CN102759758A - Optical film, polaroid, and liquid crystal display apparatus - Google Patents

Abstract

Provided is an optical film, which is capable of fully keeping close cooperation between the active energy radial solidifying layer and the acylation cellulose membrane even exposed to sunlight for a long while. Even as polaroid protective film assembled to Polaroid and used for a long time at a high temperature, the optical film can still keep excellent polarization performance. Moreover, the thickness of the optical film is reduced. In addition, the invention also provides a polaroid and a liquid crystal display apparatus employing the optical film. The optical film of the invention is provided with an acylation cellulose membrane and an active energy radial solidifying layer. The acylation cellulose membrane comprises at least one plasticizer selected from the group consisting of a carbohydrate ramification, polyol ester, and contracting polyester. Moreover, the active energy radial solidifying layer comprises hindered amine compound.

Description

Blooming, polaroid and liquid crystal indicator

Technical field

The present invention relates to blooming, used the polaroid and the liquid crystal indicator of above-mentioned blooming.

Background technology

In recent years, be the center with the TV purposes, the maximization of liquid crystal indicator develops, and accompanies therewith, requires the raising of image quality and the reduction of price day by day.In addition, estimate that from now on so-called mobile purposes such as electronic signs and mobile phone, smart mobile phone etc. be center and can increasing to some extent in outdoor frequency of utilization, require also can be durable under the environment harsher than the past liquid crystal indicator.

On the other hand, about the surface of the polaroid of beholder's side, require to give functions such as anti-scratch, antireflection, electrostatic prevention.As the method for giving above-mentioned functions, generally be on cellulose acylate film etc., to apply the active energy beam cured layer and process the polaroid protective film that has functional layer.In above-mentioned mobile purposes, the thickness of parts is just in attenuation, and the requirement that reduces for the thickness of polaroid protective film is also improving.

Polaroid in the liquid crystal indicator uses the polaroid of following structure widely: the structure of having used the polarizer of polyvinyl alcohol (PVA) (PVA) and iodine to form through polaroid protective film clampings such as cellulose acylate films.But, used the polarizer of PVA and iodine to have the weakness of the easy deterioration of performance of the polarizer under hot and humid environment, in order to tackle the performance that requires of outdoor, need improve.

In the purposes,, also require the permanance stricter more without than indoor purposes for the above-mentioned functions layer.Wherein, be the project of particular importance to the stability of light, still,,, require to improve if having irradiates light for a long time then problem that the active energy beam cured layer is peeled off from cellulose acylate film easily for the prior function layer.

As the sunproof means that improve resin molding, generally be to add ultraviolet light absorber or anti-oxidant, for example in patent documentation 1, disclose following resin molding, wherein,, ultraviolet hardening is added with hindered amine light stabilizer in resinizing layer firmly.In addition, in patent documentation 2, disclose the cellulose acylate film that comprises the hindered amines anti-oxidant.

The prior art document

Patent documentation

Patent documentation 1:JP spy opens the 2003-94573 communique

Patent documentation 2:JP spy opens the 2006-123513 communique

Summary of the invention

The problem that invention will solve

But the inventor inquires into the method for record in patent documentation 1 and patent documentation 2, and the result is, functional layer and adaptation cellulose acylate film between of the film that obtains through these methods when irradiates light for a long time is insufficient.Particularly when using thin cellulose acylate film, the stage of weak point just begins deficiency to the adaptation between functional layer and the cellulose acylate film from irradiation time.Known in addition, in patent documentation 1 and patent documentation 2 in the method for record, have the problem that the polarizer performance when adding hindered amine compound and under hot and humid environment, use for a long time significantly worsens.

The present invention be directed to such situation proposes; The problem that invention will solve is to provide a kind of blooming; Even it still can keep the driving fit between active energy beam cured layer and the cellulose acylate film under light-struck situation for a long time fully; Even still can keep good polarization property being assembled in as polaroid protective film in the polaroid under situation about using for a long time under the hot and humid condition, and its thickness can reduce.In addition, the invention problem that will solve is to provide polaroid and the liquid crystal indicator that has used this blooming.

Be used to solve the means of problem

The inventor finds out: if use disclosed blooming in patent documentation 1 and patent documentation 2; Then hindered amine compound can promote the decomposition of the iodo-complexes in the polarizer, and the performance of the polarizer when under hot and humid environment, using for a long time is deterioration significantly.

To this new problem; The inventor finds: through comprise the active energy beam cured layer of hindered amine compound the acylated cellulose that comprises the specific plastifier of from carbohydrate derivates, polyol ester and polycondensation ester, selecting setting; Not only the driving fit between active energy beam cured layer and the cellulose acylate film is good thus; And above-mentioned specific plastifier can be brought into play the effect of the free volume portion of landfill cellulose acylate film; Suppress thus hindered amine compound from cellulose acylate film through being diffused into polarizer layer; The degradation of the polarizer performance when under hot and humid environment, using chronically diminishes, and mar resistance also can improve.

Find in addition: when on thin cellulose acylate film, the active energy beam cured layer being set, the driving fit between active energy beam cured layer and the cellulose acylate film receives the influence of physical characteristics on the top layer of cellulose acylate film especially easily.That is, if reduce the thickness of cellulose acylate film, then the top layer of cellulose acylate film becomes hard and crisp, is easy to generate near the brittle rupture the top layer of cellulose acylate film thus.Find: in such system; Improve effect even in cellulose acylate film, still can't obtain sufficient adaptation under the situation of interpolation hindered amine compound; Relative therewith; If in the active energy beam cured layer, add hindered amine compound, then active energy beam cured layer behind the irradiates light and the adaptation between the cellulose acylate film improve significantly for a long time.The present invention accomplishes according to this viewpoint.

That is, the present invention is following formation.

(1) a kind of blooming, it has cellulose acylate film and active energy beam cured layer; Above-mentioned cellulose acylate film comprises at least a kind of plastifier from carbohydrate derivates, polyol ester and polycondensation ester, selecting, and above-mentioned active energy beam cured layer comprises hindered amine compound.

(2) according to (1) described blooming, wherein, the thickness of above-mentioned cellulose acylate film is more than the 10 μ m and below the 35 μ m.

(3) according to (1) or (2) described blooming, wherein, the content of the above-mentioned plastifier in the above-mentioned cellulose acylate film is 1～20 mass parts with respect to acylated cellulose 100 mass parts.

(4) according to each described blooming in (1)～(3), wherein, above-mentioned active energy beam cured layer comprises bonding agent, and the content of above-mentioned hindered amine compound is 0.001～10 mass parts with respect to above-mentioned bonding agent 100 mass parts.

(5) a kind of polaroid, it comprises polarizer layer and at least 1 blooming, and it is each described blooming in above-mentioned (1)～(4) to be fitted near the mode of above-mentioned polarizer layer according to the face of an opposite side with the active energy beam cured layer form.

(6) a kind of liquid crystal indicator, it has each described blooming or above-mentioned (5) described polaroid at least 1 above-mentioned (1)～(4).

The effect of invention

According to the present invention; It can obtain following blooming: even still can keep the driving fit between active energy beam cured layer and the cellulose acylate film under situation of long-term irradiation light fully; Even it still can keep good polarizing properties being assembled in as polaroid protective film in the polaroid under hot and humid long-term down situation about using, and its mar resistance is good.In addition, according to the present invention, can provide the permanance of having used this film high polaroid.In addition, be loaded in the liquid crystal indicator liquid crystal indicator that can provide permanance to be improved through the polarizer group that will use this film.

Description of drawings

Fig. 1 uses the skeleton diagram with the example of mould when curtain coating is come the cellulose acylate film of curtain coating 3-tier architecture altogether simultaneously of curtain coating altogether for expression.

Symbol description

Coating is used on 1 top layer

2 sandwich layers are used coating

3 are total to the curtain coating coating machine

4 curtain coatings are used supporter

Embodiment

Down in the face of blooming of the present invention, its manufacturing approach, wherein employed adjuvant etc. is elaborated.

The explanation of the constitutive requirements of record is carried out according to representative embodiments of the present invention sometimes below, but the invention is not restricted to such embodiment.In addition, in this manual, use the numerical range of "～" expression to be meant the scope that the numerical value of place, the front and back record of "～" is included as lower limit and higher limit.

[blooming]

Blooming of the present invention is characterised in that; It has cellulose acylate film and active energy beam cured layer; This cellulose acylate film comprises at least a kind of plastifier from carbohydrate derivates, polyol ester and polycondensation ester (ester oligomer), selecting, and this active energy beam cured layer comprises hindered amine compound.

At first, the cellulose acylate film that blooming of the present invention had is described.

1. cellulose acylate film

At least a kind of plastifier that the employed cellulose acylate film of blooming of the present invention comprises acylated cellulose and from carbohydrate derivates, polyol ester and ester oligomer, selects.

< 1-1: acylated cellulose >

As the cellulose of the raw material of the acylated cellulose that is used for above-mentioned cellulose acylate film, cotton linter, wood pulp (broad leaf tree slurry, softwood pulp) etc. are arranged, the acylated cellulose that obtains from arbitrary raw cellulose can use, and also can according to circumstances mix use.For these raw cellulose detailed records, can be used in, for example Marusawa, Uda of "plastic material Lectures (17) cellulose resin" ("plastic su チ boots black material Lectures (17) Textile cellulose resin") Nikkan Kogyo Shimbun (1970 was issued), Institute of Invention and Technology Public Company Technical Report No. 2001-1745 No. (7 to 8) described cellulose.

The acyl group of the employed acylated cellulose of above-mentioned cellulose acylate film can only be a kind both, also can use the acyl group more than 2 kinds.It is that 2～4 acyl group is as substituting group that the employed acylated cellulose of above-mentioned cellulose acylate film preferably has carbon number.When the acyl group that uses more than 2 kinds, wherein a kind is preferably acetyl group, is 2～4 acyl group as carbon number, is preferably propiono or bytyry.Can make the good solution of dissolubility through these acylated celluloses, particularly in non-chlorine class organic solvent, can make good solution.In addition, can form the solution that viscosity is low, filterableness is good.

Carry out write up in the face of being preferably used for acylated cellulose of the present invention down.The glucose unit that constitutes cellulosic β-1,4 bonding has free hydroxyl at 2,3 and 6.Acylated cellulose for through acyl group with the part of these hydroxyls or all carry out the polymkeric substance that acidylate obtains.The acyl substituted degree is meant that the cellulosic hydroxyl that is positioned on 2,3 and 6 has carried out the summation of the ratio of acidylate (degree of substitution is 1 during everybody last 100% acidylate).

Total acyl substituted degree of above-mentioned acylated cellulose is preferably 2.0～2.97, more preferably more than 2.5 but less than 2.97, be preferably 2.70～2.95 especially.

Carbon number as above-mentioned acylated cellulose is the acyl group more than 2, both can be fatty group, also can be aryl, does not limit especially.They for example are cellulosic alkyl-carbonyl ester, alkenyl carbonyl ester or aromatic series carbonyl ester, aromatic series alkyl-carbonyl ester etc., also can further have the group that has replaced respectively.As their preferred example, can enumerate out acetyl group, propiono, bytyry, heptanoyl group, caproyl, caprylyl, capryl, dodecane acyl group, tridecane acyl group, tetradecane acyl group, hexadecane acyl group, octadecanoyl, isobutyryl, uncle's bytyry, cyclohexane carbonic acyl radical, oleoyl, benzoyl, naphthalene carbonic acyl radical, cinnamoyl etc.Wherein more preferably acetyl group, propiono, bytyry, dodecane acyl group, octadecanoyl, uncle's bytyry, oleoyl, benzoyl, naphthalene carbonic acyl radical, cinnamoyl etc.; Be preferably acetyl group, propiono, bytyry (carbon number at acyl group is) especially at 2～4 o'clock, further be preferably acetyl group (when acylated cellulose is acetyl cellulose) especially.

In cellulosic acidylate, when acylating agent uses acid anhydrides or acyl chlorides, use organic acid for example acetic acid, methylene chloride etc. as the organic solvent of reaction dissolvent.

As catalyzer, when acylating agent is acid anhydrides, preferably use the such protic catalyzer of sulfuric acid, be acyl chlorides (CH for example at acylating agent ₃CH ₂COCl) time, use alkali compounds.

The industrial preparative method of prevailing cellulosic mixed aliphatic ester is the method for cellulose being carried out acidylate with acetyl group and other the corresponding fatty acid of acyl group (acetate, propionic acid, valeric acid etc.) or the mixed organic acid composition that comprises their acid anhydrides through using.

Above-mentioned acylated cellulose can synthesize through the method for for example in the flat 10-45804 communique of TOHKEMY, putting down in writing.

In above-mentioned cellulose acylate film, from the viewpoint of moisture permeability,, preferably comprise the acylated cellulose of 5～99 quality % as above-mentioned resin, more preferably comprise 20～99 quality %, especially preferably comprise 50～95 quality %.

< 1-2: plastifier >

(carbohydrate derivates)

Above-mentioned carbohydrate derivates is preferably the derivant (being also referred to as carbohydrate derivates class plastifier below) of the carbohydrates that comprises monose or 2～10 monosaccharide units.

For the monose or the polysaccharide of the above-mentioned carbohydrate derivates class of preferred formation plastifier, the commutable group (for example hydroxyl, carboxyl, amino, sulfydryl etc.) in the preferred molecule is substituted.The example of structure that forms as being substituted can be enumerated out alkyl, aryl, acyl group etc.In addition, can enumerate out the ether structure that forms through the alkoxy substituted hydroxy, the ester structure that forms through the acyl substituted hydroxyl, replace the amide structure that forms or imide structure etc. through amino.

As the above-mentioned example that comprises the carbohydrates of monose or 2～10 monosaccharide units, for example can enumerate out erythrose, threose, ribose, arabinose, wood sugar, lyxose, allose, altrose, glucose, fructose, mannose, gulose, idose, galactose, talose, trehalose, isotrehalose, neotrehalose, mycosamine, kojibiose, nigerose, maltose, maltitol, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, lactose, lactose amine, lactitol, lettuce disaccharides, close disaccharides, primeverose, rutinose, scillabiose, sucrose, Sucralose, turanose, vicianose, cellotriose, chacotriose, gentianose, Isomaltotriose, isopanose, maltotriose, manninotriose, melezitose, glucityl maltose, plantain seed sugar, gossypose, solatriose, umbelliferose, lycotetraose, maltotetraose, stachyose, maltopentaose, verbascose (ベ Le バ Le コ one ス), MALTOHAXAOASE, alpha-cyclodextri, beta-schardinger dextrin-, gamma-cyclodextrin, δ-cyclodextrin, xylitol, D-sorbite etc.

Be preferably ribose, arabinose, wood sugar, lyxose, glucose, fructose, mannose, galactose, trehalose, maltose, cellobiose, lactose, sucrose, Sucralose, alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin, δ-cyclodextrin, xylitol, D-sorbite; More preferably arabinose, wood sugar, glucose, fructose, mannose, galactose, maltose, cellobiose, sucrose, beta-schardinger dextrin-, gamma-cyclodextrin are preferably wood sugar, glucose, fructose, mannose, galactose, maltose, cellobiose, sucrose, xylitol, D-sorbite especially.

In addition; Substituent example as above-mentioned carbohydrate derivates class plastifier; Can enumerate out alkyl (preferred carbon number is 1～22, more preferably carbon number is 1～12, especially preferably carbon number is 1～8 alkyl, for example methyl, ethyl, propyl group, hydroxyethyl, hydroxypropyl, 2-cyanoethyl, benzyl etc.); Aryl (preferred carbon number is 6～24, more preferably carbon number is 6～18, especially preferably carbon number is 6～12 aryl, for example phenyl, naphthyl); Acyl group (preferred carbon number is 1～22, more preferably carbon number is 2～12, especially preferably carbon number is 2～8 acyl group, for example acetyl group, propiono, bytyry, valeryl, caproyl, caprylyl, benzoyl, toluyl groups, phthalyl, naphthalene diformyl etc.).In addition, as replace the preferred structure that forms through amino, can enumerate out amide structure (preferred carbon number is 1～22, more preferably carbon number is 2～12, especially preferably carbon number is 2～8 acid amides, for example formamide, acetamide etc.); Imide structure (preferred carbon number is 4～22, more preferably carbon number is 4～12, especially preferably carbon number is 4～8 acid imide, for example succimide, phthalimide etc.).

Wherein, more preferably alkyl, aryl or acyl group are preferably acyl group especially.

As the preferred example of above-mentioned carbohydrate derivates class plastifier, can enumerate out following material.But can be used for carbohydrate derivates class plastifier of the present invention and be not limited to these.

Preferred wood sugar four acetates; Glucose five acetates; Fructose five acetates; Mannose five acetates; Galactose five acetates; Maltose eight acetates; Cellobiose eight acetates; Sucrose octaacetate; Xylitol five acetates; Sorbitol hexaacetate; Wood sugar four propionic esters; Glucose five propionic esters; Fructose five propionic esters; Mannose five propionic esters; Galactose five propionic esters; Maltose eight propionic esters; Cellobiose eight propionic esters; Sucrose eight propionic esters; Xylitol five propionic esters; D-sorbite six propionic esters; Wood sugar four butyric esters; Glucose five butyric esters; Fructose five butyric esters; Mannose five butyric esters; Galactose five butyric esters; Maltose eight butyric esters; Cellobiose eight butyric esters; Sucrose eight butyric esters; Xylitol five butyric esters; D-sorbite six butyric esters; Wood sugar four benzoic ethers; Glucose pentaphene formic ether; Fructose pentaphene formic ether; Mannose pentaphene formic ether; Galactose pentaphene formic ether; Maltose eight benzoic ethers; Cellobiose eight benzoic ethers; Sucrose benzoate; Xylitol pentaphene formic ether; D-sorbite six benzoic ethers etc.More preferably wood sugar four acetates; Glucose five acetates; Fructose five acetates; Mannose five acetates; Galactose five acetates; Maltose eight acetates; Cellobiose eight acetates; Sucrose octaacetate; Xylitol five acetates; Sorbitol hexaacetate; Wood sugar four propionic esters; Glucose five propionic esters; Fructose five propionic esters; Mannose five propionic esters; Galactose five propionic esters; Maltose eight propionic esters; Cellobiose eight propionic esters; Sucrose eight propionic esters; Xylitol five propionic esters; D-sorbite six propionic esters; Wood sugar four benzoic ethers; Glucose pentaphene formic ether; Fructose pentaphene formic ether; Mannose pentaphene formic ether; Galactose pentaphene formic ether; Maltose eight benzoic ethers; Cellobiose eight benzoic ethers; Sucrose benzoate; Xylitol pentaphene formic ether; D-sorbite six benzoic ethers etc.Preferred especially maltose eight acetates; Cellobiose eight acetates; Sucrose octaacetate; Wood sugar four propionic esters; Glucose five propionic esters; Fructose five propionic esters; Mannose five propionic esters; Galactose five propionic esters; Maltose eight propionic esters; Cellobiose eight propionic esters; Sucrose eight propionic esters; Wood sugar four benzoic ethers; Glucose pentaphene formic ether; Fructose pentaphene formic ether; Mannose pentaphene formic ether; Galactose pentaphene formic ether; Maltose eight benzoic ethers; Cellobiose eight benzoic ethers; Sucrose benzoate; Xylitol pentaphene formic ether; D-sorbite six benzoic ethers etc.

Above-mentioned carbohydrate derivates preferably has pyranose structure or furanose structure.

Be used for the compound that carbohydrate derivates of the present invention illustrates below preferred especially.But can be used for carbohydrate derivates of the present invention and be not limited to these compounds.In addition, in the following structures formula, R representes hydrogen atom or substituting group arbitrarily respectively independently, a plurality of R both can be identical also can be different.

In following table, substituting group 1,2 is represented the R of optional position respectively.In addition, degree of substitution is represented the number that R representes when being this substituting group.When " nothing ", R is a hydrogen atom.

Table 1

Table 2

Table 3

Table 4

(acquisition methods)

Acquisition methods as above-mentioned carbohydrate derivates; Can change into the commercially available article of system, the acquisitions such as commercially available article of Aldrich system by Co., Ltd. Tokyo, perhaps can come synthetic through commercially available carbohydrates being carried out known ester derivant method (method of for example in the flat 8-245678 communique of TOHKEMY, putting down in writing).

Acquisition methods as above-mentioned carbohydrate derivates class plastifier; Can change into the commercially available article of system, the acquisitions such as commercially available article of Aldrich system by Co., Ltd. Tokyo, perhaps can come synthetic through commercially available carbohydrates being carried out known ester derivant method (method of for example in the flat 8-245678 communique of TOHKEMY, putting down in writing).

(polyol ester)

The molecular weight of polyol ester used in the present invention has no particular limits, but is preferably 300～1500, and more preferably 350～750.From the aspect of retention, this molecular weight is preferably bigger, from moisture-penetrability, with the aspect of the compatibility of cellulose esters, this molecular weight is preferably less.

In the present invention, the carboxylic acid in the polyol ester both can be a kind of, also can be the amalgam more than 2 kinds.In addition, the hydroxyl in the polyvalent alcohol can all carry out esterification, also can make one of which part of hydroxyl former state residual.Preferably in molecule, have aromatic rings or cycloalkyl ring more than 3.

The example that is used for polyol ester of the present invention illustrates below.

In the above-mentioned polyol ester; Preferred trimethylolpropane tris benzoic ether (TMPTB), trimethylolpropane tris acetate, trimethylolpropane tris propionic ester, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, 1; Ester, trimethylolpropane and the acetate of 3-dibutylene glycol dibenzoate, TEG dibenzoate, trimethylolpropane and acetate and benzoic mixed ester, trimethylolpropane and cyclohexane carboxylic and the mixed ester of cyclohexane carboxylic, 3-methylpentane-1; 3; The ester of 5-triol and cyclohexane carboxylic, 3-methylpentane-1,3, the ester of 5-triol and benzoic ester, xylitol and benzoic ester, xylitol and cyclohexane carboxylic.

(polycondensation ester)

Above-mentioned polycondensation ester (being also referred to as the polycondensation ester plasticizer below) preferably is 2.5～8.0 aliphatic diol acquisition by dicarboxylic acid with at least a aromatic rings (being also referred to as aromatic dicarboxylic acid) and at least a average carbon number.In addition, also preferably be 2.5～8.0 aliphatic diol acquisition by the potpourri of aromatic dicarboxylic acid and at least a aliphatic dicarboxylic acid and at least a average carbon number.

The calculating of the average carbon number of above-mentioned dicarboxylic acid residue is carried out respectively by dicarboxylic acid residue and diol residue.

With the ratio of components (molar ratio) of above-mentioned dicarboxylic acid residue with constituting that carbon number multiplies each other the value calculated as average carbon number.For example when being made up of hexane diacid residue and each 50 moles of % of phthalic acid residue, average carbon number is 7.0.

In addition, also be same during above-mentioned diol residue, the average carbon number of diol residue be diol residue ratio of components (mol ratio) with constitute the value that carbon number multiplies each other and calculates.For example by 50 moles of % of glycol residue and 1, when 50 moles of % of 2-propylene glycol residue constituted, average carbon number was 2.5.

The number-average molecular weight of above-mentioned polycondensation ester is preferably 500～2000, and more preferably 600～1500, further be preferably 700～1200.If the number-average molecular weight of polycondensation ester is more than 500, then volatility is low, and film fault that volatilization caused under the hot conditions the during stretching of cellulose acylate film or operation are polluted and be difficult to take place.In addition, if this number-average molecular weight is then high with the compatibility of cellulose esters below 200, oozing out during with heat drawing is difficult to generation during the system film.

The number-average molecular weight of above-mentioned polycondensation ester can be measured and estimate through gel permeation chromatography.In addition, when not having the polyester polyol of sealing endways, also can calculate through the amount of hydroxyl groups (being also referred to as hydroxyl value below) of unit mass.In the present invention, for hydroxyl value, be that the amount (mg) to the required potassium hydroxide of the neutralization of superfluous acetic acid is measured after polyester polyol is carried out acetylation.

With the potpourri of aromatic dicarboxylic acid and aliphatic dicarboxylic acid during as the dicarboxylic acid composition, the mean value of carbon number that is preferably the dicarboxylic acid composition is at 5.5～10.0 dicarboxylic acid, and more preferably the mean value of the carbon number of dicarboxylic acid composition is at 5.6～8 dicarboxylic acid.

If the mean value of carbon number more than 5.5, then can obtain the good polaroid of permanance.If the mean value of carbon number is below 10.0, then the compatibility with cellulose esters is good, can in the process of making cellulose acylate film, suppress the generation of oozing out.

In the polycondensation ester that obtains by the two pure and mild dicarboxylic acid that comprise aromatic dicarboxylic acid, comprise aromatic dicarboxylic acid residue.

In this manual, residue be meant the polycondensation ester part-structure, be part-structure with characteristic of the monomer that forms the polycondensation ester.The dicarboxylic acid residue that is for example formed by dicarboxylic acid HOOC-R-COOH is-OC-R-CO.Here, R representes divalent group arbitrarily.

The aromatic dicarboxylic acid residue ratio of polycondensation ester used in the present invention is preferably more than the 40mol%, more preferably 40mol%～95mol%.

Through making the aromatic dicarboxylic acid residue ratio more than 40mol%, can obtain to appear sufficient optically anisotropic cellulose ester membrane, can obtain the good polaroid of permanance.In addition, if the aromatic dicarboxylic acid residue ratio below 95mol%, then the compatibility with cellulose esters is good, even when the making of cellulose ester membrane and heat drawing, also be difficult to ooze out.

As the spendable aromatic dicarboxylic acid of the formation that can be used for polycondensation ester of the present invention, can enumerate out for example phthalic acid, terephthalic acid (TPA), m-phthalic acid, 1,5-naphthalene dicarboxylic acids, 1; 4-naphthalene dicarboxylic acids, 1; 8-naphthalene dicarboxylic acids, 2,8-naphthalene dicarboxylic acids or 2,6-naphthalene dicarboxylic acids etc.Wherein preferred phthalic acid, terephthalic acid (TPA), 2,6-naphthalene dicarboxylic acids, more preferably phthalic acid, terephthalic acid (TPA), further preferred terephthalic acid (TPA).

In above-mentioned polycondensation ester, be formed with the aromatic dicarboxylic acid residue of deriving by the aromatic dicarboxylic acid that uses in mixing.

Promptly; Above-mentioned aromatic dicarboxylic acid residue preferably comprises at least a kind in phthalic acid residue, terephthalic acid residue, the isophthalic acid residues; More preferably comprise at least a kind among phthalic acid residue, the terephthalic acid residue, further preferably comprise the terephthalic acid residue.

In the mixing in the formation of above-mentioned polycondensation ester, through using terephthalic acid (TPA) as aromatic dicarboxylic acid, can form compatibility with cellulose esters better, be difficult to produce the cellulose ester membrane that oozes out when the making of cellulose ester membrane and during heat drawing.In addition, above-mentioned aromatic dicarboxylic acid both can use a kind, also can use more than 2 kinds.When using 2 kinds, preferably use phthalic acid and terephthalic acid (TPA).

Through and with phthalic acid and these 2 kinds of aromatic dicarboxylic acids of terephthalic acid (TPA), can the polycondensation ester under the normal temperature be softened, be preferred from the processing easy aspect that becomes.

Terephthalic acid residue's in the dicarboxylic acid residue of above-mentioned polycondensation ester content is preferably 40mol%～100mol%.

Ratio through making the terephthalic acid residue then can obtain to appear sufficient optically anisotropic cellulose ester membrane more than 40mol%.

In the polycondensation ester that obtains by the two pure and mild dicarboxylic acid that comprise aliphatic dicarboxylic acid, comprise the aliphatic dicarboxylic acid residue.

As the aliphatic dicarboxylic acid that can form the polyesters hydrophobing agent that contracts that the present invention can preferably use; Can enumerate out for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, dodecanedicarboxylic acid or 1,4-cyclohexane dicarboxylic acid etc.

In the polycondensation ester, be formed with the aliphatic dicarboxylic acid residue of deriving by employed aliphatic dicarboxylic acid in mixing.

The average carbon number of aliphatic dicarboxylic acid residue is preferably 5.5～10.0, and more preferably 5.5～8.0, further be preferably 5.5～7.0.If the average carbon number of aliphatic dicarboxylic acid residue is below 10.0, then the heating reduction of compound can reduce, the generation that the operation that oozing out in the time of can preventing to be considered to acylated cellulose net drying caused is polluted the planar fault that is caused.In addition,, be difficult to produce separating out of polycondensation ester if the average carbon number of aliphatic dicarboxylic acid residue is that then compatibility is good more than 5.5, from but preferred.

Specifically, above-mentioned aliphatic dicarboxylic acid residue preferably comprises the succinic acid residue, when using 2 kinds, preferably comprises succinic acid residue and hexane diacid residue.

That is, in the mixing in the formation of polycondensation ester, aliphatic dicarboxylic acid both can use a kind, also can use more than 2 kinds, when using 2 kinds, preferably used succinic acid and hexane diacid.In the mixing in the formation of polycondensation ester, when using a kind of aliphatic dicarboxylic acid, preferably use succinic acid.This from can with the average carbon number of aliphatic dicarboxylic acid residue adjust to required value, with the aspect of the compatibility of cellulose esters be preferred.

In the present invention, in the mixing in the formation of polycondensation ester, preferably use 2 kinds or 3 kinds of dicarboxylic acid.When using 2 kinds, preferably use each a kind of aliphatic dicarboxylic acid and aromatic dicarboxylic acid, when using 3 kinds, can use a kind of aliphatic dicarboxylic acid and 2 kinds of aromatic dicarboxylic acids, or use 2 kinds of aliphatic dicarboxylic acids and a kind of aromatic dicarboxylic acid.This is because can adjust the value of the average carbon number of dicarboxylic acid residue easily, and can to make the content of aromatic dicarboxylic acid residue be preferred range, can improve the permanance of the polarizer.

In the polycondensation ester that obtains by the two pure and mild dicarboxylic acid that comprise dicarboxylic acid, comprise diol residue.

In this manual, the diol residue that is formed by glycol (HO-R-OH) is-O-R-O-.Here, R representes divalent group arbitrarily.

As the glycol that forms the polycondensation ester, can enumerate out aromatic diol and aliphatic diol.Being used for the employed polycondensation ester of above-mentioned hydrophobing agent of the present invention is preferably formed by aliphatic diol at least.

It is 2.5～7.0 aliphatic diol residue that above-mentioned polycondensation ester preferably comprises average carbon number, more preferably comprises average carbon number and be 2.5～4.0 aliphatic diol residue.If the average carbon number of above-mentioned aliphatic diol residue is below 7.0; Then the compatibility with cellulose esters improves, and is difficult to ooze out, in addition; The heating reduction of compound is difficult to increase, and the operation when being considered to acylated cellulose net drying is polluted the planar fault that is caused and is difficult to take place.In addition, if the average carbon number of fat family diol residue is more than 2.5, then easily synthetic.

As forming the aliphatic diol that can be used for the polyesters hydrophobing agent that contracts of the present invention, can alkyl diol or ester ring type glycols be enumerated for example preferred monoethylene glycol (ethane diol), 1,2-propylene glycol, 1, ammediol, 1 as preferred example; 2-butylene glycol, 1,3 butylene glycol, 2-methyl isophthalic acid, ammediol, 1,4-butylene glycol, 1,5-pentanediol, 2; 2-dimethyl-1, ammediol (neopentyl glycol), 2,2-diethyl-1, ammediol (3,3-dihydroxymethyl pentane), 2-normal-butyl-2-ethyl-1; Ammediol (3,3-dihydroxymethyl heptane), 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexanediol, 2; 2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl isophthalic acid; 8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,12-octacosanol, diethylene glycol, cyclohexanedimethanol etc.These compositions preferably use as the potpourri more than a kind or 2 kinds with monoethylene glycol.

As preferred above-mentioned aliphatic diol, be monoethylene glycol, 1,2-propylene glycol and 1, in the ammediol at least a kind is preferably monoethylene glycol and 1 especially, in the 2-propylene glycol at least a kind.When using 2 kinds of above-mentioned aliphatic diols to form above-mentioned polycondensation ester, preferably make spent glycol and 1, the 2-propylene glycol.Through using 1,2-propylene glycol or 1, ammediol can prevent the crystallization of polycondensation ester.

In above-mentioned polycondensation ester, form diol residue by the glycol that is used to mix.

That is, in above-mentioned polycondensation ester, diol residue preferably comprises glycol residue, 1,2-propylene glycol residue and 1, in the ammediol residue at least a kind, glycol residue or 1 more preferably, 2-propylene glycol residue.

In the aliphatic diol residue that in above-mentioned polycondensation ester, comprises, glycol residue preferably contains 10mol%～100mol%, more preferably contains 20mol%～100mol%.

The end of above-mentioned polycondensation ester both can not seal and be in the state of glycol or carboxylic acid, monocarboxylic acid class or unary alcohol are reacted and implements so-called endcapped.

The monocarboxylic acid class that is used to seal is preferably acetate, propionic acid, butyric acid, benzoic acid etc.The unary alcohol that is used to seal is preferably methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutyl alcohol etc., most preferably is methyl alcohol.If the carbon number of the terminal employed monocarboxylic acid class of polycondensation ester is below 7, then the heating reduction of compound can not increase, and planar fault can not take place.

The end of above-mentioned polycondensation ester does not more preferably seal and is in the state of diol residue or seals through acetate or propionic acid or benzoic acid.

For two ends of above-mentioned polycondensation ester, sealing of each end is implemented has or not whether identical it doesn't matter.

When two ends of condensation body did not seal, preferred polycondensation ester was a polyester polyol.

As one of mode of above-mentioned polycondensation ester, the carbon number that can enumerate out the aliphatic diol residue is 2.5～8.0, two terminal untight polycondensation esters of polycondensation ester.

With two endcappeds of polycondensation ester the time, preferably react and seal with monocarboxylic acid.At this moment, two of this polycondensation ester ends are the monocarboxylic acid residue.In this manual, the monocarboxylic acid residue that is formed by monocarboxylic acid R-COOH is R-CO-.When two ends of polycondensation ester seal through monocarboxylic acid; Above-mentioned monocarboxylic acid is preferably aliphatics monocarboxylic acid residue; More preferably the monocarboxylic acid residue is that carbon number is the aliphatics monocarboxylic acid residue below 22, and further preferred monocarboxylic acid residue is that carbon number is the aliphatics monocarboxylic acid residue below 3.In addition, preferred carbon number is the aliphatics monocarboxylic acid residue more than 2, and preferred especially carbon number is 2 aliphatics monocarboxylic acid residue.

As one of mode of above-mentioned polycondensation ester, the carbon number that can enumerate out the aliphatic diol residue is greater than 2.5 and be below 7.0, two ends of polycondensation ester are by the polycondensation ester of monocarboxylic acid residue sealing.

If the carbon number of the monocarboxylic acid residue of two ends of sealing polycondensation ester is below 3, then volatility reduces, and the heating reduction of polycondensation ester can not increase, and can reduce the generation of operation pollution or the generation of planar fault.

Promptly; The monocarboxylic acid class that is used to seal is preferably the aliphatics monocarboxylic acid; Monocarboxylic acid more preferably carbon number is 2～22 aliphatics monocarboxylic acid, and further preferred carbon number is 2～3 aliphatics monocarboxylic acid, and preferred especially carbon number is 2 aliphatics monocarboxylic acid residue.

For example preferred acetate, propionic acid, butyric acid, benzoic acid and derivant thereof etc., more preferably acetate or propionic acid, most preferably acetate.

The monocarboxylic acid that is used to seal also can mix more than 2 kinds.

Two ends of above-mentioned polycondensation ester are preferred through acetate or propionic acid sealing, most preferably make two ends be acetonyl ester residue (being sometimes referred to as acetyl residue) through the acetate sealing.

With two endcappeds of above-mentioned polycondensation ester the time, it is solid shape that the state under the normal temperature of can obtaining is difficult to, it is good to handle, humidity stability, polaroid permanance fiber with excellent cellulose ester film in addition.

At the object lesson J-1～J-39 of above-mentioned polycondensation ester shown in the following table 5, but the present invention is not limited to these.

Table 5

Table 6 (connecing table 5)

Table 7 (connecing table 5, table 6)

Following compound represented respectively in abbreviation in above-mentioned table 5～7.PA: phthalic acid; TPA: terephthalic acid (TPA), AA: hexane diacid; SA: succinic acid; 2,6-NPA:2,6-naphthalene dicarboxylic acids.

For synthesizing of above-mentioned polycondensation ester; Arbitrary method through in heat fusing condensation method or the interface condensation method all can easily be synthesized; Said heat fusing condensation method is to utilize the polyesterification reaction of two pure and mild dicarboxylic acid or the method for ester exchange reaction according to conventional method, and said interface condensation method is the interface condensation method of these sour acyl chlorides and glycols.In addition, for above-mentioned polycondensation ester, in village's well filial piety one editor " its theoretical and application of plasticizer " (" the theoretical と ying of plastic drug そ is used ") (Co., Ltd. good fortune study, clear and the 1st edition distribution of first edition on March 1st, 48), detailed record is arranged.In addition, the material of in flat 05-155809 number of TOHKEMY, flat 05-155810 number of TOHKEMY, flat 05-197073 number of TOHKEMY, TOHKEMY 2006-259494 number, flat 07-330670 number of TOHKEMY, TOHKEMY 2006-342227 number, TOHKEMY 2007-003679 number each communique etc., putting down in writing also capable of using.

These plasticizer dosage are 1～20 mass parts with respect to acylated cellulose 100 mass parts preferably.If more than 1 mass parts, then obtain polarizer permanance easily and improve effect, in addition,, then ooze out and also be difficult to take place if below 20 mass parts.Preferred consumption is 2～15 mass parts, is preferably 5～15 mass parts especially.

For these plastifier are made an addition to the opportunity in the cellulose acylate film,, then have no particular limits as long as add in the moment of making film.For example both can add, mix with acylated cellulose in the time of also can preparing in the smears in the synthetic moment of acylated cellulose.

(1-3: other adjuvant)

Also can in above-mentioned cellulose acylate film, add adjuvants such as ultraviolet light absorber, anti-oxidant, matting agent.

(anti-oxidant)

In the present invention, can in cellulose acylate film, add known anti-oxidant, for example 2; 6-two-tert-butyl group-4-methylphenol, 4; 4 '-thiobis-(the 6-tert-butyl group-3-methylphenol), 1,1 '-bis(4-hydroxyphenyl)cyclohexane, 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol)), 2; 5-two-TBHQ, pentaerythrite-four phenol or hydroquinone type anti-oxidants such as [3-(3,5-two-tert-butyl-hydroxy phenyl) propionic esters].In addition; Be preferably three (4-methoxyls-3; The 5-diphenyl) phosphate, three (nonyl phenyl) phosphate, three (2; 4-two-tert-butyl-phenyl) Phosphorus anti-oxidants such as phosphate, two (2,6-two-tert-butyl group-4-aminomethyl phenyl) pentaerythritol diphosphate, two (2,4-two-tert-butyl-phenyl) pentaerythritol diphosphate.For the addition of anti-oxidant, preferably add 0.05～5.0 mass parts with respect to cellulosic resin 100 mass parts.

(ultraviolet light absorber)

In the present invention, from the viewpoint of the degradation that prevents polaroid or liquid crystal etc., also can in cellulose acylate film, add ultraviolet light absorber.As ultraviolet light absorber,, preferably use the above few ultraviolet light absorber of absorption of visible light of wavelength 400nm from the viewpoint of the good and good liquid crystal expressivity of the ultraviolet receptivity below the wavelength 370nm.As the object lesson that is preferably used for ultraviolet light absorber of the present invention, can enumerate out for example hindered phenol compound, hydroxy benzophenone ketone compounds, benzotriazole compound, salicylate compounds, benzophenone compound, cyanoacrylate compound, nickel complex salt compounds etc.As the example of hindered phenol compound, can enumerate out 2, [3-(3 for 6-two-tert-butyl group-paracresol, pentaerythrite-four; 5-two-tert-butyl-hydroxy phenyl) propionic ester], N, N '-hexa-methylene two (3,5-two-tertiary butyl-4-hydroxy-hydrocinnamamide), 1; 3,5-trimethyl-2,4; 6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) benzene, three-(3,5-two-tertiary butyl-4-hydroxy benzyl)-isocyanuric acid ester etc.As the example of benzotriazole compound, can enumerate out 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2, (4-(1 for the 2-di-2-ethylhexylphosphine oxide; 1,3,3-tetramethyl butyl)-6-(2H-benzotriazole 2-yl) phenol), (2; 4-pair-(positive hot sulfenyl)-6-(4-hydroxyl-3,5-two-tert-butyl benzene amido)-1,3; 5-triazine, triethylene glycol-two [3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester], N, N '-hexa-methylene two (3,5-two-tertiary butyl-4-hydroxy-hydrocinnamamide), 1; 3,5-trimethyl-2,4; 6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) benzene, 2 (2 '-hydroxyl-3 ', 5 '-two-tert-butyl-phenyl)-5-chlorinated benzotriazole, (2 (2 '-hydroxyls-3 '; 5 '-two-tertiary pentyl phenyl)-and 5-chlorinated benzotriazole, 2,6-two-tert-butyl group-paracresol, pentaerythrite-four [3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester] etc.For the addition of these ultraviolet light absorbers, be preferably 1ppm～1.0%, more preferably 10～1000ppm in the mass ratio in blooming integral body.

(matting agent)

From the slickness and the stable viewpoint of making of film, also can in above-mentioned cellulose acylate film, add matting agent.Above-mentioned matting agent both can be the matting agent of mineral compound, also can be the matting agent of organic compound.

Preferred object lesson as the matting agent of above-mentioned mineral compound; Preferably comprise silicon mineral compound (for example silicon dioxide, cure calcium silicate, afwillite, alumina silicate, magnesium silicate etc.), titanium dioxide, zinc paste, aluminium oxide, baryta, zirconia, strontium oxide strontia, antimony oxide, tin oxide, tin-antiomony oxide, lime carbonate, talcum, clay, cure porcelain earth and calcium phosphate etc.; The mineral compound, the zirconia that more preferably comprise silicon; Owing to can reduce the turbidity of cellulose acylate film, so especially preferably use silicon dioxide.The particulate of above-mentioned silicon dioxide can use for example have AEROSIL R972, the commercially available article of trade names such as R974, R812,200,300, R202, OX50, TT600 (above produce for Japanese AEROSIL Co., Ltd.).Above-mentioned zirconic particulate for example can use with commercially available particulates of trade name such as AEROSIL R976 and R811 (above produce for Japanese AEROSIL Co., Ltd.).

Preferred object lesson as the matting agent of above-mentioned organic compound is preferably for example polymkeric substance such as silicones, fluororesin and acryl resin, wherein preferably uses silicones.In silicones; Especially preferably have three-dimensional cancellated silicones, for example can use and have Tospearl 103, Tospearl 105, Tospearl 108, Tospearl 120, Tospearl 145, Tospearl 3120 and Tospearl 240 the commercially available article of trade names such as (more than be that Toshiba Silicone Co., Ltd. produces).

When making an addition to these matting agents in the acylated cellobiose cellulose solution, there is not special qualification for its method, as long as it is can both obtain desirable acylated cellobiose cellulose solution, then no problem through arbitrary method.For example both can comprise additive, also can after making mixed solution, add additive with acylated cellulose and solvent in stage with acylated cellulose and solvent.In addition, also can mix at once, use so-called preceding adding method adding before the smears curtain coating, its mixing be online be provided with spiral mixing.Specifically, the preferred such static mixer of line mixer, in addition, line mixer is preferably the for example such mixer of static mixer SWJ (mixer Hi-Mixer in the eastern beautiful silent oscillation pipe) (Toray Engineering production).In addition; Add about pipeline; For cohesion of eliminating density unevenness, particle etc.; In TOHKEMY 2003-053752 communique, record following invention: in the manufacturing approach at cellulose acylate film, be below 5 times of main material pipe arrangement inner diameter d through the distance L between the initiating terminal that makes the interpolation spray nozzle front end that mixes the different annex solutions of forming in the main material smears and line mixer, thus the cohesion of elimination density unevenness, delustring particle etc.Be logged into as preferred mode: make the distance (L) between the initiating terminal that mixes with the front end opening of the annex solution supply nozzle of the different compositions in main material smears and line mixer be below 10 times of internal diameter (d) of supply nozzle front end opening, line mixer is interior mixer of the no agitating type pipe of static state or the interior mixer of dynamic agitation type pipe.The throughput ratio that more specifically discloses cellulose acylate film main material smears/pipeline annex solution is 10/1～500/1, is preferably 50/1～200/1.In addition; Purpose be that adjuvant oozes out less and TOHKEMY 2003-014933 number of the invention of peeling off the phase retardation film that phenomenon does not have yet, slickness is good in addition, the transparency is good of interlayer in also be logged into: as the method for adding adjuvant; Both can make an addition in the fusion still; Also can fusion still～altogether between the curtain coating mould with adjuvant or dissolve or the solution that is dispersed with adjuvant makes an addition in the smears in the liquor charging; When being the latter,, mixed organizations such as static mixer are set preferably in order to improve Combination.

If in above-mentioned cellulose acylate film, add above-mentioned matting agent in large quantities, when then under the situation that the mist degree of film does not increase, being used for liquid crystal indicator practically, be difficult to take place the reduction of contrast, the unfavorable conditions such as generation of bright spot.In addition, if not very few, then can realize mar resistance.From these viewpoints, preferably the ratio with 0.01～5.0 quality % contains, and more preferably the ratio with 0.03～3.0 quality % contains, and especially preferably the ratio with 0.05～1.0 quality % contains.

(the layer structure of film)

Above-mentioned cellulose acylate film both can be individual layer, also can be the duplexer more than 2 layers.

When above-mentioned cellulose acylate film is the duplexer more than 2 layers, is preferably sandwich layer and the duplexer on the top layer more than at least 1 layer is arranged at least one surperficial laminated of this sandwich layer.This duplexer is 2 layers of structure or 3-tier architecture more preferably, is preferably 3-tier architecture.When being 3-tier architecture, preferably have: the layer that when film of the present invention is made through solution film-forming, contacts (be also referred to as below and support dignity, table B layer) with above-mentioned metal support; The layer (being also referred to as air surface, Table A layer below) of the air interface of an opposite side with above-mentioned metal support; And be held on 1 layer of sandwich layer therebetween.That is, film of the present invention is preferably the 3-tier architecture of table B layer/sandwich layer/Table A layer.

(mist degree)

The mist degree of above-mentioned cellulose acylate film is more preferably less than 0.15% preferably less than 0.20%, especially preferably less than 0.10%.Through making mist degree, can improve the contrast ratio when being assembled in the liquid crystal indicator less than 0.2%.In addition, also have the transparency of film higher, be more prone to advantage as blooming.

(thickness)

The thickness of above-mentioned cellulose acylate film is preferably 10～100 μ m, and more preferably 10～60 μ m further are preferably 10～35 μ m.Through making this thickness more than 10 μ m, the processing property in the time of can guaranteeing to make netted film, in addition through making this thickness below 35 μ m, variation that can easy corresponding humidity.

In addition, when above-mentioned cellulose acylate film had the stepped construction more than 3 layers, the thickness of above-mentioned sandwich layer was preferably 5～70 μ m, and more preferably 5～50 μ m are preferably 5～30 μ m especially.When film of the present invention had the stepped construction more than 3 layers, more preferably the thickness of the superficial layer on film two sides (Table A layer and table B layer) especially preferably was 0.5～10 μ m all at 0.5～20 μ m, more especially preferably is 0.5～3 μ m.

(film width)

The film width of above-mentioned cellulose acylate film is preferably 700～3000mm, and more preferably 1000～2800mm is preferably 1400～2500mm especially.

< 1-4: the manufacturing approach of cellulose acylate film >

Be elaborated in the face of the manufacturing approach that is used for cellulose acylate film of the present invention down.

Above-mentioned cellulose acylate film is preferably made through the solvent cast method.About the manufacturing example of the cellulose acylate film that utilized the solvent cast method, can be with reference to each instructions of No. the 2739070th, No. the 2336310th, United States Patent (USP), No. the 2367603rd, United States Patent (USP), No. the 2492078th, United States Patent (USP), No. the 2492977th, United States Patent (USP), No. the 2492978th, United States Patent (USP), No. the 2607704th, United States Patent (USP), No. the 2739069th, United States Patent (USP) and United States Patent (USP); Each instructions that No. the 736892nd, No. the 640731st, BrP and BrP; And communiques such as special public clear 45-4554 number of JP, special public clear 49-5614 number of JP, the clear 60-176834 of TOHKEMY number, the clear 60-203430 of TOHKEMY number and the clear 62-115035 of TOHKEMY number.In addition, also can carry out stretch processing to above-mentioned cellulose acylate film.About the method and the condition of stretch processing, but each communique such as flat 4-152125 number of the clear 62-115035 of reference example such as TOHKEMY number, TOHKEMY, flat 4-284211 number of TOHKEMY, flat 4-298310 number of TOHKEMY, flat 11-48271 number of TOHKEMY.

(casting method)

The casting method of solution has extruding the method on metal support through the smears of preparation equably from adding pressing mold; Utilize through scraper regulate earlier on metal support curtain coating the method for scraping blade of thickness of smears; The method of utilization through the reverse rollers coating machine regulated of roller of counter-rotating etc., the preferred method that adds pressing mold of utilizing.Adding pressing mold has coating hanging type or T model etc., and they all can preferably use.In addition; Except the method for here enumerating; Also can utilize the existing known the whole bag of tricks that the triacetate fiber cellulose solution is carried out casting film to implement; The difference of the boiling point through considering solvent for use etc. is set each condition, can obtain the effect identical with the content of in each communique, putting down in writing.

" curtain coating altogether "

In the formation of above-mentioned cellulose acylate film, preferred The tape casting, the range upon range of The tape casting such as The tape casting, rubbing method one by one used altogether, particularly using simultaneously The tape casting altogether is preferred especially from the stable viewpoint made from the production cost reduction.

When passing through to be total to The tape casting and The tape casting is made one by one, at first prepare the cellulose acetate solution (smears) of each layer usefulness.Altogether The tape casting (multilayer is curtain coating simultaneously) be following The tape casting: curtain coating with supporter (be with or tin) on; By each curtain coating of side by side extruding each layer (can be 3 layers or more layer) from other slit etc. with the curtain coating of smears with extrusion coated dose of coating machine (Giesser); In each layer curtain coating side by side; Peel off from supporter the period being fit to, and carries out drying and form film.Showing with cut-open view among Fig. 1 uses altogether curtain coating coating machine 3 top layer to be carried out 3 layers of state of extruding simultaneously and making its curtain coating with smears 1 and sandwich layer with smears 2 in curtain coating on supporter 4.

The tape casting is following The tape casting one by one: the curtain coating in that curtain coating is at first extruded the 1st layer of usefulness from the curtain coating coating machine on supporter is used the smears, makes its curtain coating, is carrying out drying or is not carrying out under the dry situation; The curtain coating of extruding the 2nd layer of usefulness from the curtain coating coating machine is above that used the smears; Make its curtain coating, according to these main points, as required one by one curtain coating and range upon range of coating machine up to more than the 3rd layer; Peel off from supporter the period being fit to, and carries out drying and form film.Rubbing method is generally following method: through the solution film-forming method film of sandwich layer is configured as film; The coating fluid on the top layer is coated in preparation; The coating machine that use is fit to, one side one side ground or 2 faces side by side are coated with and drying coated liquid on film, thus the film of cambium layer stack structure.

As the metal support that constantly moves that is used to make above-mentioned cellulose acylate film, use the surface to carry out bright finished tube or carried out bright finished stainless steel band (being also referred to as " band ") through surface grinding through chromium plating.The used pressing mold that adds also can carry out 1 base or the setting more than 2 bases in the top of metal support.Be preferably 1 base or 2 bases.2 bases are being set when above, also can with the coating dosage of institute's curtain coating according to various proportional distributions to each mould, also can according to each ratio the smears be delivered on the mould from a plurality of accurate quantitative gear pumps.The temperature of the employed smears of curtain coating (resin solution) is preferably-10～55 ℃, more preferably 25～50 ℃.At this moment, both all the solution temperature of operation was identical, also can be different at the solution temperature everywhere of operation.Not not simultaneously, as long as be required temperature before the horse back curtain coating.

In addition, the material about above-mentioned metal support has no particular limits, but SUS system (for example SUS316) more preferably.

(stretch processing)

In the manufacturing approach of above-mentioned cellulose acylate film, preferably include the operation that stretches behind the system film.As noted earlier, optical compensation films optimal wavelength dispersing characteristic of the present invention also is improved, and can give such optical property through stretch processing, in addition, can give required delay to above-mentioned cellulose acylate film.The draw direction of above-mentioned cellulose acylate film the film carriage direction and with the perpendicular direction (Width) of this carriage direction on all preferred; But from after the viewpoint of polaroid processing technology of this film of use of then carrying out, be preferably the direction (Width) perpendicular especially with the film carriage direction.

On the books in each communique such as flat 4-152125 number of the clear 62-115035 of for example TOHKEMY number, TOHKEMY, flat 4-284211 number of TOHKEMY, flat 4-298310 number of TOHKEMY, flat 11-48271 number of TOHKEMY in the method that stretches on the Width.When the stretching of length direction, the speed of transporting roller of for example regulating film makes the peeling rate of the coiling speed of film greater than film, and then film is stretched.When the stretching of Width, can in the width that keeps film through stenter, transport, enlarge the width of stenter at leisure, also can film be stretched.Also can stretch (the preferred uniaxial tension that uses long drawing machine) at the dry back use drawing machine of film.

The stretching ratio of above-mentioned cellulose acylate film is preferably more than 5% and below 200%, more preferably more than 10% and below 100%, is preferably more than 20% especially and below 50%.

With above-mentioned cellulose acylate film during,, preferably the slow axis in the face of the axis of homology of the polarizer and blooming of the present invention is laterally arranged in order to suppress oblique light leak when watching polaroid as the diaphragm of the polarizer.Because the axis of homology of the polarizer that the roller of making continuously is membranaceous generally is the Width that is parallel to the roller film; Therefore in order to be fitted continuously with the diaphragm that the membranaceous above-mentioned cellulose acylate film of roller constitutes by the membranaceous polarizer of above-mentioned roller, the interior slow axis of the face of the diaphragm that preferred roller is membranaceous is parallel to the Width of film.Thus, preferably on Width, stretch more.In addition; Stretch processing both can be carried out in the process of film making process; Also can be and the blank that batch carries out stretch processing to the system film, but owing to be to comprise under the state of residual solvent to stretch in manufacturing approach of the present invention, therefore preferably in the process of film making process, stretch.

(drying)

From postponing the viewpoint of expression power, comprise in the manufacturing approach of preferred above-mentioned cellulose acylate film above-mentioned cellulose acylate film is carried out dry operation; With the operation that under the temperature more than Tg-10 ℃, dried blooming of the present invention is stretched.

The drying of the smears on the metal support in the manufacturing of above-mentioned cellulose acylate film generally has the method that from the face side of metal support (tube or band), promptly contacts hot blast from the surface that is positioned at the net on the metal support; Contact the method for hot blast from the back side of tube or band; From as the back side contact of the opposition side of the smears curtain coating face of band or tube through temperature controlled liquid, heat with back side liquid heat transfer method that surface temperature is controlled etc. to tube or band through conducting heat, preferred back side liquid heat transfer mode.The surface temperature of the metal support before the curtain coating then can be arbitrary temp as long as below the boiling point of the solvent that is used for the smears.But in order to promote drying, for the flowability on the metal support is disappeared, the boiling point of the solvent that the temperature that preferably sets is minimum than the boiling point in the employed solvent hangs down 1～10 ℃ in addition.In addition, the curtain coating smears is not cooled off and dry situation under when peeling off, be not limited to this.

(peeling off)

The manufacturing approach of above-mentioned cellulose acylate film preferably comprises the operation of peeling off above-mentioned smears film from above-mentioned metal support.The method of peeling off about in the manufacturing approach of above-mentioned cellulose acylate film has no particular limits, and when using known method, can improve fissility.

For the adjustment of thickness, according to the mode that forms desired thickness regulate the slit gap of the die orifice of the concentration that is contained in the solid state component in the smears, mould, the pressure extruded from mould, metal support speed etc. get final product.

The length of the above-mentioned cellulose acylate film that as above obtains is batched according to per 1 roller, 100～10000m, and more preferably 500～7000m further is preferably 1000～6000m.When take-up, preferably give annular knurl at least one end, the width of annular knurl is preferably 3mm～50mm, and more preferably 5mm～30mm highly is preferably 0.5～500 μ m, more preferably 1～200 μ m.It both can be single pressure, also can be two the pressure.

Generally in big picture display device, because the reduction of oblique contrast and band look become obviously, therefore above-mentioned cellulose acylate film is particularly suitable for big picture liquid crystal indicator.When the optical compensation films of using as big picture liquid crystal indicator, for example preferably make the film width 1470mm with on form.In addition, in blooming of the present invention, but not only comprise according to former state be assembled in the film of the diaphragm mode that the size in the liquid crystal indicator cuts off, but also comprise through continuous system and make strip and the film of the mode rolled with the roller shape.The blooming of latter's mode as polaroid protective film under this state by keeping with transport etc., when when in fact being assembled in the liquid crystal indicator or with the polarizer etc., fitting, cut off according to required size and to use.In addition, with the polarizer that constitutes by the polyvinyl alcohol film that likewise is made into strip etc. etc. after the state of strip is fitted, when in fact being assembled in the liquid crystal indicator, cutting off according to required size and to use.As a mode of the optical compensation films of rolling with the roller shape, can enumerate out that roller is long to be the above form of rolling with the roller shape of 2500m.

2. active energy beam cured layer

Blooming of the present invention is characterised in that to have the active energy beam cured layer that is laminated on the above-mentioned cellulose acylate film, and this active energy beam cured layer comprises hindered amine compound.In this manual, the active energy beam cured layer is meant and comprises and can solidify formed layer through active energy beam through resin (for example bonding agent), this resin that active energy beam solidifies.

Describe in the face of above-mentioned active energy beam cured layer down.

< 2-1: the composition of active energy beam cured layer >

In blooming of the present invention, above-mentioned hindered amine compound is contained in the above-mentioned active energy beam cured layer.

Specifically, above-mentioned hindered amine compound preferably contains 0.001～10 mass parts with respect to resin (bonding agent) 100 mass parts that constitute above-mentioned active energy beam cured layer, more preferably contains 0.005～5 mass parts, especially preferably contains 0.01～2 mass parts.

In addition, only otherwise violate purport of the present invention, also can in above-mentioned active energy beam cured layer, add adjuvant.

(hindered amine compound)

The structure of hindered amine compound is near nitrogen-atoms, to have bulky organic group (for example bulky branched alkyl).It is a compound known; For example as putting down in writing in the 3rd～5 hurdle of the 5th～11 hurdle of No. 4619956 instructions of United States Patent (USP) and No. 4839405 instructions of United States Patent (USP); Comprise 2; 2,6, the complex compound of 6-tetraalkyl piperidine compounds or their acid-addition salts or their metallizing things.Such compound comprises the compound of formula (2).

In following formula, R1 and R2 are hydrogen atom or substituting group.In the object lesson of hindered amine compound, can enumerate out 4-hydroxyl-2,2,6,6-tetramethyl piperidine, 1-allyl-4-hydroxyl-2,2,6,6-tetramethyl piperidine, 1-benzyl-4-hydroxyl-2; 2,6,6-tetramethyl piperidine, 1-(the 4-tert-butyl group-2-butenyl group)-4-hydroxyl-2,2,6,6-tetramethyl piperidine, 4-stearoyl-oxy-2,2,6; 6-tetramethyl piperidine, 1-ethyl-4-bigcatkin willow acyloxy-2,2,6,6-tetramethyl piperidine, 4-methacryloxy-1,2,2,6,6-pentamethyl piperidines, 1; 2,2,6,6-pentamethyl piperidin-4-yl-β (3,5-two-tert-butyl-hydroxy phenyl)-propionic ester, 1-benzyl-2,2,6,6-tetramethyl-4-piperidyl maleate, (two-2; 2,6,6-tetramethyl piperidine-4-yl)-adipate, (two-2,2,6,6-tetramethyl piperidine-4-yl)-sebacate, (two-1,2,3; 6-tetramethyl-2,6-diethyl-piperidin-4-yl)-and sebacate, (two-1-allyl-2,2,6,6-tetramethyl-piperidin-4-yl)-phthalic ester, 1-acetyl group-2,2,6,6-tetramethyl piperidine-4-base-acetate, trimellitic acid-three-(2; 2,6,6-tetramethyl piperidine-4-yl) ester, 1-acryloyl group-4-benzyloxy-2,2,6,6-tetramethyl piperidine, dibutyl-malonic acid-two-(1,2; 2,6,6-pentamethyl-piperidin-4-yl)-ester, dibenzyl-malonic acid-two-(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl)-ester, dimethyl-two-(2; 2,6,6-tetramethyl piperidine-4-oxygen base)-silane, three-(1-propyl group-2,2,6,6-tetramethyl piperidine-4-yl)-phosphite ester, three-(1-propyl group-2,2; 6,6-tetramethyl piperidine-4-yl)-and phosphate, N, N '-two-(2,2,6,6-tetramethyl piperidine-4-yl)-hexa-methylene-1,6-diamines, four (2; 2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylic acid esters, four (1,2; 2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylic acid esters, N, N '-two-(2; 2,6,6-tetramethyl piperidine-4-yl)-hexa-methylene-1,6-diacetayl amide, 1-acetyl group-4-(N-cyclohexyl acetamide)-2,2,6,6-tetramethyl-piperidines, 4-benzyl amino-2; 2,6,6-tetramethyl piperidine, N, N '-two-(2,2,6,6-tetramethyl piperidine-4-yl)-N; N '-dibutyl-adipamide, N, N '-two-(2,2,6,6-tetramethyl piperidine-4-yl)-N, N '-dicyclohexyl-(2-hydroxyl propylene), N, N '-two-(2; 2,6,6-tetramethyl piperidine-4-yl)-and terephthaldehyde's base-diamines, 4-(two-the 2-hydroxyethyl)-amino-1,2,2,6,6-pentamethyl piperidines, 4-Methacrylamide-1; 2,2,6,6-pentamethyl piperidines, alpha-cyano-Beta-methyl-β-[N-(2,2,6,6-tetramethyl piperidine-4-yl)]-amino-methyl acrylate etc.

In addition, also can enumerate out N, N ', N ", N " '-four-[4,6-pair-[butyl-(N-methyl-2,2; 6,6-tetramethyl piperidine-4-yl) amino]-triazine-2-yl]-4,7-diaza decane-1,10-diamines, dibutylamine and 1,3,5-triazines/N; N '-two (2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylene diamine and N-(2,2; 6,6-tetramethyl-4-piperidyl)-and condensed polymer (BASF AG produces CHIMASSORB 2020FDL), dibutylamine and the 1,3,5-triazines and the N of butylamine, N '-two (2,2; 6,6-tetramethyl-4-piperidyl) condensed polymer of butylamine, gather [{ (1,1,3, the 3-tetramethyl butyl) amino-1,3; 5-triazine-2,4-two bases } { (2,2,6,6-tetramethyl-4-piperidyl) imino group } hexa-methylene { (2,2; 6,6-tetramethyl-4-piperidyl) imino group }] (BASF AG produces CHIMASSORB 944FDL), 1,6-hexane diamine-N, N '-two (2,2,6; 6-tetramethyl-4-piperidyl) and morpholine-2,4, the condensed polymer of 6-three chloro-1,3,5-triazines, gather [(6-morpholino-s-triazine-2,4-two bases) [(2; 2,6,6-tetramethyl-4-piperidyl) imino group]-HMW HALS that hexa-methylene piperidine rings such as [(2,2,6,6-tetramethyl-4-piperidyl) imino groups] forms through a plurality of bondings of triazine skeleton; Dimethyl succinate and 4-hydroxyl-2,2,6, the polymkeric substance, 1,2 of 6-tetramethyl-1-piperidines ethanol; 3,4-BTCA and 1,2,2,6; 6-pentamethyl-4-hydroxy piperidine and 3, two (2-hydroxyl-1, the 1-dimethyl ethyls)-2,4 of 9-; 8, the HMW HALS that piperidine rings such as the undecanoic mixed ester compound of 10-four oxaspiros [5,5] form through the ester bond bonding etc., but be not limited to these.Wherein, preferred dibutylamine and 1,3,5-triazines and N, N '-two (2; 2,6,6-tetramethyl-4-piperidyl) condensed polymer of butylamine, gather [{ (1,1,3; The 3-tetramethyl butyl) amino-1,3,5-triazines-2,4-two bases } { (2,2; 6,6-tetramethyl-4-piperidyl) imino group } hexa-methylene { (2,2,6; 6-tetramethyl-4-piperidyl) imino group }], dimethyl succinate and 4-hydroxyl-2,2,6, number-average molecular weight (Mn) is at 2000～5000 compound in the polymkeric substance of 6-tetramethyl-1-piperidines ethanol etc.

In the example of preferred hindered amine compound, comprise following HALS-1) and HALS-2).N representes number of repeat unit.

In above-mentioned object lesson; The Cyasorb UV-3346 (CAS-No.82541-48-7) that the CHIMASSORB2020FDL (CAS-No.192268-64-7) that BASF AG's (preceding Ciba Specialty Chemicals Co., Ltd.) produces and CHIMASSORB944FDL (CAS-No.71878-19-8), TINUVIN 123 (CAS-No.129757-67-1), TINUVIN 152 (CAS-No.191743-75-6), TINUVIN 770DF (CAS-No.52829-07-9), Sun Chemical Co., Ltd. produce, the Cyasorb UV-3529 (CAS-No.193098-40-7) of Sun Chemical Co., Ltd. production sell on market; The property obtained is good, is preferred therefore.

In addition, above-mentioned hindered amine compound can obtain from commercial sources as above-mentioned, also can use the compound of making through synthetic.Synthetic method as above-mentioned hindered amine compound has no particular limits, and can synthesize through the gimmick in the common organic synthesis.In addition, as the generation method, can suitably use distillation, recrystallization, precipitate, use the method for filtering agent and adsorbent again.In addition; Usually the commercially available compound that can cheap obtain is not independent above-mentioned hindered amine compound but potpourri sometimes; Which kind of form no matter all can not rely on manufacturing approach, composition, fusing point, acid number etc. and utilizes the compound that obtains from commercial sources but in the present invention.

Be used for above-mentioned hindered amine compound of the present invention and both can be low-molecular-weight; Also can be polymkeric substance with repetitive; But, be preferably HMW in order to make hindered amine compound concentrate the near interface that is present in active energy beam cured layer and cellulose acylate film.On the other hand, if molecular weight is too high, then the compatibility with acylated cellulose is not enough, and the mist degree of film can uprise.

The molecular weight of above-mentioned hindered amine compound is preferably 300～100000, and more preferably 700～50000, be preferably 2000～30000 especially.

In addition, be used for the preferably said hindered amine compound more than ketones solvent dissolving 0.01 quality % of above-mentioned hindered amine compound of the present invention.Through using so above-mentioned hindered amine compound; When making blooming of the present invention; Making an addition to above-mentioned hindered amine compound in the above-mentioned cellulose acylate film can be dissolved in the ketones solvent that preferably uses when stating the active energy beam cured layer after the formation and move; Finally in above-mentioned active energy beam cured layer, comprise above-mentioned hindered amine compound, from but preferred.

In addition, about the optimal way of above-mentioned ketones solvent, in the explanation of active energy beam cured layer, describe in the back.

< 2-2: the kind of active energy beam cured layer >

Functions such as the above-mentioned active energy beam cured layer in the blooming of the present invention preferably has forward scattering, anti-dazzle, gas barrier, smooth, electrostatic prevention, primary coat, is coated with firmly, antireflection, protection.That is, above-mentioned active energy beam cured layer is preferably functional layers such as forward scattering layer, antiglare layer, gas-barrier layer, smooth layer, antistatic backing, undercoat, hard conating, anti-reflection layer or protective seam.

Above-mentioned active energy beam cured layer is anti-reflection layer or hard conating more preferably, is preferably hard conating especially.

In addition, anti-reflection layer in the also preferred antireflection film in one deck and except that the active energy beam cured layer of these functional layers or the optical anisotropic layer in other the compensation film for angular field of view etc. are mutual uses compoundly.

These active energy beam cured layers are preferably disposed at least one surface in the blooming of the present invention.In addition, when blooming of the present invention is constituted polaroid as the combination of polaroid protective film and the polarizer, can be arranged on any single face or the two sides in polarizer side and the face (near the face of air side) opposite and use with the polarizer.

Describe in the face of functional layer down as active energy beam cured layer of the present invention.

In addition, blooming of the present invention is characterised in that on above-mentioned cellulose acylate film, to have at least 1 layer of active energy beam cured layer.Blooming of the present invention also can have as each functional layer of stating behind the active energy ray-curable, also can further have other nonactive energy ray-curable after each functional layer of stating.In addition, in blooming of the present invention, the active energy beam cured layer both can only be provided with 1 layer, also multilayer can be set, and in addition, a plurality of each active energy beam cured layer both can be identical, also can be different.

(1) hard conating

Because blooming of the present invention is given mechanical strengths such as mar resistance, therefore preferably hard conating is arranged on the surface of above-mentioned cellulose acylate film as the active energy beam cured layer.

The thickness of hard conating is preferably 0.2～100 μ m, and more preferably 0.5～50 μ m is preferably 1～20 μ m especially.

The intensity of hard conating preferably is more than the H, more preferably more than the 2H, most preferably to be more than the 3H in according to the pencil hardness test of JIS K5400.In addition, in the bevel-type test according to JIS K5400, the abrasion value of the test film before and after the test is few more preferred more.

The material (bonding agent) that forms hard conating can use the compound that comprises the ethylenic unsaturated group, the compound that comprises ring-opening polymerization property group, and these compounds can use or make up use separately.

As the above-mentioned preferred example that comprises the compound of ethylenic unsaturated group, can be with the polyacrylic acid lipid of polyvalent alcohols such as glycol diacrylate, trimethylolpropane triacrylate, double trimethylolpropane tetraacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, double pentaerythritol C5 methacrylate, double pentaerythritol methacrylate; The diacrylate of bisphenol A diglycidyl ether, the epoxy acrylate classes such as diacrylate of hexanediol diglycidyl ether; Comprising the preferred compound of conducts such as urethane acrylate that the reaction of the acrylic ester of hydroxyl obtains through polyisocyanate and hydroxy-ethyl acrylate etc. enumerates out.

In addition; As the above-mentioned commercial compound that comprises the compound of above-mentioned ethylenic unsaturated group, can enumerate out PET-30 (Nippon Kayaku K. K's production), Biscoat 360 (Osaka Organic Chemical Industry Co., Ltd.'s production), EB-600, EB-40, EB-140, EB-1150, EB1290K, IRR214, EB-2220, TMPTA, TMPTMA (above), UV-6300, UV-1700B (above) etc. by The Nippon Synthetic Chemical Industry Co., Ltd's production by the production of DAICEL-UCB Co., Ltd..

In addition; As the above-mentioned preferred example that comprises the compound of ring-opening polymerization property group, that can enumerate out ethylene glycol diglycidylether as the diglycidyl ethers, bisphenol A diglycidyl ether, trimethylolethane trimethacrylate glycidol ether, trihydroxymethylpropanyltri diglycidyl ether, T 55, triglycidyl group trihydroxy ethyl isocyanuric acid ester, D-sorbite four glycidol ethers, pentaerythrite four glycidol ethers, the polyglycidyl ether of cresols novolac resin, the polyglycidyl ether of phenol novolac resin etc., the CELLOXIDE 2021P as the ester ring type epoxies, CELLOXIDE 2081, Epolead GT-301, Epolead GT-401, EHPE3150CE (above produced by Daicel chemical industry Co., Ltd.), phenol novolac resin gathers cyclohexyl epoxy methyl ether etc., the OXT-121 as the oxetanes class, OXT-221, OX-SQ, PNOX-1009 (above produced by Toagosei Co., Ltd) etc.In addition, also can with the polymkeric substance of (methyl) glycidyl acrylate or with can and the multipolymer of the monomer of (methyl) glycidyl acrylate copolymerization be used for hard conating.

For the adaptation of the cure shrinkage, raising and the base material that reduce hard conating, give light diffusing, reduce of the present invention being coated with firmly and handle curling of article, preferably also in hard conating, add the crosslinked particulate of the organic fine particles such as cross-linked rubber particulate etc. of oxide fine particle or tygon, the polyphenyl alkene of silicon, titanium, zirconium, aluminium etc., the crosslinked particle that gathers (methyl) esters of acrylic acid, dimethyl silicone polymer etc., SBR, NBR etc.The mean grain size of these crosslinked particulates is preferably 1nm～20000nm.In addition, the shape of crosslinked particulate can be spherical, bar-shaped a, needle-like, tabular etc., can use with having no particular limits.The addition of particulate is preferably below the 60 volume % of the hard conating after the curing, more preferably below the 40 volume %.

When adding the inorganic particles of above-mentioned record; General owing to poor with the affinity of binder polymer, therefore go back the surface conditioning agent that preferably uses metals such as comprising silicon, aluminium, titanium and have functional groups such as alkoxide group, carboxylic acid group, sulfonic group, phosphonate group and carry out surface treatment.

Hard conating preferably the curable compound through utilizing light and/or heat cross-linking reaction or form by polyreaction.Preferred light polymerism functional group of curable functional group.

In addition, also can further use the organometallics that comprises water-disintegrable functional group.The above-mentioned preferred organic polyglycidyl compounds of organometallics that comprises water-disintegrable functional group.

In addition, also polymerization initiator, levelling agent can be added in the hard conating, known arbitrarily material can be used.

As the concrete formation constituent of hard conating, can preferably use the composition of record in for example TOHKEMY 2002-144913 communique, TOHKEMY 2000-9908 communique, WO2000/46617 communique etc.

(2) anti-reflection layer

For blooming of the present invention, also can anti-reflection layer be arranged on the surface of above-mentioned cellulose acylate film as the active energy beam cured layer.

It is about 1.5% layer that above-mentioned anti-reflection layer can use low-index material such as fluorine-based polymer only to give the reflectivity that forms with individual layer, or utilized film multi-coated interference reflectivity 1% below layer in any one.Among the present invention, the preferred use in the transparent supporting body laminated has forming low-refractive-index layer and the structure with the refractive index that is higher than low-index layer at least 1 layer (being high refractive index layer, middle index layer).In addition, also can preferably use skill newspaper, vol.38, No.1, may, the anti-reflection layer of record in 2000,26 pages～28 pages, TOHKEMY 2002-301783 number etc. in day east.

The reflectivity of each layer satisfies following relation.

The refractive index of the refractive index＞low-index layer of the refractive index＞transparent supporting body of the refractive index of high refractive index layer＞middle index layer

The transparent supporting body that is used for antireflection film can preferably use the transparent polymer film of the diaphragm that is used for the above-mentioned polarizer.

The refractive index of low-index layer is 1.20～1.55, is preferably 1.30～1.50.Low-index layer be preferably used as have mar resistance, the outermost layer of soil resistance.In order to improve mar resistance, the material that also preferred use comprises silicone base, fluorine is given slickness to the surface.

Fluorochemicals for example can preferably use the compound of in the 0027th～0028 section in the instructions of the 0019th～0030 section in the instructions of the 0018th～0026 section in the instructions of the flat 9-222503 communique of TOHKEMY, the flat 11-38202 communique of TOHKEMY, TOHKEMY 2001-40284 communique, TOHKEMY 2000-284102 communique etc., putting down in writing.

Contain the compound that silicone compounds preferably has polysiloxane structure, but also can use reactive silicone (for example Silaplane (production of Chisso Co., Ltd.)), comprise polysiloxane (TOHKEMY is put down the 11-258403 communique) of silanol group etc. at two ends.Organometallics such as silane coupling agent is solidified (at the clear 58-142958 communique of TOHKEMY with the silane coupling agent that comprises specific fluorine-containing alkyl; The clear 58-147483 communique of TOHKEMY; The clear 58-147484 communique of TOHKEMY; TOHKEMY is put down the 9-157582 communique; TOHKEMY 11-106704 communique; TOHKEMY 2000-117902 communique; TOHKEMY 2001-48590 communique; The compound of putting down in writing in the TOHKEMY 2002-53804 communique etc.).

Also preferably in low-index layer, comprise filling agent as the adjuvant except that above-mentioned (for example silicon dioxide, fluorine-containing particle primary particle mean diameters such as (magnesium fluoride, calcium fluoride, barium fluorides) are the low-refraction mineral compound of 1～150nm, the organic fine particles in the 0020th～0038 section of TOHKEMY 11-3820 communique, put down in writing etc.), silane coupling agent, smoothing preparation, surfactant etc.

Low-index layer also can pass through vapor phase method (vacuum vapour deposition, sputtering method, ion plating method, plasma CVD method etc.) and form, but the aspect from making at an easy rate preferably forms through rubbing method.As rubbing method, can preferably use dip coating, airblade coating method, curtain to be coated with method, rolling method, coiling rod rubbing method, intaglio plate rubbing method, miniature intagliotype.

The thickness of low-index layer is preferably 30～200nm, and more preferably 50～150nm most preferably is 60～120nm.

The mineral compound ultramicron that middle index layer and high refractive index layer are preferably the high index of refraction of mean grain size below 100nm is scattered in parent with the structure that forms in the material.The mineral compound particulate of high index of refraction can preferably use refractive index at the oxide of the mineral compound more than 1.65, for example Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, In etc., comprise the composite oxides of these metallic atoms etc.

Such ultramicron can following mode use: particle surface is handled that (silane coupling agent etc.: TOHKEMY is put down the flat 11-153703 communique of 11-295503 communique, TOHKEMY, TOHKEMY 2000-9908 communique through surface conditioning agent; Anionic property compound or organic metal coupling agent: TOHKEMY 2001-310432 communique etc.); Perhaps forming and making the high index of refraction particle is the core shell structure (TOHKEMY 2001-166104 communique etc.) of core, perhaps and with particular dispersing agent (for example TOHKEMY is put down 11-153703 communique, US6210858B1 patent, TOHKEMY 2002-2776069 communique etc.) etc.

Parent can use existing known thermoplastic resin, curable resin epithelium etc. with material, but also can use the curable film by the metal alkoxide compositions acquisition of record in the multi-functional material, TOHKEMY 2001-293818 communique etc. of record in TOHKEMY 2000-47004 communique, TOHKEMY 2001-315242 communique, TOHKEMY 2001-31871 communique, TOHKEMY 2001-296401 communique etc.

The refractive index of high refractive index layer is preferably 1.70～2.20.The thickness of high refractive index layer is preferably 5nm～10 μ m, more preferably 10nm～1 μ m.

The refractive index of middle index layer is adjusted according to the mode of the value between the refractive index of refractive index that is in low-index layer and high refractive index layer.The refractive index of middle index layer is preferably 1.50～1.70.

The mist degree of anti-reflection layer is preferably below 5%, more preferably below 3%.In addition, film strength is preferably more than the H in the pencil hardness test according to JIS K5400, more preferably more than the 2H, most preferably is more than the 3H.

(3) forward scattering layer

In blooming of the present invention, also can the forward scattering layer be arranged on the surface of above-mentioned cellulose acylate film as the active energy line curing layer.

The forward scattering layer is to use for the viewing angle characteristic (form and aspect and Luminance Distribution) that improves the direction up and down when polaroid of the present invention is used for liquid crystal indicator.Among the present invention; The structure that the microparticulate that preferred index is different forms in bonding agent for example can be used the flat 11-38208 communique of the TOHKEMY of forward scattering coefficient specialization, the relative index of refraction of transparent resin and particulate is located at TOHKEMY 2000-199809 communique in the particular range, haze value is defined as the structure in the TOHKEMY 2002-107512 communique more than 40% etc.In addition, for the viewing angle characteristic of the mist degree of controlling polarizer of the present invention, also can be preferably and 31 pages～39 pages of technical reports of Sumitomo Chemical " exhibiting optical function film " (" ray machine can property Off イ Le system ") in " the Le ミ ス テ イ " of record be used in combination.

(4) antiglare layer

For blooming of the present invention, also can antiglare layer be arranged on the surface of above-mentioned acylated cellulose as the active energy beam cured layer.

Antiglare layer is used in order to prevent reflection light diffusing from mirroring.Anti-dazzle function forms concavo-convex the acquisition through going up on the surface (demonstration side) of liquid crystal indicator.Mist degree with blooming of anti-dazzle function is preferably 3～30%, and more preferably 5～20%, most preferably be 7～20%.

Can for example preferably use forming concavo-convex method on the film surface: add particulate on the film surface, to form concavo-convex method (for example TOHKEMY 2000-271878 communique etc.); Add the method (for example TOHKEMY 2000-281410 communique, TOHKEMY 2000-95893 communique, TOHKEMY 2001-100004 communique, TOHKEMY 2001-281407 communique etc.) that forms uneven-surface film than macroparticle (particle diameter is at 0.05～2 μ m) of a small amount of (0.1～50 quality %); On the film surface with the method for physics mode transfer printing concaveconvex shape (, in the clear 63-278839 communique of TOHKEMY, the flat 11-183710 communique of TOHKEMY, TOHKEMY 2000-275401 communique etc., putting down in writing) etc. for example as the embossing job operation.

< 2-3: the manufacturing approach of active energy beam cured layer >

The formation method of above-mentioned active energy beam cured layer has no particular limits, and can use known method.After the material (bonding agent) that wherein, preferably will form above-mentioned active energy beam cured layer is dissolved in the organic solvent it is coated on the above-mentioned cellulose acylate film and forms.

As above-mentioned organic solvent, can known organic solvent be used separately or multiple mixing use.Wherein, preferred ketones solvent, acetates solvent, the varsol of using among the present invention.

As above-mentioned solvent, can enumerate out for example MiBK (methyl isobutyl ketone), MEK (methyl ethyl ketone), ethyl acetate, toluene etc.

About applying the concrete method of above-mentioned active energy beam cured layer, also have no particular limits, but can preferably use miniature gravure coating mode.In addition, the travelling speed about when coating also has no particular limits, and preferably under travelling speed is 1～100m/ minute condition, is coated with.Drying about after the coating also has no particular limits, and is 25～140 ℃ of following dryings 30～1000 seconds at baking temperature preferably.

For above-mentioned active energy beam cured layer; More preferably use radioactive ray, gamma rays, α-ray, electron ray, ultraviolet isoreactivity energy-ray in the active energy beam; If consider security, throughput rate, especially preferably use electron ray, ultraviolet ray.When solidifying through heat, consider the thermotolerance of plastics itself, heating-up temperature is preferably below 140 ℃, more preferably below 100 ℃.

When the irradiation active energy beam, shine while preferably carry out nitrogen removing (purge) (oxygen concentration is below 0.5%).About the intensity of active energy beam etc., also have no particular limits, but in irradiation for example during ultraviolet ray, preferably shining illumination is 10～1000mW/cm ², exposure is 50～1000mJ/cm ²Ultraviolet ray.

(polaroid)

In addition, the invention still further relates to a kind of polaroid, it is characterized in that, use the blooming of at least 1 anticipatory remark invention.

Polaroid of the present invention preferably have the polarizer and on a face of this polarizer as the blooming of the present invention of polaroid protective film.More preferably following polaroid: it comprises polarizer layer and at least 1 blooming, and it is blooming of the present invention to be fitted near the mode of above-mentioned polarizer layer according to the face of an opposite side with the active energy beam cured layer form.

Same with optical compensation films of the present invention; But the form of polaroid of the present invention not only comprise according to former state the size that is assembled in the liquid crystal indicator cut off the polaroid of the diaphragm form form, but also comprise through continuous production and be made into strip and the polaroid of the form (for example roller length is more than the 2500m or the form more than 3900m) rolled with the roller shape.In order to be used as big picture liquid crystal indicator purposes, as stated, the width of polaroid is preferably more than 1470mm.

The concrete structure of polaroid of the present invention has no particular limits, and can adopt known structure, can adopt the structure of for example in Fig. 6 of TOHKEMY 2008-262161 communique, putting down in writing.

(quadrature transmission change)

In this manual, the quadrature transmissivity CT of polaroid uses UV3100PC (Shimadzu Seisakusho Ltd.'s production) to measure.In mensuration, under 410nm, measure, use the mean value of measuring for 10 times.

The polaroid endurancing can polaroid be pasted on form on glass and carries out as follows via bonding agent.Make 2 polarizing plate stickings in sample on glass (about 5cm * 5cm).In veneer quadrature transmissivity is measured, a side of the film of this sample is set and measured towards light source.Respectively 2 samples are measured, with the quadrature transmissivity of its mean value as polaroid of the present invention.

Polaroid of the present invention is in the polaroid endurancing, and its variable quantity is more little preferred more.

For polaroid of the present invention is that the variable quantity (%) of the quadrature veneer transmissivity when leaving standstill 1000 hours 95% time is below 1.40% at 60 ℃, relative humidity preferably.

Be that the variable quantity (%) of the quadrature veneer transmissivity when leaving standstill 1000 hours 95% time is below 1.00%, to be preferably below 0.5% especially more preferably at 60 ℃, relative humidity.Here, variable quantity is for deducting the value that the preceding measured value of test obtains from test the back measured value.

If satisfy the scope of the variable quantity of above-mentioned quadrature transmissivity, then can guarantee polaroid in hot and humid down long-time use or the stability in the keeping process, from but preferred.

[liquid crystal indicator]

The invention still further relates to liquid crystal indicator with blooming of the present invention or polaroid of the present invention.

Liquid crystal indicator of the present invention is preferably the liquid crystal indicator of IPS, OCB or VA pattern; It is the liquid crystal indicator with liquid crystal cells and a pair of polaroid of the both sides that are arranged at this liquid crystal cells; It is characterized in that at least one in the above-mentioned polaroid is polaroid of the present invention.

Concrete structure about liquid crystal indicator of the present invention has no particular limits, and can use known structure.In addition, also can preferably use the structure of in Fig. 2 of TOHKEMY 2008-262161 communique, putting down in writing.

Embodiment

Enumerating embodiment below explains the present invention more specifically.For the shown material of following embodiment, reagent, amount and ratio, operation etc., only otherwise break away from purport of the present invention, can suitably change.Therefore, scope of the present invention is not limited to following object lesson.

[embodiment 101]

(1) the system film of cellulose acylate film

< preparation of acylated cellulose >

The preparation degree of substitution with acetyl group is 2.87 acylated cellulose.Wherein, add sulfuric acid (is 7.8 mass parts with respect to cellulose 100 mass parts), add the carboxylic acid of the raw material that becomes acyl substituent, under 40 ℃, carry out acylation reaction as catalyzer.In addition, after acidylate, under 40 ℃, carry out slaking.Then, wash and remove with the low molecular weight compositions of acetone this acylated cellulose.

< top layer is with the preparation of smears (solution) 101 >

(preparation of the solution 1 of acylated cellulose)

Following composition is dropped in the blending bin, stir with each composition dissolving preparation acylated cellobiose cellulose solution 1.

In addition, to use the degree of substitution of benzoyl be 8 replacement body at 15 moles below the %, degree of substitution is that to be aggregated in 70 moles below the %, degree of substitution be that to be aggregated in 40 moles of average substitution degrees below the % be 5～6 sucrose benzoate for 5～3 replacement body for 7,6 replacement body as the sucrose benzoate of above-mentioned plastifier.

(preparation of matting agent solution 2)

Following composition is dropped in the dispersion machine, stir with each composition dissolving preparation matting agent solution 2.

Use line mixer that 1.3 mass parts of above-mentioned matting agent solution 2 and 98.7 mass parts of acylated cellobiose cellulose solution 1 are mixed, the preparation top layer is with solution 101.

< sandwich layer is with the preparation of smears 101 >

(preparation of acylated cellobiose cellulose solution 2)

Following composition is dropped in the blending bin, stir each composition dissolving, the preparation sandwich layer is with smears 101

The sucrose benzoate of above-mentioned plastifier uses and the identical sucrose benzoate of sucrose benzoate that in acylated cellobiose cellulose solution 1, uses.

Ultraviolet light absorber C

< curtain coating >

Use the cylinder casting device, from the curtain coating mouth equably with the smears (sandwich layer is with smears 101) of above-mentioned preparation, be positioned at its both sides the top layer with the mode curtain coating to the curtain coating supporter of stainless steel (supporter temperature be-9 ℃) of smears 101 with 3 layers of while.Residual solvent amount in the smears of each layer is that roughly the state of 70 quality % peels; Through pin stenter the two ends of the Width of film are fixed; Drying is carried out on the 1.28 times of one side that stretch in the horizontal on one side, is the state of 3～5 quality % up to the residual solvent amount.Then,, carry out drying again, obtain the cellulose acylate film of embodiment 1 through between the roller of annealing device, transporting.The thickness of the cellulose acylate film that obtains is that 60 μ m, width are 1480mm.

(2) the system film of active energy beam cured layer

< hard conating is with the preparation of coating fluid (HC-1) >

Make each composition according to the composition shown in the table below, the use aperture is that the film of the polypropylene system of 30 μ m filters, and the preparation hard conating is used coating fluid.

The compound of above-mentioned use illustrates below.

PET-30: the potpourri of pentaerythritol triacrylate, tetramethylol methane tetraacrylate (Nippon Kayaku K. K's production);

Biscoat 360: trimethylolpropane PO modification triacrylate (Osaka Organic Chemical Industry Co., Ltd.'s production);

8 μ m crosslink propylene bases/styrene particulate 30%MiBK dispersion liquid (light diffusing particle): with mean grain size is the MiBK dispersion liquid that 8.0 μ m (Sekisui Fine Chemical Co., Ltd.'s production) obtained with the 10000rpm dispersion through the Polytron dispersion machine in 20 minutes;

Irgacure 127: polymerization initiator (BASF AG's production);

FP-13: the fluorine class surface modifier of record in 0341 section in TOHKEMY 2009-063983 communique (use the form dissolving back with the 10 quality % solution of MEK);

CHIMASSORB 2020 FDL (hindered amine compound that BASF AG produces).

In addition, above-mentioned in, MiBK representes methyl isobutyl ketone, MEK representes methyl ethyl ketone, is ketones solvent.

< formation of hard conating >

On the face that when the formation of the above-mentioned cellulose acylate film of processing, contacts (be called below " support dignity ") with supporter, according to miniature gravure coating mode be in travelling speed under 30m/ minute the condition coating hard conating with coating fluid (HC-1).After under 60 ℃ dry 150 seconds, when carrying out nitrogen removing (purge) (oxygen concentration is below 0.5%), use air cooling metal halide lamp (production of Eye Graphics Co., Ltd.) the irradiation illumination of 160W/cm to be 400mW/cm ², exposure is 150mJ/cm ²Ultraviolet ray, make coating layer be solidified to form hard conating.The thickness of hard conating is 6 μ m.

With the blooming (polaroid protective film) of the polaroid protective film that has hard conating that is obtained as embodiment 101.

(3) making of polaroid

[saponification of polaroid protective film is handled]

Under 55 ℃, the polaroid protective film of the embodiment 101 that makes impregnated in the sodium hydrate aqueous solution of 2.3mol/L 3 minutes.In the washing bath of room temperature, wash, use the sulfuric acid of 0.05mol/L to neutralize down at 30 ℃.In the washing bath of room temperature, wash once more, the hot blast of following with 100 ℃ carries out drying.So the blooming (polaroid protective film) of embodiment 101 is carried out the saponification processing on surface.

[making of polaroid]

Iodine is adsorbed on the polyvinyl alcohol film of drawn, makes the polarizer.

Use the polyvinyl alcohol bonding agent will be pasted on a side of the polarizer through the face of the opposite side in the polaroid protective film of the embodiment 101 that saponification is handled with hard conating.To commercially available three cellulose acetate membrane (FUJITAC TD80UF; Fuji Photo Film Co., Ltd.'s system) carries out identical saponification and handle, use three cellulose acetate membrane after the polyvinyl alcohol bonding agent is handled saponification to be pasted on and to post on the face of the polarizer of the opposite side of a side of blooming (polaroid protective film) of embodiment 101 of made.

At this moment, the perpendicular mode of slow axis according to the polaroid protective film of the embodiment 101 of the axis of homology of the polarizer and made is provided with.In addition, the slow axis of the axis of homology of the polarizer and commercially available three cellulose acetate membrane also is to be provided with according to perpendicular mode.

So make the polaroid of embodiment 101.

[embodiment 102～118 and comparative example 201～203]

[making of the blooming (polaroid protective film) of embodiment 102～118 and comparative example 201～203]

Except as record in the table 8, changing the kind and addition, the film thickness that make an addition to the plastifier in the acylated cellulose among the embodiment 101, making an addition to the kind of the hindered amine compound in the active energy beam cured layer and the addition, likewise make the blooming (polaroid protective film) of embodiment 102～118 and comparative example 201～203.

In addition, in following table 8, the addition of plastifier is represented the mass parts with respect to acylated cellulose resin 100 mass parts.In addition; In following table 8; Sucrose benzoate represent the degree of substitution of benzoyl be 8 replacement body 15 moles below the %, degree of substitution be 7～6 replacement body be aggregated in 70 moles below the %, degree of substitution be 5～3 replacement body to be aggregated in 40 moles of average substitution degrees below the % be 5～6 sucrose benzoate, sucrose acetate isobutyrate is represented the SAIB100 that Eastman Chemical company produces.

Above-mentioned polycondensation ester J-39

[the saponification processing of polaroid protective film and the making of polaroid]

The polaroid protective film of the blooming (polaroid protective film) of embodiment 102～118 and comparative example 201～203 is carried out the saponification processing identical with embodiment 101 and the making of polaroid respectively, make the polaroid of each embodiment and comparative example.

[evaluation]

< evaluation of adaptation >

At first; To each embodiment of above-mentioned making and the polaroid protective film that has hard conating of comparative example, utilizing the Suga Test Instruments of Co., Ltd. system Super Xenon Weather Meter SX75 is that 50% environment shone for 100 little time down at 60 ℃, relative humidity.

Then, be that 25 ℃, relative humidity are under 60% the condition in temperature, the polaroid protective film that has hard conating is carried out damping in 2 hours.On the surface of a side with hard conating; Carry out vertical 11, horizontal 11 cutting through cutting knife with go flaking trellis; Carve and amount to 100 foursquare lattice, the polyester-bonded adhesive tape (No.31B) that stickup Nitto Denko Corp produces on its face.After through 30 minutes, vertically adhesive tape to be peeled off apace, the number of the lattice that number goes out to peel off is estimated according to the benchmark of 4 following grades.Carry out 3 same driving fit evaluations, average.

Do not see fully in the A:100 lattice and peel off.

Visible 1～2 lattice peels off in the B:100 lattice.

The peeling off of visible 3～10 lattice (in the allowed band) in the C:100 lattice.

Above the peeling off of visible 11 lattice in the D:100 lattice.

The result that record obtains to some extent in above-mentioned table 8.

< evaluation of pencil hardness >

Carry out the pencil hardness evaluation of record in JIS K 5400.In temperature is that 25 ℃, humidity are with the polaroid protective film damping after 2 hours under the 60%RH; Use the test of the H～5H of regulation among the JIS S 6006 to use pencil; Load with 500g is estimated through the judgement of following that kind, and the maximum hardness that will reach OK is as evaluation of estimate.

In the evaluation of n=5, do not hinder～1 place and hinder: OK

In the evaluation of n=5, the above wound in 2 places: NG is arranged

(polaroid Evaluation of Durability)

Use the method for putting down in writing in this instructions to measure the quadrature transmissivity of the polarizer under the wavelength 410nm to each embodiment of above-mentioned making and the polaroid of comparative example.

Then, be that 95% environment is preserved down after 1000 hours also through identical method mensuration quadrature transmissivity to 60 ℃, relative humidity.Obtain the variation of the quadrature transmissivity of elapsed-time standards front and back, as polarizer permanance, its result is recorded in the above-mentioned table 8 with it.

Result by above-mentioned table 8 can know, in cellulose acylate film, do not comprise plastifier comparative example 201, comprise the plastifier beyond the plastifier of the present invention comparative example 202 all in degradation, polarizer poor durability through the hot and humid back generation polarizer.Can know that in addition the adaptation of comparative example 203 that in the active energy beam cured layer, does not comprise hindered amine compound is poor.

Can know that on the other hand the polaroid that blooming of the present invention is used as the embodiment 101～118 of polaroid protective film all is difficult to take place the degradation of the polarizer after process is hot and humid, be preferred.Can know that in addition even as the blooming of the present invention of polaroid protective film irradiates light for a long time, the adaptation between hard conating and the cellulose acylate film is also good, be difficult to peel off, and mar resistance be also high, be preferred.

[embodiment 301]

[making of liquid crystal indicator]

Peel off the polaroid of beholder's side of commercially available liquid crystal TV set (the BRAVIA J5000 of SONY Co., Ltd.), the polaroid of the present invention of the polaroid protective film that has used embodiment 101 is pasted via bonding agent according to the mode that the polaroid protective film of embodiment 101 is positioned at liquid crystal cell side.The axis of homology of the polaroid of beholder's side is provided with on above-below direction.In addition, except the polaroid protective film that uses comparative example 201～203, likewise make the liquid crystal indicator of comparative example.The liquid crystal indicator of so making of the present invention is compared with the liquid crystal indicator of the polaroid protective film that uses each comparative example, uses for a long time even contact without under the environment of direct sunlight, and the deterioration of display performance is also little, is preferred.

[embodiment 401]

(1) the system film of cellulose acylate film

(preparation of acylated cellobiose cellulose solution 41)

Following composition is dropped in the blending bin, stir with each composition dissolving preparation acylated cellobiose cellulose solution 41.

(preparation of matting agent solution 42)

Following composition is dropped in the dispersion machine, stir with each composition dissolving preparation matting agent solution 42.

(curtain coating)

The acylated cellobiose cellulose solution 41 that adds above-mentioned matting agent solution 42,98.7 mass parts of 1.3 mass parts uses line mixer to mix.Use the band casting device, with the smears curtain coating (the supporter temperature is 22 ℃) to the curtain coating supporter of stainless steel of above-mentioned preparation.The state that residual solvent amount in the smears is roughly 20 quality % peels; Hold the two ends of the Width of film through stenter; In the residual solvent amount is under the state of 5～10 quality %, on one side under 120 ℃ temperature, stretch in the horizontal 1.20 times (20%) carry out drying on one side.Then,, carry out drying again, obtain the cellulose acylate film of embodiment 401 through between the roller of annealing device, transporting.The thickness of the acylated cellulose that is obtained is that 33 μ m, width are 1480mm.

(2) the system film of active energy beam cured layer

< hard conating is with the preparation that applies liquid (HC-1) >

Make each composition according to the composition shown in the table below, the use aperture is that the filtrator of the polypropylene system of 30 μ m filters, and the preparation hard conating is used coating fluid.

To the above-mentioned compound that uses, except the compound of describing in front, illustrate below.

CHIMASSORB 944 FDL (hindered amine compound that BASF AG produces)

< formation of hard conating >

On the face that when the formation of the above-mentioned cellulose acylate film of processing, contacts (be called below " support dignity ") with supporter, according to miniature gravure coating mode, in travelling speed be under 30m/ minute the condition coating hard conating with coating fluid (HC-1).After under 80 ℃ dry 120 seconds, when carrying out nitrogen removing (oxygen concentration is below 0.5%), use air cooling metal halide lamp (production of Eye Graphics Co., Ltd.) the irradiation illumination of 160W/cm to be 400mW/cm ², exposure is 150mJ/cm ²Ultraviolet ray, make coating layer be solidified to form hard conating.The thickness of hard conating is 3 μ m.

With the blooming (polaroid protective film) of the polaroid protective film that has hard conating that is obtained as embodiment 401.

(3) making of polaroid

[saponification of polaroid protective film is handled]

Under 55 ℃, the polaroid protective film of the embodiment 401 that makes impregnated in the sodium hydrate aqueous solution of 2.3mol/L 3 minutes.In the washing bath of room temperature, wash, use the sulfuric acid of 0.05mol/L to neutralize down at 30 ℃.In the washing bath of room temperature, wash once more, the hot blast of following with 100 ℃ carries out drying.So the blooming (polaroid protective film) of embodiment 401 is carried out the saponification processing on surface.

[making of polaroid]

Iodine is adsorbed on the polyvinyl alcohol film of drawn, makes the polarizer.

Use the polyvinyl alcohol bonding agent will be pasted on a side of the polarizer through the face of the opposite side in the polaroid protective film of the embodiment 401 that saponification is handled with hard conating.To commercially available three cellulose acetate membrane (FUJITAC T40UZ; Fuji Photo Film Co., Ltd. produces) carry out identical saponification and handle, use three cellulose acetate membrane after the polyvinyl alcohol bonding agent is handled saponification to be pasted on and to post on the face of the polarizer of the opposite side of a side of blooming (polaroid protective film) of embodiment 401 of making.

At this moment, the perpendicular mode of slow axis according to the polaroid protective film of the embodiment 401 of the axis of homology of the polarizer and making is provided with.In addition, the slow axis of the axis of homology of the polarizer and commercially available three cellulose acetate membrane also is provided with according to perpendicular mode.

So make the polaroid of embodiment 401.

[comparative example 402～404]

The value of the table of stating after the thickness of polaroid protective film becomes in the polaroid of embodiment 401 is made 9, likewise make the polaroid of embodiment 402～404 with embodiment 401.

[comparative example 411]

Except the hard conating in embodiment 401 with not adding in the coating fluid (HC-1) the CHIMASSORB 944FDL (BASF AG produce hindered amine compound), likewise make the polaroid 411 of comparative example with embodiment 401.

[comparative example 412]

Except in the cellulose acylate film of comparative example 411, adding CHIMASSORB 944 FDL (hindered amine compound that BASF AG produces) of 1.5 mass parts, likewise make cellulose acylate film 412 with comparative example 411 with respect to acylated cellulose 100 mass parts.

[comparative example 413～415]

The value of the table of after the thickness with cellulose acylate film in the comparative example 412 becomes, stating 9, likewise make cellulose acylate film 413～415 with comparative example 412.

[embodiment 501]

(preparation of acrylic acid solution 51)

Following composition is dropped in the blending bin, stir with each composition dissolving preparation acrylic acid solution 51.

(preparation of acylated cellobiose cellulose solution 52)

Following composition is dropped in the blending bin, stir with each composition dissolving preparation acylated cellobiose cellulose solution 52.

In addition, employed sucrose benzoate uses the sucrose benzoate identical with embodiment 101 among the embodiment 501.

(curtain coating)

Use aforesaid propylene acid solution 51 and acylated cellobiose cellulose solution 52; Through can 3 layers the curtain coating coating machine of curtain coatings altogether; On the metal support near the side on the metal support, carry out curtain coating according to the mode that the layer that forms acrylate layer/acylated cellulose layer/acrylate layer=30 μ m/10 μ m/30 μ m constitutes.Be positioned on the metal support during dry wind through 40 ℃ the smears carried out drying form film, then it is peeled off, through pin the two ends of film are fixed, Yi Bian keep with same intervals during this period, on one side with 105 ℃ dry wind drying 5 minutes.After pin taken off, again 130 ℃ dry 20 minutes down, batch with the state of stacked film.

At first peel off the acrylic film on upper strata from the stacked film of manufacturing like this and after it is removed, utilize the method identical, process the active energy beam cured layer through on the acylated cellulose layer, being coated with hard conating with embodiment 401.Then, the acrylic film of lower floor is peeled off, utilized and carry out the saponification processing with embodiment 401 identical methods and fit manufacturing polaroid 501.

[embodiment 502～503]

Except the thickness of the polaroid protective film in the making of the polaroid of embodiment 501 is changed into the value of record in following table 9, likewise make the polaroid of embodiment 502 and 503.

[evaluation]

< evaluation of adaptation >

At first; To each embodiment of above-mentioned making and the polaroid that has hard conating of comparative example, utilizing the Suga Test Instruments of Co., Ltd. system Super Xenon Weather Meter SX75 is that 50% environment shone for 196 little time down at 60 ℃, relative humidity.

Then, be that 25 ℃, relative humidity are under 60% the condition in temperature, the polaroid that has hard conating is carried out damping in 2 hours.On the surface of a side with hard conating; Carry out vertical 11, horizontal 11 cutting through cutting knife with go flaking trellis; Carve and amount to 100 foursquare lattice, the polyester-bonded adhesive tape (No.31B) that stickup Nitto Denko Corp produces on its face.After through 30 minutes, vertically adhesive tape to be peeled off apace, the number of the lattice that number goes out to peel off is estimated according to the benchmark of 4 following grades.Carry out 3 same driving fit evaluations, average.

Do not see fully in the A:100 lattice and peel off.

Visible 1～2 lattice peels off in the B:100 lattice.

The peeling off of visible 3～10 lattice (in the allowed band) in the C:100 lattice.

Above the peeling off of visible 11 lattice in the D:100 lattice.

The result that record obtains to some extent in above-mentioned table 9.

< evaluation of pencil hardness >

Utilize with the identical method of blooming (polaroid protective film) of embodiment 101～118 and comparative example 201～203 and estimate.

(polaroid Evaluation of Durability)

Utilize with the identical method of blooming (polaroid protective film) of embodiment 101～118 and comparative example 201～203 and estimate

The result is recorded in the following table 9.

Result by above-mentioned table 9 can know, in the active energy beam cured layer, comprises the polaroid of the present invention (embodiment 401～404,501～503) of hindered amine compound even under the situation of the thickness attenuation of polaroid protective film, still can keep good adaptation.Can know that in addition relative therewith, the adaptation of comparative example 411～415 that in the active energy beam cured layer, does not comprise hindered amine compound is poor.Particularly when the thickness of polaroid protective film approaches, can know that being difficult to obtain sufficient driving fit through the method for in the polaroid protective film (cellulose acylate film) as putting down in writing in the TOHKEMY 2006-123513 communique, adding hindered amine compound improves effect.Can know in addition; When under identical thickness, comparing, adding in the polaroid protective film of that kind of in above-mentioned communique, putting down in writing (cellulose acylate film) in the method for hindered amine compound, is the preservation after 1000 hours down of 90% environment at 60 ℃, relative humidity; Polarization property is deterioration significantly; Relative therewith, the deterioration of polarization property of polaroid of the present invention (embodiment 401～404,501～503) that in the active energy beam cured layer, comprises hindered amine compound is little, is preferred.

Claims (7)

1. blooming, it has cellulose acylate film and active energy beam cured layer;

Said cellulose acylate film comprises at least a kind of plastifier from carbohydrate derivates, polyol ester and polycondensation ester, selecting, and said active energy beam cured layer comprises hindered amine compound.

2. blooming according to claim 1, wherein, the thickness of said cellulose acylate film is more than the 10 μ m and below the 35 μ m.

3. blooming according to claim 1 and 2, wherein, the content of the said plastifier in the said cellulose acylate film is 1～20 mass parts with respect to acylated cellulose 100 mass parts.

4. blooming according to claim 1 and 2, wherein, said active energy beam cured layer comprises bonding agent, and the content of said hindered amine compound is 0.001～10 mass parts with respect to said bonding agent 100 mass parts.

5. blooming according to claim 3, wherein, said active energy beam cured layer comprises bonding agent, and the content of said hindered amine compound is 0.001～10 mass parts with respect to said bonding agent 100 mass parts.

6. polaroid, it comprises polarizer layer and at least 1 blooming, and it is each described blooming in the claim 1～5 to be fitted near the mode of said polarizer layer according to the face of an opposite side with the active energy beam cured layer form.

7. liquid crystal indicator, it has each described blooming or the described polaroid of claim 6 at least 1 claim 1～5.