CN1768280A - Polarizing plate and manufacturing method thereof, and image display device - Google Patents
Polarizing plate and manufacturing method thereof, and image display device Download PDFInfo
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- CN1768280A CN1768280A CNA2004800085254A CN200480008525A CN1768280A CN 1768280 A CN1768280 A CN 1768280A CN A2004800085254 A CNA2004800085254 A CN A2004800085254A CN 200480008525 A CN200480008525 A CN 200480008525A CN 1768280 A CN1768280 A CN 1768280A
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Abstract
A method for manufacturing a polarizing plate comprising: bonding an antireflection film containing a transparent support and an antireflection structure including a plurality of layers different in refractive index each comprising a cured film to a polarizing film, wherein at least one layer of the plurality of layers different in refractive index is a layer having a higher refractive index than that of the transparent support and a thickness of 10 nm to 2 mum, and the antireflection film is bonded to the polarizing film after being subjected to a hydrophilization treatment so that a contact angle to water of a surface of the antireflection film to be bonded to the polarizing film falls within a range of 20 degrees to 50 degrees.
Description
Technical field
The present invention relates to use antireflection film as the polaroid of at least one surface protection film with use the image display apparatus of described antireflection film.
Background technology
The surface that antireflection film is arranged in display is to prevent that for example liquid crystal indicator (LCD), plasma display panel (PDP), electroluminescent display (ELD) and cathode-ray tube display (CRT) reduce because of the contrast that the dazzle of external reflection of light or image causes at various different image display apparatus.For this reason, require antireflection film to have high physical strength (for example wearing quality), chemical resistance and against weather (for example humidity resistance and photostability).
With regard to the anti-reflection layer (for example high refractive index layer, intermediate-index layer and low-index layer) that is used for antireflection film, the multilayer film that uses the metal oxide transparent film to pile up each other widely.The metal oxide transparent film is normally by chemical vapour desposition (CVD) method or physical vapor deposition (PVD) method, especially forms as a kind of vacuum vapor deposition method of physical vapor deposition method.
Yet the productive rate of method that forms the metal oxide transparent film by vapor deposition is low, is not suitable for producing in batches.For this reason, the method for a kind of high productivity by coated and molded proposed.
When by coating preparation antireflection film, can use the high resin of refractive index to form high refractive index layer.In addition, also can disperse thinlyyer, and it is joined in the film form by the fine inorganic particle that refractive index is high.Back one method is because the controllable refractive index wide ranges, and because the transparency of gained film and physical strength are excellent by preferred.Keep finely divided state simultaneously by in film, adding the high fine inorganic particle of a large amount of refractive indexes, form the higher transparent high refractive index layer of refractive index (for example referring to, JP-A-8-110401, JP-A-8-179123, JP-A-11-153703, JP-A-2001-166104, JP-A-2001-188104, JP-A-2002-116323 and JP-A-2002-156508).
It is very effective that the titania particulate that refractive index is very high joins in the high refractive index layer.Yet the titania particulate has photo-catalysis function.Therefore, when this high refractive index layer (antireflection film) used under daylight for a long time, these particulates decomposed organic compound contained in this high refractive index layer, make physical strength and optical property significantly reduce.This phenomenon keeps particularly evident in the high refractive index layer of finely divided state at the titania particulate.
Therefore, wish that a kind of can passing through of preparation is coated with production, contain the titania particulate, and the also excellent high refractive index layer of against weather (particularly photostability).Yet this demand does not also realize satisfactorily.
Found by carrying out hydrophilicity-imparting treatment this rete is combined on the polarizing coating that comprises polyvinyl alcohol (PVA) and iodine; for example, by the saponification of film immersion in aqueous slkali handled, to use the surface protection film of this film as polaroid; this is a purpose of the present invention, and the problem of front is particularly outstanding.This is because each layer of formation anti-reflection structure is extremely thin, also is not vulnerable to influence even it is not a superficial layer.Because this influence, that mentions has following two kinds of situations: the fine inorganic particle that (1) adds wrecks and wash-out under the influence that saponification is handled, titania particulate particularly, inherence have suppress photocatalysis the surface coated material in aqueous slkali by wash-out; (2) be used for the bonding agent hydrolysis that includes organic polymer bonding between the titania particulate.These the influence contain a large amount of fine inorganic particles as filler the layer in, particularly have high index of refraction the layer in particularly outstanding.
Yet in recent years, the screen size of liquid crystal indicator (LCD) is increasing, and it is more and more that the quantity of liquid crystal indicator of antireflection film wherein is installed.
In liquid crystal indicator (LCD), polaroid is essential optical material.In general, it makes polarizing coating be protected by two diaphragms through structure.Yet, also provide the quantity of the formation layer that the antireflection film with against weather and anti-reflective function makes display panel to increase, therefore aspect two of manufacturing cost and function performances, be very limited.By giving the diaphragm anti-reflective function of liquid crystal indicator, can expect a kind of display, and make cost reduce and the thickness minimizing with against weather, physical protection performance and antireflection property.Therefore, wished it is developed.
Summary of the invention
The present invention finishes under above-mentioned background.An one purpose is with low cost and the polaroid that the anti-reflection layer that has excellent physical strength and against weather separately is provided in enormous quantities; this purpose is the condition optimization by necessary saponification treatment step in the processing of the surface protection film that will have anti-reflection layer separately, and will form optimization as the element of the titanium dioxide granule of the essential composition that contains in the anti-reflection layer and realize.Another purpose provides by suitable mode and stands the image display apparatus that antireflection is handled.
Above-mentioned purpose of the present invention is to realize by the polaroid of the antireflection film that uses following structure (1)-(13) separately and the image display apparatus of (14) and (15).
(1) a kind of preparation method of polaroid, comprise: antireflection film and polarizing coating is bonding, described antireflection film has on the one side of transparent support by the different multilayer of refractive index and each layer and comprises cured film and the anti-reflection structure that forms, it is characterized in that one deck at least in the different multilayer of refractive index is that refractive index and the thickness that refractive index is higher than transparent support is the layer of 10nm-2 μ m, and antireflection film makes the adhesive surface of antireflection film and the contact angle of water spend in the scope of-50 degree 20 through bonding with polarizing coating after the hydrophilicity-imparting treatment.
(2) according to the preparation method of (1) described polaroid, be characterised in that carrying out hydrophilicity-imparting treatment makes contact angle in the scope of 30-40 degree.
(3) according to the preparation method of (1) or (2) described polaroid, be characterised in that carrying out hydrophilicity-imparting treatment makes contact angle in the scope of 40-50 degree.
(4) according to the preparation method of each described polaroid of (1)-(3), be characterised in that hydrophilicity-imparting treatment comprises the step that antireflection film is immersed in the aqueous slkali that is used for saponification.
(5) a kind of preparation method of polaroid, comprise: antireflection film and polarizing coating is bonding, described antireflection film has on the one side of transparent support by the different multilayer of refractive index and each layer and comprises cured film and the anti-reflection structure that forms, it is characterized in that will with its on form anti-reflection structure the surface of surperficial relative antireflection film as adhesive surface, and only this adhesive surface is stood saponification and handles the contact angle that makes with water in the scopes that 10 degree-50 are spent.
(6), but be characterised in that the cured film that forms anti-reflection structure is by coating, dry and solidify the coating composition that contains at least a film forming solute and at least a solvent and obtain according to the preparation method of (1)-(5) each described polaroids.
(7) preparation method of the polaroid of each described method preparation of basis (1)-(6) is characterised in that the layer that forms anti-reflection structure contains fine inorganic particle.
(8) preparation method of the polaroid of the described method preparation of basis (7), be characterised in that the use antireflection film, comprise in these multilayers that wherein at least one refractive index is higher than the high refractive index layer of refractive index of support and the low-index layer of the refractive index that refractive index is lower than support, and high refractive index layer is that refractive index is the formation layer of 1.55-2.40, it contains the fine inorganic particle of titania as principal ingredient, and contains at least a element that is selected from cobalt, aluminium and zirconium.
(9), be characterised in that at least a compound that is selected from mineral compound, organometallics and the organic compound that fine inorganic particle was lowered or destroyed photocatalytic activity separately covers according to the preparation method of (8) described polaroid.
(10) a kind of polaroid is characterised in that by preparing according to each described preparation method of (1)-(9).
(11) according to (10) described polaroid; be characterised in that except that the antireflection film in surface protection film; one film that is used to form polaroid be one with the surface of the bonding surperficial facing surfaces diaphragm of surface protection film and polarizing coating on have the optical compensation films of the optical compensating layer that comprises optical anisotropic layer; this optical anisotropic layer is the layer with negative birefringence; and comprise that one has the compound of disk-shaped structure unit; the dish face of this disk-shaped structure unit is with respect to the surface protection film face tilt, and the angle that forms between the dish face of disk-shaped structure unit and surface protection face changes at the thickness direction of optical anisotropic layer.
(12) has at least one liquid crystal indicator according to (10) or (11) described polaroid.
(13), be characterised in that it belongs to the TN of transmission-type, reflection-type or Semitransmissive, STN, VA, IPS or ocb mode as (12) described liquid crystal indicator.
According to the content of this instructions, antireflection film has the high refractive index layer that contains fine inorganic particle, and this fine inorganic particle contains and at least aly is selected from the element of cobalt, aluminium and zirconium and contains titania as principal ingredient; And has a low-index layer that comprises the cured film of multipolymer; described multipolymer comprises the repetitive that derives from fluorine-containing vinyl monomer; have the repetitive of (methyl) acryloyl group with each comfortable side chain, with this antireflection film under the described saponification condition of this instructions through saponification Processing of Preparation polaroid.As a result, can provide the antireflection film that has excellent physical strength and against weather (particularly, photostability) separately polaroid low-cost, in large quantities as surface protection film.
And, a kind of image display apparatus that keeps aforementioned feature can be provided thus.
The accompanying drawing summary
Fig. 1 shows the cross sectional representation of the antireflection film of use antireflection property excellence as the layer structure of the polaroid of surface protection film.
Fig. 2 is the synoptic diagram that shows the embodiment that implements equipment of the present invention.
[explanation of Reference numeral and symbol]
1 transparent support
2 hard conatings
3 intermediate-index layers
4 high refractive index layers
5 low-index layers (outermost layer)
6 bonding coats
7 polarizing coatings
8 surface protection films on opposite face
9 adhering agent layers
101 feeds
102 first are coated with stop
103 first dry sections
104 first ultraviolet irradiation apparatus
105 second are coated with stop
106 second dry sections
107 second ultraviolet irradiation apparatus
108 the 3rd are coated with stop
109 the 3rd dry sections
110 the 3rd ultraviolet irradiation apparatus
111 dry sections
112 coilers
Below, describe the present invention in detail.
Anti-reflection structure of the present invention comprises at least one deck low-index layer and at least one floor height index layer. Form separately that the film of layer is cured film, but they separately can be by coating, dry and solidify a coating composition that preferably contains at least a film forming solute and at least a solvent and obtain. Film-formable solute refers to dissolve or be dispersed in for the wet material that is coated on the base-material of state that dissolves or disperse its at least a solvent herein, and basically exists with form membrane on base-material after with solvent seasoning. Incidentally, in this manual, term " (value 1) is to (value 2) " refers to " more than or equal to (value 1) with less than or equal to (value 2).
[transparent support]
The transparent support that is used for antireflection film of the present invention is plastic foil preferably. Plastic foil comprises that cellulose esters (for example; tri acetyl cellulose, diacetyl cellulose, propiono cellulose, bytyry cellulose, acetyl group propiono cellulose and NC Nitroncellulose) and the film of polyolefin (for example, polypropylene, polyethylene and polymethylpentene). Preferably tri acetyl cellulose and polyolefin are used for polarizer, this is because their phase difference is little and optical homogeneity is high. Particularly, preferred tri acetyl cellulose when using it for liquid crystal indicator.
When transparent support is the tri acetyl cellulose film, preferably will be dissolved in the tri acetyl cellulose solution (referred to as dope) for preparing in the solvent by tri acetyl cellulose by the pouring procedure of pouring into a mould altogether with individual layer cast or multilayer and pour into a mould the tri acetyl cellulose film for preparing.
Particularly, from the angle of environmental protection, the preferred tri acetyl cellulose film that tri acetyl cellulose is dissolved in the tri acetyl cellulose dope preparation that makes in the solvent that is substantially free of carrene by dissolution in low temperature method or high-temperature digestion method that uses. Detailed description can be referring to Japan Institute of Invention and Innovation'sJournal of Technical Disclosure(
KOUKAI GIHOU)2001-No.1745。
Individual layer tri acetyl cellulose film comprises that by preparations such as disclosed cylinder cast among the JP-A-7-11055 etc., Strip castings the tri acetyl cellulose film of multilayer is by altogether casting preparation such as disclosed what is called among JP-A-61-94725, the JP-B-62-43846 etc.
For example, material web is dissolved in solvent, and for example halogenated hydrocarbons (for example, carrene), alcohols (for example, methyl alcohol, ethanol and butanols), ester class be (for example, methyl formate and methyl acetate) and ethers (for example ， diox, dioxolanes and diethyl ether). If necessary, to wherein adding various additives for example plasticizer, ultra-violet absorber, regression inhibitor, lubricant and release promoter. With dope charging gear (referred to as mould) gained solution (dope) is cast on the support that comprises horizontal ring-type metal tape or cylinder.
With regard to individual layer, single dope is poured into individual layer, with regard to multilayer, pour into a mould altogether the low concentration dope in high concentration cellulose esters dope both sides. Thereby then this dope is dried at support and to a certain degree gives the gained film with rigidity. Release film from the support, then use various conveying arrangements by dry section with desolventizing.
Aforementioned in order to the solvent that dissolves tri acetyl cellulose carrene normally. Yet from the angle of global environment and working environment, preferred solvent is substantially free of for example carrene of halogenated hydrocarbons. Word " is substantially free of " and refers to that the ratio of halogenated hydrocarbons in organic solvent is less than 5 % by weight (preferably less than 2 % by weight). When the solvent that is substantially free of carrene etc. when use prepares the dope of tri acetyl cellulose, preferably use the described specific dissolving method in back.
First method will be described below referred to as the hot-cold lysis method. At first, under the temperature (10 to 40 ℃) of near room temperature, when stirring, tri acetyl cellulose is joined in the solvent gradually. Then, mixture is cooled to-100 to-10 ℃ (preferred-80 to-10 ℃, more preferably-50 to-20 ℃, most preferably-50 to-30 ℃). Cooling can be carried out in dry ice/methanol bath (75 ℃) or in the diethylene glycol solution (30 to-20 ℃) of cooling. This cooling is so that the mixture solidified of tri acetyl cellulose and solvent. Be heated to 0-200 ℃ (preferred 0-150 ℃, more preferably 0-120 ℃, most preferably 0-50 ℃) again, be converted into thus solution, wherein tri acetyl cellulose can flow in solvent. Can only heat up by curing mixture is statically placed under the room temperature, perhaps also can in temperature is bathed, heat up.
Second method is referred to as the high-temperature digestion method, and will be described below. At first, under the temperature (10 to 40 ℃) of near room temperature, when stirring, tri acetyl cellulose is joined in the solvent gradually. Tri acetyl cellulose solution of the present invention is preferably by joining tri acetyl cellulose in the mixed solvent that contains different solvents in advance swelling. In the method, preferably tri acetyl cellulose is dissolved to 30 % by weight or less concentration, yet, the drying efficiency during in view of film forming, this concentration is preferably high as far as possible. Then, the solution that under the pressure of 0.2MPa-30MPa this organic solvent is mixed is heated to 70-240 ℃ (preferred 80-220 ℃, more preferably 100-200 ℃, most preferably 100-190 ℃). This heated solution can not former state be coated with, and therefore need to be cooled under the temperature of the minimum boiling point that is lower than solvent for use. In this case, solution is cooled to-10 to 50 ℃ usually, and returns to normal pressure. This cooling can be only rests on room temperature by the high pressure-temperature container of storing tri acetyl cellulose solution or pumping system and gets off to carry out. More preferably, this equipment also can use for example water quench of refrigerant.
Thickness to transparent support has no particular limits. Yet this thickness is preferably 1-300 μ m, preferred 30-150 μ m, particularly preferably 40-120 μ m, most preferably 40-100 μ m.
The light transmittance of transparent support preferably 80% or larger, more preferably 86% or larger. The muddiness of transparent support preferably 2.0% or less, more preferably 1.0% or less (term used herein " muddiness " is defined as to have usually to its implication that provides, and it is such as the Science Council on Scientific terms of Ministry of Education, Culture, Sports, photograph term among the Japanese Scientific Terms (Gakujyutsu Yougo Syu) that Science and Technology publishes provides, and can be fixed by general muddy instrumentation). The refractive index of transparent support is 1.4-1.7 preferably. In this transparent support, can add infrared absorbent or ultra-violet absorber. Take the amount of transparent support as the basis, the addition of infrared absorbent is the 0.01-20 % by weight preferably, more preferably the 0.05-10 % by weight. Also the inert inorganic compounds particle can be joined in the transparent support as lubricant. The example of this inorganic compound can comprise SiO2、TiO
2、BaSO
4、CaCO
3, talcum and kaolin.
[fine inorganic particle]
In the high refractive index layer of antireflection film of the present invention, can add be used to the particle with high index of refraction that obtains required refractive index. As these particles, can mention the fine inorganic particle of titanium dioxide, zirconia, aluminium oxide etc. Wherein, because titanium dioxide has extra high refractive index, therefore by preferred. Therefore yet titanium dioxide has photocatalysis performance, particularly preferably containing at least a element that is selected from cobalt, aluminium and zirconium, and contains titanium dioxide and uses as the form of the fine inorganic particle of main component. Main component refers to content (% by weight) the highest component in the component that forms particle.
High refractive index layer of the present invention has the refractive index of 1.55-2.40, and it is the layer referred to as so-called high refractive index layer or intermediate-index layer. Yet in this manual, this layer can be commonly referred to as high refractive index layer.
Contain titanium dioxide among the present invention and have preferred 1.90-2.80 as the fine inorganic particle of main component, more preferably 2.10-2.80, the most preferably refractive index of 2.20-2.80.
Contain titania and have preferred 1-200nm, more preferably 5-150nm, even more preferably 10-100nm, the weight average particle diameter of preferred especially 10-80nm as the primary particle of the fine inorganic particle of principal ingredient.
The particle diameter of each fine inorganic particle can be measured by the mode of light scattering method or electron micrograph.Fine inorganic particle has preferred 10-400m
2/ g, more preferably 20-200m
2/ g, most preferably 30-150m
2The specific surface area of/g.
In view of crystal structure, contain titania as the fine inorganic particle of principal ingredient preferably contain have rutile, the component of rutile/anatase mixed crystal, anatase or amorphous structure is as principal ingredient, the component that especially preferably has rutile structure is as principal ingredient.Principal ingredient is meant content (weight %) the highest component in the component that forms particle.
By making that contain titania contains the element of at least a Co of being selected from (cobalt), A1 (aluminium) and Zr (zirconium) as the fine inorganic particle of principal ingredient, can suppress the photocatalytic activity that titania has.Can improve the against weather of high refractive index layer of the present invention like this.
Particularly preferred element is Co (cobalt).These elements also can preferably mix use with its two or more.
Based on the amount of Ti (titanium), the amount of relative Ti, the amount of Co (cobalt), Al (aluminium) or Zr (zirconium) is 0.05-30 weight % preferably, more preferably 0.1-10 weight %, even more preferably 0.2-7 weight %, preferred especially 0.3-5 weight %, most preferably 0.5-3 weight %.
Co (cobalt), Al (aluminium) and Zr (zirconium) are present in contain titania as the inside of each fine inorganic particle of principal ingredient or surface one of at least.Yet, they preferably are present in contain the inside of titania as the fine inorganic particle of principal ingredient, most preferably not only be present in its inside but also be present in its surface.
Can make Co (cobalt), Al (aluminium) and Zr (zirconium) exist (for example, blending) with the whole bag of tricks in containing the inside of titania as the fine inorganic particle of principal ingredient.For example, can mention
Ion Implantation Method(Vol.18, No.5, pp.262-268,1998; Yasushi Aoki) and the method described in JP-A-11-263620, JP-T-11-512336 (term used herein " JP-T " is meant the disclosed PCT patented claim of Japanese Translator), EP 0335773 and the JP-A-5-330825.
Particularly preferably in containing the technology (for example being described in JP-T-11-512336, EP No.0335773 or JP-A-5-330825) that adds Co (cobalt), Al (aluminium) and Zr (zirconium) in the granulation process of titania as the fine inorganic particle of principal ingredient.
Co (cobalt), Al (aluminium) and Zr (zirconium) also preferably exist with oxide form separately.
According to required purpose, contain titania and also can also contain other element as the fine inorganic particle of principal ingredient.In other element can be included in the alloy form.The example of these other elements can comprise Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Mg, Si, P and S.
Be used for the titania that contains of the present invention and can pass through surface treatment as the fine inorganic particle of principal ingredient.Its surface treatment can further reduce or destroy the photocatalytic activity of fine inorganic particle.Use has the mineral compound, organic compound and the organometallics that reduce or destroy photocatalytic activity and carries out this surface treatment.The example that is used for this surface-treated mineral compound can comprise and contains cobalt mineral compound (CoO for example
2, Co
2O
3And Co
3O
4), contain aluminium mineral compound (Al for example
2O
3And Al (OH)
3), contain zirconium mineral compound (ZrO for example
2And Zr (OH)
4), silicon-containing inorganic compound (SiO for example
2) and iron content mineral compound (Fe for example
2O
3).
Especially preferably contain the cobalt mineral compound, contain the aluminium mineral compound and contain the zirconium mineral compound.Preferred especially the use contains the oxyhydroxide of cobalt mineral compound and Al and Zr or their combination.
The example that is used for the surface-treated organic compound can comprise polyvalent alcohol, alkanolamine and stearic acid.On the other hand, the example of organometallics can comprise silane coupling agent and titanate coupling agent.Wherein, silane coupling agent most preferably.Particularly, the organometallics of preferably representing with following formula A and derivant thereof carries out this surface treatment.
Formula A:
(R
1)
m-Si(OR
2)
n
In formula A, R
1Represent replacement or unsubstituted alkyl or aryl; R
2Represent replacement or unsubstituted alkyl or acyl group; And m represents 0 or the integer of 1-3, and n represents the integer of 1-4, and prerequisite is that the sum of m and n is 4.
In formula A, R
1Represent replacement or unsubstituted alkyl or aryl.As alkyl, can mention methyl, ethyl, propyl group, isopropyl, hexyl, the tert-butyl group, sec-butyl, hexyl, decyl, cetyl etc.R
1The carbon number of the alkyl of representative is 1-30, more preferably 1-16, especially preferably 1-6.As R
1The aryl of representative can be mentioned phenyl, naphthyl etc., preferred phenyl.
Although substituting group is had no particular limits; but preferred halogen atom (fluorine for example; chlorine or bromine); hydroxyl; sulfydryl; carboxyl; epoxy radicals; alkyl (methyl for example; ethyl; isopropyl; the propyl group or the tert-butyl group); aryl (for example phenyl or naphthyl); fragrant heterocyclic radical (furyl for example; pyrazolyl or pyridine radicals); alkoxy (methoxyl for example; 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 (for example acetoxyl group or (methyl) acryloyl group); alkoxy carbonyl (for example methoxycarbonyl or ethoxy carbonyl); aryloxycarbonyl (for example phenyloxycarbonyl); carbamyl (carbamyl for example; N-methyl carbamyl; N, N-dimethylamino formoxyl or N-methyl-N-octyl group carbamyl); acyl amino (acetyl-amino for example; benzoyl-amido; acryloyl group amino or methacryl amino) etc.
Wherein, more preferably hydroxyl, sulfydryl, carboxyl, epoxy radicals, alkyl, alkoxysilyl, acyloxy or acyl amino.Preferred especially epoxy radicals, polymerisable acyloxy (for example (methyl) acryloyl group) or polymerisable acyl amino (for example acryloyl group amino or methacryl amino).Yet these substituting groups can also be substituted.
R
2Represent replacement or unsubstituted alkyl or acyl group.Alkyl, acyl group and substituent explanation and R
1In identical.R
2Preferably unsubstituted alkyl or unsubstituted acyl, preferred especially unsubstituted alkyl.
M represents 0 or the integer of 1-3, and n represents the integer of 1-4, and prerequisite is that the summation of m and n is 4.When there being a plurality of R
1Or R
2The time, a plurality of R
1Or R
2Can be identical or different respectively.M is preferably 0,1 or 2, is preferably 1 especially.
Below, show the non-limiting instantiation of the compound of formula A of the present invention representative.
(1)(C
2H
5O)
4-Si
(2)(C
3H
7O)
4-Si
(3)(i·C
3H
7O)
4-Si
(4)(CH
3CO
2)
4-Si
(5)(CH
3CO
2)
2-Si-(OC
2H
5)
2
(6)CH
3-Si-(OC
2H
5)
3
(7)C
2H
5-Si-(OC
2H
5)
3
(8)t-C
4H
9-Si-(OCH
3)
3
(16)C
3F
7CH
2CH
2-Si-(OC
2H
5)
3
(17)C
6F
13CH
2CH
2-Si-(OC
2H
5)
3
(26)
NH
2CH
2CH
2CH
2-Si-(OCH
3)
3
(27)
HS-CH
2CH
2CH
2-Si-(OCH
3)
3
(30)
(CH
3O)
3-Si-CH
2CH
2CH
2CH
2-Si-(OCH
3)
3
(31)
(CH
3O)
3-Si-CH
2CH
2CH
2CH
2CH
2CH
2-Si-(OCH
3)
3
(43)
CH
2＝CH-Si-(OCH
3)
3
In these instantiations, preferred especially (1), (12), (18), (19) etc.
Based on the total solids content of high refractive index layer, the content of the compound of formula A is 1-90 weight % preferably, more preferably 2-80 weight %, especially preferably 5-50 weight %.
The example of titanate coupling agent can comprise for example tetramethoxy titanium, purity titanium tetraethoxide and tetraisopropoxy titanium and PLENACT (for example KR-TTS, KR-46B, KR-55 or KR-41B of metal alkoxide; By Ajinomoto Co., Inc. makes).
The example that is used for the surface-treated organic compound can comprise, and is preferred, and polyvalent alcohol, alkanolamine and have the organic compound of other anionic group are preferred especially, have the organic compound of carboxyl, sulfonic group or phosphate.
Can preferably use stearic acid, lauric acid, oleic acid, leukotrienes, linoleic acid etc.
Be used for the surface-treated organic compound and also preferably have crosslinkable or polymerisable functional group.As crosslinkable or polymerisable functional group; having of can mentioning can be through the ethylenic unsaturated group of free radical material addition reaction/polyreaction (for example; (methyl) acryloyl group, allyl, styryl and ethyleneoxy), cationic polymerizable group (for example epoxy radicals, oxatanyl and ethyleneoxy) but and polycondensation group (for example hydrolyzable silicyl and N-methylol), and preferably have the group of ethylenic unsaturated group.
Being used for these materials of surface-treated can use in its two or more mixing.Preferred especially mixing is used and is contained the aluminium mineral compound and contain the zirconium mineral compound.
The titania that contains of the present invention also can have nuclear core/shell mechanism as the fine inorganic particle of principal ingredient by surface treatment, described in JP-A-2001-166104.
The titania that contains that comprises in the high refractive index layer preferably has grain of rice shape, spherical, cubic, spindle shape or indefinite shape as the fine inorganic particle of principal ingredient, especially preferably has indefinite shape or spindle shape.
[spreading agent]
Can use spreading agent to disperse to contain the fine inorganic particle of titania, be used for the high refractive index layer of antireflection film of the present invention as principal ingredient.
The preferred especially spreading agent with anionic group that uses disperses the fine inorganic particle that contains titania as principal ingredient of the present invention.
Anionic group is effective group for example carboxyl, sulfonic group (and sulfo group), phosphate (and phosphono) and the sulfonamido with acid proton; and their salt; preferred especially carboxyl, sulfonic group and phosphate and their salt, preferred especially carboxyl and phosphate.It is necessary containing one or more anionic groups in each molecule of spreading agent.
In order to improve the dispersiveness of fine inorganic particle biglyyer, also can contain many anionic groups.Preferably contain average two or more anionic groups, more preferably five or more, preferred especially 10 or more.As for anionic group contained in the spreading agent, also can contain polytype anionic group in each molecule.
Spreading agent also preferably contains crosslinkable or polymerisable functional group.As crosslinkable or polymerisable functional group; can mention can be through the ethylenic unsaturated group of free radical material addition reaction/polyreaction (for example; (methyl) acryloyl group, allyl, styryl and ethyleneoxy), cationic polymerizable group (for example epoxy radicals, oxatanyl and ethyleneoxy) but and polycondensation group (for example hydrolyzable silicyl and N-methylol), and preferably have the group of ethylenic unsaturated group.
Be used for being dispersed in that high refractive index layer of the present invention uses contains titania and preferably have anionic group and crosslinkable or polymerisable functional group as the spreading agent of the fine inorganic particle of principal ingredient, and have the spreading agent of crosslinkable or polymerisable group at side chain.
To having anionic group and crosslinkable or polymerisable functional group, and have no particular limits in the weight-average molecular weight (Mw) that side chain has a spreading agent of crosslinkable or polymerisable group.Be preferably 1000 or bigger.The weight-average molecular weight of spreading agent (Mw) is 2000-100000 more preferably, and more preferably 5000-200000 is preferably 10000-100000 especially.
Anionic group is effective group for example carboxyl, sulfonic group (and sulfo group), phosphate (and phosphono) and the sulfonamido with acid proton; and their salt; preferred especially carboxyl, sulfonic group and phosphate and their salt, preferred especially carboxyl and phosphate.In the spreading agent quantity of the anionic group of each contained molecule on average preferably two or more, more preferably 5 or more, preferred especially 10 or more.As for anionic group contained in the spreading agent, also can contain polytype anionic group in each molecule.
Have anionic group and crosslinkable or polymerisable functional group, and the spreading agent that has crosslinkable or polymerisable group at side chain is at side chain or have anionic group endways.Can utilize polymerization, for example, contain the 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 and mono phosphoric acid ester-2-(methyl) acryloxy ethyl ester) of anionic group method, acid anhydrides is acted on have the method for polymkeric substance of hydroxyl, amino etc. or the synthetic of polymer reaction of other method that these anionic groups are joined in the side chain.
Have in the spreading agent of anionic group at side chain, based on total repetitive quantity, the ratio of components of repetitive that contains anionic group in the scope of 10-4-100 mole %, preferred 1-50 mole %, preferred especially 5-20 mole %.
On the other hand, method by under the situation that the chain-transferring agent (for example mercaptoacetic acid) that contains anionic group is arranged, carrying out polyreaction, use the polymerization initiator that contains anionic group (V-501 for example, by Wako Pure Chemical Industries, Ltd. makes) carry out the method for polyreaction or other method is synthetic anionic group can be joined end.
Particularly preferred spreading agent is the spreading agent that has anionic group at side chain.
As crosslinkable or polymerisable functional group; can mention can be through the ethylenic unsaturated group of free radical material addition reaction/polyreaction (for example; (methyl) acryloyl group, allyl, styryl and ethyleneoxy), cationic polymerizable group (for example epoxy radicals, oxatanyl and ethyleneoxy) but and polycondensation group (for example hydrolyzable silicyl and N-methylol), and preferably have the group of ethylenic unsaturated group.
In the spreading agent quantity of the crosslinkable or polymerisable functional group of each contained molecule on average preferably two or more, more preferably 5 or more, preferred especially 10 or more.As for crosslinkable or polymerisable functional group contained in the spreading agent, also can contain polytype anionic group in each molecule.
Be used for preferred dispersants of the present invention, it is poly--1 that the example that has a repetitive of ethylenic unsaturated group at side chain comprises, 2-butadiene and poly--1, the repetitive of 2-isoprene structure or (methyl) acrylate or acid amides.Wherein those that are connected with specific residue (COOR or-R group among the CONHR) at each repetitive are useful.The example of specific residue (R group) can comprise :-(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-CR
1=CR
2R
3With-(CH
2CH
2O)
2-X (R wherein
1-R
3Represent hydrogen atom, halogen atom separately or have alkyl, aryl, alkoxy or the aryloxy group of 1-20 carbon atom, and R
1And R
2Or R
3Also can combination with one another form ring, n is the integer of 1-10, and X is the bicyclopentadiene residue).The instantiation of ester residue can comprise-CH
2CH=CH
2(being equivalent to (methyl) allyl acrylate polymkeric substance 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 is the dicyclopentadienyl residue).The instantiation of acyl ammonia residue can comprise-CH
2CH=CH
2,-CH
2CH
2-Y (wherein Y is a 1-cyclohexene residue) and-CH
2CH
2-OCO-CH=CH
2With-CH
2CH
2-OCO-C (CH
3)=CH
2
In spreading agent with ethylenic unsaturated group, in the unsaturated link group, add free radical (the growth free radical in the polymerization process of polymerization initiator free radical or polymerizable compound), directly or through the chain polymerization of polymerizable compound cause polyaddition reaction intermolecular.Cause forming crosslinked like this, solidify.Perhaps, the atom in the molecule (for example, the hydrogen atom on the carbon atom adjacent with the unsaturated link group) is taken away the generation polymer residue by free radical.Their combinations with one another form crosslinked between molecule, solidify.
Described in JP-A-3-249653, the copolymerization of copolymerization, butadiene or the isoprene of monomer (for example (methyl) allyl acrylate, (methyl) glycidyl acrylate and methacrylic acid trialkoxysilyl propyl ester) that can be by containing crosslinkable or polymerisable functional group or have the copolymerization of the vinyl monomer of 3-chloropropionic acid ester moiety, carry out dehydrochlorination then, crosslinkable or polymerisable functional group can be joined in the side chain.Perhaps, can synthesize or other crosslinkable or polymerisable functional group of method adding by polymer reaction (polyreaction that for example contains the vinyl monomer and the carboxylic polymkeric substance of epoxy radicals).
The unit that contains crosslinkable or polymerisable functional group can constitute all repetitives except that the repetitive that contains anionic group.Yet they account for the 5-50 mole % of the total amount of crosslinkable or polymerisable repetitive, preferred especially 5-30 mole %.
Preferred dispersants of the present invention can be the multipolymer of the proper monomer except that the monomer with crosslinkable or polymerisable functional group and anionic group.These copolymerizable components are had no particular limits.Yet, from different perspectives for example dispersion stabilization, with the compatibility of other monomer component with form film strength and select them.Its preferred embodiment can comprise (methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate and styrene.
Form to preferred dispersants of the present invention has no particular limits.Yet spreading agent is segmented copolymer or random copolymers preferably, according to cost and synthetic easness, and preferred especially random copolymers.
Show the instantiation that is preferred for spreading agent of the present invention below.Incidentally, except as otherwise noted, demonstration be random copolymers.
x y z R Mw
P-(1) 80 20 0 - 40,000
P-(2) 80 20 0 - 110,000
P-(3) 80 20 0 - 10,000
P-(4) 90 10 0 - 40,000
P-(5) 50 50 0 - 40,000
P-(6) 30 20 50 CH
2CH
2CH
3 30,000
P-(7) 20 30 50 CH
2CH
2CH
2CH
3 50,000
P-(8) 70 20 10 CH(CH
3)
3 60,000
P-(9) 70 20 10
150,000
P-(10) 40 30 30
15,000
X/y/z represents mol ratio
A Mw
P-(11)
20,000
P-(12)
30,000
P-(13)
100,000
P-(14)
20,000
P-(15)
50,000
P-(16)
15,000
A Mw
P-(17)
20,000
P-(18)
25,000
P-(19)
18,000
P-(20)
20,00O
P-(21)
35,000
R
1 R
2 x y z Mw
P-(22)
C
4H
9(n) 10 10 80 25,000
P-(23)
C
4H
9(t) 10 10 80 25,000
P-(24)
C
4H
9(n) 10 10 80 500,000
P-(25)
C
4H
9(n) 10 10 80 23,000
P-(26)
C
4H
9(n) 80 10 10 30,000
P-(27)
C
4H
9(n) 50 20 30 30,000
P-(28)
C
4H
9(t) 10 10 80 20,000
P-(29)
CH
2CH
2OH 50 10 40 20,000
P-(30)
C
4H
9(n) 10 10 80 25,000
P-(31)
Mw＝60,000
P-(32)
Mw＝10,000
P-(33)
Mw＝20,000
P-(34)
Mw＝30,000
(segmented copolymer)
P-(35)
Mw=15,000 (segmented copolymer)
(segmented copolymer) (segmented copolymer)
P-(36)
Mw＝8,000
P-(37)
Mw＝5,000
P-(38)
Based on fine inorganic particle, the consumption of spreading agent is preferably in the scope of 1-50 weight %, more preferably in the scope of 5-30 weight %, most preferably in the scope of 5-20 weight %.And spreading agent can two or more mix use.
[high refractive index layer and forming method thereof]
The fine inorganic particle that is used for high refractive index layer can use with the form that forms the dispersion that high refractive index layer uses.
With regard to the dispersion of fine inorganic particle, can under the situation that has aforementioned spreading agent to exist, in dispersion medium, disperse.
As dispersion medium, preferably use boiling point to be 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), aliphatic hydrocarbon (for example, hexane and cyclohexane), halogenated hydrocarbon (for example, methylene chloride, chloroform and phenixin), 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 and tetrahydrofuran) and ether alcohol class (for example, 1-methoxyl-2-propyl alcohol).Preferred toluene, dimethylbenzene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanols.
Particularly preferred dispersion medium is methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
Disperse fine inorganic particle by dispersion machine.The example of dispersion machine can comprise sand mill (for example, being equipped with the ball mill of pin), quick runner comminutor, pebble plain, roller mill, refiner and colloid mill.Preferred especially sand mill and quick runner comminutor.Yet, also can carry out pre-dispersed processing.The example that is used for the dispersion machine of pre-dispersed processing can comprise bowl mill, three-roll mill, kneading machine and extruder.
Fine inorganic particle preferred size in dispersion medium reduces as far as possible for a short time, and weight average particle diameter is 1-200nm, preferred 5-150nm, more preferably 10-100nm, preferred especially 10-80nm.Can be under the situation of not damaging transparency, by the fine inorganic particle size being reduced to 200nm or the littler high refractive index layer that forms.
Being used for high refractive index layer of the present invention preferably forms as follows.The former mode of stating is by being dispersed in fine inorganic particle in the dispersion for preparing in the dispersion medium, preferably, also add and form the necessary adhesive precursor of matrix (for example multifunctional monomer or the multi-functional oligomer of ionization radiation curing), the coating fluid that Photoepolymerizationinitiater initiater etc. are used with preparation formation high refractive index layer.Gained is formed the coating fluid that high refractive index layer uses be applied on the transparent support, and the cross-linking reaction or the polyreaction of the compound (for example multifunctional monomer or multi-functional oligomer) that solidifies by ionization radiation are solidified.
And, preferably in this layer of coating or after being coated with this layer, make bonding agent and spreading agent process cross-linking reaction or polyreaction in the high refractive index layer.
As for the bonding agent in the high refractive index layer of preparation by this way, for example, multifunctional monomer that preferred dispersing agent and ionization radiation solidify or multi-functional oligomer are through crosslinked or polyreaction.The anionic group of acquisition spreading agent joins the form in the bonding agent like this.And, in the bonding agent in high refractive index layer, anionic group has the function of the disperse state that keeps fine inorganic particle, and crosslinked or paradigmatic structure gives the bonding agent film forming ability, thereby improves physical strength, chemical resistance and the against weather of the high refractive index layer that contains fine inorganic particle.
The multifunctional monomer that ionization radiation solidifies or the functional group of multi-functional oligomer preferably light-, electron beam-or radiation-polymerisable functional group.The functional group of preferred especially photopolymerization.
As the functional group of photopolymerization, can mention undersaturated polymerisable functional group for example (methyl) acryloyl group, vinyl, styryl and allyl etc.Wherein, preferred (methyl) acryloyl group.
The instantiation of multifunctional monomer of photopolymerization with functional group of photopolymerization can comprise:
(methyl) diester acrylates of alkylene glycol is neopentyl glycol acrylate, 1 for example, 6-hexanediol (methyl) acrylate and propylene glycol two (methyl) acrylate;
(methyl) diester acrylates of polyoxyalkylene glycol is triethylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate and polypropylene glycol two (methyl) acrylate for example;
(methyl) diester acrylates of polyvalent alcohol is pentaerythrite two (methyl) acrylate for example; With (methyl) diester acrylates of oxirane or propylene oxide adduct for example 2,2-two { 4-(acryloxy-diethoxy) phenyl } propane and 2,2-two 4-(acryloyl-oxy-poly-propoxyl group) phenyl) propane.
And, also preferably use epoxy radicals (methyl) acrylate, urethane (methyl) acrylate and polyester (methyl) acrylate multifunctional monomer as photopolymerization.
Wherein, preferred polyol and (methyl) acrylic acid ester.The multifunctional monomer that more preferably has 3 or more a plurality of (methyl) acryloyl group in each molecule.Its instantiation can comprise: trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, 1,2,4-cyclohexane four (methyl) acrylate, five glycerol tri-acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, (two) pentaerythritol triacrylate, (two) pentaerythrite five acrylate, (two) pentaerythrite four (methyl) acrylate, (two) pentaerythrite six (methyl) acrylate, tripentaerythritol triacrylate and tripentaerythritol six acrylate.
Multifunctional monomer also can use in its two or more mixing.
The polyreaction that preferably a Photoepolymerizationinitiater initiater is used for the multifunctional monomer of photopolymerization.Photoepolymerizationinitiater initiater is radical photopolymerization initiating agent or cationic photopolymerization initiating agent preferably.Preferred especially radical photopolymerization initiating agent.
The example of radical photopolymerization initiating agent can comprise: acetophenones, benzophenone, Michler ' s benzoyl benzoic ether, α-amyl group oxime (amyloxime) ester class, tetra methylthiuram monosulfide and thioxanthene ketone.
Radical photopolymerization initiating agent as commercially available acquisition, can mention Co. by NIPPONKAYAKU, Ltd. the KAYACURE of Zhi Zaoing (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, MCA etc.), by Ciba-Geigy Japan, Ltd. the Irgacure of Zhi Zaoing (651,184,500,907,369,1173,2959,4265,4263 etc.), the Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT etc.) that makes by Sartomer Co., or the like.
Particularly, but preferred photodestruciton type radical photopolymerization initiating agent.But photodestruciton type radical photopolymerization initiating agent is described in
SAISHIN UV KOKA GIJUTSU(Latest UVCuring Technique) (the 159th page, publisher; Kazuhiro Takausu, publisher; GIJUTSU JOHO KYOKAI, Co., Ltd., distribution in 1991).
But as the photodestruciton type radical photopolymerization initiating agent of commercially available acquisition, can mention Japan by Ciba-Geigy, the Irgacure (651,184 or 907) that Ltd. makes, or the like.
In the multifunctional monomer of per 100 weight portions, Photoepolymerizationinitiater initiater preferably in the scope with the 0.1-15 weight portion, more preferably use by the amount in the scope of 1-10 weight portion.
Except Photoepolymerizationinitiater initiater, also can use photosensitizer.The instantiation of photosensitizer can comprise n-butylamine, triethylamine, tri-n-butyl phosphine, Michler ' s ketone and thioxanthones.
As the photosensitizer of commercially available acquisition, can mention Co. by NIPPON KAYAKU, the KAYACURE (DMBI or EPA) that Ltd. makes, or the like.
Photopolymerization reaction is preferably undertaken by the ultraviolet ray irradiation after high refractive index layer coating and drying.
Be used for compound and/or its derivative compound that high refractive index layer of the present invention also can contain formula A representative.
Bonding agent in the high refractive index layer preferably also has silanol group.In bonding agent, also comprise physical strength, chemical resistance and against weather that silanol group will further improve high refractive index layer.
Silanol group can join in the bonding agent in the following manner.For example, compound formula A representative, that have crosslinkable or polymerisable functional group is joined form in the coating composition that high refractive index layer uses.The gained coating composition is applied on the transparent support, makes the compound of spreading agent, multifunctional monomer or multi-functional oligomer and formula A representative carry out cross-linking reaction or polyreaction.
The compound of the formula A representative in bonding agent to be added especially preferably has the compound of (methyl) acryloyl group as crosslinkable or polymerisable functional group.The example can comprise 3-acryloxy propyl trimethoxy monosilane and 3-methacryloxypropyl trimethoxy monosilane.
Bonding agent in the high refractive index layer also preferably has amino or quaternary ammonium group.
The bonding agent that has amino or quaternary ammonium group in the high refractive index layer can form as follows.For example, the monomer that will have crosslinkable or polymerisable functional group and amino or a quaternary ammonium group joins and forms in the coating composition that high refractive index layer uses.The gained coating composition is applied on the transparent support, makes and to carry out cross-linking reaction or polyreaction with spreading agent and multifunctional monomer or multi-functional oligomer.
Monomer with amino or quaternary ammonium group plays the dispersing aid of fine inorganic particle in coating composition.And, after coating, carry out cross-linking reaction or polyreaction with spreading agent and multifunctional monomer or multi-functional oligomer, obtain bonding agent.Can keep fine inorganic particle favourable dispersiveness in high refractive index layer like this, and can processing machinery intensity, the high refractive index layer of chemical resistance and against weather excellence.
As preferred monomers with amino or quaternary ammonium group, can mention (methyl) acrylic acid N, N-dimethylamino ethyl ester, (methyl) acrylic acid N, N-dimethylamino propyl ester, chlorination Hydroxyproyl Trimethyl ammonium (methyl) acrylate, chlorination dimethyl-allyl-ammonium etc.
Based on the amount of spreading agent, the consumption of monomer with amino or quaternary ammonium group is preferably in the scope of 1-40 weight %, more preferably in the scope of 3-30 weight %, in the scope particularly preferably in 3-20 weight %.Bonding agent is to form by crosslinked or polyreaction in the coating high refractive index layer or after the coating high refractive index layer.These monomers were played a role before the coating high refractive index layer effectively.
The main chain that this crosslinked or polymeric binder has polymkeric substance is crosslinked or the structure of polymerization.The example of the main chain of polymkeric substance can comprise polyolefin (stable hydrocarbon), polyethers, polyureas, polyurethane, polyester, polyamine, polyamide and melamine resin.Preferred polyolefm main chain, polyether backbone and polyureas main chain, more preferably polyolefin backbone and polyether backbone, most preferably polyolefin backbone.
Polyolefin backbone comprises stable hydrocarbon.Polyolefin backbone can obtain by the polyaddition reaction of for example unsaturated polymerizable group.Polyether backbone comprises each other by ehter bond (O-) continuous repetitive.Polyether backbone can obtain by the ring-opening polymerization of for example epoxy radicals.The polyureas main chain comprises each other by urea key (NH-CO-NH-) continuous repetitive.The polyureas main chain for example can obtain by the polycondensation reaction between isocyanate group and amino.Polyurethane backbone comprises each other by urethane bonds (NH-CO-O-) continuous repetitive.Polyurethane backbone for example can obtain by the polycondensation reaction between isocyanate group and hydroxyl (comprising the N-methylol).Polyester backbone comprises each other by ester bond (CO-O-) continuous repetitive.Polyester backbone for example can obtain by the polycondensation reaction between carboxyl (comprising the acyl halide group) and hydroxyl (comprising the N-methylol).The polyamine main chain comprises each other by imido base key (NH-) continuous repetitive.The polyamine main chain for example can obtain by the ring-opening polymerization of Ethylenimine.Polyamide skeleton comprises each other by acylamino-key (NH-CO-) continuous repetitive.Polyamide skeleton for example can obtain by the reaction between isocyanate group and the carboxyl (comprising the acyl group halogen).The polycondensation reaction that the melamine resin main chain for example can pass through between triazine group (for example, melamine) and the aldehyde (for example, formaldehyde) obtains.Incidentally, in melamine resin, main chain itself has crosslinked or paradigmatic structure.
Anionic group preferably is connected on the main chain through linking group with the side chain of bonding agent.
The linking group that anionic group is connected with the main chain of bonding agent preferably-CO-,-O-, alkylidene, arlydene and be selected from the divalent group of their combination.This crosslinked or paradigmatic structure chemically connects (preferred, covalently bound) two or more main chains.Crosslinked or paradigmatic structure preferably covalently ground connects three or more main chains.Crosslinked or paradigmatic structure preferably include CO-,-O-,-S-, nitrogen-atoms, phosphorus atoms, aliphatic residue, aromatic residues and be selected from the divalent group of their combination.
Bonding agent preferably has the repetitive of anionic group and has the multipolymer of another repetitive of crosslinked or paradigmatic structure.The ratio preferably 2-96 mole %, more preferably 4-94 mole %, most preferably the 6-92 mole % that have the repetitive of anionic group in the multipolymer.This repetitive can have two or more anionic groups.The ratio preferably 4-98 mole %, more preferably 6-96 mole %, most preferably the 8-94 mole % that have the repetitive of crosslinked or paradigmatic structure in the multipolymer.
The repetitive of bonding agent also can have crosslinked or paradigmatic structure again by existing anionic group.Bonding agent can also contain other repetitive (both not had anionic group also not have the repetitive of crosslinked or paradigmatic structure).
Another repetitive preferably has the repetitive of silanol group, amino or quaternary ammonium group.
In having the repetitive of silanol group, silanol group directly links to each other with the main chain of bonding agent, perhaps links to each other with main chain by linking group.Silanol group preferably links to each other with main chain by linking group as side chain.Connect silanol group and bonding agent main chain linking group preferably-CO-,-O-, alkylidene or arlydene or be selected from the divalent group of their combination.When bonding agent contained the repetitive with silanol group, its ratio is 2-98 mole % preferably, more preferably 4-96 mole %, most preferably 6-94 mole %.
In the repetitive with amino or quaternary ammonium group, amino or quaternary ammonium group directly link to each other with the main chain of bonding agent, perhaps link to each other with main chain by linking group.Amino or quaternary ammonium group preferably link to each other with main chain by linking group as side chain.Amino or quaternary ammonium group be secondary amino group, uncle's amino or quaternary ammonium group preferably, more preferably uncle's amino or quaternary ammonium group.The group that links to each other with the nitrogen-atoms of secondary amino group, uncle's amino or quaternary ammonium group is alkyl preferably, is more preferably the alkyl with 1-12 carbon atom, and then preferably has the alkyl of 1-6 carbon atom.The counter ion of quaternary ammonium group is the halogen ion preferably.The linking group that amino or quaternary ammonium group are linked to each other with the main chain of bonding agent preferably-CO-,-NH-,-O-, alkylidene, arlydene and be selected from the divalent group of their combination.When bonding agent contained the repetitive with amino or quaternary ammonium group, its ratio is 0.1-32 mole % preferably, more preferably 0.5-30 mole %, most preferably 1-28 mole %.
Incidentally, even when repetitive or have when containing silanol group and amino or quaternary ammonium group in the repetitive of crosslinked or paradigmatic structure, also can obtain identical effect with anionic group.
Crosslinked or polymeric binder preferably forms as follows.The coating composition that the formation high refractive index layer is used is applied on the transparent support.In coating or after coating, carry out crosslinked or polyreaction.
Fine inorganic particle has the effect of the refractive index of control high refractive index layer, and the function that suppresses curing and shrink.
In high refractive index layer, fine inorganic particle preferably disperses as far as possible carefully, and has the weight average particle diameter of 1-200nm.Fine inorganic particle in the high refractive index layer has preferred 5-150nm, more preferably 10-100nm, the especially preferably weight average particle diameter of 10-80nm.
Be reduced to 200nm or littler by size, can form the high refractive index layer that transparency is not had influence fine inorganic particle.
Based on the weight of high refractive index layer, the content of fine inorganic particle in high refractive index layer is 10-90 weight % preferably, more preferably 15-80 weight %, especially preferably 15-75 weight %.Fine inorganic particle can be used for high refractive index layer with two or more combination.
When antireflection film had low-index layer on high refractive index layer, the refractive index of high refractive index layer preferably was higher than the refractive index of transparent support.
With regard to high refractive index layer, the compound that the ionization radiation that also can preferably use the compound that solidifies by the ionization radiation that will contain aromatic rings, contains the halogen (for example, Br, I or C1) outside the defluorination solidifies, contain the compound that the ionization radiation such as the atom of S, N or P etc. solidifies and carry out bonding agent crosslinked or that polyreaction obtains.
In order to form low-index layer on high refractive index layer, and make antireflection film thus, the refractive index of high refractive index layer is 1.55-2.40 preferably, more preferably 1.60-2.20, preferred once more 1.65-2.10, most preferably 1.80-2.00.
Except aforementioned component (for example fine inorganic particle, polymerization initiator and photosensitizer), also can in high refractive index layer, add resin, surfactant, antistatic agent, coupling agent, thickening agent, anti-coloring agent, colorant (pigment or dyestuff), defoamer, levelling agent, fire retardant, ultraviolet light absorber, infrared absorbent, tackifier, polymerization inhibitor, antioxidant, surface modifier, conducting metal particulate etc.
Yet also can make high refractive index layer contain the described mean grain size in back is the particle of 0.2-10 μ m, and it also can be as the anti-dazzle photosphere that obtains the anti-dazzle function thus.
Can high refractive index layer be designed to suitable thickness according to required purpose.When high refractive index layer is used as the described optical interference layer in back, 30-200nm when thickness is preferred, more preferably 50-170nm, especially preferably 60-150nm.When high refractive index layer also was used as hard conating, thickness is 0.5-10 μ m preferably, more preferably 1-7 μ m, especially preferably 2-5 μ m.
With regard to the formation of high refractive index layer, be the cross-linking reaction or the polyreaction of carrying out the compound that ionization radiation solidifies in 10 volume % or the lower environment preferably at oxygen concentration.
By being to form high refractive index layer under 10 volume % or the lower environment at oxygen concentration, can improve physical strength, chemical resistance and the against weather of high refractive index layer, and the viscosity between high refractive index layer and the layer adjacent with high refractive index layer.
By being 6 volume % or lower in preferred oxygen concentration, more preferably oxygen concentration is 4 volume % or lower, special preferred oxygen concentration is 2 volume % or lower, and the cross-linking reaction or the polyreaction of most preferably carrying out the compound that ionization radiation solidifies in 1 volume % or the lower environment form high refractive index layer.
In the following manner oxygen concentration is adjusted to 10 volume % or lower.Air (nitrogen concentration: about 79 volume %, oxygen concentration: about 21 volume %) preferably replace, especially preferably use nitrogen (using nitrogen wash) to replace with another gas.
The preferred coating solvent of high refractive index layer is methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
Coating solvent can contain the solvent except that ketones solvent.The example can comprise: alcohols (for example, methyl alcohol, ethanol, isopropyl alcohol, butanols and phenmethylol), the ester class (for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate and butyl formate), aliphatic hydrocarbon (for example, hexane and cyclohexane), halogenated hydrocarbon (for example, methylene chloride, chloroform and phenixin), 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 and tetrahydrofuran) and ether alcohol class (for example, 1-methoxyl-2-propyl alcohol).
Based on the solvent total amount that contains in the coating composition, in coating solvent, the content of ketones solvent is 10 weight % or bigger preferably.Preferred 30 weight % or bigger, more preferably 60 weight % or bigger.
In the pencil hardness test according to JIS K5400, the intensity of high refractive index layer is H or bigger preferably, more preferably 2H or bigger, most preferably 3H or bigger.
Yet, according to the Taber coomb's test Coomb of JIS K5400, preferably the test before and afterwards test film more a spot of wear extent is arranged.
High refractive index layer preferably has lower muddiness when it does not contain the particle of giving the anti-dazzle function.This muddiness preferably 5% or littler, more preferably 3% or littler, preferred especially 1% or littler.
High refractive index layer preferably directly is formed on the transparent support or by another layer and is formed on the transparent support.
[low-index layer]
The low-index layer of antireflection film of the present invention is by comprising that the repetitive that has (methyl) acryloyl group on the repetitive that derives from fluorine-containing vinyl monomer and each comfortable side chain is film formed as the curing of the multipolymer of necessary constituent.The component that derives from multipolymer preferably accounts for 70 weight % or bigger of the solids content of film, more preferably 80 weight % or bigger, preferred especially 90 weight % or bigger.From realizing preferably not adding the pattern of hardening agent for example multi-functional (methyl) acrylate simultaneously than low-refraction with than the angle of high film hardness and compatibility.
The refractive index of low-index layer is 1.20-1.49 preferably, more preferably 1.20-1.45, especially preferably 1.20-1.44.
The thickness of low-index layer is 50-400nm preferably, more preferably 50-200nm.The muddiness of low-index layer preferably 3% or littler, more preferably 2% or littler, most preferably 1% or littler.The certain strength of low-index layer preferably H or bigger, more preferably 2H or bigger, most preferably 3H or bigger in 1-kg load pencil hardness test.
Yet, in order to improve the antifouling property of antireflection film, preferably 90 ° or bigger of the water contact angles on surface, more preferably 95 ° or bigger, preferred especially 100 ° or bigger.
Below, the multipolymer that is used for low-index layer of the present invention is described.
As fluorine-containing vinyl monomer, (for example can mention fluoroolefins class (for example fluorothene, difluoroethylene, tetrafluoroethene, hexafluoroethylene and hexafluoropropylene), (methyl) acrylic acid partially or completely fluorinated alkyl ester derivant, BISCOAT 6FM (trade (brand) name, by Osaka OrganicChemical Industry, Ltd. make) and M-2020 (trade (brand) name, by Daikin Industries, Ltd. makes)) and the vinyl ether fluoridized wholly or in part.Preferred perfluoroolefine.From refractive index, solubleness, transparency, availability equal angles, preferred especially hexafluoropropylene.The ratio of components that increases these fluorine-containing vinyl monomers can reduce refractive index, but reduces coated film intensity.In the present invention, add fluorine-containing vinyl monomer so that the fluorine content of multipolymer 20-60 weight % preferably, more preferably 25-55 weight %, preferred especially 30-50 weight %.
Multipolymer of the present invention has the repetitive of (methyl) acryloyl group as necessary constituent at side chain.The method that (methyl) acryloyl group is joined in the multipolymer has no particular limits.The example can comprise: method (1), and synthetic have nucleophilic group for example hydroxyl or an amino polymkeric substance, and the effects such as mixed acid anhydride that make (methyl) acrylic acid chlorine, (methyl) acrylic anhydride, (methyl) acrylic acid and methane-sulforic acid then are on it; Method (2) acts on the polymkeric substance with nucleophilic group (methyl) acrylic acid under the catalyzer situation that for example sulfuric acid exists; Method (3), make not only have isocyanate group for example methacryloxypropyl isocyanates but also compound effects with (methyl) acryloyl group on polymkeric substance with nucleophilic group; Method (4), synthetic polymkeric substance with epoxy radicals then, makes the effect of (methyl) acrylic acid on it; Method (5), make not only have epoxy radicals for example glycidyl methacrylate but also compound effects with (methyl) acryloyl group on polymkeric substance with carboxyl; And method (6), will have the polymerization of vinyl monomer of 3-chloropropionic acid ester moiety separately, carry out dehydrochlorination then.In the present invention, select with the method in these methods (1) or (2) (methyl) acryloyl group is joined in the polymkeric substance with hydroxyl.
When the ratio of components of the repetitive that contains (methyl) acryloyl group increased, coated film intensity increased, but refractive index also increases.The repetitive that contains (methyl) acryloyl group accounts for different ratios along with the kind difference of the repetitive that derives from fluorine-containing vinyl monomer.Yet in general, this repetitive preferably accounts for 5-90 weight %, more preferably accounts for 30-70 weight %, especially preferably accounts for 40-60 weight %.
With regard to being used for multipolymer of the present invention; from comprising and the viscosity of base-material, the Tg of polymkeric substance (favourable), the different angles of solubleness, transparency, sliding and dustproof and antifouling property solvent to film hardness, also can be with other vinyl monomer copolymerization suitably that on the repetitive that derives from fluorine-containing vinyl monomer and each comfortable side chain, has the repetitive of (methyl) acryloyl group.These vinyl monomers can be according to required purpose with its multiple being used in combination, and amount based on multipolymer, their total amount preferably in the scope of 0-65 mole %, more preferably in the scope of 0-40 mole %, adds in the scope particularly preferably in 0-30 mole %.
The vinyl monomer unit that can mix use is had no particular limits.The example can comprise: olefines (ethene for example, propylene, isoprene, vinyl chloride and dichloroethylene), esters of acrylic acid (methyl acrylate for example, ethyl acrylate, 2-EHA and acrylic acid 2-hydroxy methacrylate), methyl acrylic ester (methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate and 2-hydroxyethyl methacrylate), styrene derivative (styrene for example, to hydroxymethyl styrene with to methoxy styrene), vinyl ether (methyl vinyl ether for example, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether and hydroxybutyl vinyl ether), vinyl esters (vinyl acetate for example, propionate and vinyl cinnamate), unsaturated carboxylic acid (acrylic acid for example, methacrylic acid, crotonic acid, maleic acid and itaconic acid), acrylic amide (N for example, the N-DMAA, N tert butyl acrylamide and N-cyclohexyl acrylamide) and Methacrylamide (N, N-dimethylmethacryl amide) and vinyl cyanide.
As the preferred form that is used for multipolymer of the present invention, can mention the form of following formula (1):
In formula (1), the L representative has the linking group of 1-10 carbon atom; M represents 0 or 1; X represents halogen atom or methyl; The A representative derives from the repetitive of the vinyl monomer that provides, and can comprise one-component or various ingredients; And x, y and z represent its molar percentage of constituent separately, and these values satisfy 30≤x≤60,5≤y≤70 and 0≤z≤65 respectively.
In formula (1), the L representative has the linking group of 1-10 carbon atom, and the linking group that more preferably has 1-6 carbon atom, the linking group that especially preferably has 2-4 carbon atom, it can have the straight or branched structure, maybe can have ring structure, and can have the heteroatoms that is selected from O, N and S.
Its preferred embodiment can comprise:
*-(CH
2)
2-O-
*,
*-(CH
2)
2-NH-
*,
*-(CH
2)
4-O-
*,
*-(CH
2)
6-O-
*,
*-(CH
2)
2-O-(CH
2)
2-O-
*,
*-CONH-(CH
2)
3-O-
*,
*-CH
2CH (OH) CH
2-O-
*With
*-CH
2CH
2OCONH (CH
2)
3-O-
*(
*Representative is at the link position of main polymer chain side,
*Representative is at the link position of (methyl) acryloyl group side).M represents 0 or 1.
In formula (1), X represents hydrogen atom or methyl.From more preferably hydrogen atom of the angle of solidification reactivity.
In formula (1), A representative derives from the repetitive of the vinyl monomer that provides, and has no particular limits, if it be can with the constituent of the monomer of hexafluoropropylene copolymerization.It can suitably be selected from comprising with the viscosity of base-material, the Tg of polymkeric substance (favourable to film hardness), the different angles of solubleness, transparency, sliding and dustproof and antifouling property solvent.It can comprise single ethylene base monomer or multiple vinyl monomer according to required purpose.
Its preferred embodiment can comprise: vinyl ether is methyl vinyl ether, ethyl vinyl ether, tert-Butyl vinyl ether, cyclohexyl vinyl ether, isopropyl-ethylene base ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether and allyl vinyl ether for example; Vinyl esters is vinyl acetate, propionate and vinyl butyrate for example; Methacrylate is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) Hydroxyethyl Acrylate, glycidyl methacrylate, (methyl) allyl acrylate and (methyl) acryloxy propyl trimethoxy monosilane for example; Styrene derivative is styrene and to hydroxymethyl styrene for example; With unsaturated carboxylic acid for example crotonic acid, maleic acid and itaconic acid, and derivant.More preferably vinyl ether derivant and vinyl esters derivant, special preferred vinyl ether derivant.
X, y and z represent its molar percentage of constituent separately, and the value of 30≤x≤60,5≤y≤70 and 0≤z≤65 is satisfied in representative respectively.The situation of preferred 35≤x≤55,30≤y≤60 and 0≤z≤20.The situation of preferred especially 40≤x≤55,40≤y≤55 and 0≤z≤10.
As the particularly preferred form that is used for multipolymer of the present invention, can mention the form of following formula (2):
In formula (2), identical with described in the formula (1) of X, x and y; The B representative derives from the repetitive of the vinyl monomer that provides, and can comprise one-component or various ingredients; Z1 and z2 represent its molar percentage of constituent separately, and the value of 0≤z1≤65 and 0≤z2≤65 is satisfied in representative respectively; The integer of 2≤n≤10 is satisfied in the n representative.
In formula (2), identical those in X, x and y representative and the formula (1), and its preferable range is also identical respectively.
The integer of 2≤n≤10 is satisfied in the n representative.Preferred 2≤n≤6, preferred especially 2≤n≤4.
The B representative derives from the repetitive of the vinyl monomer that provides, and can comprise one-component or various ingredients.The example is enumerated corresponding to A in the formula (1).
Z1 and Z2 represent its molar percentage of constituent separately, and the value of 0≤z1≤65 and 0≤z2≤65 is satisfied in representative respectively.Their preferred respectively satisfied 0≤z1≤30 and 0≤z2≤10, preferred especially 0≤z1≤10 and 0≤z2≤5.
The multipolymer of formula (1) or (2) representative for example can join (methyl) acryloyl group in the multipolymer that comprises hexafluoropropylene component and hydroxy alkyl vinyl ether component synthetic by above-mentioned arbitrary method.
Shown the non-limiting preferred embodiment that can be used for multipolymer of the present invention below.
x y m L1 X
P-1 50 0 1 *-CH
2CH
2O-** H
P-2 50 0 1 *-CH
2CH
2O-** CH
3
P-3 45 5 1 *-CH
2CH
2O-** H
P-4 40 10 1 *-CH
2CH
2O-** H
P-5 30 20 1 *-CH
2CH
2O-** H
P-6 20 30 1 *-CH
2CH
2O-** H
P-7 50 0 0 —— H
P-8 50 0 1 *-C
4H
8O-** H
P-9 50 0 1
H
P-10 50 0 1
H
*Representation polymer main chain side,
*Representative (methyl) acryloyl group side
x y m L1 X
P-11 50 0 1 *-CH
2CH
2NH-** H
P-12 50 0 1
H
P-13 50 0 1
CH
3
P-14 50 0 1
CH
3
P-15 50 0 1
H
P-16 50 0 1
H
P-17 50 0 1
H
P-18 50 0 1
CH
3
P-19 50 0 1
CH
3
P-20 40 10 1 *-CH
2CH
2O-** CH
3
*Representation polymer main chain side,
*Representative (methyl) acryloyl group side
a b c L1 A
P-21 55 45 0 *-CH
2CH
2O-** -
P-22 45 55 0 *-CH
2CH
2O-** -
P-23 50 45 5
P-24 50 45 5
P-25 50 45 5
P-26 50 40 10 *-CH
2CH
2O-**
P-27 50 40 10 *-CH
2CH
2O-**
P-28 50 40 l0 *-CH
2CH
2O-**
*Representation polymer main chain side,
*Representative (methyl) acryloyl group side
x y Z1 Z2 n X B
P-29 50 40 5 5 2 H
P-30 50 35 5 10 2 H
P-31 40 40 10 10 4 CH
3
a b Y Z
P-32 45 5
P-33 40 10
x y z Rf L
P-34 60 40 0 -CH
2CH
2C
8F
17-n -CH
2CH
2O-
P-35 60 30 10 -CH
2CH
2C
4F
8H-n -CH
2CH
2O-
P-36 40 60 0 -CH
2CH
2C
6F
12H -CH
2CH
2CH
2CH
2O-
x y z n Rf
P-37 50 50 0 2 -CH
2C
4F
8H-n
P-38 40 55 5 2 -CH
2C
4F
8H-n
P-39 30 70 0 4 -CH
2C
8F
17-n
P-40 60 40 0 2 -CH
2CH
2C
8F
16H-n
Being used for the synthetic of multipolymer of the present invention can carry out in the following manner.With synthetic precursor of following various polymerization solution polymerizations, precipitation polymerization, suspension polymerization, bulk polymerization and emulsion polymerization such as hydroxyl polymer-containing.Then, by polyreaction to wherein adding (methyl) acryloyl group.This polyreaction can be known intermittence, operation semicontinuous, continuous and other type carry out.
The method of initiated polymerization comprises the method for using radical initiator, the method for utilizing light or radiation and other method.The method of these polymerizations and initiated polymerization for example is described in Teiji Tsuruta,
Polymer Synthesis Method(
KOUBUNSHI GOSEI HOUHOU), revised edition, (by The Nikkan Kogyo Shimbun, Ltd. publishes, 1971) and
Experiment Method of Polymer Synthesis(
KOUBUNSHI GOUSEI NO JIKKEN HOUHOU), write by Takayuki Ootsu and MasaetsuKinoshita, by Kagaku-Dojin Publishing Company, INC. publishes, and 1972, the 124-154 page or leaf.
In above-mentioned polymerization, especially preferably use the solution polymerization process of radical initiator.The example that is used for the solvent of solution polymerization process can comprise: various organic solvents are ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, diox, N for example, dinethylformamide, N, N-dimethyl acetamide, benzene, toluene, acetonitrile, methylene chloride, chloroform, ethylene dichloride, methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol and 1-butanols, they can use separately or two or more mix use, perhaps can also use with mixed solvent with water.
Need to adjust polymerization temperature according to the molecular weight of final polymkeric substance, the kind of initiating agent etc.It can be 0 ℃ or more be low to moderate 100 ℃ or higher.Yet polyreaction is preferably carried out under the temperature in 50-100 ℃ scope.
Suitable choice reaction pressure.It is 1-100kg/cm normally
2, especially preferably about 1-30kg/cm
2Reaction time is about 5-30 hour.
The solvent that is used for resulting polymers precipitation is isopropyl alcohol, hexane, methyl alcohol etc. preferably.
The composition of formation low-index layer of the present invention presents liquid form usually, and contains this multipolymer as necessary constituent.If necessary, it is made by various adjuvants and radical polymerization initiator are dissolved in the appropriate solvent.In this step, the concentration of solids content thing is suitably selected according to required purpose.Normally about 0.01-60 weight %, preferred 0.5-50 weight %, preferred especially about 1 weight %-20 weight %.
As mentioned above, from the angle of the film hardness of low-index layer, for example rigidizer is not necessarily useful to add adjuvant.Yet, from with angle and other angle of the interfacial viscosity of high refractive index layer, also can add rigidizer for example multi-functional (methyl) acrylate compounds, polyfunctional epoxy compound, polyisocyanate compounds, amino plastics or polyprotonic acid or its acid anhydrides, fine inorganic particles such as perhaps a small amount of silicon dioxide.When adding them, based on the total solids content of low-refraction tunic, they with preferred in the scope of 0-30 weight %, more preferably 0-20 weight %, the amount adding of preferred especially 0-10 weight %.
Yet,, also can suitably add known silicone or fluorine-containing anti fouling agent, the lubricant etc. of containing in order to give such as features such as antifouling property, water proofing property, chemical resistance and slidings.When adding these adjuvants, based on the total solids content of low-index layer, they preferably add with the amount in the scope of 0-20 weight %, and more preferably with in the scope of 0-10 weight %, the amount of preferred especially 0-5 weight % adds.
Radical initiator can present by heat effect and produces the form of free radical or produce the form of free radical by light action.
Compound as cause free radical polymerization by heat effect can use organic or inorganic superoxide, organic azo and diazo-compounds etc.
Particularly, can mention: organic peroxide is for example hydrogen peroxide, ammonium persulfate and potassium persulfate of benzoyl peroxide, peroxidating halobenzene formyl, lauroyl peroxide, acetyl peroxide, dibutyl superoxide, cumene hydroperoxide and butyl hydroperoxides, inorganic peroxide for example; Azo-compound is for example diazo aminobenzene and p-nitrophenyl diazonium etc. of 2-azo-two-isobutyronotrile, 2-azo-two-propionitrile and 2-azo-two-adiponitrile, diazo-compounds for example.
When use causes the compound of free radical polymerization by light action, can carry out the curing of film by radiation exposure by active.
The example of this radical photopolymerization initiating agent can comprise: acetophenones, benzoin class, benzophenone, phosphinoxides, ketal class, anthraquinone class, thioxanthene ketone, azo-compound, superoxide, 2,3-dialkyl group dione compounds, di-sulphide compounds, fluorine amines and fragrant sulfonium.The example of acetophenone can comprise: 2, and 2-diethoxy acetophenone, to dimethyl acetophenone, 1-hydroxyl 3,5-dimethylphenyl ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-4-methyl mercapto-2-morpholine and propiophenone and 2-benzyl-2-dimethylamino-1-(4-morpholine and phenyl)-butanone.The example of benzoin class can comprise: benzoin benzene sulfonate, benzoin tosylate, benzoin methyl ether, benzoin ethylether and benzoin isopropyl ether.The example of benzophenone can comprise: benzophenone, 2,4-dichloro benzophenone, 4,4-dichloro benzophenone and to chlorobenzophenone.The example of phosphinoxides can comprise 2,4,6-trimethylbenzoyl diphenyl phosphine oxide.Also can preferably use sensitizing dye with these radical polymerization initiators.
Only the addition that causes the compound of free radical polymerization by heat or light action be can cause the carbon-to-carbon double bond polymerization amount this be necessary.In general, based on the total solids content of the composition that forms low-index layer, this measures preferably 0.1-15 weight %, more preferably 0.5-10 weight %, especially preferably 2-5 weight %.
Contained solvent has no particular limits in the low-index layer coating fluid composition, as long as it can dissolve or disperse wherein to contain the composition of fluorinated copolymer equably, can not cause precipitation.Also multiple solvent can be used.Its preferred embodiment can comprise: ketone (for example acetone, methyl ethyl ketone and methyl isobutyl ketone), ester class (for example ethyl acetate and butyl acetate), ethers (for example tetrahydrofuran and 1,4-diox), alcohols (for example methyl alcohol, ethanol, isopropyl alcohol, butanols and ethylene glycol), arene (for example toluene and dimethylbenzene) and water.
Low-index layer can also contain filler (for example, fine inorganic particle and organic particulate), silane coupling agent, lubricant (silicone compounds is dimethyl silicone etc. for example), surfactant etc. except containing fluorochemicals.Particularly, preferably contain fine inorganic particle, silane coupling agent and lubricant.
Fine inorganic particle is silicon dioxide (silica) particulate, fluorine-containing particle (magnesium fluoride, potassium fluoride and barium fluoride particle) etc. preferably.Preferred especially silicon dioxide (silica) particulate.The weight average particle diameter of the primary particle of these fine inorganic particles is 1-150nm preferably, more preferably 1-100nm, most preferably 1-80nm.These fine inorganic particles are dispersed in the outermost layer preferably thinlyyer.The shape of fine inorganic particle is grain of rice shape, spherical, cubic, spindle shape, staple fiber shape, ring-type or indefinite shape preferably.
Can use compound and/or its derivative compound of formula A representative as silane coupling agent.It is the silane coupling agent of hydroxyl, sulfydryl, carboxyl, epoxy radicals, alkyl, alkoxysilyl, acyloxy or acyl amino preferably.The silane coupling agent that especially preferably contains epoxy radicals, polymerisable acyloxy ((methyl) acryloxy) or polymerisable acyl amino (acryloyl group amino or methacryl amino).
The compound of formula A representative especially preferably has the compound of (methyl) acryloyl group as crosslinkable or polymerisable functional group.The example can comprise: 3-acryloxy propyl trimethoxy monosilane and 3-methacryloxypropyl trimethoxy monosilane.
Lubricant is dimethyl silicone and have a fluorochemicals that wherein adds polysiloxane segment preferably.
Low-index layer preferably forms in the following manner.The coating composition of fluorochemicals and other given component (if necessary) that contains is wherein dissolved or disperses in coating.In coating or after coating, carry out cross-linking reaction or polyreaction by the irradiation of rayed, electron beam or by heating.
Particularly when the cross-linking reaction of the compound that solidifies by ionization radiation or polyreaction form low-index layer, cross-linking reaction or polyreaction are to carry out in 10 volume % or the lower environment at oxygen concentration preferably.By being to form low-index layer in 10 volume % or the lower environment at oxygen concentration, can obtain the outermost layer of physical strength and chemical resistance excellence.
Oxygen concentration is 6 volume % or lower preferably, and oxygen concentration is 4 volume % or lower preferably also, and oxygen concentration especially preferably 2 volume % or lower, most preferably 1 volume % or lower.
Oxygen concentration preferably is adjusted to 10 volume % or lower in the following manner.Preferably replace air (nitrogen gas concn: about 79 volume %, oxygen concentration: about 21 volume %), especially preferably use nitrogen (using nitrogen wash) to replace with another gas.
[hard conating]
The hard conating of antireflection film of the present invention is provided on the surface of transparent support so that give the antireflection film physical strength.Particularly, preferably it is provided between transparent support and the high refractive index layer.
The cross-linking reaction or the polyreaction of the compound that hard conating preferably solidifies by ionization radiation form.For example, it can contain the multifunctional monomer of ionization radiation curing and the coating composition of multi-functional oligomer by coating on transparent support, and carries out the cross-linking reaction or the polyreaction formation of multifunctional monomer and multi-functional oligomer.
The multifunctional monomer that ionization radiation solidifies and the functional group of multi-functional oligomer preferably light-, electron beam or the polymerisable functional group of radiation.Wherein, the functional group of preferred photopolymerization.
As the functional group of photopolymerization, can mention undersaturated polymerisable functional group for example (methyl) acryloyl group, vinyl, styryl and allyl etc.Wherein, preferred (methyl) acryloyl group.
The instantiation of multifunctional monomer of photopolymerization with functional group of photopolymerization can comprise those that high refractive index layer is enumerated, and they preferably use Photoepolymerizationinitiater initiater and photosensitizer polymerization.Photopolymerization reaction is preferably undertaken by the ultraviolet ray irradiation after coating and dry hard conating.
In order to give its physical strength, preferably adding mean grain size in hard conating is the fine inorganic particle of 0.001-0.1 μ m.
The instantiation of fine inorganic particle can comprise the particle of silicon dioxide, titania, zirconia, aluminium oxide, tin oxide, ITO, zinc paste and lime carbonate.More little with the difference of the refractive index of bonding agent, light scattering reduces big more.For this reason, preferably use silicon dioxide or aluminium oxide.
The preferably about 5-50 weight of the addition of fine inorganic particle %.When this amount is too big, the brittleness deficiency.Yet, when this amount too hour, add the effect deficiency of fine inorganic particle.
In order to give its brittleness, preferably in this hard conating, add weight-average molecular weight and be 500 or bigger oligomer and/or polymkeric substance according to required purpose.
As oligomer and polymkeric substance, can mention (methyl) acrylic ester type, cellulose type and styrene type polymer, urethanes acrylate, polyester acrylate etc.Preferably, can mention poly-((methyl) glycidyl acrylate) and ((methyl) allyl acrylate) that have functional group at side chain, or the like.
Based on the general assembly (TW) of hard conating, oligomer and/or the polymkeric substance content in hard conating is 5-50 weight % preferably, more preferably 15-40 weight %, especially preferably 20-30 weight %.
As mentioned above, high refractive index layer also can be used as hard conating.When high refractive index layer also was used as hard conating, this layer preferably was finely dispersed in the hard conating by the fine inorganic particle of the technology described in the high refractive index layer with high index of refraction, particulate is contained in wherein forms.
The particle that also can to make hard conating also contain following described mean grain size be 0.2-10 μ m is thus also as the anti-dazzle photosphere that obtains the anti-dazzle function.
The thickness of hard conating can suitably design according to required purpose.The thickness of hard conating is 0.2-10 μ m preferably, more preferably 1-9 μ m, especially preferably 5-8 μ m.
In the pencil hardness test according to JIS K5400, the intensity of hard conating is H or bigger preferably, more preferably 2H or bigger, most preferably 3H or bigger.
Yet, according to JIS K5400 the Taber coomb's test Coomb, preferably this test before and the test film wear extent is less afterwards.
As for the formation of hard conating, when the cross-linking reaction of the compound that solidifies by ionization radiation or polyreaction formed, this cross-linking reaction or polyreaction were to carry out in 10 volume % or the lower environment at oxygen concentration preferably.By being to form this layer in 10 volume % or the lower environment at oxygen concentration, can form the hard conating of physical strength and chemical resistance excellence.
In preferred oxygen concentration is 6 volume % or lower, more preferably oxygen concentration is 4 volume % or lower, special preferred oxygen concentration is 2 volume % or lower, and most preferably the cross-linking reaction or the polyreaction of the compound that solidifies by ionization radiation in 1 volume % or the lower environment form this layer.
Oxygen concentration is adjusted to 10 volume % or lower in the following manner.Preferably replace air (nitrogen gas concn: about 79 volume %, oxygen concentration: about 21 volume %), especially preferably use nitrogen (using nitrogen wash) to replace with another gas.
Preferably coating forms the coating composition formation hard conating that hard conating is used on the surface of transparent support.
The ketones solvent that coating solvent is preferably enumerated high refractive index layer.By using ketones solvent, the surface of transparent support (particularly, tri acetyl cellulose support) and the viscosity between the hard conating further improve.
Particularly preferred coating solvent is methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
Coating solvent can contain the solvent except the cited ketones solvent of high refractive index layer.
In coating solvent, based on the total amount of solvent contained in the coating composition, the content of ketones solvent is 10 weight % or bigger preferably.Preferred 30 weight % or bigger, more preferably 60 weight % or bigger.
[surface irregularity of antireflection film]
Be used for antireflection film of the present invention and also can have the scrambling that on surface, forms, thereby obtain the anti-dazzle performance with high refractive index layer side.
Anti-dazzle photosensitiveness is relevant with average surface roughness (Ra).The scrambling on surface is preferably worked as from 100-cm
2Take out 1-mm in the area at random
2During area, average surface roughness (Ra) is preferred 0.01-0.4 μ m, more preferably 0.03-0.3 μ m, more preferably 0.05-0.25 μ m, especially preferably 0.07-0.2 μ m/1-mm
2The surface area that takes out.
Average surface roughness (Ra) is described in
TECHNO COMPACT SERIES (6)(
Measurement/Evaluation Method of Surface Roughness(
HYOUMEN ARASANO SKUTEI HYOUKAHOU), the author; JIROU NARA, publisher; Sougou Gijyutu Center Co., Ltd.).
Can estimate the shape of the scrambling on the surface be used for antireflection film of the present invention by atomic force microscope (AFM).
As the method that forms this surperficial scrambling, can use known method.In the present invention, preferred under high pressure have the method (for example, embossing) of erose plate formation scrambling and make the random layer of antireflection film contain the method that forms scrambling as the particle of anti-dazzle photosphere thus on the surface of antireflection film in the film surface pressure.
For form the method for scrambling on the surface by embossing, can use already known processes.Yet, especially preferably form scrambling by the technology described in the JP-A-2000-329905.
When the random layer that makes antireflection film contained the particle that forms anti-dazzle photosphere, the particle that is used for anti-dazzle photosphere preferably mean grain size was the particle of 0.2-10 μ m.Mean grain size as herein described is the weight average particle diameter of secondary (primary particle that particle does not flocculate).
As these particles, can mention inorganic particle and organic granular.The instantiation of inorganic particle can comprise the particle of silicon dioxide, titania, zirconia, aluminium oxide, tin oxide, ITO, zinc paste, lime carbonate, barium sulphate, talcum, porcelain earth, calcium sulphate etc.Preferred silicon dioxide and aluminium oxide.
Organic granular is resin particle preferably.The instantiation of resin particle can comprise the particle that is made by silicones, melamine resin, benzoguanamine resin, plexiglass, polystyrene resin and poly-difluoroethylene.The preferred particle that makes by melamine resin, benzoguanamine resin, plexiglass and polystyrene resin.The preferred especially particle that makes by plexiglass, benzoguanamine resin and polystyrene resin.
In order to form scrambling, the particle that is used for anti-dazzle photosphere is resin particle preferably.
The mean grain size of particle is 0.5-7.0 μ m preferably, more preferably 1.0-5.0 μ m, especially preferably 1.5-4.0 μ m.
The refractive index of particle is 1.35-1.80 preferably, more preferably 1.40-1.75, more preferably 1.45-1.75.
Preferably has particle than small particle size distribution.Below equation represented the S value of particle grain size distribution to indicate, and preferred 2 or littler, more preferably 1.0 or littler, preferred especially 0.7 or littler.
S＝[S(0.9)-D(0.1)]/D(0.5)
D (0.1): 10% equivalent particle size of the integrated value of volume equivalent particle size;
D (0.5): 50% equivalent particle size of the integrated value of volume equivalent particle size; With
D (0.9): 90% equivalent particle size of the integrated value of volume equivalent particle size.
Yet the refractive index of particle has no particular limits.Yet preferred, roughly the refractive index with anti-dazzle photosphere identical (difference of refractive index is in 0.005) perhaps differs 0.02 or bigger.
By the refractive index of rough balance granules and the refractive index of anti-dazzle photosphere, the contrast that makes antireflection film be installed on the visual display surface improves.
The difference of the refractive index by causing particle and the refractive index of anti-dazzle photosphere makes that the visibility (for example dazzle defective or viewing angle characteristic) when antireflection film is installed in the liquid crystal indicator surface improves.
When producing difference between the refractive index of the refractive index of particle and anti-dazzle photosphere, it is 0.03-0.5 preferably, more preferably 0.03-0.4, preferred especially 0.05-0.3.
Can contain the particle of giving anti-dazzle photosensitiveness in the random layer that in antireflection film, forms.These particles preferably join in hard conating, low-index layer or the high refractive index layer, preferred especially hard conating or high refractive index layer.Also these particles can be joined in the multilayer.
[other layer of antireflection film]
In order to prepare antireflection film with more excellent antireflection property, preferably provide refractive index at high refractive index layer refractive index and the intermediate-index layer between the refractive index of transparent support.
Intermediate-index layer is preferably to prepare with the described identical mode of high refractive index layer of the present invention.Can adjust refractive index by the content of fine inorganic particle in the controlling diaphragm.
In antireflection film, also can provide the layer except that aforementioned layers.For example, also can provide bonding coat, screen layer, sliding layer and antistatic backing.Provide screen layer with shielding electromagnetic wave or infrared ray.
Yet, when being installed in this antireflection film on the liquid crystal indicator,, can forming again and wherein add the internal coating that mean grain size is the particle of 0.1-10 μ m in order to improve the purpose of viewing angle characteristic, perhaps these particles are joined in the hard conating, be the light scattering hard conating thus.The mean grain size of particle is 0.2-5.0 μ m preferably, more preferably 0.3-4.0 μ m, especially preferably 0.5-3.5 μ m.
The refractive index of particle is 1.35-1.80 preferably, more preferably 1.40-1.75, preferred once more 1.45-1.75.
Preferably than the particle of small particle size distribution.Above-mentioned equation has been represented the S value indication of particle grain size distribution, and preferred 1.5 or littler, and more preferably 1.0 or littler, preferred especially 0.7 or littler.
Yet, the difference of the refractive index between particle and internal coating preferably 0.02 or bigger.More preferably, refractive index difference is 0.03-0.5, and more preferably refractive index difference is 0.05-0.4, and is preferred especially, and refractive index difference is 0.07-0.3.
As joining internally coated particle, can mention described inorganic particle of anti-dazzle photosphere and organic granular.
Preferably between hard conating and transparent support, form internal coating.And it also can be used as hard conating.
When the particle that with mean grain size is 0.1-10 μ m joined internal coating, internally coated muddiness is 3-60% preferably.Be more preferably 5-50%, 7-45% preferably once more, preferred especially 10-40%.
[the formation method of antireflection film etc.]
Each layer of antireflection film can for example metal bar rubbing method, intaglio plate rubbing method, nick version rubbing method or mould be coated with method formation by coating process.From the angle of the minimum dampness elimination amount of being coated with, preferred little intagliotype and intagliotype, and eliminate the drying mark degree thus.From being coated with the film thickness homogeneity and the inhomogeneity angle of film thickness along its length of the long-time interior broad ways in back, particularly preferably be the forward intagliotype, wherein support evenly is clipped between plate cylinder and the impression cylinder; Perhaps reverse little intagliotype, it is configured such that the unlikely broad ways of coating fluid scraping pressure and the length direction fluctuation of blade.From the angle of the processing cost of the two-layer at least antireflection film by the single step of feeding in raw material, forming blooming separately and roll film of support film being formed a plurality of bloomings of the present invention, it is preferred.When antireflection film is three-decker, more preferably form three layers with one step.This job operation can be coated with stop by providing, and dry and curing area many groups are provided with and realize, and the quantity of these numbers organized and the blooming of connecting as many more, and perhaps the quantity than blooming is many.
Fig. 2 has shown an example of device configurations.Fig. 2 has shown such example: what comprise the zone of the coiler (112) from feeder (101) to the coiling film of finishing a process that is fed between rolling first is coated with stop (102), first dry section (103), the first ultraviolet irradiation apparatus (104), second is coated with stop (105), second dry section (106), the second ultraviolet irradiation apparatus (107), the 3rd is coated with stop (108), the 3rd dry section (109), the 3rd ultraviolet irradiation apparatus (110) and back dry section (111).In a process, can form functional layer intermediate-index layer, high refractive index layer and low-index layer three layers for example like this up to three layers, hard conating, high refractive index layer and low-index layer three layers, perhaps three layers of hard conating, anti-dazzle photosphere and low-index layer.As other preferred form, can mention the form that adopts following job operation: a kind of method, wherein, if necessary, adopt and a plurality ofly to be coated with the equipment that stop is reduced to two and to construct, in a process, only form the two-layer of intermediate-index layer and high refractive index layer, and the testing result of feedback surface situation, thickness etc. perhaps comprises the two-layer anti-dazzle antireflection film of anti-dazzle photosphere and low-index layer to improve productive rate with the low cost manufacturing; And other method, wherein adopt quantity to increase to 4 equipment structure, in a process, form hard conating, intermediate-index layer, high refractive index layer and low-index layer, make the coating cost reduce greatly.Yet when thermosets was used as primary raw material, back dry section (111) also was used for promoting to solidify, and it does not need when using the curable resin of ionising radiation as primary raw material.
[surface of antireflection film]
In the present invention, with regard to antireflection film, in order to improve physical strength (for example wearing quality), at the kinetic friction coefficient on surface preferably 0.25 or littler with high refractive index layer side.The kinetic friction coefficient of this paper be meant when diameter be that the rigidity stainless steel ball of 5mm is along having under the load of surface at 0.98N of high refractive index layer side the kinetic friction coefficient that has when speed with 60cm/min moves between the surface of high refractive index layer side and the rigidity stainless steel ball that diameter is 5mm.It is preferably 0.17 or littler, preferred especially 0.15 or littler years old.
Yet, with regard to this antireflection film, in order to improve antifouling property, preferably 90 ° or bigger of the contact angles of surface with high refractive index layer side and water, more preferably 95 ° or bigger, preferred especially 100 ° or bigger.
When antireflection film did not have the anti-dazzle function, preferred muddiness was lower.
When antireflection film has the anti-dazzle function, its muddy preferred 0.5-50%, more preferably 1-40%, most preferably 1-30%.
[structure of antireflection film]
An example of the structure of antireflection film of the present invention is described with reference to the accompanying drawings.
Fig. 1 is layer sectional view of constructing with antireflection film of excellent antireflection property.This antireflection film has the layer structure of transparent support 1, hard conating 2, intermediate-index layer 3, high refractive index layer 4 and low-index layer (outermost layer) 5 successively.Transparent support 1, intermediate-index layer 3, high refractive index layer 4 and low-index layer 5 have the refractive index that satisfies following relation separately.
The refractive index of the refractive index＞low-index layer of the refractive index＞transparent support of the refractive index＞intermediate-index layer of high refractive index layer
With regard to layer structure shown in Figure 1, described in JP-A-59-50401, preferred intermediate-index layer, high refractive index layer and low-index layer satisfy following mathematic(al) representation (I), mathematic(al) representation (II) and mathematic(al) representation (III) respectively, thereby can prepare the antireflection film with more excellent antireflection property.
Mathematic(al) representation (I):
(hλ/4)×0.7＜n
3d
3＜(hλ/4)×1.3
In mathematic(al) representation (I), h is positive integer (normally 1,2 or 3), n
3Be the refractive index of intermediate-index layer, d
3It is the bed thickness (nm) of intermediate-index layer.λ is wavelength of visible light (nm), and is the value in the scope of 380-680nm.Mathematic(al) representation (II):
(iλ/4)×0.7＜n
4d
4＜(iλ/4)×1.3
In mathematic(al) representation (II), i is positive integer (normally 1,2 or 3), n
4Be the refractive index of high refractive index layer, d
4It is the bed thickness (nm) of high refractive index layer.λ is wavelength of visible light (nm), and is the value in the scope of 380-680nm.Mathematic(al) representation (III):
(jλ/4)×0.7＜n
5d
5＜(jλ/4)×1.3
In mathematic(al) representation (III), j is positive odd number (normally 1), n
5Be the refractive index of low-index layer, d
5It is the bed thickness (nm) of low-index layer.λ is wavelength of visible light (nm), and is the value in the scope of 380-680nm.
With regard to layer structure shown in Figure 1, preferred especially intermediate-index layer, high refractive index layer and low-index layer satisfy following mathematic(al) representation (IV), mathematic(al) representation (V) and mathematic(al) representation (VI) separately.
Wherein, λ is 500nm, and h is 1, and j is 1.
Mathematic(al) representation (IV):
(hλ/4)×0.80＜n
3d
3＜(hλ/4)×1.00
Mathematic(al) representation (V):
(iλ/4)×0.75＜n
4d
4＜(iλ/4)×0.95
Mathematic(al) representation (VI):
(jλ/4)×0.95＜n
5d
5＜(jλ/4)×1.05
Thereby preferably making hard conating, intermediate-index layer and high refractive index layer contain mean grain size is the antireflection film that the particle preparation of 0.2-10 μ m has the anti-dazzle function.
[diaphragm of polaroid]
In order to form polaroid of the present invention; so that use the surface protection film (diaphragm of polaroid) of antireflection film as polarizing coating; must be by making the surface of the transparent support relative with having the anti-reflection structure side, the surface hydrophilic of the side that promptly links to each other with polarizing coating improves the viscosity of adhesive surface.
As the transparent support of antireflection film, especially preferably use the tri acetyl cellulose film.
As the technology of the diaphragm for preparing polaroid of the present invention, can design following two kinds of technologies: (1) is coated with the technology of each layer (for example, high refractive index layer, hard conating and outermost layer) on the one side of the transparent support that saponification was in advance handled; (2) coating each layer (for example, high refractive index layer, hard conating and outermost layer) on the one side of transparent support, the face that will link to each other with polarizing coating stands the technology that saponification is handled then.Technology (1) wherein, even it is also hydrophilic to be coated with the face of hard conating.Make like this and be difficult to guarantee viscosity between support and the hard conating.For this reason, selection process (2).
[saponification processing]
(1) infusion process
Infusion process is a kind ofly under proper condition antireflection film to be immersed in the aqueous slkali, makes that whole surface and the alkali at film has the method that reactive all faces are handled through saponification.This method does not need particular device, and therefore the angle from cost is preferred.Aqueous slkali is sodium hydrate aqueous solution preferably.Concentration is 0.5-3mol/l preferably, preferred especially 1-2mol/l.Preferably 30-70 ℃ of the solution temperature of aqueous slkali, preferred 40-60 ℃ especially.
The combination of saponification condition is the combination of temperate condition relatively preferably.Yet, can adjust according to the structure and the target contact angle of material and antireflection film.
After film was flooded in aqueous slkali, preferred, the film water fully washed or floods with the neutralization bases component in diluted acid, makes and no longer leave alkaline constituents in film.
Handle the surface hydrophilic that makes with surperficial relative transparent support with anti-reflection layer by saponification.The diaphragm of polaroid uses in such a way, and the water-wetted surface and the polarizing coating of transparent support are bonding.
This water-wetted surface improves effectively and contains the viscosity of polyvinyl alcohol (PVA) as the bonding coat of principal ingredient.
With regard to saponification is handled, from the angle of the viscosity of polarizing coating, preferably the contact angle of the surface of the transparent support relative with having the high refractive index layer side and water is lower.On the other hand, use infusion process, the surface with high refractive index layer is destroyed by alkali simultaneously, and it is important therefore adjusting required minimal reaction condition.Surface when the transparent support relative with having the anti-reflection structure side; it is the adhesive surface of antireflection film; during the index of the destruction of being caused by alkali as anti-reflection layer with the contact angle of water; this contact angle is 20 degree-50 degree; preferred 30 degree-50 degree; more preferably 40 degree-50 degree are under the situation about being made by tri acetyl cellulose at support particularly.Not preferred 50 degree or bigger contact angles, this is because it brings the problem bonding with polarizing coating.On the other hand, preferably less than the contact angle of 20 degree, this is not because it causes too havoc to antireflection film, causes physical strength and photostability impaired.
(2) aqueous slkali rubbing method
As avoiding the front infusion process to destroy the method for antireflection film, preferred only use under proper condition with the surperficial facing surfaces with antireflection film on be coated with aqueous slkali, then heating washes with water and dry aqueous slkali rubbing method.Incidentally, coating in this case only is meant the operation that the face handled through saponification and aqueous slkali etc. contact.In this step,, preferably carry out saponification and handle that to make the adhesive surface of antireflection film and the contact angle of water be the 10-50 degree.Except coating, this method also comprises spraying, the operation that should the surface contacts with the band that contains solution etc., perhaps other operation.Adopt this method, need the miscellaneous equipment and the step of coating aqueous slkali.For this reason, from the angle of cost, this method is not as infusion process (1).On the other hand, because aqueous slkali only contacts with the face of handling through saponification, can have the layer of use to the material of aqueous slkali sensitivity with its facing surfaces.For example, deposited film or sol gel film are subjected to for example burn into dissolving or peel off of various influences through aqueous slkali, therefore adopt infusion process, and it is unfavorable that this film is provided.Yet, adopting this rubbing method, film does not contact with solution, therefore can use without any problem ground.
Any can carry out method for saponification (1) and (2) after the debatching film from roller shape support, and forms layer separately, is therefore also undertaken by the operation of another series after the antireflection film procedure of processing in front.And, same, by carrying out continuously and will comprising the polaroid-bindnig step together of debatching support, can more effectively form polaroid for basic same steps as than each sheet.
[polaroid]
Preferred polaroid of the present invention has antireflection film of the present invention at least one diaphragm (diaphragm of polaroid) as polarizing coating.With regard to the diaphragm of polaroid, as mentioned above, the surface of the transparent support relative with having the high refractive index layer side, the surface on the side that promptly links to each other with polarizing coating is preferably spent in the scope of-50 degree 20 with the contact angle of water.
The antireflection film of the application of the invention can prepare the polaroid with excellent mechanical strength and photostability and anti-reflective function as the diaphragm of polaroid.Can reduce cost and reduce the thickness of display so greatly.
Yet; the antireflection film of the application of the invention is as a diaphragm of polaroid; and use has the described optically anisotropic optical compensation films in back another diaphragm as polarizing coating; the preparation polaroid; can also prepare and to improve the contrast of liquid crystal indicator in bright chamber, and enlarge the polaroid at vertical and horizontal visual angle greatly.
[optical compensating layer]
Polaroid of the present invention can with the surface that provides antireflection film as the relative polarizing coating of the face of surface protection film on provide the film with optical compensating layer, i.e. an optical compensation films.
By using the polaroid that provides film on it to be used for liquid crystal indicator, can improve the viewing angle characteristic of liquid crystal indicator screen with optical compensating layer (phase separation layer).
As optical compensating layer, can use known.Yet, the preferred use has the optical compensating layer that comprises tool disk-shaped structure unit and have the layer of optically anisotropic compound, be characterised in that the surface inwardly changes the angle that forms along thickness direction from optical compensation films between dish type compound and optical compensation face, described in JP-A-2001-100042.
This angle is preferably with increasing with distance on the surface of the optical compensation films of the side that links to each other with polarizing coating.
When using this optical compensation films, preferred through the saponification processing on the surface of the side that links to each other with polarizing coating as the diaphragm of polarizing coating.This processing is preferably handled according to foregoing saponification and is carried out.
The transparent support that also preferred optical anisotropic layer also contains the embodiment of cellulose esters, form another embodiment of oriented layer and have an optical compensating layer of optical anisotropic layer between optical anisotropic layer and transparent support has optical negative single shaft performance and optical axis is present in the direction vertical with the transparent support face, and an embodiment again that meets the following conditions.
20≤{(nx+ny)/2-nz}×d≤400
In the conditional expression, nx: representative is along postponing the refractive index of the direction (direction of refractive index maximum) of axle mutually in the aspect in the above; Ny: representative is along shifting to an earlier date the refractive index of the direction (direction of refractive index minimum) of axle mutually in the aspect; Nz: represent along the refractive index of the thickness direction of layer; And d: the thickness of representing optical compensating layer.
[image display apparatus]
Polaroid with antireflection film can be used for image display apparatus for example liquid crystal indicator (LCD) or electroluminescent display (ELD).With regard to polaroid, the transparent support side of antireflection film links to each other with visual display surface.
Fig. 1 has shown a preferred implementation will using antireflection film to be used for LCD as the polaroid of transparent protective film.In Fig. 1; the transparent support of antireflection film (1) links to each other with the bonding coat (6) of polarizing coating (7) through comprising polyvinyl alcohol (PVA), and another diaphragm (8) of polarizing coating links to each other through bonding coat (6) with the surface of the surperficial relative polarizing coating (7) of bonding antireflection film.This polaroid has adhering agent layer (9) on the surface of surperficial relative another diaphragm (8) that links to each other with polarizing coating, and directly, perhaps through another layer, link to each other with the glass of the liquid crystal cell of liquid crystal indicator, and use.
The polaroid that is used for use antireflection film of the present invention can be preferred for transmission-type, reflection-type or the transflective liquid crystal display device of twisted nematic (TN), STN Super TN (STN), vertical orientated (VA), face internal conversion (IPS), optical compensation curved unit (OCB) or other pattern.
Yet, when using it for transmission-type or transflective liquid crystal display device, use the film (have the polarization separating film that polarized light is selected layer, for example, the D-BEF that makes by Sumitomo 3M Ltd.) of the raising brightness of commercially available acquisition can obtain to have the more display of high-visibility.
And, close use by hardening with λ/4, polaroid can be used as the polaroid of reflection-type liquid-crystal display device or as the surface protection board of OLED display to reduce from surface and inner reflected light.
[embodiment]
More specifically describe the present invention below by embodiment, yet scope of the present invention is not limited to this.
[embodiment 1]
(preparation of the coating fluid of hard conating)
Under agitation to dipentaerythritol five acrylate of 230 weight portions and the potpourri (DPHA of dipentaerythritol acrylate, by Nippon Kayaku Co., Ltd. make) the middle trimethylolpropane triacrylate (BISCOAT360 that adds the oxirane modification of 76 weight portions, by Osaka Organic Chemical Industry, Ltd. make), the methyl ethyl ketone of 181 weight portions, the cyclohexanone of 55 weight portions, (Irgacure 184 for the Photoepolymerizationinitiater initiater of 8 weight portions, by Ciba-Geigy Japan, Ltd. make) and the silicasol (MEK-ST of 450 weight portions, by NISSAN CHEMICAL INDUSTRIES, Ltd. makes).The gained potpourri is that the filtrator of 0.4 μ m filters the coating fluid that makes hard conating through the aperture of polypropylene manufacturing.
(preparation of titania particulate dispersion)
As the titania particulate, use contain cobalt and use aluminium hydroxide and zirconium hydroxide surface-treated titania particulate (MPT-129C, by ISHIHARA SANGYO KAISHA, Ltd. makes, TiO
2: Co
3O
4: Al
2O
3: ZrO
2=90.5: 3.0: 4.0: 0.5 weight ratios).
In these particles of 257.1g, add the cyclohexanone of following spreading agent of 38.6g and 704.3g, and in DYNO-Mill, gained potpourri decentralized system is got the titanium dioxide dispersion that weight average particle diameter is 70nm.
(preparation of the coating fluid of intermediate-index layer)
Under agitation in the above-mentioned titanium dioxide dispersion of 88.9g, add dipentaerythritol five acrylate of 58.4g and the potpourri (DPHA of dipentaerythritol acrylate, by Nippon Kayaku Co., Ltd. make), 3.1g Photoepolymerizationinitiater initiater (Irgacure907, by Speciality Chemicals, Ltd. make), 1.1g photosensitizer (KAYACURE-DETX, by Nippon Kayaku Co., Ltd. make), 482.4g methyl ethyl ketone and the cyclohexanone of 1869.8g, after enough stirring, be that the filtrator of 0.4 μ m filters the coating fluid that makes intermediate-index layer through the aperture of polypropylene manufacturing with the gained potpourri.
(preparation of the coating fluid of high refractive index layer)
Under agitation in the aforementioned titanium dioxide dispersion of 586.8g, add dipentaerythritol five acrylate of 47.9g and the potpourri (DPHA of dipentaerythritol acrylate, by Nippon Kayaku Co., Ltd. manufacturing), the Photoepolymerizationinitiater initiater (Irgacure907 of 4.0g, by Ciba-Geigy, Japan, Ltd. manufacturing), the photosensitizer of 1.3g (KAYACURE-DETX, by Nippon Kayaku Co., Ltd. makes), the methyl ethyl ketone of 455.8g and the cyclohexanone of 1427.8g.The gained potpourri is that the filtrator of 0.4 μ m filters the coating fluid that makes high refractive index layer through the aperture of polypropylene manufacturing.
(preparation of the coating fluid of low-index layer)
The concentration of multipolymer of the present invention (P-1) with 7 weight % is dissolved in the methyl isobutyl ketone.In gained solution, add and contain the acrylate-based silicone resin X-22-164C of terminal methyl group (by Shin-Etsu Chemical Co. based on 3 weight % of solids content, Ltd. make), and be that the optical free radical of basic 5 weight % produces agent Irgacure 907 (trade (brand) names) with solids content.After fully stirring, the gained potpourri is that the filtrator of 0.45 μ m (definitely filtering diameter) filters the coating fluid that makes low-index layer through the aperture that Teflon makes.
(preparation of antireflection film 1)
Use nick version spreader that the coating fluid 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) on.After 90 ℃ of following dryings, using 160W/cm air cooling metal halide lamp (by EYEGRAPHICSCo., Ltd. makes) is 400mW/cm with illumination
2With exposure be 350mJ/cm
2Ultraviolet ray it is shone, be 1.0 volume % or lower environment with nitrogen wash so that obtain oxygen concentration simultaneously.As a result, coating layer is solidify to form the thick hard conating of 4.9 μ m.
Use has 3 coating fluid, the coating fluid of high refractive index layer and the coating fluids of low-index layer that are coated with nick version spreader continuous coating intermediate-index layer on this hard conating of stop.
The drying condition of intermediate-index layer is adjusted at 100 ℃ of following dry 30 seconds.The following ultraviolet ray irradiation condition of cure of adjusting: with nitrogen wash so that when obtaining oxygen concentration and be 0.5 volume % or lower environment, using 180W/cm air cooling metal halide lamp (by EYEGRAPHICS Co., the Ltd. manufacturing) adjustment illumination is 400mW/cm
2With exposure be 350mJ/cm
2
Intermediate-index layer after solidifying has 1.630 refractive index and the thickness of 67nm.
The drying condition of high refractive index layer is adjusted at 100 ℃ of following dry 30 seconds.The following ultraviolet ray irradiation condition of cure of adjusting: with nitrogen wash so that when obtaining oxygen concentration and be 0.5 volume % or lower environment, using 240W/cm air cooling metal halide lamp (by EYEGRAPHICS Co., the Ltd. manufacturing) adjustment illumination is 500mW/cm
2With exposure be 500mJ/cm
2
High refractive index layer after solidifying has 1.905 refractive index and the thickness of 107nm.
The drying condition of low-index layer is adjusted at 90 ℃ of following dry 30 seconds.The following ultraviolet ray irradiation condition of cure of adjusting: with nitrogen wash so that when the acquisition oxygen concentration is 0.5 volume % or lower environment, using two 240W/cm air cooling metal halide lamps (by EYEGRAPHICS Co., Ltd. makes) adjustment illumination is 500mW/cm
2With exposure be 1000mJ/cm
2
Low-index layer after solidifying has 1.440 refractive index and the thickness of 83nm.
Thus, make antireflection film 1.
(preparation of antireflection film sample 2)
In addition, in the process of preparation antireflection film sample 1, the titanium dioxide granule that will be used for intermediate-index layer and high refractive index layer is changed into and is used the titania particulate that surface of aluminum hydroxide handles (TTO-55B is by ISHIHARA SANGYO KAISHA, Ltd. make TiO
2: Al
2O
3=92.0: 8.0 weight ratios) use, make antireflection film 2 thus.
(preparation of polaroid)
Under condition shown in the table 1, the gained antireflection film is passed through the different processing of saponification degree separately, and water washs fully.Then, each film neutralizes in dilute sulfuric acid aqueous solution, and then water fully washs.Afterwards, film 100 ℃ of abundant down dryings, is obtained the diaphragm of polaroid.
The polyvinyl alcohol film that 75 μ m are thick (by Kurary Co., Ltd. make) is dipping absorption iodine in the aqueous solution of the potassium iodide of the iodine of the water that comprises 1000 weight portions, 7 weight portions and 105 weight portions.Then, this film uniaxial tension in 4 weight % boric acid aqueous solutions keeping dry under the extended state, is made polarizing coating then thus to 4.4 times of its initial length.
Use the polyvinyl alcohol bonding agent as bonding agent, will be bonding through a surface of the tri acetyl cellulose face of the antireflection film (diaphragm of polaroid) of saponification processing and polarizing coating.And, use identical polyvinyl alcohol bonding agent, at the another side of polarizing coating, bonding tri acetyl cellulose film, this tri acetyl cellulose film are handled through saponification in the mode identical with embodiment sample 1 in the table 1.
[table 1]
| Sample | Antireflection film | Alkaline matter | N | Alkali liquid temperature | Processing |
| Embodiment sample | |||||
| 1 | 1 | NaOH | 1.5mol/l | 55℃ | 100 |
| Embodiment sample | |||||
| 2 | 1 | NaOH | 1.5mol/l | 55℃ | 60 seconds |
| Embodiment sample 3 | 1 | NaOH | 1.5mol/l | 55℃ | 15 seconds |
| Embodiment sample 4 | 1 | NaOH | 1.5mol/l | 40℃ | 30 seconds |
| Embodiment sample 5 | 1 | NaOH | 1.5mol/l | 35℃ | 60 |
| Embodiment sample | |||||
| 6 | 1 | NaOH | 2.5mol/l | 70℃ | 15 |
| Embodiment sample | |||||
| 7 | 1 | NaOH | 2.5mol/l | 70℃ | 30 seconds |
| Comparative example 1 | 1 | NaOH | 1.5mol/l | 55℃ | 180 seconds |
| Comparative example 2 | 1 | NaOH | 1.5mol/l | 55℃ | 180 seconds |
(evaluation of the antireflective surfaces of polaroid)
Antireflection face to each polaroid of making is estimated the following.In the table 1 each sample with have the face facing surfaces of antireflection film and the contact angle and the evaluation result of water is shown in table 2.
(1) steel wool scrapes
Each sample is scraped under the load of 200g 10 times back and forth with the #0000 steel wool, and based on the degree that scrapes of following each sample of standard evaluation:
◎: do not have cut fully;
Zero: cut slightly, but not obvious;
△: cut is arranged, but keep low-index layer; With
*: scratch fully
(2) pencil test
Carry out the pencil test described in the JIS K 5400.Antireflection film continues 2 hours under the relative humidity of 25 ℃ temperature and 60%.Then, use the mensuration pencil of JIS S 6006 regulations, under the load of 500g, estimate with n=5, do not observe cut on one point yet, perhaps can observe the highest pencil hardness in the hardness of one or cut still less, as the pencil hardness of antireflection film.
(3) evaluation of against weather
Use is adjusted to the xenon arc lamp type against weather analyzer (XF pattern) of outdoor average sunlight conditions by borosilicate glass filtrator and Guartz filter, is that 80klux and blackbody temperature are to carry out the weathering test that irradiation time is respectively 0 hour, 300 hours, 600 hours and 900 hours under 63 ℃ in relative humidity is 50% environment in the surperficial illumination of irradiation.
In temperature is that 25 ℃ and relative humidity are to continue to control in 2 hours the moisture of each polaroid after exposure under 60% the condition.
On surface with each polaroid on the face of antireflection film, use cutting knife with lattice pattern 11 vertical incisions of cutting and 11 horizontal cut, cut 100 squares altogether thus.Exerting pressure thereon adheres to by Nitto Denko Co., and the polyester adhesive tape (NO.31B) that Ltd. makes is so that repeat viscosity test 3 times in same position.Whether visual inspection peels off, and estimates according to following 1 to 4 rank.
◎: in 100, do not observe fully and peel off;
Zero: in 100, observe 2 or peeling off still less;
△: in 100, observe the 3-10 sheet and peel off; With
*: in 100, observe peeling off more than 10.
[table 2]
| Sample | Contact angle with water | Steel wool scrapes | Pencil hardness | Against weather is estimated |
| | 26 degree | ○ | 3H | ◎ |
| | 30 degree | ○ | 3H | ◎ |
| Embodiment sample 3 | 46 degree | ◎ | 3H | ◎ |
| Embodiment sample 4 | 46 degree | ◎ | 3H | ◎ |
| Embodiment sample 5 | 39 degree | ◎ | 3H | ◎ |
| | 28 degree | ○ | 3H | ◎ |
| | 29 degree | ○ | 3H | ◎ |
| Comparative example 1 | 19 degree | △ | H | △ |
| Comparative example 2 | 19 degree | × | 2B | × |
Table 2 explanation polaroid of the present invention can be realized excellent physical strength and against weather.
[embodiment 2]
(evaluation of image display apparatus)
Being equipped with thus thereon, the TN liquid crystal indicator of the polaroid of the present invention of preparation has excellent antireflection property and very excellent visibility.
[embodiment 3]
(preparation of the polaroid that the visual angle enlarges)
Optical compensation films (the Wide View Film SA-12B that under the condition identical, will have optical compensating layer by infusion process with the film 1 of embodiment 1, by Fuji Photo Film, Co., Ltd. handle through saponification on surface manufacturing), the relative transparent support face tilt of the dish face of disk-shaped structure unit wherein, and the angle that forms between the dish face of disk-shaped structure unit and transparent support face changes at the thickness direction of optical anisotropic layer.Use the optical compensation aspect of the identical bonding optical compensation films of polyvinyl alcohol bonding agent to replace the tri acetyl cellulose of the saponification in the polaroid 1 of embodiment 1.As a result, form the polaroid that two surfaces all are subjected to the visual angle expansion of antireflection film and optical compensation films protection.
(evaluation of image display apparatus)
The liquid crystal indicator that optical compensation aspect by the bonding polaroid that makes thus on the glass surface of the observation side of transmission-type TN element makes has in bright chamber than the contrast that the liquid crystal indicator excellence of the polaroid that does not use optical compensation films is installed thereon, and the vertical and horizontal visual angle with non-constant width, more excellent antireflection property and very excellent visibility and display quality.
Simultaneously; for STN, IPS, VA or ocb mode transmission-type, reflection-type or transflective liquid crystal display device; antireflection film of the present invention is used in when using suitable phase retardation film if desired between the glass elements of the polaroid of observing side and filling liquid crystal, perhaps as the film on the liquid crystal cell face of observing two diaphragms that side forms polaroid.As a result, can improve the visibility of each mode display.
The application is based on the Japanese patent application JP 2003-91770 of on March 28th, 2003 application and the Japanese patent application JP 2003-341323 of application on September 30th, 2003, thus by reference with their full text adding this paper.
Claims (17)
1, a kind of preparation method of polaroid, it comprises: antireflection film and polarizing coating is bonding, described antireflection film contains transparent support and the anti-reflection structure that comprises that multilayer that refractive index is different and each layer comprise cured film, wherein the one deck at least in the multilayer that refractive index is different is that refractive index and thickness that refractive index is higher than described transparent support are the layer of 10nm-2 μ m, and described antireflection film is through bonding with described polarizing coating after the hydrophilicity-imparting treatment, makes the surface that described antireflection film and polarizing coating are bonding and the contact angle of water spend in-50 scopes of spending 20.
2, method according to claim 1, wherein said hydrophilicity-imparting treatment comprises the step that described antireflection film is immersed in the aqueous slkali that is used for saponification.
3, a kind of preparation method of polaroid, it comprises: antireflection film and polarizing coating is bonding, described antireflection film contains transparent support and the anti-reflection structure that comprises that multilayer that refractive index is different and each layer comprise cured film, wherein will with its on be formed with anti-reflection structure the surface of surperficial relative antireflection film as the surface bonding with described polarizing coating, and only with this adhesive surface through saponification handle make its with the contact angle of water in the scopes that 10 degree-50 are spent.
4, method according to claim 1, but wherein said cured film is by coating, dry and solidify the coating composition that contains at least a film forming solute and at least a solvent and obtain.
5, method according to claim 3, but wherein said cured film is by coating, dry and solidify the coating composition that contains at least a film forming solute and at least a solvent and obtain.
6, method according to claim 1, the one deck at least in the different multilayer of wherein said refractive index contains inorganic particle.
7, method according to claim 3, the one deck at least in the different multilayer of wherein said refractive index contains inorganic particle.
8, method according to claim 6, the multilayer that wherein said refractive index is different comprises that at least one refractive index is higher than the high refractive index layer and the described low-index layer that is lower than the refractive index of support of at least one refractive index of the refractive index of described support, and described high refractive index layer has the refractive index of 1.55-2.40 and contains titania and at least a inorganic particle that is selected from the element of cobalt, aluminium and zirconium.
9, method according to claim 7, the multilayer that wherein said refractive index is different comprises that at least one refractive index is higher than the high refractive index layer of refractive index of described support and the low-index layer that at least one refractive index is lower than the refractive index of described support, and described high refractive index layer has the refractive index of 1.55-2.40 and contains titania and at least a inorganic particle that is selected from the element of cobalt, aluminium and zirconium.
10, method according to claim 8, wherein said inorganic particle are had at least a compound that is selected from mineral compound, organometallics and the organic compound that reduces or destroy photocatalytic activity separately and are covered.
11, method according to claim 9, wherein said inorganic particle are had at least a compound that is selected from mineral compound, organometallics and the organic compound that reduces or destroy photocatalytic activity separately and are covered.
12, the polaroid of preparation method's preparation according to claim 1.
13, the polaroid of preparation method's preparation according to claim 3.
14, polaroid according to claim 12, wherein said polaroid comprise a plurality of surface protection films that comprise described antireflection film; The antireflection film that comprises in described a plurality of surface protection films, have an optical compensation films, optical compensating layer that contains optical anisotropic layer that provides on the one side of optical compensation films is provided for it, described with will be relative with the bonding face of polarizing coating; Described optical anisotropic layer is the layer with negative birefringence; and contain compound with disk-shaped structure unit; the dish face of described disk-shaped structure unit is with respect to the face tilt of described surface protection film, and the angle that forms between the face of the dish face of described disk-shaped structure unit and described surface protection film changes at the thickness direction of optical anisotropic layer.
15, polaroid according to claim 13, wherein said polaroid comprise a plurality of surface protection films that comprise described antireflection film; The antireflection film that comprises in described a plurality of surface protection films, have an optical compensation films, optical compensating layer that contains optical anisotropic layer that provides on the one side of optical compensation films is provided for it, described with will be relative with the bonding face of polarizing coating; Described optical anisotropic layer is the layer with negative birefringence; and contain compound with disk-shaped structure unit; the dish face of described disk-shaped structure unit is with respect to the face tilt of described surface protection film, and the angle that forms between the face of the dish face of described disk-shaped structure unit and described surface protection film changes at the thickness direction of optical anisotropic layer.
16, the liquid crystal indicator that contains polaroid as claimed in claim 12.
17, the liquid crystal indicator that contains polaroid as claimed in claim 13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP091770/2003 | 2003-03-28 | ||
| JP2003091770 | 2003-03-28 | ||
| JP341323/2003 | 2003-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1768280A true CN1768280A (en) | 2006-05-03 |
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ID=36743335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800085254A Pending CN1768280A (en) | 2003-03-28 | 2004-03-25 | Polarizing plate and manufacturing method thereof, and image display device |
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| Country | Link |
|---|---|
| CN (1) | CN1768280A (en) |
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| CN1673778B (en) * | 2004-03-26 | 2010-12-01 | 柯尼卡美能达精密光学株式会社 | Antireflective film, polarized light plate and image display device |
| CN103091732A (en) * | 2011-11-01 | 2013-05-08 | 富士胶片株式会社 | Optical film, polarizing plate, picture display apparatus, and 3d picture display system |
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| CN1673778B (en) * | 2004-03-26 | 2010-12-01 | 柯尼卡美能达精密光学株式会社 | Antireflective film, polarized light plate and image display device |
| CN103091732A (en) * | 2011-11-01 | 2013-05-08 | 富士胶片株式会社 | Optical film, polarizing plate, picture display apparatus, and 3d picture display system |
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| TWI752014B (en) * | 2016-03-30 | 2022-01-11 | 日商半導體能源研究所股份有限公司 | Display panel, input/output panel, and data processing device |
| CN108700699B (en) * | 2016-06-22 | 2021-01-15 | 株式会社Lg化学 | Optical film and polarizing plate including the same |
| CN108700699A (en) * | 2016-06-22 | 2018-10-23 | 株式会社Lg化学 | Optical film and polarizer including it |
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| CN107390303B (en) * | 2016-12-27 | 2021-01-26 | 住华科技股份有限公司 | Optical film, display panel module and manufacturing method thereof |
| CN107390303A (en) * | 2016-12-27 | 2017-11-24 | 住华科技股份有限公司 | Optical film, display panel module and manufacturing method thereof |
| CN110520764A (en) * | 2017-04-12 | 2019-11-29 | 富士胶片株式会社 | Antireflection film and optical component |
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| US11703614B2 (en) | 2017-04-12 | 2023-07-18 | Fujifilm Corporation | Antireflection film and optical member |
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