CN102749668B

CN102749668B - Polaroid and liquid crystal indicator

Info

Publication number: CN102749668B
Application number: CN201210118606.6A
Authority: CN
Inventors: 深川伸隆; 内藤游; 田村显夫; 野副宽
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2011-04-21
Filing date: 2012-04-20
Publication date: 2016-02-24
Anticipated expiration: 2032-04-20
Also published as: CN102749668A

Abstract

The invention provides the polaroid that hot and humid polarizer permanance down and under high temperature low humidity is all enhanced.This polaroid comprises the polarizer and is configured at 2 polaroid protective films of both sides of this polarizer, at least 1 polaroid protective film 60 DEG C, relative humidity 95%, through time to process 24 little moisture permeabilitys be constantly 500g/m ²above and 2000g/m ²below, containing boric acid in the polarizer, 60 DEG C, relative humidity 95%, through time process 800 hours before be less than 30% with the slip of the boric acid in the polarizer afterwards.

Description

Polaroid and liquid crystal indicator

Technical field

The present invention relates to polaroid and liquid crystal indicator.Even if the polaroid also excellent in particular to polarizer permanance under any one environment in hot and humid and high temperature low humidity and there is the liquid crystal indicator of this polaroid.

Background technology

Liquid crystal indicator is little and space-efficient image display device as consumes power, and its purposes expands year by year.In the past, the shortcoming that of liquid crystal indicator is very large is that the view angle dependency of display image is large, but along with the wide viewing angle liquid crystal modes such as VA pattern are practical, even if require in the market of high quality image at televisor etc., the needs of liquid crystal indicator are also constantly expanding rapidly.

The basic comprising of liquid crystal indicator is the formation being provided with polaroid in the both sides of liquid crystal cells.Described polaroid has the effect only making the light of the plane of polarization of specific direction pass through, about the performance of the liquid crystal indicator performance largely by polaroid.Polaroid is generally and makes the polarizer be made up of polyvinyl alcohol film etc. of iodine or Dye Adsorption orientation and paste forming of transparent diaphragm in the positive and negative both sides of this polarizer.As polaroid protective film, be that the polaroid protective film of the acylated cellobiose prime system of representative is high due to the transparency with cellulose acetate, and easily can guarantee the adaptation of the polyvinyl alcohol (PVA) used with the polarizer, so extensively used always.

In recent years, along with the purposes of liquid crystal indicator expands, the large scale of televisor etc. and high-quality purposes constantly expand, and the requirement for the quality of polaroid and polaroid protective film also improves further.Particularly large scale and the liquid crystal indicator of high-quality purposes is compared with the past, also needs such as to use under digital signage purposes etc. take outdoor as the environment of the various harshnesses of representative, needs the use under the hot environment of various harshness especially.From the viewpoint, in recent years, for the polaroid used in liquid crystal indicator, strongly be desirably in the improvement of polarizer permanance under the hot environment of various harshness always, specifically, strong expectation suppresses orthogonal transmission (hereinafter also referred to the cross transmittance) change of the hot and humid polarizer down and under high temperature low humidity simultaneously.

In order to improve the polarizer permanance under hot environment, known suppression water immerses to the polarizer and regulates the pH of the polarizer to be effective all the time, such as, Patent Document 1 discloses and use moisture permeability for 150g/m in polaroid protective film ²the method of the film of less than/24 hours.In addition, Patent Document 2 discloses solution-treated that to use by pH be 1.0 to 6.0 and adsorb dichromatism pigment and boric acid and the polarization element film that formed of the hydrophilic macromolecule film be stretched, and impart the polaroid of the layer that polymer resin composition is solidified.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 11-142645 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2008-70571 publication

Summary of the invention

Invent problem to be solved

But the research through inventors of the present invention is known, polaroid described in above-mentioned patent documentation can not meet the requirement in hot and humid polarizer permanance down and under high temperature low humidity.

The moisture permeability recorded in above-mentioned patent documentation 1 is 150g/m by inventors of the present invention ²the polaroid protective film of less than/24 hours combines with the conventional polarizer; manufacture polaroid; study the polarizer permanance of its hot and humid orthogonal transmission change down and under high temperature low humidity; result learn hot and humid under polarizer permanance improve, but be surprised to find that the polarizer permanance under high temperature low humidity worsens on the contrary.

In addition, inventors of the present invention manufacture by the polaroid that obtains of method recorded in above-mentioned patent documentation 2 and study its performance, result learn 60 DEG C, relative humidity 95%, through time condition under orthogonal transmission change still very greatly.In addition; from the viewpoint of manufacture method; after the polarizer (polarization element film) and polaroid protective film bonding, also need on this diaphragm, polymer resin composition solidify, therefore known its be comprise manufacturing cost viewpoint and need the method for further improvement.

That is, not yet learn the polaroid that the polarizer permanance under hot and humid and the polarizer permanance under high temperature low humidity are all enhanced at present, thus need to improve.

The object of the present invention is to provide the polaroid be all enhanced in hot and humid polarizer permanance down and under high temperature low humidity.

For the means of dealing with problems

Inventors of the present invention further investigate for the purpose of solving the problem, found that complex compound stabilization in order to hydrophilic macromolecule (such as polyvinyl alcohol (PVA)) and dichromatism pigment (such as iodine) and the boric acid that the adds content in the polarizer hot and humid through reduce at present be hot and humid through time in one of the reason that rises of the cross transmittance of the polarizer.

In addition, find density by increasing polaroid protective film and reduce the evolving path of boric acid, even if in the polaroid protective film with certain moisture permeability, also can suppress described hot and humid through time in the minimizing of polarizer mesoboric acid content.

And; find by adding specific organic acid in polaroid protective film; can hot and humid through slowly regulating pH at present; so compared with the method regulating the pH of the polarizer when making with the polarizer recorded in such as patent documentation 2, be more difficult to occur hot and humid through time polarization property deterioration.When using cellulose acylate film in polaroid protective film, the moisture permeability of being undertaken causing by this acylated cellulose acid-hydrolyzed rises, the permeability rising of boric acid can become hot and humid through time the reason of polarizer performance degradation.Inventors of the present invention find when the pH of the polarizer being adjusted to low pH by water-soluble high low-molecular-weight acid as described in patent documentation 2; this acid is moved in polaroid protective film layer, facilitates the acid hydrolysis of polaroid protective film (cellulose acylate film).In contrast, inventors of the present invention find, by using suitable acid ionization constant and water-soluble low organic acid, can suppress the acid hydrolysis of polaroid protective film, and at the hot and humid lower pH that can reduce the polarizer.In addition, found to be difficult to occur high temperature low humidity through time polarization property deterioration.

In addition, find except organic acid, when also adding the specific polymkeric substance containing phenyl ring on specific phenol system compound or main chain, played excellent effect too.

That is, the problems referred to above are solved by the present invention of following formation.

1. a polaroid, its comprise containing from the boron of boric acid the polarizer and be configured at 2 polaroid protective films of both sides of this polarizer,

At least 1 polaroid protective film 60 DEG C, relative humidity 95%, through time to process 24 little moisture permeabilitys be constantly 500g/m ²above and 2000g/m ²below,

60 DEG C, relative humidity 95%, through time to process before 800 hours with the slip of the boron from boric acid in the polarizer be afterwards less than 30%.

2. the polaroid recorded in above-mentioned 1, wherein, the density of described polaroid protective film is 1.293g/cm ³above.

3. the polaroid recorded in above-mentioned 1 or 2, wherein, the polaroid protective film meeting described characteristic contains the polymkeric substance of the repetitive comprised from the monomer shown in following general formula (1).

Chemical formula 1

In general formula (1), R ¹represent that hydrogen atom or carbon number are the fatty group of 1 ~ 4.R ²represent substituting group.(A) represent for the formation of the atom group required for 5 or 6 rings.N represents the integer of 0 ~ 4.

4. the polaroid recorded in above-mentioned 3, wherein, described polymkeric substance is for comprising from the repetitive of monomer shown in described general formula (1) and the interpolymer of other repetitives different from this repetitive.

5. the polaroid recorded in above-mentioned 3 or 4, wherein, the R in described general formula (1) ¹for hydrogen atom, (A) represents 5 rings, R ²for hydrogen atom, methyl or hydroxyl.

6. the polaroid recorded in any one in above-mentioned 3 ~ 5, wherein, from the repetitive of the monomer shown in described general formula (1) by shown in following general formula (2-1), general formula (2-2), general formula (2-3), general formula (2-4), general formula (2-5) or general formula (2-6).

Chemical formula 2

In formula, R ¹⁰~ R ¹⁹separately represent substituting group.N1, n2, n5, n6, n8 and n10 separately represent the integer of 0 ~ 4.N3, n7 and n9 separately represent 0 ~ 2.N4 separately represents 0 or 1.R ^1Arepresent that hydrogen atom or carbon number are the fatty group of 1 ~ 4.

7. the polaroid recorded in any one in above-mentioned 3 ~ 6, wherein, described polymkeric substance is for containing the coumarone resin of 3 compositions shown in following general formula (P-1) as repetitive.

Chemical formula 3

formula P-1

In formula, R ²¹, R ²², R ²³and R ²⁴separately represent substituting group.X, y, z represents the molar ratio relative to the total repetitive contained by polymkeric substance, and x represents that 1 ~ 40%, y represents that 5 ~ 95%, z represents 1 ~ 70%.M1, m2 separately represent the integer of 0 ~ 4.M3 represents the integer of 0 ~ 2.M4 represents the integer of 0 ~ 5.R ¹⁰¹, R ¹⁰², R ¹⁰³separately represent that hydrogen atom or carbon number are the fatty group of 1 ~ 4.

8. the polaroid recorded in any one in above-mentioned 3 ~ 7, wherein, the weight-average molecular weight of described polymkeric substance is 200 ~ 10000.

9. the polaroid recorded in above-mentioned 1 or 2, wherein, the polaroid protective film acid ionization constant contained in the mixed solvent of the volume ratio of at least a kind of tetrahydrofuran/water=6/4 at 25 DEG C meeting described characteristic is the organic acid of 2 ~ 7.

10. the polaroid recorded in above-mentioned 1,2 or 9, wherein, the polaroid protective film meeting described characteristic comprises the compound shown in following general formula (3).

General formula (3)

Chemical formula 4

In general formula (3), R ²⁶represent aryl, R ²⁷and R ²⁸separately represent hydrogen atom, alkyl, aryl.R ²⁶and R ²⁷also substituting group can be had respectively.

The polaroid recorded in 11. above-mentioned 1 or 2, wherein, the polaroid protective film meeting described characteristic contains the compound shown in following general formula (4).

Chemical formula 5

In general formula (4), R ¹represent hydrogen atom or substituting group, R ²represent the substituting group shown in following general formula (5); N1 represents the integer of 0 ~ 4, when n1 is more than 2, and multiple R ¹can identical mutually also can be different; N2 represents the integer of 1 ~ 5, when n2 is more than 2, and multiple R ²can identical mutually also can be different;

Chemical formula 6

In general formula (5), A represents substituted or unsubstituted aromatic ring; R ³and R ⁴separately represent alkyl or the substituting group shown in general formula (6) that hydrogen atom, carbon number are 1 ~ 5; R ⁵represent that singly-bound or carbon number are the alkylidene of 1 ~ 5; X represents substituted or unsubstituted aromatic ring; N3 represents the integer of 0 ~ 10, when n3 is more than 2, and multiple R ⁵with X can identical mutually also can be different;

Chemical formula 7

In general formula (6), X represents substituted or unsubstituted aromatic ring; R ⁶, R ⁷, R ⁸, and R ⁹separately represent that hydrogen atom or carbon number are the alkyl of 1 ~ 5; N5 represents the integer of 1 ~ 11, when n5 is more than 2, and multiple R ⁶, R ⁷, R ⁸with X can identical mutually also can be different.

The polaroid recorded in 12. above-mentioned 11, wherein, A and X in described general formula (5) and described general formula (6) is phenyl ring.

The polaroid recorded in 13. above-mentioned 11 or 12, wherein, described general formula (5) is by shown in following general formula (5 ").

Chemical formula 8

General formula (5 ") in, n3 represents the integer of 0 ~ 5.

The polaroid recorded in any one in 14. above-mentioned 11 ~ 13, wherein, described general formula (6) is by shown in following general formula (6 ").

Chemical formula 9

General formula (6 ") in, n4 represents the integer of 0 ~ 10.

The polaroid recorded in 15. above-mentioned 11 ~ 14, wherein, the R in described general formula (4) ¹for hydrogen atom or carbon number are the alkyl of 1 ~ 8, R ²shown in general formula (5 "), n1 represents the integer of 2 ~ 4, and n2 represents the integer of 1 ~ 3, and n3 represents the integer of 0 ~ 2.

The polaroid recorded in any one in 16. above-mentioned 11 ~ 15, wherein, as the compound shown in described general formula (4), containing at least 2 kinds of mutual different compounds.

The polaroid recorded in any one in 17. above-mentioned 11 ~ 16, wherein, the weight-average molecular weight of the compound shown in described general formula (4) is 200 ~ 1200.

The polaroid recorded in any one in 18. above-mentioned 1 ~ 17, wherein, the polaroid protective film meeting described characteristic is cellulose acylate film.

19. 1 kinds of liquid crystal indicators, it is at least containing the polaroid recorded in any one in 1 described 1 ~ 18.

The effect of invention

According to the present invention, can provide and not make the polarizer permanance under high temperature low humidity worsen, improve hot and humid under the polaroid of polarizer permanance and manufacture method.In addition, the liquid crystal indicator employing polaroid of the present invention can be provided.

Accompanying drawing explanation

Fig. 1 is the skeleton diagram of the example representing liquid crystal indicator of the present invention.

Embodiment

[polaroid]

Polaroid of the present invention is following polaroid: this polaroid comprise containing from the boron of boric acid the polarizer and be configured in 2 polaroid protective films of both sides of this polarizer, at least 1 polaroid protective film 60 DEG C, relative humidity 95%, through time to process 24 little moisture permeabilitys be constantly 500g/m ²above and 2000g/m ²below, 60 DEG C, relative humidity 95%, through time to process before 800 hours with the slip of the boron from boric acid in the polarizer be afterwards less than 30%.

In the polarizer, usual boric acid is crosslinked, so in the present invention, the content of the boric acid in the polarizer is with the Content evaluation of the boron from boric acid.

Polaroid in the past reduces at hot and humid boric acid content in the polarizer at present, the situation of the complex compound destabilization of hydrophilic macromolecule (such as polyvinyl alcohol (PVA)) and dichromatism pigment (such as iodine) is more, and this is the reason of polarization property deterioration.Relative to this; polaroid of the present invention suppresses the boric acid content in the polarizer to reduce by making the density in polaroid protective film increase; on the other hand, by making the moisture permeability of polaroid protective film remain certain value, suppress the polarization property deterioration under high temperature low humidity conditions.

Below, polaroid of the present invention is described in detail.

The performance > of < polaroid

(orthogonal transmission CT)

The orthogonal transmission CT of polaroid is preferably CT≤2.0, is CT≤1.3 as preferred scope, most preferably is CT≤0.6 (unit is %).

(orthogonal transmission change)

In addition, with afterwards before polaroid endurancing, the variable quantity of preferred orthogonal transmission is little.

Polaroid of the present invention preferably 60 DEG C, the relative humidity 95% time variable quantity (%) that leaves standstill 800 little orthogonal single plate transmittance is constantly less than 0.65%, and 105 DEG C, (it is the state not having damping, refers to that relative humidity is 0% ~ 20% in an embodiment of the present invention) leaves standstill 50 little orthogonal single plate transmittance constantly under dry (Dry) environment variable quantity (%) is less than 0.05%.

60 DEG C, the relative humidity 95% time variable quantity (%) that leaves standstill 800 little orthogonal single plate transmittance is constantly preferably less than 0.30%, is more preferably less than 0.20%.

105 DEG C, the variable quantity (%) that leaves standstill 500 little orthogonal single plate transmittance constantly under dry environment is preferably less than 0.03%.

Wherein, the value that before the variable quantity of orthogonal transmission refers to and deduct test measured value after test, measured value obtains, is calculated by following formula.

Variable quantity (%)=(orthogonal transmission (%) before orthogonal transmission (the %)-endurancing after endurancing of orthogonal transmission

If meet the scope of the variable quantity of above-mentioned orthogonal transmission, then can guarantee that polaroid is in hot and humid stability down and under high temperature low humidity in long-time use or in keeping, so preferably.

In the present invention, the orthogonal transmission CT of polaroid uses UV3100PC (Shimadzu Scisakusho Ltd's system) to measure.In mensuration, measure with 410nm and 510nm, use the mean value measured for 10 times.

Wherein, polaroid endurancing can be carried out as follows in (1) 2 kinds of modes of mode that only polaroid is pasted onto on glass via bonding agent by the mode of polaroid and (2).

In the mensuration of (1) only polaroid, with clip between 2 polarizers described 60 DEG C, relative humidity 95%, through time process 24 little moisture permeabilitys constantly for 500g/m ²above and 2000g/m ²the mode of following polaroid protective film combines, and prepares 2 and absorbs the mutually orthogonal polaroid of axle.

In (2) polaroid is pasted onto in the mensuration under the mode on glass via bonding agent, make 2 samples (about 5cm × 5cm), this sample by with described 60 DEG C, relative humidity 95%, through time process 24 little moisture permeabilitys constantly for 500g/m ²above and 2000g/m ²following polaroid protective film, in the mode of glass side, polaroid is pasted by glass and obtains.In veneer orthogonal transmission measures, the film side of this sample is arranged towards light source and measures.Measure 2 samples respectively, its mean value is set to veneer orthogonal transmission.In an embodiment of the present invention, among the test method of above-mentioned (1) and (2), adopt the test method of (2).

(other characteristics)

About other preferred optical characteristics etc. of polaroid of the present invention, on the books in (0238) of Japanese Unexamined Patent Publication 2007-086748 publication ~ (0255), preferably meet these characteristics.

< shape forms >

The shape of polaroid of the present invention not only comprises and is cut to and can enters the polaroid of the diaphragm form of the size of liquid crystal indicator by direct-assembling, also comprises and is made as strip by continuous seepage and the polaroid being wound as the form (the long mode for more than 2500m or more than 3900m of such as reel) of drum.In order to for large picture liquid crystal indicator, the width of polaroid is preferably set to more than 1470mm.

Polaroid of the present invention is made up of the polaroid protective film on the polarizer and its two sides of protection, but the formation of also preferred fit further on this polaroid face protective film, stripping film of fitting on opposing sides.

Described protective film and described stripping film when in polaroid shipment, product examination time etc. protection polaroid for the purpose of and use.Now, protective film of fitting for the purpose of the surface protecting polaroid, uses it for the opposed faces side in the face to liquid crystal board laminating polaroid.In addition, stripping film uses to cover for the purpose of the adhesion layer of liquid crystal board laminating, uses it for the side, face to liquid crystal board laminating polaroid.

Below, the detailed content of the polarizer that can use in polaroid of the present invention and 2 polaroid protective films is described.

< polarizer >

First, the polarizer used in polaroid of the present invention is described.

As the described polarizer that can use in polaroid of the present invention, preferably be made up of polyvinyl alcohol (PVA) (PVA) and dichroic molecules, but also can as described in Japanese Unexamined Patent Publication 11-248937 publication, use by by PVA or Polyvinylchloride dehydration, dechlorination and generate polyene structure, the polyvinylene (Polyvinylene) that its orientation is obtained is the polarizer.

(1-1)PVA

As described PVA, the polymer raw materials preferably saponifying polyvinyl acetate obtained, but such as can contain unsaturated carboxylic acid, unsaturated sulfonic acid, olefines, vinyl ethers such can with the composition of vinyl acetate copolymerization.In addition, the modified PVA containing acetoacetyl, sulfonic group, carboxyl, oxyalkylene (Oxyalkylene) base etc. can also be used.

Other, in polaroid of the present invention, preferably can use that 1, the 2-ethylene glycol binding capacity recorded in No. 3021494th, Jap.P. is the PVA film of less than 1.5 % by mole, the optics impurity of more than 5 μm recorded in Japanese Unexamined Patent Publication 2001-316492 publication is every 100cm ²in PVA film, the hot water in the TD direction of film recorded in No. 2002-030163, Japanese Unexamined Patent Publication of less than 500 cut off temperature and be not the PVA film of less than 1.5 DEG C, also have the PVA film obtained by the solution of the polyvalent alcohol 1 ~ 100 % by weight being mixed with glycerine etc. 3 ~ 6 yuan or the solution that is mixed with more than the plastifier 15 quality % recorded in Japanese Unexamined Patent Publication 06-289225 publication.

(1-2) dichroic molecules

Dichroic molecules preferably can use I ₃-or I ₅-wait iodide ion or the dichroic dye of high order.

In the present invention, the iodide ion of high order is particularly preferably used.The iodide ion of high order can as " application of polaroid " forever the good volume in field, CMC publishes or industrial materials, the 28th volume, No. 7, p.39 ~ p.45 described in, PVA is immersed in liquid iodine being dissolved in and obtaining in potassium iodide aqueous solution and/or boric acid aqueous solution, generates with the state of adsorbing, being oriented on PVA.

When using dichroic dye as dichroic molecules, preferred azo system pigment, particularly preferably bisdiazo system and trisazo-system pigment.The preferred water miscible dyestuff of dichroic dye, therefore preferably imports the hydrophilics such as sulfonic group, amino, hydroxyl in dichroic molecules, and the salt as free acid or alkali metal salt, ammonium salt, amine uses.As the object lesson of such dichroic dye, the dichroic dye recorded in Japanese Unexamined Patent Publication 2007-086748 publication can be enumerated.

(1-3) boric acid

Polaroid of the present invention contains boric acid as crosslinking chemical in the polarizer.By being cross-linked the polarizer by boric acid, then the stability of the complex compound formed by dichroic molecules and PVA improves, and can suppress the polarization property deterioration under hot and humid condition.The containing ratio of the boric acid in the polarizer of polaroid of the present invention is preferably more than 1 mass parts relative to the polarizer 100 mass parts and below 100 mass parts, more preferably more than 5 mass parts and below 50 mass parts.By the containing ratio of boric acid being controlled, in above-mentioned scope, just can make the polarizer of hue balancing.

Polaroid of the present invention 60 DEG C, relative humidity 95%, through time to process before 800 hours with the slip of the boric acid in the polarizer be afterwards less than 30%.The slip of this boric acid is preferably less than 25%, is more preferably less than 20%.

(1-4) organic acid

In addition, the described polarizer only otherwise violate purport of the present invention, then also can containing organic acid contained in polaroid protective film described later.

Now, described organic acid content is preferably 0.01 ~ 10 mass parts relative to resin (" forming the resin of the major component of the polarizer " refers to the resin maximum containing quality ratio in the resin contained by the polarizer, is preferably polyvinyl alcohol (PVA)) 100 mass parts of the major component forming the polarizer.If be more than 0.01 mass parts, then easily obtaining polarizer permanance improved effect, in addition, if be below 10 mass parts, being then difficult to the white casse caused by being separated in the polarizer occurs.Described organic acid content is more preferably 0.1 ~ 8 mass parts, is particularly preferably 0.1 ~ 5 mass parts.

In addition, when polaroid of the present invention contains described organic acid in polaroid protective film described later, even if do not comprise organic acid in the polarizer, the effect of polaroid of the present invention can also fully be obtained.

(1-5) thickness of the polarizer

The thickness of film before the polarizer stretches is not particularly limited, but the homogeneous viewpoint of the stability kept from film, stretching, preferably 1 μm ~ 1mm, particularly preferably 20 ~ 200 μm.In addition, as described in Japanese Unexamined Patent Publication 2002-236212 publication, the stress produced when also can be used in water the stretching carrying out 4 times ~ 6 times is the such thin PVA film of below 10N.

< polaroid protective film >

Then, 2 polaroid protective films used in polaroid of the present invention are described.

(2-1) characteristic of polaroid protective film

Described polaroid protective film 60 DEG C, relative humidity 95%, through time to process 24 little moisture permeabilitys be constantly 500g/m ²above and 2000g/m ²below.

(moisture permeability of polaroid protective film)

Polaroid protective film of the present invention 60 DEG C, relative humidity 95%, through time to process 24 little moisture permeabilitys be constantly 500g/m ²above and 2000g/m ²below.The moisture permeability of polaroid protective film of the present invention is more preferably 800 ~ 1800g/m ²my god, be particularly preferably 1000 ~ 1600g/m ²my god.By the moisture permeability of polaroid protective film is set to 500g/m ²above, the polarizer performance degradation under high temperature low humidity conditions can be suppressed.In addition, by moisture permeability is set to 2000g/m ²below, the polarization property deterioration under hot and humid condition can be suppressed.

The moisture permeability of film can be reduced by the thickness increasing film.In addition, the tendency that the resin that hydrophilic and free volume is large has moisture permeability higher, when using the resin of acylated cellulose as polaroid protective film, can by adding hydrophobing agent described later or polarizer permanance modifying agent reduces moisture permeability.

The value of the moisture permeability in this instructions tests (cup type method) according to the moisture permeability of JISZ0208, and in the atmosphere of temperature 60 C, relative humidity 95%, measuring 24 hours by area is 1m ²the value that obtains of the weight (g) of water vapor of sample.

(density of polaroid protective film)

The density of polaroid protective film of the present invention is preferably 1.293g/cm ³above, 1.294g/cm is more preferably ³above, 1.295g/cm is particularly preferably ³above.Density is larger, then the free volume part in film is fewer, can suppress boric acid in polaroid protective film through, and the boric acid content in the polarizer can be suppressed to reduce.The density of polaroid protective film can have the rigidization compound of ring texture by interpolation in molecule and increase.Particularly by adding following polarizer permanance modifying agent, the density of film effectively can be increased.In addition, the carbohydrate derivates with pyranose ring or furanose ring mentioned in the project of following hydrophobing agent also has the effect of the density increasing film, can preferably use.

Density can be measured by commercially available automatic densitometer (such as the MINIDENS etc. of iPros society).

(thickness of polaroid protective film)

Described 60 DEG C, relative humidity 95%, through time to process 24 little moisture permeabilitys be constantly 500g/m ²above and 2000g/m ²the thickness of following polaroid protective film preferably 30 μm ~ 100 μm, more preferably 30 μm ~ 80 μm, particularly preferably 35 μm ~ 65 μm.

On the other hand, the thickness not meeting the polaroid protective film of described characteristic is preferably 30 μm ~ 100 μm, is more preferably 35 ~ 80 μm, is particularly preferably 35 ~ 65 μm.

Wherein, 2 polaroid protective films that polaroid of the present invention uses can be all same polaroid protective film, also can be different polaroid protective films.

When the polaroid protective film of the characteristic meeting described (1) and (2) is only 1; as the polaroid protective film of characteristic not meeting described (1) and (2), can be used in 60 DEG C, relative humidity 90%, through time process 24 hours after moisture permeability be with described 60 DEG C, relative humidity 95%, through time to process 24 little moisture permeabilitys be constantly 500g/m ²above and 2000g/m ²the film of the amount of the equilibrium of following polaroid protective film.

In addition, in addition, water percentage, spring rate etc. is preferably considered to select other polaroid protective film described.

As the polaroid protective film of the characteristic of dissatisfied described (1) and (2); can preferably use record in commercially available three cellulose acetate membrane (FujitacTD80UF, Fuji Photo Film (Ltd.)), Japanese Unexamined Patent Publication 2006-58322 publication containing the acrylic resin etc. recorded in the fluoropolymer resin film of ester ring type structure, Japanese Unexamined Patent Publication 2009-122644 publication.

Below, the resin used described polaroid protective film, polarizer permanance modifying agent are described.

(2-2) resin

Then, the resin as the film substrate used in described polaroid protective film is described.

As the resin that described polaroid protective film uses, known resin can be used, only otherwise violating purport of the present invention is just not particularly limited.As described film substrate, acylated cellulose, acryl resin, cyclic olefine resin can be enumerated, wherein preferred cellulose acylate resin.That is, described polaroid protective film preferably comprises acylated cellulose.

(acylated cellulose)

Below, the acylated cellulose that can use in the present invention is described in detail.

The degree of substitution of acylated cellulose means the ratio being present in 3 hydroxyls in cellulosic Component units (glucose of (β) Isosorbide-5-Nitrae-glycoside link) and being acylated.Degree of substitution (acylation degree) can be calculated by the conjugated fatty acid amount measured in the cellulosic Component units of per unit mass.In the present invention, the degree of substitution of cellulose bodies by being dissolved in by cellulose bodies in the dimethyl sulfoxide (DMSO) equal solvent that replaced by deuterium, can measure ¹³c-NMR spectrogram, tries to achieve from the peak intensity ratio of the carbonyl carbon acyl group and calculates.After the remaining hydroxyl of acylated cellulose is substituted by other acyl groups different from the acyl group that acylated cellulose itself has, can pass through ¹³c-NMR measures and tries to achieve.About the detailed content of assay method, on the books in the paper of Shou mound etc. (Carbohydrate.Res., 273 (1995) 83-91).

Total acyl substitution of the acylated cellulose that can use in the present invention is preferably 2.0 ~ 2.97, is more preferably 2.2 ~ 2.95, is particularly preferably 2.3 ~ 2.95.Polarizer permanance modifying agent used in the present invention is particularly at the acylated cellulose of the scope with so total acyl substitution and the used time, and polaroid durability improvement effect is high.

As the acyl group of the acylated cellulose that can use in the present invention, particularly preferably acetyl group, propiono, bytyry, particularly preferred acetyl group.

The mixed aliphatic ester be made up of acyl groups more than 2 kinds also can preferably use as acylated cellulose in the present invention.Now, as acyl group, also preferably acetyl group and carbon number are the acyl group of 3 ~ 4.In addition, when using mixed aliphatic ester, the degree of substitution of acetyl group is preferably less than 2.5, is more preferably less than 1.9.On the other hand, carbon number is that the degree of substitution of the acyl group of 3 ~ 4 is preferably 0.1 ~ 1.5, is more preferably 0.2 ~ 1.2, is particularly preferably 0.5 ~ 1.1.

In the present invention, to can be used together, substituting group used in combination and/or the different 2 kinds of acylated celluloses of degree of substitution, also can by the tape casting altogether described later etc., form the multiple layer be made up of different acylated celluloses and the film formed.

In addition, the middle mixed acid ester with fatty acid acyl and substituted or unsubstituted aromatic acyl recorded in (0023) ~ (0038) of Japanese Unexamined Patent Publication 2008-20896 publication also can preferably use in the present invention.

The acylated cellulose used in the present invention preferably has the equal degree of polymerization of matter of 250 ~ 800, more preferably has the equal degree of polymerization of matter of 300 ~ 600.The acylated cellulose used in the present invention in addition preferably has the number-average molecular weight of 70000 ~ 230000, more preferably has the number-average molecular weight of 75000 ~ 230000, most preferably has the number-average molecular weight of 78000 ~ 120000.

The acylated cellulose used in the present invention can use acid anhydrides or acyl chlorides to synthesize as acylating agent.When described acylating agent is acid anhydrides, use organic acid (such as acetic acid) or methylene chloride as reaction dissolvent.In addition, the protic catalyzer that sulfuric acid can be used such is as catalyzer.When acylating agent is acyl chlorides, alkali compounds can be used as catalyzer.In industrially the most conventional synthetic method, cellulose is used the esterification of mixed organic acid composition and synthetic cellulose ester that contain the organic acid (acetic acid, propionic acid, butyric acid) corresponding with acetyl group and other acyl group or their acid anhydrides (acetic anhydride, propionic andydride, butyric anhydride).

In the process, cotton linter or the such cellulose of wood pulp, after the organic acid activation such with acetic acid, under the existence of sulfuric acid catalyst, use the mixed liquor of Determination of Organic Acids as described above to carry out the situation of esterification more.Organic acid anhydride composition uses with excess quantity relative to the amount of the hydroxyl existed in cellulose usually.In this esterification treatment, outside esterification, also carry out cellulosic backbone (β) Isosorbide-5-Nitrae-glycosidic bond) hydrolysis reaction (depolymerization reaction).If the hydrolysis reaction of main chain carries out, then the degree of polymerization of cellulose esters reduces, thus the physical property of the cellulose ester membrane manufactured reduces.Therefore, the reaction conditions of temperature of reaction and so on preferably considers that the degree of polymerization of obtained cellulose esters and molecular weight decide.

(2-3) polarizer permanance modifying agent

< particular polymers >

Polaroid protective film (preferred cellulose acylate film) in the present invention preferably containing the polymkeric substance comprised from the repetitive of the monomer shown in following general formula (1) as polarizer permanance modifying agent.

Chemical formula 10

·R ¹

In formula, R ¹represent that hydrogen atom or carbon number are the fatty group of 1 ~ 4.R ¹be not particularly limited, but be preferably hydrogen atom, methyl or ethyl.

·R ²

R ²represent substituting group, alternatively base preferred aliphat base or aromatic series base.

R ²be not particularly limited, but as fatty group, preferred alkyl, alkenyl, alkynyl, naphthenic base, more preferably carbon number is the alkyl of 1 ~ 6, further preferable methyl, ethyl, propyl group, butyl, particularly preferably methyl, the tert-butyl group.As aromatic series base, preferred phenyl, naphthyl, xenyl, particularly preferably phenyl.

·n

N represents the integer of 0 ~ 4, preferably 0 ~ 2, more preferably 0 ~ 1.In addition, when n is 0, substituent R ²do not exist, but in chemical formula, as long as mean there is hydrogen atom here.Explain as described above in other chemical formulas of this instructions.

·(A)

(A) represent for the formation of the atom group required for 5 or 6 rings, be preferably the aromatic rings of 5 or 6 yuan.Aromatic rings refers to not containing heteroatomic aromatic ring and the concept with heteroatomic saturated, undersaturated heterocycle in this manual.

In the present invention, from the repetitive of the monomer shown in described general formula (1) preferably by shown in following general formula (2-1), general formula (2-2), general formula (2-3), general formula (2-4), general formula (2-5) or general formula (2-6).

Chemical formula 11

·R ¹⁰～R ¹⁹

In formula, R ¹⁰~ R ¹⁹separately represent substituting group.Substituting group is not particularly limited, but can enumerate following substituting group T, and its preferable range meaning is identical.

·n1～n10

N1, n2, n5, n6, n8 and n10 separately represent the integer of 0 ~ 4, preferably 0 ~ 2.N3 and n7 separately represents 0 ~ 2, preferably 0 ~ 1.N4 and n9 separately represents 0 or 1, preferably 0.

·R ^1A

R ^1Arepresent that hydrogen atom or carbon number are the fatty group of 1 ~ 4.R ^1Abe not particularly limited, but be preferably hydrogen atom, methyl or ethyl.

In the present invention, described particular polymers is preferably containing the coumarone resin of 3 compositions shown in following general formula (P-1) as repetitive.Wherein coumarone resin refers to from the resin with specific copolymerization ratio synthesized by petroleum residue, in addition, also means by any one in coumarone-indenes-styrene or the general name of multipolymer that is all made up of it.Therefore, the multipolymer shown in following general formula (P-1) is included in the category of coumarone resin.

Chemical formula 12

formula P-1

In formula, R ²¹, R ²², R ²³, and R ²⁴separately represent substituting group.X, y, z represents the molar ratio relative to the total repetitive contained by polymkeric substance, and x represents that 1 ~ 40%, y represents that 5 ~ 95%, z represents 1 ~ 70%.M1, m2 represent the integer of 0 ~ 4.M3 represents the integer of 0 ~ 2.M4 represents the integer of 0 ~ 5.R ¹⁰¹, R ¹⁰², R ¹⁰³represent that hydrogen atom or carbon number are the fatty group of 1 ~ 4.

·R ²¹～R ²⁴

R ²¹, R ²², R ²³, R ²⁴separately represent substituting group.Substituting group is not particularly limited, but can enumerate following substituting group T, and its preferable range also meaning is identical.

·R ¹⁰¹～R ¹⁰³

R ¹⁰¹~ R ¹⁰³represent that hydrogen atom or carbon number are the fatty group of 1 ~ 4.R ¹¹~ R ¹³be not particularly limited, but be preferably hydrogen atom, methyl or ethyl.

·x，y，z

X represents 1 ~ 40% with molar ratio, preferably 1 ~ 30%, more preferably 1 ~ 20%.

Y represents 5 ~ 95% with molar ratio, preferably 10 ~ 90%, more preferably 30 ~ 90%.

Z represents 1 ~ 70% with molar ratio, preferably 1 ~ 60%, more preferably 1 ~ 50%.

X+y+z can not be also 100 (%), but when being less than 100, means the copolymer composition containing other.As other copolymer composition, vinyltoluene, isopropenyl toluene, α-methyl styrene, alkyl indenes, dicyclopentadiene etc. can be enumerated.

Copolymerization ratio (molar ratio) t of other copolymer compositions preferably 0 ~ 30%, more preferably 0 ~ 20%.

·m1～m4

M1, m2 represent the integer of 0 ~ 4, preferably 0 ~ 2.M3 represents the integer of 0 ~ 2, preferably 0.M4 represents the integer of 0 ~ 5, preferably 0 ~ 3, more preferably 0 ~ 1.

In addition, the terminal groups of particular polymers can be any group, typically be addition hydrogen on vinyl and stop be polymerized structure.

Below, represent that there is the object lesson of the particular polymers of the repetitive of the monomer shown in self-drifting (1), but the present invention is not limited to this makes an explanation.In addition, following structural formula represents chemical constitution and the constituent ratio thereof of the repetitive of principal ingredient, also can contain other compositions as mentioned above.

Chemical formula 13

(matter average molecular weight)

The matter average molecular weight of above-mentioned particular polymers is preferably 200 ~ 10000, is more preferably 300 ~ 8000, is particularly preferably 400 ~ 4000.If above-mentioned molecular weight is more than described lower limit, then can expect effectively to suppress the moisture permeability of film and the effect of water percentage, if below higher limit, then can expect to improve with the compatibility of acylated cellulose, so preferably.

Molecular weight and dispersion degree are just set to unless otherwise specified and use GPC (gel filtration chromatography) method to measure the value obtained, and molecular weight is set to the matter average molecular weight with polystyrene conversion.The gel of filling in post used in GPC method preferably has the gel of aromatics in repetitive, such as, can enumerate the gel be made up of styrene diethylene benzene copoly mer.Post preferably 2 ~ 6 connections uses.The solvent used can enumerate the acid amides series solvents such as ether series solvent, 1-METHYLPYRROLIDONE such as tetrahydrofuran.The flow velocity measuring preferred solvent carries out the scope of 0.1 ~ 2mL/ minute, most preferably carries out the scope of 0.5 ~ 1.5mL/ minute.By measuring within the scope of this, can not load be applied to device and more effectively measure.For mensuration temperature, preferably carry out at 10 ~ 50 DEG C, most preferably carry out at 20 ~ 40 DEG C.In addition, the post of use and carrier suitably can be selected according to the physical property of the macromolecular compound as determination object.

(addition)

The addition of described particular polymers is not particularly limited; but relative to forming resin (preferred acylated cellulose) 100 mass parts of polaroid protective film; be preferably 0.1 ~ 100 mass parts, be more preferably 0.5 ~ 50 mass parts, be particularly preferably 1.0 ~ 30 mass parts.If above-mentioned addition is more than described lower limit, then that can expect film can suppress the moisture permeability of film and the effect of water percentage effectively, if be below higher limit, then can expect to maintain high transparent.

In this manual, condensate or polymkeric substance refer to except the condensate of the macromolecular compound of the routine be polymerized in a large number as monomer, and also meaning that to comprise monomer be such as several molecular weight be polymerized is compound and the oligomer of hundreds of left and right.In addition, when being called condensate or polymkeric substance, unless otherwise specified, just mean and comprise interpolymer or multipolymer.

In addition, when in this manual " compound " being added in suffix address, or during with specific title or by chemical formulation, except this compound itself, also for comprising the meaning of its salt, complex compound, its ion.In addition, the scope of the effect desired by playing, means the derivant that the form comprising to specify is modified.And, in this manual, for substituting group " base " is added in suffix call specific atom group time, meaning can have arbitrary substituting group on this group.This looks like also identical for clearly not recording replacement, unsubstituted compound.As preferred substituting group, following substituting group T can be enumerated.

Alternatively base T, can enumerate following radicals.

(preferred carbon number is the alkyl of 1 ~ 20, such as methyl to alkyl, ethyl, isopropyl, the tert-butyl group, amyl group, heptyl, 1-ethyl pentyl group, benzyl, 2-ethoxyethyl group, 1-ethyloic etc.), (preferred carbon number is the alkenyl of 2 ~ 20, such as vinyl to alkenyl, allyl, oleyl (Oleyl) etc.), (preferred carbon number is the alkynyl of 2 ~ 20, such as ethinyl to alkynyl, butynyl, phenylene-ethynylene etc.), (preferred carbon number is the naphthenic base of 3 ~ 20, such as cyclopropyl to naphthenic base, cyclopentyl, cyclohexyl, 4-methylcyclohexyl etc.), (preferred carbon number is the aryl of 6 ~ 26, such as phenyl to aryl, 1-naphthyl, 4-methoxyphenyl, 2-chlorphenyl, 3-aminomethyl phenyl etc.), (preferred carbon number is the heterocyclic radical of 2 ~ 20 to heterocyclic radical, such as 2-pyridine radicals, 4-pyridine radicals, 2-imidazole radicals, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl etc.), (preferred carbon number is the alkoxy of 1 ~ 20, such as methoxyl to alkoxy, ethoxy, isopropoxy, benzyloxy etc.), (preferred carbon number is the aryloxy group of 6 ~ 26, such as phenoxy group to aryloxy group, 1-naphthoxy, 3-methylphenoxy, 4-methoxyphenoxy etc.), (preferred carbon number is the alkoxy carbonyl group of 2 ~ 20, such as carbethoxyl group to alkoxy carbonyl group, 2-ethyl hexyl oxygen carbonyl etc.), (preferred carbon number is the amido of 0 ~ 20 to amido, such as amino, N, N-dimethyl amido, N, N-diethyl amido, N-ethyl amido, anilino-etc.), (preferred carbon number is the sulfoamido of 0 ~ 20 to sulfoamido, such as N, N-dimethyl sulfonamide, N-phenyl-sulfamide etc.), (preferred carbon number is the acyloxy of 1 ~ 20, such as acetoxyl group to acyloxy, benzoyloxy group etc.), (preferred carbon number is the carbamyl of 1 ~ 20 to carbamyl, such as N, N-formyl-dimethylamino, N-phenylcarbamoyl etc.), (preferred carbon number is the amide group of 1 ~ 20, such as acetamido to amide group, benzamido etc.), cyano group or halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.), be more preferably alkyl, alkenyl, aryl, heterocyclic radical, alkoxy, aryloxy group, alkoxy carbonyl group, amino, amide group, cyano group or halogen atom, particularly preferably alkyl, alkenyl, heterocyclic radical, alkoxy, alkoxy carbonyl group, amino, amide group or cyano group.

< organic acid >

At least 1 in the polaroid protective film that can use in polaroid of the present invention preferably contains resin, and is that organic acid 0.1 ~ 20 mass parts of 2 ~ 7 is as polarizer permanance modifying agent relative to this resin 100 mass parts acid ionization constant contained in the mixed solvent of the volume ratio of tetrahydrofuran/water=6/4 at 25 DEG C.By using such organic acid, described polaroid protective film can not make the polarizer permanance under high temperature low humidity worsen and improve hot and humid under polarizer permanance.

If use described specific organic acid with described specific content; then can not cause the spinoffs such as the acid hydrolysis of the Primary resins of polaroid protective film (acylated cellulose etc.) (cause the moisture permeability of polaroid protective film rises, the diffusion of boric acid promote); and the pH of the polarizer can be regulated, so preferably.

(solubleness)

Described organic acid, from the acid-hydrolyzed viewpoint of Primary resins suppressing the polaroid protective film such as acylated cellulose, is preferably below 0.1 quality % relative to the solubleness of water at 25 DEG C.Described organic acid is more preferably below 0.06 quality % relative to the solubleness of water at 25 DEG C, is more preferably below 0.03 quality %.

As the assay method of the described solubleness in the present invention, the method recorded in 153 pages ~ 156 pages of the experimental chemistry lecture the 4th edition adopting ball kind (strain) to print.

(acid ionization constant)

Described organic acid is the acid ionization constant in the mixed solvent of the volume ratio of THF/ water=6/4 at 25 DEG C is the organic acid of 2 ~ 7.The acid-hydrolyzed viewpoint of the resin that the acid ionization constant of described organic acid in the mixed solvent of the volume ratio of tetrahydrofuran (THF)/water=6/4 uses from polaroid protective films such as suppressing acylated cellulose; be preferably 2.5 ~ 7; be more preferably 2.5 ~ 6.5, be particularly preferably 3 ~ 5.

As the assay method of the described acid ionization constant in the present invention, the alkali titration recorded in 215 pages ~ 217 pages of the experimental chemistry lecture the 2nd edition adopting ball kind (strain) to print.

(molecular weight)

Described organic acid molecular weight is preferably 200 ~ 1000, is more preferably 250 ~ 800, is particularly preferably 280 ~ 500.If molecular weight is more than the lower limit of above-mentioned scope, then the polarizer permanance under high temperature low humidity is improved, if molecular weight is below the higher limit of above-mentioned scope, then the polarizer permanance under hot and humid is improved, so preferably.

(structure)

Described organic acid is from the view point of the density of film, and preferably containing aromatic ring structure, preferably containing carbon number is the aryl of 6 ~ 12, particularly preferably containing phenyl.Described organic acid aromatic ring structure also can form condensed ring with other ring.Described organic acid aromatic ring structure also can have substituting group, as this substituting group, only otherwise violating purport of the present invention is just not particularly limited, but be preferably halogen atom or alkyl, be more preferably halogen atom or carbon number is the alkyl of 1 ~ 6, be particularly preferably chlorine atom or methyl.

Described organic acid is preferably by shown in following general formula (3).

General formula (3)

Chemical formula 14

Described R ²⁶being preferably carbon number is the aryl of 6 ~ 18, is more preferably the aryl that carbon number is 6 ~ 12, is particularly preferably phenyl.

Described R ²⁷and R ²⁸preferably separately for hydrogen atom, carbon number be 1 ~ 12 alkyl (also comprising naphthenic base) or carbon number be the aryl of 6 ~ 12, be more preferably hydrogen atom, carbon number be 1 ~ 6 alkyl (also comprising naphthenic base) or phenyl, be particularly preferably hydrogen atom, methyl, ethyl, cyclohexyl or phenyl.

As described R ²⁶the substituting group that can have, only otherwise violating purport of the present invention is just not particularly limited, but is preferably halogen atom or alkyl, is more preferably halogen atom or carbon number is the alkyl of 1 ~ 6, is particularly preferably chlorine atom or methyl.

As described R ²⁷the substituting group that can have, only otherwise violating purport of the present invention is just not particularly limited, but preferably carbon number is the aryl of 6 ~ 12, is more preferably phenyl.

Below, illustrate the organic acid object lesson shown in general formula (3), but the present invention is not limited to following content.

Chemical formula 15

(organic acid preparation method)

Organic acid used in the present invention both can obtain commercially, also can be synthesized by known method.

(organic acid content)

Described organic acid is preferably 1 ~ 20 quality % relative to the resin (resin of major component refers to the resin maximum containing quality ratio in the resin contained by polaroid protective film) of the major component forming polaroid protective film.If be more than 1 quality %, then easily obtaining polarizer permanance improved effect, in addition, if be below 20 quality %, being then difficult to ooze out or seepage when manufacturing polaroid protective film.Described organic acid content is more preferably 1 ~ 15 quality %, is particularly preferably 1 ~ 10 quality %.

(organic acid acid ionization constant)

Acid ionization constant in the mixed solvent of the volume ratio of tetrahydrofuran/water=6/4 of described organic acid preferably at 25 DEG C is 2 ~ 7, is more preferably 3 ~ 6.

< phenol system compound >

In polaroid protective film (preferred cellulose acylate film) in the present invention, preferably contain the compound shown in general formula (4) as polarizer permanance modifying agent.

Chemical formula 16

In general formula (4), R ¹represent hydrogen atom or substituting group, R ²represent the substituting group shown in following general formula (5); N1 represents the integer of 0 ~ 4, when n1 is more than 2, and multiple R ¹can identical mutually also can be different; N2 represents the integer of 1 ~ 5, when n2 is more than 2, and multiple R ²can identical mutually also can be different.

Chemical formula 17

Chemical formula 18

In general formula (6), X represents substituted or unsubstituted aromatic ring; R ⁶, R ⁷, R ⁸and R ⁹separately represent that hydrogen atom or carbon number are the alkyl of 1 ~ 5; N5 represents the integer of 1 ~ 11, when n5 is more than 2, and multiple R ⁶, R ⁷, R ⁸, R ⁹with X can identical mutually also can be different.

R ¹represent hydrogen atom or substituting group.Alternatively the example of base, is not particularly limited, and (preferred carbon number is the alkyl of 1 ~ 10, such as methyl can to enumerate alkyl, ethyl, isopropyl, the tert-butyl group, amyl group, heptyl, 1-ethyl pentyl group, benzyl, 2-ethoxyethyl group, 1-ethyloic etc.), (preferred carbon number is the alkenyl of 2 ~ 20, such as vinyl to alkenyl, allyl, oleyl etc.), (preferred carbon number is the alkynyl of 2 ~ 20, such as ethinyl to alkynyl, butynyl, phenylene-ethynylene etc.), (preferred carbon number is the naphthenic base of 3 ~ 20, such as cyclopropyl to naphthenic base, cyclopentyl, cyclohexyl, 4-methylcyclohexyl etc.), (preferred carbon number is the aryl of 6 ~ 26, such as phenyl to aryl, 1-naphthyl, 4-methoxyphenyl, 2-chlorphenyl, 3-aminomethyl phenyl etc.), (preferred carbon number is the heterocyclic radical of 2 ~ 20 to heterocyclic radical, such as 2-pyridine radicals, 4-pyridine radicals, 2-imidazole radicals, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl etc.), (preferred carbon number is the alkoxy of 1 ~ 20, such as methoxyl to alkoxy, ethoxy, isopropoxy, benzyloxy etc.), (preferred carbon number is the aryloxy group of 6 ~ 26, such as phenoxy group to aryloxy group, 1-naphthoxy, 3-methylphenoxy, 4-methoxyphenoxy etc.), (preferred carbon number is the alkoxy carbonyl group of 2 ~ 20, such as carbethoxyl group to alkoxy carbonyl group, 2-ethyl hexyl oxygen carbonyl etc.), (preferred carbon number is the amido of 0 ~ 20 to amido, such as amino, N, N-dimethyl amido, N, N-diethyl amido, N-ethyl amido, anilino-etc.), (preferred carbon number is the sulfoamido of 0 ~ 20 to sulfoamido, such as N, N-dimethyl sulfonamide, N-phenyl-sulfamide etc.), (preferred carbon number is the acyloxy of 1 ~ 20, such as acetoxyl group to acyloxy, benzoyloxy group etc.), (preferred carbon number is the carbamyl of 1 ~ 20 to carbamyl, such as N, N-formyl-dimethylamino, N-phenylcarbamoyl etc.), (preferred carbon number is the amide group of 1 ~ 20, such as acetamido to amide group, benzamido etc.), cyano group, or halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.), hydroxyl.R ¹preferred hydrogen atom, carbon number are alkyl, the hydroxyl of 1 ~ 20, more preferably hydrogen atom, hydroxyl, methyl.In addition, R ¹substituting group also can have the described substituting group of more than 1.

N1 represents the integer of 0 ~ 4, preferably 2 ~ 4.

N2 represents the integer of 1 ~ 5, preferably 1 ~ 3.

R2 represents the substituting group shown in following general formula (5).

Chemical formula 19

In general formula (5), A represents substituted or unsubstituted aromatic ring; R ³and R ⁴separately represent alkyl, the substituting group shown in general formula (6) that hydrogen atom, carbon number are 1 ~ 5; R ⁵represent that singly-bound or carbon number are the alkylidene of 1 ~ 5; X represents substituted or unsubstituted aromatic ring; N3 represents the integer of 0 ~ 10, when n3 is more than 2, and multiple R ⁵with X can identical mutually also can be different.

A represents substituted or unsubstituted aromatic ring.Aromatic ring also can for comprising the heteroatomic heterocycles such as nitrogen-atoms, oxygen atom, sulphur atom.As the example of A, phenyl ring, indenes ring, naphthalene nucleus, fluorenes ring, phenanthrene ring, anthracene nucleus, cyclohexyl biphenyl, pyrene ring, pyranoid ring, diox ring, dithiane ring, thiphene ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, triazine ring etc. can be enumerated.In addition, other 6 rings or 5 rings also can condensations.The preferred phenyl ring of A.As the substituting group that A can have, halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.), alkyl, hydroxyl etc. can be enumerated.

R ³and R ⁴separately represent alkyl, the substituting group shown in following general formula (6) that hydrogen atom or carbon number are 1 ~ 5.R ³and R ⁴the alkyl that preferred hydrogen atom, carbon number are 1 ~ 3, the substituting group shown in general formula (6), more preferably hydrogen atom, methyl, the substituting group shown in general formula (6).

Chemical formula 20

R ⁶, R ⁷, R ⁸and R ⁹separately represent that hydrogen atom or carbon number are the alkyl of 1 ~ 5.R ³and R ⁴preferred hydrogen atom, carbon number are the alkyl of 1 ~ 3, more preferably hydrogen atom, methyl.

The object lesson of X is identical with the X in general formula (5) with preferable range.

N5 represents the integer of 1 ~ 11, preferably 1 ~ 9, more preferably 1 ~ 7.

Described general formula (6) is preferably by shown in following general formula (6 ').

Chemical formula 21

The definition of each mark of general formula (6 ') is identical with the meaning of each mark in general formula (6), and preferable range is also identical.

Described general formula (6) is preferably by shown in following general formula (6 ").

Chemical formula 22

General formula (6 ") in, n4 represents the integer of 0 ~ 10.

N4 represents the integer of 0 ~ 10, preferably 0 ~ 8, more preferably 0 ~ 6.

In general formula (5), R ⁵represent that singly-bound or carbon number are the alkylidene of 1 ~ 5, can substituting group be had.R ⁵preferred carbon number is the alkylidene of 1 ~ 4, and more preferably carbon number is the alkylidene of 1 ~ 3.As R ⁵the substituting group that can have, can enumerate alkyl (such as methyl, ethyl, isopropyl, the tert-butyl group), halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.), hydroxyl etc. that carbon number is 1 ~ 5.

In general formula (5), X represents substituted or unsubstituted aromatic ring.Aromatic ring can for containing the heteroatomic heterocycles such as nitrogen-atoms, oxygen atom, sulphur atom.As the example of X, phenyl ring, indenes ring, naphthalene nucleus, fluorenes ring, phenanthrene ring, anthracene nucleus, cyclohexyl biphenyl, pyrene ring, pyranoid ring, diox ring, dithiane ring, thiphene ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, triazine ring etc. can be enumerated.In addition, also can other 6 rings or 5 yuan of cyclic condensations.The preferred phenyl ring of X.As the substituting group that X can have, identical with the example that the substituting group as A is enumerated.

N3 represents the integer of 0 ~ 10, preferably 0 ~ 2, more preferably 0 ~ 1.In addition, when n3 is the integer of more than 2, multiple-(R ₅-X) shown in base can distinguish identical mutually also can be different, respectively with A bonding.

Described general formula (5) is preferably by shown in following general formula (5 ').

Chemical formula 23

In general formula (5 '), R ³the alkyl that expression hydrogen atom, carbon number are 1 ~ 5 or the substituting group shown in described general formula (1-3); R ⁵represent that singly-bound or carbon number are the alkylidene of 1 ~ 5; X represents substituted or unsubstituted aromatic ring; N3 represents the integer of 0 ~ 5, when n3 is more than 2, and multiple R ⁵with X can identical mutually also can be different.

The preferable range of each mark in general formula (5 ') is identical with each mark in general formula (5).

Described general formula (5) is preferably by shown in following general formula (5 ").

Chemical formula 24

The n3 of general formula (5 ") represents the integer of 0 ~ 5.

The preferable range of n3 is identical with the preferable range of the n3 in general formula (5).

Compound shown in general formula (4) is preferably as under type: R ¹for hydrogen atom or carbon number are the alkyl of 1 ~ 5, R ²shown in general formula (5 "), n1 represents the integer of 2 ~ 4, and n2 represents the integer of 1 ~ 3, and n3 represents the integer of 0 ~ 2.

Below, represent the object lesson of the compound shown in general formula (4), but be not limited to following object lesson.

Chemical formula 25

Chemical formula 26

The weight-average molecular weight of the compound shown in general formula (4) is preferably 200 ~ 1200, is more preferably 250 ~ 1000, is particularly preferably 300 ~ 800.

If molecular weight is less than 200, then sometimes become problem from the volatilization diffusion of film, if more than 1200, then mist degree raises sometimes.

The addition of the compound shown in general formula (4) is not particularly limited, but relative to acylated cellulose 100 mass parts, is preferably 0.1 ~ 100 mass parts, is more preferably 0.2 ~ 80 mass parts, is particularly preferably 0.3 ~ 60 mass parts.

If addition is less than 0.1 mass parts, then sometimes effectively can not reduce moisture permeability, if more than 100 mass parts, then mist degree raises sometimes.

In addition, the styrenated phenol in order to make hydroxyl value different at many places hydrogen bonding, also can be set to the potpourri containing the compounds shown in general formula of more than two kinds (4) different mutually.As an example, the potpourri of the styrenated phenol that the oligomer alkylation on phenol about the styrenated phenol obtained relative to phenol, alkylation 1 ~ 3 mole of styrene, the styrenated phenol obtained with alkylated styrene further at alkylating cinnamic phenyl position and cinnamic 2 ~ 4 aggressiveness obtains can be enumerated.

Compound shown in general formula (4) can be synthesized by the phenylethylene adding more than 1 equivalent in the phenol of 1 equivalent in the presence of acid catalyst usually, also can use commercially available product.In addition, also the potpourri obtained by above-mentioned synthetic method can directly be used.

(acyl modified novolak phenolics)

In polaroid protective film (preferred cellulose acylate film) in the present invention, preferably contain the acyl modified novolak phenolics shown in following general formula (I) as polariscope permanance modifying agent.

Chemical formula 27

(in general formula (I), R ₁represent the substituted or unsubstituted alkyl-carbonyl of formoxyl or carbon number 2 ~ 15, R ₂, R ₃, R ₄separately represent the alkyl of carbon number 1 ~ 4, m, n separately represent the integer of more than 0, but can not be 0 simultaneously.R ₁, R ₂, R ₃, R ₄multiple can distinguish when existing identical also can be different.)

Acyl modified novolak phenolics (hereinafter sometimes referred to " novolaks based compound ") is represented by above-mentioned general formula (I).In the present invention, acyl modifiedly refer to that the hydroxyl of novolak phenolics is by acyl group.As acyl group, the substituted or unsubstituted alkyl-carbonyl of preferred formoxyl, carbon number 2 ~ 15, wherein particularly preferably acetyl group, propiono, bytyry, pivaloyl group.

Cellulose acylate film in the present invention by containing the acyl modified novolak phenolics shown in general formula (I), can make inverse dispersed large, mist degree is low, moisture permeability is low.

Acyl modified novolak phenolics in the present invention needs the hydroxyl of novolak phenolics to carry out acyl group, preferably by 50 ~ 100% acyl groups of this hydroxyl.As acyl group rate more preferably 70 ~ 100%, further preferably 85 ~ 100%, particularly preferably 90 ~ 100%.If this acyl group rate is in above-mentioned scope, even if the film that with the addition of phenolic varnish type compound then also can be prevented under hot and humid environment to be colored as yellow.

As long as the acyl group of the hydroxyl of novolak phenolics can by the hydroxyl acyl group of phenolics, then its manufacture method does not limit.When acetylating, can be undertaken by the method for the routine using acetic anhydride method etc.Such as can manufacture by phenolics is reacted (No. 9-40608, Japanese Unexamined Patent Publication etc.) with acetyl chloride or acetic anhydride under the existence of alcohols and alkali metal hydroxide.

As the novolak phenolics of the raw material of acyl group, can be the common novolak phenolics that phenol and aldehyde (formalin) are obtained by reacting under the acidic catalysts such as oxalic acid exist usually.As the raw material of this phenol, be not particularly limited, such as, can use phenol, orthoresol, paracresol, metacresol, p-t-butyl phenol, nonyl phenol, octyl phenol etc. and their potpourri.In addition, as the raw material of aldehyde, formaldehyde, paraformaldehyde, acetaldehyde etc. and their potpourri can be used.

Below enumerate the object lesson of the acyl modified novolak phenolics shown in general formula (I), but the present invention is not limited to this.

Chemical formula 28

Chemical formula 29

< molar absorptivity >

Acyl modified novolak phenolics in the present invention, is preferably that the absorbance of the 230nm ~ 700nm wavelength coverage in the solution of 0.01g/L is less than 0.05 in concentration, is more preferably less than 0.03, and more preferably less than 0.02.

If the absorbance in 230nm ~ 700nm wavelength coverage of acyl modified novolak phenolics is above-mentioned scope; then due to the delay of acyl modified novolak phenolics, to show the wavelength dispersion change caused little, so can obtain inverse dispersed larger, mist degree is lower, moisture permeability is lower cellulose acylate film.

Molar absorptivity can by being measured the absorbance of the solution of the mass concentration of regulation and the absorbance obtained being measured divided by number-average molecular weight by commercially available spectrophotometer (such as the UV3150 etc. of society of (strain) Hitachi).

< number-average molecular weight >

The number-average molecular weight of acyl modified novolak phenolics used in the present invention preferably less than more than 500 6000, more preferably more than 500 and less than 5000, further preferably more than 500 and less than 3000.If number-average molecular weight is more than 500, then film retention is excellent, if number-average molecular weight is less than 6000, then abundant with the compatibility of acylated cellulose, can prevent mist degree from rising, so preferably.

< dispersion degree >

The dispersion degree (molecular weight distribution) of acyl modified novolak phenolics used in the present invention usually 1.05 ~ 3.0, preferably 1.1 ~ 2.5, more preferably use in the scope of 1.1 ~ 2.0.

< addition >

The addition of acyl modified novolak phenolics of the present invention, relative to acylated cellulose 100 mass parts, is preferably set to 1 ~ 30 mass parts, is more preferably set to 2 ~ 25 mass parts, be preferably set to 5 ~ 20 mass parts further.If addition is below 30 mass parts, then there is mist degree not rise such advantage, if addition is more than 1 mass parts, then have moisture permeability to reduce effect advantage so greatly.

In the present invention, acyl modified novolak phenolics can coordinate separately, and also two or more kinds may be used.

(2-4) hydrophobing agent

Polaroid protective film of the present invention preferably contains carbohydrate derivates as hydrophobing agent.

(carbohydrate derivates system plastifier)

As described hydrophobing agent, the derivant (hereinafter referred to as carbohydrate derivates system plastifier) of preferred monose or the carbohydrates containing 2 ~ 10 monosaccharide units.

The monose of preferred formation described carbohydrate derivates system plastifier or the feature of polysaccharide are, the group (such as hydroxyl, carboxyl, amino, sulfydryl etc.) that can replace in molecule is substituted.The example of alternatively formed structure, can enumerate alkyl, aryl, acyl group etc.In addition, can enumerate ether structure that replacement thus formed, by acyl group hydroxyl replaced formed ester structure, replace formed amide structure or imide structure etc. by amino.

As described monose or the example of carbohydrates comprising 2 ~ 10 monosaccharide units, such as, erythrose can be enumerated, 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, lactulose, melibiose, primeverose, rutinose, scillabiose, sucrose, Sucralose, turanose, vicianose, cellotriose, chacotriose, gentianose, Isomaltotriose, isopanose (Isopanose), maltotriose, manninotriose, melezitose, panose, planteose, gossypose, solatriose (Solatriose), umbelliferose, lycotetraose, maltotetraose, stachyose, maltopentaose (Maltopentaose), verbascose (Verbascose), MALTOHAXAOASE, alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin, δ-cyclodextrin, xylitol, sorbierite 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, sorbierite, be more preferably arabinose, wood sugar, glucose, fructose, mannose, galactose, maltose, cellobiose, sucrose, beta-schardinger dextrin-, gamma-cyclodextrin, be particularly preferably wood sugar, glucose, fructose, mannose, galactose, maltose, cellobiose, sucrose, xylitol, sorbierite.

In addition, as the substituent example of described carbohydrate derivates system plastifier, (preferred carbon number is 1 ~ 22 can to enumerate alkyl, more preferably carbon number is 1 ~ 12, particularly preferably carbon number is the alkyl of 1 ~ 8, such as methyl, ethyl, propyl group, hydroxyethyl, hydroxypropyl, 2-cyanoethyl, benzyl etc.), (preferred carbon number is 6 ~ 24 to aryl, more preferably 6 ~ 18, the particularly preferably aryl of 6 ~ 12, such as phenyl, naphthyl), (preferred carbon number is 1 ~ 22 to acyl group, more preferably carbon number is 2 ~ 12, particularly preferably carbon number is the acyl group of 2 ~ 8, such as acetyl group, propiono, bytyry, valeryl, caproyl, caprylyl, benzoyl, toluyl, phthalyl, naphthalene formyl (Naphthal) base etc.).In addition, formed preferred structure is replaced as by amino, can enumerate amide structure (preferred carbon number is 1 ~ 22, more preferably carbon number be 2 ~ 12, particularly preferably carbon number be the acid amides of 2 ~ 8, such as formamide, acetamide etc.), imide structure (preferred carbon number is 4 ~ 22, more preferably carbon number be 4 ~ 12, particularly preferably carbon number be the acid imide of 4 ~ 8, such as succimide, phthalimide etc.).

Among them, more preferably alkyl, aryl or acyl group, be particularly preferably acyl group.

As the preferred example of described carbohydrate derivates system plastifier, following material can be enumerated.But, the carbohydrate derivates system plastifier that can use in the present invention not limited by these.

Preferred xylose tetraacetate, alpha-glucose pentaacetate, fructose pentaacetate, Mannose pentaacetate, galactose pentaacetate, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylitol pentaacetate, sorbitol hexaacetate, wood sugar four propionic ester, glucose pentapropiopanoate, fructose five propionic ester, mannose five propionic ester, galactose five propionic ester, maltose eight propionic ester, cellobiose eight propionic ester, sucrose octapropanoate, xylitol five propionic ester, sorbierite six propionic ester, wood sugar four butyric ester, Glucose Pentabutyrate, fructose five butyric ester, mannose five butyric ester, galactose five butyric ester, maltose eight butyric ester, cellobiose eight butyric ester, sucrose eight butyric ester, xylitol five butyric ester, sorbierite six butyric ester, wood sugar four benzoic ether, glucose pentaphene formic ether, fructose pentaphene formic ether, mannose pentaphene formic ether, galactose pentaphene formic ether, maltose eight benzoic ether, cellobiose eight benzoic ether, sucrose eight benzoic ether, xylitol pentaphene formic ether, sorbierite six benzoic ether etc.More preferably xylose tetraacetate, alpha-glucose pentaacetate, fructose pentaacetate, Mannose pentaacetate, galactose pentaacetate, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylitol pentaacetate, sorbitol hexaacetate, wood sugar four propionic ester, glucose pentapropiopanoate, fructose five propionic ester, mannose five propionic ester, galactose five propionic ester, maltose eight propionic ester, cellobiose eight propionic ester, sucrose octapropanoate, xylitol five propionic ester, sorbierite six propionic ester, wood sugar four benzoic ether, glucose pentaphene formic ether, fructose pentaphene formic ether, mannose pentaphene formic ether, galactose pentaphene formic ether, maltose eight benzoic ether, cellobiose eight benzoic ether, sucrose eight benzoic ether, xylitol pentaphene formic ether, sorbierite six benzoic ether etc.Particularly preferably maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, wood sugar four propionic ester, glucose pentapropiopanoate, fructose five propionic ester, mannose five propionic ester, galactose five propionic ester, maltose eight propionic ester, cellobiose eight propionic ester, sucrose octapropanoate, wood sugar four benzoic ether, glucose pentaphene formic ether, fructose pentaphene formic ether, mannose pentaphene formic ether, galactose pentaphene formic ether, maltose eight benzoic ether, cellobiose eight benzoic ether, sucrose eight benzoic ether, xylitol pentaphene formic ether, sorbierite six benzoic ether etc.

Described carbohydrate derivates system hydrophobing agent preferably has pyranose structure or furanose structure.

As carbohydrate derivates used in the present invention, compound particularly preferably shown below.But the carbohydrate derivates that can use in the present invention is not limited to this.In addition, in following structural formula, R separately represents hydrogen atom or arbitrary substituting group, and multiple R can be identical, also can be different.In following structure, substituting group 1,2 represents arbitrary R respectively.In addition, degree of substitution represents that R is with the number shown in this substituting group."None" represents that R is hydrogen atom.

Chemical formula 31

Chemical formula 32

Chemical formula 33

Chemical formula 34

(preparation method)

As the preparation method of described carbohydrate derivates, the acquisition such as the product of system, the product of Aldrich can be changed into as commercially available product from (strain) Tokyo, maybe can synthesize by carrying out known ester derivant method (method recorded in such as Japanese Unexamined Patent Publication 8-245678 publication) to commercially available carbohydrates.

As the preparation method of described carbohydrate derivates system plastifier, the acquisition such as the product of system, the product of Aldrich can be changed into as commercially available product from (strain) Tokyo, maybe can synthesize by carrying out known ester derivant method (method recorded in such as Japanese Unexamined Patent Publication 8-245678 publication) to commercially available carbohydrates.

Hydrophobing agent of the present invention is preferably 1 ~ 30 quality % relative to the resin (resin of major component refers to the resin maximum containing quality ratio in the resin contained by polaroid protective film) of the major component forming polaroid protective film.If be more than 1 quality %, then easily obtaining polarizer permanance improved effect, in addition, if be below 30 quality %, being then difficult to ooze out or seepage when manufacturing polaroid protective film.The content of described hydrophobing agent is preferably 5 ~ 20 quality %, is particularly preferably 5 ~ 15 quality %.

[manufacture method of polaroid]

Below, about the manufacture method of polaroid of the present invention, be described with the order of the functionalization of the laminating method of the manufacture method of the manufacture method of polaroid protective film, the polarizer, polaroid protective film and the polarizer, polaroid.

The manufacture method > of < polaroid protective film

Described 60 DEG C, relative humidity 95%, through time to process 24 little moisture permeabilitys be constantly 500g/m ²above and 2000g/m ²following polaroid protective film can be manufactured by solution casting method.Below, for described 60 DEG C, relative humidity 95%, through time to process 24 little moisture permeabilitys be constantly 500g/m ²above and 2000g/m ²the manufacture method of following polaroid protective film, to use acylated cellulose to be described as the mode of base material for example, but also can manufacture containing described organic acid polaroid protective film when using other resin equally.In solution casting method, use is dissolved with the large solution of acylated cellobiose (dope) in organic solvent and manufactures film.

Described organic solvent preferably comprise be selected from carbon number be 3 ~ 12 ether, carbon number be 3 ~ 12 ketone, carbon number be 3 ~ 12 ester and carbon number be solvent in the halogenated hydrocarbon of 1 ~ 6.

Described ether, ketone and ester also can have ring texture.In addition, the compound of any one had in the functional group (that is ,-O-,-CO-and-COO-) of 2 the above ether, ketone and esters also can use as described organic solvent.Described organic solvent also can have other such functional groups of alcohol hydroxyl group.When having the organic solvent of functional group of more than two kinds, the above-mentioned preferred carbon number that its carbon number preferably has the solvent of any one functional group is in scope.

Be in the example of the ethers of 3 ~ 12 at described carbon number, comprise diisopropyl ether, dimethoxymethane, dimethoxy-ethane, Isosorbide-5-Nitrae-diox, 1,3-dioxolane, tetrahydrofuran, anisole and phenetol.

Be in the example of the ketone of 3 ~ 12 at described carbon number, comprise acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methyl cyclohexanone.

Be in the example of ester class of 3 ~ 12 at described carbon number, comprise ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate and pentyl acetate.

In addition, have in the example of the organic solvent of functional group of more than two kinds, comprise 2-ethoxyethyl acetate, 2-methyl cellosolve and butoxy ethanol.

Carbon number is the carbon number of the halogenated hydrocarbon of 1 ~ 6 is be preferably 1 or 2, most preferably is 1.The halogen of halogenated hydrocarbon is preferably chlorine.The ratio that the hydrogen atom of halogenated hydrocarbon is substituted by halogen is preferably 25 ~ 75 % by mole, is more preferably 30 ~ 70 % by mole, more preferably 35 ~ 65 % by mole, is particularly preferably 40 ~ 60 % by mole.Methylene chloride is representational halogenated hydrocarbon.

In addition, also can more than 2 kinds used in combination organic solvent.

The method preparation of the routine that cellulose acylate solutions (dope) can be consisted of the step of carrying out processing at the temperature (normal temperature or high temperature) more than 0 DEG C.The preparation of cellulose acylate solutions can use the preparation method of the dope in common solution casting method and device to implement.In addition, when the method for routine, halogenated hydrocarbon (particularly methylene chloride) is preferably used as organic solvent.

The amount of the acylated cellulose in cellulose acylate solutions is adjusted in obtained solution containing 10 ~ 40 quality %.The amount of acylated cellulose is more preferably 10 ~ 30 quality %.Also arbitrary adjuvant described later can be added in advance in organic solvent (main solvent).

Cellulose acylate solutions can by stirring acylated cellulose and organic solvent is prepared under normal temperature (0 ~ 40 DEG C).The solution of high concentration also can stir under pressurization and heating condition.Specifically, acylated cellulose and organic solvent are added in pressurizing vessel airtight, more than the boiling point of the normal temperature of solvent under elevated pressure to heat while stirring at the solvent temperature of scope of not seething with excitement.Heating-up temperature is generally more than 40 DEG C, is preferably 60 ~ 200 DEG C, is more preferably 80 ~ 110 DEG C.

Also in advance each composition slightly can be mixed and then add in container.In addition, can drop in container in turn.Container needs to be formed in the mode that can stir.Can pressurize to container by the inactive gas such as nitrogen injection.In addition, also can utilize by the rising of the vapor pressure heating the solvent caused.Or, also after by container closure, each composition can be added under stress.

When heating, preferably from the external heating of container.Such as can use the heating arrangement of jacketed pipe type.In addition, also by the outer setting heating plate at container, liquid-circulating can be made via pipe arrangement and heating container is overall.

Stir and preferably paddle is set at internal tank, use paddle to carry out.Paddle preferably has the length arrived near chamber wall.In order to upgrade the liquid film of chamber wall, the end of paddle is preferably arranged scrapes oar.

The gauging instrument such as pressure gauge, thermometer class also can be set in a reservoir.In container, each composition is dissolved in a solvent.Take out from container after the dope cooling prepared, or use the coolings such as heat exchanger after taking out.

Also can pass through hot-cold lysis method, prepare cellulose acylate solutions.About the detailed content of hot-cold lysis method, the technology recorded in (0115) ~ (0122) of Japanese Unexamined Patent Publication 2007-86748 publication can be used.

From the cellulose acylate solutions (dope) of preparation, manufacture cellulose acylate film by solution casting method.In dope, preferably add delay realize agent.Dope is at cylinder or bring curtain coating, makes solvent evaporate and form film.The mode that dope before curtain coating is preferably 18 ~ 35% with solid constituent amount adjusts concentration.The surface of cylinder or band is preferably processed as mirror status in advance.Dope is preferably the cylinder of less than 10 DEG C in surface temperature or brings curtain coating.

About the drying means in solution casting method, No. 2336310th, United States Patent (USP), No. 2367603rd, United States Patent (USP), No. 2492078th, United States Patent (USP), No. 2492977th, United States Patent (USP), No. 2492978th, United States Patent (USP), No. 2607704th, United States Patent (USP), each instructions of No. 2739069th, United States Patent (USP) and No. 2739070th, United States Patent (USP), each instructions of No. 640731st, BrP and No. 736892nd, BrP, and No. 45-4554, Japanese Patent Publication, No. 49-5614, Japanese Patent Publication, No. 60-176834, Japanese Laid-Open Patent Publication, on the books in each publication of No. 60-203430, Japanese Laid-Open Patent Publication and No. 62-115035, Japanese Laid-Open Patent Publication.Drying on band or cylinder can be undertaken by sending into the inactive gas such as air, nitrogen.

In addition, also can by the film obtained from cylinder or bring stripping, then carry out drying with the high warm air changing temperature to 100 DEG C ~ 160 DEG C gradually, make evaporate residual solvent.Above method is on the books in Japanese Patent Publication 5-17844 publication.If according to the method, then can shorten from curtain coating to the time of peeling off.In order to implement the method, under needing the surface temperature of the cylinder when curtain coating or band, make dope gelation.

The curtain coating that the cellulose acylate solutions of preparation (dope) also can be used to carry out more than 2 layers carrys out filming.Now, cellulose acylate film is made preferably by solution casting method.Dope is at cylinder or bring curtain coating, solvent is evaporated and forms film.Dope before curtain coating is preferably that the mode of the scope of 10 ~ 40 quality % adjusts concentration with solid constituent amount.The surface of cylinder or band is preferably processed as mirror status in advance.

When multiple cellulose acylate solutions of curtain coating more than 2 layers; can the multiple cellulose acylate solutions of curtain coating; the solution casting containing acylated cellulose is made respectively, while make its stacked limit make film from the multiple curtain coating mouths in the setting spaced apart of the travel direction of supporter.These such as can use the method recorded in each publication of No. 61-158414, Japanese Laid-Open Patent Publication, No. 1-122419, Japanese Unexamined Patent Publication and No. 11-198285, Japanese Unexamined Patent Publication.In addition, also by from 2 curtain coating mouth curtain coating cellulose acylate solutions, membranization can be carried out.This such as can use the method recorded in each publication of No. 60-27562, Japanese Patent Publication, No. 61-94724, Japanese Laid-Open Patent Publication, No. 61-947245, Japanese Laid-Open Patent Publication, No. 61-104813, Japanese Laid-Open Patent Publication, No. 61-158413, Japanese Laid-Open Patent Publication and No. 6-134933, Japanese Unexamined Patent Publication.And, also can use the casting method liquid stream of high viscosity cellulose acylate solutions also being extruded simultaneously the cellulose acylate film of the cellulose acylate solutions of this high and low viscosity by low viscous cellulose acylate solutions parcel recorded in Japanese Laid-Open Patent Publication 56-162617 publication.

In addition, also can pass through use 2 curtain coating mouths, the film be formed in by the first curtain coating mouth on supporter is peeled off, carry out the second curtain coating in the side that connects with support dignity, thus make film.Such as, the method recorded in Japanese Patent Publication 44-20235 publication can be enumerated.

The cellulose acylate solutions of curtain coating can use same solution, also can use two or more different cellulose acylate solutions.In order to give multiple acylated cellulose layer function, from each curtain coating mouth by extruding the cellulose acylate solutions of function.And, cellulose acylate solutions of the present invention also can with other functional layer (such as adhesion layer, dye coating, antistatic backing, antihalation layer, UV-absorbing layer, polarization layer etc.) simultaneously curtain coating.

(interpolation of polarizer permanance modifying agent)

As the manufacture method of polaroid of the present invention; preferably include: in described polaroid protective film at least 1 operation using following composition to be filmed, said composition comprises resin and in be 0.1 ~ 20 mass parts relative to this resin 100 mass parts the described organic acid as polarizer permanance modifying agent, the particular polymers shown in general formula (1) and the compound shown in general formula (4) at least a kind.Relative to the cellulose acylate solutions of the resin raw material as polaroid protective film; add the opportunity of at least a kind in described organic acid, the compound shown in the particular polymers shown in general formula (1) and general formula (4), be just not particularly limited as long as add during masking.Such as can add between the synthesis phase of acylated cellulose, also can mix with acylated cellulose when prepared by dope.

(interpolation of ultraviolet light absorber)

In the present invention in cellulose acylate solutions, from the view point of preventing the deterioration such as polaroid or liquid crystal, also can add and preferably using ultraviolet light absorber.As ultraviolet light absorber, from the view point of the liquid crystal display that wavelength be below 370nm ultraviolet absorption can be excellent and good, preferably use the ultraviolet light absorber that the absorption of the visible ray that wavelength is more than 400nm is few.As the object lesson of the ultraviolet light absorber that the present invention preferably uses, such as, can enumerate hindered phenol based compound, dihydroxy benaophenonel based compound, benzotriazole based compound, salicylate based compound, benzophenone based compound, cyanoacrylate based compound, nickel complex salt based compound etc.As the example of hindered phenol based compound, 2,6-di-t-butyl-paracresol, pentaerythrite-four (3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester), N can be enumerated, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxy-hydrocineamide), 1,3,5-trimethyl-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, three (3,5-di-tert-butyl-4-hydroxyl benzyl)-isocyanates etc.As the example of benzotriazole based compound, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole can be enumerated, 2, 2-di-2-ethylhexylphosphine oxide (4-(1, 1, 3, 3-tetramethyl butyl)-6-(2H-benzotriazole-2-base) phenol), (2, 4-pair-(n-octylthio)-6-(4-hydroxyl-3, 5-di-tert-butyl amido)-1, 3, 5-triazine, triethylene glycol-bis-(3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester), N, N '-hexa-methylene two (3, 5-di-t-butyl-4-hydroxy-hydrocineamide), 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 2 (2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole, (2 (2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl)-5-chlorobenzotriazole, 2, 6-di-t-butyl-paracresol, pentaerythrite-four (3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester) etc.The addition of these ultraviolet preventing agents is preferably 0.1 mass parts ~ 10.0 mass parts relative to blooming 100 mass parts.

(interpolation of other adjuvant)

Also anti-deterioration agent (such as antioxidant, peroxide decomposer, free radical inhibitors, metal passivator, sour trapping agent, amine etc.) can be added in polaroid protective film.About anti-deterioration agent, on the books in each publication of No. 3-199201, Japanese Unexamined Patent Publication, No. 5-1907073, Japanese Unexamined Patent Publication, No. 5-194789, Japanese Unexamined Patent Publication, No. 5-271471, Japanese Unexamined Patent Publication, No. 6-107854, Japanese Unexamined Patent Publication.In addition, the addition of described anti-deterioration agent is preferably 0.01 ~ 1 quality % of the solution (dope) of preparation, is more preferably 0.01 ~ 0.2 quality %.If addition is more than 0.01 quality %, then due to the effect of anti-deterioration agent can be given full play to so preferably, if addition is below 1 quality %, then owing to being difficult to produce the oozing out (bleedout) etc., so preferably of surface of anti-deterioration agent to film.As the example of particularly preferred anti-deterioration agent, Yoshinox BHT (BHT), tribenzyl amine (TBA) can be enumerated.

In addition, in polaroid protective film, preferably add particulate as matting agent.As particulate used in the present invention, silicon dioxide, titania, aluminium oxide, zirconia, calcium carbonate, talcum, clay, calcined kaolin, baked calcium silicate, afwillite, alumina silicate, magnesium silicate and calcium phosphate can be enumerated.From the viewpoint of the particulate that the preferred particulate that mist degree is low is containing silicon, particularly preferably silicon dioxide.The particulate of silicon dioxide preferably 1 mean grain size is below 20nm, and apparent specific gravity is 70g/ rise more than.Apparent specific gravity preferably 90 ~ 200g/ rise more than, more preferably 100 ~ 200g/ rise more than.Apparent specific gravity is larger, then more can make the dispersion liquid of high concentration, and mist degree, agglutinator optimization, so preferably.

These particulates form 2 particles that mean grain size is 0.1 ~ 3.0 μm usually, and these particulates exist as the agglutination body of 1 particle in the film, form 0.1 ~ 3.0 μm concavo-convex on the surface of film.2 mean grain sizes preferably 0.2 μm ~ 1.5 μm, more preferably 0.4 μm ~ 1.2 μm, most preferably 0.6 μm ~ 1.1 μm.1 time, 2 times particle diameters by the particle in scanning electron microscope viewing film, using external for particle diameter of a circle as particle diameter.In addition, change position and observe 200 particles, using its mean value as mean grain size.

The particulate of silicon dioxide such as can use AerosilR972, R972V, R974, R812,200,200V, 300, the commercially available product such as R202, OX50, TT600 (above is Japanese Aerosil (strain) system).Zirconic particulate such as can use with the commercially available particulate of the ProductName of AerosilR976 and R811 (above for Japanese Aerosil (strain) system).

In them, Aerosil200V, AerosilR972V are that 1 mean grain size is below 20nm and apparent specific gravity is the particulate that 70g/ rises above silicon dioxide, mist degree due to blooming keeps lower, and the effect reducing friction factor is large, so particularly preferably.

In order to obtain having the polaroid protective film of the little particle of 2 mean grain sizes in the present invention, various method can be considered when preparing the dispersion liquid of particulate.Such as there is following method: the previously prepared particle dispersion liquid being uniformly mixed solvent and particulate; this particle dispersion liquid is added in a small amount of cellulose acylate solutions prepared in addition; stirring and dissolving, then mix with main cellulose acylate solutions (dope liquid).The method the good dispersion of silicon dioxide microparticle, silicon dioxide microparticle be difficult to further aggegation again in be preferred preparation method.In addition, add a small amount of cellulose esters in a solvent in addition, after stirring and dissolving, add particulate wherein and disperseed by dispersion machine, it can be used as particulate annex solution, by this particulate annex solution by line mixer (In-linemixer) and the well-mixed method of dope liquid.The present invention is not limited to these methods, but silicon dioxide microparticle is mixed concentration preferably 5 ~ 30 quality % of silicon dioxide when disperseing with solvent etc., more preferably 10 ~ 25 quality %, most preferably 15 ~ 20 quality %.Because dispersion concentration Gao Ze is low relative to the liquid mist degree of addition, mist degree, agglutinator optimization, so preferably.The addition of the matting agent particulate in the rich liquor solution of final acylated cellulose is at every 1m ³in be preferably 0.01 ~ 1.0g, more preferably 0.03 ~ 0.3g, most preferably 0.08 ~ 0.16g.

The solvent used, as lower alcohols, preferably enumerates methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols etc.Be not particularly limited as the solvent beyond lower alcohol, but preferably use the solvent used during the masking of cellulose esters.

These can in air atmosphere also can under the inactive gas atmosphere such as nitrogen from the operation of curtain coating to rear drying.The coiling machine used in the manufacture of the polaroid protective film in the present invention is the coiling machine usually used, and can be batched by method for coiling such as the constant program tension control method of identical tension method, permanent torque method, taper tension method, internal stress.

(stretch processing)

Also stretch processing can be carried out to described polaroid protective film.Can by stretch processing to the delay needed for polaroid protective film imparting.The draw direction of cellulose acylate film is preferably any one direction in Width, length direction.

In the method that Width stretches, such as, be recorded in each publications such as No. 62-115035, Japanese Laid-Open Patent Publication, No. 4-152125, Japanese Unexamined Patent Publication, No. 4-284211, Japanese Unexamined Patent Publication, No. 4-298310, Japanese Unexamined Patent Publication, No. 11-48271, Japanese Unexamined Patent Publication.

The stretching of film is implemented in a heated condition.Film can be stretched by the process in drying, is effective especially when solvent is remaining.When length direction stretches, if such as regulate the speed of the transport roller of film to make the coiling speed of film be greater than the peeling rate of film, then film is stretched.When Width stretches, the width slowly expanding stenter by keeping the width edge of film to carry out carrying by stenter limit also can oriented film.After film drying, drawing machine also can be used to carry out stretch (uniaxial tension preferably using long drawing machine).

The stretching of described polaroid protective film preferably uses the glass transition temperature Tg of described polaroid protective film; carry out at the temperature of (Tg-5 DEG C) ~ (Tg+40 DEG C); be more preferably Tg ~ (Tg+35 DEG C), be particularly preferably (Tg+10 DEG C) ~ (Tg+30 DEG C).During dry film, preferably 130 DEG C ~ 200 DEG C.

In addition, when stretching with the state that dope solvent is remaining after curtain coating, can stretch at the temperature lower than dry film, now, preferably 100 DEG C ~ 170 DEG C.

The stretching ratio of described polaroid protective film (length growth rate relative to the film before stretching) preferably 1% ~ 200%, more preferably 5% ~ 150%.Particularly preferred Width with 1% ~ 200% stretch, be more preferably 5% ~ 150%, be particularly preferably 30 ~ 45%.

Draw speed preferably 1%/minute ~ 300%/minute, more preferably 10%/minute ~ 300%/minute, most preferably 30%/minute ~ 300%/minute.

In addition, described polaroid protective film, preferably after being stretched to maximum tension multiplying power, passes through to manufacture lower than the stretching ratio of maximum tension multiplying power keeps the operation (below sometimes also referred to as " mitigation operation ") of certain hour.Relax 50% ~ 99% of the preferred maximum tension multiplying power of stretching ratio in operation, more preferably 70% ~ 97%, most preferably 90% ~ 95%.In addition, preferably 1 second ~ 120 seconds time of operation is relaxed, more preferably 5 seconds ~ 100 seconds.

And described polaroid protective film can manufacture in the Width clamping film side contraction process that makes it shrink well by comprising limit.

Be in the manufacture method of feature in the stretching process stretched with the Width being included in film, the contraction process that makes it shrink in the carrying direction (length direction) of film, can be kept by the stenter of bow collector (Pantograph) formula or linear electric machine formula, while slowly reduce the interval of folder on carrying direction on the Width stretching limit of film, make film shrunk thus.

The method of described explanation can be carried out in stretching process and contraction process at least partially simultaneously.

In addition, as the stretching device specifically carrying out stretching process, the FITZ machine etc. using city's metal working industry society can be wished, in described stretching process, any one direction in the length direction of film as described above or Width is stretched, and another direction is shunk, makes the thickness of film increase simultaneously.About this device, be recorded in (Japanese Unexamined Patent Publication 2001-38802 publication).

As the stretching ratio in stretching process and the shrinkage factor in contraction process, can according to the value of the delay Rth as the delay Re in the face of target and thickness direction, select value suitable arbitrarily, but preferably the stretching ratio of stretching process is more than 10%, and the shrinkage factor in contraction process is located at more than 5%.

Particularly preferably be included in the stretching process of the Width stretching more than 10% of film, and make the carrying direction of film shrink the contraction process of more than 5% in the Width limit of film clamping film side.

Wherein, in the present invention, said shrinkage factor refers to the meaning of length relative to the ratio of the length of the perisystolic film in shrinkage direction of the film shrunk after contraction.

As shrinkage factor preferably 5 ~ 40%, particularly preferably 10 ~ 30%.

(saponification process)

Described polaroid protective film gives the adaptation of the material of the polarizer such with polyvinyl alcohol (PVA) by carrying out saponification process, can use as polaroid protective film.

About the method for saponification, (0211) of Japanese Unexamined Patent Publication 2007-86748 publication and the method described in (0212) can be used.

Such as described polaroid protective film saponification process preferably with behind impregnated thin film surface in aqueous slkali by acid solution and, washing dry circulation carry out.As described aqueous slkali, potassium hydroxide solution, sodium hydroxide solution can be enumerated, the concentration of hydroxide ion preferably in the scope of 0.1 ~ 5.0mol/L, more preferably in the scope of 0.5 ~ 4.0mol/L.The scope of aqueous slkali temperature preferably in room temperature ~ 90 DEG C, more preferably the scope of 40 ~ 70 DEG C.

Also can replace saponification process, implement the easy adhesion processing described in Japanese Unexamined Patent Publication 6-94915 publication, Japanese Unexamined Patent Publication 6-118232 publication.

The manufacture method > of the < polarizer

As the manufacture method of the described polarizer in the manufacture method of polaroid of the present invention, be not particularly limited, but such as preferred by after described PVA membranization, import dichroic molecules and form the polarizer.The manufacture of PVA film can log in No. 3342516 instructions, Japanese Unexamined Patent Publication 09-328593 publication, Japanese Unexamined Patent Publication 2001-302817 publication, Japanese Unexamined Patent Publication 2002-144401 publication etc. and carry out with reference to the method recorded in (0213) of Japanese Unexamined Patent Publication 2007-86748 publication ~ (0237), Jap.P..

Specifically, particularly preferably with record the preparation section of PVA system resin solution, curtain coating operation, swelling operation, dyeing process, dura mater operation, stretching process, drying process order carry out the manufacture method of the described polarizer successively.In addition, online planar also can be set in described operation or afterwards and check operation.

(preparation of PVA system resin solution)

In the preparation section of described PVA system resin solution, preferably prepare stoste PVA system resin dissolves obtained in water or organic solvent.The concentration of the polyvinyl alcohol resin in stoste is preferably 5 ~ 20 quality %.Such as be preferably as follows method: the wet cake of PVA is put into dissolving tank, add plastifier, water as required, stir while blast water vapor limit from bottom land.Internal resin temperature is preferably warmed to 50 ~ 150 DEG C, also can give pressurization in system.

In addition, acid can not be added in the described polarizer, also can add acid, but preferably add in this operation when adding.In addition, when adding acid in the polarizer, the acid identical with the described organic acid contained by described polaroid protective film can also be used.

(curtain coating)

Described curtain coating operation preferably uses the method for film forming by the PVA system resin solution stoste curtain coating of above-mentioned preparation usually.As the method for curtain coating, be not particularly limited, but preferably by the described PVA system resin solution stoste supply double screw extrusion machine of heating, be filmed to supporter from deliverying unit (preferred mold, more preferably T-shaped slit die) salivation by gear-type pump.In addition, the temperature about the resin solution of discharging from mould is not particularly limited.

As described supporter, preferred casting drum, about diameter, width, rotating speed, the surface temperature of cylinder, is not particularly limited.

Then, preferably make the inside of obtained reel and Surface Edge alternately through dryer roll, while carry out drying.

(swelling)

Described swelling operation is preferably only undertaken by water, but described in Japanese Unexamined Patent Publication 10-153709 publication, in order to optical property stabilization and avoid on production line polaroid base material generation fold, also polaroid base material can be made swelling by boric acid aqueous solution, manage the swellbility of polaroid base material.

In addition, although the temperature of swelling operation, time can set arbitrarily, preferably 10 DEG C ~ 60 DEG C, 5 seconds ~ 2000 seconds.

In addition, also can stretch a little when swelling operation, such as, preferably be stretched to the mode of about 1.3 times.

(dyeing)

Described dyeing process can use the method recorded in Japanese Unexamined Patent Publication 2002-86554 publication.In addition, can be not only dipping as colouring method, can also be the method arbitrarily such as the coating of iodine or dye solution or spraying.In addition, also described in Japanese Unexamined Patent Publication 2002-290025 publication, the method that the body lotion limit in the stretching ratio in the concentration of iodine, dye bath temperature, bath and limit stirring bath makes it dye can be used.

When using the iodide ion of high order as dichroic molecules, in order to obtain the polaroid of high-contrast, dyeing process preferably uses the solution being dissolved in by iodine and obtaining in potassium iodide aqueous solution.The mode recorded in Japanese Unexamined Patent Publication 2007-086748 publication can be used about the iodine of IKI aqueous solution now and the mass ratio of potassium iodide.

In addition, also can log in described in No. 3145747 instructions as Jap.P., in dyeing liquor, add the borate compounds such as boric acid, borax.

(dura mater)

Described dura mater operation is preferably flooded in cross-linking agent solution or coating solution makes it contain crosslinking chemical.In addition, also described in Japanese Unexamined Patent Publication 11-52130 publication, dura mater operation can be divided into and carry out for several times.

As described crosslinking chemical, the crosslinking chemical recorded in U.S. Reissue patent No. 232897 instructions can be used, described in Jap.P. No. 3357109 instructions, in order to improve dimensional stability, also can use polyaldehyde as crosslinking chemical, but most preferably use boric acid class.During the crosslinking chemical used in using boric acid as dura mater operation, metallic ion can be added in boric acid-potassium iodide aqueous solution.As the preferred zinc chloride of metallic ion, but also described in Japanese Unexamined Patent Publication 2000-35512 publication, zinc chloride can be replaced, and uses the zinc salts such as the zinc halides such as zinc iodide, zinc sulfate, zinc acetate.

In addition, the boric acid-potassium iodide aqueous solution being added with zinc chloride can be made, make it flood PVA film and carry out dura mater, the method recorded in Japanese Unexamined Patent Publication 2007-086748 publication can be used.

In addition, wherein, both can carry out as the raising permanance method under hot environment by the dip treating of known acid solution, also can not carry out this process.As the described process by acid solution, the method recorded in Japanese Unexamined Patent Publication 2001-83329 publication, Japanese Unexamined Patent Publication 6-254958 publication, International Publication WO2006/095815 publication etc. can be enumerated.

(stretching)

Described stretching process preferably can use the longitudinal uniaxial tension mode as United States Patent (USP) No. 2454515 instructionss etc. are described or the such stenter mode described in Japanese Unexamined Patent Publication 2002-86554 publication.Preferred stretching ratio is 2 times ~ 12 times, is more preferably 3 times ~ 10 times.In addition; also preferably can carry out the relation of stretching ratio, raw thickness and polarizer thickness to be set to (the polarizer thickness/raw material thickness after diaphragm laminating) × (total stretching ratio) > 0.17 recorded in Japanese Unexamined Patent Publication 2002-040256 publication, or the relation from the polarizer width when width of polarizer when finally bathing out and diaphragm laminating is set to 0.80≤(polarizer width during diaphragm laminating/from the width of polarizer when finally bathing out)≤0.95 recorded in Japanese Unexamined Patent Publication 2002-040247 publication.

(drying)

Described drying process can be used in known method in Japanese Unexamined Patent Publication 2002-86554 publication, but preferred range is 30 DEG C ~ 100 DEG C, and preferred drying time is 30 seconds ~ 60 minutes.In addition, also can preferably carry out as Jap.P. logs in described in No. 3148513 instructions, carry out thermal treatment temperature of fading in water being set to more than 50 DEG C, or described in Japanese Unexamined Patent Publication 07-325215 publication or Japanese Unexamined Patent Publication 07-325218 publication, carry out aging under the atmosphere of temperature and humidity management.

Preferably by such operation, manufacture the polarizer that thickness is 10 ~ 200 μm.In addition, the control of thickness can be controlled by known method, such as can by the die slit width in described curtain coating operation or stretching condition are set as that suitable value controls.

The laminating method > of the < polarizer and polaroid protective film

Manufacture method stacked 2 polaroid protective films on the two sides of the described polarizer obtained above of polaroid of the present invention.In addition, preferably as mentioned above, a slice in the polaroid protective film that uses of polaroid of the present invention be described 60 DEG C, relative humidity 95%, through time to process 24 little moisture permeabilitys be constantly 500g/m ²above and 2000g/m ²following diaphragm, another sheet does not meet described characteristic.

In the manufacture method of polaroid of the present invention; carry out alkali treatment preferably by by polaroid protective film, use complete saponified polyvinyl alcohol aqueous solution to make it be fitted in polyvinyl alcohol film flooded in iodine solution and stretch and the method made on the two sides of the polarizer obtained makes.

As for the treated side of described polaroid protective film and the adhesive of the polarizer of fitting, such as, can enumerate the ethene base system latexes etc. such as the polyethenol series such as polyvinyl alcohol (PVA), polyvinyl butyral adhesive or butyl acrylate.

The polaroid protective film of polaroid of the present invention, to the applying method of the described polarizer, is preferably fitted in the mode that the slow axis of the axis of homology of the polarizer and described polaroid protective film is substantial parallel.

Wherein, substantial parallel refer to described 60 DEG C, relative humidity 95%, through time to process 24 little moisture permeabilitys be constantly 500g/m ²above and 2000g/m ²the deviation in the direction of the direction of the principal refractive index nx of following polaroid protective film and the axis of homology of polaroid is within 5 °, within being preferably 1 °, is more preferably within 0.5 °.If deviation is within 1 °, then the degree of polarization performance under polaroid Nicol crossed is difficult to reduce, thus is difficult to light leakage occur, so preferably.

The functionalization > of < polaroid

The functionalization polaroid that polaroid of the present invention also can be preferably used as the antireflection film of the observability for improving display, brightness enhancement film or be composited with the blooming with functional layers such as hard conating, forward scattering layer, anti-dazzle (antiglare) layers.About antireflection film, brightness enhancement film, other functional optical films, hard conating, forward scattering layer, antiglare layer for functionalization, record in (0257) of Japanese Unexamined Patent Publication 2007-86748 publication ~ (0276), can record according to these polaroid making functionalization.

(3-1) antireflection film

Polaroid of the present invention can combinationally use with antireflection film.Antireflection film can use the raw-material reflectivity of low-refraction such as give only individual layer fluorine system condensate be about 1.5% film or the reflectivity of multi-coated interference that make use of film be any one in the film of less than 1%.In the present invention, the formation of the layer (that is, high refractive index layer, middle index layer) of at least one deck transparent supporting body being laminated with low-index layer and there is the refractive index than low-refraction floor height is preferably used in.In addition, also preferably can use day east skill report, vol.38, No.1, May, the antireflection film that 2000,26 pages ~ 28 pages and Japanese Unexamined Patent Publication 2002-301783 publication etc. are described.

The refractive index of each layer meets following relation.

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

The transparent supporting body used in antireflection film preferably can use the clear polymer film used in the diaphragm of the described polarizer.

The refractive index of low-index layer is preferably 1.20 ~ 1.55, is more preferably 1.30 ~ 1.50.Low-index layer is preferably as the outermost layer use with mar resistance, soil resistance.In order to improve mar resistance, also preferably carry out using the starting material such as silicone compounds or the fluorochemicals containing fluorine that contain containing silicone base (Siliconegroup) to give sliding to surface.

As described fluorochemicals, such as, preferably can use the compound recorded in Japanese Unexamined Patent Publication 9-222503 publication [0018] ~ [0026], Japanese Unexamined Patent Publication 11-38202 publication [0019] ~ [0030], Japanese Unexamined Patent Publication 2001-40284 publication [0027] ~ [0028], Japanese Unexamined Patent Publication 2000-284102 publication etc.

Described preferably have the compound of polysiloxane structure containing silicone compounds, but also can use reactive silicone (such as Silaplane (Chisso (strain) system) or contain the polysiloxane (Japanese Unexamined Patent Publication 11-258403 publication) etc. of silanol base at two ends.Under catalyzer coexists, made the organometallicss such as silane coupling agent and the specific fluorine-containing silane coupling agent containing alkyl solidify (Japanese Laid-Open Patent Publication 58-142958 publication by condensation reaction, Japanese Laid-Open Patent Publication 58-147483 publication, Japanese Laid-Open Patent Publication 58-147484 publication, Japanese Unexamined Patent Publication 9-157582 publication, Japanese Unexamined Patent Publication 11-106704 publication, Japanese Unexamined Patent Publication 2000-117902 publication, Japanese Unexamined Patent Publication 2001-48590 publication, the compound etc. that Japanese Unexamined Patent Publication 2002-53804 publication is recorded).

In low-index layer, also can preferably carry out making it contain filling agent (the such as primary particle mean grain size such as silicon dioxide (Silica), fluorine-containing particle (magnesium fluoride, calcium fluoride, barium fluoride) is the low-refraction mineral compound of 1 ~ 150nm, the middle organic fine particles etc. recorded in [0020] ~ [0038] of Japanese Unexamined Patent Publication 11-3820 publication), silane coupling agent, lubricant, surfactant etc. as adjuvant other than the above.

Described low-index layer also can pass through vapor phase method (vacuum vapour deposition, sputtering method, ion plating method, plasma CVD method etc.) and be formed, but from the viewpoint of manufacturing at an easy rate, is preferably formed by rubbing method.As rubbing method, dip coating, air knife coating method, curtain coating method, rolling method, coiling rod rubbing method, gravure rubbing method, micro-gravure rubbing method preferably can be used.

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

It is the formation that the mineral compound ultra micron of the high index of refraction of below 100nm is dispersed in base body material that middle index layer and high refractive index layer are preferably set to mean grain size.As the mineral compound particulate of high index of refraction, can preferably use refractive index be more than 1.65 mineral compound, the oxide of such as Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, In etc., comprise the composite oxides etc. of these metallic atoms.

Such ultra micron can use as follows: by particle surface by surface conditioning agent process (silane coupling agent etc.: Japanese Unexamined Patent Publication 11-295503 publication, Japanese Unexamined Patent Publication 11-153703 publication, Japanese Unexamined Patent Publication 2000-9908 publication, anionic property compound or organic metal coupling agent: Japanese Unexamined Patent Publication 2001-310432 publication etc.), or using the core shell structure (Japanese Unexamined Patent Publication 2001-166104 publication etc.) of high index of refraction particle as core, and with specific spreading agent (such as Japanese Unexamined Patent Publication 11-153703 publication, United States Patent (USP) 6210858B1 instructions, Japanese Unexamined Patent Publication 2002-2776069 publication etc.) etc.

As described base body material, existing known thermoplastic resin, curable resin epithelium etc. can be used, but also can use the curability film obtained by the metal alkoxide compositions recorded in the multi-functional material recorded in Japanese Unexamined Patent Publication 2000-47004 publication, Japanese Unexamined Patent Publication 2001-315242 publication, Japanese Unexamined Patent Publication 2001-31871 publication, Japanese Unexamined Patent Publication 2001-296401 publication etc. or Japanese Unexamined Patent Publication 2001-293818 publication etc.

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

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

The mist degree of described antireflection film is preferably less than 5%, is more preferably less than 3%.In addition, thin film strength, being preferably more than H according in the pencil hardness test of JISK5400, being more preferably more than 2H, most preferably being more than 3H.

(3-2) brightness enhancement film

Polaroid of the present invention can combinationally use with brightness enhancement film.Brightness enhancement film has the separation function of circularly polarized light or rectilinearly polarized light, is configured between polaroid and backlight, at circularly polarized light or the rectilinearly polarized light of the backreflection of backlight side or backward scattering one side.From backlight portion reflected beam portion again change polarized light state, reenter be mapped in brightness enhancement film and polaroid time, fractional transmission, therefore by repeating this process, light utilization efficiency improve, front face brightness brings up to about 1.4 times.There will be a known anisotropic emission mode and anisotropic scattering mode as brightness enhancement film, all can combine with polaroid of the present invention.

In anisotropic emission mode, known laminate multilayer monadic stretching membrane and unstretching film, be there is by the refringence of expansion draw direction the anisotropic brightness enhancement film of reflectivity and transmissivity, there will be a known multilayer film mode (each instructions of International Publication No. 95/17691 pamphlet, International Publication No. 95/17692 pamphlet, International Publication No. 95/17699 pamphlet is recorded) or the cholesteric crystal mode (European Patent 606940A2 instructions, Japanese Unexamined Patent Publication 8-271731 publication are recorded) of the principle employing dielectric mirror.As the brightness enhancement film of multilayer mode of principle employing dielectric mirror, preferably use DBEF-E, DBEF-D, DBEF-M (being 3M Inc.) in the present invention, as preferably using NIPOCS (day east electrician (strain) system) in brightness enhancement film the present invention of cholesteric crystal mode.About NIPOCS, can with reference to day east skill report, vol.38, No.1, May, 2000,19 pages ~ 21 pages etc.

In addition, in the present invention, also preferably with by the positive intrinsic birefringence condensate recorded in each publication of each instructions of International Publication No. 97/32223 pamphlet, International Publication No. 97/32224 pamphlet, International Publication No. 97/32225 pamphlet, International Publication No. 97/32226 pamphlet and No. 9-274108, Japanese Unexamined Patent Publication, No. 11-174231, Japanese Unexamined Patent Publication and the blended brightness enhancement film of carrying out the anisotropic scattering mode that uniaxial tension obtains of negative intrinsic birefringence condensate combinationally use.As anisotropic scattering mode brightness enhancement film, preferred DRPF-H (3M Inc.).

Polaroid of the present invention also preferably be provided with hard conating, forward scattering layer, anti-dazzle (anti-dizzy) layer, gas-barrier layer, sliding layer, antistatic backing, undercoat or protective seam etc. functional optical film combinationally use.In addition, the mutual compound use in same layer such as the anti-reflection layer in the antireflection film that these functional layers are also preferred and described or optical anisotropic layer.These functional layers can be arranged on polarizer side and with any one side in polarizer opposed faces (face by air side) or two sides on use.

(3-3) hard conating

In order to give the mechanical property intensity such as mar resistance, the functional optical film that polaroid of the present invention preferably carries out being provided with the surface at transparent supporting body hard conating combines.When hard conating being applied to described antireflection film, be particularly preferably arranged between transparent supporting body and high refractive index layer.

Described hard conating is formed preferably by the cross-linking reaction of the curability compound caused by light and/or heat or polyreaction.As curability functional group, preferred light polymerizable functional group, in addition, the organometallics containing water-disintegrable functional group is preferably organoalkoxysilane base (Alkoxysilyl) compound.As the concrete formation composition of hard conating, such as, preferably can use the composition that Japanese Unexamined Patent Publication 2002-144913 publication, Japanese Unexamined Patent Publication 2000-9908 publication, International Publication No. 00/46617 pamphlet etc. are recorded.

The thickness of hard conating is preferably 0.2 μm ~ 100 μm.

The intensity of hard conating, being preferably more than H according in the pencil hardness test of JISK5400, being more preferably more than 2H, most preferably being more than 3H.In addition, more few better with the abrasion loss of test film afterwards before optimization test in testing according to the Taibo of JISK5400.

The material forming hard conating can use containing the compound of olefinic unsaturated group, the compound containing ring-opening polymerization base, and these compounds can be used alone or in combination.As the preferred example of the compound containing olefinic unsaturated group, the polyacrylate of the polyvalent alcohols such as glycol diacrylate, trimethylolpropane triacrylate, two trimethylolpropane tetra-acrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate can be enumerated; The Epoxy Acrylates such as the diacrylate of bisphenol A diglycidyl ether, the diacrylate of hexanediol diglycidyl ether; Urethane acrylate obtained etc. is reacted as preferred compound by the hydroxy acryl acid such as polyisocyanate and hydroxyethylmethacry,ate ester.In addition, as commercial compound, can enumerate EB-600, EB-40, EB-140, EB-1150, EB-1290K, IRR214, EB-2220, TMPTA, TMPTMA (more than, Daicel-UCB (strain) makes), UV-6300, UV-1700B (more than, Japanese synthetic chemical industry (strain) make) etc.

In addition, as the preferred example of the compound containing ring-opening polymerization base, ethylene glycol diglycidylether can be enumerated as diglycidyl ethers, bisphenol A diglycidyl ether, trimethylolethane trimethacrylate glycidol ether, trihydroxymethylpropanyltri diglycidyl ether, glycerin triglycidyl ether, triglycidyl group trihydroxyethyl isocyanates, sorbierite four glycidol ether, pentaerythrite four glycidol ether, the polyglycidyl ether of cresol novolac resin, the polyglycidyl ether etc. of phenol resol resins, CELLOXIDE2021P can be enumerated as ester ring type epoxies, CELLOXIDE2081, EPOLEADGT-301, EPOLEADGT-401, EHPE3150CE (being Daicel chemical industry (strain) system above), the polycyclic hexyl epoxy methyl ether etc. of phenol resol resins, OXT-121 can be enumerated as oxetanes class, OXT-221, OX-SQ, PNOX-1009 (being East Asia synthesis (strain) system above) etc.Other also can use in hard conating the polymkeric substance of (methyl) glycidyl acrylate or (methyl) glycidyl acrylate with can the multipolymer of monomer of copolymerization.

In order to reduce hard conating cure shrinkage, improve with the adaptation of base material, reduce in the present invention and be firmly coated with the curl processing article, preferably carry out adding the oxide fine particle of silicon, titanium, zirconium, aluminium etc. or tygon, polystyrene in hard conating, gather the crosslinked fine particles such as organic fine particles such as the cross-linked rubber such as crosslinked particle, SBR, NBR particulate of (methyl) esters of acrylic acid, dimethyl silicone polymer etc.The mean grain size of these crosslinked fine particles is preferably 1nm ~ 20000nm.In addition, the shape of crosslinked fine particles can use spherical, bar-shaped, needle-like, tabular etc. without particular limitation.The addition of particulate is preferably 60 below volume % of the hard conating after solidifying, and is more preferably 40 below volume %.

When being added on the inorganic particles of above-mentioned record, due to usually poor with the compatibility of binder polymer, so also preferably carry out use to contain the metals such as silicon, aluminium, titanium and the surface conditioning agent with functional groups such as alkoxy, carboxylic acid group, sulfonic group, phosphonate groups carries out surface treatment.

Hard conating preferably uses heat or active energy ray to be cured, wherein more preferably use radioactive ray, gamma ray, alpha ray, electron ray, ultraviolet isoreactivity energy line, if consider security, productivity, then particularly preferably use electron ray, ultraviolet.When making it solidify by heat, consider the thermotolerance of plastics itself, heating-up temperature is preferably less than 140 DEG C, is more preferably less than 100 DEG C.

(3-4) forward scattering layer

Forward scattering layer is for improveing the viewing angle characteristic (form and aspect and Luminance Distribution) in the direction up and down when the polaroid in the present invention being applied to liquid crystal indicator.In the present invention, particulates different for refractive index is preferably carried out the formation that bonding agent (Binder) disperses to obtain by forward scattering layer, such as can use by the Japanese Unexamined Patent Publication 11-38208 publication of forward scattering coefficient specialization, the relative index of refraction of transparent resin and particulate is set to particular range Japanese Unexamined Patent Publication 2000-199809 publication, by haze value the formation of Japanese Unexamined Patent Publication 2002-107512 publication being defined as more than 40% etc.In addition, in order to control the viewing angle characteristic of mist degree, " Lumisty " described in technical report " exhibiting optical function film " 31 pages ~ 39 pages that preferably can carry out polaroid in the present invention and Sumitomo Chemical (strain) combinationally uses.

(3-5) antiglare layer

Anti-dazzle (anti-dizzy) layer is used for making reflection light diffusing and prevents reflection.Anti-dazzle function can by being formed concavo-convex in the most surface (display side) of liquid crystal indicator and obtain.The mist degree with the blooming of anti-dazzle function is preferably 3 ~ 30%, is more preferably 5 ~ 20%, most preferably is 7 ~ 20%.

Form concavo-convex method at film surface such as preferably to use and add particulate and form concavo-convex method (such as Japanese Unexamined Patent Publication 2000-271878 publication etc.) at film surface, the larger particle (particle size is 0.05 ~ 2 μm) adding a small amount of (0.1 ~ 50 quality %) forms method (the such as Japanese Unexamined Patent Publication 2000-281410 publication of uneven-surface film, Japanese Unexamined Patent Publication 2000-95893 publication, Japanese Unexamined Patent Publication 2001-100004 publication, Japanese Unexamined Patent Publication 2001-281407 publication etc.), in the method for film surface physically transfer printing concaveconvex shape (such as embossing job operation, Japanese Laid-Open Patent Publication 63-278839 publication, Japanese Unexamined Patent Publication 11-183710 publication, the records such as Japanese Unexamined Patent Publication 2000-275401 publication) etc.

[liquid crystal indicator]

Then, liquid crystal indicator of the present invention is described.

The feature of liquid crystal indicator of the present invention is at least containing 1 polaroid of the present invention.

Fig. 1 is the skeleton diagram of the example representing liquid crystal indicator of the present invention.In FIG, liquid crystal indicator 10 comprises and has liquid crystal layer 5 and be configured in the liquid crystal cells of its upper and lower liquid crystal cells upper electrode substrate 3 and liquid crystal cells lower electrode substrate 6, the upside polaroid 1 being configured in the both sides of liquid crystal cells and lower-side polarizing plate 8.Also color filter can be configured between liquid crystal cells and each polaroid.When using described liquid crystal indicator 10 as transmission-type, be configured to cold cathode or thermic cathode fluorimetric pipe or light emitting diode, field emission component, electroluminescent cell overleaf as the backlight of light source.

What upside polaroid 1 and lower-side polarizing plate 8 had that the mode that clips the polarizer by 2 polaroid protective films is laminated respectively is formed, and in liquid crystal indicator 10 of the present invention, preferably at least one polaroid is polaroid of the present invention.Liquid crystal indicator 10 of the present invention is preferably stacked with the order of the transparent protective film of routine, the polarizer, described polaroid protective film from the outside (side away from liquid crystal cells) of device.

Image direct viewing type, image projection type and light modulation type is comprised in liquid crystal indicator 10.The active matrix liquid crystal display apparatus employing 3 such terminals of TFT or MIM or 2 terminal semiconductor elements is effective in the present invention.Certainly to be called that the passive matrix liquid crystal display device that the STN pattern of time-division driving is representative is also effective.

(VA pattern)

The liquid crystal cells of liquid crystal indicator of the present invention is preferably VA pattern.

In VA pattern, by by dielectric anisotropy between upper and lower base plate be bear, Δ n=0.0813, liquid crystal about Δ ε=-4.6 carry out friction orientation, makes the sensing of the direction of orientation of display liquid crystal molecules, so-called arrow pitch angle with about 89 °.The thickness d of the liquid crystal layer 5 of Fig. 1 is preferably set to about 3.5 μm.Wherein, according to the size of the long-pending Δ nd of thickness d and refractive anisotrop Δ n, brightness change during white display.Therefore, in order to obtain maximum brightness, the thickness of liquid crystal layer is set in the mode of the scope reaching 0.2 μm ~ 0.5 μm.

The absorption axle 2 of the upside polaroid 1 of liquid crystal cells and the absorption axle 9 of lower-side polarizing plate 8 generally perpendicularly stacked.The inner side of each alignment films of electrode base board 3 and liquid crystal cells lower electrode substrate 6 forms transparency electrode (not shown) on liquid crystal cell, but do not apply the non-driven state of driving voltage on electrode under, liquid crystal molecule in liquid crystal layer 5 is relative to real estate generally perpendicularly orientation, consequently, had almost no change by the polarisation of light state of liquid crystal panel.That is, in liquid crystal indicator, the black display of realizing ideal in non-driven state.On the other hand, at any driving condition, liquid crystal molecule tilts in a parallel direction at real estate, changes polarization state by the light of liquid crystal panel by the liquid crystal molecule of described inclination.In other words, in liquid crystal indicator, under driving condition, white display can be obtained.In addition, in FIG, symbol 4 and 7 is tropism control direction.

Wherein, owing to applying electric field between upper and lower base plate, so preferably using liquid crystal molecule vertically to carry out the such dielectric constant anisotropy of response on direction of an electric field is negative liquid crystal material.In addition, by electrode configuration on one substrate and real estate at parallel transversely applying electric field time, use and there is the liquid crystal material of positive dielectric constant anisotropy.

In addition, in the liquid crystal indicator of VA pattern, interpolation less use due to dynamic response characteristic can be made deteriorated of usual used chiral agent in the liquid crystal indicator of TN pattern, but add to reduce orientation bad sometimes.

The feature of VA pattern is that high-speed response and contrast are high.But, although contrast is high in front, have the problem in vergence direction deterioration.When black display, liquid crystal molecule is vertical orientated at real estate.If observed from front, then the birefringence of liquid crystal molecule is not owing to almost having, so transmissivity is low, can obtain high-contrast.But, when observing from vergence direction, liquid crystal molecule generation birefringence.In addition, the angle of reporting to the leadship after accomplishing a task that upper and lower polaroid absorbs axle is 90 ° orthogonal in front, but is just greater than 90 ° when vergence direction is observed.Due to these two main causes, produce light at vergence direction and leak, thus contrast declines.Described 60 DEG C, relative humidity 95%, through time to process 24 little moisture permeabilitys be constantly 500g/m ²above and 2000g/m ²when following polaroid protective film is phase retardation film, described polaroid protective film can be configured to solve this problem as optical compensating gage (phase retardation film).

In addition, when showing in vain, liquid crystal molecules tilt, but reverse at vergence direction and its, the birefringent of liquid crystal molecule when observing from vergence direction varies in size, and brightness and tone also create a difference.In order to solve this problem, be also preferably set to the structure being called as multidomain liquid crystal indicator pixel segmentation being become multiple region.

(multidomain)

Such as in VA mode by apply electric field, liquid crystal molecule in a pixel in different multiple regional dips thus viewing angle characteristic be averaged.In order to division alignment in a pixel, electrode arranges slit, or projection is set and changes direction of an electric field, thus make electric field density have deviation.In order to obtain impartial visual angle in whole direction, increase this Segmentation Number, but by being set to 4 segmentations or the above visual angle that just can obtain almost equalization of 8 segmentations.Particularly polaroid can be absorbed axle during 8 segmentation and be set as arbitrary angle, so preferably.

In addition in the zone boundary of orientation segmentation, liquid crystal molecule is difficult to response.Therefore, in normal black display, owing to maintaining black display, cause the problem that brightness reduces.Therefore, can add chiral agent in liquid crystal material makes borderline region reduce.

Embodiment

Below, enumerate embodiment, more specific description is carried out to the present invention.The material represented in following embodiment, reagent, material amount and ratio, operation etc. are only otherwise departing from purport of the present invention just can suitably change.Therefore, scope of the present invention is not limited to following object lesson.

[embodiment 101]

(1) masking of cellulose acylate film

The preparation > of < acylated cellulose

Prepare the acylated cellulose that degree of substitution with acetyl group is 2.87.Wherein, add sulfuric acid (be 7.8 mass parts relative to cellulose 100 mass parts) and, as catalyzer, add the carboxylic acid of the raw material as acyl substituent, at 40 DEG C, carry out acylation reaction.In addition, after acidylate, at 40 DEG C, maturation is carried out.Again the cleaning of the low molecular weight compositions acetone of this acylated cellulose is removed.

(making of polaroid protective film)

The < air side top layer preparation > of dope 101 liquid

(preparation of cellulose acylate solutions)

Following composition is added stirred pot, carries out stirring each component dissolves, prepare cellulose acylate solutions 1.

Sucrose benzoate uses the degree of substitution of benzoyl to be average substitution degree to be the sucrose benzoate of 5 ~ 6, and namely 8 substituents are less than 15%, 7,6 substituents add up to less than 70%, and 5 ~ 3 substituents add up to less than 40%.

(preparation of Mat agent solution 2)

Following composition is added dispersion machine, carries out stirring each component dissolves, prepare Mat agent solution 2.

Add 1.3 mass parts above-mentioned Mat agent solution 2 and 98.7 mass parts cellulose acylate solutions 1, use line mixer mixing, preparation air side top layer solution 101.

The < basic unit preparation > of dope 101

(preparation of cellulose acylate solutions)

Following composition is added stirred pot, carries out stirring by each component dissolves, preparation basic unit dope 101.

Ultraviolet light absorber C

Chemical formula 35

< supports the preparation > of top layer, side dope 101 liquid

Use line mixer to be blended in dope 101 liquid of top layer, air layer side and mix 1.3 obtained mass parts Mat agent solution 2 and 99.3 mass parts cellulose acylate solutions 1, preparation supports top layer, side solution 101.

< curtain coating >

Use cylinder casting device, by the dope (basic unit's dope) of described preparation and in its both sides by top layer dope with on the curtain coating supporter (supporter temperature is for-9 DEG C) at stainless steel while of 3 layers from curtain coating mouth curtain coating equably.Peel off under the state that residual solvent amount in the dope of each layer is roughly 70 quality %, fixed at the two ends of the Width of film by pin stenter, be the state of 3 ~ 5 quality % in residual solvent amount, carries out drying cross directional stretch 1.28 times.Then, by carrying between the roller of annealing device, dry further, obtain the polaroid protective film (cellulose acylate film) of embodiment 101.The thickness of the cellulose acylate film obtained is 60 μm (air side top layer is 3 μm, and basic unit is 54 μm, and supporting top layer, side is 3 μm), and width is 1480mm.

(the saponification process of polaroid protective film)

The polaroid protective film of obtained embodiment 101 is flooded 3 minutes in the sodium hydrate aqueous solution of 2.3mol/L at 55 DEG C.Clean in the washing bath of room temperature, to use at 30 DEG C in the sulfuric acid of 0.05mol/L and.Again clean in the washing bath of room temperature, drier with the warm air of 100 DEG C.Like this, the polaroid protective film of embodiment 101 is carried out to the saponification process on surface.

(making of polaroid)

Be about 2400 by average degree of polymerization, to be the thickness be made up of polyvinyl alcohol (PVA) of more than 99.9 % by mole be saponification degree that the polyvinyl alcohol film of 75 μm is immersed in after in the pure water of 30 DEG C, the weight ratio being immersed in iodine/potassium iodide/water at 30 DEG C is in the aqueous solution of 0.02/2/100.Then, the weight ratio being immersed in potassium iodide/boric acid/water under 56.5 ∑s is in the aqueous solution of 12/5/100.Then, after the pure water cleaning of 8 DEG C, dry at 65 DEG C, obtain the polarizing coating of gas absorption quantity iodine on polyvinyl alcohol film.Stretch and mainly carry out with iodine staining and the acid-treated operation of boron, total stretching ratio is 5.3 times.

Use polyethenol series adhesive, the polaroid protective film of the embodiment 101 of saponification process is pasted on the side of the above-mentioned obtained polarizer.Same saponification process is carried out to commercially available three cellulose acetate membrane (FujitacTD80UF, FUJIFILM (strain) make).Use polyethenol series adhesive, paste obtained embodiment 101 polaroid protective film side opposite side the polarizer face on, paste the three cellulose acetate membrane after saponification process.Wherein, the thickness of commercially available three cellulose acetate membrane is 80 μm, and moisture permeability is 400g/m ²my god.

Now, to make the axis of homology of the polarizer mode parallel with the slow axis of the polaroid protective film of obtained embodiment 101 be configured.In addition, to make the slow axis of the axis of homology of the polarizer and commercially available three cellulose acetate membrane configure in an orthogonal manner.

Like this, the polaroid of embodiment 101 is made.

[embodiment 102 ~ 119, comparative example 201 ~ 202]

(making of the polaroid protective film of embodiment 102 ~ 119 and comparative example 201 ~ 202)

Except the kind of the kind addition of the degree of substitution of acylated cellulose, hydrophobing agent, polarizer permanance modifying agent and addition, thickness being changed as recorded in following table 1 in the making of the polaroid protective film of embodiment 101; same operation, manufactures the polaroid protective film of embodiment 102 ~ 119 and comparative example 201 ~ 202.Wherein, the kind of the degree of substitution of cellulosic acylate, the kind of hydrophobing agent and addition, adjuvant and addition on air side top layer, basic unit, be all set in 3 layers of top layer, support side identical.

(the saponification process of polaroid protective film and the making of polaroid)

For the polaroid protective film of embodiment 102 ~ 119 and the polaroid protective film of comparative example 201 ~ 202, also operate same with embodiment 101 carries out saponification process and polaroid makes respectively, makes the polaroid of each embodiment and comparative example.

[comparative example 203]

The polaroid of 203 (making)

Use polyethenol series adhesive, the commercially available three cellulose acetate membrane (FujitacTD80UF, FUJIFILM (strain) make) of saponification process is pasted onto the side operating the obtained polarizer similarly to Example 1.On the face of the polarizer of the opposite side again in the three cellulose acetate membrane side commercially available with stickup, use and always grind the SK adhesive sheet that chemistry (strain) makes and paste commercially available ZEONOR film (ZF14 of Japanese Zeon), the polaroid of comparison example 203.

[evaluation]

(mensuration of the moisture permeability of polaroid protective film)

Test (cup type method) according to the moisture permeability of JISZ0208, in the atmosphere of temperature 60 C, relative humidity 95%, measuring 24 hours by area is 1m ²the weight (g) of water vapor of sample, calculate moisture permeability.

(density measurement of polaroid protective film)

The density of film is measured by automatic densitometer (ProductName: MINIDENS, Co., Ltd. iPros system).

(evaluation of polaroid permanance)

To the polaroid of above-mentioned obtained each embodiment and comparative example, the orthogonal transmission of the method recorded by this instructions measures wavelength to be 410nm and wavelength the be polarizer of 510nm.

Then, to 60 DEG C, to preserve under the environment of relative humidity 95% after 800 hours and 105 DEG C, without preserving each polaroid after 50 hours under damping, with same gimmick mensuration orthogonal transmission.Obtain through time before with the change of orthogonal transmission afterwards, it can be used as polarizer permanance to record its result in following table 1.In addition, be the scope of 0% ~ 20% without the relative humidity under the environment of damping.

(mensuration of the Boron contents slip from boric acid in the polarizer)

< through time before the polarizer in the quantitative > of the Boron contents from boric acid

Polaroid is stamped into 1cm × 1cm, after adding nitric acid 3cc, at maximum temperature 230 DEG C, carries out ashing process with microwave.Add after total amount is set to 50g by water, use the ICP-OES (Optima7300DV) of PerkimElmer society to measure boron amount.

< at 60 DEG C, 95%, 800 hours through time after the quantitative > of boric acid content

From through time after polaroid peel off polaroid protective film, only take out the polarizer.By it is carried out with through time front same process, the boron amount in the quantitative polarizer.

Utilize following formula calculate 60 DEG C, relative humidity 95%, 800 hours through time before with the slip of boric acid content afterwards.

From the boron of boric acid slip=1-(through time after Boron contents)/(through time before Boron contents) (%)

Acid ionization constant in the mixed solvent of the volume ratio of tetrahydrofuran/water=6/4 at 25 DEG C recorded by described method is as follows.

The acid ionization constant of organic acid (3-3): 3.8

The acid ionization constant of organic acid (3-5): 3.7

The acid ionization constant of organic acid (3-6): 3.6

The acid ionization constant of organic acid (3-7): 4.0

The acid ionization constant of organic acid (3-8): 3.8

Above-mentioned P-01, P-02, P-03 are the condensate of following structure.In following structural formula, the numeric representation molar ratio on the right side of each repetitive.

Chemical formula 36

Above-mentioned A-02, A-12, A-62 are the polymkeric substance of following structure.

Chemical formula 37

(A-02)

Chemical formula 38

(A-12)

Chemical formula 39

(A-62)

As can be known from the results of Table 1 by the moisture permeability of polaroid protective film is set to 500g/m ²above, 105 DEG C can be suppressed to be the rising of the cross transmittance of 510nm without the wavelength under the condition of damping.In addition, the moisture permeability of known use polaroid protective film is set to 2000g/m ²below film, the density of film is 1.293g/cm ³60 DEG C of the polaroid of above polaroid protective film, relative humidity 95%, through time process 800 hours after before change little, so preferably with the cross transmittance of 410nm afterwards.

[embodiment 301]

(making of liquid crystal indicator)

2 polaroids of commercially available liquid crystal TV set (BRAVIAJ5000 of SONY (strain)) are peeled; using at the polaroid of the present invention of polaroid protective film employing the embodiment 101 as polaroid of the present invention depending on the person of recognizing side and backlight side with the polaroid protective film of embodiment 101 respectively in the mode of liquid crystal cell side, paste a slice via bonding agent respectively in observer side and backlight side.To make the axis of homology of the polaroid of observer side at above-below direction, and to make the mode of the axis of homology at left and right directions of the polaroid of backlight side, be set to cross Nicols configuration.Relative to commercially available liquid crystal TV set, even if liquid crystal indicator of the present invention obtained like this changes ambient humidity, when being observed by vergence direction contrast change and tonal variation also little, and in two kinds of situations under hot and humid and under high temperature low humidity, even if use for a long time, the reduction of contrast is also little, so preferably.

Symbol description

Polaroid on the upside of in the of 1

On the upside of in the of 2, polaroid absorbs the direction of axle

3 liquid crystal cells upper electrode substrate

The tropism control direction of 4 upper substrates

5 liquid crystal layers

6 liquid crystal cells lower electrode substrate

The tropism control direction of 7 infrabasal plates

8 lower-side polarizing plate

9 lower-side polarizing plate absorb the direction of axle

10 liquid crystal indicators

Claims

1. a polaroid, its comprise containing from the boron of boric acid the polarizer and be configured at 2 polaroid protective films of both sides of this polarizer, wherein,

At least 1 polaroid protective film 60 DEG C, relative humidity 95%, through time process 24 hours moisture permeability be 500g/m ²above and 2000g/m ²below,

60 DEG C, relative humidity 95%, through time to process before 800 hours with the slip of the boron from boric acid in the polarizer be afterwards less than 30%,

Described polaroid protective film contains the polymkeric substance of the repetitive comprised from the monomer shown in following general formula (1),

In general formula (1), R ¹represent that hydrogen atom or carbon number are the fatty group of 1 ~ 4, R ²represent substituting group, (A) represents for the formation of the atom group required for 5 or 6 rings, and n represents the integer of 0 ~ 4,

Acid ionization constant in the mixed solvent of the volume ratio of described polaroid protective film at least containing a kind of tetrahydrofuran/water=6/4 at 25 DEG C is the organic acid of 2 ~ 7.

2. polaroid according to claim 1, wherein, the density of described polaroid protective film is 1.293g/cm ³above.

3. polaroid according to claim 1, wherein, described polymkeric substance is for comprising from the repetitive of monomer shown in described general formula (1) and the interpolymer of other repetitives different from this repetitive.

4. polaroid according to claim 1, wherein, the R in described general formula (1) ¹for hydrogen atom, (A) represents 5 rings, R ²for hydrogen atom, methyl or hydroxyl.

5. polaroid according to claim 1, wherein, from the repetitive of the monomer shown in described general formula (1) by shown in following general formula (2-1), general formula (2-2), general formula (2-3), general formula (2-4), general formula (2-5) or general formula (2-6)

In formula, R ¹⁰~ R ¹⁹separately represent substituting group, n1, n2, n5, n6, n8 and n10 separately represent the integer of 0 ~ 4, and n3, n7 and n9 separately represent that 0 ~ 2, n4 separately represents 0 or 1, R ^1Arepresent that hydrogen atom or carbon number are the fatty group of 1 ~ 4.

6. polaroid according to claim 1, wherein, described polymkeric substance for containing the coumarone resin of 3 compositions shown in following general formula (P-1) as repetitive,

In formula, R ²¹, R ²², R ²³and R ²⁴separately represent substituting group, x, y, z represents the molar ratio relative to the total repetitive contained by polymkeric substance, and x represents 1 ~ 40%, y represents that 5 ~ 95%, z represents that 1 ~ 70%, m1, m2 separately represent the integer of 0 ~ 4, m3 represents the integer of 0 ~ 2, and m4 represents the integer of 0 ~ 5, R ¹⁰¹, R ¹⁰², R ¹⁰³separately represent that hydrogen atom or carbon number are the fatty group of 1 ~ 4.

7. polaroid according to claim 1, wherein, the weight-average molecular weight of described polymkeric substance is 200 ~ 10000.

8. polaroid according to claim 1 and 2, wherein, described polaroid protective film comprises the compound shown in following general formula (3),

General formula (3)

In general formula (3), R ²⁶represent aryl, R ²⁷and R ²⁸separately represent hydrogen atom, alkyl, aryl, R ²⁶and R ²⁷substituting group can be had respectively.

9. polaroid according to claim 1 and 2, wherein, described polaroid protective film comprises the compound shown in following general formula (4),

In general formula (6), X represents substituted or unsubstituted aromatic ring; R ⁶, R ⁷, R ⁸and R ⁹separately represent that hydrogen atom or carbon number are the alkyl of 1 ~ 5; N5 represents the integer of 1 ~ 11, when n5 is more than 2, and multiple R ⁶, R ⁷, R ⁸with X can identical mutually also can be different.

10. polaroid according to claim 9, wherein, A and X in described general formula (5) and described general formula (6) is phenyl ring.

11. polaroids according to claim 9, wherein, described general formula (5) by shown in following general formula (5 "),

General formula (5 ") in, n3 represents the integer of 0 ~ 5.

12. polaroids according to claim 9, wherein, described general formula (6) by shown in following general formula (6 "),

General formula (6 ") in, n4 represents the integer of 0 ~ 10.

13. polaroids according to claim 9, wherein, the R in described general formula (4) ¹for hydrogen atom or carbon number are the alkyl of 1 ~ 8, R ²shown in following general formula (5 "), n1 represents the integer of 2 ~ 4, and n2 represents the integer of 1 ~ 3, and n3 represents the integer of 0 ~ 2,

14. polaroids according to claim 9, wherein, as the compound shown in described general formula (4), containing at least 2 kinds of mutual different compounds.

15. polaroids according to claim 9, wherein, the weight-average molecular weight of the compound shown in described general formula (4) is 200 ~ 1200.

16. polaroids according to claim 1 and 2, wherein, described polaroid protective film is cellulose acylate film.

17. 1 kinds of liquid crystal indicators, it at least comprises the polaroid described in 1 claim 1 or 2.