CN102171020B

CN102171020B - Optical film, method for producing optical film, polarizing plate and liquid crystal display device

Info

Publication number: CN102171020B
Application number: CN2009801388295A
Authority: CN
Inventors: 玉川美典
Original assignee: Konica Minolta Opto Inc
Current assignee: Konica Minolta Opto Inc
Priority date: 2008-10-06
Filing date: 2009-08-10
Publication date: 2013-09-11
Anticipated expiration: 2029-08-10
Also published as: KR20110086797A; WO2010041513A1; CN102171020A; TW201030080A; JPWO2010041513A1; JP5397382B2

Abstract

Disclosed is an optical film having improved moisture absorption, heat resistance and brittleness at the same time. The optical film rarely causes light leakage, and has good reworkability. Also disclosed are a method for producing the optical film, a polarizing plate and a liquid crystal display device. The optical film is characterized in that the film contains an acrylic resin (A) and a cellulose ester resin (B) at a mass ratio of from 95:5 to 30:70, that the acrylic resin (A) has a weight average molecular weight Mw of not less than 110,000 but not more than 1,000,000, that the total degree of substitution (T) of acyl groups of the cellulose ester resin (B) is not less than 2.0 but not more than 3.0, and the substitution degree of acyl groups having 3 to 7 carbon atoms is not less than 1.2 but not more than 3.0, that the cellulose ester resin (B) has a weight average molecular weight Mw of not less than 75,000 but not more than 300,000, that the film has a tension softening point of 105 to 145 DEG C and a folding endurance of 50 to 100 times, and that the film is produced by melt casting.

Description

The manufacture method of blooming, blooming, polarizer and liquid crystal indicator

Technical field

The present invention relates to manufacture method, polarizer and the liquid crystal indicator of blooming, blooming, in more detail, relate to light leak, operation (rework) property good optical film, polarizer and liquid crystal indicator again be difficult for to take place.

Background technology

Because the purposes such as LCD of LCD TV, PC need increasing to liquid crystal indicator.

Usually; liquid crystal indicator is made of liquid crystal pond and 2 polarizers being located at its both sides; described liquid crystal pond forms with glass plate clamping transparency electrode, liquid crystal layer, colour filter etc., and each polarizer is formed by 2 bloomings (polaroid protective film) clamping polarizer (being also referred to as the polarizer, light polarizing film).As this polaroid protective film, can use the cellulosic triacetate film usually.

On the other hand, in recent years along with development of technology, when the maximization of liquid crystal indicator obtained accelerating, it is diversified that the purposes of liquid crystal indicator also becomes.For example, can enumerate, as the use of the giant display of being located at street corner, storefront, the advertisement of public place that be used for to use the display device that is called as digital signage (デヅタ Le サイネ one ヅ) is with display etc.

With regard to these purposes, outdoor because supposition is used for, the deterioration that causes because of the light polarizing film moisture absorption becomes problem, requires polaroid protective film to have higher moisture-proof.But be difficult to obtain sufficient moisture-proof with the cellulose ester membranes such as cellulosic triacetate film that use in the past.

As the technology that is used for improving moisture-proof; disclose in acrylic resin with 60～90/40～10 amount than combination resistance to impact acrylic rubber-methylmethacrylate copolymer or the cellulosic method of butyl modification acetyl group (patent documentation 1); but with regard to this method; the easy fracture that acrylic resin film has, crisp character (fragility) are significantly; in the operating procedure fracture etc. taking place, especially is difficult to stably make the blooming that large-scale liquid crystal indicator is used when film is made or again.

In addition, also have following problems:, at high temperature use, in the process such as long-term use for the acrylic resin film of representative lacks hear resistance usually with polymethyl methacrylate (below, abbreviate PMMA as), shape can change.

This problem not only concerns the rerum natura of film simple substance itself, and also is unusual important problem for the polarizer that uses this film, display unit.That is to say that in liquid crystal indicator, along with the distortion of film, polarizer takes place to curl, therefore the problem of meeting generating plane slab integral warpage.

Film distortion and the problem that causes does not occur over just the back lighting side, and when watching (Visual Recognize) side surface position to use, also can take place.

For cellulose ester membrane, in order to control plasticizer, optical characteristics, the technology (patent documentation 2) of mixing acrylic resin is disclosed also.But because the molecular weight of the disclosed acrylic resin of the document is little, can't obtain sufficient moisture-proof, the light leak that causes because of the problems such as optical value change of polarizer deterioration or blooming under high humidity environment can't improve.

Patent documentation 3 discloses acrylic resin and cellulose ester resin has been mixed the film of using fusion curtain coating manufactured.This method also can't be improved fragility fully.

Patent documentation 3 has also been put down in writing and has been added the example of plasticizer, but original essential hear resistance has been worsened, and can't take into account fragility and hear resistance.

The prior art document

Patent documentation

Patent documentation 1: Japanese kokai publication hei 5-119217 communique

Patent documentation 2: TOHKEMY 2003-12859 communique

Patent documentation 3: TOHKEMY 2008-88417 communique

Summary of the invention

The problem that invention will solve

In view of the above problems, the object of the present invention is to provide hygroscopicity, hear resistance and fragility improved blooming simultaneously, be difficult for taking place light leak, operability good optical film, its manufacture method, polarizer and liquid crystal indicator again thereby provide.

The method of dealing with problems

Above-mentioned purpose of the present invention realizes by following proposal.

1. blooming; it contains acrylic resin with 95:5～30:70 mass ratio; (A) and cellulose ester resin; (B); the aforesaid propylene acid resin; (A) weight average molecular weight Mw is more than 110000 and below 1000000; this cellulose ester resin; (B) the total substitution value of acyl group; (T) be more than 2.0 and below 3.0; carbon number is more than 3 and the substitution value of 7 following acyl groups is more than 1.2 and below 3.0; this cellulose ester resin; (B) weight average molecular weight Mw is more than 75000 and below 300000

This blooming is made by fusion curtain coating film-forming method, and its tension force softening point is 105～145 ℃, and folding strength is 50～100 times.

2. the manufacture method of a blooming, this method comprises: above-mentioned 1 described blooming is stretched along any direction at least in direction of transfer or the cross direction, thereby make blooming, its draft temperature is Tg～Tg+50 ℃ of the blooming before stretching.

3. polarizer, it has above-mentioned 1 described blooming.

4. liquid crystal indicator, it has above-mentioned 3 described polarizers.

The effect of invention

According to the present invention, hygroscopicity, hear resistance and fragility improved blooming simultaneously can be provided, and then can provide and be difficult for taking place light leak, operability good optical film, its manufacture method, polarizer and liquid crystal indicator again.

Description of drawings

[Fig. 1] is general flowchart, and it shows an embodiment for the device of implementing blooming manufacture method of the present invention.

Symbol description

1 extruder

2 filters

3 static mixers

4 casting heads

5 rotation supports (the 1st chill roll)

6 cramping rotary bodies (touch roll)

7 rotation supports (the 2nd chill roll)

8 rotation supports (the 3rd chill roll)

9,10,11,13,14 transport roller

12 stretching-machines

15 cutting cutters

16 coiling machines

F blooming of the present invention

The specific embodiment

Below, just be used for implementing preferred forms of the present invention and be elaborated.

Blooming of the present invention; its major technique feature comprises: the mass ratio of acrylic resin (A) and cellulose ester resin (B) is 95: 5～30: 70; the weight average molecular weight Mw of aforesaid propylene acid resin (A) is more than 110000 and below 1000000; the total substitution value of acyl group (T) of this cellulose ester resin (B) is more than 2.0 and below 3.0; carbon number is more than 3 and the substitution value of 7 following acyl groups is more than 1.2 and below 3.0; the weight average molecular weight Mw of this cellulose ester resin (B) is more than 75000 and below 300000; with regard to the character of this blooming; the tension force softening point is 105～145 ℃; folding strength is 50～100 times, and its manufacture method is fusion curtain coating embrane method processed.

＜acrylic resin (A) 〉

The acrylic resin that the present invention uses also comprises methacrylic resin.Be not particularly limited as resin, preferably comprise the methyl methacrylate units of 50～99 quality % and 1～50 quality % can with other monomeric unit of its generation copolymerization.

As can with other monomer of its copolymerization, can enumerate, the carbon number of alkyl is 2～18 alkyl methacrylate, the carbon number of alkyl is 1～18 alkyl acrylate, acrylic acid, α such as methacrylic acid, beta-unsaturated acid, maleic acid, fumaric acid, itaconic acids etc. contain the dicarboxylic acids of unsaturated group, styrene, aromatic ethenyl compounds such as AMS, acrylonitrile, α such as methacrylonitrile, alpha, beta-unsaturated nitriles, maleic anhydride, maleimide, N-substituted maleimide amine, glutaric anhydride etc., they can use separately, perhaps combination of monomers more than 2 kinds are used.

Wherein, consider from the heat-resisting decomposability of copolymer, mobile aspect, preferred methyl acrylate, ethyl acrylate, acrylic acid n-propyl, n-butyl acrylate, sec-butyl acrylate, 2-ethylhexyl acrylate etc. are especially preferably used methyl acrylate, n-butyl acrylate.

With regard to being used for the acrylic resin (A) of blooming of the present invention, consider that from improving as the fragility of blooming and the transparent aspect when compatible with cellulose ester resin (B) special preferable weight-average molecular weight (Mw) is more than 120000 and below 1000000.

The weight average molecular weight (Mw) of most preferred acrylic resin (A) is in 130000～300000 scopes.

The weight average molecular weight of acrylic resin of the present invention can be measured by gel permeation chromatography (being designated hereinafter simply as GPC).Condition determination is as follows.

Solvent: carrene

Chromatographic column: Shodex K806, K805, K803G (clear and electrician's (strain) system, 3 series connection are used)

Chromatogram column temperature: 25 ℃

Sample solution concentration: 0.1 quality %

Detector: RI Model 504 (GL Science corporate system)

Pump: L6000 (Hitachi (strain) system)

Flow: 1.0ml/min

Calibration curve: use by polystyrene standard STK standard polystyrene (eastern Cao (strain) system) Mw=2,13 calibration curves that sample is made of 800,000～500.Preferred 13 samples substantially uniformly-spaced use.

Manufacture method as the acrylic resin among the present invention (A) is not particularly limited, and can adopt known method such as suspension polymerisation, emulsion polymerisation, polymerisation in bulk or polymerisation in solution arbitrarily.Here, as polymerization initiator, can use common peroxide and azo class polymerization initiator, also can use redox class polymerization initiator.About polymerization temperature, suspend or can when 30～100 ℃, body or polymerisation in solution, can implement down at 80～160 ℃ during emulsion polymerisation.In order to control the reduced viscosity of gained copolymer, can use alkyl hydrosulfide etc. to carry out polymerization as chain-transferring agent.

As acrylic resin of the present invention, also can use commercially available product.For example can enumerate Delpet60N, 80N (Chemicals of Asahi Chemical Industry (strain) system), DIANAL BR52, BR80, BR83, BR85, BR88 (Rayon (strain) system), KT75 (electrochemical industry (strain) system) etc.Also acrylic resin more than 2 kinds can be used in combination.

＜cellulose ester resin (B) 〉

With regard to cellulose ester resin of the present invention (B); from improving fragility or the transparent aspect when compatible with acrylic resin (A) is considered, the substitution value that total substitution value (T) of preferred especially acyl group is 2.0～3.0, carbon number is 3～7 acyl group is 1.2～3.0, preferably the substitution value of the acyl group of carbon number 3～7 is 2.0～3.0.That is, cellulose ester resin of the present invention is to be the cellulose ester resin that 3～7 acyl substituted forms by carbon number, particularly, preferably uses propiono, bytyry etc., especially preferably uses propiono.

Total substitution value of the acyl group of cellulose ester resin (B) is lower than at 2.0 o'clock; 2,3,6 residual degree of going up hydroxyl that are the cellulose esters molecule are higher than at 1.0 o'clock; acrylic resin (A) can't be compatible fully with acrylic resin (B), when using as blooming, can produce the problem of mist degree.

In addition, be more than 2.0 but carbon number is the substitution value of 3～7 acyl group is lower than under 1.2 the situation at total substitution value of acyl group, also can't obtain sufficient compatibility, perhaps fragility reduces.For example, even total the substitution value of acyl group is 2.0 when above, carbon number is 2 acyl group, be that the substitution value of the acyl group of the substitution value height of acetyl group but carbon number 3～7 is lower than under 1.2 the situation, and compatibility reduces, and mist degree rises.

In addition, even total the substitution value of acyl group is 2.0 when above, the substitution value of the acyl group of the substitution value height of the acyl group of carbon number more than 8 but carbon number 3～7 is lower than under 1.2 the situation, and the fragility deterioration can't obtain desired characteristic.

With regard to the acyl substituted degree of cellulose ester resin of the present invention (B); as long as the substitution value that total substitution value (T) is 2.0～3.0, carbon number is 3～7 acyl group is 1.2～3.0, preferred carbon number be 3～7 in addition acyl group, be that acetyl group or carbon number are the ading up to below 1.3 of substitution value of the acyl group more than 8.

In addition, more preferably total substitution value (T) of the acyl group of cellulose ester resin (B) is 2.5～3.0 scopes.

In the present invention, above-mentioned acyl group can be aliphatic acyl radical, also can be aromatic acyl.Under the situation for aliphatic acyl radical, can be straight chain, also can be side chain, also can further have substituting group.The carbon number of acyl group of the present invention comprises the substituting group of acyl group.

Above-mentioned cellulose ester resin (B) has aromatic acyl as under the substituent situation, and the number that preferably is substituted in the substituent X on the aromatic ring is 0～5.In this case, it should be noted that: the carbon number that comprises substituting group is that the substitution value of 3～7 acyl group is necessary for 1.2～3.0.For example, the carbon number of benzoyl is 7, has under the substituent situation of carbon containing, becomes more than 8 as the carbon number of benzoyl, is not included in carbon number and is in 3～7 the acyl group.

In addition, be substituted in substituent number on the aromatic ring and be 2 when above, substituting group can be the same or different each other, can also be connected to each other to form fused-polycyclic compounds (for example naphthalene, indenes, indane, phenanthrene, quinoline, isoquinolin, chromene, chroman, phthalazines, acridine, indoles, dihydroindole etc.).

With regard to above-mentioned cellulose ester resin (B), be at least a kind of structure that to have in the aliphatic acyl radical that contains carbon number 3～7, as the structure of using in the celluosic resin of the present invention.

With regard to the substitution value of cellulose ester resin of the present invention (B), the substitution value that total substitution value (T) of acyl group is 2.0～3.0, carbon number is 3～7 acyl group is 1.2～3.0.

In addition, preferred following structure: carbon number is beyond 3～7 the acyl group, be that acetyl group and carbon number are that the summation of the substitution value of the acyl group more than 8 is below 1.3.

As cellulose ester resin of the present invention (B), be preferably selected from especially in cellulose ethanoate propionic ester, cellulose acetate butyrate, cellulose ethanoate benzoic ether, cellulose propionate, the cellulose butylate at least a, namely preferably have the acyl group of

carbon number

3 or 4 as substituting group.

Wherein, particularly preferred cellulose ester resin is cellulose ethanoate propionic ester, cellulose propionate.

Do not existed with the form of hydroxyl usually by the part of acyl substituted.These resins can be synthetic by known method.

Need to prove that the substitution value of acetyl group or the substitution value of other acyl group can be tried to achieve by the method for ASTM-D817-96 regulation.

With regard to the weight average molecular weight (Mw) of cellulose ester resin of the present invention, especially consider from improving the aspect with compatibility, the fragility of acrylic resin (A), be preferably 75000 or more, preferably in 75000～300000 scope, further preferred 100000～240000 scope, preferred especially 160000～240000.Be lower than in the weight average molecular weight (Mw) of cellulose ester resin under 75000 the situation, hear resistance or fragility to improve effect insufficient, can't obtain effect of the present invention.The present invention can mix use with celluosic resin more than 2 kinds.

Blooming of the present invention contains acrylic resin (A) and cellulose ester resin (B) with compatible state, and the mass ratio of acrylic resin (A) and cellulose ester resin (B) is 95: 5～30: 70, preferred 95: 5～50: 50, further preferred 90: 10～60: 40.

With respect to the mass ratio of acrylic resin (A) and cellulose ester resin (B) 95: 5, if the amount of acrylic resin (A) is greater than aforementioned proportion, then can't obtain the effect by cellulose ester resin (B) generation fully, with respect to the mass ratio of acrylic resin (A) and cellulose ester resin (B) 30: 70, if the amount of acrylic resin is less than aforementioned proportion, then moisture-proof is insufficient.

In the blooming of the present invention, preferably contain acrylic resin (A) and cellulose ester resin (B) with compatible state.

Whether acrylic resin (A) and cellulose ester resin (B) are compatible state, can judge by for example glass transition temperature Tg.

For example, under the different situation of the glass transition temperature of two kinds of resins, during with two kinds of mixed with resin, because there is glass transition temperature in each resin, so the glass transition temperature of mixture exists more than 2, and during two kinds of resin compatibles, the intrinsic glass transition temperature of each resin disappears, become 1 glass transition temperature, become the glass transition temperature of compatible resin.

In addition, said glass transition temperature is the intermediate point glass transition temperature (Tmg) of measuring, trying to achieve according to JIS K7121 (1987) with 20 ℃/minute of programming rates with differential scanning calorimetry device (Perkin Elmer corporate system DSC-7 type) here.

Preferred acrylic resins (A) and cellulose ester resin (B) are respectively non-crystalline resin, any one can or have the macromolecule of partially crystalline for crystalline polymer, in the present invention, preferred acrylic resins (A) and cellulose ester resin (B) are by the compatible non-crystalline resin that becomes.

The weight average molecular weight (Mw) of acrylic resin in the blooming of the present invention (A), weight average molecular weight (Mw) or the substitution value of cellulose ester resin (B), can utilize two kinds of resin differential separations for solvent solubility after, measure separately and obtain.

During separation resin, in the solvent that only dissolves any one resin, add the resin after compatible, can be with the resin extract and separate of dissolving, can carry out heating operation or backflow this moment.Can make up the combination of these above solvents of 2 steps, thus separation resin.With the dissolving resin with separate as the residual resin filter of insoluble matter, for the solution that contains extract, can be with resin isolation by the operation that makes the solvent evaporation drying.

The resin of these separation can be determined by high molecular general structure elucidation.When blooming of the present invention contains in addition resin of acrylic resin (A) and cellulose ester resin (B), also can use the same method and separate.

In addition, under the situation that the weight average molecular weight of compatible resin (Mw) differs from one another, in gel permeation chromatography (GPC) method, high molecular weight material is in early days by elution, the low-molecular-weight thing through the more long time by elution, therefore not only can easily separate, but also can carry out molecular weight determination.

In addition, when utilizing GPC that compatible resin is carried out molecular weight determination, get the resin solution of elution by the time branch, the distillation desolventizing obtains dried resin, the dry resin that obtains is carried out structure elucidation quantitatively, the resin that detects different molecular magnitude part is thus formed, thereby can determine compatible resin respectively.With utilizing the resin that the dissolubility difference branch of solvent is got to measure each molecular weight distribution by GPC in advance, can detect compatible resin respectively thus.

In addition, in the present invention, " containing acrylic resin (A) and cellulose ester resin (B) with compatible state " refers to, by each resin (polymer) is mixed, the result makes it become compatible state.The precursor of acrylic resins such as monomer, dimer or oligomer is mixed with cellulose ester resin (B), then, lead to and carry out polymerization, make it not comprise the resin of admixture.

For example, mix the step that afterwards obtains hybrid resin by polymerization with cellulose ester resin (B) about the precursor with acrylic resins such as monomer, dimer or oligomer, the polymerisation complexity is made resin with this method, be difficult to the control reaction, also be difficult to adjust molecular weight.In addition, during with such method synthetic resin, glycerol polymerization, cross-linking reaction, cyclization mostly occur, can't occur mostly easily being dissolved in situation in the solvent, maybe can't be by the situation of heating and melting, be difficult to weight average molecular weight (Mw) is measured in the acrylic resin elution in the hybrid resin, therefore be difficult to the control rerum natura, can not use as the resin of stably making blooming.

Only however infringement as the function of blooming, blooming of the present invention also can contain resin or the additive except acrylic resin (A) and cellulose ester resin (B).

When containing the resin except acrylic resin (A) and cellulose ester resin (B), the resin of interpolation can be compatible state, also can be inconsistent admixture.

In the preferred blooming of the present invention the gross mass of acrylic resin (A) and cellulose ester resin (B) be 55 quality % of blooming above, more preferably more than the 60 quality %, more than the preferred especially 70 quality %.

When using resin except acrylic resin (A) and cellulose ester resin (B) or additive, preferably in the scope of not damaging blooming function of the present invention, adjust addition.

＜acrylic compounds particle (C) 〉

Blooming of the present invention also can contain the acrylic compounds particle.

Acrylic compounds particle of the present invention (C) is illustrated in compatible state and contains in the blooming of aforesaid propylene acid resin (A) and cellulose ester resin (B), with the acrylic compounds composition of particle state (being also referred to as the non-conforming state) existence.

With regard to aforesaid propylene acids particle (C), for example, the blooming of getting a certain amount of making makes it to be dissolved in the solvent, after stirring makes it fully dissolve dispersion, the molecular filter that use has the PTFE system in the aperture that is lower than acrylic compounds particle (C) average grain diameter filters, and the weight of the insoluble matter of preferred trap filter accounts for more than the 90 quality % of the acrylic compounds particle (C) that adds in the blooming.

The acrylic compounds particle (C) that the present invention uses is not particularly limited, and preferably has the acrylic compounds particle (C) of the layer structure more than 2 layers, the granular complex of preferred especially following sandwich construction acrylic compounds.

The granular complex of sandwich construction acrylic compounds refers to, the particle shape acrylic polymer that has following structure from central part to peripheral part, described structure be interior hard layer polymer, demonstrate the crosslinked soft layer polymer of caoutchouc elasticity and the structure that outermost hard layer polymer is formed by stacking with stratiform.

That is to say that the granular complex of sandwich construction acrylic compounds refers to, the granular complex of sandwich construction acrylic compounds that is made of interior hard layer, crosslinked soft layer and outermost hard layer from central part to peripheral part.The preferred granular complex of sandwich construction acrylic compounds that uses these 3 layers of core shell structures.

Preferred embodiment as the granular complex of sandwich construction acrylic compounds that can be used for acrylic resin composition of the present invention can be listed below described embodiment.The granular complex of described acrylic compounds has the 3-tier architecture that is made of following polymer (a)～(c):

(a) making the carbon number that contains methyl methacrylate 80～98.9 quality %, alkyl is the interior hard layer polymer that the polymerization of mixtures of the monomer of 1～8 alkyl acrylate 1～20 quality % and multi-functional grafting agent 0.01～0.3 quality % obtains;

(b) in the presence of interior above-mentioned hard layer polymer, making the carbon number that contains alkyl is the crosslinked soft layer polymer that the polymerization of mixtures of the monomer of 4～8 alkyl acrylate 75～98.5 quality %, multi-functional crosslinking agent 0.01～5 quality % and multi-functional grafting agent 0.5～5 quality % obtains;

(c) in the presence of the polymer that is constituted by interior above-mentioned hard layer and crosslinked soft layer, making the carbon number that contains methyl methacrylate 80～99 quality % and alkyl is the outermost hard formation polymer that the polymerization of mixtures of the monomer of 1～8 alkyl acrylate 1～20 quality % obtains

And, gained 3-tier architecture polymer is the granular complex of acrylic compounds that is made of interior hard layer polymer (a) 5～40 quality %, soft layer polymer (b) 30～60 quality % and outermost hard layer polymer (c) 20～50 quality %, when using acetone separation, there is insoluble part in the granular complex of this acrylic compounds, the MEK swellbility of this insoluble part is 1.5～4.0.

In addition, as disclosed in the public clear 60-17406 of spy number or special fair 3-39095 number, not only composition, the particle diameter of granular each layer of complex of sandwich construction acrylic compounds are stipulated, and be set in the particular range by the MEK swellbility with the granular complex tensile modulus of elasticity of sandwich construction acrylic compounds, the insoluble part of acetone, also can realize the balance of sufficient resistance to impact and proof stress albefaction.

Wherein, the preferred interior hard layer polymer (a) that constitutes the granular complex of sandwich construction acrylic compounds is that to make the carbon number that contains methyl methacrylate 80～98.9 quality %, alkyl be that the polymerization of mixtures of the monomer of 1～8 alkyl acrylate 1～20 quality % and multi-functional grafting agent 0.01～0.3 quality % obtains.

Wherein, it is 1～8 alkyl acrylate as the carbon number of alkyl, can enumerate, methyl acrylate, ethyl acrylate, acrylic acid n-propyl, n-butyl acrylate, sec-butyl acrylate, 2-ethylhexyl acrylate etc. are preferably used methyl acrylate, n-butyl acrylate.

The ratio of the acrylic acid alkyl ester units in the interior hard layer polymer (a) is 1～20 quality %, when this unit is lower than 1 quality %, the pyrolytic of polymer increases, otherwise, when the ratio of this unit is higher than 20 quality %, the glass transition temperature of interior hard layer polymer (c) reduces, and the effect of giving of the resistance to impact of the granular complex of acrylic compounds of 3-tier architecture reduces, and is therefore all not preferred.

As multi-functional grafting agent, have the multi-functional monomer of the functional group of different taken place polymerizations, for example can enumerate, the allyl esters of acrylic acid, methacrylic acid, maleic acid, fumaric acid etc. preferably use allyl methacrylate.Multi-functional grafting agent is used for making interior hard layer polymer and soft layer polymer generation chemical bonding, and during its interior hard layer polymerization, the ratio that this grafting agent uses is 0.01～0.3 quality %.

The preferred crosslinked soft layer polymer (b) that constitutes the granular complex of acrylic compounds, be in the presence of interior above-mentioned hard layer polymer (a), making the carbon number that contains alkyl is that the polymerization of mixtures of the monomer of 1～8 alkyl acrylate 75～98.5 quality %, multi-functional crosslinking agent 0.01～5 quality % and multi-functional grafting agent 0.5～5 quality % obtains.

Wherein, be 4～8 alkyl acrylate as the carbon number of alkyl, preferably use n-butyl acrylate, 2-ethylhexyl acrylate.

In addition, but can make other simple function monomer of the following copolymerization of 25 quality % carry out copolymerization with these polymerizable monomers.

But as other simple function monomer of copolymerization, can enumerate styrene and substituted styrene derivative.With regard to alkyl acrylate and cinnamic ratio that the carbon number of alkyl is 4～8, the former is more many, and the glass transition temperature of polymer (b) is more low, namely more can softening.

On the other hand, consider from the transparent aspect of resin combination, make soft layer polymer (b) refractive index at normal temperatures and interior hard layer polymer (a), outermost hard layer polymer (c) and hard thermoplasticity acrylic resin more approaching more favourable, can consider selected the two the ratio of these factors.

As multi-functional grafting agent, can use in the project of above-mentioned innermost layer rigid polymer (a) cited.Multi-functional grafting agent used herein, in order to make soft layer polymer (b) and outermost hard layer polymer (c) carry out chemical bonding and to use, the ratio of using during its interior hard layer polymerization is given the effect aspect from resistance to impact and is considered, is preferably 0.5～5 quality %.

As multi-functional crosslinking agent; can use known crosslinking agent usually such as divinyl compound, diallyl compound, two acryl compound, dimethyl propylene enoyl compound, but preferably use polyethyleneglycol diacrylate (molecular weight 200～600).

Multi-functional crosslinking agent used herein is in order to produce cross-linked structure when soft layer (b) polymerization, and shows resistance to impact and give effect and use.If but when the soft layer polymerization, use previous multi-functional grafting agent, then produce the cross-linked structure of soft layer (b) to a certain extent, so multi-functional crosslinking agent and nonessential composition, but the ratio when multi-functional crosslinking agent is used for the soft layer polymerization is given the effect aspect from resistance to impact and is considered to be preferably 0.01～5 quality %.

The preferred outermost hard layer polymer (c) that constitutes the granular complex of sandwich construction acrylic compounds is in the presence of interior above-mentioned hard layer polymer (a) and soft layer polymer (b), and making the carbon number that contains methyl methacrylate 80～99 quality % and alkyl is that the polymerization of mixtures of the monomer of 1～8 alkyl acrylate 1～20 quality % obtains.

Wherein, as alkyl acrylate (ア Network リ Le ア Le キレ one ト), above-claimed cpd be can use, methyl acrylate, ethyl acrylate preferably used.The ratio of the acrylic acid alkyl ester units in the preferred outermost hard layer (c) is 1～20 quality %.

In addition, when the polymerization of outermost hard layer (c), for the purpose that improves with the compatibility of acrylic resin (A), also can use alkyl hydrosulfide etc. to regulate molecular weight as chain-transferring agent.

Consider with the balance aspect of resistance to impact from improving elongation, be provided with the gradient that molecular weight successively decreases laterally successively from the inboard in the especially preferred outermost hard layer.As concrete method, the mixture that is used to form the monomer of outermost hard layer is divided into more than 2 parts, increase each chain-transferring agent amount of adding successively, by such method the molecular weight of the polymer that forms the outermost hard layer is reduced laterally gradually by the granular complex of sandwich construction acrylic compounds inboard.

The molecular weight that form this moment can be by following method adjustment: the mixture of the monomer of each time use is carried out polymerization respectively separately, the molecular weight of mensuration resulting polymers under the same conditions.

The particle diameter of the acrylic compounds particle (C) that the present invention preferably uses is not particularly limited, and preferred 10nm is above, below the 1000nm, more preferably 20nm above, below the 500nm, especially most preferably 50nm above, below the 400nm.

In the granular complex of the acrylic compounds of the multilayer structure polymer that preferably uses as the present invention, the mass ratio of core and shell is not particularly limited, but with multilayer structure polymer during all as 100 mass parts, the amount of preferred sandwich layer be 50 mass parts above, below 90 mass parts, more preferably 60 mass parts above, below 80 mass parts.Need to prove that said sandwich layer refers to interior hard layer here.

Example as the commercially available product of so granular complex of sandwich construction acrylic compounds, for example can enumerate, the Rayon of Mitsubishi corporate system " Metablen ", clock deep pool chemical industrial company's system " Kane Ace ", Wu Yu chemical industrial company system " Paraloid ", Rohm and Haas corporate system " Acryloid ", Ganz change into industrial group's system " Staphyroid " and Kuraray corporate system " Parapet SA " etc., and these complexs can use separately also and can will be used in combination more than 2 kinds.

In addition, the preferred graft copolymer that uses of acrylic compounds particle (C) that preferably uses as the present invention is the concrete example of acrylic compounds particle (Cl), can enumerate, in the presence of rubber polymer, make comprise unsaturated carboxylate type monomer, unsaturated carboxylic acid class monomer, aromatic vinyl base class monomer and optionally can carry out the graft copolymer that copolymerization forms with the monomer mixture of other vinyl monomer of these monomer copolymerizations.

For can be used for the rubber polymer that graft copolymer is acrylic compounds particle (Cl), be not particularly limited, can use polydiene, acrylic rubber and vinyl rubber etc.As concrete example, can enumerate the block copolymer of polybutadiene, SB, styrene-butadiene, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, polyisoprene, butadiene-methylmethacrylate copolymer, butyl acrylate-methylmethacrylate copolymer, butadiene-acrylic acid ethyl ester copolymer, ethylene-propylene copolymer, ethylene-propylene-dienes copolymer, ethene-isoprene copolymer and ethylene-methyl acrylate copolymer etc.These rubber polymers can use the mixture more than a kind or 2 kinds.

In addition, add under the situation of acrylic compounds particle (C) in the blooming of the present invention, the refractive index of the refractive index of the mixture of preferred acrylic resins (A) and cellulose ester resin (B) and acrylic compounds particle (C) approaches, because can obtain the high film of the transparency like this.Particularly, the refringence of preferred acrylic compounds particle (C) and acrylic resin (A) be below 0.05, more preferably below 0.02, especially preferred below 0.01.

In order to satisfy such refractive index condition, the method of each the monomeric unit ratio of components by adjusting acrylic resin (A) and/or adjust the rubber polymer that is used for acrylic compounds particle (C) or the method for the ratio of components of monomer etc., refringence can be reduced, thereby the excellent blooming of the transparency can be obtained.

In addition, here said refringence is represented: make blooming of the present invention be dissolved in the solvent of solubilized acrylic resin (A) under proper condition fully, make gonorrhoea solution, be separated into solvent soluble fraction and insoluble part by operations such as centrifugations, respectively with behind this soluble fraction (acrylic resin (A)) and insoluble part (acrylic compounds particle (the C)) purifying, the refractive index of mensuration (23 ℃, measure wavelength: 550nm) poor.

In the present invention, be not particularly limited to the middle method of mixing acrylic compounds particle (C) of acrylic resin (A), the following method of preferred employing, after acrylic resin (A) and other any composition be pre-mixed, carry out melting mixing equably on 200～350 ℃ of following acrylic compounds particle (C) limits of adding by single screw rod or double screw extruder usually.

In addition, can use the solution that will be dispersed with acrylic compounds particle (C) in advance to add to and be dissolved with the method for mixing in the solution (rubber cement liquid) of acrylic resin (A) and cellulose ester resin (B), or online interpolation is through dissolving, mixed the methods such as solution that acrylic compounds particle (C) and other any additive form.

As acrylic compounds particle of the present invention, also can use commercially available product.

For example can enumerate MetablenW-341 (C2) (Rayon of Mitsubishi (strain) system), Chemisno MR-2G (C3), MS-300X (C4) (combining chemistry (strain) system of grinding) etc.

In blooming of the present invention, with respect to the gross mass of the resin that constitutes this film, preferably contain the acrylic compounds particle (C) of 0.5～30 quality %, more preferably contain in 1.0～15 quality % scopes.

＜other additive 〉

Preferably contain plasticizer, the antioxidant that prevents the film deterioration, the ultra-violet absorber of giving the ultraviolet radiation absorption function of giving the film processability in the blooming of the present invention, give film particulate with smooth property (delustering agent (マット)) etc. and add power and add agent.

＜plasticizer 〉

As plasticizer, can enumerate phthalate, fatty acid ester, trimellitate class, phosphoric acid ester, polyesters or epoxies etc.

Wherein, preferably use the plasticizer of polyesters and phthalate.The polyesters plasticizer is compared with phthalic ester plasticizers such as dioctyl phthalates, non-migrating or anti-extractibility excellence, but plasticization effect or compatibility are poor slightly.

Therefore, select or be used in combination these plasticizer according to purposes, applicable to the purposes of broad range.

The polyesters plasticizer is the product of monobasic～quaternary carboxylic acid and monobasic～hexahydroxylic alcohols, the product that mainly uses the reaction of dicarboxylic acids and glycol to obtain.As representational dicarboxylic acids, can enumerate glutaric acid, itaconic acid, adipic acid, phthalic acid, azelaic acid, decanedioic acid etc.

Especially when using adipic acid, phthalic acid etc., can obtain the goods of plasticising excellent.As glycol, can enumerate ethylene glycol, propane diols, 1,3-butanediol, 1,4-butanediol, 1, glycol such as 6-hexylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, DPG.These dicarboxylic acids and glycol can be distinguished use separately, perhaps mix and use.

This ester plasticizer all may optionally be ester, oligoester, polyester-type, and molecular weight can be in 100～10000 scopes, preferred 600～3000 scopes, and plasticization effect is strong.

In addition, the viscosity of plasticizer is relevant with molecular structure or molecular weight, uses under the situation of adipic acid class plasticizer, and when considering the concerning of compatibility, plasticizing efficiency, its viscosity can be in the scope of 200～5000MPas (25 ℃).In addition, multiple polyesters plasticizer combinations can be used.

With respect to blooming 100 mass parts of the present invention, preferably add plasticizer 0.5～30 mass parts.If the addition of plasticizer is higher than 30 mass parts, then therefore surfaces of tacky considers it is not preferred from practical aspect.

＜antioxidant 〉

In the present invention, as antioxidant, can use known product usually.

Can especially preferably use lactone, sulphur class, phenols, two key class, hindered amines, Phosphorus compound.

For example, preferably comprise the commodity " IrgafosXP40 " by name of Ciba Japan strain formula meeting corporate system, the commercially available product of " IrgafosXP60 ".

As above-mentioned phenolic compound, preferably have 2,6-dialkyl phenol structure, preference as, Ciba Japan strain formula can company, the commercially available product of commodity " Irganox1076 ", " Irganox1010 " by name, (strain) ADEKA commodity " ADEKA STAB AO-50 " by name.

Preferred above-mentioned Phosphorus compound is for for example, and the commodity of Sumitomo Chemical Co's system be called commodity " ADK STAB PEP-24G " by name, " commodity of ADK STAB PEP-36 and " ADK STAB 3010 ", Ciba Japan Co., Ltd. system are called " IRGAFOS P-EPQ of " SumilizerGP ", Asahi Denka Co., Ltd.'s system ", the commodity of Sakai Chemical Industry Co., Ltd.'s system are called the commercially available product of " GSY-P101 ".

Preferred above-mentioned hindered amine compound is for for example, and the commodity of Ciba Japan Co., Ltd. system are called the commercially available product of the commodity " ADK STAB LA-52 " by name of " Tinuvin144 " and " Tinuvin770 ", Asahi Denka Co., Ltd.'s system.

Preferred above-mentioned sulphur compounds is for for example, the commercially available product of the commodity of Sumitomo Chemical Co's system " Sumilizer TPL-R " and " Sumilizer TP-D " by name.

The commercially available product of the commodity " Sumilizer GM " and " Sumilizer GS " by name that preferred above-mentioned pair of key compounds is Sumitomo Chemical Co's system.

In addition, as sour agent for capturing, as United States Patent (USP) the 4th, 137, put down in writing in No. 201 specifications like that, also can contain the compound with epoxy radicals.

Step when these antioxidants etc. can use according to regeneration decides suitable addition, adds in the scope that with respect to the resin as the main material of film is 0.05～20 quality %, preferred 0.1～1 quality % usually.

With regard to these antioxidants, and only use a kind of comparing, can obtain synergy by being used in combination multiple different types of compound.For example, preferred compositions is used lactone, Phosphorus, phenols and two key compounds.

＜colouring agent 〉

In the present invention, preferably use colouring agent.Colouring agent refers to dyestuff or pigment, but in the present invention, refers to have the effect that the tone furnishing cyan of liquid crystal panel is transferred, and maybe can adjust the material of yellow colour index, reduction mist degree.

As colouring agent, can use various dyestuffs or pigment, anthraquinone dye, azo dyes, phthalocyanine color etc. are effective.

＜ultra-violet absorber 〉

The ultra-violet absorber that the present invention uses is not particularly limited, and can enumerate for example oxo benzophenone (oxybenzophenone) compounds, benzotriazole compound, salicylate compounds, benzophenone compound, cyanoacrylate compound, compound in triazine class, nickel complex salt compounds, inorganic powder etc.It can also be the polymer electrolyte ultra-violet absorber.

＜delustering agent 〉

In the present invention, in order to give the smooth property of film, preferably add delustering agent.

As the delustering agent that uses among the present invention, only otherwise the transparency of infringement gained film, hear resistance during fusion gets final product, may optionally be inorganic compound or organic compound, for example, talcum, mica, zeolite, diatomite, calcined diatomite (burn till Gui and become soil), kaolin, sericite, bentonite, smectite, clay, silica, quartz powder, bead, glass dust, glass flake, milled fibre, wollastonite, boron nitride, boron carbide, titanium boride, magnesium carbonate, powdered whiting, precipitated calcium carbonate, calcium silicates, alumina silicate, magnesium silicate, Almasilate, aluminium oxide, silica, zinc oxide, titanium dioxide, iron oxide, magnesia, zirconia, aluminium hydroxide, calcium hydroxide, magnesium hydroxide, calcium sulfate, barium sulfate, carborundum, aluminium carbide, titanium carbide, aluminium nitride, silicon nitride, titanium nitride, white carbons etc. can be enumerated.These delustering agents can use separately, also can will be used in combination more than 2 kinds.

By being used in combination the different particle of particle diameter, shape (for example needle-like with spherical etc.), can take into account the transparency and smooth property to heavens.

Wherein, since close with the refractive index of cellulose esters, the preferred especially excellent silica of the transparency (mist degree) that uses.

As the concrete example of silica, can preferably use have Aerosil 200V, Aerosil R972V, the commercially available product of Aerosil R972, R974, R812,200,300, R202, OX50, TT600, NAX50 (above Japanese Aerosil (strain) system), Seahostar KEP-10, Seahostar KEP-30, Seahostar KEP-50 (above, Nippon Catalyst K. K.'s system), Sylophobic 100 (Silysia of Fuji system), NIPSEAL E220A (Japanese silica industry system), ADMAFINE SO trade names such as (Admatechs systems) etc.

As the shape of particle, can use amorphous, needle-like, flat, spherical etc. without restriction, can make the transparency of gained film good when using spherical particle, therefore preferred especially.

The size of particle and wavelength of visible light near the time, light generation scattering, the transparency reduces, so the size of preferred particle is less than wavelength of visible light, more preferably visible wavelength below 1/2.If particle is big or small too small, then smooth property can't improve sometimes, therefore the scope of preferred especially 80nm～180nm.

Need to prove that the size of particle is under the situation of primary particles aggregate body, to refer to the size of agglutination body at particle.In addition, particle is not under the spherical situation, refers to be equivalent to the diameter of a circle of its projected area.

＜viscosity reducers 〉

In the present invention, for the purpose that reduces melt viscosity, can add the hydrogen bonding solvent.The hydrogen bond solvent refers to, as J.N.Israelachvili (イスラエ Le アチ PVC リ) work, (nearly rattan protects " molecular separating force and surface force ", the wide row in big island is translated, Mcgraw-hill (マグロウヒ Le) publishes, 1991) middle put down in writing such, can be at the charged atom (oxygen that is negative, nitrogen, fluorine, chlorine) produce the organic solvent of hydrogen atom media " key " and between the charged atom that is negative between the hydrogen atom of covalent bonding, namely, this organic solution is owing to contain the big and hydrogeneous key of bonding moment (モ one メソト), O-H (oxygen hydrogen bond) for example, N-H (hydrogen bound to nitrogen), F-H (fluorine hydrogen bond) can make adjacent intermolecular the arrangement.

These hydrogen bonding solvents have following ability: can and cellulose between form the hydrogen bond stronger than the intermolecular hydrogen bonding of celluosic resin, in the present invention in the fusion The tape casting of Cai Yonging, glass transition temperature when adding melt temperature that the hydrogen bond solvent can make the celluosic resin composition than used celluosic resin individualism is lower, even perhaps under the situation of same melt temperature, also can make the melt viscosity of the celluosic resin composition that contains the hydrogen bond solvent lower than celluosic resin.

In the present invention, as the index of fragility, can judge for benchmark by whether being " blooming that does not cause ductile fracture ".By obtaining not cause ductile fracture, the improved blooming of fragility, even when making large-scale liquid crystal indicator and use polarizer, also can be made into the blooming of fracture when not taking place to make, crack, operability excellence.

Here, said ductile fracture is defined as: under the effect of the bigger stress of the intensity that has than certain material and the fracture that produces, before final fracture, with remarkable elongation or the stretching (Twisted り of material) destruction.In the present invention, whether be that " blooming that does not cause ductile fracture " can be by following method evaluation: even under the effect of the stress that film can be bent into 2 foldings, destructions (this evaluation is called folding strength) such as fracture can not taken place yet.So long as apply the blooming that ductile fracture does not take place big like this stress yet; under situation about using with polaroid protective film as the liquid crystal indicator that maximizes; just can reduce the problems such as fracture when making fully; and; under the situation of again it being peeled off after the applying once and using as blooming; do not rupture yet, can realize the slimming of blooming fully.

If folding strength is 50～100 times; under the situation of the polaroid protective film of using as the liquid crystal indicator that maximizes; can reduce the problems such as fracture that take place when making fully; and under the situation about after fitting once, using with its stretch release and as blooming again; do not rupture, can tackle the slimming of blooming fully yet.Folding strength is lower than under 50 times the situation, easily ruptures during manufacturing, and operability variation again.Otherwise, folding strength is surpassed 100 times, the thickening thickness can be realized, but can't tackle the slimming of liquid crystal indicator.Therefore, make under the situation of film, folding strength be 50～100 times be suitable.

In the present invention, as stable on heating index, adopt the tension force softening point.Because the maximization of liquid crystal indicator, not only the brightness of back illumination radiant is higher, and because when being used for outdoor application such as digital signage, require higher brightness, therefore require blooming can tolerate use under hot environment more, if the tension force softening point is 105 ℃～145 ℃, then can determines that it is and have sufficient stable on heating blooming.Especially more preferably the tension force softening point is controlled at 110 ℃～130 ℃.If the tension force softening point is lower than 105 ℃, then can't tolerate the heat that the back illumination radiant sends, film distortion, light leak easily take place.Need to prove, containing with compatible state under the such formation of acrylic resin (A) and cellulose ester resin (B), can only confirm to reach 145 ℃.Therefore, to be 105 ℃～145 ℃ be suitable to the tension force softening point.

Concrete assay method as the temperature of representing blooming tension force softening point, can try to achieve by following method, for example, with TENSIRON testing machine (ORIENTEC corporate system, RTC-1225A) blooming is cut into 120mm (length) * 10mm (wide), heat up with the programming rate of 30 ℃/min continuously with the tension force of the 10N limit that stretches in the limit, temperature when mensuration reaches 9N 3 times is calculated by its mean value.

In addition, consider from the hear resistance aspect that the glass transition temperature (Tg) of preferred blooming is more than 110 ℃.More preferably more than 120 ℃.Be preferably especially more than 150 ℃.

In addition, here said glass transition temperature refers to measure for 20 ℃/minute with programming rate with differential scanning calorimetry device (Perkin Elmer corporate system DSC-7 type), the intermediate point glass transition temperature of obtaining according to JIS K7121 (1987) (Tmg).

As judging blooming index of transparency of the present invention, adopt haze value (turbidity).Especially the liquid crystal indicator of outdoor application, even require also to obtain in bright place sufficient brightness, high contrast, so haze value is necessary for below 1.0%, more preferably below 0.5%.

Utilization contains the blooming of the present invention of acrylic resin (A) and cellulose ester resin (B), can obtain the high transparency, and using the acrylic compounds particle to improve under the situation of purpose of other rerum natura, by reducing the refringence of resin (acrylic resinoid (A) and cellulose ester resin (B)) and acrylic compounds particle (C), can prevent that haze value from rising.

In addition because surface roughness is also influential to haze value as surperficial mist degree, with the particle diameter of acrylic compounds particle (C), addition control in above-mentioned scope when reducing film processed the surface roughness of film contact site also be effective.

In addition, about the hygroscopicity of blooming of the present invention, estimate by changing corresponding change in size with humidity.

Evaluation method as the change in size corresponding with the humidity variation can adopt following method.

Curtain coating direction at the blooming of making is done 2 place's marks (cross), carries out handling in 1000 hours under 60 ℃, 90%RH, with the light microscope determining distance of mark (cross) before and after treatment, obtains size changing rate (%).Size changing rate (%) is represented with following formula.

Size changing rate (%)=((a1-a2)/a1) * 100

A1: the distance before the heat treatment

A2: the distance after the heat treatment

Use under the situation of blooming as the protective film for polarizing plate of liquid crystal indicator, because the change in size that moisture absorption causes, problems such as contrast reduction, color spot take place in the variation that can produce uneven or phase difference value on the blooming.In particular for the polaroid protective film of the liquid crystal indicator of outdoor application, the problems referred to above are remarkable.If but the size changing rate under the above-mentioned condition (%) is lower than 0.5%, then can be evaluated as the blooming that shows abundant agent of low hygroscopicity.More preferably less than 0.3%.

In addition, preferably the defective more than the face interior diameter 5 μ m of blooming of the present invention be 1/10cm square below.More preferably 0.5/10cm square below, further preferred 0.1/10cm square below.

Here, the diameter of defective is represented its diameter when defective is circle, and the scope of defective is not observed decision by following method with microscope during for circle, adopts its maximum diameter (external diameter of a circle).

Be under the situation of bubble, impurity in defective, the size of the scope of defective shadow for the viewed in transmitted light defective of differential interference microscope the time.Defective is under surface configurations such as the roller transfer printing of hindering, the scratch situation about changing, and with the viewed in reflected light defective of differential interference microscope, determines its size.

In addition, under the situation of observing with reverberation, if defective is big or small not obvious, observe at surperficial AM aluminum metallization, platinum.

Obtain the film of the grade excellence represented with described defect frequency well for productivity, following method is effective: to polymer solution before being about to curtain coating, carry out after high accuracy is filtered, is improved the cleannes around the casting machine and sets curtain coating stage by stage drying condition, in high efficiency and suppress to carry out drying under the condition of foaming.

If the number of defective is square greater than 1/10cm, then for example in subsequent step, add man-hour etc., if film is applied tension force, sometimes with the defective for the basic point film can rupture, productivity reduces.In addition, if the diameter of defective is more than the 5 μ m, then can determine by range estimations such as polarizer observations, when using as optics, produce bright spot sometimes.

Need to prove, under the unascertainable situation of range estimation, when this film forms hard conating etc., occur to be formed uniformly the defective (holiday) of paint sometimes.Here, defective refers in the drying steps of solution film-forming because of the rapid cavity (foaming defective) in the film that causes of evaporation of solvent, or impurity (impurity defect) in the film that causes because of the impurity of sneaking in the impurity in the pleurodiaphragmatic in terspace liquid processed, the film processed.

In addition, blooming of the present invention is that preferably the elongation at break of at least one direction is more than 10%, more preferably more than 20% in the process measured of benchmark according to JIS-K7127-1999.

The upper limit of elongation at break is not particularly limited, and is about 250% in the reality.Increasing elongation at break, is effective to defective in the film that suppresses to cause because of impurity, foaming.

The thickness of preferred blooming of the present invention is more than the 20 μ m.More preferably more than the 30 μ m.

Preferred its full light transmittance of blooming of the present invention is more than 90%, more preferably more than 93%.In addition, in the reality on be limited to about 99%.For the excellent transparency that realizes representing with described full light transmittance, following method is effective: do not import the additive, the combined polymerization composition that absorb visible light, or remove by filter impurity in the polymer by high accuracy, thereby can reduce diffusion or the absorption of film interior lights.

If blooming of the present invention satisfies above-mentioned rerum natura, especially the polaroid protective film that can preferably use as the liquid crystal indicator of large-scale liquid crystal indicator, outdoor application uses.

＜utilize fusion curtain coating embrane method processed to make the method for blooming 〉

The manufacture method of blooming of the present invention is to contain the composition fusion of acrylic resin (A) and cellulose ester resin (B) with 95: 5～30: 70 mass ratio, extrudes the also manufacture method of the blooming of curtain coating on chill roll by die head.

Below, tell about the overall process of manufacture method.

＜melt granules manufacturing step 〉

Usually preferably will form mixingly in advance with composition be used to the blooming that melt extrudes and comprise acrylic resin (A), cellulose ester resin (B), other additive, and make it granulating.

Granulating can adopt known method; for example can be undertaken by following method; dry acrylic resin (A), the plain ester resin (B) of dried fibres or other additive are supplied with extruder with feed appliance; carry out mixing with single screw rod or double screw extruder; be extruded into the strand shape by die head; carry out the cooling of water cooling or air, and cut.

Before extruding raw material are carried out drying in advance, this is for preventing that raw-material decomposition from being very important.Especially therefore the easy moisture absorption of cellulose esters more than 3 hours, is preferably controlled moisture rate below the 200ppm, more preferably below the 100ppm 70～140 ℃ of dryings in advance with dehumidifying air drier or vacuum drier.

Additive can supply in the extruder altogether together, also can be supplied in the extruder by feed appliance separately respectively.For minor amounts of additives such as antioxidant are evenly mixed, preferably in advance with its mixing.

The mixing of antioxidant can mix between solid, optionally antioxidant can be dissolved in the solvent in advance, contains to be immersed in acrylic resin (A), the cellulose ester resin (B) to mix the mixing of perhaps spraying.

Preferred vacuum Nauta mixers (Nauta Mixer) etc. are because it can carry out drying and mixing simultaneously.In addition, under the outlet of feed appliance portion, die head etc. and situation that air contacts, preferably at the air of dehumidifying, the N of dehumidifying ₂Carry out under the atmosphere such as gas.

With regard to extruder, preferably suppress shearing force, but and in granulating and process under the low temperature, so that deterioration (molecular weight reduces, painted, gel generation etc.) does not take place resin as far as possible.For example, under the situation of double screw extruder, preferably use the deep channel type screw rod and make it in equidirectional rotation.Consider preferred occlusal pattern from mixing uniformity aspect.

With the particle film processed that obtains through aforesaid operations.Also can not carry out granulating, directly raw-material powder be supplied with extruder with feed appliance, directly film processed.

＜molten mixture is expressed into step on the chill roll by die head 〉

At first, melt temperature Tm when the particle of making is extruded with single screw rod or double-screw type extruder is about 200～300 ℃, after removing by filter impurity with leaf dish-type filter etc., be coextruded into membranaceous by the T die head, be cured at chill roll, limit and Elastic Contact roller squish lip carry out curtain coating.

When being imported to extruder by loading hopper, preferably under vacuum or the decompression under, carry out under the non-active gas atmosphere, in case oxidation decomposition etc.Need to prove that Tm is the temperature of extruder die head exit portion.

When if there is wound at the die head place or is attached with the impurity such as coagulation of plasticizer, produce the defective of striated sometimes.This defective is called as the die head line, and in order to reduce blemish such as die head line, preferably the pipe arrangement from extruder to die head forms and reduces the structure that resin is detained part as far as possible.Preferably use at few die heads such as die head inside, lip wounds.

Extruder, die head etc. and the contacted inner surface of molten resin, preferred use can reduce the low material of surface roughness or surface energy etc., and impose the Surface Machining that molten resin is difficult for adhering to.Particularly, can enumerate, the surface after hard plating, the ceramic spraying plating is ground, making surface roughness is below the 0.2S.

Be not particularly limited for chill roll of the present invention, but the metallic roll of high rigidity preferably, and this roller is that inside has circulation the thermal medium that can control temperature or the structure of cold medium are arranged, size without limits, but get final product so long as can fully cool off the size of the film after melt extruding, the diameter of chill roll is about 100mm～1m usually.

The Facing material of chill roll can be enumerated carbon steel, stainless steel, aluminium, titanium etc.In order to improve the fissility of surperficial hardness, improvement and resin, preferably implement surface treatments such as hard plating, nickel plating, noncrystalline chromium plating etc., ceramic spraying plating.

The surface roughness Ra on preferred chill roll surface is below the 0.1 μ m, more preferably below the 0.05 μ m.The roller surface is more level and smooth, and the surface of gained film is also more level and smooth.Certainly, preferably above-mentioned surface roughness is further ground to reach in the surface through Surface Machining.

As Elastic Contact roller of the present invention, can use the surface of record in Japanese kokai publication hei 03-124425 number, Japanese kokai publication hei 08-224772 number, Japanese kokai publication hei 07-100960 number, Japanese kokai publication hei 10-272676 number, WO97-028950, Japanese kokai publication hei 11-235747 number, TOHKEMY 2002-36332 number, TOHKEMY 2005-172940 number, TOHKEMY 2005-280217 number to be coated with the polysiloxane rubber roller of film metal sleeve pipe.

When film is peeled off from chill roll, preferably control tension force, prevent the distortion of film.

＜stretching step 〉

In the present invention, preferably the film that will obtain according to aforesaid operations by with step that chill roll contacts after, stretch 1.01～3.0 times at least 1 direction again.Can realize fragility of the present invention by stretching.

Preferably stretch 1.1～2.0 times respectively at vertical (film carriage direction), horizontal (cross direction) both direction.

The method that stretches can preferably be used known roller stretching-machine or expander etc.Especially under the situation of blooming double as polaroid protective film, be cross direction by making draw direction, can carry out lamination with light polarizing film with the scroll attitude, therefore preferred.

By stretching at cross direction, the slow axis that can make blooming is cross direction.

Usually, stretching ratio is 1.1～3.0 times, preferred 1.2～1.5 times, and draft temperature carries out in Tg～Tg+50 ℃, preferred Tg～Tg+50 ℃ temperature range of the resin that constitutes film usually.

The preferred uniform temperature branch in length direction or cross direction control that stretches plants and carries out.Preferably ± 2 ℃ with interior, further preferably ± 1 ℃ with interior, particularly preferably in ± 0.5 ℃ in.

For the delay of adjusting the blooming of making of said method, reduce size changing rate, film is shunk at length direction or cross direction.

For example, want when length direction shrinks, can adopt for example following method, temporarily unclamp the wide interval that makes it or adjacent clip by make cross directional stretch machine lax along length direction to stretching and slowly narrow down to make film to shrink.

The uniformity of slow axis direction is also very important, with respect to the film cross direction, optimized angle-5～+ 5 °, more preferably in-1～+ 1 ° of scope, particularly preferably in-0.5～+ 0.5 ° of scope in, particularly preferably in-0.1～+ 0.1 ° of scope in.These deviations can realize by the optimization of stretching condition.

Blooming of the present invention is more than the 300nm by the summit of adjacent peak to the height of the end point of paddy preferably, and is that length direction more than the 300nm/mm does not have continuous striped in gradient.

The shape of striped is fixed with the surface roughness instrumentation, particularly, use Mitutoyo SV-3100S4 processed, the limit is the heavy burden that the contact pilotage (diamond pin) of 60 ° in circular cone, tip curvature radius 2 μ m applies mensuration power 0.75mN to pointed shape, the limit is scanned at the cross direction of film with the finding speed of 1.0mm/sec, Z axle (thick direction) resolution ratio is 0.001 μ m, measures cross section curve.

By read the vertical range (H) between the end point from the summit at peak to paddy from this curve thus can obtain the height of striped.By reading the horizontal range (L) between the end point from the summit at peak to paddy, and with vertical range (H) divided by horizontal range (L), can try to achieve the gradient of striped.

＜solvent 〉

Because blooming of the present invention is made of fusion curtain coating film-forming method, therefore in the moment that is rolled into the web-like film, the quantity of solvent that contains is below the 0.01 quality %.The amount that contains solvent can be measured according to following method.

Each sample 20ml is added in the airtight glass container, after handling under following headroom (head space) heating condition, in advance the solvent that uses is made lubber-line with following gas-chromatography and measure.The amount that contains solvent is used with respect to the mass parts of all quality of blooming and is represented.

Machine: the 5890SERIES II of HP company

Chromatographic column: the DB-WAX of J﹠W company (internal diameter 0.32mm, long 30m)

Detect: FID

GC intensification condition: after 5 minutes, be warming up to 100 ℃ with 80 ℃/minute 40 ℃ of maintenances

Headroom heating condition: 120 ℃, 20min

＜cleaning equipment 〉

Be equipped with in the preferred manufacturing installation of the present invention automatically to the device of being with and roller cleans.Clearing apparatus is not particularly limited, and for example has following mode: the mode of clamping brush and roller, suction roll, adhesive roller, application roll etc.; Blast the air blast mode of pure air; Utilize laser incinerator mode or with mode of the combination of these modes etc.

When adopting the clamping cleaning to use the mode of roller, when changing band linear velocity and roller linear velocity, the cleaning effect is better.

Preferred blooming of the present invention is rectangular film, particularly, is the film about 100m～5000m, provides with the web-like form usually.In addition, the width of preferred film is 1.3～4m, more preferably 1.4～2m.

The thickness of blooming of the present invention is not particularly limited, and is used under the situation of aftermentioned polaroid protective film, is preferably 20～200 μ m, more preferably 25～100 μ m, preferred especially 30～80 μ m.

(polarizer)

Under the situation of blooming of the present invention as the protective film for polarizing plate use, polarizer can adopt usual way to make.The rear side of preferred blooming of the present invention is provided with tack coat, fits to be on the face of at least one side of the polarizer of dipping stretching making in the iodine solution.

Another side can use blooming of the present invention, also can use other polaroid protective film.For example, the preferred commercially available cellulose ester membrane (for example, Konica Minolta Tech KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC8UE, KC4UE, KC4FR-3, KC4FR-4, KC4HR-1, KC8UY-HA, KC8UX-RHA, above by Konica Minolta Opto (strain) system) etc. that uses.

Be the element of the light of plane of polarization that only can be by certain orientation as the main composition key element polarizer of polarizer, the known representational polarizer has polyvinyl alcohol light polarizing film (light polarizing film that the polyvinyl alcohol film is formed with iodine staining and the light polarizing film that forms with dichroic dye dyeing are arranged) now.

The polarizer preferably uses following goods: with polyvinyl alcohol water solution film processed, it is carried out carrying out simple tension after simple tension and dyeing or the dyeing, preferably carry out durability with boron compound then and handle the goods that obtain.

As the binding agent that can be used for above-mentioned tack coat, at least a portion of preferably using tack coat is 1.0 * 10 25 ℃ storage modulus ⁴Pa～1.0 * 10 ⁹The binding agent of pa scope, the preferred curing type binding agent that uses coating binding agent, the back of fitting to form HMW body or cross-linked structure by various chemical reactions.

As concrete example, for example can enumerate 2 liquid type moment binding agents of moment binding agent, acrylate and the peroxide of anaerobic adhesives such as curing type binding agents such as polyurethanes binding agent, epoxy base class binding agent, aqueous macromolecule-isocyanate class binding agent, thermohardening type acrylic adhesive, moisture cure urethanes binding agent, polyethers methacrylate type, ester class methacrylate type, oxidized form polyethers methacrylate, cyanoacrylate etc.

As above-mentioned binding agent, can be 1 liquid type, be the type that 2 liquid are above, mix use before also can being to use.

In addition, above-mentioned binding agent can be for being the solvent based of medium with the organic solvent, and medium is water classes such as the emulsion-type, colloidal dispersion type, aqueous solution type of principal component with water, also can be no-solvent type.The concentration of above-mentioned binder liquid can wait suitably and determine according to thickness, coating process, the coating condition after the bonding, is generally 0.1～50 quality %.

(liquid crystal indicator)

Install in the liquid crystal indicator by the polarizer group that will be fitted with blooming of the present invention, can make various visual excellent liquid crystal indicators, especially be preferred for the liquid crystal indicator of outdoor application such as large-scale liquid crystal indicator, digital signage.Polarizer of the present invention is fitted with the liquid crystal pond by above-mentioned tack coat etc.

Polarizer of the present invention can be effective to the LCD of reflection-type, transmission-type, transflective LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type various type of drive such as (comprising the FFS mode).Especially picture is above, the big picture display devices of 30 types～54 types especially of 30 types, and the picture peripheral part does not produce deinking etc., its effect can be for a long time between maintenance.

In addition, the look inequality, dazzling, fluctuation is uneven few, watches the effect that also can not cause visual fatigue for a long time even have.

Embodiment

Below, can enumerate the present invention of embodiment and be specifically described, but the present invention is not limited.

Embodiment 1

(preparation of acrylic resin)

Adopt known method to prepare following acrylic resin A2-A7 and MS1,2.

3), Mw120000 A2: monomer mass is than (MMA: MA=97:

3), Mw140000 A3: monomer mass is than (MMA: MA=97:

3), Mw200000 A4: monomer mass is than (MMA: MA=97:

3), Mw500000 A5: monomer mass is than (MMA: MA=97:

3), Mw550000 A6: monomer mass is than (MMA: MA=97:

6), Mw1000000 A7: monomer mass is than (MMA: MA=94:

MMA: methyl methacrylate

MA: methyl acrylate

In addition, used following commercially available acrylic resin.

A1 ACRYPET V (Rayon of Mitsubishi (strain) system) Mw100000

Ratio in the SumilizerGS (Sumitomo Chemical (strain) system) of the Irganox1010 (Ciba Japan (strain) system) of the ADK STAB PEP-36 (rising sun electrochemical industry (strain) system) of the Tinuvin928 (Ciba Japan (strain) system) of the A2 of 70 mass parts, the cellulose ethanoate propionic ester as cellulose esters of 30 mass parts (degree of substitution with acetyl group 0.19, propiono substitution value 2.56, total acyl substituted degree 2.75, Mw=200000), 1.5 mass parts, 0.01 mass parts, 0.5 mass parts, 0.2 mass parts is mixed, and has formed the composition 1 of formation blooming 1.

Above-mentioned composition was mixed 3 hours under 80 ℃, the condition of 1Torr with the vacuum Nauta mixer respectively, and carry out drying.Use double screw extruder in 235 ℃ of melting mixing dried composition, carried out granulating.

For above-mentioned particle, use single screw extrusion machine to carry out lamination with the T die head respectively, it is melt extruded in surface temperature in 240 ℃ of melt temperatures and be on 90 ℃ the 1st chill roll and make it to membranaceous, obtained the casting films of total film thickness 150 μ m by extrusion molding.At this moment, on the 1st chill roll, use the Elastic Contact roller with the thick metal surface of 2mm that film is pushed.

Then, use utilizes the stretching-machine of roller difference down this film to be stretched 1.3 times at carriage direction in 155 ℃ (Tg of composition is 125 ℃), again it is imported in the expander as the cross direction stretching-machine, described expander as the cross direction stretching-machine has the preheating zone, stretch zones, retaining zone, (each is interregional also to have zone line to cooled region, each is interregional heat insulation for making conscientiously), stretch after 1.3 times at cross direction in 155 ℃ then, be cooled to 30 ℃, at last, it is decontroled from clip, sanction is removed the clip retained part, has obtained wide 2500mm, the blooming 1 of thickness 80 μ m.

Making as above-mentioned blooming 1, obtained the present invention and blooming 2～30 relatively, different is: with kind, molecular weight, the ratio of components of acrylic resin (A), cellulose ester resin (B), have or not plasticizer, stretching condition, thickness to change to shown in the table 1.

And their solvent amount is below the 0.01 quality %.

Plasticizer 1:DOA (dioctyl adipate)

For the gained blooming, carried out following evaluation.

" evaluation method "

(glass transition temperature)

The Tg of the blooming before stretching is substantially the same with the blooming that is made into, therefore, by measuring the Tg of blooming, the Tg of the blooming before replacing stretching.

Glass transition temperature under 23 ℃, the atmosphere of 55%RH refers to: use differential scanning calorimetry device (Perkin Elmer corporate system DSC-7 type), programming rate with 20 ℃/minute is measured, and the intermediate point glass transition temperature (Tmg) of trying to achieve according to JIS K7121 (1987) (℃).

(tension force softening point)

Under 23 ℃, the atmosphere of 55%RH, (the ORIENTEC corporate system RTC-1225A), is estimated as follows to use the TENSILON testing machine.

Blooming is cut into 120mm (length) * 10mm (wide), with the tension force of 10N carry out tractive on one side, heat up continuously with 30 ℃/minute programming rate on one side, the temperature when reaching moment of 9N (℃) carry out 3 times and measure, obtain its mean value.

(folding strength)

Blooming is cut into 120mm (length) * 10mm (wide), in the room that is adjusted to 23 ℃ of temperature, relative humidity 55%RH, adjusts humidity after 4 hours, according to ISO8776/2-1988, obtain the reciprocal time when disconnecting because of bending.

[table 2]

The making of＜polarizer and liquid crystal indicator 〉

The making of＜polarizer 〉

Made as follows with the polarizer of each blooming as polaroid protective film.

The long paper polyvinyl alcohol film of thickness 120 μ m impregnated in the aqueous solution 100 mass parts that contain iodine 1 mass parts, boric acid 4 mass parts, stretches 5 times at carriage direction in 50 ℃, has made the polarizer.

Then, after the blooming 1 enforcement sided corona treatment of making among the embodiment 1, use acroleic acid binding agent that it is fitted on the one side of this polarizer.

And, fit as the Konica minolta TUCH KC8UCR-5 (Konica minolta OPTO (strain) system) of the phase retardation film that passes through the alkali soap processing at the another side of the polarizer, carry out drying, made polarizer P1.Similarly, use blooming 2～30 to make polarizer P2～P30.

(operability again)

Under 23 ℃, the atmosphere of 55%RH, the polarizer severing of making is become the square of 20cm * 20cm size, use acrylic adhesive with itself and glass substrate applying.Then, the polarizer after fitting is peeled off from glass with the intensity of 5N from the part on the angle.Carry out this operation at a kind of sample with 100 polarizers, to polarizer crackle appears, the number of the polarizer that do not strip down fully counts.Operability is by following benchmark ratings again.

Zero: 0～5

Zero △: 6～10

△: 11～15

*: more than 16

As long as operability is then practical no problem for more than the △ level again, is preferably more than the zero △ level, is preferably zero level especially.

The making of＜liquid crystal indicator 〉

Use each polarizer of above-mentioned making, carried out the display characteristic evaluation of blooming.

The polarizer that will be fitted in advance on the two sides of 32 inches TV AQ-32AD5 of SHARP (strain) system peels each polarizer of the above-mentioned making of fitting respectively.Make Konica minolta TUCH KC8UCR-5 be positioned at the glass face side in liquid crystal pond, and absorption axes is towards the direction identical with the polarizer of fitting in advance, thereby made liquid crystal indicator respectively.

Then, under 23 ℃, the environment of 55%RH, the back illumination lamp was lighted 12 hours continuously, visual observations black show state is comprehensively estimated light leak in the darkroom.The result is as shown in table 3.

(light leak)

Light leak during black the demonstration is estimated by following benchmark by range estimation.

Zero: do not have light leak fully

*: the strong light leak in 1～2 place is arranged

[table 3]

As can be known: blooming of the present invention is preferred aspect operability again, and it is difficult for taking place light leak, with respect to relatively, has obtained improvement.

Embodiment 2

The preparation of＜acrylic particles (Cl) 〉

60 liters of internal volumes and take back stream cooler reactor in, add 38.2 liters of ion exchange waters, aerosol OT 111.6g, rotating speed with 250rpm stirs, and is warming up to 75 ℃ simultaneously under nitrogen atmosphere, forms the state that in fact not influenced by oxygen.Drop into APS 0.36g, stir and add the monomer mixture of being formed by MMA 1657g, BA 21.6g and ALMA 1.68g after 5 minutes in the lump, detect exothermal peak after, kept again 20 minutes, finished the polymerization of interior hard layer.

Then, drop into APS 3.48g, stir after 5 minutes, spend 120 minutes and add the monomer mixture of being made up of BA8105g, PEGDA (200) 31.9g and ALMA 264.0g continuously, interpolation kept 120 minutes after finishing again, had finished the polymerization of soft layer.

Then, drop into APS 1.32g, stirs after 5 minutes cost and added the monomer mixture of being formed by MMA 2106g, BA 201.6g in 20 minutes continuously, after the interpolation end, kept again 20 minutes, finished the polymerization of outermost hard layer 1.

Then, drop into APS 1.32g, the monomer mixture of being made up of MMA 3148g, BA 201.6g and n-OM10.1g was added in cost in 20 minutes continuously after 5 minutes, and interpolation kept 20 minutes after finishing again.Then, be warming up to 95 ℃ and kept 60 minutes, finished the polymerization of outermost hard layer 2.

The polymer emulsion of the such acquisition that takes a morsel, obtaining its average grain diameter by absorbance method is 0.10 μ m.The latex of remainder is dropped in the 3 quality % sodium sulphate warm water solution, saltout and solidify, dewater repeatedly then and clean, carry out drying again, obtained the acrylic particles (Cl) of 3-tier architecture.

Above-mentioned ellipsis is following material.

MMA: methyl methacrylate

MA: methyl acrylate

BA: n-butyl acrylate

ALMA: allyl methacrylate

PEGDA: polyethyleneglycol diacrylate (molecular weight 200)

N-OM: n-octyl mercaptan

APS: ammonium persulfate

Below, manufacture method as embodiment 1 described blooming 2, blooming 2-1 and 2-2 have been made, made blooming 1-1～1-6 as the manufacture method of blooming 1, different is: change to acrylic resin (A), cellulose ester resin (B), acrylic particles (C), ratio of components as shown in table 4.

And, as 2-2, made and contained acrylic resin film 2-3, but when adding other resins, added following ultra-violet absorber.

TINUVIN109 (Ciba Japan (strain) system) 1.5 mass parts

TINUVIN171 (Ciba Japan (strain) system) 0.7 mass parts

And the quantity of solvent that contains of these bloomings is below the 0.01 quality %.

For these samples, as embodiment 1, estimate.The result is as shown in table 5.

[table 5]

As above-mentioned, when in blooming of the present invention, further adding the acrylic acid particulate, can further improve folding strength, operability again.

Claims

1. blooming, it contains acrylic resin (A) and cellulose ester resin (B), and the total substitution value of acyl group (T) of this cellulose ester resin (B) is more than 2.0 and below 3.0, and this blooming is made by fusion curtain coating film-forming method, it is characterized in that,

The mass ratio of acrylic resin (A) and cellulose ester resin (B) is 95:5～30:70; the weight average molecular weight Mw of aforesaid propylene acid resin (A) is more than 110000 and below 1000000; in the described cellulose ester resin (B) carbon number be 3 or more and 7 below the substitution value of acyl group be more than 1.2 and below 3.0; the weight average molecular weight Mw of this cellulose ester resin (B) is more than 75000 and below 300000; the tension force softening point of this blooming is 105～145 ℃, and folding strength is 50～100 times.

2. method of making blooming, this method comprises: the described blooming of claim 1 is stretched along at least one direction in direction of transfer or the cross direction, thereby make blooming, its draft temperature is Tg～Tg+50 ℃ of the blooming before stretching.

3. blooming according to claim 1, wherein, aforesaid propylene acid resin (A) forms compatible noncrystalline resin with cellulose ester resin (B).

4. blooming according to claim 1, wherein, the gross mass of aforesaid propylene acid resin (A) and cellulose ester resin (B) is more than the 55 quality % of blooming.

5. blooming according to claim 1, it also contains the acrylic compounds particle.

6. blooming according to claim 5, wherein, aforesaid propylene acids particle has the layer structure more than 2 layers.

7. blooming according to claim 1, it also contains at least a in phthalate, fatty acid ester, trimellitate class, phosphoric acid ester, polyesters or the epoxy plasticiser.

8. blooming according to claim 1, it also contains at least a antioxidant that is selected from lactone, sulphur class, phenols, two key class, hindered amines, the Phosphorus compound.

9. polarizer, it has the described blooming of claim 1.

10. liquid crystal indicator, it has the described polarizer of claim 9.