CN1756969A - High refractive index layer production process of curable coating composition, antireflection film, polarizing plate and image display device using thereof - Google Patents

High refractive index layer production process of curable coating composition, antireflection film, polarizing plate and image display device using thereof Download PDF

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CN1756969A
CN1756969A CN 200480005907 CN200480005907A CN1756969A CN 1756969 A CN1756969 A CN 1756969A CN 200480005907 CN200480005907 CN 200480005907 CN 200480005907 A CN200480005907 A CN 200480005907A CN 1756969 A CN1756969 A CN 1756969A
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refractive index
film
compound
layer
group
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CN100390570C (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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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 high refractive index layer, curable coating composition, antireflective film, polaroid and use
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 plastic matrix in residuite so far with antireflection ability.Particularly, this antireflective film is installed in is used for for example surface of the display of LCD (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 to reduce.Therefore, require this antireflective film to have high physical strength (for example, scratch resistance), chemical resistance and against weather (for example, humidity resistance and photostability).In addition, as the antireflective film of image demonstration usefulness, the high refractive index layer that also requires antireflective film to have the refractive index higher than the refractive index of the antireflective film that is used for synthetic resin lens, and this high refractive index layer is colourless and transparent.
In recent years, LCD (LCD) maximizes day by day, is equipped with the quantity of the LCD of antireflective film also increasing.
Equally, in LCD (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 display greatly.
Antireflective film is formed by the film of multilayer usually, and the film of described multilayer 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 refractive indexes differed from one another.The transparent membrane 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 (ultraviolet ray irradiation: referring to JP-A-9-157855; Cement Composite Treated by Plasma: referring to JP-A-2000-9908) forms this film.
Yet the throughput rate of the method for the transparent membrane 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 refractive index of 1.45-1.55 usually, therefore by selecting to be used for the kind of inorganic particle wherein and the refractive index that quantity is suitably adjusted each layer.Specifically, with regard to high refractive index layer, need the high fine inorganic particle of refractive index, and the fine inorganic particle that described refractive index 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 refractive index, known refractive index 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; 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, titania is the compound with high refractive index, and this compound is added extremely effectively (for example, JP-A-2000-9908 and JP-A-2001-310423) as particulate.Yet titania has photo-catalysis capability and has extremely poor against weather.Therefore, when long-time use high refractive index film (antireflective film) under sunshine, titania 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 durability of film.Be head it off, proposed a kind of technology, it is with the surface of other metallic compound capping oxidation titanium particle, thereby the particulate of laminate structures is provided, to improve against weather (for example, JP-A-2001-166104 and JP-A-2000-204301).
On the other hand, many various composite metal oxides (double oxide) (for example, JP-A-8-234001JP-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.The high refractive index film of the height composite oxides that contain titaniferous specifically, is wherein disclosed.For example, the composite metal oxide for example composite oxides (JP-A-8-113760) of the composite metal oxide of titanium dioxide-cerium oxide-monox (JP-A-2000-204301), titanium dioxide-Zirconium oxide-tin oxide and the composite oxides (JP-A-10-306258) of tin oxide-titanium dioxide have been proposed.
In addition, proposed when composite oxides contain Si, Al etc. and the refrangible metallic element of above-mentioned height to improve the dispersiveness of particle and the technology of film performance (referring to, for example, JP-A-9-21901, JP-A-11-140207 and JP-A-2002-30250).
Yet this titanium-containing composite oxide makes photostability reduce, although they can keep refractive index in higher level ground when increasing the content of the titanium dioxide with high index of refraction.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 against weather (particularly, photostability excellence) and film strength (for example, anti-embrittlement, hardness and cohesive).Yet above-mentioned requirements is also failed satisfied fully.On the other hand, the composite oxides of titanium dioxide and bismuth oxide have been proposed as the luminescence 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 against weather excellence.
Another purpose of the present invention provides the antireflective film of the against weather excellence of marked down ground large-scale production.
Another object of the present invention provides the preparation method of the curable coating composition of optical characteristics and durability excellence.
Another purpose of the present invention provides the cured film of optical characteristics and against weather excellence.
Another purpose of the present invention provides the antireflective film of the optical characteristics and the durability excellence of the large-scale production 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 index of refraction composite oxides,
The particulate of wherein said high index of refraction composite oxides is the particulates that contain the composite oxides of titanium elements and at least a metallic element, the oxide of wherein said at least a metallic element have 1.95 or bigger refractive index and
Described composite oxides and at least a metal ion mixing that is selected from Co ion, Zr ion and Al ion.
2, as the 1st described high refractive index layer, the particulate of wherein said high index of refraction 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 bond, organometallics and their partial hydrolysate.
4, as each described high refractive index layer of 1-3 item, it has the refractive index of 1.75-2.4.
5, as each described high refractive index layer of 1-4 item; it is by passing through the use spreading agent composition that described high index of refraction composite oxide particle disperses to obtain to be formed, and wherein said spreading 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 spreading 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 refractive index less than 1.55 low-index layer.
8, antireflective film, it comprises transparent carrier successively; Two-layer refractive index differing from each other as each described high refractive index layer of 1-6 item; With refractive index less than 1.55 low-index layer.
9, as the 7th or 8 described antireflective film, it also comprises hard conating 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 the compound with disk-shaped structure unit, the relative transparent carrier face tilt of the dish face of wherein said disk-shaped structure unit, 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 index of refraction composite oxides, the particulate of wherein said high index of refraction composite oxides contains: bismuth element and at least a metallic element, the oxide of wherein said at least a metallic element has 1.95 or bigger refractive index
Wherein said method comprises uses medium wet disperse high index of refraction composite oxide particle and the spreading agent of mean grain size less than 1mm, makes mean grain size thus and be the particulate of 150nm or littler high index of refraction composite oxides.
15, as the 14th described method, wherein said spreading 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 spreading 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 bond, organometallics and their partial hydrolysate.
19, cured film, it has the refractive index 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 mean grain size are 100nm or littler high index of refraction composite oxides, the particulate of described high index of refraction composite oxides comprises: bismuth element and at least a metallic element, the oxide of wherein said at least a metallic element have 1.95 or bigger refractive index.
20, antireflective film, it comprises successively: transparent carrier; As the 19th described cured film; With refractive index less than 1.55 low-index layer.
21, antireflective film, it comprises successively: transparent carrier; Two-layer refractive index differing from each other as the 19th described cured film; With refractive index less than 1.55 low-index layer.
22, as the 20th or 21 described antireflective film, it also comprises hard conating 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 the compound with disk-shaped structure unit, the described relatively transparent carrier face tilt of the dish face of wherein said disk-shaped structure unit, 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 display 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 displays 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 of described at least a metallic element has 1.95 or bigger refractive index.
High refractive index layer of the present invention has preferred 1.75-2.40, more preferably 1.80-2.40, even the more preferably refractive index of 1.85-2.30.
(particulates of high index of refraction composite oxides)
The high index of refraction 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 and has 1.95 or the metallic element of bigger refractive index, this composite oxides doped metallic ion that at least a Co of being selected from ion, Zr ion and Al ion are arranged.Have 1.95 or the metallic element of bigger refractive index as its oxide, preferred Ta, Zr, IN, Nd, Sb, Sn and Bi, wherein preferred especially Ta, Zr, Sn and Bi.
With titania (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 crystal structure for example rutile structure, rutile/anatase mixed-crystal structure, anatase structured or amorphous structure.The principal ingredient of particle particularly belongs to rutile structure.
This composite oxide particle is the composite oxide particle that is doped with the metallic ion of at least a Co of being selected from ion, Zr ion and Al ion.As the metallic ion that mixes, preferred Co ion and Zr ion, wherein preferred especially Co ion.
In view of the level that keeps refractive index, based on the amount of all metals [Ti+Met] of constituting composite oxides, the content of the metallic ion that mixes in the composite oxides is preferably in the scope that is no more than 25 weight %.This content is more preferably 0.05-10 weight %, even more preferably 0.1-5 weight %, most preferably 0.3-3 weight %.
The ion that mixes can metallic ion and arbitrary form of metallic atom 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 index of refraction particulate of gained composite oxides can obtain good transparency and the high index of refraction in the 380nm-600nm scope, and wherein undesirable photocatalytic activity is significantly suppressed or removes.The refractive index of these particles can be adjusted in the scope of 1.98-2.60, preferably refractive index is adjusted in the scope of 2.00-2.55.
The weight average particle diameter of the primary particle of the high index of refraction 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 refractive index and transparency, high index of refraction 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, adding Si forms ternary compound oxides and is used to make particle thinner and improve the dispersiveness of particle.
The high index of refraction composite oxides can be synthetic according to the known sintering process of routine, sol-gel process, 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 Kabushikikai sha 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 adulterant 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 patented claim is open) or the EP-A-0335773.
The high index of refraction 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 modifier of metal oxide or inorganic pigment of inorganic filler that is used for.For example, they are described in Ganryo Bunsan Anteika To Hyomen Shori GiiutsuHyoka, 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 index of refraction complex oxide fine particle is had the polar group of affinity.The example that the surface of high index of refraction complex oxide fine particle is had the polar group of affinity comprises carboxyl, phosphono, hydroxyl, sulfydryl, cyclic acid anhydride group and amino.The compound that preferably in molecule, has at least one polar group.The example (for example comprises long-chain fat family carboxylic acid; stearic acid, lauric acid, oleic acid, linoleic acid, leukotrienes etc.), polyol compound (for example; the glycerol tri-acrylate of pentaerythritol triacrylate, five acrylic acid dipentaerythritol ester, ECH-modification etc.), the compound that contains phosphono (for example; the tricresyl phosphate acrylate of EO (oxirane)-modification etc.), alkanolamine (for example, ethylenediamine EO addition product (5mol) etc.).
As coupling compound, conventional known organometallics 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 index of refraction complex oxide fine particle with organic compound and/or organometallics, this organic compound and/or organometallics with polar group is dissolved in the organic solvent, and will through or be not scattered in this solution through the surface-treated high index of refraction 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/shell mechanism, and wherein particle is made of the nuclear core with the shell that comprises mineral compound.As shell, preferably include the oxide 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 index of refraction 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 index of refraction composite oxides)
High refractive index layer of the present invention preferably by using spreading agent to disperse the high index of refraction 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 spreading agent of high index of refraction 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 affinity.
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, phenethyl and cyclohexyl) of 1-18 carbon atom.In these polar groups, the group with proton of disassociation can be the form of salt.Amino and quaternary ammonium group can be primary amino radical, 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.
Spreading agent can have the various polarity group in its molecule.
Spreading 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) acryloyl group, allyl, styryl or ethylene oxy carbonyl or ethyleneoxy) carry out addition reaction or polyreaction ethylenic unsaturated group, cationically polymerizable group (for example; epoxy radicals, sulfo-epoxy radicals, oxetanyl group, ethyleneoxy or spiro original acid ester base) and the polycondensation reaction group is (for example; hydrolyzable silicyl or N-methylol), wherein preferred ethylenic unsaturated group and epoxy radicals.
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 spreading agent that is used to disperse be used for the particulate of the thin and tall refractive index composite oxides of high refractive index layer of the present invention, preferred polymers spreading 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 preferably 1 * 10 3Or it is bigger.Mw is more preferably 2 * 10 3-1 * 10 6, even be more preferably 5 * 10 3-2 * 10 5, especially preferred 1 * 10 4-1 * 10 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 side chain of the unit 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 maleic acid of (methyl) acrylic acid, maleic acid, partial esterification, itaconic acid, crotonic acid, (methyl) acrylic acid 2-carboxyl ethyl ester, (methyl) acrylic acid 2-sulfo group ethyl ester, (methyl) acrylic acid 2-phosphonato ethyl ester, (methyl) acrylic acid 2,3-dihydroxy propyl ester, (methyl) acrylic acid 2-N, N-dimethylamino ethyl ester or (methyl) acryloxy ethyl trimethyl ammonium PF 6Ion salt) technology of the technology of polymerization 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 general assembly (TW) 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-transferring agent of polar functionalities, mercaptoacetic acid) carries out the technology of polyreaction under the situation of Cun Zaiing, the initiating agent that use contains polar group (for example, V-501, by Wako Pure ChemicalIndustries, Ltd. make) carry out the technology of polyreaction and use chain-transferring agent or have reactive group for example halogen atom, hydroxyl or amino polymerization initiator carry out polyreaction, add the technology of polar group then by polymer reaction.
Particularly preferred spreading agent is the spreading 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) acryloyl group, allyl, styryl or ethyleneoxy) carry out addition reaction or polyreaction ethylenic unsaturated group, cationically polymerizable group (for example; epoxy radicals, oxetanyl group or ethyleneoxy) and the polycondensation reaction group is (for example; hydrolyzable silicyl 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, silicon atom 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.
Spreading 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-butadiene 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, alkoxy, aryloxy group 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 acylamino-part 2CH=CH 2,-CH 2CH 2-Y (wherein Y represents 1-cyclohexenyl group residue) ,-CH 2CH 2-OCO-CH=CH 2With-CH 2CH 2-OCO-C (CH 3)=CH 2
With regard to spreading 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 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) 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.Content as for unit 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 spreading agent, the content 1-80 weight % preferably that contains the unit of crosslinkable or polymerisable group, especially preferred 3-60 weight %.
Spreading 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, with the compatibility of other monomer component with become film strength to select.Its preferred embodiment comprises methyl acrylic ester, esters of acrylic acid, vinyl carboxylate class, (methyl) acrylamide and derivant, styrene and derivant thereof and vinyl cyanide.
Spreading 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 spreading agents for example is described in JP-A-11-153703 [0023]-[0042] section.
The content of the relative high index of refraction complex oxide fine particle of spreading 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 spreading agent to exist, the high index of refraction 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, isopropyl alcohol, butanols and phenmethylol), ketone (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone), the ester class (for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate and butyl formate), halogenated hydrocarbon (for example, methylene chloride, chloroform or methyl chloroform), arene (for example, benzene, toluene and dimethylbenzene), amide-type (for example, dimethyl formamide, dimethyl acetamide and n-methyl pyrrolidone), ethers (for example, diethyl ether diox, tetrahydrofuran and glycol dimethyl ether) and ether alcohol class (for example, 1-methoxyl-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 isobutyl ketone, cyclohexanone and butanols.
The preferred dispersion machine that uses disperses the high index of refraction complex oxide fine particle.The example of dispersion machine comprises sand mill (for example, needle-like bowl mill), quick runner comminutor, pebble plain, roller mill, attitor and colloidal mill.Particularly, preferred sand mill and quick runner comminutor.In addition, can carry out pre-dispersed processing.The example that is used for the dispersion machine of pre-dispersed processing comprises bowl mill, three-roll mill, kneading machine and extruder.
The high index of refraction 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 index of refraction 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 index of refraction complex oxide fine particle is 10-90 weight % preferably, more preferably 15-80 weight %, especially preferably 15-75 weight %.Two or more high index of refraction complex oxide fine particles can be used for high refractive index layer.
Finish after the dispersion treatment, the high index of refraction complex oxide fine particle is prepared the coating fluid that forms high refractive index layer as the dispersion liquid that also comprises spreading 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 index of refraction 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 and has 1.95 or the metallic element of bigger refractive index, this method comprises: use medium wet disperse high index of refraction composite oxide particle and the spreading agent of mean grain size less than 1mm, making mean grain size thus is 150nm or littler high index of refraction 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 index of refraction composite oxides of at least a bismuth element and at least a metallic element, and the refractive index that described at least a metallic element is selected from its oxide is 1.95 or bigger metallic element.
(high index of refraction complex oxide fine particle)
The high index of refraction 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 refractive index that described at least a metallic element is selected from its oxide is 1.95 or bigger metallic element.Have 1.95 or the metallic element of bigger refractive index as its oxide, 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 index of refraction 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, potpourri or amorphism material or its composite oxides of the oxide of element separately.Do not help to improve refractive index 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 (that is Bi, 2O 3) or Met oxide (that is TiO, 2, Ta 2O 5, ZrO 2Deng) high refractive index.Equally, in view of obtaining high index of refraction, this complex oxide fine particle preferably has crystal 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, adding Si or Al is used to make particle thinner and improve the dispersiveness of particle.
Complex oxide fine particle can be synthetic according to the known sintering process of routine, sol-gel process, 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 inorganic filler surface modifier of metal oxide or inorganic pigment for example.For example, they are described in Ganryo Bunsan Anteika To Hyomen Shori Giiutsu Hyoka, 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 the metallic ion of at least a Co of being selected from ion, Zro ion and Al ion.In view of keeping refractive index value, based on the general assembly (TW) of the metal that constitutes composite oxides, the content that is doped in the metallic 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 %.The metallic ion that mixes can exist with the state of metallic ion or metallic atom, and may reside in any appropriate location from the surface to inside.
The complex oxide fine particle that well keeps high index of refraction with the metal ion mixing complex oxide fine particle with the acquisition photostability simultaneously.In above-mentioned metallic ion, the Co ion preferably mixes.
As method, can use conventional known method with the metal ion mixing particle.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 general assembly (TW) 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 index of refraction.This complex oxide fine particle can two or more mix use.
(spreading agent)
The spreading 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 affinity.
The example of the polar group that spreading agent of the present invention has comprise hydroxyl, sulfydryl, carboxyl, sulfo group, phosphono, phosphine oxide acyl group ,-P (=O) (R 1) (OH) group, acylamino-(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, phenethyl 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 radical, 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, spreading agent can have the various polarity group in molecule.
Spreading 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) acryloyl group, allyl, styryl, ethyleneoxy carboxyl or vinyl oxygen base) carry out addition reaction or polyreaction ethylenic unsaturated group, cationically polymerizable group (for example; epoxy radicals, sulfo-epoxy radicals, oxetanyl group, ethyleneoxy or spiro original acid ester group); and polycondensation reaction group (for example hydrolyzable silicyl or N-methylol), wherein preferred ethylenic unsaturated group and epoxy radicals.
Particularly, those that describe have for example been described in the section of JP-A-2001-310423 [0013]-[0015].
As spreading 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 1 * 10 3Or it is bigger.This Mw is more preferably 2 * 10 3-1 * 10 6, even more preferably 5 * 10 3-1 * 10 5, especially preferred 8 * 10 3-8 * 10 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 aggregation 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 side chain of unit 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-transferring agent of polar functionalities, mercaptoacetic acid) carries out the technology of polyreaction under the situation of Cun Zaiing, the initiating agent 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-transferring agent or have reactive group for example halogen atom, hydroxyl or amino polymerization initiator 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 maleic acid of (methyl) acrylic acid, maleic acid, partial esterification, itaconic acid, crotonic acid, (methyl) acrylic acid 2-carboxyl ethyl ester, (methyl) acrylic acid 2-sulfo group ethyl ester, (methyl) acrylic acid 2-phosphonato ethyl ester, (methyl) acrylic acid 2,3-dihydroxy propyl ester, (methyl) acrylic acid 2-N, N-dimethylamino ethyl ester, (methyl) acryloxy ethyl trimethyl ammonium PF 6Ion salt) or the technology of the addition product polymerization of the unsaturated compound of hydroxyl and cyclic acid anhydride (for example maleic anhydride, glutaric anhydride or phthalate anhydride) and utilize polymer reaction technology (for example, the reaction between the acid compound that hydroxyl, amino or epoxy radicals and acid anhydrides or halogen replace and isocyano group or carboxyl with have hydroxyl or the acid compound of amino between reaction).
As the instantiation of the polymers compositions 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 general assembly (TW) 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, silicon atom 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.
Spreading 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-butadiene 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, alkoxy, aryloxy group 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 acylamino-part 2CH=CH 2,-CH 2CH 2-Y (wherein Y represents 1-cyclohexenyl group residue) ,-CH 2CH 2-OCO-CH=CH 2With-CH 2CH 2-OCO-C (CH 3)=CH 2
With regard to spreading 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 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) 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 spreading agent, the content 1-70 weight % preferably that contains the unit of crosslinkable or polymerisable group, especially preferred 5-50 weight %.
Spreading 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 strength to select.Its preferred embodiment comprises methyl acrylic ester, esters of acrylic acid, vinyl carboxylate class, (methyl) acrylamide and derivant, styrene and derivant 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 instantiation of other polymerizable components.
Spreading 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 spreading 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 organometallics (for example, lithium alkyl, 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 initiating agent 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 polymer initiating agents synthetic (Akira Ueda and Susumu Nagai, Kagaku To Kogyo, 60,57 (1986) etc.).
The amount of the relative complex oxide fine particle of spreading 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, phenmethylol, ethylene glycol, propylene glycol and ethylene glycol acetate), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and methyl cyclohexanone), the ester class (for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl formate, propyl formate, butyl formate and ethyl lactate), aliphatic hydrocrbon (for example, hexane and cyclohexane), halogenated hydrocarbons (for example, methyl chloroform), aromatic hydrocarbon (for example, benzene, toluene and dimethylbenzene), acid amides (for example, dimethyl formamide, dimethyl acetamide and n-methyl pyrrolidone), ethers (diox for example, tetrahydrofuran, glycol dimethyl ether and propylene glycol dimethyl ether) and ether alcohol (for example, 1-methoxyl-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 isobutyl ketone, cyclohexanone 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 spreading agent with a certain amount of use.In this scope, disperse easily, and obtain dispersion liquid with good workability viscosity.
(refinement high index of refraction composite oxide particle)
High index of refraction complex oxide fine particle of the present invention is that 150nm or littler thin attitude are dispersed in the curable coating composition with the mean grain size.Therefore, the cured film that is formed by this curable coating composition can be the cured film with transparent, high index of refraction of uniform optical characteristic.
Only by using mean grain size to be not more than the medium of 1mm and the wet dispersion method of spreading agent just can realize making the high index of refraction composite oxide particle be separated into the particulate of above-mentioned mean grain size.
As wet dispersion machine, can be conventional known, for example sand mill (for example, needle-like bowl mill), dynomil, quick runner comminutor, pebble plain, roller mill, attitor and colloidal mill.Specifically, for complex oxide fine particle of the present invention being dispersed into particulate, preferred sand mill, dynomil and quick runner comminutor.
As the medium that is used for dispersion machine, use mean grain size to be 100nm or the littler and uniform fine inorganic particle of particle diameter to obtain mean grain size less than the medium of 1mm.The mean grain size of medium is 0.8mm or littler preferably, more preferably 0.1-0.5mm.
In addition, as being used for the wet medium that disperses, preferred pearl.Its instantiation comprises zirconium oxide bead, beaded glass, ceramic bead and steel ball.Because its durability and little particle diameter, preferred especially mean grain 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 spreading agent on composite oxide particle suitably, can not take place from the dispersion stabilization defective that the particle desorb causes because of spreading 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 bowl mill, three-roll mill, kneading machine and extruder.
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 mean grain size of complex oxide fine particle is 5-150nm preferably, more preferably 10-100nm, even more preferably 10-80nm.
In addition, not contain mean grain size be 500nm or bigger bulky grain to preferred particulate.Based on all particles, these oarse-grained content preferably 10% or littler.And mean grain size is that the content of 300nm or bigger particle is 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 index of refraction complex oxide fine particle of the present invention can preferably be examined the particulate of core/shell mechanism, and its center core is that particulate and shell comprise mineral compound.As for shell, the preferred at least a oxide 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 index of refraction complex oxide fine particle and film forming curable compound by coating, forms with the form of homogeneous film through light and/or heat curing 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 index of refraction of 1.90-2.30.
In addition, the size that is present in the particulate in the matrix of cured film is that mean grain size is 100nm or littler, preferred 5-100nm, more preferably 10-100nm, most preferably 10-80nm.
Describe matrix that is used for high refractive index layer and the curable compound that is used for film forming below in detail.
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 bond and (2) and has at least a in the organometallics of hydrolyzable functional group and/or its partial condensate.
The film forming curable compound is that (1) curable organic bond and (2) have at least a in the organometallics of hydrolyzable functional group and/or its partial condensate.The preferred combination of using (1) and (2).
(1) curable organic bond
As curable organic bond, it is the bonding agent that is formed by following substances:
(i) the known thermoplastic resin of routine;
The (ii) conventional known reactive curable resin and the combination of hardening agent; With
The (iii) combination of binder precursor (curable polyfunctional monomer that this paper back will be described or multifunctional oligomer) and polymerization initiator.
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 bonding agent (iii), high index of refraction complex oxide fine particle and spreading 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 adhesive component.For example, have by the heating or rayed at least a mode cause the cross-linking reaction of curing compound (for example, polyfunctional monomer or polyfunctional group oligomer) or the method for polyreaction.Particularly, preferably use above-mentioned combination (iii) to cause the cross-linking reaction of curable compound or the method that polyreaction forms cure adhesive by rayed.
And, preferably in the coating coating composition or cause the cross-linking reaction or the polyreaction of spreading agent contained in the dispersion liquid of high index of refraction complex oxide fine particle afterwards.
In high refractive index layer that makes thus or cured film, the presoma of spreading agent and bonding agent, curable polyfunctional monomer or polyfunctional group oligomer, through crosslinked or polyreaction, so the anionic group in the spreading agent is brought in the bonding agent.And, bonding agent in high refractive index layer or cured film works and makes anionic group can keep the disperse state of fine inorganic particle, therefore should be crosslinked or paradigmatic structure give the bonding agent film forming ability, thereby raising contains physical strength, chemical resistance and the against weather of the high refractive index layer or the cured film of high index of refraction complex oxide fine particle.
The example of thermoplastic resin comprises polystyrene resin, vibrin, celluosic resin, polyether resin, vestolit, vinyl acetate resin, vinyl chloride/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 thermosetting and/or ionising radiation-curable resin.The example of thermoset resin comprises phenolics, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, urethane resin, epoxy resin, amino-alkyd resin, melamine-urea cocondensation resin, silicone resin and polyorganosiloxane resin.The example of ionising radiation-curable resin comprise have functional group for example free redical polymerization unsaturated group (for example, acryloxy, styryl or ethyleneoxy) and/or the group of cationically polymerizable is (for example, epoxy resin or sulfo-epoxy) resin, and the example of these resins has vibrin, polyether resin, acryl resin, epoxy resin, urethane resin, alkyd resin, spiral shell acetal resin, polybutadiene and polymercaptan polyene resin.
These reactive curable resins if necessary, can for example crosslinking chemical be (for example by adding conventional compound known, epoxy compound, polyisocyanate compounds, polyol compound, polyamino compound or melamine compound), polymerization initiator (for example, the ultraviolet initiating agent is azo two compounds, organic peroxy compound, organic halogen compound, salt compound or ketonic compound for example) and polymerization accelerator (for example, organometallics, 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 bonding agent by the crosslinked or polyreaction that causes curable compound with rayed with reference to the method for optimizing that forms cure adhesive.
As the polyfunctional monomer that can photocuring or the functional group of polyfunctional group oligomer, describe have can polymerization by ultraviolet ray, electron beam or radiation irradiation functional group.Wherein, but the functional group of preferred especially polymerizable ultraviolet.The functional group of photo curable polyfunctional monomer or polyfunctional group oligomer can be free redical polymerization or cationically polymerizable.
As the group of free redical polymerization, describing has ethylenic unsaturated group for example (methyl) acryloyl group, ethyleneoxy, styryl and allyl, wherein preferred (methyl) acryloyl group.
The polyfunctional monomer that preferably in molecule, has the group of 2 or more free redical polymerizations.
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.More preferably in molecule, have 2-6 end and be the compound of ethylenic unsaturated link.These compounds are widely known in the polymeric material 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 oligomer or its potpourri or its multipolymer.The example of the monomer of free redical polymerization comprises that unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid or maleic 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 displacement of fluorine base for example acid amides and the addition product between simple function group or many functional group isocyanates or the epoxy compound 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 radicals 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 styrene to replace the compound of unsaturated carboxylic acid preparation.
The aliphatic polyol examples for compounds comprises ethylene glycol, propylene glycol, butylene glycol, hexanediol, diglycol, neopentyl glycol, trimethylolpropane, trimethylolethane, cyclohexanediol, phloroglucite, inositol, cyclohexanedimethanol, pentaerythrite, D-sorbite, dipentaerythritol, tripentaerythritol, glycerine and diglycerol.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 esters, ALMA, acrylic 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 instantiation of the polymerisable amide monomer between aliphatic polyamine compound and unsaturated carboxylic acid comprises methylene two-(methyl) acrylamide, 1,6-hexa-methylene two-(methyl) acrylamide, diethylene triamine 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 in molecule, have 2 or a plurality of polymerisable vinyl 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 oligomer 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 cross-linking reaction can radiation exposure the time.Its representative instance comprises epoxy compound, 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 in molecule, have the compound of the group of 2-10 cationically polymerizable, wherein especially preferably have the compound of the group of 3-5 cationically polymerizable.The molecular weight of hardening 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 compatibility variation of cellulose-acrylate doped compositions, this molecular weight is not preferred.
As epoxy compound, describing has aliphatic epoxy compound and aromatic epoxy compound.
As aliphatic epoxy resin, the homopolymer or the multipolymer of many ethylene oxidic esters, glycidyl acrylate or the glycidyl methacrylate of polyglycidyl ether that aliphatic polyol or its alkylene oxide addition product are arranged, long aliphatic chains polyprotonic acid for example described.And, except above-mentioned epoxy compound, the monoglycidyl ether of aliphatic higher alcohol, ethylene oxidic 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, cyclohexene, cyclopentene, 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 addition product described.As these epoxy compounds, 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 compounds, in view of the rapidly-curable energy, 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 epoxide ring of above-claimed cpd by cyclosubstituted those compounds of sulfo-epoxy radicals.
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 radicals.
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 isopropenyl compound, Vol.34,2051 (1996).
These compounds can two or more suitably mix use.
In addition, as polyfunctional compound of the present invention, preferably use the compound of the group of the group that in molecule, has at least one above-mentioned free redical polymerization and cationically polymerizable.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 initiator that is used for mixing use in the aforementioned combination (3) below with binder precursor.
As polymerization initiator, 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 ultraviolet range.
When being rayed, the polymerization initiator that is preferred for generation free radical of the present invention produces the Photoepolymerizationinitiater initiater of polymerization 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 initiator and select suitable use.The polymerization initiator that produces free radical can use separately or two or more mixing uses.
As the polymerization initiator that produces free radical, describing has amines (being described in JP-B-44-20189), organic halogenation compound, carbonyls, Metallocenic compound, Hexaarylbiimidazole compound, organic boronic compound and two sulphones (being described in JP-A-61-166544).Wherein, preferred carbonyls.
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 instantiation in (1979), and its instantiation comprises that trihalomethyl replaces De oxazole compound and s-triazine.More preferably, Striazine 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 carbonyls, for example have Saishin UV Koka Giiutsu, the compound described in the pp.60-62 (Kabushiki Kaisha Giiutsu Joho Kyokai in 1991 publish), acetophenone compound, hydroxy acetophenone compound, benzophenone compound, thioxane compound, benzoin compound be benzoin ethyl ether and benzoin 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 compounds, for example, Jap.P. 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 total amount of the monomer 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 acid agent that can be used as Photoepolymerizationinitiater initiater in detail.
As acid agent, describing has known compound for example light trigger, photoquenching agent (for example, dyestuff), the phototropic agent used of light cationic polymerization and the acid agent that becomes known for microresists, and composition thereof.
The example of acid agent comprises organic halogenated compound, two sulphones and compound.As the instantiation 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 diazo 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 acid agent especially, particularly, and in view of photonasty and the stability of material of compound, preferably diazo salt, salt compounded of iodine, sulfonium salt and inferior amine salt because of causing photopolymerization reaction.
The instantiation of salt comprises the salt described in the sulfonium salt of the S-phenyul thiobenzoate 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 acid agent, the organic metal/organic halogenation compounds described in JP-A-2002-29162 [0059]-[0062] section is arranged, have the photoacid generator of adjacent nitrobenzyl fundamental mode blocking group and can produce the compound of sulfonic acid through photodissociation.
These acid agents can use separately or can two or more mix use.Based on all polymerizable compounds of 100 weight portions, these acid 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, acid 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 general assembly (TW) 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 photosensitizer.The instantiation of photosensitizer comprises organic amine compound (n-butylamine, triethylamine and N-phenylglycine), phosphine class (for example, tri-n-butyl phosphine), Michler's keton and thioxanthones.As the photosensitizer of commercially available acquisition, describe the KAYACURE have Nihon Kayaku K.K. to make (DMBI, EPA), or the like.
Photopolymerization reaction is preferably by shining with ultraviolet ray after coating and drying coated composition.
(2) has the organometallics of hydrolyzable functional group
As the matrix that is used for high refractive index layer of the present invention or cured film, organometallics and/or its hydrolysate that also preferred use has hydrolyzable functional group form coated thin film by sol gel reaction, solidify this film then.As this organometallics, describing has the compound that comprises Si, Ti, Zr, Al etc.As hydrolyzable functional group, describing has alkoxy, alkoxy carbonyl, halogen atom and hydroxyl, and wherein preferred especially alkoxy is methoxyl, ethoxy, propoxyl group or butoxy for example.
Organosilicone compounds and partial hydrolystate (partial condensate) thereof that the preferred embodiment of organometallics is preferably represented by following general formula.In addition, well-known, the organo-silicon 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, cetyl, octadecyl, benzyl, phenethyl, cyclohexyl, cyclohexyl methyl, hexenyl, decene base and dodecene 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 radicals; alkyl (for example; methyl; ethyl; isopropyl; the propyl group or the tert-butyl group); aryl (for example; phenyl or naphthyl); aromatic heterocycle group (furyl; pyrazolyl or pyridine radicals); alkoxy (for example; methoxyl; ethoxy; isopropoxy or own oxygen base); aryloxy group (for example; phenoxy group); alkylthio group (for example methyl mercapto 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) acryloyl group); alkoxy carbonyl (for example; methoxycarbonyl or ethoxy carbonyl); aryloxycarbonyl (for example; phenyloxycarbonyl); carbamyl (for example; carbamyl; N-methylamino formoxyl; N, N-formyl-dimethylamino or N-methyl-N-octyl group carbamyl); and acyl amino (acetyl-amino; benzoyl-amido; acryloyl group amino or methacryl amino).
Wherein, more preferably hydroxyl, sulfydryl, carboxyl, epoxy radicals, alkyl, alkoxysilyl, acyloxy and acyl amino, wherein epoxy radicals, polymerisable acyloxy ((methyl) acryloyl group) and polymerisable acyl amino (acryloyl group amino or methacryl 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 solid 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 instantiation 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 bond preferably has silanol.The silanol that exists in bonding agent is used for further improving physical strength, chemical resistance and the against weather of high refractive index layer or cured film.
Silanol for example can join in the bonding agent by the following method, with constitute coating composition as the organo-silicon compound that contain crosslinkable or polymerisable functional group of general formula (1) representative of the component that forms bonding agent and binder precursor (for example, curable polyfunctional monomer or polyfunctional group oligomer), contained spreading agent chemical combination together in the dispersion liquid of polymerization initiator and high index of refraction complex oxide fine particle, and this coating composition is applied on the transparent carrier, then at spreading agent, cause cross-linking reaction or polyreaction in the compound of polyfunctional monomer or polyfunctional group oligomer and general formula (1) representative.
Contain under the situation of repetitive 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 organometallics 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, methane-sulforic acid and toluenesulfonic acid for example, inorganic base is NaOH, potassium hydroxide and ammoniacal liquor for example, organic base 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 organometallics, the content of catalyst compounds 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 disperse 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 spreading 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 index of refraction complex oxide fine particle and spreading agent, with the binder precursor with particular polarity group (for example, curable polyfunctional monomer or polyfunctional group oligomer 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 initiator of general formula (1) representative and organo-silicon 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 spreading agent, the simple function group monomer, cause cross-linking reaction or polyreaction between the organo-silicon compound of polyfunctional monomer or polyfunctional group oligomer and/or general formula (1) representative.
In coating composition, the simple function group monomer with particular polarity group plays the dispersing aid of fine inorganic particle.And, after the coating said composition, thereby monomer and spreading agent, polyfunctional monomer or polyfunctional group oligomer with particular polarity group carry out cross-linking reaction and/or polyreaction formation bonding agent, obtain to have excellent physical intensity, chemical resistance and against weather thus and keep the high refractive index layer of fine inorganic particle in the dispersiveness of high refractive index layer simultaneously.
Based on spreading agent, have content preferably 0.5-50 weight %, more preferably the 1-30 weight % of the simple function group monomer of amino or quaternary ammonium group.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 bonding agent.
As another matrix of high refractive index layer of the present invention, description has corresponding with organic 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 polyolefin (being made of stable hydrocarbon), polyethers, polyureas, polyurethane, polyester, polyamine, polyamide and melamine resin.Wherein, preferred polyolefm, polyethers and polyureas, more preferably polyolefin and polyethers.As the weight-average molecular weight of the organic polymer before solidifying preferably 1 * 10 3-1 * 10 6, more preferably 3 * 10 3-1 * 10 5
On the other hand, the cured film that contains the bonding 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 cross-linking reaction or polyreaction with spreading agent, polyfunctional monomer or polyfunctional group oligomer and organometallics with hydrolyzable functional group.
In curable coating composition, the monomer with particular polarity group plays the dispersing aid of high index of refraction complex oxide fine particle.And, after the coating said composition, monomer and spreading agent, polyfunctional monomer or polyfunctional group oligomer with particular polarity group carry out cross-linking reaction and/or polyreaction formation bonding agent, obtain to have the cured film that excellent physical intensity, chemical resistance and against weather 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 bonding agent.
Based on spreading agent, have amino or quaternary ammonium group as the content of the monomer 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 bond, organometallics/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 polyolefin (being made up of stable hydrocarbon), polyethers, polyureas, polyurethane, polyester, polyamine, polyamide 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 preferably 1 * 10 before solidifying 3-1 * 10 6, more preferably 3 * 10 3-1 * 10 5.
Organic polymer before solidifying preferably have with at the repetitive of the described identical particular polarity group of spreading agent with have the multipolymer of the repetitive of crosslinked or paradigmatic structure.Based on all repetitives, have content preferably 0.5-99 weight %, more preferably 3-95 weight %, most preferably the 6-90 weight % of the repetitive of anionic group in the polymkeric substance.Repetitive can have two or more, identical or different anionic groups.
When containing the repetitive with silanol, its content is 2-98 mole % preferably, more preferably 4-96 mole %, most preferably 6-94 mole %.
When containing the repetitive 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 repetitive with anionic group or have cross-linked structure or the repetitive 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 repetitive 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 refractive index height of the refractive index ratio transparent carrier of preferred high refractive index layer, and since add outside aromatic rings, the defluorination halogens (for example, Br, I or Cl) or for example the atom of S, N or P improved the refractive index of organic compound, the bonding 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 refractive index 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 initiator and photosensitizer) outside, can in high refractive index layer or curable coating composition, add resin, surfactant, antistatic agent, coupling agent, thickening agent, anti-blushing agent, colorant (pigment and dyestuff), defoamer, levelling agent, fire retardant, ultraviolet light absorber, infrared absorbent, tackifier, polymerization inhibitor, antioxidant, surface modifier and conducting metal particulate.
By adding mean grain 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 conating, 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, amide-type, ethers, ether-ether class, hydro carbons and halogenated hydrocarbon.Particularly, as at compound identical described in the spreading agent.Preferably mainly contain ketone solvent () coating solvent for example, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, 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 wear extent of coupons afterwards preferably as far as possible little.
Do not contain at high refractive index layer under the situation of the particle of giving dazzle reduction performance, 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 rubbing method, intaglio plate rubbing method, nick version rubbing 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, it is desirable solidifying with rayed.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 rubbing method, intaglio plate rubbing method, nick version rubbing method or extrusion coated method, and dry and with rayed or heating.From quick-setting angle, it is desirable solidifying with rayed.And, also preferably heat-treat in the second half section that photocuring is handled.
As the light source that is used for light-struck ultraviolet light, describing has ultrahigh pressure mercury lamp, high-pressure sodium lamp, medium pressure mercury lamp, low pressure mercury lamp, chemical substance lamp, carbon arc lamp, metal halide lamp, xenon lamp and sunshine.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 cross-linking reaction or the polyreaction of more carrying out ionising radiation-curable compound under the circlet border preferably at oxygen concentration.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 against weather of cured film and the viscosity of the layer adjacent with cured film.Oxygen concentration 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 concentration 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 concentration: about 21 volume %).
The thickness of cured film of the present invention can suitably be determined according to final 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 conating, 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 wear extent 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 index of refraction 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 refractive index 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 constitutional repeating unit, contain the constitutional repeating unit of crosslinkable or polymerisable functional group and comprise the multipolymer of other substituent repetitive (this paper back is referred to as " other constitutional repeating unit ").As crosslinkable or polymerisable functional group, describing has the functional group identical with the functional group of high refractive index layer.As other constitutional repeating 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 polymer 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 siloxane 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 initiator and sensitizer, 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 condensation product, 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 agent (for example, silicone compounds for example dimethyl siloxane) and surfactant.Particularly, preferably add fine inorganic particle, silane coupling agent or slip agent.
As fine inorganic particle, preferably has for example fluorine-containing particle of compound (for example, magnesium fluoride, calcium fluoride 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 refractive index 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 index of refraction hard conating or high index of refraction 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 refractive index 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 rubbing method or vapor phase method (for example, vacuum deposition method, sputtering method, ion plating or plasma CVD method).Because production cost is low, therefore preferred rubbing 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 wear extent 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 conating)
In order to give antireflective film enough physical strengths, on the surface of transparent carrier, provide hard conating.Specifically, preferably between transparent carrier and high refractive index layer, provide hard conating.
Hard conating preferably by light-and/or the cross-linking reaction of heat-curable compound or polyreaction form.For example, can contain polyester (methyl) acrylate, polyurethane (methyl) acrylate, polyfunctional monomer or polyfunctional group oligomer or contain the coating composition of the organometallics of hydrolyzable functional group by coating on transparent carrier, and cause the cross-linking 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 organometallics with hydrolyzable functional group.
The instantiation of these compounds is those that described at high refractive index layer.
The mean grain size that hard conating 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, mean grain size is meant weight average particle diameter.Hard conating with no impaired transparency can be adjusted to 200nm or littler formation by the mean grain size with primary particle.
Fine inorganic particle works to increase the hardness of hard conating, simultaneously, works to suppress the coating cure shrinkage.Equally, add their refractive indexes with the control hard conating.
Concrete structure about hard conating 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 general assembly (TW) of hard conating, the content of fine inorganic particle in hard conating 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 conating.When high refractive index layer also produces the function of hard conating, preferably by in hard conating, 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 conating with the described mean grain size in this paper back.
The thickness of hard conating can suitably design according to final use.The thickness of hard conating 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 conating is H or bigger preferably, and more preferably hardness is 2H or bigger, most preferably is 3H or bigger.
In addition, the wear extent 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 plastic sheeting 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 penetrability 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 refractive index of transparent carrier is 1.4-1.7 preferably.
The example that constitutes the plastic sheeting of transparent carrier comprises that cellulose esters (for example; tri acetyl cellulose; diacetyl cellulose; the propiono cellulose; the bytyry cellulose; acetyl group propiono cellulose or NC Nitroncellulose); polyamide; 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); polyolefin (for example, polypropylene; tygon 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 LCD 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 build method, can adopt, for example, 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 adjuvants (for example, plastifier, particulate, ultraviolet screener, anti aging dope, optical anisotropy controlling agent, exfoliant and infrared absorbent) according to final use.Based on transparent carrier, these adjuvants addition 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 treatment, ultraviolet treatment with irradiation, high frequency processing, glow discharge processing, reactive plasma treatment, laser treatment, acid treatment, ozone Oxidation Treatment and alkali treatment.Preferred glow discharge processing, ultraviolet treatment with irradiation, Corona discharge Treatment and flame treatment, wherein preferred especially glow discharge processing, Corona discharge Treatment and alkali treatment.
(other layer in the antireflective film)
In order to form antireflective film with better antireflection property, the preferred intermediate-index layer between the refractive index of refractive index that provides refractive index 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 refractive index 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 adhesive phase, shielding layer, sliding layer, antistatic backing and prime coat.Shielding layer is used for electromagnetic wave shielding or infrared ray.
In addition, antireflective film is being used under the situation of LCD, can providing and contain the internal coating that mean grain size is the particle of 0.1-10 μ m in order to improve viewing angle characteristic.Term used herein " mean grain size " is meant the weight average particle diameter of secondary particle (perhaps, when particle is not assembled, being primary particle).The mean grain size of these particles is 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.
The refractive index of these particles is 1.35-1.80 preferably, more preferably 1.40-1.75.
Preferably between hard conating and transparent carrier, form internal coating.This internal coating also can have the function of hard conating.
In adding mean grain size in internal coating is that internally coated turbidity is 3-60% preferably, more preferably 5-50% under the situation of the particle 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 rubbing method.When forming by rubbing method, each layer can be according to forming at the described rubbing 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 rubbing method, preferable alloy rod rubbing method, intaglio plate rubbing method and nick version rubbing method.
In addition, can in each layer of anti-reflection layer, add other compound for example resin, spreading agent, surfactant, antistatic agent, thickening agent, anti-blushing agent, colorant (pigment and dyestuff), defoamer, levelling agent, fire retardant, ultraviolet light absorber, tackifier, polymerization inhibitor, antioxidant and surfactant according to purposes and purpose.
(physical property of antireflective film)
In the present invention, the outmost surface of the antireflective film on the high index of refraction 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 index of refraction 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 index of refraction 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 index of refraction 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 pair 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 known method.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 mean grain size by adding particle in the random layer at antireflective film with 0.2-10 μ m.Term used herein " mean grain 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 refractive index of particle 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 conating, low reflection layer or high refractive index layer, especially preferred hard conating 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 refractive index 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 refractive index that satisfies following relation:
The refractive index of the refractive index＞low-index layer of the refractive index＞transparent carrier of high refractive index layer
Also can between transparent carrier and high refractive index layer, provide hard conating.And this film can comprise that high index of refraction hard conating or high index of refraction 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 refractive index that satisfies following relation:
The refractive index of the refractive index＞transparent carrier of the refractive index＞intermediate-index layer of high refractive index layer＞
The refractive index of low-index layer
Also can between transparent carrier and intermediate-index layer, provide hard conating.And this film can comprise middle refractive index hard conating, 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 sandwich construction has thickness of each layer described in JP-A-2001-188104 and the relation between the wavelength of visible light.
In addition, term " high index of refraction ", " middle refractive index " and " low-refraction " are meant relation higher or lower relatively between layer.
By add mean grain size in hard conating, 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 LCD in the contrast 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 index of refraction 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 conating 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 conating 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 Solution, handle carry out saponification with the laminated surface of polarization film thus.
Giving water wettability 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 aqueous slkali or be coated with aqueous slkali thereon and carry out saponification thus and handle.
As aqueous slkali and disposal route, 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), physical property (for example; anti-scraping performance), chemical resistance, antifouling property are (for example; soil resistance) and against weather (for example; humidity resistance and photostability), 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 LCD.
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 the optical anisotropic layer that comprises the compound with disk-shaped structure unit, 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 esters 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 LCD (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 conating coating solution)
The dispersion liquid (MEK-ST of fine particles of silica in methyl ethyl ketone with 450.0g; The content of solid constituent: 30 weight %; Make by Nissan Kagaku K.K.), (Irgacure 907 for the methyl ethyl ketone of 15.0g, the cyclohexanone 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 potpourri (DPHA of dipentaerythritol acrylate; Make by Nihon Kayaku K.K.) in, and the gained potpourri stirred.Stir the mixture through the aperture of polypropylene manufacturing is that the filtrator of 0.4 μ m filters the coating solution make hard conating.
(preparation of the dispersion liquid of high index of refraction complex oxide fine particle (PL1-1))
The methyl isobutyl ketone of the polymerization inhibitor of the tertiary butylated hydroquinone of the spreading agent (D-1) of the following structure of 38.6g, 0.5g and 702g is joined the Ti of the Co ion that contains doping (content is 3 weight %) of 218g and the composite oxides (P-1) [Ti/Ti+Zr=0.80 weight ratio (based on oxide)] of Zr, and in dynomil, this potpourri decentralized system got the dispersion liquid (PL-1) of particulate that weight average particle diameter is the high index of refraction composite oxides of 65nm.
Spreading agent
(D-1)
Figure A20048000590700611
(preparation of the coating solution of intermediate-index layer)
Photosensitizer (KayacureDETX with Irgacure 907, the 1.1g of DPHA, the 3.1g of 58.4g, make by Nihon Kayaku K.K.), the cyclohexanone of the methyl ethyl ketone of 482.4g and 1869.8g joins in the dispersion liquid (PL1-1) of above-mentioned high index of refraction complex oxide fine particle of 88.9g, stir then.Stirred mixture is that the filtrator 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 cyclohexanone 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 index of refraction complex oxide fine particle of 586.8g, then stir.Stirred mixture is that the filtrator 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 refractive index and be the solvent (OpsterJN7228 of the fluoropolymer of 1.42 thermally cross-linkable; The content of solid constituent: 6 weight %; Make by JSR K.K.) fluoropolymer that obtains thermally cross-linkable in methyl isobutyl ketone 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 solid constituent: 30 weight %; Make by Nissan Kagaku K.K.), the following silane compound of 1.75g, the methyl isobutyl ketone of 73.0g and the cyclohexanone of 33.0g, then stir.Stirred mixture is that the filtrator 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 monosilane (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 stirrer and reflux condenser, 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 conating 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 exposure be 300mJ/cm 2Ultraviolet ray shine this coating layer, simultaneously with this environment of nitrogen wash so that the oxygen concentration of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form the thick hard conating of 3.5 μ m.
Use the intaglio plate spreader on this hard conating, 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 exposure be 600mJ/cm 2Ultraviolet ray shine this coating layer, simultaneously with this environment of nitrogen wash so that the oxygen concentration of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form intermediate-index layer (refractive index: 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 exposure be 600mJ/cm 2Ultraviolet ray shine this coating layer, simultaneously with this environment of nitrogen wash so that the oxygen concentration of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form high refractive index layer (refractive index: 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 exposure be 600mJ/cm 2Ultraviolet ray shine this coating layer, and 120 ℃ of down heating 10 minutes, simultaneously with this environment of nitrogen wash so that the oxygen concentration of environment remains on 1.0 volume % or littler level, form low-index layer (refractive index: 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 aluminium 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 ° incident angle.Be determined at the interior average reflectance of wavelength coverage 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 sunshine 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 index of refraction 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 viscosity test of the adhesive tape of the polyester manufacture of making by Nitto Denko K.K. (NO.31B) in same position by recess.The generation of visual inspection layering 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
Turbidity reflectivity against weather cohesive pencil hardness scratch resistance After exposing after exposing after exposing after exposing before exposing Embodiment 1-1 0.3％ 1.0％ A A ○○ 3H A The comparative example Ex.1-A0.3% 1.1% A C * be lower than 1H C
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 cohesive, 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 cohesive, pencil hardness and the scratch resistance, finds thus actually to use.
As mentioned above, film sample of the present invention shows extremely excellent against weather, 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 refractive index 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 analyzer (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 index of refraction complex oxide fine particle of high index of refraction complex oxide fine particle separately with embodiment 1-1.
In addition, in the scope of mean grain size at 60-90nm of the discrete particles in the dispersion liquid (PL1-2 to PL1-4) of high index of refraction complex oxide fine particle separately, and these particles show good monodispersity energy.
Table 2
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 conating)
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 denaturated alcohol 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 filtrator that is 1 μ m with its aperture through the polypropylene manufacturing filters.
Use excellent spreader that the coating solution that gained forms hard conating is applied on the tri acetyl cellulose film of TAC-TD80U, then dry down at 120 ℃.Afterwards, coating layer forms the thick hard conating of 7.5 μ m with the ultraviolet ray irradiation.
(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 cyclohexanone of the spreading 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 index of refraction particulate of 55nm in dynomil.
Spreading agent
Figure A20048000590700681
Mw:1.5 * 10 4(weight ratio)
(preparation of the coating solution of intermediate-index layer)
The cyclohexanone 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 index of refraction complex oxide fine particle of 88.9g, stir then.Stirred mixture is that the filtrator 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 portions and the γ of 77.9 weight portions-glycidoxypropyl methyl diethoxy monosilane are joined one and be equipped with in the glass container 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 portions.Drip after the end, stirred 0.5 hour, obtain the partial hydrolystate of tetraethoxysilane and γ-glycidoxypropyl methyldiethoxysilane.30.5 weight %), the butyl cellosolve of 65 weight portions and joining as the ammonium perchlorate of the pentanedione acid aluminium of 2.6 weight portions of hardening agent and 0.5 weight portion in the partial hydrolystate of the tetraethoxysilane of 137 weight portions and γ-glycidoxypropyl methyldiethoxysilane then, with the dispersion liquid (PL2-1) of the high index of refraction complex oxide fine particle of 397.8 weight portions (concentration:.After fully stirring, the agitating 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 conating, 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 exposure be 600mJ/cm 2Ultraviolet ray shine this coating layer, simultaneously with this environment of nitrogen wash so that the oxygen concentration of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form intermediate-index layer (refractive index: 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 (refractive index: 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 (refractive index: 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 index of refraction complex oxide fine particle separately with embodiment 2-1.
In addition, in the scope of mean grain 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.
Table 3
Figure A20048000590700711
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 index of refraction complex oxide fine particle))
In sand mill (1/4G sand mill) under 1600rpm with 92g be doped with cobalt ions (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 potpourri of the cyclohexanone 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 heated 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 cyclohexanone 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 filtrator of 0.4 μ m filters the coating solution make high refractive index layer.
＜polymerisable compound 〉
＜sulfonium compound 〉
Figure A20048000590700731
(pasting the structural formula of the 126th page of original text)
(preparation of the dispersion liquid of stain-proofing layer)
With isopropyl alcohol join thermally cross-linkable, fluoropolymer (JN-7214; Make by NihonGosei Gomu K.K.) in make the dispersion liquid that 0.6 weight % rough segmentation is loose.Be cut to finely dividedly with this thick dispersion liquid of ultrasonic Treatment, 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 conating 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 exposure be 600mJ/cm 2Ultraviolet ray shine this coating layer, simultaneously with this environment of nitrogen wash so that the oxygen concentration 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 (refractive index: 1.94; Thickness: 105nm).
On this high refractive index layer, form the thick silica membrane (refractive index: 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 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 polyvinyl alcohol film that 75 μ m are thick (by Kurary Co., Ltd. make) soaks in the aqueous solution of being made up of the potassium iodide of the iodine of the water of 1000g, 7g and 105g and adsorbed iodine in 5 minutes.Then, with this film 4.4 times of uniaxial tensions longitudinally in 4 weight % boric acid aqueous solutions, and make polarization film keeping being dried under the extended state.
Use the polyvinyl alcohol bonding agent as bonding 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 bonding 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, the relative transparent carrier face tilt of the dish face of disk-shaped structure unit the and wherein dish face and the angle between the transparent carrier face of disk-shaped structure unit change at the thickness direction of optical anisotropic layer wherein.
The tri acetyl cellulose superficial layer that uses the polyvinyl alcohol bonding agent as bonding 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 bonding 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 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 LCD 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 conating)
The dispersion liquid (MEK-ST of fine particles of silica in methyl ethyl ketone with 450.0g; The content of solid constituent: 30 weight %; Make by Nissan Kagaku K.K.), (Irgacure 907 for the methyl ethyl ketone of 15.0g, the cyclohexanone 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 potpourri (DPHA of dipentaerythritol acrylate; Make by Nihon Kayaku K.K.) in, and the gained potpourri stirred.Stir the mixture through the aperture of polypropylene manufacturing is that the filtrator of 0.4 μ m filters the coating solution make hard conating.
(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 aluminium oxide and the stearic acid (content of composite oxides: 85%) (P-1), the cyclohexanone of cationic acrylate, DMAEA (being made by K.K.Kojin) and the 700g of spreading 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 mean grain 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 the content of 500nm or bigger particle is 0%.
Spreading agent
Figure A20048000590700761
In addition,, find in dispersion liquid, not observe precipitation, the particle diameter of discrete particles and 1 month before identical, and the content maintenance 0% of 500nm or bigger particle when placing when measuring the performance of gained dispersion liquid after 1 month.
(preparation of the coating solution of intermediate-index layer)
Photosensitizer (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 cyclohexanone 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 filtrator 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 cyclohexanone 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 filtrator of 0.4 μ m filters the coating solution make high refractive index layer.
(preparation of the coating solution of low-index layer)
Replace refractive index and be the solvent (OpsterJN7228 of the fluoropolymer of 1.42 thermally cross-linkable; The content of solid constituent: 6 weight %; Make by JSR K.K.) fluoropolymer that obtains thermally cross-linkable in methyl isobutyl ketone 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 solid constituent: 30 weight %; Make by Nissan Kagaku K.K.), the following silane compound of 1.75g, the methyl isobutyl ketone of 73.0g and the cyclohexanone of 33.0g, then stir.Stir the mixture through the aperture of polypropylene manufacturing is that the filtrator of 0.4 μ m filters the coating solution make low-index layer.
(preparation of silane compound)
3-acryloxy propyl trimethoxy monosilane (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 stirrer and reflux condenser, 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 oligomer 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 conating 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 exposure be 300mJ/cm 2Ultraviolet ray shine this coating layer, simultaneously with this environment of nitrogen wash so that the oxygen concentration of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form the thick hard conating of 3.5 μ m.
Use the intaglio plate spreader on this hard conating, 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 exposure be 600mJ/cm 2Ultraviolet ray shine this coating layer, simultaneously with this environment of nitrogen wash so that the oxygen concentration of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form intermediate-index layer (refractive index: 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 exposure be 600mJ/cm 2Ultraviolet ray shine this coating layer, simultaneously with this environment of nitrogen wash so that the oxygen concentration of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form high refractive index layer (refractive index: 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 exposure be 600mJ/cm 2Ultraviolet ray shine this coating layer, and 120 ℃ of down heating 10 minutes, simultaneously with this environment of nitrogen wash so that the oxygen concentration of environment remains on 1.0 volume % or littler level, low-index layer (refractive index: 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 cyclohexanone 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, to make mean grain size be 65nm and contain the dispersion liquid (PL11-2) of complex oxide fine particle that 0% particle diameter is the particle of 500nm.
Polymeric dispersant:
Mw=2 * 10 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 the content maintenance 0% of 500nm or bigger particle 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 beaded glass of 0.2mm for the beaded glass of 1.0mm.The discrete particles of gained dispersion liquid has extremely wide size distribution and has the mean grain 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 aluminium oxide and the surface-treated titania 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 dioxide: 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 refractive index 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 amount increase of particle, 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 refractive index 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 amount increase of particle, 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 ° incident angle.Be determined at the interior mean refractive index of wavelength coverage 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 sunshine 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 index of refraction 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 viscosity 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 generation of visual inspection layering 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 turbidity average reflectance bleaches and tests cohesive pencil hardness scratch resistance After exposing before exposing after exposing before exposing after exposing before exposing Embodiment 6-10.8％ 0.3％ A ○○ ○ 3H ? 3H ? A A Embodiment 6-20.5％ 0.25％ A ○○ ○ 3H ? 3H ? A A Contrast Ex.6-A5% 1% A △ △ 2H-3H (irregular) 2H-3H (irregular) B B
Table 4 (B)
The turbidity value average reflectance bleaches and tests cohesive pencil hardness scratch resistance After exposing before exposing after exposing before exposing after exposing before exposing Contrast Ex.6-B1.3% 0.38% C 00 * 3H 1H or littler A B Contrast Ex.6-C-yellow-yellow A 00 3H 3H A A
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, cohesive, 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 cohesive, 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 against weather 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 refractive index 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 analyzer (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 mean grain 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.
Table 5
Figure A20048000590700851
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 conating)
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 denaturated alcohol 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 filtrator that is 1 μ m with its aperture through the polypropylene manufacturing filters.
Use excellent spreader that the coating solution that gained forms hard conating is applied on the tri acetyl cellulose film of TAC-TD80U, then dry down at 120 ℃.Afterwards, coating layer forms the thick hard conating of 7.5 μ m with the ultraviolet ray irradiation.
(preparation of the dispersion liquid of complex oxide fine particle (PL2-1))
The cyclohexanone of the spreading 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 mean grain size of 75nm in the thus obtained dispersion liquid, and wherein the content of 500nm or bigger particle is 0%.
Spreading agent
Figure A20048000590700861
Mw:4 * 10 4(Mw:8 * 10 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 cyclohexanone 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 filtrator 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 portions and the γ of 77.9 weight portions-glycidoxypropyl methyldiethoxysilane are joined one to be equipped with in the glass container 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 portions.Drip after the end, stirred 0.5 hour, obtain the partial hydrolystate of tetraethoxysilane and γ-glycidoxypropyl methyldiethoxysilane.30.5 weight %), the butyl cellosolve of 65 weight portions and joining as the ammonium perchlorate of the pentanedione acid aluminium of 2.6 weight portions of hardening agent and 0.5 weight portion in the partial hydrolystate of the tetraethoxysilane of 137 weight portions and γ-glycidoxypropyl methyldiethoxysilane then, with the dispersion liquid (PL2-1) of the complex oxide fine particle of 397.8 weight portions (concentration:.After fully stirring, the agitating 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 conating, 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 exposure be 600mJ/cm 2Ultraviolet ray shine this coating layer, simultaneously with this environment of nitrogen wash so that the oxygen concentration of environment remains on 1.0 volume % or littler level, thus coating layer is solidified.Therefore, form intermediate-index layer (refractive index: 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 (refractive index: 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 (refractive index: 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
The turbidity average reflectance bleaches and tests cohesive pencil hardness scratch resistance After exposing before exposing after exposing before exposing after exposing before exposing Embodiment 7-1 0.9% 0.4% A 000 3H 3H A A
[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 mean grain 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.
Table 6
Figure A20048000590700901
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 potpourri of the cyclohexanone 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 heated 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 〉
(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 cyclohexanone 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 filtrator of 0.4 μ m filters the coating solution make high refractive index layer.
＜polymerisable compound 〉
＜sulfonium compound 〉
Figure A20048000590700921
(preparation of the dispersion liquid of stain-proofing layer)
With isopropyl alcohol join thermally cross-linkable, fluoropolymer (JN-7214; Make by NihonGosei Gomu K.K.) in make the dispersion liquid that 0.6 weight % rough segmentation is loose.Be cut to finely dividedly with this thick dispersion liquid of ultrasonic Treatment, 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 conating 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 exposure be 600mJ/cm 2Ultraviolet ray shine this coating layer, simultaneously with this environment of nitrogen wash so that the oxygen concentration 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 (refractive index: 1.94; Thickness: 105nm).
On this high refractive index layer, form the thick silica membrane (refractive index: 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 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 warm-up mills each film, use rod to be coated with device then thereon with 15cc/m 2The following aqueous slkali of forming (S) of coating weight 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 dry sections keep 5 second drying.
The composition of aqueous slkali (S):
Potassium hydroxide 8.55 weight %
Water 23.235 weight %
Isopropyl alcohol 54.20 weight %
Surfactant (K-1; C 14H 29O (CH 2CH 2O) 20H) 1.0 weight %
Propylene glycol 13.0 weight %
Defoamer (Surfinol DF110D; Make by Nissin Kagaku Kogyo 0.015 weight %K.K.)
(preparation of polarization film)
The polyvinyl alcohol film that 75 μ m are thick (by Kurary Co., Ltd. make) soaks in the aqueous solution of being made up of the potassium iodide of the iodine of the water of 1000g, 7g and 105g and adsorbed iodine in 5 minutes.Then, with this film 4.4 times of uniaxial tensions longitudinally in 4 weight % boric acid aqueous solutions, and make polarization film keeping being dried under the extended state.
Use the polyvinyl alcohol bonding agent as bonding 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 bonding 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, the relative transparent carrier face tilt of the dish face of disk-shaped structure unit the and wherein dish face and the angle between the transparent carrier face of disk-shaped structure unit change at the thickness direction of optical anisotropic layer wherein.
The tri acetyl cellulose superficial layer that uses the polyvinyl alcohol bonding agent as bonding 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 bonding agent laminated optical compensating film on the another side of polarization film to handle.
(evaluation of image display device)
The contrast of LCD 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 LCD 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 (26)

1, high refractive index layer, it comprises the particulate of matrix and high index of refraction composite oxides,
The particulate of wherein said high index of refraction composite oxides is the particulates that contain the composite oxides of titanium elements and at least a metallic element, the oxide of wherein said at least a metallic element have 1.95 or bigger refractive index and
Described composite oxides and at least a metal ion mixing that is selected from Co ion, Zr ion and Al ion.
2, high refractive index layer as claimed in claim 1, the particulate of wherein said high index of refraction composite oxides carries out surface treatment with at least a compound that is selected from mineral compound and organic compound.
3, high refractive index layer as claimed in claim 1 or 2, wherein said matrix contain at least a cured product that is selected from the material of organic bond, organometallics and their partial hydrolysate.
4, as each described high refractive index layer of claim 1-3, it has the refractive index of 1.75-2.4.
5, as each described high refractive index layer of claim 1-4; it is by passing through the use spreading agent composition that described high index of refraction composite oxide particle disperses to obtain to be formed, and wherein said spreading 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, high refractive index layer as claimed in claim 5, wherein said spreading agent are the compounds that contains crosslinkable or polymerisable functional group.
7, antireflective film, it comprises successively: transparent carrier; As each described high refractive index layer of claim 1-6; With refractive index less than 1.55 low-index layer.
8, antireflective film, it comprises transparent carrier successively; Two-layer refractive index differing from each other as each described high refractive index layer of claim 1-6; With refractive index less than 1.55 low-index layer.
9, as claim 7 or 8 described antireflective films, it also comprises hard conating 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 claim 7-9.
11, polaroid comprises polarization film and protective film thereof, and one of them protective film is as each described antireflective film of claim 7-9, 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 contains the compound with disk-shaped structure unit, the relative transparent carrier face tilt of the dish face of wherein said disk-shaped structure unit, and the angle between this dish face and this 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 claim 7-9 or as each described polaroid of claim 10-12.
14, the preparation method of curable coating composition, described curable coating composition comprises the particulate of film forming curable compound and high index of refraction composite oxides, the particulate of wherein said high index of refraction composite oxides contains: bismuth element and at least a metallic element, the oxide of wherein said at least a metallic element has 1.95 or bigger refractive index
Wherein said method comprises uses medium wet disperse high index of refraction composite oxide particle and the spreading agent of mean grain size less than 1mm, makes mean grain size thus and be the particulate of 150nm or littler high index of refraction composite oxides.
15, method as claimed in claim 14, wherein said spreading agent are the polymeric dispersants with polar group.
16, method as claimed in claim 15, wherein said polar group are at least a anionic groups that is selected from carboxyl, sulfo group, phosphono and phosphine oxide acyl group.
17, as claim 15 or 16 described methods, wherein said spreading agent is the compound with crosslinkable or polymerisable functional group.
18, as each described method of claim 14-17, wherein said film forming curable compound is at least a in curable organic bond, organometallics and their partial hydrolysate.
19, cured film, it has the refractive index 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 mean grain size are 100nm or littler high index of refraction composite oxides, the particulate of described high index of refraction composite oxides includes: bismuth element and at least a metallic element, the oxide of wherein said at least a metallic element have 1.95 or bigger refractive index.
20, antireflective film, it comprises successively: transparent carrier; Cured film as claimed in claim 19; With refractive index less than 1.55 low-index layer.
21, antireflective film, it comprises successively: transparent carrier; The cured film as claimed in claim 19 that two-layer refractive index is differing from each other; With refractive index less than 1.55 low-index layer.
22, as claim 20 or 21 described antireflective films, it also comprises hard conating 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 claim 20-22.
24, polaroid comprises polarization film and protective film thereof, and one of them protective film is as each described antireflective film of claim 20-22, and another protective film is to have optically anisotropic optical compensating film.
25, polaroid as claimed in claim 24, wherein said optical compensating film comprises transparent carrier and comprises the optical compensating layer of optical anisotropic layer, described optical anisotropic layer comprises the compound with disk-shaped structure unit, the relative transparent carrier face tilt of the dish face of wherein said disk-shaped structure unit, and the angle between described dish face and 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 claim 20-22 or as each described polaroid of claim 23-25.
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