-71103; JP-A-11-228139; Description among JP-A-11-79746 and the JP-A-2002-206062.
As method, can use conventional known method with doping agent Co ion, Al ion or Zr ion doping composite oxides.For example, can prepare doping oxide (the Ion Beam Oyo Gijutsu that for example is described in that Shun-ichi Gonda, Junzo isikawa and Eiji Kamijo edit and published in 1989 by K.K.CMC according to ion implantation; YasushiAoki, Hyomen Kagaku, Vol.18 (5), the 262nd page 1998; With Hyomen KagakuVol.20 (2), the 60th page, 1999) or the method described in JP-A-5-330825, JP-A-11-263620, JP-T-11-512336 (term used herein " JP-T " is meant that the translator of Japanese of PCT patent application is open) or the EP-A-0335773.
The high refractive index particulate of complex oxide fine particle of the present invention can pass through surface treatment.This surface treatment can be undertaken by using at least a compound modified particle surface that is selected from mineral compound and organic compound, and described compound is used for adjusting the wet performance of particle surface so that these particles are thinner and improve dispersiveness or dispersion stabilization in the composition that forms high refractive index layer at organic solvent.The example that is used for the surface-treated mineral compound comprises and contains cobalt mineral compound (for example, CoO 2, Co 2O 3And Co 3O 4), aluminum contained compound (for example, Al 2O 3And Al (OH) 3), contain zirconium mineral compound (for example, ZrO 2And Zr (OH) 4) and silicon-containing inorganic compound (for example, SiO 2).
As being used for the surface-treated organic compound, can use the conventional known for example surface-modifying agent of metal oxide or mineral dye of mineral filler that is used for.For example, they are described in Ganryo Bunsan Anteika To Hyomen Shori GijutsuHyoka, the 1st chapter (publishing in calendar year 2001) by Gijutsu Joho Kyokai.
More particularly, described and had organic compound and the coupling compound that the surface of high refractive index complex oxide fine particle is had the polar group of avidity.The example that the surface of high refractive index complex oxide fine particle is had the polar group of avidity comprises carboxyl, phosphono, hydroxyl, sulfydryl, cyclic acid anhydride group and amino.The compound that preferably has at least one polar group at intramolecularly.The example (for example comprises long-chain fat family carboxylic acid; stearic acid, lauric acid, oleic acid, linolic acid, linolenic acid etc.), polyol compound (for example; the glycerol tri-acrylate of pentaerythritol triacrylate, five vinylformic acid dipentaerythritol ester, ECH-modification etc.), the compound that contains phosphono (for example; the tricresyl phosphate acrylate of EO (oxyethane)-modification etc.), alkanolamine (for example, quadrol EO affixture (5mol) etc.).
As coupling compound, conventional known organometallic compound has been described, comprise silane coupling agent, titanate coupling agent and aluminate coupling agent.Silane coupling agent most preferably.Particularly, for example be described in those compounds in JP-A-2002-9908 and JP-A-2001-31-423 [0011]-[0015] section.
Be used for the surface-treated above-claimed cpd and can two or more mix use.In order to have hydrophobic performance through surface treatment by the surface that makes the high refractive index complex oxide fine particle with organic compound and/or organometallic compound, this organic compound and/or organometallic compound with polar group is dissolved in the organic solvent, and will through or be not scattered in this solution through the surface-treated high refractive index complex oxide fine particle of mineral compound, then organic solvent is evaporated fully, particle surface is coated with thus.
Complex oxide fine particle of the present invention can be used as the particulate of nuclear core/containment structure, and wherein particle is made of the nuclear core with the shell that comprises mineral compound.As shell, preferably include the oxide compound of the element of at least a Al of being selected from, Si and Zr.Particularly, for example, be described among the JP-A-2001-166104 those.
Shape to the particulate of high refractive index composite oxides contained in the high refractive index layer has no particular limits, and can be grain of rice shape, spherical, cubic, spindle shape, needle-like and uncertain shape.
(dispersion of the particulate of high refractive index composite oxides)
High refractive index layer of the present invention preferably by using dispersion agent to disperse the high refractive index composite oxide particle to prepare the composition that is used to form high refractive index layer, is applied to said composition on transparent carrier or other layer, and is dry then and form.
Be used to disperse the dispersion agent of high refractive index complex oxide fine particle preferably to have low molecular compound or the polymer compound that the surface of complex oxide fine particle is had the polar group of avidity.
The example of polar group comprise hydroxyl, sulfydryl, carboxyl, sulfo group, phosphono, phosphine oxide acyl group ,-P (=O) (R) (OH) group ,-O-P (=O) (R) (OH) group, sulfonamido, the group that contains cyclic acid anhydride, amino and quaternary ammonium group.In above-mentioned group, the R representative contains the alkyl (for example, methyl, ethyl, propyl group, butyl, hexyl, octyl group, decyl, dodecyl, octadecyl, benzyl, styroyl and cyclohexyl) of 1-18 carbon atom.In these polar groups, the group with dissociative proton can be the form of salt.Amino and quaternary ammonium group can be primary amino, secondary amino group and uncle's amino arbitrarily, wherein more preferably uncle's amino or quaternary ammonium group.With the group that secondary amino group, uncle's amino link to each other with nitrogen-atoms in the quaternary ammonium group preferably contain 1-12 carbon atom aliphatic group (for example, with above-mentioned R mention identical).In addition, uncle's amino can be to form the amino (for example, piperidine ring, morpholine ring, piperadine ring or pyridine ring) that contains azo-cycle, and quaternary ammonium group can be the quaternary ammonium group of above-mentioned ring amino.Specifically, those groups that more preferably have the alkyl that contains 1-6 carbon atom.
As the counter ion of quaternary ammonium group, preferred halogen ion, PF 6Ion, SbF 6Ion, BF 4Ion, sulfonate ion etc.
Polar group is anionic group preferably.Specifically, the salt of preferred carboxyl, sulfo group, phosphono, phosphine oxide acyl group and these groups, wherein more preferably carboxyl, phosphono and phosphine oxide acyl group.
Dispersion agent can have the various polarity group at its intramolecularly.
Dispersion agent more preferably has crosslinkable or polymerisable functional group.Term used herein " crosslinkable or polymerisable functional group " is meant the functional group that can polymerization forms polymkeric substance and by can the be cross-linked to each other functional group of polymer chain of polymer chain.
Example crosslinkable or polymerisable functional group comprise can with the free radical material (for example; (methyl) acryl, allyl group, styryl or ethylene oxy carbonyl or vinyloxy group) carry out addition reaction or polyreaction ethylenic unsaturated group, cationically polymerizable group (for example; epoxy group(ing), sulfo-epoxy group(ing), oxetanyl group, vinyloxy group or spiro original acid ester base) and the polycondensation group is (for example; hydrolyzable silyl or N-methylol), wherein preferred ethylenic unsaturated group and epoxy group(ing).
Especially, be described in those of the section of JP-A-2001-310423 [0013]-[0015] for example, although compound of the present invention is not limited in them.
As the dispersion agent that is used to disperse be used for the particulate of the thin and tall specific refractory power composite oxides of high refractive index layer of the present invention, preferred polymers dispersion agent also.Specifically, preferably has anionic group and have the polymeric dispersant of crosslinkable or polymerisable functional group.
Weight-average molecular weight (Mw) to polymeric dispersant has no particular limits, but 1x10 preferably 3Or it is bigger.Mw is more preferably 2x10 3-1x10 6, even be more preferably 5x10 3-2x10 5, especially preferred 1x10 4-1x10 5
Polar group in the polymeric dispersant and crosslinkable or polymerisable functional group be included in the terminal of main polymer chain or as substituting group in the unitary side chain that forms polymkeric substance (this paper back also is referred to as " side chain ").The polymeric dispersant that preferred polar group links to each other with the main polymer chain end and/or with side chain and crosslinkable or polymerisable functional group links to each other with side chain.As the technology that polar group is joined in the side chain, for example have will contain anionic group monomer (for example, the toxilic acid of (methyl) vinylformic acid, toxilic acid, partial esterification, methylene-succinic acid, Ba Dousuan, (methyl) vinylformic acid 2-carboxyl ethyl ester, (methyl) vinylformic acid 2-sulfo group ethyl ester, (methyl) vinylformic acid 2-phosphonato ethyl ester, (methyl) vinylformic acid 2,3-dihydroxyl propyl ester, (methyl) vinylformic acid 2-N, N-dimethylamino ethyl ester or (methyl) acryloxy ethyl trimethyl ammonium PF 6Ion salt) technology of polymeric technology and the polymer reaction that utilizes acid anhydrides on polymkeric substance, to act on hydroxyl or amino.
Have in the polymeric dispersant of polar group at side chain, based on the gross weight of polymerized unit, the content of polymerized unit that contains polar group is more preferably 1-80 weight %, especially preferably 5-50 weight % preferably in the scope of 0.1-100 weight %.
On the other hand, as the technology that polar group is joined the main chain end, (for example have at the chain-transfer agent of polar functionalities, Thiovanic acid) carries out the technology of polyreaction under the situation of Cun Zaiing, the initiator that use contains polar group (for example, V-501, by Wako Pure ChemicalIndustries, Ltd. make) carry out the technology of polyreaction and use chain-transfer agent or have reactive group for example halogen atom, hydroxyl or amino polymerization starter carry out polyreaction, add the technology of polar group then by polymer reaction.
Particularly preferred dispersion agent is the dispersion agent that has anionic group at its side chain.
As crosslinkable or polymerisable functional group; described can with the free radical material (for example; (methyl) acryl, allyl group, styryl or vinyloxy group) carry out addition reaction or polyreaction ethylenic unsaturated group, cationically polymerizable group (for example; epoxy group(ing), oxetanyl group or vinyloxy group) and the polycondensation group is (for example; hydrolyzable silyl or N-methylol), wherein preferred ethylenic unsaturated group.In addition, in these crosslinkable or polymerisable functional groups, total atom number (not comprising the hydrogen atom that links to each other with carbon atom, nitrogen-atoms, Siliciumatom etc.) between main polymer chain and crosslinkable or polymerisable group preferably 6 or more, more preferably 8-22 carries out crosslinked or polyreaction thus more reposefully.
Dispersion agent of the present invention has at side chain ethylenic unsaturated group polymerized unit as crosslinkable or polymerisable functional group is arranged.The example that has the polymerized unit of ethylenic unsaturated group at side chain, can use poly--1,2-divinyl or poly--1, the polymerized unit of 2-isoprene structure perhaps uses (methyl) acrylate that connects specific residue (COOR or-R group among the CONHR) or the polymerized unit of acid amides.The example of specific residue (R) comprises-(CH 2) n-CR 1=CR 2R 3,-(CH 2O) n-CH 2CR 1=CR 2R 3,-(CH 2CH 2O) n-CH 2CR 1=CR 2R 3,-(CH 2) n-NH-CO-O-CH 2CR 1=CR 2R 3,-(CH 2) n-O-CO-R 1=CR 2R 3With-(CH 2CH 2O) 2-X (R wherein 1-R 3Represent hydrogen atom, halogen atom (for example, fluorine atom or chlorine atom) separately, contain alkyl, aryl, alkoxyl group, aryloxy or the cyano group of 1-20 carbon atom, R 1And R 2Or R 3Optional being connected with each other forms ring, and n represents the integer of 1-10, and X represents the dicyclopentadienyl residue).The example of the specific residue in the ester moiety comprises-CH 2CH=CH 2(polymkeric substance that is equivalent to (methyl) allyl acrylate described in 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 2With-CH 2CH 2O-X (wherein X represents the dicyclopentadienyl residue).The example of specific residue comprises-CH in the amido part 2CH=CH 2,-CH 2CH 2-Y (wherein Y represents 1-cyclohexenyl residue) ,-CH 2CH 2-OCO-CH=CH 2With-CH 2CH 2-OCO-C (CH 3)=CH 2
With regard to dispersion agent, when free radical (polymerization causes the growth free radical that produces in the polymerization process of free radical or polymerizable compound) being joined the unsaturated link(age) group directly to cause or can solidify when causing polyaddition reaction intermolecular through the polymer chain of polymerizable compound intermolecular with ethylenic unsaturated group.Perhaps, the atom in molecule (for example, the hydrogen atom on the carbon atom adjacent with unsaturated link(age)) is taken away the generation free polymer readical by free radical, and this free polymer readical is connected with each other then between molecule to form and can solidifies when crosslinked.
As the technology that crosslinkable or polymerisable functional group is joined side chain, can be referring to for example, the description that provides among the JP-A-3-249653.As for unitary content with crosslinkable or polymerisable functional group, this unit can comprise all polymerized units except that the polymerized unit of polar functionalities, and total polymerization unit based on dispersion agent, the unitary content that contains crosslinkable or polymerisable group is 1-80 weight % preferably, especially preferred 3-60 weight %.
Dispersion agent of the present invention can be the polymerizable components that contains polar group, contain the polymerizable components of crosslinkable or polymerisable functional group and the multipolymer of other polymerizable components.Other copolymerizable component is had no particular limits, and can be from different perspectives for example dispersion stabilization, select with the consistency and the film forming intensity of other monomer component.Its preferred embodiment comprises methyl acrylic ester, esters of acrylic acid, vinyl carboxylate class, (methyl) acrylamide and derivative, vinylbenzene and derivative thereof and vinyl cyanide.
Dispersion agent of the present invention specifically is not limited to polymerized form, preferred block copolymer or random copolymers.In view of production cost and synthetic easness, preferred especially random copolymers.
The preferred embodiment of these dispersion agents for example is described in JP-A-11-153703 [0023]-[0042] section.
The content of the relative high refractive index complex oxide fine particle of dispersion agent preferably in the scope of 1-50 weight %, more preferably 5-30 weight %, most preferably 5-20 weight %.Two or more dispersant can be used.
Preferably under the situation that has above-mentioned dispersion agent to exist, the high refractive index complex oxide fine particle is distributed to and disperses this particulate in the dispersion medium.
As dispersion medium, preferably use boiling point at 60-170 ℃ liquid.
The example of dispersion medium comprises water, alcohols (for example, methyl alcohol, ethanol, Virahol, butanols and phenylcarbinol), ketone (for example, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and pimelinketone), the ester class (for example, methyl acetate, ethyl acetate, propyl acetate, butylacetate, methyl-formiate, ethyl formate, propyl formate and butyl formate), halogenated hydrocarbon (for example, methylene dichloride, chloroform or trichloroethane), arene (for example, benzene, toluene and dimethylbenzene), amides (for example, dimethyl formamide, N,N-DIMETHYLACETAMIDE and n-methyl-2-pyrrolidone), ethers (for example, diethyl ether diox, tetrahydrofuran (THF) and glycol dimethyl ether) and ether alcohol class (for example, 1-methoxyl group-2-propyl alcohol, ethyl cellosolve and carbinol methine).They can use separately or can two or more mix use.Preferred dispersion medium comprises toluene, dimethylbenzene, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone and butanols.
The preferred dispersion machine that uses disperses the high refractive index complex oxide fine particle.The example of dispersion machine comprises sand mill (for example, needle-like ball mill), quick runner pulverizer, pebble mill, roller mill, attritor and colloidal mill.Particularly, preferred sand mill and quick runner pulverizer.In addition, can carry out pre-dispersed processing.The example that is used for the dispersion machine of pre-dispersed processing comprises ball mill, three-roll mill, kneading machine and extrusion machine.
The high refractive index complex oxide fine particle preferably is dispersed in the dispersion medium as far as possible carefully, and weight average particle diameter 1-200nm preferably, more preferably 3-150nm, even more preferably 5-100nm, especially preferred 10-80nm.
Can be under the situation of not damaging transparency, by making the high refractive index complex oxide fine particle carefully to 200nm or the littler high refractive index layer that forms.
Based on the weight of high refractive index layer, the content of high refractive index complex oxide fine particle is 10-90 weight % preferably, more preferably 15-80 weight %, especially preferably 15-75 weight %.Two or more high refractive index complex oxide fine particles can be used for high refractive index layer.
Finish after the dispersion treatment, the high refractive index complex oxide fine particle is prepared the coating fluid that forms high refractive index layer as the dispersion liquid that also comprises dispersion agent.
Secondly, describe the preparation method of curable coating composition of the present invention below in detail.
Method of the present invention is the preparation method of curable coating composition, described composition contains high refractive index complex oxide fine particle and a kind of film forming curable compound of at least a bismuth element and at least a metallic element, described at least a metallic element is selected from its oxide compound and has 1.95 or the metallic element of bigger specific refractory power, this method comprises: use medium wet disperse high refractive index composite oxide particle and the dispersion agent of median size less than 1mm, making median size thus is 150nm or littler high refractive index complex oxide fine particle.
[curable coating composition]
Curable coating composition of the present invention contains particulate and a kind of film forming curable compound of the high refractive index composite oxides of at least a bismuth element and at least a metallic element, and the specific refractory power that described at least a metallic element is selected from its oxide compound is 1.95 or bigger metallic element.
(high refractive index complex oxide fine particle)
The high refractive index complex oxide fine particle comprises the complex oxide fine particle of bismuth element (Bi) and at least a metallic element (this paper also is abbreviated as the back " Met "), and the specific refractory power that described at least a metallic element is selected from its oxide compound is 1.95 or bigger metallic element.Have 1.95 or the metallic element of bigger specific refractory power as its oxide compound, preferred Ti, Ta, Zr, IN, Nd, Sb and Sn, wherein more preferably Ti, Ta and Zr.
In addition, in mol ratio [Bi/Bi+Met], the ratio of Bi in complex oxide fine particle be 0.01-0.15 preferably, more preferably 0.02-0.13, especially preferably 0.03-0.10.The particulate of ratio in this scope can obtain having remarkable high refractive index keeps good transparency simultaneously in the scope of 380nm-600nm wavelength cured film.
The structure of complex oxide fine particle is considered to one matter, mixture or amorphism material or its composite oxides of the oxide compound of element separately.Do not help to improve specific refractory power although know which factor, because the existence of Met-Bi-O mode configuration, complex oxide fine particle of the present invention has than Bi oxide compound (that is Bi, 2O 3) or Met oxide compound (that is TiO, 2, Ta 2O 5, ZrO 2Deng) high specific refractory power.Equally, in view of obtaining high refractive index, this complex oxide fine particle preferably has crystalline structure.
Complex oxide fine particle of the present invention does not have can also contain other element in the scope of infringement in refractive index and transparency according to final purpose, forms the multielement composite oxides thus.Other element can be used as impurity and involved, therefore has no particular limits.The example of other element comprises Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Sn, Sb, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb etc.For example, add Si or Al and be used to make the thinner and raising particulate dispersiveness of particle.
Complex oxide fine particle can be synthetic according to the known sintering process of routine, sol-gel method, sputtering method or CVD method.For example, can be with reference to editors' such as Kozo Tabe Kinzoku Sankabutsu To Fukugo Sankabutsu(publishing in 1978) by Kabushikikaisha Kodansha; Jpn.J.Appl.Phys.Vol.32, pp.4158-4162 (1993); JP-A-11-71103; JP-A-11-228139; Description among JP-A-11-79746 and the JP-A-2002-206062.
Composite oxide particle of the present invention can pass through surface treatment.This surface treatment can be undertaken by using mineral compound and/or organic compound modified particles surface, and described surface treatment is used for adjusting the wet performance of particle surface so that particle is thinner and improve dispersiveness or dispersion stabilization in the composition that forms high refractive index layer at organic solvent.
As being used for the surface-treated mineral compound, be adsorbed on the mineral compound on the particle surface with having described physical chemistry, the example comprises silicon-containing inorganic compound (SiO for example 2), contain aluminium mineral compound (Al for example 2O 3, Al (OH) 3Deng), contain cobalt mineral compound (for example, CoO 2, CO 2O 3, CO 3O 4Deng), contain zirconium mineral compound (for example, ZrO 2, Zr (OH) 4Deng) and iron content mineral compound (for example, Fe 2O 3).
As being used for the surface-treated organic compound, can use conventional known to the mineral filler surface-modifying agent of metal oxide or mineral dye for example.For example, they are described in Ganryo Bunsan Anteika To Hyomen Shori GijutsuHyoka, Chapter 1 (publishing in calendar year 2001) by GijutsuJoho Kyokai.
More particularly, above-mentioned organic compound has been described.
In addition, complex oxide fine particle of the present invention can be doped with at least a Co of being selected from ion, Zr ion and Al ionic metal ion.In view of keeping refractive index value, based on the gross weight of the metal that constitutes composite oxides, the content that is doped in the metal ion in the composite oxides preferably is no more than 20 weight %.This content is 0.05-10 weight % more preferably, even more preferably 0.1-5 weight %, most preferably 0.3-3 weight %.Adulterated metal ion can exist with the state of metal ion or atoms metal, and may reside in any appropriate location from the surface to inside.
The complex oxide fine particle that well keeps high refractive index with the metal ion mixing complex oxide fine particle with the acquisition photostabilization simultaneously.In above-mentioned metal ion, the Co ion preferably mixes.
As with metal ion mixing particulate method, can use conventional known method.For example, can use the inject ions method (by Shun-ichi Konta, Junzo Isikawa with EijiKamijo edits and published in 1989 by Kabusiki Kaisha CMC Ion Beam Oyo KijutsuYasushi Aoki, Hyomen Kagaku, Vol.18 (5), p262,1998; With Shoichi Abo etc., Hyomen Kagaku, Vol.20 (2), p60,1999).
Based on the gross weight of curable coating composition, the content of complex oxide fine particle in curable coating composition is preferably 40-75 weight %, more preferably 45-65 weight %.Fashionable when adding with the content in this scope, the cured film that uses this curable coating composition to form has gratifying film strength and high refractive index.This complex oxide fine particle can two or more mix use.
(dispersion agent)
The dispersion agent that is used for preparation method of the present invention is had no particular limits, but preferred micromolecular compound or have the polymer compound that the surface of complex oxide fine particle is had the polar group of avidity.
The example of the polar group that dispersion agent of the present invention has comprise hydroxyl, sulfydryl, carboxyl, sulfo group, phosphono, phosphine oxide acyl group ,-P (=O) (R 1) (OH) group, amido (CONHR 2,-SO 2NHR 2), contain group, amino and the quaternary ammonium group of cyclic acid anhydride.In above-mentioned group, R 1Representative contains the alkyl (for example, methyl, ethyl, propyl group, butyl, hexyl, oxtyl, decyl, dodecyl, octadecyl, chloroethyl, methoxy ethyl, cyano ethyl, benzyl, methyl-benzyl, styroyl and cyclohexyl) of 1-18 carbon atom.Equally, R 2Represent hydrogen atom or and R 1Identical group.
In these polar groups, these groups with disassociation proton can be the form of salt.
In addition, amino and quaternary ammonium group can be primary amino, secondary amino group and uncle's amino arbitrarily, wherein more preferably uncle's amino or quaternary ammonium group.The group that links to each other with nitrogen-atoms in secondary amino group, uncle's amino or the quaternary ammonium group preferably contains the aliphatic group (for example, described identical with above-mentioned R) of 1-12 carbon atom.In addition, uncle's amino can be to form the amino (for example, piperidine ring, morpholine ring, piperadine ring or pyridine ring) that contains azo-cycle, and quaternary ammonium group can be the quaternary ammonium group of above-mentioned ring amino.Specifically, those groups that more preferably have the alkyl that contains 1-6 carbon atom.
As the counter ion of quaternary ammonium group, preferred halogen ion, PF 6Ion, SbF 6Ion, BF 4Ion, B (R 3) 4Ion (R wherein 3Representation hydrocarbyl, for example butyl, phenyl, tolyl, naphthyl or butyl phenyl, sulfonate ion etc.).
Polar group is anionic group preferably.Specifically, the salt of preferred carboxyl, sulfo group, phosphono, phosphine oxide acyl group and these groups, wherein even more preferably carboxyl, phosphono and phosphine oxide acyl group.
In addition, dispersion agent can have the various polarity group at intramolecularly.
Dispersion agent more preferably has crosslinkable or polymerisable functional group.Example crosslinkable or polymerisable functional group comprise can with the free radical material (for example; (methyl) acryl, allyl group, styryl, vinyloxy group carboxyl or vinyl oxygen base) carry out addition reaction or polyreaction ethylenic unsaturated group, cationically polymerizable group (for example; epoxy group(ing), sulfo-epoxy group(ing), oxetanyl group, vinyloxy group or spiro original acid ester group); and polycondensation group (for example hydrolyzable silyl or N-methylol), wherein preferred ethylenic unsaturated group and epoxy group(ing).
Particularly, those that describe have for example been described in the section of JP-A-2001-310423 [0013]-[0015].
As dispersion agent of the present invention, more preferably polymeric dispersant.Specifically, preferably has anionic group as polar group and have the polymeric dispersant of crosslinkable or polymerisable functional group.
In view of the polystyrene of measuring according to the GPC method, the weight-average molecular weight (Mw) of polymeric dispersant is had no particular limits, but be preferably 1x10 3Or it is bigger.This Mw is more preferably 2x10 3-1x10 6, even more preferably 5x10 3-1x10 5, especially preferred 8x10 3-8x10 4
The polymeric dispersant effect of Mw in this scope is fully to disperse these particulates and stable dispersion is provided, and do not form aggregate or precipitation.
Polar group in the polymeric dispersant and crosslinkable or polymerisable functional group are included in main chain terminal of polymkeric substance or form as substituting group in the unitary side chain of polymkeric substance (this paper back also is referred to as " side chain ").Polar group preferably links to each other with the terminal of main polymer chain and/or with side chain, and crosslinkable or polymerisable functional group preferably links to each other with side chain.
As the technology that polar group is joined the main chain end, (for example have at the chain-transfer agent of polar functionalities, Thiovanic acid) carries out the technology of polyreaction under the situation of Cun Zaiing, the initiator of use polar functionalities (for example, V-5-1, by Wako Pure Chemical Industries, Ltd. make) carry out the technology of polyreaction and use chain-transfer agent or have reactive group for example halogen atom, hydroxyl or amino polymerization starter carry out polyreaction, add the technology of polar group then by polymer reaction.
As the technology that polar group is joined side chain, (for example for example have the monomer of polar functionalities, the toxilic acid of (methyl) vinylformic acid, toxilic acid, partial esterification, methylene-succinic acid, Ba Dousuan, (methyl) vinylformic acid 2-carboxyl ethyl ester, (methyl) vinylformic acid 2-sulfo group ethyl ester, (methyl) vinylformic acid 2-phosphonato ethyl ester, (methyl) vinylformic acid 2,3-dihydroxyl propyl ester, (methyl) vinylformic acid 2-N, N-dimethylamino ethyl ester, (methyl) acryloxy ethyl trimethyl ammonium PF 6Ion salt) or the affixture polymeric technology of the unsaturated compound of hydroxyl and cyclic acid anhydride (for example maleic anhydride, Pyroglutaric acid or phthalate anhydride) and utilize polymer reaction technology (for example, the reaction between the acid compound that hydroxyl, amino or epoxy group(ing) and acid anhydrides or halogen replace and isocyano group or carboxyl with have hydroxyl or the acid compound of amino between reaction).
As the specific examples of the polymeric constituent of polar functionalities, can be with reference to the description that provides in the section of JP-A-11-153703 [0024]-[0041].
In addition, have in the polymeric dispersant of polar group at side chain, based on the gross weight of polymerized unit, the content of polymerized unit that contains polar group preferably in the scope of 0.5-50 weight %, more preferably 1-40 weight %, especially preferred 5-30 weight %.
In addition, when crosslinkable or polymerisable group links to each other with side chain, total atom number (not comprising the hydrogen atom that links to each other with carbon atom, nitrogen-atoms, Siliciumatom etc.) between main polymer chain and crosslinkable or polymerisable group preferably 6 or more, even more preferably 8-22, carry out crosslinked or polyreaction thus more reposefully.
Dispersion agent of the present invention preferably has at side chain ethylenic unsaturated group polymerized unit as crosslinkable or polymerisable functional group is arranged.The example that has the polymerized unit of ethylenic unsaturated group at side chain, can utilize poly--1,2-divinyl or poly--1, the polymerized unit of 2-isoprene structure or connect (methyl) acrylate of specific residue (COOR or-R among the CONHR) or the polymerized unit of acid amides.The example of specific residue (R) comprises-(CH 2) n-CR 1=CR 2R 3,-(CH 2O) n-CH 2CR 1=CR 2R 3,-(CH 2CH 2O) n-CH 2CR 1=CR 2R 3,-(CH 2) n-NH-CO-O-CH 2CR 1=CR 2R 3,-(CH 2) n-O-CO-R 1=CR 2R 3With-(CH 2CH 2O) 2-X (R wherein 1-R 3Represent hydrogen atom, halogen atom (for example, fluorine atom or chlorine atom) separately, contain alkyl, aryl, alkoxyl group, aryloxy or the cyano group of 1-20 carbon atom, R 1And R 2Or R 3Optional being connected with each other forms ring, and n represents the integer of 1-10, and X represents the dicyclopentadienyl residue).The example of the specific residue in the ester moiety comprises-CH 2CH=CH 2(polymkeric substance that is equivalent to (methyl) allyl acrylate described in 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 2With-CH 2CH 2O-X (wherein X represents the dicyclopentadienyl residue).The example of specific residue comprises-CH in the amido part 2CH=CH 2,-CH 2CH 2-Y (wherein Y represents 1-cyclohexenyl residue) ,-CH 2CH 2-OCO-CH=CH 2With-CH 2CH 2-OCO-C (CH 3)=CH 2
With regard to dispersion agent, when free radical (polymerization causes the growth free radical that produces in the polymerization process of free radical or polymerizable compound) being joined the unsaturated link(age) group directly to cause or can solidify when causing polyaddition reaction intermolecular through the polymer chain of polymerizable compound intermolecular with ethylenic unsaturated group.Perhaps, the atom in molecule (for example, the hydrogen atom on the carbon atom adjacent with unsaturated link(age)) is taken away the generation free polymer readical by free radical, and this free polymer readical is connected with each other then between molecule to form and can solidifies when crosslinked.
As the technology that crosslinkable or polymerisable functional group is joined side chain, can be referring to for example, the description that provides among the JP-A-3-249653.
In addition, about having the content of crosslinkable or polymerisable functional group, this group can comprise all polymerized units except that the polymerized unit of polar functionalities, and total polymerization unit based on dispersion agent, the unitary content that contains crosslinkable or polymerisable group is 1-70 weight % preferably, especially preferred 5-50 weight %.
Dispersion agent of the present invention can be the polymerizable components that contains polar group, contain the polymerizable components of crosslinkable or polymerisable functional group and the multipolymer of other polymerizable components.Other polymerizable components is had no particular limits, as long as it can with corresponding to the polymerizable components of polar functionalities with contain the monomer copolymerizable of the copolymerizable component of crosslinkable or polymerisable functional group, and can be from different perspectives for example dispersion stabilization with become film toughness to select.Its preferred embodiment comprises methyl acrylic ester, esters of acrylic acid, vinyl carboxylate class, (methyl) acrylamide and derivative, vinylbenzene and derivative thereof and vinyl cyanide.Based on all polymerizable components, the content of other polymerizable components in polymeric dispersant is 5-95 weight % preferably, more preferably 30-85 weight %.For example in the section of JP-A-11-153703 [0023]-[0042], provided the specific examples of other polymerizable components.
Dispersion agent of the present invention specifically is not limited to polymerized form, preferred block copolymer or random copolymers.And, preferably by the polymer blocks A of the polymerizable components that contains crosslinkable or polymerisable group (block A) with contain AB block copolymer, ABA block polymer and the graft type segmented copolymer that the polymer blocks B of the polymerizable components (B block) of polar functionalities constitutes.The block copolymer structure of dispersion agent makes people complex oxide fine particle can be transformed into particulate and improves the stability of gained dispersion liquid and the thickness of cured film.This may be owing to polymer chain in dispersion solvent is adsorbed on the complex oxide fine particle with the shape of tail form, is convenient to easier the carrying out of solidify reaction process that high polymer is adsorbed on the particulate and makes polymer blocks (block A) like this.
Can prepare these segmented copolymers according to the known living polymerization method of routine.Promptly, AB type and ABA block polymer can be by for example ionic polymerization reactions of known so-called living polymerization (using organometallic compound (for example, lithium alkylide, LDA or alkyl magnesium halide) or hydrogen iodide/iodine system), use porphyrin metal complex to move polyreaction as photopolymerization reaction, the group of catalyzer or use the compound that contains dithiocarbamate groups group and/or contain the polyreaction of the compound of xanthate group as initiator under the irradiation of light.
This living polymerization can be according to for example P.Lutz, P.Masson etc., Polym.Bull.12,79 (1984), B.C.Anderson, G.D.Andrews etc., Macromolecules, 14,1601 (1981), Koichi Migite and Koichi Hatada, Kobunshi Kako, 36,366 (1987), Toshinobu Higashimura and Mitsuo Sawamoto, Kobunshi Ronbunshu, 46,189 (1989), M.Kuroki and T.Aida, J.Am.Chem.Soc., 109,4737 (1987), D.Y.Sogah, W.R.Hertler etc., Macromolecules, 20,1473 (1987), Takayuki Otsu, Kobunshi, 37, k 248 (1988) and Shun-ichiHimori and Ryuichi Otsu, Polym.Rep.Jap., the synthetic method described in 37,3508 (1988) is carried out.
AB block copolymer also can by use the synthetic big monomer of simple function group through the method for the synthetic graft type copolymer of Raolical polymerizable synthetic (the synthetic big monomer methods of simple function group is described in document Yoshiki Nakajo and Yuya Yamashita, Senryo To Yakuhin, 30,232 (1985), Akira Ueda and Susumu nagai, Kagaku To Kogyo, 60,57 (1986), P.F.Pempp and E.Franta, Advances in Polymer Science, in 58,1 (1984) etc.) or the method for Raolical polymerizable that can be by using azo two high polymers initiators synthetic (Akira Ueda and Susumu Nagai, Kagaku To Kogyo, 60,57 (1986) etc.).
The amount of the relative complex oxide fine particle of dispersion agent preferably in the scope of 1-100 weight %, more preferably 5-50 weight %, most preferably 10-40 weight %.Two or more dispersant can be used.
(dispersion medium)
As the wet dispersion medium that disperses complex oxide fine particle of the present invention, preferably using boiling point is 50 ℃ or bigger liquid.More preferably boiling point is 60 ℃-180 ℃ a organic solvent.
The example that is used for dispersion medium of the present invention comprises that alcohols (for example, methyl alcohol, ethanol, propyl alcohol, butanols, phenylcarbinol, ethylene glycol, propylene glycol and ethylene glycol acetate), ketone (for example, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone and methylcyclohexanone), the ester class (for example, methyl acetate, ethyl acetate, propyl acetate, butylacetate, ethyl formate, propyl formate, butyl formate and ethyl lactate), aliphatic hydrocrbon (for example, hexane and hexanaphthene), halohydrocarbon (for example, trichloroethane), aromatic hydrocarbon (for example, benzene, toluene and dimethylbenzene), acid amides (for example, dimethyl formamide, N,N-DIMETHYLACETAMIDE and n-methyl-2-pyrrolidone), ethers (diox for example, tetrahydrofuran (THF), glycol dimethyl ether and propylene glycol dimethyl ether) and ether alcohol (for example, 1-methoxyl group-2-propyl alcohol, ethyl cellosolve and carbinol methine).They can use separately or two or more mix use.Preferred dispersion medium comprises toluene, dimethylbenzene, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone and butanols.
Dispersion medium makes components contents preferably 5-50 weight %, more preferably the 10-30 weight % of all dispersive compositions comprise complex oxide fine particle and dispersion agent with a certain amount of use.In this scope, disperse easily, and obtain dispersion liquid with good workability viscosity.
(refinement high refractive index composite oxide particle)
High refractive index complex oxide fine particle of the present invention is that 150nm or littler thin attitude are dispersed in the curable coating composition with the median size.Therefore, the cured film that is formed by this curable coating composition can be the cured film with transparent, high refractive index of uniform optical characteristic.
Only by using median size to be not more than the medium of 1mm and the wet dispersion method of dispersion agent just can realize making the high refractive index composite oxide particle be separated into the particulate of above-mentioned median size.
As wet dispersion machine, can be conventional known, for example sand mill (for example, needle-like ball mill), dynomil, quick runner pulverizer, pebble mill, roller mill, attritor and colloidal mill.Specifically, for complex oxide fine particle of the present invention being dispersed into particulate, preferred sand mill, dynomil and quick runner pulverizer.
As the medium that is used for dispersion machine, use median size to be 100nm or the littler and uniform fine inorganic particle of particle diameter to obtain median size less than the medium of 1mm.The median size of medium is 0.8mm or littler preferably, more preferably 0.1-0.5mm.
In addition, as being used for wet dispersive medium, preferred pearl.Its specific examples comprises zirconium oxide bead, granulated glass sphere, ceramic bead and steel ball.Because its wearing quality and little particle diameter, preferred especially median size is the zirconium oxide bead of 0.1-0.5mm.
Preferably 20-60 ℃ of the dispersion temperature of dispersion steps, more preferably 25-45 ℃.Disperse particulate can not cause reassociating of discrete particles under the temperature in this scope and precipitate.This may be owing to carry out the absorption of dispersion agent on composite oxide particle suitably, can not take place from the dispersion stabilization defective that the particle desorb causes because of dispersion agent thus.
In addition, before wet dispersion steps, can carry out pre-dispersed processing.The example that is used for the dispersion machine of pre-dispersed processing comprises ball mill, three-roll mill, kneading machine and extrusion machine.
The present invention is preferably thin as far as possible in dispersion medium by the complex oxide fine particle of wet dispersion method preparation, and its weight average particle diameter in curable coating composition is 150nm or littler.Only in this scope, composition can form the high refractive index film that does not damage transparency and have excellent homogeneous refractive index.The median size of complex oxide fine particle is 5-150nm preferably, more preferably 10-100nm, even more preferably 10-80nm.
In addition, not contain median size be 500nm or bigger macrobead to preferred particulate.Based on all particles, these oarse-grained content preferably 10% or littler.And median size is that 300nm or bigger particulate content are 10% or littler.
Shape to complex oxide fine particle has no particular limits, and can be grain of rice shape, spherical, cubic, spindle shape, staple fibre shape and uncertain shape.
In addition, high refractive index complex oxide fine particle of the present invention can preferably be examined the particulate of core/containment structure, and its center core is that particulate and shell comprise mineral compound.As for shell, the preferred at least a oxide compound that is selected from following element al, Si and Zr.Particularly, for example described in the JP-A-2001-166104.
[cured film]
Cured film of the present invention is the curable coating composition that contains at least a high refractive index complex oxide fine particle and film forming curable compound by coating, forms with the form of uniform thin film through light and/or thermofixation then.
The cured film that is formed by curable coating composition of the present invention preferably has 1.85-2.50, more preferably the high refractive index of 1.90-2.30.
In addition, the size that is present in the particulate in the matrix of cured film is that median size is 100nm or littler, preferred 5-100nm, more preferably 10-100nm, most preferably 10-80nm.
Describe the matrix that is used for high refractive index layer below in detail and be used for film forming curable compound.
High refractive index layer contains the particulate and the matrix of at least a high refractive index oxide.
According to a preferred embodiment of the present invention, the matrix that is used for high refractive index layer is to be used to form the composition of high refractive index layer and it is solidified to form by coating, and described composition contains (1) curable organic binder bond and (2) and has at least a in the organometallic compound of hydrolyzable functional group and/or its partial condensate.
The film forming curable compound is that (1) curable organic binder bond and (2) have at least a in the organometallic compound of hydrolyzable functional group and/or its partial condensate.The preferred combination of using (1) and (2).
(1) curable organic binder bond
As curable organic binder bond, it is the tackiness agent that is formed by following substances:
(i) conventional known thermoplastic resin;
The combination of (ii) conventional known reactive curable resin and solidifying agent; With
The (iii) combination of binder precursor (curable polyfunctional monomer that this paper back will be described or multifunctional oligopolymer) and polymerization starter.
Be used to form the coating composition of high refractive index layer or curable coating composition (this and after, term " coating composition " not only is meant the coating composition that is used to form high refractive index layer but also is meant curable coating composition) be above-mentioned by containing (i), (ii) or the dispersion liquid of the component that forms tackiness agent (iii), high refractive index complex oxide fine particle and dispersion agent preparation.This coating composition is applied to forms coated thin film on the transparent carrier, solidify by the method that is fit to used formation special adhesive component then, form high refractive index layer thus.Curing is suitably to select according to the kind of binder ingredients.For example, have by the heating or rayed at least a mode cause the crosslinking reaction of curing compound (for example, polyfunctional monomer or polyfunctional group oligopolymer) or the method for polyreaction.Particularly, preferably use above-mentioned combination (iii) to cause the crosslinking reaction of curable compound or the method that polyreaction forms cure adhesive by rayed.
And, preferably in the coating coating composition or cause the crosslinking reaction or the polyreaction of dispersion agent contained in the dispersion liquid of high refractive index complex oxide fine particle afterwards.
In high refractive index layer that makes thus or cured film, the presoma of dispersion agent and tackiness agent, curable polyfunctional monomer or polyfunctional group oligopolymer, through crosslinked or polyreaction, so the anionic group in the dispersion agent is brought in the tackiness agent.And, tackiness agent in high refractive index layer or cured film works and makes anionic group can keep the dispersion state of fine inorganic particle, therefore should be crosslinked or paradigmatic structure give the tackiness agent film forming ability, thereby raising contains physical strength, chemical resistance and the weathering resistance of the high refractive index layer or the cured film of high refractive index complex oxide fine particle.
The example of thermoplastic resin comprises polystyrene resin, vibrin, celluosic resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinylchlorid/vinyl acetate copolymer resin, polyacrylic resin, polymethacrylate resin, polyolefin resin, urethane resin, silicone resin and imide resin.
In addition, as reactive curable resin, preferably use thermoset and/or ionizing rays-curable resin.The example of thermosetting resin comprises resol, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, urethane resin, Resins, epoxy, amino-alkyd resin, melamine-urea cocondensation resin, silicone resin and polyorganosiloxane resin.The example of ionizing rays-curable resin comprise have functional group for example free redical polymerization unsaturated group (for example, acryloxy, styryl or vinyloxy group) and/or the group of cationically polymerizable is (for example, Resins, epoxy or sulfo-epoxy) resin, and the example of these resins has vibrin, polyether resin, acrylic resin, Resins, epoxy, urethane resin, Synolac, spiral shell acetal resin, polybutadiene and polythiol polyene resin.
These reactive curable resins if necessary, can for example linking agent be (for example by adding conventional compound known, epoxy compounds, polyisocyanate compounds, polyol compound, polyamino compound or melamine compound), polymerization starter (for example, the ultraviolet initiator is azo two compounds, organic peroxy compound, organic halogen compound, salt compound or ketone compound for example) and polymerization accelerator (for example, organometallic compound, acid compound or alkali cpd) and using.Particularly, for example, write at Shinzo Yamasita and Tosuke Kaneko Kakyo HandbookThose compounds of describing in (publishing in 1981) by Taiseisha.
Now, be described, promptly adopt the foregoing combination of this paper (3) to form the method for tackiness agent by the crosslinked or polyreaction that causes curable compound with rayed with reference to the preferred method that forms cure adhesive.
As the polyfunctional monomer that can photocuring or the functional group of polyfunctional group oligopolymer, describe that have can polymeric functional group by ultraviolet ray, electron beam or radiation irradiation.Wherein, but the functional group of preferred especially polymerizable ultraviolet.The functional group of photo curable polyfunctional monomer or polyfunctional group oligopolymer can be free redical polymerization or cationically polymerizable.
As the group of free redical polymerization, describing has ethylenic unsaturated group for example (methyl) acryl, vinyloxy group, styryl and allyl group, wherein preferred (methyl) acryl.
The polyfunctional monomer that preferably has the group of 2 or more free redical polymerizations at intramolecularly.
The polyfunctional monomer of free redical polymerization is preferably to be selected from has the compound that at least two ends are the ethylenic unsaturated link(age).More preferably have 2-6 end and be the compound of ethylenic unsaturated link(age) at intramolecularly.These compounds are widely known in the polymer materials field, and they can use without any specific limited ground.For example they can be monomer, prepolymer, that is, and and the chemical species of dipolymer, trimer or oligopolymer or its mixture or its multipolymer.The monomeric example of free redical polymerization comprises that unsaturated carboxylic acid (for example, vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, iso-crotonic acid or toxilic acid), their ester or acid amides, and ester and the acid amides between unsaturated carboxylic acid and aliphatic poly-amine compound between preferred unsaturated carboxylic acid and the aliphatic polyol compound.Equally, can use at esters of unsaturated carboxylic acids or have nucleophilic substitution base for example acid amides and the affixture between simple function group or many functional group isocyanates or the epoxy compounds and the dehydration condensation of polyfunctional group carboxylic acid of hydroxyl, amino or sulfydryl.In addition, preferably at esters of unsaturated carboxylic acids or have electrophilic substituent for example isocyano group or the acid amides of epoxy group(ing) and the reaction product between simple function group or polyfunctional group alcohols, amine or the thio-alcohol.As other example, also can use by using unsaturated phosphoric acid or vinylbenzene to replace the compound of unsaturated carboxylic acid preparation.
The aliphatic polyol examples for compounds comprises ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, glycol ether, neopentyl glycol, TriMethylolPropane(TMP), trimethylolethane, cyclohexanediol, phloroglucite, inositol, cyclohexanedimethanol, tetramethylolmethane, Sorbitol Powder, Dipentaerythritol, tripentaerythritol, glycerine and Glycerol dimer.As the polymerisable examples for compounds between aliphatic polyol and unsaturated carboxylic acid, have at the compound described in the section of JP-A-2001-139663 [0026]-[0027].
As other example of polymerisable ester, can preferably use the aliphatic alcohol class ester described in methacrylic acid vinyl ester, allyl methacrylate, vinylformic acid allyl ester, JP-B-46-27926, JP-B-51-47334 and the JP-A-57-196231 for example, have fragrant skeleton and be described among the JP-A-2-226149 those, also can preferably use the amino compound that has described in the JP-A-1-165613.
In addition, the specific examples of the polymerisable amide monomer between aliphatic polyamine compound and unsaturated carboxylic acid comprises methylene radical two-(methyl) acrylamide, 1,6-hexa-methylene two-(methyl) acrylamide, diethylenetriamine three (methyl) acrylamide, xylylene two (methyl) acrylamide and have the cyclohexylidene structure and be described in compound among the JP-B-54-21726.
In addition, also can use have 2 or a plurality of polymerisable vinyl at intramolecularly the vinyl urethane compounds (for example, JP-B-48-41708), the urethane acrylate class (for example, JP-B-2-16765), the urethane compounds with ethylene oxide skeleton (for example, JP-B-62-39418), the polyester acrylate class (for example, JP-B-52-30490) and Nihon Secchaku Kyokaishi, vol.20, No.7, photo curable monomer and the oligopolymer described in the pp.300-308 (1984).
The polyfunctional monomer of these free redical polymerizations can use in its two or more mixing.
Next, describe the group contain cationically polymerizable compound (this and after be referred to as " compound of cationically polymerizable " or " organic compound of cationically polymerizable ").
As the compound that is used for cationically polymerizable of the present invention, can use active can situation radiation-sensitive, that cationic polymerization initiators exists under with active any compound through polyreaction and/or crosslinking reaction can radiation exposure the time.Its representative instance comprises epoxy compounds, epithio ether compound, cyclic ether compounds, spiro original acid ester compound and vinyl ether compound.In the present invention, can use the compound of one or more cationically polymerizables.
As the compound of the group that contains cationically polymerizable, preferably have the compound of the group of 2-10 cationically polymerizable at intramolecularly, wherein especially preferably have the compound of the group of 3-5 cationically polymerizable.The molecular weight of solidifying agent is 3000 or littler, preferably in the scope of 200-2000, in the scope particularly preferably in 400-1500.If molecular weight is too little, the evaporation in the film forming step process becomes problem, and if molecular weight is too big, therefore with the consistency variation of cellulose-acrylate doped compositions, this molecular weight is not preferred.
As epoxy compounds, describing has aliphatic epoxy compounds and aromatic epoxy compound.
As aliphatic epoxy resin, the homopolymer or the multipolymer of many glycidyl esters, glycidyl acrylate or the glycidyl methacrylate of polyglycidyl ether that aliphatic polyol or its alkylene oxide affixture are arranged, long aliphatic chains polyprotonic acid for example described.And, except above-mentioned epoxy compounds, the monoglycidyl ether of aliphatic higher alcohols, glycidyl ester, epoxidised soybean oil, butyl epoxy stearate, octyl epoxy stearate, epoxidized linseed and the epoxidized polybutadiene of higher aliphatic acid for example can be arranged.
In addition, as alicyclic epoxide compound, description have the polyvalent alcohol with at least one alicyclic ring polyglycidyl ether and by with the suitable oxidizing agent for example hydrogen peroxide or peracid epoxidation contain that the compound of unsaturated cycloaliphatic ring (for example, tetrahydrobenzene, cyclopentenes, bicyclooctene or tricyclo decene) obtains contain cyclohexene oxide-or cyclopentene oxide-compound.
In addition, as the aromatic epoxy compound, for example, list that monobasic with at least one aromatic proton or multi-phenol are arranged-or polyglycidyl ether or its alkylene oxide affixture described.As these epoxy compoundss, for example, the compound described in compound described in the section of JP-A-11-242101 [0084]-[0086] and JP-A-10-158385 [0044]-[0046] section is arranged.
In these epoxy compoundss, in view of the fast setting performance, preferred fragrance epoxide and cycloaliphatic epoxides, wherein preferred especially cycloaliphatic epoxides.In the present invention, epoxide can use separately or so that two or more suitably mix use in them.
As the epithio ether compound, describing has the oxirane ring of above-claimed cpd by cyclosubstituted those compounds of sulfo-epoxy group(ing).
The compound that contains the oxetanyl group as cyclic ethers has 1-10, and preferred 1-4, the oxetanyl group.These compounds preferably use with the compound that contains epoxy group(ing).
Particularly, for example, have at the compound described in the section of JP-A-2000-239309 [0024]-[0025].
As the spiro original acid ester compound, for example, describing has at the compound described in the JP-T-2000-506908.
As the vinyl hydrocarbon compound, distyryl compound is arranged, the clicyclic hydrocarbon compound of vinyl substituted (for example, vinyl cyclohexane and vinyl bicycloheptene), the compound of describing at the monomer of free redical polymerization (wherein V1 be equivalent to-O-), the propenyl compound (for example is described in Journal of Polymer Science:Part A:Polymer Chemistry, Vol.32,2895 (1994)), alkoxypropan two ethylenic compounds (for example are described in Journal of PolymerScience:Part A:Polymer Chemistry, Vol.34,1015 (1996) and JP-A-2002-29162), (for example be described in Journal of PolymerScience:Part A:Polymer Chemistry with the pseudoallyl compound, Vol.34,2051 (1996).
These compounds can two or more suitably mix use.
In addition, as polyfunctional compound of the present invention, the preferred compound that has the group of the group of at least one above-mentioned free redical polymerization and cationically polymerizable at intramolecularly that uses.For example, at the compound described in [0015] section of JP-A-8-277320 [0031]-[0052] section and the JP-A-2000-191737.Be used for compound of the present invention and be not limited in them.
Compound in free redical polymerization: the compound of cationically polymerizable, the compound of contained free redical polymerization and the compound of cationically polymerizable are preferably with 90: 10-20: 80, more preferably 80: 20-30: 70 weight ratio exists.
Next, be described in detail in the polymerization starter that is used for mixing use in the aforementioned combination (3) below with binder precursor.
As polymerization starter, describing has thermal polymerization and Photoepolymerizationinitiater initiater.
The example of thermal polymerization comprises conventional known organic peroxy compound (for example, the compound described in [0019] section of the JP-A-2001-139663), azo two compounds and this paper compound described below.
As Photoepolymerizationinitiater initiater, describing has the compound that can produce free radical or acid through rayed.Be used for Photoepolymerizationinitiater initiater of the present invention and have preferred 400nm or littler maximum absorption wavelength.Absorbing wavelength can be operated under white lamps at the compound of this ultra-violet region.
When being rayed, the polymerization starter that is preferred for generation free radical of the present invention produces the polymeric Photoepolymerizationinitiater initiater that free radical and initiation and acceleration have the compound of polymerisable unsaturated group.
As the compound that produces free radical, can and have the compound of little bond dissociation energy from known polymerization starter and select suitable use.The polymerization starter that produces free radical can use separately or two or more mixing uses.
As the polymerization starter that produces free radical, describing has amine compound (being described in JP-B-44-20189), organic halogenation compound, carbonyl compound, Metallocenic compound, Hexaarylbiimidazole compound, organic boronic compound and two sulphones (being described in JP-A-61-166544).Wherein, preferred carbonyl compound.
As the organic halogenation compound, at Wakabayashi etc., Bull Chem.Soc.Japan, 42,2924 (1969), U.S. Patent No. 3,905,815, M.P.Hutt, Journal of Heterocyclic Chemistry, 1 (No.3) described specific examples in (1979), and its specific examples comprises that trihalogenmethyl replaces De oxazole compound and s-triazine.More preferably, s-triazine derivative, wherein at least one one-, two-or the methyl that three-halogen replaces link to each other with the s-triazine ring.
As other organic halogen compound, ketone, thioether, sulfone and the nitrogen atom heterocyclic group described in the section of JP-A-5-27830 [0039]-[0048] arranged.
As carbonyl compound, for example have Saishin UV Koka Gijutsu, the compound described in the pp.60-62 (Kabushiki Kaisha Gijutsu Joho Kyokai in 1991 publish), acetophenone compound, hydroxy acetophenone compound, benzophenone compound, thioxane compound, bitter almond oil camphor compound be ethoxybenzoin and bitter almond oil camphor ethyl isobutyl ether, benzoate derivatives ESCAROL 507 ethyl ester and to diethylamino ethyl benzoate, benzyl dimethyl ketal and acylphosphine oxide for example for example.
As Metallocenic compound, describe the cyclopentadiene titanium compound arranged (for example, JP-A-5-83588) and the iron arene complex compound (for example, JP-A-1-152109).As the Hexaarylbiimidazole compound, JP-B-6-29285 and U.S. Patent No. 4,622 are arranged, the compound described in 286.As the organic boronic ester cpds, for example, Japanese Patent No.2764769, JP-A-2002-116539, Kunts are arranged, Martin, Rad Tech ' 98.Proceeding April 19-22,1988, compound described in the Chicago, about other organoboron compound, organic boron transition metal coordination complexes is described (for example, JP-A-7-292014).
These compounds that produce free radical can add separately or two or more mixing addings in them.Based on the monomeric total amount of light free redical polymerization, they can 0.1-30 weight %, preferred 0.5-25 weight %, and the amount of especially preferred 1-20 weight % adds.When they add fashionablely with the amount in this scope, the gained coating composition obtains satisfactorily stability in time and shows high polymerization.
Next, describe the acidogenic agent that can be used as Photoepolymerizationinitiater initiater in detail.
As acidogenic agent, describing has known compound for example light trigger, photoquenching agent (for example, dyestuff), the phototropic agent used of light cationoid polymerisation and the acidogenic agent that becomes known for microresists, and composition thereof.
The example of acidogenic agent comprises organic halogenated compound, two sulphones and compound.As the specific examples of organic halogenation compound and two sulphones, the identical compound of compound that has with respect to producing free radical is described.
Examples for compounds comprises diazonium salt, ammonium salt, inferior amine salt (iminium salts), phosphonium salt, salt compounded of iodine, sulfonium salt, Arsenic salt and selenium salt and for example be described in those compounds described in the section of JP-A-2002-29162 [0058]-[0059].These salt are preferably used as acidogenic agent especially, particularly, and in view of photosensitivity and the stability of material of compound, preferably diazonium salt, salt compounded of iodine, sulfonium salt and inferior amine salt because of causing photopolymerization reaction.
The specific examples of salt comprises the salt described in the sulfonium salt of the S-phenyul thiobenzoic acid described in [0017] section of the diaryl group iodized salt described in the amyl group sulfonium salt described in [0035] section of the JP-A-9-268205, JP-A-2000-71366 [0010]-[0011] section or triarylsulfonium salt, the JP-A-2001-288205 and JP-A-2001-133696 [0030]-[0033] section.
As other example of acidogenic agent, the organo-metallic/organic halogenation compounds described in JP-A-2002-29162 [0059]-[0062] section is arranged, have the light acid producing agent of adjacent nitrobenzyl fundamental mode blocking group and can produce the compound of sulfonic acid through photodissociation.
These acidogenic agents can use separately or can two or more mix use.Based on all polymerizable compounds of 100 weight parts, these acidogenic agents can be with 0.1-50 weight %, preferred 0.5-20 weight %, and the amount of especially preferred 1-15 weight % adds.In view of the stability and the polymerisation reactivity of gained coating composition, acidogenic agent preferably adds with the amount in above-mentioned scope.
When in coating composition, mix using the organic compound of the organic compound of free redical polymerization and cationically polymerizable, based on the gross weight of composition, preferably add the radical polymerization initiator of 0.5-10 weight % and the cationic polymerization initiators of 1-10 weight %.More preferably, radical polymerization initiator adds with the amount of 1-5 weight % and cationic polymerization initiators adds with the amount of 2-6 weight %.
Except Photoepolymerizationinitiater initiater, can use photosensitizers.The specific examples of photosensitizers comprises organic amine compound (n-butylamine, triethylamine and N-phenylglycine), phosphine class (for example, tri-n-butyl phosphine), Michler's keton and thioxanthone.As the photosensitizers of commercially available acquisition, describe the KAYACURE have Nihon Kayaku K.K. to make (DMBI, EPA), or the like.
Photopolymerization reaction is preferably by using uviolizing after coating and drying coated composition.
(2) has the organometallic compound of hydrolyzable functional group
As the matrix that is used for high refractive index layer of the present invention or cured film, organometallic compound and/or its hydrolyzate that also preferred use has hydrolyzable functional group form coated thin film by sol gel reaction, solidify this film then.As this organometallic compound, describing has the compound that comprises Si, Ti, Zr, Al etc.As hydrolyzable functional group, describing has alkoxyl group, alkoxy carbonyl, halogen atom and hydroxyl, and wherein preferred especially alkoxyl group is methoxyl group, oxyethyl group, propoxy-or butoxy for example.
Organosilicone compounds and partial hydrolystate (partial condensate) thereof that the preferred embodiment of organometallic compound is preferably represented by following general formula.In addition, well-known, the silicoorganic compound of general formula (1) representative are easy to hydrolysis and pass through dehydration condensation then.
General formula (1):
(R a)m-Si(X)n
In general formula (1), R aAliphatic group or the replacement or the unsubstituted aromatic yl group that contains 6-14 carbon atom of a representative replacement or the unsubstituted 1-30 of a containing carbon atom, X represents halogen atom (for example, chlorine atom or bromine atoms), OH group, OR bGroup or OCOR bGroup (R wherein bRepresentative replaces or unsubstituted alkyl), m represents the integer of 0-3, and n represents the integer of 1-4, and wherein m and n sum are 4, and prerequisite is when m represents 0, X represents OR bOr OCOR b
In general formula (1), R aThe preferred embodiment of the aliphatic group of representative comprises the aliphatic group (for example, methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, decyl, dodecyl, hexadecyl, octadecyl, benzyl, styroyl, cyclohexyl, cyclohexyl methyl, hexenyl, decene base and laurylene base) that contains 1-18 carbon atom.More preferably contain 1-12 carbon atom, especially preferably contain 1-8 carbon atom.R aThe example of the aromatic yl group of representative comprises phenyl, naphthyl and anthryl, wherein preferred phenyl.
Substituting group has no particular limits; but its preferred embodiment comprises that halogen atom (for example; fluorine; chlorine or bromine); hydroxyl; sulfydryl; carboxyl; epoxy group(ing); alkyl (for example; methyl; ethyl; sec.-propyl; the propyl group or the tertiary butyl); aryl (for example; phenyl or naphthyl); aromatic heterocycle group (furyl; pyrazolyl or pyridyl); alkoxyl group (for example; methoxyl group; oxyethyl group; isopropoxy or hexyloxy); aryloxy (for example; phenoxy group); alkylthio (for example methylthio group or ethylmercapto group); arylthio (for example; thiophenyl); alkenyl (for example; vinyl or 1-propenyl); alkoxysilyl (for example; trimethoxysilyl or triethoxysilyl); acyloxy (acetoxyl group or (methyl) acryl); alkoxy carbonyl (for example; methoxycarbonyl or ethoxy carbonyl); aryloxycarbonyl (for example; phenyloxycarbonyl); formamyl (for example; formamyl; N-methylamino formyl radical; N, N-formyl-dimethylamino or N-methyl-N-octyl group formamyl); and acyl amino (acetylamino; benzoyl-amido; acryl amino or methacryloyl amino).
Wherein, more preferably hydroxyl, sulfydryl, carboxyl, epoxy group(ing), alkyl, alkoxysilyl, acyloxy and acyl amino, wherein epoxy group(ing), polymerisable acyloxy ((methyl) acryl) and polymerisable acyl amino (acryl amino or methacryloyl amino).These substituting groups can also be substituted.
R bRepresentative replaces or unsubstituted alkyl.As the substituting group of alkyl, can use with at R aDescribed identical those.
M represents the integer of 0-3.N represents the integer of 1-4.M and n sum are 4.M preferably represents 0,1 or 2, and especially preferred 1.When m represented 0, X represented OR bGroup or OCOR bGroup.
Based on the total solids component of high refractive index layer or cured film, the preferred 10-90 weight of the content % of the compound of general formula (1), more preferably 20-70 weight %, especially preferably 30-50 weight %.
The specific examples of the compound of general formula (1) is the compound described in the section of JP-A-2001-166104 [0054]-[0056].
In high refractive index layer or cured film, organic binder bond preferably has silanol.The silanol that exists in tackiness agent is used for further improving physical strength, chemical resistance and the weathering resistance of high refractive index layer or cured film.
Silanol for example can join in the tackiness agent by the following method, with constitute coating composition as the silicoorganic compound that contain crosslinkable or polymerisable functional group of general formula (1) representative of the component that forms tackiness agent and binder precursor (for example, curable polyfunctional monomer or polyfunctional group oligopolymer), contained dispersion agent chemical combination together in the dispersion liquid of polymerization starter and high refractive index complex oxide fine particle, and this coating composition is applied on the transparent carrier, then at dispersion agent, cause crosslinking reaction or polyreaction in the compound of polyfunctional monomer or polyfunctional group oligopolymer and general formula (1) representative.
Contain under the situation of repeating unit of silanol the preferred 2-98 mole of its content %, more preferably 4-96 mole %, most preferably 6-94 mole % in adding.
The hydrolyzing reaction of solidifying organometallic compound of the present invention is preferably carried out under the situation of catalyzer having.The example of catalyzer comprises mineral acid for example hydrochloric acid, sulfuric acid and nitric acid, organic acid is oxalic acid, acetate, formic acid, trifluoroacetic acid, methylsulfonic acid and toluenesulphonic acids for example, mineral alkali is sodium hydroxide, potassium hydroxide and ammoniacal liquor for example, organic bases is triethylamine and pyridine for example, metal alkoxide is for example beta-diketon and 'beta '-ketoester of aluminium isopropoxide, tetrabutyl zirconate and four titanium butoxide and metal-chelating compounds for example.Particularly, the compound described in JP-A-2000-275403.
Based on organometallic compound, the content of catalyst compound in composition is 0.01-50 weight %, preferred 0.1-30 weight %, more preferably 0.5-10 weight %.The preferred reaction conditions of suitably adjusting.
For the matrix or the film forming curable compound of high refractive index layer, also preferably have and be used for keeping or improve the particular polarity group of complex oxide fine particle of the present invention in the dispersion state of high refractive index layer.The particular polarity examples of groups comprises anionic group, amino and quaternary ammonium group.As anionic group, amino and quaternary ammonium group, describing has and the identical polar group of describing at dispersion agent.
The matrix that has the particular polarity group in the high refractive index layer is by following acquisition: the dispersion liquid and the coating composition chemical combination that is used to form high refractive index layer that will contain high refractive index complex oxide fine particle and dispersion agent, with the binder precursor with particular polarity group (for example, curable polyfunctional monomer or polyfunctional group oligopolymer with particular polarity group) and have particular polarity group and crosslinkable or polymerisable functional group and by at least a chemical combination in the combination of the polymerization starter of general formula (1) representative and silicoorganic compound, and if necessary with the simple function group monomer chemical combination with particular polarity group and crosslinkable or polymerisable functional group, then said composition is applied to transparent carrier, and at dispersion agent, the simple function group monomer, cause crosslinking reaction or polyreaction between the silicoorganic compound of polyfunctional monomer or polyfunctional group oligopolymer and/or general formula (1) representative.
In coating composition, the simple function group monomer with particular polarity group plays the dispersing auxiliary of fine inorganic particle.And, after the coating said composition, thereby monomer and dispersion agent, polyfunctional monomer or polyfunctional group oligopolymer with particular polarity group carry out crosslinking reaction and/or polyreaction formation tackiness agent, obtain to have excellent physical intensity, chemical resistance and weathering resistance thus and keep the high refractive index layer of fine inorganic particle in the dispersiveness of high refractive index layer simultaneously.
Based on dispersion agent, the monomeric content of simple function group with amino or quaternary ammonium group is 0.5-50 weight %, more preferably 1-30 weight % preferably.In the coating high refractive index layer or afterwards, can make the simple function group monomer bring into play its effect effectively by crosslinked or polyreaction formation tackiness agent.
As another matrix of high refractive index layer of the present invention, description has corresponding with organic binder bond (1) and has the matrix of the conventional known organic polymer formation of crosslinkable or polymerisable group by curing.This polymkeric substance preferably had another crosslinked or paradigmatic structure after forming high refractive index layer.The example of this polymkeric substance comprises polyolefine (being made of stable hydrocarbon), polyethers, polyureas, urethane, polyester, polyamine, polymeric amide and melamine resin.Wherein, preferred polyolefm, polyethers and polyureas, more preferably polyolefine and polyethers.As the weight-average molecular weight of the organic polymer before solidifying 1x10 preferably 3-1x10 6, more preferably 3x10 3-1x10 5
On the other hand, the cured film that contains the tackiness agent with polar group can join curable coating composition by the monomer that will have the particular polarity group, said composition is applied to transparent carrier, and causes crosslinking reaction or polyreaction with dispersion agent, polyfunctional monomer or polyfunctional group oligopolymer and organometallic compound with hydrolyzable functional group.
In curable coating composition, the monomer with particular polarity group plays the dispersing auxiliary of high refractive index complex oxide fine particle.And, after the coating said composition, monomer and dispersion agent, polyfunctional monomer or polyfunctional group oligopolymer with particular polarity group carry out crosslinking reaction and/or polyreaction formation tackiness agent, obtain to have the cured film that excellent physical intensity, chemical resistance and weathering resistance keep the good dispersiveness of particulate simultaneously thus.
In this curable coating fluid of coating or afterwards, can make these monomers before this cured film of coating, bring into play its effect effectively by crosslinked or polyreaction formation tackiness agent.
Based on dispersion agent, have amino or quaternary ammonium group as the monomeric content of particular polarity group preferably 0.5-50 weight %, more preferably 1-30 weight %.
In addition, as being used for film forming curable compound of the present invention, except curable organic binder bond, organometallic compound/and or its partial hydrolystate, describing has the known organic polymer with crosslinkable group or polymerisable group.Use this polymkeric substance can form the cured film that main polymer chain wherein has crosslinked or paradigmatic structure.The example of main polymer chain comprises polyolefine (being made up of stable hydrocarbon), polyethers, polyureas, urethane, polyester, polyamine, polymeric amide and melamine resin.Wherein, preferred polyolefm main chain, polyether backbone and polyureas main chain, the more preferably polyolefin backbone and the polyether backbone that obtain of the group by the addition polymerization unsaturated polymerizable.The weight-average molecular weight of organic polymer 1x10 preferably before solidifying 3-1x10 6, more preferably 3x10 3-1x10 5.
Organic polymer before solidifying preferably have with at the repeating unit of the described identical particular polarity group of dispersion agent with have the multipolymer of the repeating unit of crosslinked or paradigmatic structure.Based on all repeating units, have content preferably 0.5-99 weight %, more preferably 3-95 weight %, most preferably the 6-90 weight % of the repeating unit of anionic group in the polymkeric substance.Repeating unit can have two or more, identical or different anionic groups.
When containing the repeating unit with silanol, its content is 2-98 mole % preferably, more preferably 4-96 mole %, most preferably 6-94 mole %.
When containing the repeating unit with amino or quaternary ammonium group, its content is 0.1-50 mole % preferably, more preferably 0.5-30 mole %.
In addition, in addition when the repeating unit with anionic group or have crosslinking structure or the repeating unit of paradigmatic structure in also can obtain same effect when containing aforementioned silanol, amino or quaternary ammonium group.
The content preferably 1-90 weight %, more preferably 5-80 weight %, most preferably the 8-60 weight % that have the repeating unit of crosslinked or paradigmatic structure in the polymkeric substance.
The matrix optimization that forms by crosslinked or polymeric binder is to be applied on the transparent carrier and in coating or cause crosslinked afterwards or polyreaction forms by the coating composition that will be used to form high refractive index layer.
According to purposes and purpose, high refractive index layer of the present invention or curable coating composition can also contain other suitable compound.For example, under the situation that low-index layer is provided on the high refractive index layer, the specific refractory power height of the refractive index ratio transparent carrier of preferred high refractive index layer, and since add outside aromatic nucleus, the defluorination halogens (for example, Br, I or Cl) or for example the atom of S, N or P improved the specific refractory power of organic compound, the tackiness agent that also can preferably use the crosslinked or polyreaction of the curable compound by containing described organic compound to obtain.
In order to form antireflective film by form low-index layer on high refractive index layer, the specific refractory power of high refractive index layer is 1.65-2.40 preferably, more preferably 1.75-2.20, especially preferably 1.80-2.20.
Except aforementioned component (for example, fine inorganic particle, polymerization starter and photosensitizers) outside, can in high refractive index layer or curable coating composition, add resin, tensio-active agent, antistatic agent, coupling agent, thickening material, anti-blushing agent, tinting material (pigment and dyestuff), defoamer, levelling agent, fire retardant, UV light absorber, infrared absorbent, tackifier, polymerization retarder, antioxidant, surface-modifying agent and conducting metal particulate.
By adding median size is the particle of 0.2-10 μ m, and high refractive index layer can also play the described dazzle with optically-active reduction ability in this paper back and reduce layer.
The thickness of high refractive index layer can suitably design according to purposes.Using under the situation of high refractive index layer as optical interference layer, this thickness is 30-200nm preferably, more preferably 50-170nm, especially preferably 60-150nm.Also play a part at high refractive index layer under the situation of hard coat, thickness is 0.5-10 μ m, more preferably 1-7 μ m preferably, especially preferred 2-5 μ m.
The coating solvent that is used for high refractive index layer is suitably selected to use from water and organic solvent.The example of organic solvent comprises alcohols, ketone, ester class, amides, ethers, ether-ether class, hydro carbons and halogenated hydrocarbon.Particularly, as at compound identical described in the dispersion agent.Preferably mainly contain ketone solvent () coating solvent for example, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or pimelinketone, and based on the weight of all contained in coating composition solvents, the content of ketone solvent is 10 weight % or bigger preferably.This content is 30 weight % or bigger more preferably, even more preferably 60 weight % or bigger.
The intensity of high refractive index layer is H or bigger preferably, more preferably 2H or bigger, and 3H or bigger most preferably, described intensity is to measure according to the pencil hardness test of JIS K5400.
In addition, according to before the Taber coomb's test Coomb of JIS K5400 and the abrasion loss of coupons afterwards preferably as far as possible little.
Do not contain under the particulate situation of giving dazzle reduction performance at high refractive index layer, can make the turbidity of this layer as far as possible little.This turbidity preferably 5% or littler, more preferably 3% or littler, especially preferred 1% or littler.
High refractive index layer preferably directly or through other layer forms on transparent carrier.
In the present invention, high refractive index layer is by being prepared as follows: for example dip coating, airblade coating method, curtain coating method, rolling method, metal bar coating method, intaglio plate coating method, nick version coating method or extrusion coated method are coated with the coating composition that is used to form high refractive index layer, dry and usefulness rayed and/or heating on the transparent substrate film according to known film forming method.From quick-setting angle, solidifying with rayed is ideal.And, also preferably heat-treat in the second half section that photocuring is handled.
(formation of cured film)
Cured film of the present invention preferably directly or through other layer forms on transparent carrier.
In the present invention, cured film can make by following: on the transparent carrier film, be coated with curable coating composition of the present invention according to known film forming rule such as dip coating, airblade coating method, curtain coating method, rolling method, metal bar coating method, intaglio plate coating method, nick version coating method or extrusion coated method, and dry and with rayed or heating.From quick-setting angle, solidifying with rayed is ideal.And, also preferably heat-treat in the second half section that photocuring is handled.
As the light source that is used for light-struck UV-light, describing has ultrahigh pressure mercury lamp, high voltage mercury lamp, medium pressure mercury lamp, low pressure mercury lamp, chemical substance lamp, carbon arc lamp, metal halide lamp, xenon lamp and sunlight.Description has the multi beam irradiation as the 350-420nm LASER Light Source of the various wavelength that can obtain that use.
When forming cured film, be 10 volume % or the crosslinking reaction or the polyreaction of more carrying out ionizing rays-curable compound under the circlet border preferably at oxygen concn.At the oxygen environment is to form this cured film under 10 volume % or the littler atmosphere can improve physical strength, chemical resistance and the weathering resistance of cured film and the viscosity of the layer adjacent with cured film.Oxygen concn is more preferably 6 volume % or littler, even more preferably 4 volume % or littler, especially preferred 2 volume % or littler, most preferably 1 volume % or littler.
As the technology that oxygen concn is reduced to 10 volume % or littler level, preferably with other gas preferably when nitrogen (use nitrogen wash), replacement protoatmosphere atmosphere (nitrogen concentration: about 79 volume %; Oxygen concn: about 21 volume %).
The thickness of cured film of the present invention can suitably be determined according to end-use.Under for the situation of use cured film of the present invention as the described antireflective film in this paper back, thickness is 30-200nm preferably, more preferably 50-170nm, especially preferably 60-150nm.Play a part simultaneously at cured film of the present invention under the situation of hard coat, thickness is 0.5-10 μ m preferably, more preferably 1-7 μ m, especially preferably 2-5 μ m.In addition, cured film of the present invention can add as the particle of this paper 0.2-10 μ described later m and reduces layer so that play dazzle simultaneously.
When measuring according to the pencil hardness test of JIS K5400, the hardness of cured film of the present invention is H or bigger preferably, and more preferably hardness is 2H or bigger, most preferably 3H or bigger.
In addition, before according to the Taber coomb's test Coomb of JIS K5400 and the abrasion loss of afterwards coupons being measured preferably as far as possible little.
When cured film did not contain the particle of giving dazzle reduction function, the turbidity of preferred consolidation film was low as far as possible.Be preferably 5% or littler, more preferably 3% or littler, especially preferred 1% or littler.
High refractive index layer of the present invention or cured film are used for antireflective film or polaroid.In these cases, preferably on high refractive index aspect or cured film face, provide outermost layer with anti-scraping performance and antifouling property.Outermost layer is described below.
As the mode that improves anti-scraping performance, giving sliding for the surface of this layer is effectively, and can make for example add silicon-containing compound or fluorochemicals in a known manner in outermost layer.
Fluorochemicals has preferred 1.35-1.50, more preferably the specific refractory power of 1.36-1.47.Equally, fluorochemicals contains the fluorine atom that content is 35-80 weight %.
The example of fluorochemicals comprises fluoropolymer, fluorochemical surfactant, fluorine-containing ether and fluorine containing silane compound.Particularly, the compound described in JP-A-9-222503 [0018]-[0026] section, JP-A-11-38202 [0019]-[0030] section and JP-A-2001-40284 [0027]-[0028] section.
As fluoropolymer, preferably include contain fluorine atoms repeated structural unit, contain the repeated structural unit of crosslinkable or polymerisable functional group and comprise the multipolymer of other substituent repeating unit (this paper back is referred to as " other repeated structural unit ").As crosslinkable or polymerisable functional group, describing has the functional group identical with the functional group of high refractive index layer.As other repeated structural unit, in order to satisfy the solubility property in coating solvent, the preferred copolymerizable component of hydro carbons.Preferably to the fluoropolymer that wherein adds this component of about 50%.In this case, preferably mix with silicone compounds.
As this silicone compounds, the compound that preferably has polysiloxane structure, in the high polymers chain, contains curable functional group or polymerisable functional group and in film, have bridged linkage.For example, for example compound that links to each other with the two ends of polysiloxane structure of the Saila Plane of commercially available acquisition (for example, being made by Chisso K.K.) and silanol groups described in the JP-A-11-258403 of responding property siloxanes is described.
The crosslinked or polyreaction of fluoropolymer with crosslinkable or polymerisable group is preferably by being used to form in the outermost coating composition or carrying out with rayed or heating afterwards in coating.As polymerization starter and sensitizing agent, describing has and is used for identical those of high refractive index layer.
As the matrix of high refractive index layer or cured film, also preferably by silane coupling agent (for example, the compound of aforementioned formula (1)) with have the sol-gel cured product that the condensation reaction between the silane coupling agent of specific fluorine-containing alkyl obtains.
For example, description (for example has the silane compound of polyfluorinated alkyl or its partial hydrolysis condenses, compound described in JP-A-58-142958, JP-A-58-147483 and the JP-A-58-147484), the silane coupling agent that contains perfluoroalkyl described in the JP-A-9-157582 and contain the silyl compound (for example, the compound described in JP-A-2000-117902, JP-A-2001-48590 and the JP-A-2002-53804) of the fluorine-containing long chain alkyl group of poly-" perfluoroalkyl ethers " group.
As catalyzer as used herein, describe have at high refractive index layer described those.
Except said components, outermost layer can contain filler (for example, fine inorganic particle and organic particulate), silane coupling agent, slip(ping)agent (for example, silicone compounds for example dimethyl siloxane) and tensio-active agent.Particularly, preferably add fine inorganic particle, silane coupling agent or slip(ping)agent.
As fine inorganic particle, preferably has for example fluorine-containing particle of compound (for example, magnesium fluoride, Calcium Fluoride (Fluorspan) or barium fluoride) of low-refraction, preferred especially silicon-dioxide (silica).The weight average particle diameter of the primary particle in the fine inorganic particle is 1-150nm preferably, more preferably 1-100nm.In outermost layer, particle disperses preferably thinlyyer.
Outermost layer of the present invention has preferred 0.25 or littler surface dynamic friction coefficient.Kinetic friction coefficient used herein be meant this surface and diameter be between the Stainless Steel Ball of 5mm by the speed with 60cm/min moves steel ball along this surface, apply the kinetic friction coefficient that the load of 0.98N is measured to steel ball simultaneously.This kinetic friction coefficient preferably 0.17 or littler, especially preferred 0.15 or littler.
In addition, preferably 90 ° or bigger of the contact angles of outmost surface and water, more preferably 95 ° or bigger, especially preferred 100 ° or bigger.
[antireflective film]
High refractive index layer of the present invention or cured film can be preferred for forming antireflective film.More particularly, high refractive index layer of the present invention or cured film can be used as by laminated two-layer or multilayer and have one deck in the multilayer antireflective film that layer (photic zone) that light transmission and specific refractory power differ from one another forms.High refractive index layer of the present invention or cured film mainly are used as the high refractive index layer or the intermediate-index layer of antireflective film, and also can reduce layer as high refractive index hard coat or high refractive index dazzle.In addition, in this multilayer antireflective film, the layer with maximum refractive index is referred to as high refractive index layer, and the layer with lowest refractive index is referred to as low-index layer, and other layer with middle refractive index is referred to as intermediate-index layer.The intermediate-index layer of anti-reflection layer can be the layer that is made of the high refractive index film that curable coating composition of the present invention forms.
When antireflective film of the present invention did not have dazzle reduction function, its turbidity was preferably low as far as possible.When antireflective film has dazzle reduction function, the preferred 0.5-50% of its turbidity, more preferably 1-40%, most preferably 1-30%.
(low-index layer)
Low-index layer also can play outermost effect or can be below outermost.
Also play at low-index layer under the situation of outermost effect, also can be referring to of the explanation of this paper front at the outermost layer description.Under the situation of low-index layer below outermost, low-index layer preferably contains silicon-containing compound.
In addition, the specific refractory power of low-index layer is 1.20-1.55, preferred 1.30-1.50, more preferably 1.35-1.48, especially preferably 1.40-1.48.
When providing low-index layer below outermost, it can form by coating method or vapor phase process (for example, vacuum deposition method, sputtering method, ion plating or plasma CVD method).Because production cost is low, therefore preferred coating method.The thickness of low-index layer is 30-200nm preferably, more preferably 50-150nm, most preferably 60-120nm.
When low-index layer did not contain the particle of giving dazzle reduction function, the turbidity of preferred consolidation film was low as far as possible.Turbidity value preferably 5% or littler, more preferably 3% or littler, especially preferred 1% or littler.
When measuring according to the pencil hardness test of JIS K5400, the hardness of low-index layer is H or bigger preferably, and more preferably hardness is 2H or bigger, most preferably 3H or bigger.
In addition, as the abrasion loss by measuring, kinetic friction coefficient according to the Taber coomb's test Coomb of JISK5400 and with the contact angle of water, preferably have the performance identical with skin.
In addition, when providing low-index layer below outermost layer, low-index layer preferably contains silicon compound.
(hard coat)
In order to give antireflective film enough physical strengths, on the surface of transparent carrier, provide hard coat.Specifically, preferably between transparent carrier and high refractive index layer, provide hard coat.
Hard coat preferably by light-and/or the crosslinking reaction of heat-curable compound or polyreaction form.For example, can contain polyester (methyl) acrylate, urethane (methyl) acrylate, polyfunctional monomer or polyfunctional group oligopolymer or contain the coating composition of the organometallic compound of hydrolyzable functional group by coating on transparent carrier, and cause the crosslinking reaction or the polyreaction of curable compound.
As the curable functional group that contains in the curable compound, the functional group of preferred photopolymerization, and the organoalkoxysilane based compound preferably of the organometallic compound with hydrolyzable functional group.
The specific examples of these compounds is those that described at high refractive index layer.
The median size that hard coat preferably contains primary particle is 300nm or littler fine inorganic particle.Preferred fine inorganic particle has the size of 10-150nm, and even preferred fine inorganic particle have the size of 20-100nm.Here, median size is meant weight average particle diameter.Hard coat with no impaired transparency can be adjusted to 200nm or littler formation by the median size with primary particle.
Fine inorganic particle works to increase the hardness of hard coat, simultaneously, works to suppress coating curing and shrinks.Equally, add their specific refractory poweres with the control hard coat.
Concrete structure about hard coat is formed, can be referring to the explanation that provides among JP-A-2002-144913, JP-A-2000-9908, the WO0/46617 etc.
Based on the gross weight of hard coat, the content of fine inorganic particle in hard coat is 10-90 weight % preferably, more preferably 15-80 weight %.
Foregoing as this paper, the high refractive index layer of antireflective film can produce the function of hard coat.When high refractive index layer also produces the function of hard coat, preferably by in hard coat, add using the finely divided complex oxide fine particle of the technology described at high refractive index layer of the present invention to form this layer.
And, can be that the particle of 0.2-10 μ m joins the function of giving the dazzle depressant with dazzle reduction performance in the hard coat with the described median size in this paper back.
The thickness of hard coat can suitably design according to end-use.The thickness of hard coat is 0.2-10 μ m preferably, more preferably 0.5-7 μ m, especially preferably 0.7-5 μ m.
When measuring by pencil hardness test according to JIS K5400, the hardness of hard coat is H or bigger preferably, and more preferably hardness is 2H or bigger, most preferably is 3H or bigger.
In addition, the abrasion loss to coupons mensuration is preferably as far as possible little before the Taber coomb's test Coomb and afterwards according to JIS K5400.
(transparent carrier)
Transparent carrier is plastics film preferably.The thickness of transparent carrier has no particular limits, but 1-300 μ m preferably, more preferably 30-150 μ m, even more preferably 40-120 μ m.The transparence of transparent carrier preferably 80% or bigger, more preferably 86% or bigger.The turbidity of transparent carrier preferably 2.0% or littler, more preferably 1.0% or littler.The specific refractory power of transparent carrier is 1.4-1.7 preferably.
The example that constitutes the plastics film of transparent carrier comprises that cellulose ester (for example; tri acetyl cellulose; diacetyl cellulose; the propionyl Mierocrystalline cellulose; the butyryl radicals Mierocrystalline cellulose; ethanoyl propionyl Mierocrystalline cellulose or Nitrocellulose); polymeric amide; polycarbonate; polyester (for example; polyethylene terephthalate; Polyethylene Naphthalate; poly--1; 4-cyclohexanedimethyleterephthalate terephthalate; poly-ethylidene 1; 2-biphenoxyl ethane-4; 4 '-dicarboxylic ester or polybutylene terephthalate); polystyrene (for example; syndiotactic polystyrene); polyolefine (for example, polypropylene; polyethylene or polymethylpentene); polysulfones; polyethersulfone; the poly-allylat thing; polyetherimide; polymethylmethacrylate and polyetherketone.Wherein, preferred tri acetyl cellulose, polycarbonate, polyethylene terephthalate and Polyethylene Naphthalate.Particularly, be used under the situation of liquid-crystal display preferred tri acetyl cellulose.
When transparent carrier was the tri acetyl cellulose film, the tri acetyl cellulose film was preferably by the cast individual layer or pour into a mould altogether that multilayer obtains by the casting that tri acetyl cellulose is dissolved in the tri acetyl cellulose dope that makes in the solvent.As film, can adopt, example adds, Hatsumei Kyokai Kokai GihoMethod described in (Kogi No.2001-1745 is published March 15 calendar year 2001 by Hatsumei Kyokai) 22-30 page or leaf.
Can in transparent carrier, add various additives (for example, softening agent, particulate, ultraviolet screener, protective agent, optical anisotropy control agent, exfoliant and infrared absorbent) according to end-use.Based on transparent carrier, these additives add-on separately is 0.01-20 weight % preferably, more preferably 0.05-10 weight %. Hatsumei Kyokai Kokai Giho(Kogi No.2001-1745 is published March 15 calendar year 2001 by Hatsumei Kyokai) 16-22 page or leaf has provided their detailed description, and has preferably used wherein said material.
Transparent carrier can pass through surface treatment.The surface-treated example comprises chemical treatment, mechanical treatment, Corona discharge Treatment, flame treating, uviolizing processing, high frequency processing, glow discharge processing, reactive plasma treatment, laser treatment, acid treatment, ozone Oxidation Treatment and alkaline purification.Preferred glow discharge processing, uviolizing processing, Corona discharge Treatment and flame treating, wherein preferred especially glow discharge processing, Corona discharge Treatment and alkaline purification.
(other layer in the antireflective film)
In order to form antireflective film with better antireflection property, the preferred intermediate-index layer between the specific refractory power of specific refractory power that provides specific refractory power at high refractive index layer between transparent carrier and the high refractive index layer and transparent carrier.
Intermediate-index layer is preferably to prepare with the described identical mode of high refractive index layer of the present invention, and wherein specific refractory power is to adjust by the content of fine inorganic particle in the key-course.
Other layer except that this paper is noted earlier can be provided in anti-reflection layer.For example, can provide binder layer, shielding layer, sliding layer, antistatic backing and prime coat.Shielding layer is used for electromagnetic wave shielding or infrared rays.
In addition, antireflective film is being used under the situation of liquid-crystal display, can providing and contain the particulate undercoat that median size is 0.1-10 μ m in order to improve viewing angle characteristic.Term used herein " median size " is meant the weight average particle diameter of secondary particle (perhaps, when particle is not assembled, being primary particle).These particulate median sizes are 0.2-5.0 μ m preferably, more preferably 0.3-4.0 μ m.As these particles, describe being useful on inorganic particle and the organic granular that dazzle reduces layer.
These particulate specific refractory poweres are 1.35-1.80, more preferably 1.40-1.75 preferably.
Preferably between hard coat and transparent carrier, form undercoat.This undercoat also can have the function of hard coat.
Add median size in undercoat is that internally coated turbidity is 3-60% preferably, more preferably 5-50% under the particulate situation of 0.1-10 μ m.
(the formation method of antireflective film)
In the present invention, each layer of formation antireflective film preferably forms by coating method.When forming by coating method, each layer can be according to forming at the described coating method of high refractive index layer.Also can be coated with two-layer simultaneously or multilayer.(be described in, Coating Kogaku is write and published the 253rd page by Asakura Shoten in 1973 by Yuji Harazaki) as coating method, preferable alloy rod coating method, intaglio plate coating method and nick version coating method.
In addition, can in each layer of anti-reflection layer, add other compound for example resin, dispersion agent, tensio-active agent, antistatic agent, thickening material, anti-blushing agent, tinting material (pigment and dyestuff), defoamer, levelling agent, fire retardant, UV light absorber, tackifier, polymerization retarder, antioxidant and tensio-active agent according to purposes and purpose.
(physicals of antireflective film)
In the present invention, the outmost surface of the antireflective film on the high refractive index aspect has preferred 0.25 or littler surface dynamic friction coefficient.It is to apply the kinetic friction coefficient that the load of 0.98N is measured to steel ball simultaneously by moving steel ball along this surface with the speed of 60cm/min between the Stainless Steel Ball of 5mm that kinetic friction coefficient used herein is meant at the surface on the high refractive index aspect and diameter.This kinetic friction coefficient preferably 0.17 or littler, especially preferred 0.15 or littler.
In addition, preferably 90 ° or bigger of the antireflective film on the high refractive index aspect and the contact angles of water, more preferably 95 ° or bigger, especially preferred 100 ° or bigger.
Do not have dazzle to reduce under the situation of performance at antireflective film, it preferably has alap turbidity.
Have at antireflective film under the situation of dazzle reduction performance, its turbidity is 0.5-50% preferably, more preferably 1-40%, most preferably 1-30%.
(the surperficial irregularity of antireflective film)
Can on the surface of the high refractive index aspect of antireflective film of the present invention, form irregularity and reduce performance to give dazzle.
It is relevant with this surperficial average surface roughness (Ra) that dazzle reduces performance.Based on area is 100cm 2The area that takes out with form at random of surface be 1mm 2The average surface roughness (Ra) on surface, the irregularity on above-mentioned surface is 0.01-0.4 μ m preferably, more preferably 0.03-0.3 μ m, even more preferably 0.05-0.25 μ m, especially preferred 0.07-0.2 μ m.
About average surface roughness (Ra), Technocompact Series (6), Hyomen Arasa No Sokutei Hyoka Ho, provided explanation in writing and publish by Jiro Nara by K.K.Sogo GijutsuCenter.
Can estimate by atom pairs atomic force microscope (AFM) at the lip-deep recess of antireflective film of the present invention and the shape at protruding place.
As the method that forms surperficial irregularity, can use currently known methods.In the present invention, preferably the plate that will have an irregular surface with high pressure is pressed in film surface and forms the method (for example, the embossing described in the JP-A-2000-329905) of irregularity and form dazzle and reduce layer comes to form irregularity on the surface of antireflective film a method by add particle in the random layer of antireflective film.
Forming in the dazzle reduction layer particles used median size by adding particle in the random layer at antireflective film with 0.2-10 μ m.Term used herein " median size " is meant the weight average particle diameter of secondary particle (being primary particle perhaps) when particle is not assembled.
As particle, describing has inorganic particle and organic granular.The example comprises the compound described in [0014] section of the JP-A-2001-33625.
The particulate specific refractory power is 1.35-1.80 preferably, more preferably 1.40-1.75, more preferably 1.45-1.75.
The particle of giving dazzle reduction performance can join in the random layer that forms on antireflective film, preferred hard coat, low reflection layer or high refractive index layer, especially preferred hard coat or high refractive index layer.They can be joined in the multilayer.
[formation of antireflective film]
High refractive index layer of the present invention constitutes one or more layers of multilayer antireflective film that has light transmission and comprise two-layer or the laminated layer (photic zone) that the multilayer specific refractory power differs from one another.
The antireflective film that comprises two-layer laminated layer has the layer structure that is followed successively by transparent carrier, high refractive index layer and low-index layer (outermost layer).Transparent carrier, high refractive index layer and low-index layer have the specific refractory power that satisfies following relation:
The specific refractory power of the specific refractory power＞low-index layer of the specific refractory power＞transparent carrier of high refractive index layer
Also can between transparent carrier and high refractive index layer, provide hard coat.And this film can comprise that high refractive index hard coat or high refractive index dazzle reduce layer and low-index layer.
Comprise that the antireflective film of three-layered lamination layer has the layer structure that is followed successively by transparent carrier, intermediate-index layer, high refractive index layer and low-index layer (outermost layer) at least.Transparent carrier, intermediate-index layer, high refractive index layer and low-index layer have the specific refractory power that satisfies following relation: the specific refractory power of the specific refractory power＞low-index layer of the specific refractory power＞transparent carrier of the specific refractory power＞intermediate-index layer of high refractive index layer
Also can between transparent carrier and intermediate-index layer, provide hard coat.And this film can comprise middle refractive index hard coat, high refractive index layer and low-index layer.
In view of the antireflective film that formation has more excellent antireflection ability, each layer in the preferred multilayered structure has thickness of each layer described in JP-A-2001-188104 and the relation between the wavelength of visible light.
In addition, term " high refractive index ", " middle refractive index " and " low-refraction " are meant relation higher or lower relatively between layer.
By add median size in hard coat, intermediate-index layer or high refractive index layer is that the particle of 0.2-10 μ m forms that to have the antireflective film that dazzle reduces performance also be preferred.
In addition, when low-index layer comprises inorganic compound layer, preferably provide stain-proofing layer as the superiors.
[polaroid]
Preferred polaroid of the present invention has antireflective film of the present invention at least one protective film as polaroid.Foregoing as this paper, the protective film of polaroid has the surface of the transparent carrier relative with the face of high refractive index layer,, is laminated to the surface on the polarization film that is, and the contact angle of this surface and water is 40 ° or littler.
Have antireflective film that the contact angle of antireflection ability can the application of the invention and form, make the thickness of production cost and display apparatus reduce greatly like this as the protective film of polaroid.
In addition, the antireflective film of the application of the invention is as a protective film of polaroid and use that this paper back is described to have optically anisotropic optical compensating film and form polaroid as another protective film of polaroid and can obtain to be used for further improving the polaroid of liquid-crystal display in the contrast gradient of bright chamber.Above-mentioned polaroid has the visual angle of the upper and lower, left and right of remarkable increase.
(protective film of polaroid)
Using under the situation of antireflective film of the present invention as the protective film of polarization film, in order to obtain the enough viscosity with polarization film, the contact angle on the surface of preferably relative with high refractive index aspect transparent carrier is 40 ° or littler.
In this case, especially preferably use the tri acetyl cellulose film as transparent carrier.
As the method for the protective film that forms polaroid of the present invention, describing has following two kinds of methods:
(1) method of above-mentioned each layer (for example, high refractive index layer, hard coat and outermost layer) of coating on the one side of the transparent carrier that saponification was handled; With
(2) above-mentioned each layer (for example, high refractive index layer, hard coat and outermost layer) of coating on the one side of transparent carrier, and the method for the face of laminated polarization film on it is handled in saponification.
And, also can on the surface of the transparent carrier of using the laminated antireflective film of polarization film, be coated with the saponification treatment soln, handle carry out saponification with the laminated surface of polarization film thus.
Giving wetting ability to the surface of antireflective film of the present invention handles and can carry out in a known way.For example, preferably transparent carrier or antireflective film are soaked appropriate time in alkaline solution or be coated with alkaline solution thereon and carry out saponification thus and handle.
As alkaline solution and treatment process, can be with reference to the explanation that provides among JP-A-2002-82226 and the WO02/46809.The contact angle of the film surface that this processing is preferably handled with saponification is that 45 ° or littler mode are carried out.
The possess hydrophilic property surface of the protective film of polaroid is bonded on the polarization film uses.
As for optical property (for example; antireflection property and dazzle reduce performance), physicals (for example; anti-scraping performance), chemical resistance, antifouling property are (for example; didirtresistance) and weathering resistance (for example; humidity resistance and photostabilization), the protective film of polaroid is preferably had at the described performance of antireflective film of the present invention.
(optical compensating film)
Optical compensating film (phase-contrast film) can improve the viewing angle characteristic of liquid-crystal display.
As optical compensating film, can use known, but, in view of widening the visual angle, optical compensating film described in the preferred JP-A-2001-100042, it has and comprises the optical anisotropic layer with the unitary compound of disk-shaped structure, and wherein the angle between dish type compound and carrier changes at thickness direction.
In addition, this angle advantageous variant is so that its distance with the carrier side of distance optical anisotropic layer increases.
Using under the situation of optical compensating film as the protective film of polarization film, laminated have the surface of polarization film preferred through the saponification processing.This processing is preferably handled according to aforementioned saponification with alkali and is carried out.
In addition, also preferred wherein optical anisotropic layer also contains an embodiment of cellulose ester and wherein form an embodiment of oriented layer between optical anisotropic layer and transparent carrier.
[image display device]
This antireflective film can be used for image display device for example liquid-crystal display (LCD), plasma display panel (PDP), electroluminescent display (ELD) and cathode-ray tube display (CRT), the transparent carrier face of antireflective film is adhered to the visual display surface of image display device.
Antireflective film of the present invention and polaroid preferably can be used for transmission-type, reflection-type or the semi-transmission type liquid crystal display device such as twisted nematic (TN) pattern, STN Super TN (STN) pattern, vertical orientated (VA) pattern, face internal conversion (IPS) pattern or optical compensation curved unit (OCB) pattern.
In addition, under the situation that is used for transmission-type or semi-transmission type liquid crystal display device, use the film (have the polarization separation film that polarized light is selected layer, for example, the D-BEF that makes by Sumitomo 3M K.K.) of the raising brightness of commercially available acquisition can make displaying appliance that higher visibility is arranged.
In addition, close when using when hardening with λ/4, polaroid of the present invention or antireflective film can be used as the polaroid of reflection LCD or as the surface protection board of OLED display to reduce from surface and inner reflected light.
[embodiment]
The present invention is more specifically described below.Yet the present invention is not limited to this.
[embodiment 1-1]
(preparation of hard coat coating solution)
The dispersion liquid (MEK-ST of fine particles of silica in methyl ethyl ketone with 450.0g; The content of solids component: 30 weight %; Make by Nissan Kagaku K.K.), (Irgacure 907 for the methyl ethyl ketone of 15.0g, the pimelinketone of 220.0g and the Photoepolymerizationinitiater initiater of 16.0g; Make by Nihon Ciba Geigy K.K.) join Dipentaerythritol five acrylate of 315.0g and the mixture (DPHA of dipentaerythritol acrylate; Make by Nihon Kayaku K.K.) in, and the gained mixture stirred.Stir the mixture through the aperture of polypropylene manufacturing is that the strainer of 0.4 μ m filters the coating solution make hard coat.
(preparation of the dispersion liquid of high refractive index complex oxide fine particle (PL1-1))
The polymerization retarder of the tertiary butylated hydroquinone of the dispersion agent (D-1) of the following structure of 38.6g, 0.5g and the methyl iso-butyl ketone (MIBK) of 702g are joined the Ti of adulterated Co ion of containing of 218g (content is 3 weight %) and the composite oxides (P-1) [Ti/Ti+Zr=0.80 weight ratio (based on oxide compound)] of Zr, and in dynomil, this mixture decentralized system got the dispersion liquid (PL-1) of particulate that weight average particle diameter is the high refractive index composite oxides of 65nm.
Dispersion agent
Figure A20081009306500601
(preparation of the coating solution of intermediate-index layer)
Photosensitizers (KayacureDETX with Irgacure 907, the 1.1g of DPHA, the 3.1g of 58.4g, make by Nihon Kayaku K.K.), the pimelinketone of the methyl ethyl ketone of 482.4g and 1869.8g joins in the dispersion liquid (PL1-1) of above-mentioned high refractive index complex oxide fine particle of 88.9g, stir then.Stirred mixture is that the strainer of 0.4 μ m filters the coating solution that makes intermediate-index layer through the aperture of polypropylene manufacturing.
(preparation of the coating solution of high refractive index layer)
The pimelinketone of the methyl ethyl ketone of Kayacure DETX, the 455.8g of Irgacure 907, the 1.3g of DPHA, the 4.0g of 47.9g and 1427.8g is joined in the dispersion liquid (PL1-1) of above-mentioned high refractive index complex oxide fine particle of 586.8g, then stir.Stirred mixture is that the strainer of 0.4 μ m filters the coating solution that makes high refractive index layer through the aperture of polypropylene manufacturing.
(preparation of the coating solution of low-index layer)
Replace specific refractory power and be the solvent (OpsterJN7228 of the fluoropolymer of 1.42 thermally cross-linkable; The content of solids component: 6 weight %; Make by JSR K.K.) fluoropolymer that obtains thermally cross-linkable in methyl iso-butyl ketone (MIBK) and solid component concentration be the solution of 10 weight %.Dispersion liquid (the MEK-ST of fine particles of silica in methyl ethyl ketone that in the fluoropolymer solutions of the thermally cross-linkable of 56.0g, adds 8.0g; The content of solids component: 30 weight %; Make by Nissan Kagaku K.K.), the following silane compound of 1.75g, the methyl iso-butyl ketone (MIBK) of 73.0g and the pimelinketone of 33.0g, then stir.Stirred mixture is that the strainer of 0.4 μ m filters the coating solution that makes low-index layer through the aperture of polypropylene manufacturing.
(preparation of silane compound)
3-acryloxy propyl trimethoxy silicomethane (KBM-5103 with 161g; Make by Shin-etsu Kagaku Kogyo K.K.), the oxalic acid of 123g and the ethanol of 415g joins in the reactor that is equipped with agitator and reflux exchanger, after 70 ℃ are reacted 4 hours down, reaction mixture is cooled to room temperature obtains silane compound as curable compositions.
(preparation of antireflective film)
Use the intaglio plate spreader that the coating solution of hard coat is applied to the thick tri acetyl cellulose film (TD-80UF of 80 μ m; By Fuji Photo Film Co., Ltd. makes).After 100 ℃ of following dryings, use 160W/cm air cooling metal halide lamp (making) to be 400mW/cm with intensity by Ai Graphics K.K 2With irradiation dose be 300mJ/cm 2This coating layer of uviolizing, simultaneously with this environment of nitrogen wash so that the oxygen concn of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form the thick hard coat of 3.5 μ m.
Use the intaglio plate spreader on this hard coat, to be coated with the coating solution of intermediate-index layer.After 100 ℃ of following dryings, use 240W/cm air cooling metal halide lamp (making) to be 550mW/cm with intensity by Ai GraphicsK.K 2With irradiation dose be 600mJ/cm 2This coating layer of uviolizing, simultaneously with this environment of nitrogen wash so that the oxygen concn of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form intermediate-index layer (specific refractory power: 1.65; Thickness: 67nm).
Use the intaglio plate spreader on intermediate-index layer, to be coated with the coating solution of high refractive index layer.After 100 ℃ of following dryings, use 240W/cm air cooling metal halide lamp (making) to be 550mW/cm with intensity by AiGraphics K.K 2With irradiation dose be 600mJ/cm 2This coating layer of uviolizing, simultaneously with this environment of nitrogen wash so that the oxygen concn of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form high refractive index layer (specific refractory power: 1.96; Thickness: 105nm).
Use the intaglio plate spreader on high refractive index layer, to be coated with the coating solution of low-index layer.After 80 ℃ of following dryings, use 160W/cm air cooling metal halide lamp (making) to be 550mW/cm with intensity by Ai GraphicsK.K 2With irradiation dose be 600mJ/cm 2This coating layer of uviolizing, and 120 ℃ of down heating 10 minutes, simultaneously with this environment of nitrogen wash so that the oxygen concn of environment remains on 1.0 volume % or littler level, form low-index layer (specific refractory power: 1.43 thus; Thickness: 86nm).Therefore, form antireflective film.
[Comparative Examples 1-A]
To prepare antireflective film, only be to use the complex oxide fine particle of the particulate replacement embodiment 1-1 of the composite oxides [Ti/Ti+Zr=0.80] of using aluminum oxide and stearic acid surface-treated Ti and Zr with embodiment 1 identical mode.
(evaluation of antireflective film)
Each antireflective film that makes thus at following project evaluation.The results list is in table 1.
(1) evaluation of turbidity
Use turbidimeter (NHD-1001DP; Make by Nihon Denshoku Kogyo K.K.) estimate the turbidity of antireflective film.
(2) evaluation of reflectivity
Use spectrophotometer (V-550, ARV-474; Make by Nihon Bunko K.K.) measure spectral reflectivity at the wavelength zone of 380-780nm with 5 ° input angle.Be determined at the interior average reflectance of wavelength region of 450-650nm.
(3) climatic test
Be to use sunlight weather instrument (S-80 under the condition of minute of light source, 60% relative humidity and 100 hours at the sunlight carbon arc lamp; Make by Suga Shikenki K.K.) carry out climatic test.Observe antireflective film before exposing and degree of bleaching afterwards and according to following Three Estate evaluation:
A: be observed visually and do not bleach.
B: be observed visually slightly and bleach.
C: be observed visually seriously and bleach.
(4) fusible evaluation
To nurse one's health through humidity in 25 ℃ the temperature and the condition of 60% relative humidity through each antireflective film of overtesting (3).
Use cutting knife on the surface of the high refractive index aspect of each antireflective film, to form recess with lattice pattern, wherein vertically forming 11 recesses, laterally forming 11 recesses, form 100 square area of being surrounded altogether thus, and use the adhesive test of the adhesive tape of the polyester manufacture of making by Nitto Denko K.K. (NO.31B) in same position by recess.The stratified generation of visual inspection and according to following 4 level evaluations:
00: in 100, do not observe layering fully.
Zero: 100 2 or still less sheet observe layering.
△: the 3-10 sheet at 100 is observed layering.
*: 100 observe layering greater than 10.
(5) evaluation of pencil hardness
Before antireflective film is standing to expose and after, under the condition of the relative humidity of 25 ℃ temperature and 60%, carry out using the specific mensuration pencil of JIS S6006 to estimate based on the pencil hardness under the 1kg load after the humidity conditioning according to the evaluation method of the pencil hardness described in the JIS K5400.
(6) evaluation of steel wool scratch resistance
Observing before exposing uses the #0000 steel wool at 1Kg/cm with antireflective film afterwards 2Load under swipe the back and forth state of drawing the road that forms for 10 times and according to following 3 grade evaluations:
A: do not form fully and draw the road.
B: form several strokes of roads, observe although be difficult to.
C: form the serious road of drawing.
Table 1
The embodiment comparative example
1-1 Ex.1-A
Turbidity 0.3% 0.3%
Reflectivity 1.0% 1.1%
A A before weathering resistance exposes
A C after exposing
After binding property exposes 00 *
3H was lower than 1H after pencil hardness exposed
A C after scratch resistance exposes
The sample that embodiment 1-1 and Comparative Examples 1-A obtain had good optical characteristic and physical strength as antireflective film before with the exposure test of fedeometer.
And the evaluation of sample after climatic test shows that the sample thin film of embodiment 1-1 does not bleach and the performance before keeping test aspect binding property, pencil hardness and the scratch resistance.
On the other hand, the sample that obtains among the Comparative Examples 1-A exists film seriously to bleach, and is being badly damaged aspect binding property, pencil hardness and the scratch resistance, finds thus actually to use.
As mentioned above, film sample of the present invention shows extremely excellent weathering resistance, is good antireflective film therefore.
And the surface of antireflective film of the present invention is 101 ° to the contact angle of water, and kinetic friction coefficient is 0.08.Its mensuration is carried out in the following manner.
(7) evaluation of contact angle
Sample carried out 2 hours humidity conditioning under the condition of the relative humidity of 25 ℃ temperature and 60%.Think poorly of the contact angle of the surface of the antireflective film on the specific refractory power aspect to water.
(8) evaluation of kinetic friction coefficient
As the index of the sliding capability on the surface of antireflective film on the low-refraction aspect, estimate kinetic friction coefficient.This kinetic friction coefficient be use kinetic friction coefficient tester (HEIDON-14) and diameter as the Stainless Steel Ball of 5mm under the condition of the speed of the load of 100g, 60cm/min sample through condition in the humidity of 25 ℃ temperature and 60% under mensuration after 2 hours the humidity conditioning.
[embodiment 1-2]-[embodiment 1-4]
Prepare antireflective film in the mode identical, only be to use the dispersion liquid (PL1-1) of dispersion liquid (PL1-2 to PL1-4) the replacement high refractive index complex oxide fine particle of high refractive index complex oxide fine particle separately with embodiment 1-1.
In addition, in the scope of median size at 60-90nm of the discrete particles in the dispersion liquid (PL1-2 to PL1-4) of high refractive index complex oxide fine particle separately, and these particles show good monodispersity energy.
Estimate the performance of thus obtained antireflective film in the mode identical, show identical, perhaps big than it with the performance of the film that obtains among the embodiment 1-1 with embodiment 1-1.
[embodiment 2-1]
(formation of hard coat)
The multi-functional acrylate's monomer of the DPHA of 125g and the urethane acrylate oligomer UV-6300B of 125g (being made by Nihon Gosei Kagaku K.K.) are dissolved in the industrial methylated spirits of 439g.In gained solution, add the Irgacure 907 of 7.5g and the solution of Kayacure DETX in the methyl ethyl ketone of 49g of 5.0g.After stirring the mixture, the strainer that is 1 μ m with its aperture through the polypropylene manufacturing filters.
Use excellent spreader that the coating solution that gained forms hard coat is applied on the tri acetyl cellulose film of TAC-TD80U, then dry down at 120 ℃.Afterwards, coating layer forms the thick hard coat of 7.5 μ m with uviolizing.
(preparation of the dispersion liquid of complex oxide fine particle (PL2-1))
The composite oxides that comprise titanium and bismuth [Ti/ (Ti+Bi)=0.95 mol ratio] that the pimelinketone of the dispersion agent of the following structure of 38.6g and 704.3g is joined 257.1g (P-2) in, then decentralized system gets the dispersion liquid that weight average particle diameter is the high refractive index particulate of 55nm in dynomil.
Dispersion agent
Figure A20081009306500671
Mw:1.5x10 4(weight ratio)
(preparation of the coating solution of intermediate-index layer)
The pimelinketone of the methyl ethyl ketone of Kayacure DETX, the 482.4g of Irgacure 907, the 1.1g of the multi-functional acrylate of the DPHA of 58.4g, 3.1g and 1869.8g is joined in the dispersion liquid (PL2-1) of above-mentioned high refractive index complex oxide fine particle of 88.9g, stir then.Stirred mixture is that the strainer of 0.4 μ m filters the coating solution that makes intermediate-index layer through the aperture of polypropylene manufacturing.
(preparation of the coating solution of high refractive index layer (PL2-1))
The tetraethoxy-silicane of 22.3 weight parts and the γ of 77.9 weight parts-glycidoxypropyl methyl diethoxy silicomethane are joined one and be equipped with in the Glass Containers of magnetic stirrer, simultaneously under agitation solution temperature is remained on 5-10 ℃, during 3 hours to the 0.01 N hydrochloric acid that wherein drips 36.8 weight parts.Drip after the end, stirred 0.5 hour, obtain the partial hydrolystate of tetraethoxysilane and γ-glycidoxypropyl methyldiethoxysilane.30.5 weight %), the ethylene glycol butyl ether of 65 weight parts and joining as the ammonium perchlorate of the Acetyl Acetone acid aluminium of 2.6 weight parts of solidifying agent and 0.5 weight part in the partial hydrolystate of the tetraethoxysilane of 137 weight parts and γ-glycidoxypropyl methyldiethoxysilane then, with the dispersion liquid (PL2-1) of the high refractive index complex oxide fine particle of 397.8 weight parts (concentration:.After fully stirring, the stirred solution filtration is made the coating fluid (PL2-1) that is used to form high refractive index layer.
(preparation of antireflective film)
Use the intaglio plate spreader on this hard coat, to be coated with the coating solution of intermediate-index layer.After 100 ℃ of following dryings, use 240W/cm air cooling metal halide lamp (making) to be 550mW/cm with intensity by Ai GraphicsK.K 2With irradiation dose be 600mJ/cm 2This coating layer of uviolizing, simultaneously with this environment of nitrogen wash so that the oxygen concn of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form intermediate-index layer (specific refractory power: 1.65; Thickness: 67nm).
Use the intaglio plate spreader on intermediate-index layer, to be coated with the coating solution (PL2-1) of high refractive index layer.After 100 ℃ of following dryings, this coating layer 120 ℃ of following thermal treatments 2 hours, is solidified coating layer thus.Therefore, form high refractive index layer (specific refractory power: 1.95; Thickness: 107nm).
Use the composition of the low-index layer of wherein also describing on high refractive index layer, to form low-index layer (specific refractory power: 1.44 according to the method described in the embodiment 1 of JP-A-2000-241603; Thickness 82nm).Therefore, form antireflective film.
(evaluation of antireflective film)
To estimate the antireflective film that makes thus with the identical mode of embodiment 1-1.The result shows the superperformance identical with embodiment 1-1.
[embodiment 2-2]-[embodiment 2-4]
Prepare antireflective film in the mode identical, only be to use the dispersion liquid (PL2-1) of dispersion liquid (PL2-2-PL2-4) the replacement complex oxide fine particle of high refractive index complex oxide fine particle separately with embodiment 2-1.
In addition, in the scope of median size at 60-90nm of the discrete particles in the dispersion liquid (PL2-2 to PL2-4) of complex oxide fine particle separately, and these particles show good monodispersity energy.
Figure A20081009306500701
Estimate the performance of thus obtained antireflective film in the mode identical, show identical with the performance of the film that obtains among the embodiment 2-1 with embodiment 2-1.
[embodiment 3]
(preparation of the dispersion liquid of high refractive index complex oxide fine particle))
In sand mill (1/4G sand mill) under 1600rpm with 92g be doped with cobalt ion (doping: Ti 4 weight %) and the complex oxide fine particle of Ta [Ti/ (Ti+Ta)=0.8 mol ratio] (P-3), finely divided 6 hours of the mixture of the pimelinketone of the titanium-containing compound of the following structure of 31g and 337g.As medium, use 1mm Φ zirconium oxide bead.Then, to the 1N hydrochloric acid that wherein adds 0.1g, and under nitrogen environment with mixture heating up to 80 ℃.Stirred 4 hours.The particle diameter through surface-treated particulate of gained doped composite oxide is 60nm.
＜titanium-containing compound 〉
CH 2＝CHCOO(CH 2) 4Ti(OC 2H 5) 3
(preparation of the dispersion liquid of high refractive index layer)
The sulfonium compound with following structure, the methyl ethyl ketone of 455.8g and the pimelinketone of 1427.8g of Kayacure DETX, the 1.9g of Irgacure 907, the 0.8g of the polymerisable compound with following structure of DPHA, the 19.1g of 28.8g, 2.4g are joined in the dispersion liquid (PL3-1) of the above-mentioned complex oxide fine particle of 586.8g, then stir.Stir the mixture through the aperture of polypropylene manufacturing is that the strainer of 0.4 μ m filters the coating solution make high refractive index layer.
＜polymerisable compound 〉
Figure A20081009306500711
＜sulfonium compound 〉
Figure A20081009306500721
(pasting the structural formula of the 126th page of original text)
(preparation of the dispersion liquid of stain-proofing layer)
With Virahol join thermally cross-linkable, fluoropolymer (JN-7214; Make by NihonGosei Gomu K.K.) in make the thick dispersive dispersion liquid of 0.6 weight %.Be cut to finely dividedly with this thick dispersion liquid of ultrasonication, make the coating solution of stain-proofing layer thus.
(preparation of antireflective film)
Prepare the thick cellulose acylate film of 80 μ m according to the method described in the embodiment 1 of JP-A-151936.On this transparent carrier, form hard coat and the intermediate-index layer described in the embodiment 1.The coating solution of the high refractive index layer that makes above use intaglio plate spreader is coated with on intermediate-index layer.After 100 ℃ of following dryings, use 240W/cm air cooling metal halide lamp (making) to be 550mW/cm with intensity by Ai Graphics K.K 2With irradiation dose be 600mJ/cm 2This coating layer of uviolizing, simultaneously with this environment of nitrogen wash so that the oxygen concn of environment remains on 1.0 volume % or littler level, 100 ℃ of down heating 10 minutes, thus coating layer is solidified then.Therefore, form high refractive index layer (specific refractory power: 1.94; Thickness: 105nm).
On this high refractive index layer, form the thick silica membrane (specific refractory power: 1.46) of 88nm according to vacuum deposition method.Use the coating solution of #3 coiling rod coating anti-pollution layer on this low-index layer, then 120 ℃ dry 1 hour down.Use the coating solution of #3 coiling rod coating external coating (EC) on the low-index layer of this antireflective film, then 120 ℃ dry 1 hour down, make antireflective film.
Estimate the performance of the antireflective film that makes thus in the mode identical, show the good result that each performance is identical with embodiment 1-1 with embodiment 1-1.
(evaluation of image display device)
Image display device with antireflective film of the present invention has excellent antireflection property and and excellent visibility.
[embodiment 4]
(preparation of the protective film of polaroid)
(preparation of polaroid)
The PVA (PVOH) FILM that 75 μ m are thick (by Kurary Co., Ltd. make) is soaked in the aqueous solution of being made up of the potassiumiodide of the iodine of the water of 1000g, 7g and 105g and was adsorbed iodine in 5 minutes.Then, with this film 4.4 times of uniaxial extensions longitudinally in 4 weight % boric acid aqueous solutions, and make polarization film keeping being dried under the stretched state.
Use the polyvinyl alcohol tackiness agent as tackiness agent, in the face of under the situation of antireflective film, antireflective film of the present invention (protective film of polaroid) is laminated on the face of polarization film on the tri acetyl cellulose surface of handling with saponification.And, use identical polyvinyl alcohol tackiness agent, laminated to pass through the cellulose acylate film (TD-80UF) that saponification is handled on the another side of polarization film with top described identical mode.
(evaluation of image display device)
Transmission-type, reflection-type or semi-transmission type liquid crystal display device with TN, STN, IPS, VA or ocb mode of the polaroid of the present invention that makes thus have excellent antireflection property and extremely excellent visibility.
[embodiment 5]
(preparation of polaroid)
Under the condition identical with embodiment 4 to an optical compensating film (wide visual angle film SA-12B with optical anisotropic layer; By Fuji Photo Film Co., Ltd. make) in carry out saponification with optical anisotropy face facing surfaces and handle, wherein the relative transparent carrier face tilt of the unitary dish face of disk-shaped structure and wherein the angle between the unitary dish face of disk-shaped structure and the transparent carrier face change at the thickness direction of optical anisotropic layer.
The tri acetyl cellulose upper layer that uses the polyvinyl alcohol tackiness agent as tackiness agent the saponification of the antireflective film (protective film of polaroid) that makes among the embodiment 4 to be handled is combined on the surface of polarization film.And, the tri acetyl cellulose surface of using the saponification of identical polyvinyl alcohol tackiness agent laminated optical compensating film on the another side of polarization film to handle.
(evaluation of image display device)
Transmission-type, reflection-type or the semi-transmission type liquid crystal display device contrast gradient in bright chamber with TN, STN, IPS, VA or ocb mode of the polaroid of the present invention that makes thus is better than having the liquid-crystal display of the polaroid of not being with optical compensating film, extremely wide upper and lower a, left side and LOOK RIGHT are provided, and show extremely excellent antireflection property, therefore have extremely excellent visibility and display quality.
[embodiment 6-1]
(preparation of the coating solution of hard coat)
The dispersion liquid (MEK-ST of fine particles of silica in methyl ethyl ketone with 450.0g; The content of solids component: 30 weight %; Make by Nissan Kagaku K.K.), (Irgacure 907 for the methyl ethyl ketone of 15.0g, the pimelinketone of 220.0g and the Photoepolymerizationinitiater initiater of 16.0g; Make by Nihon Ciba Geigy K.K.) join Dipentaerythritol five acrylate of 315.0g and the mixture (DPHA of dipentaerythritol acrylate; Make by Nihon Kayaku K.K.) in, and the gained mixture stirred.Stir the mixture through the aperture of polypropylene manufacturing is that the strainer of 0.4 μ m filters the coating solution make hard coat.
(preparation of the dispersion liquid of complex oxide fine particle (PL11-1))
In dynomil with 257g with the surface-treated titanium/bismuth composite oxide [Bi/ (Ti+Bi)=0.05 mol ratio] of aluminum oxide and the stearic acid (content of composite oxides: 85%) (P-1), the pimelinketone of cationic acrylate, DMAEA (being made by K.K.Kojin) and the 700g of dispersion agent, the 2.6g of structure and the zirconium oxide bead (the YTZ ball is by the K.K.Nikkato manufacturing) that particle diameter is 0.2mm pass through dispersion steps together below the 38.6g.This dispersion steps was carried out under 35-40 ℃ temperature 8 hours.Use 200 purpose nylon cloths that pearl is separated, make the dispersion liquid (PL11-1) of complex oxide fine particle.
Measure the particle diameter of the discrete particles of thus obtained dispersion liquid by scanning electron microscope, find that particle is to have good monodispersity energy and median size is the particle of 80nm.
Equally, the size distribution of measuring dispersion liquid (is used with the device of laser analysis as the particle diameter of fundamental measurement discrete particles; LA-920; Make by Horiba Seisakusho), confirm that particle diameter is that 500nm or bigger particulate content are 0%.
Dispersion agent
Figure A20081009306500751
In addition,, find in dispersion liquid, not observe precipitation, the particle diameter of discrete particles and 1 month before identical, and 500 nm or bigger particulate content maintenance 0% when placing when measuring the performance of gained dispersion liquid after 1 month.
(preparation of the coating solution of intermediate-index layer)
Photosensitizers (KayacureDETX with Irgacure 907, the 1.1g of DPHA, the 3.1g of 58.4g, make by Nihon Kayaku K.K.), the methyl ethyl ketone of 482.4g and the pimelinketone of 1869.8g join in the dispersion liquid (PL11-1) of the above-mentioned complex oxide fine particle of 88.9g, stir then.Stir the mixture through the aperture of polypropylene manufacturing is that the strainer of 0.4 μ m filters the coating solution make intermediate-index layer.
(preparation of the coating solution of high refractive index layer)
The methyl ethyl ketone of Kayacure DETX, the 455.8g of Irgacure 907, the 1.3g of DPHA, the 4.0g of 47.9g and the pimelinketone of 1427.8g are joined in the dispersion liquid (PL11-1) of the above-mentioned complex oxide fine particle of 586.8g, then stir.Stir the mixture through the aperture of polypropylene manufacturing is that the strainer of 0.4 μ m filters the coating solution make high refractive index layer.
(preparation of the coating solution of low-index layer)
Replace specific refractory power and be the solvent (OpsterJN7228 of the fluoropolymer of 1.42 thermally cross-linkable; The content of solids component: 6 weight %; Make by JSR K.K.) fluoropolymer that obtains thermally cross-linkable in methyl iso-butyl ketone (MIBK) and solid component concentration be the solution of 10 weight %.Dispersion liquid (the MEK-ST of fine particles of silica in methyl ethyl ketone that in the fluoropolymer solutions of the thermally cross-linkable of 56.0g, adds 8.0g; The content of solids component: 30 weight %; Make by Nissan Kagaku K.K.), the following silane compound of 1.75g, the methyl iso-butyl ketone (MIBK) of 73.0g and the pimelinketone of 33.0g, then stir.Stir the mixture through the aperture of polypropylene manufacturing is that the strainer of 0.4 μ m filters the coating solution make low-index layer.
(preparation of silane compound)
3-acryloxy propyl trimethoxy silicomethane (KBM-5103 with 161g; Make by Shin-etsu Kagaku Kogyo K.K.), the oxalic acid of 123g and the ethanol of 415g joins in the reactor that is equipped with agitator and reflux exchanger, after 70 ℃ are reacted 4 hours down, reaction mixture is cooled to room temperature obtains silane compound as curable compositions.Its weight-average molecular weight is 1600, and based on the oligopolymer component, molecular weight is that the components contents of 1000-20000 is 100%.Gas chromatographic analysis confirms that raw material propylene acyloxy propyl trimethoxy silicane does not exist at all.
(preparation of antireflective film)
Use the intaglio plate spreader that the coating solution of hard coat is applied to the thick tri acetyl cellulose film (TD-80UF of 80 μ m; By Fuji Photo Film Co., Ltd. makes).After 100 ℃ of following dryings, use 160W/cm air cooling metal halide lamp (making) to be 400mW/cm with intensity by Ai Graphics K.K 2With irradiation dose be 300mJ/cm 2This coating layer of uviolizing, simultaneously with this environment of nitrogen wash so that the oxygen concn of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form the thick hard coat of 3.5 μ m.
Use the intaglio plate spreader on this hard coat, to be coated with the coating solution of intermediate-index layer.After 100 ℃ of following dryings, use 240W/cm air cooling metal halide lamp (making) to be 550mW/cm with intensity by Ai GraphicsK.K 2With irradiation dose be 600mJ/cm 2This coating layer of uviolizing, simultaneously with this environment of nitrogen wash so that the oxygen concn of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form intermediate-index layer (specific refractory power: 1.65; Thickness: 67nm).
Use the intaglio plate spreader on intermediate-index layer, to be coated with the coating solution of high refractive index layer.After 100 ℃ of following dryings, use 240W/cm air cooling metal halide lamp (making) to be 550mW/cm with intensity by AiGraphics K.K 2With irradiation dose be 600mJ/cm 2This coating layer of uviolizing, simultaneously with this environment of nitrogen wash so that the oxygen concn of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form high refractive index layer (specific refractory power: 1.96; Thickness: 105nm).
Use the intaglio plate spreader on high refractive index layer, to be coated with the coating solution of low-index layer.After 80 ℃ of following dryings, use 160W/cm air cooling metal halide lamp (making) to be 550mW/cm with intensity by Ai GraphicsK.K 2With irradiation dose be 600mJ/cm 2This coating layer of uviolizing, and 120 ℃ of down heating 10 minutes, simultaneously with this environment of nitrogen wash so that the oxygen concn of environment remains on 1.0 volume % or littler level, low-index layer (specific refractory power: 1.43 thus; Thickness: 86nm).Therefore, form antireflective film.
[embodiment 6-2]
(preparation of the dispersion liquid of complex oxide fine particle)
The polymeric dispersant of the surface-treated complex oxide fine particle (P-1) that uses among the embodiment 6-1 with 257g, the following structure of 40g and the pimelinketone of 702g join among the dynomil and with the zirconium oxide bead of particle diameter as 0.2mm and disperse.This dispersion steps was carried out under 35-40 ℃ temperature 5 hours.Therefore, making median size is 65nm and to contain 0% particle diameter be the dispersion liquid (PL11-2) of the particulate complex oxide fine particle of 500nm.
Polymeric dispersant:
Figure A20081009306500781
Mw=2x10 4(composition weight ratio)
In addition,, find in dispersion liquid, not observe precipitation, the particle diameter of discrete particles and 1 month before identical, and 500nm or bigger particulate content maintenance 0% when placing when measuring the performance of gained dispersion liquid after 1 month.
Prepare antireflective film in the mode identical, only be to use the dispersion liquid (PL11-1) of dispersion liquid (PL11-2) the replacement composite oxides of above-mentioned complex oxide fine particle with embodiment 6-1.
[Comparative Examples 6-A]
Prepare dispersion liquid in the mode identical with the dispersion liquid (PL11-1) of the composite oxides of embodiment 6-1, only being to use particle diameter is that to replace particle diameter be the granulated glass sphere of 0.2mm for the granulated glass sphere of 1.0mm.The discrete particles of gained dispersion liquid has extremely wide size distribution and has the median size of about 250nm.Equally, 500nm or bigger proportion of particles are 10 volume % or bigger.
Prepare antireflective film in the mode identical, only be to use above-mentioned dispersion liquid to replace composite oxides dispersion liquids (PL11-1) with embodiment 6-1.
[Comparative Examples 6-B]
Use aluminum oxide and the surface-treated titanium dioxide particulate (TTO-51 (C) of stearic acid to prepare antireflective film with the identical mode of embodiment 6-1, only to be to use; The content of titanium oxide: 79-85% is made by Ishihara Sangyo K.K.) replace the compound particulate (P-1) that uses among the embodiment 6-1.
Yet, recently prepare the coating solution of high refractive index layer by the weight that changes fine inorganic particle/DPHA, make the specific refractory power of the antireflective film for preparing in the mode identical and identical (1.96) among the embodiment 6-1 with embodiment 6-1.Along with the particulate amount increases, the weight ratio of fine inorganic particle/DPHA becomes 69/31 from 60/40.
[comparative example 6-C]
Use bismuth (Bi 2O 3) particulate replaces the complex oxide fine particle that uses among the embodiment 6-1.In addition, carry out the step identical and prepare anti-reflection layer with embodiment 6-1.
Yet, recently prepare the coating solution of high refractive index layer by the weight that changes fine inorganic particle/DPHA, make the specific refractory power of the antireflective film for preparing in the mode identical and identical (1.96) among the embodiment 6-1 with embodiment 6-1.Along with the particulate amount increases, the weight ratio of fine inorganic particle/DPHA becomes 73/27 from 60/40.
(evaluation of antireflective film)
Each antireflective film that makes thus at following project evaluation.The results list is in table 4.
(1) evaluation of turbidity
Use turbidimeter (NHD-1001DP; Make by Nihon Denshoku Kogyo K.K.) estimate the turbidity of antireflective film.
(2) evaluation of reflectivity
Use spectrophotometer (V-550, ARV-474; Make by Nihon Bunko K.K.) measure spectral reflectivity at the wavelength zone of 380-780nm with 5 ° input angle.Be determined at the interior mean refractive index of wavelength region of 450-650nm.
(3) test that bleaches
Be to use sunlight weather instrument (S-80 under the condition of minute of light source, 60% relative humidity and 100 hours at the sunlight carbon arc lamp; Make by Suga Shikenki K.K.) test bleaches.Observe antireflective film before exposing and degree of bleaching afterwards and according to following Three Estate evaluation:
A: be observed visually and do not bleach.
B: be observed visually slightly and bleach.
C: be observed visually seriously and bleach.
(4) fusible evaluation
To nurse one's health through humidity in 25 ℃ the temperature and the condition of 60% relative humidity through each antireflective film of overtesting (3).
Use cutting knife on the surface of the high refractive index aspect of each antireflective film, to form recess with lattice pattern, wherein vertically forming 11 recesses, laterally forming 11 recesses, form 100 square area of being surrounded altogether thus, and repeat the adhesive test of 3 uses by the adhesive tape of the polyester manufacture of Nitto Denko K.K. (NO.31B) manufacturing in same position by recess.The stratified generation of visual inspection and according to following 4 level evaluations:
00: in 100, do not observe layering fully.
Zero: 100 2 or still less sheet observe layering.
△: the 3-10 sheet at 100 is observed layering.
*: 100 surpass 10 and observe layering.
(5) evaluation of pencil hardness
Before antireflective film is exposing and after, under the condition of the relative humidity of 25 ℃ temperature and 60%, carry out using the specific mensuration pencil of JIS S6006 to estimate based on the pencil hardness under the 1kg load after the humidity conditioning according to the evaluation method of the pencil hardness described in the JIS K5400.
(6) evaluation of steel wool scratch resistance
Observing before exposing uses the #0000 steel wool at 500g/cm with antireflective film afterwards 2Load under swipe the back and forth state of drawing the road that forms for 50 times and according to following 3 grade evaluations:
A: do not form fully and draw the road.
B: form several strokes of roads, observe although be difficult to.
C: form the serious road of drawing.
Table 4 (A)
The EXAMPLE Example contrast
6-1 6-2 Ex.6-A
Turbidity 0.8% 0.5% 5%
Average reflectance 0.3% 0.25% 1%
Test A A A bleaches
0000 △ before binding property exposes
00 △ after exposing
3H 3H 2H-3H (no before pencil hardness exposed
Even)
3H 3H 2H-3H (no after exposing
Even)
A A B before scratch resistance exposes
A A B after exposing
Table 4 (B)
The contrast contrast
Ex.6-B Ex.6-C
Turbidity value 1.3%-
Yellow
Average reflectance 0.38%-
Yellow
Test C A bleaches
Before binding property exposes 000
After the exposure * zero
3H 3H before pencil hardness exposes
1H or littler 3H after exposing
A A before scratch resistance exposes
B A after exposing
Table 4 result displayed has shown the following fact.
The new film that embodiment 6-1 and 6-2 and Comparative Examples 6-B obtain had good optical performance, binding property, hardness and scratch resistance before exposure test.On the other hand, the sample of Comparative Examples 6-A acquisition shows big optical value.And it shows binding property, hardness and the scratch resistance that reduces.
On the other hand, only comprise that the sample that obtains among the Comparative Examples 6-C of bismuth oxide suffers the serious flavescence of film, make it actually can not be used as antireflective film.
And the film sample of embodiment 6-1 and 6-2 shows after climatic test almost and the identical superperformance of film before the climatic test.Yet the sample that obtains in Comparative Examples 6-B makes film bleach and film strength is badly damaged.
As mentioned above, extremely excellent weathering resistance and excellent optical property and the film strength of film sample demonstration of the present invention.
And the surface of each antireflective film that makes among embodiments of the invention 6-1 and the 6-2 is 101 ° to the contact angle of water, and kinetic friction coefficient is 0.08.Its mensuration is carried out in the following manner.
(7) evaluation of contact angle
Sample carried out 2 hours humidity conditioning under the condition of the relative humidity of 25 ℃ temperature and 60%.Think poorly of the contact angle of the surface of the antireflective film on the specific refractory power aspect to water.
(8) evaluation of kinetic friction coefficient
As the index of the sliding capability on the surface of antireflective film on the low-refraction aspect, estimate kinetic friction coefficient.This kinetic friction coefficient be use kinetic friction coefficient tester (HEIDON-14) and diameter as the Stainless Steel Ball of 5mm the load of 100g with the condition of the speed of 60cm/min under sample through the condition of the humidity of 25 ℃ temperature and 60% under mensuration after 2 hours the humidity conditioning.
[embodiment 6-3]-[embodiment 6-8]
Prepare antireflective film in the mode identical, only be to use the dispersion liquid (PL11-2) of dispersion liquid (PL11-3 to PL11-8) the replacement complex oxide fine particle of complex oxide fine particle separately with embodiment 6-2.
In addition, in the scope of median size at 60-80nm of the discrete particles in the dispersion liquid (PL11-3 to PL11-8) of complex oxide fine particle separately, and these particles show good monodispersity energy.
Estimate the performance of thus obtained antireflective film in the mode identical, show identical, perhaps big than it with the performance of the film that obtains among the embodiment 6-1 with embodiment 6-1.
[embodiment 7-1]
(formation of hard coat)
The multi-functional acrylate's monomer of the DPHA of 125g and the urethane acrylate oligomer UV-6300B of 125g (being made by Nihon Gosei Kagaku K.K.) are dissolved in the industrial methylated spirits of 439g.In gained solution, add in the solution of Kayacure DETX in the methyl ethyl ketone of 49g of the Irgacure 907 of 7.5g and 5.0g.After stirring the mixture, the strainer that is 1 μ m with its aperture through the polypropylene manufacturing filters.
Use excellent spreader that the coating solution that gained forms hard coat is applied on the tri acetyl cellulose film of TAC-TD80U, then dry down at 120 ℃.Afterwards, coating layer forms the thick hard coat of 7.5 μ m with uviolizing.
(preparation of the dispersion liquid of complex oxide fine particle (PL2-1))
The pimelinketone of the dispersion agent of the following structure of 38.6g and 704.3g is joined the composite oxides that comprise titanium, bismuth and aluminium [Bi/ (Ti+Bi+Zr)=0.08 mol ratio of 257.1g; Zr/Bi+Ti+Zr]=0.05 mol ratio] (P-2) in, in dynomil, be that the zirconium oxide bead of 0.3mm disperses then with particle diameter.This dispersion steps was carried out under 40-45 ℃ temperature 6 hours, made the dispersion liquid (PL2-1) of complex oxide fine particle.Discrete particles has the median size of 75nm in the thus obtained dispersion liquid, and wherein 500nm or bigger particulate content are 0%.
Dispersion agent
Mw:4x10 4(the Mw:8x10 of grafting part 3)
(preparation of the coating solution of intermediate-index layer)
The methyl ethyl ketone of Kayacure DETX, the 482.4g of Irgacure 907, the 1.1g of the multi-functional acrylate of the DPHA of 58.4g, 3.1g and the pimelinketone of 1869.8g are joined in the dispersion liquid (PL2-1) of the above-mentioned complex oxide fine particle of 88.9g, stir then.Stir the mixture through the aperture of polypropylene manufacturing is that the strainer of 0.4 μ m filters the coating solution make intermediate-index layer.
(preparation of the coating solution of high refractive index layer)
The tetraethoxysilane of 22.3 weight parts and the γ of 77.9 weight parts-glycidoxypropyl methyldiethoxysilane are joined one to be equipped with in the Glass Containers of magnetic stirrer, simultaneously under agitation solution temperature is remained on 5-10 ℃, during 3 hours to the 0.01N hydrochloric acid that wherein drips 36.8 weight parts.Drip after the end, stirred 0.5 hour, obtain the partial hydrolystate of tetraethoxysilane and γ-glycidoxypropyl methyldiethoxysilane.30.5 weight %), the ethylene glycol butyl ether of 65 weight parts and joining as the ammonium perchlorate of the Acetyl Acetone acid aluminium of 2.6 weight parts of solidifying agent and 0.5 weight part in the partial hydrolystate of the tetraethoxysilane of 137 weight parts and γ-glycidoxypropyl methyldiethoxysilane then, with the dispersion liquid (PL2-1) of the complex oxide fine particle of 397.8 weight parts (concentration:.After fully stirring, the stirred solution filtration is made the coating fluid that is used to form high refractive index layer.
(preparation of antireflective film)
Use the intaglio plate spreader on this hard coat, to be coated with the coating solution of intermediate-index layer.After 100 ℃ of following dryings, use 240W/cm air cooling metal halide lamp (making) to be 550mW/cm with intensity by Ai GraphicsK.K 2With irradiation dose be 600mJ/cm 2This coating layer of uviolizing, simultaneously with this environment of nitrogen wash so that the oxygen concn of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form intermediate-index layer (specific refractory power: 1.65; Thickness: 67nm).
Use the intaglio plate spreader on intermediate-index layer, to be coated with the coating solution of high refractive index layer.After 100 ℃ of following dryings, this coating layer 120 ℃ of following thermal treatments 2 hours, is solidified coating layer thus.Therefore, form high refractive index layer (specific refractory power: 1.95; Thickness: 107nm).
Use the composition of the low-index layer of wherein also describing on high refractive index layer, to form low-index layer (specific refractory power: 1.44 according to the method described in the embodiment 1 of JP-A-2000-241603; Thickness 82nm).Therefore, form antireflective film.
(evaluation of antireflective film)
To estimate the antireflective film that makes thus with the identical mode of embodiment 6-1.The results list is in table 5.
Table 5
Embodiment 7-1
Turbidity 0.9%
Average reflectance 0.4%
Test A bleaches
Before binding property exposes 00
After exposing zero
3H before pencil hardness exposes
3H after exposing
A before scratch resistance exposes
A after exposing
[embodiment 7-2]-[embodiment 7-4]
Prepare antireflective film in the mode identical, only be to use the dispersion liquid (PL2-1) of dispersion liquid (PL2-2-PL2-4) the replacement complex oxide fine particle of complex oxide fine particle separately with embodiment 7-1.
In addition, in the scope of median size at 55-80nm of the discrete particles in the dispersion liquid (PL2-2 to PL2-4) of complex oxide fine particle separately, and these particles show good monodispersity energy.
Figure A20081009306500891
Estimate the performance of thus obtained antireflective film in the mode identical, show identical with the performance of the film that obtains among the embodiment 7-1 with embodiment 7-1.
[embodiment 8]
(preparation of the dispersion liquid of complex oxide fine particle (PL3-1))
In sand mill (1/4G sand mill) under 1600rpm with particulate [Bi/ (Bi+Ti+Zr)=0.07 mol ratio of the composite oxides that comprise bismuth, zirconium and titanium of 92g; The Zr/Bi+Ti+Zr=0.05 mol ratio] (P-3), finely divided 6 hours of the mixture of the pimelinketone of the titanium-containing compound of the following structure of 31g and 337g.As medium, use the zirconium oxide bead of particle diameter as 0.2mm.Then, to the 1N hydrochloric acid that wherein adds 0.1g, and under nitrogen environment with mixture heating up to 80 ℃.Stir the dispersion liquid (PL-3) that made complex oxide fine particle in 4 hours.The particle diameter of the particulate that gained is surface-treated is 70nm.
＜titanium-containing compound 〉
Figure A20081009306500901
(preparation of the dispersion liquid of high refractive index layer)
The sulfonium compound with following structure, the methyl ethyl ketone of 455.8g and the pimelinketone of 1427.8g of Kayacure DETX, the 1.9g of Irgacure 907, the 0.8g of the polymerisable compound with following structure of DPHA, the 19.1g of 28.8g, 2.4g are joined in the dispersion liquid (PL3-1) of the above-mentioned complex oxide fine particle of 586.8g, then stir.Stir the mixture through the aperture of polypropylene manufacturing is that the strainer of 0.4 μ m filters the coating solution make high refractive index layer.
＜polymerisable compound 〉
Figure A20081009306500902
＜sulfonium compound 〉
(preparation of the dispersion liquid of stain-proofing layer)
With Virahol join thermally cross-linkable, fluoropolymer (JN-7214; Make by NihonGosei Gomu K.K.) in make the thick dispersive dispersion liquid of 0.6 weight %.Be cut to finely dividedly with this thick dispersion liquid of ultrasonication, make the coating solution of stain-proofing layer thus.
(preparation of antireflective film)
Prepare the thick cellulose acylate film of 80 μ m according to the method described in the embodiment 1 of JP-A-151936.On this transparent carrier, form hard coat and the intermediate-index layer described in the embodiment 6-1.The coating solution of the high refractive index layer that makes above use intaglio plate spreader is coated with on intermediate-index layer.After 100 ℃ of following dryings, use 240W/cm air cooling metal halide lamp (making) to be 550mW/cm with intensity by Ai Graphics K.K 2With irradiation dose be 600mJ/cm 2This coating layer of uviolizing, simultaneously with this environment of nitrogen wash so that the oxygen concn of environment remains on 1.0 volume % or littler level, 100 ℃ of down heating 10 minutes, thus coating layer is solidified then.Therefore, form high refractive index layer (specific refractory power: 1.94; Thickness: 105nm).
On this high refractive index layer, form the thick silica membrane (specific refractory power: 1.46) of 88nm according to vacuum deposition method.Use the coating solution of #3 coiling rod coating anti-pollution layer on this low-index layer, then 120 ℃ dry 1 hour down.Use the coating solution of #3 coiling rod coating external coating (EC) on the low-index layer of this antireflective film, then 120 ℃ dry 1 hour down, make antireflective film.
Estimate the performance of the antireflective film that makes thus in the mode identical, show the good result that each performance is identical with embodiment 6-1 with embodiment 6-1.
Embodiment 9
(preparation of the protective film of polaroid)
With the antireflective film that makes among embodiment 6-1 to 6-8 and the embodiment 7-1 to 7-4, in the following manner the alkali soap processing is carried out on the surface of the transparent carrier on the relative face of high refractive index layer of the present invention.
Make the temperature of film surface be increased to 40 ℃ by one 60 ℃ of electric Jie's warming mills each film, use rod to be coated with device then thereon with 15cc/m 2The following alkaline solution of forming (S) of glue spread coating, be heated under 110 ℃ at steam type far infra-red heater (making) it kept for 15 seconds by Noritake Company Limited, use rod to be coated with device and be coated with 3cc/m similarly thereon 2The pure water of amount.The temperature of its upper film is 40 ℃.Then, use spray formula spreader to wash with water and repeat 3 times with the combination of air knife dehydration, then with film 70 ℃ of drying zones keep 5 second drying.
The composition of alkaline solution (S):
Potassium hydroxide 8.55 weight %
Water 23.235 weight %
Virahol 54.20 weight %
Tensio-active agent (K-l; C 14H 29O (CH 2CH 2O) 20H) 1.0 weight %
Propylene glycol 13.0 weight %
Defoamer (Surfinol DF110D; By Nissin Kagaku Kogyo 0.015 weight %
K.K. make)
(preparation of polarization film)
The PVA (PVOH) FILM that 75 μ m are thick (by Kurary Co., Ltd. make) is soaked in the aqueous solution of being made up of the potassiumiodide of the iodine of the water of 1000g, 7g and 105g and was adsorbed iodine in 5 minutes.Then, with this film 4.4 times of uniaxial extensions longitudinally in 4 weight % boric acid aqueous solutions, and make polarization film keeping being dried under the stretched state.
Use the polyvinyl alcohol tackiness agent as tackiness agent, in the face of under the situation of antireflective film, antireflective film of the present invention (protective film of polaroid) is laminated on the face of polarization film on the tri acetyl cellulose surface of handling with saponification.And, use identical polyvinyl alcohol tackiness agent, laminated and top described identical mode is passed through the cellulose acylate film (TD-80UF) that saponification is handled on the another side of polarization film.
(evaluation of image display device)
Transmission-type, reflection-type or semi-transmission type liquid crystal display device with TN, STN, IPS, VA or ocb mode of the polaroid of the present invention that makes thus have excellent antireflection property and extremely excellent visibility.
[embodiment 10]
(preparation of polaroid)
Under the condition identical with embodiment 9 to an optical compensating film (wide visual angle film SA-12B with optical anisotropic layer; By Fuji Photo Film Co., Ltd. make) in carry out saponification with optical anisotropy face facing surfaces and handle, wherein the relative transparent carrier face tilt of the unitary dish face of disk-shaped structure and wherein the angle between the unitary dish face of disk-shaped structure and the transparent carrier face change at the thickness direction of optical anisotropic layer.
The tri acetyl cellulose upper layer that uses the polyvinyl alcohol tackiness agent as tackiness agent the saponification of the antireflective film (protective film of polaroid) that makes among the embodiment 9 to be handled is combined on the surface of polarization film.And, the tri acetyl cellulose surface of using the saponification of identical polyvinyl alcohol tackiness agent laminated optical compensating film on the another side of polarization film to handle.
(evaluation of image display device)
The contrast gradient of liquid-crystal display in bright chamber with transmission-type, reflection-type or Semitransmissive of the polaroid TN of the present invention, STN, IPS, VA or the ocb mode that make thus is better than having the liquid-crystal display of the polaroid of not being with optical compensating film, extremely wide upper and lower a, left side and LOOK RIGHT are provided, and show extremely excellent antireflection property, therefore have extremely excellent visibility and display quality.
Industrial applicibility
Use contains the high index of refraction of the high index of refraction complex oxide fine particle that comprises element-specific The antireflective film of layer composition has excellent against weather (particularly, light resistance) and can To provide on a large scale at an easy rate.
And the antireflective film with above-mentioned advantage can be used for polarizer or image display device Thereby provide the image with excellent visibility and display quality.
Equally, use by the superfine granule that contains the high index of refraction composite oxides that comprise element-specific The antireflective film of the high index of refraction cured film that forms of coating composition have excellent anti-Weather (particularly, light resistance) and can providing on a large scale at an easy rate.
And the antireflective film with above-mentioned advantage can be used for polarizer or image display device Thereby provide the image with excellent visibility and display quality.

Claims (14)

1, the preparation method of curable coating composition, described curable coating composition comprises the particulate of film forming curable compound and high refractive index composite oxides, the particulate of wherein said high refractive index composite oxides contains: bismuth element and at least a metallic element, the oxide compound of wherein said at least a metallic element has 1.95 or bigger specific refractory power
Wherein said method comprises uses medium wet disperse high refractive index composite oxide particle and the dispersion agent of median size less than 1mm, makes median size thus and be the particulate of 150nm or littler high refractive index composite oxides.
2, the method for claim 1, wherein said dispersion agent are the polymeric dispersants with polar group.
3, method as claimed in claim 2, wherein said polar group are at least a anionic groups that is selected from carboxyl, sulfo group, phosphono and phosphine oxide acyl group.
4, method as claimed in claim 2, wherein said dispersion agent are the compounds with crosslinkable or polymerisable functional group.
5, the method for claim 1, wherein said film forming curable compound are at least a in curable organic binder bond, organometallic compound and their partial hydrolysate.
6, cured film, it has the specific refractory power of 1.85-2.5 and is formed by curable coating composition, described curable coating composition contains the particulate that film forming curable compound and median size are 100nm or littler high refractive index composite oxides, the particulate of described high refractive index composite oxides includes: bismuth element and at least a metallic element, the oxide compound of wherein said at least a metallic element have 1.95 or bigger specific refractory power.
7, antireflective film, it comprises successively: transparent carrier; Cured film as claimed in claim 6; With specific refractory power less than 1.55 low-index layer.
8, antireflective film as claimed in claim 7, it comprises the cured film as claimed in claim 6 that two-layer specific refractory power is differing from each other.
9, antireflective film as claimed in claim 7, it also comprises hard coat between described transparent carrier and described cured film.
10, polaroid comprises polarization film and protective film thereof, and wherein said protective film is an antireflective film as claimed in claim 7.
11, polaroid comprises polarization film and protective film thereof, and one of them protective film is an antireflective film as claimed in claim 7, and another protective film is to have optically anisotropic optical compensating film.
12, polaroid as claimed in claim 11, wherein said optical compensating film comprises transparent carrier and comprises the optical compensating layer of optical anisotropic layer, described optical anisotropic layer comprises and has the unitary compound of disk-shaped structure, the relative transparent carrier face tilt of the unitary dish face of wherein said disk-shaped structure, and the angle between described dish face and transparent carrier face changes at the thickness direction of described optical anisotropic layer.
13, image display device, it comprises antireflective film as claimed in claim 7 on the display plotter surface.
14, image display device, it comprises polaroid as claimed in claim 10 on the display plotter surface.
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CN115038727A (en) * 2020-02-07 2022-09-09 3M创新有限公司 Curable composition for forming light scattering layer
CN113788958A (en) * 2021-08-25 2021-12-14 清远市浩宇化工科技有限公司 Sulfophosphoric acid radical-containing divinyl organic silicon modified acrylic acid aqueous dispersion and preparation method and application thereof

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CN101294003B (en) 2011-11-09

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