CN102749668A

CN102749668A - Polaroid and liquid crystal display device

Info

Publication number: CN102749668A
Application number: CN2012101186066A
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: 2012-10-24
Anticipated expiration: 2032-04-20
Also published as: CN102749668B

Abstract

The present invention provides a polaroid having a polarizer with improved durability both in high temperature high humidity and in high temperature low humidity. The polaroid comprises the polarizer and two polaroid protective films arranged at two sides of the polarizer, wherein, moisture permeability of at least one polaroid protective film is from 500 g/m<2> to 2000 g/m<2> in the state of 60 DEG C, 95% relative humidity, and 24-hour processing, the polarizer contains boric acid, and decrement rate of the boric acid in the polarizer is below 30% after 800-hour processing in the state of 60 DEG C and 95% relative humidity.

Description

Polaroid and liquid crystal indicator

Technical field

The present invention relates to polaroid and liquid crystal indicator.Even be particularly related to polaroid that polarizer permanance is also excellent under any environment in hot and humid and high temperature low humidity and liquid crystal indicator with this polaroid.

Background technology

Liquid crystal indicator is little and space-efficient image display device as consumes power, and its purposes enlarges year by year.In the past; The view angle dependency that a very big shortcoming of liquid crystal indicator is a display image is big; But along with wide viewing angle liquid crystal modes such as VA pattern by practicability, even require in the market of high quality image at televisor etc., the needs of liquid crystal indicator are also constantly enlarging rapidly.

The basic comprising of liquid crystal indicator is for being provided with the formation of polaroid in the both sides of liquid crystal cells.Said polaroid has the effect that the light of the plane of polarization that only makes specific direction passes through, and the performance of liquid crystal indicator is largely about the performance by polaroid.Polaroid is generally the polarizer that is made up of polyvinyl alcohol film etc. that makes that iodine or dyestuff absorption orientation forms and pastes constituting that transparent diaphragm forms in the positive and negative both sides of this polarizer.As polaroid protective film, the polaroid protective film of acylated cellobiose prime system that with the acetyl cellulose is representative is because the transparency is high, and can easily guarantee the adaptation with the employed polyvinyl alcohol (PVA) of the polarizer, so extensively be used always.

In recent years, along with the purposes of liquid crystal indicator enlarges, the large scale of televisor etc. and high-quality purposes constantly enlarge, for the also further raising of requirement of the quality of polaroid and polaroid protective film.Particularly the liquid crystal indicator of large scale and high-quality purposes with compared in the past, for example also need under digital signage purposes etc. with outdoor is the various rigorous environment of representative, to use, especially need be in the use under the hot environment of various harshnesses.Consider from such viewpoint; In recent years; For the polaroid that uses in the liquid crystal indicator; Be desirably in the improvement of polarizer permanance under the hot environment of various harshnesses strongly always, particularly, strong expectation suppress simultaneously hot and humid down with the quadrature transmissivity of the high temperature low humidity polarizer down (below be also referred to as the intersection transmissivity) variation.

In order to improve the polarizer permanance under the hot environment, known all the time inhibition water is effectively to the pH of the polarizer immersion and the adjusting polarizer, for example in patent documentation 1, discloses and in polaroid protective film, has used moisture permeability to be 150g/m ²The method of the film below/24 hours.In addition; In patent documentation 2, disclose and to have used the plain film of polarization that to be 1.0 to 6.0 solution-treated absorption dichromatism pigment form with boric acid and the hydrophilic macromolecule film that is stretched by pH, and given polymer resin composition is solidified form layer polaroid.

The prior art document

Patent documentation

Patent documentation 1: japanese kokai publication hei 11-142645 communique

Patent documentation 2: TOHKEMY 2008-70571 communique

Summary of the invention

Invent problem to be solved

Yet, can know through inventors' of the present invention research, the polaroid of being put down in writing in the above-mentioned patent documentation can not satisfy hot and humid down and the polarizer durability requirement under the high temperature low humidity.

Inventors of the present invention are 150g/m with the moisture permeability of record in the above-mentioned patent documentation 1 ²Polaroid protective film below/24 hours and conventional polarizer combination; Make polaroid; Study the polarizer permanance of the quadrature transmission change under its hot and humid time and the high temperature low humidity; The result learns that the polarizer permanance under hot and humid improves, but is surprised to find that the polarizer permanance under the high temperature low humidity worsens on the contrary.

In addition, inventors of the present invention make by the resulting polaroid of method of record in the above-mentioned patent documentation 2 and study its performance, the result learn 60 ℃, relative humidity 95%, through the time quadrature transmission change under the condition still very big.In addition; Consider from the viewpoint of manufacturing approach; With the polarizer (polarization plain film) and polaroid protective film bonding after, polymer resin composition is solidified, can know that therefore it is viewpoint and the method for the further improvement of needs that comprises manufacturing cost.

That is, do not learn at present the polaroid that all is enhanced in hot and humid polarizer permanance and the polarizer permanance under the high temperature low humidity down as yet, thereby need improvement.

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

The means that are used to deal with problems

Inventors of the present invention are that purpose is furtherd investigate to address the above problem, the content of boric acid in the polarizer that the result finds to add for the complex compound stabilization of hydrophilic macromolecule (for example polyvinyl alcohol (PVA)) and dichromatism pigment (for example iodine) hot and humid warp reduce at present be hot and humid through the time in one of the reason of intersection transmissivity rising of the polarizer.

In addition, find through density that increases polaroid protective film and the evolving path that reduces boric acid, even in polaroid protective film with certain moisture permeability, also can suppress said hot and humid through the time in the minimizing of polarizer mesoboric acid content.

And; Find through in polaroid protective film, adding specific organic acid; Can slowly regulate pH at present at hot and humid warp; So the method for regulating the pH of the polarizer when making with the polarizer of record in like patent documentation 2 is compared, be difficult to more to take place hot and humid through the time the polarization property deterioration.When in polaroid protective film, using cellulose acylate film, by the acid-hydrolyzed moisture permeability that causes of this acylated cellulose rise, the permeability rising of boric acid can become hot and humid through the time the reason of polarizer performance degradation.Inventors of the present invention find as patent documentation 2 said by water-soluble high low-molecular-weight acid with the pH regulator of the polarizer during for low pH, this acid is moved in the polaroid protective film layer, has promoted the acid hydrolysis of polaroid protective film (cellulose acylate film).With respect to this, inventors of the present invention find can suppress the acid hydrolysis of polaroid protective film through using suitable acid ionization constant and water-soluble low organic acid, and at the hot and humid pH that can reduce the polarizer down.In addition, found to be difficult to take place the high temperature low humidity through the time the polarization property deterioration.

In addition, found, brought into play excellent effect when also adding the specific polymkeric substance that contains phenyl ring on specific phenol system compound or the main chain too except that organic acid.

That is, the problems referred to above are able to solve through the present invention of following formation.

1. polaroid, it comprises and contains from the polarizer of the boron of boric acid and be disposed at 2 polaroid protective films of the both sides of this polarizer,

At least 1 polaroid protective film 60 ℃, relative humidity 95%, through the time moisture permeability when handling 24 hours be 500g/m ²More than and 2000g/m ²Below,

60 ℃, relative humidity 95%, through the time handle 800 hours before with afterwards the polarizer in the slip from the boron of boric acid be below 30%.

2. the polaroid of record in above-mentioned 1, wherein, the density of said polaroid protective film is 1.293g/cm ³More than.

3. the polaroid of record in above-mentioned 1 or 2, wherein, the polaroid protective film that satisfies said characteristic contains the polymkeric substance that comprises from the repetitive of the monomer shown in the formula (1).

Chemical formula 1

In the general formula (1), R ¹Expression hydrogen atom or carbon number are 1～4 fatty group.R ²The expression substituting group.(A) expression is used to form 5 or 6 yuan of needed atom groups of ring.N representes 0～4 integer.

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

5. the polaroid of record in above-mentioned 3 or 4, wherein, the R in the said general formula (1) ¹Be hydrogen atom, (A) 5 yuan of rings of expression, R ²Be hydrogen atom, methyl or hydroxyl.

6. the polaroid of putting down in writing in each in above-mentioned 3～5, wherein, from the repetitive of the monomer shown in the said general formula (1) by shown in formula (2-1), general formula (2-2), general formula (2-3), general formula (2-4), general formula (2-5) or the general formula (2-6).

Chemical formula 2

In the formula, R ¹⁰～R ¹⁹Represent substituting group respectively independently.N1, n2, n5, n6, n8 and n10 represent 0～4 integer respectively independently.N3, n7 and n9 represent 0～2 respectively independently.N4 representes 0 or 1 respectively independently.R ^1AExpression hydrogen atom or carbon number are 1～4 fatty group.

7. the polaroid of putting down in writing in each in above-mentioned 3～6, wherein, said polymkeric substance is for containing the coumarone resin of 3 compositions shown in the formula (P-1) as repetitive.

Chemical formula 3

formula P-1

In the formula, R ²¹, R ²², R ²³And R ²⁴Represent substituting group respectively independently.X, y, z represent the molar ratio of the total repetition unit contained with respect to polymkeric substance, and x representes 1～40%, and y representes 5～95%, and z representes 1～70%.M1, m2 represent 0～4 integer respectively independently.M3 representes 0～2 integer.M4 representes 0～5 integer.R ¹⁰¹, R ¹⁰², R ¹⁰³Represent independently that respectively hydrogen atom or carbon number are 1～4 fatty group.

8. the polaroid of putting down in writing in each in above-mentioned 3～7, wherein, the weight-average molecular weight of said polymkeric substance is 200～10000.

9. the polaroid of record in above-mentioned 1 or 2, wherein, it is 2～7 organic acid that the polaroid protective film that satisfies said characteristic contains acid ionization constant in the mixed solvent of volume ratio of at least a kind of tetrahydrofuran/water=6/4 under 25 ℃.

10. the polaroid of record in above-mentioned 1,2 or 9, wherein, the polaroid protective film that satisfies said characteristic comprises the compound shown in the formula (3).

General formula (3)

Chemical formula 4

In the general formula (3), R ²⁶The expression aryl, R ²⁷And R ²⁸Represent hydrogen atom, alkyl, aryl respectively independently.R ²⁶And R ²⁷Also can have substituting group respectively.

11. the polaroid of record in above-mentioned 1 or 2, wherein, the polaroid protective film that satisfies said characteristic contains the compound shown in the formula (4).

Chemical formula 5

In the general formula (4), R ¹Expression hydrogen atom or substituting group, R ²Substituting group shown in the expression formula (5); N1 representes 0～4 integer, and n1 is 2 when above, a plurality of R ¹Can be identical mutually also can be different; N2 representes 1～5 integer, and n2 is 2 when above, a plurality of R ²Can be identical mutually also can be different;

Chemical formula 6

In the general formula (5), A representes to replace or unsubstituted aromatic ring; R ³And R ⁴Represent independently that respectively hydrogen atom, carbon number are 1～5 alkyl or the substituting group shown in the general formula (6); R ⁵Expression singly-bound or carbon number are 1～5 alkylidene; X representes to replace or unsubstituted aromatic ring; N3 representes 0～10 integer, and n3 is 2 when above, a plurality of R ⁵With X can be identical mutually also can be different;

Chemical formula 7

In the general formula (6), X representes to replace or unsubstituted aromatic ring; R ⁶, R ⁷, R ⁸, and R ⁹Represent independently that respectively hydrogen atom or carbon number are 1～5 alkyl; N5 representes 1～11 integer, and n5 is 2 when above, a plurality of R ⁶, R ⁷, R ⁸With X can be identical mutually also can be different.

12. the polaroid of record in above-mentioned 11, wherein, A and X in said general formula (5) and the said general formula (6) are phenyl ring.

13. the polaroid of record in above-mentioned 11 or 12, wherein, said general formula (5) is by shown in the formula (5 ").

Chemical formula 8

General formula (5 ") in, n3 representes 0～5 integer.

14. the polaroid of putting down in writing in each in above-mentioned 11～13, wherein, said general formula (6) is by shown in the formula (6 ").

Chemical formula 9

General formula (6 ") in, n4 representes 0～10 integer.

15. the polaroid of record in above-mentioned 11～14, wherein, the R in the said general formula (4) ¹For hydrogen atom or carbon number are 1～8 alkyl, R ²Shown in general formula (5 "), n1 representes 2～4 integer, and n2 representes 1～3 integer, and n3 representes 0～2 integer.

16. the polaroid of putting down in writing in each in above-mentioned 11～15, wherein, the compound as shown in the said general formula (4) contains at least 2 kinds of mutual different compounds.

17. the polaroid of putting down in writing in each in above-mentioned 11～16, wherein, the weight-average molecular weight of the compound shown in the said general formula (4) is 200～1200.

18. the polaroid of putting down in writing in each in above-mentioned 1～17, wherein, the polaroid protective film that satisfies said characteristic is a cellulose acylate film.

19. a liquid crystal indicator, it contains the polaroid of putting down in writing in 1 said 1～18 each at least.

The effect of invention

According to the present invention, can provide the polarizer permanance that do not make under the high temperature low humidity to worsen, improve the polaroid and the manufacturing approach thereof of the polarizer permanance under hot and humid.In addition, the liquid crystal indicator that has used polaroid of the present invention can be provided.

Description of drawings

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

Embodiment

[polaroid]

Polaroid of the present invention is following polaroid: this polaroid comprises and contains from the polarizer of the boron of boric acid and be configured in 2 polaroid protective films of the both sides of this polarizer, at least 1 polaroid protective film 60 ℃, relative humidity 95%, through the time moisture permeability when handling 24 hours be 500g/m ²More than and 2000g/m ²Below, 60 ℃, relative humidity 95%, through the time handle 800 hours before with afterwards the polarizer in the slip from the boron of boric acid be below 30%.

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

Polaroid in the past hot and humid warp at present the boric acid content in the polarizer reduce, the situation of the complex compound instabilityization of hydrophilic macromolecule (for example polyvinyl alcohol (PVA)) and dichromatism pigment (for example iodine) is more, this is the reason of polarization property deterioration.With respect to this; Polaroid of the present invention increases the boric acid content minimizing that suppresses in the polarizer through making the density in the polaroid protective film; On the other hand, remain certain value, suppress the polarization property deterioration under the high temperature low humidity condition through the moisture permeability that makes polaroid protective film.

Below, polaroid of the present invention is elaborated.

< performance of polaroid >

(quadrature transmissivity CT)

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

(quadrature transmission change)

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

Polaroid of the present invention is below 0.65% at 60 ℃, the variable quantity (%) of quadrature veneer transmissivity when relative humidity leaves standstill 800 hours 95% time preferably; And the variable quantity (%) of (it is the state that does not have damping, refers to that in an embodiment of the present invention relative humidity is 0%～20%) quadrature veneer transmissivity when leaving standstill 50 hours is below 0.05% under 105 ℃, dry (Dry) environment.

Be preferably below 0.30% at 60 ℃, the variable quantity (%) of quadrature veneer transmissivity when relative humidity leaves standstill 800 hours 95% time, more preferably below 0.20%.

The variable quantity (%) of the quadrature veneer transmissivity when under 105 ℃, dry environment, leaving standstill 500 hours is preferably below 0.03%.

Wherein, the variable quantity of quadrature transmissivity is meant and from test the back measured value, deducts the value that the preceding measured value of test obtains, calculated by following formula.

The variable quantity of quadrature transmissivity (%)=(the quadrature transmissivity (%) before quadrature transmissivity (the %)-endurancing after the endurancing

If satisfy the scope of the variable quantity of above-mentioned quadrature transmissivity, then can guarantee polaroid hot and humid down with the high temperature low humidity is long-time down use in or take care of in stability, so preferably.

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

Wherein, the polaroid endurancing can only carry out polaroid via 2 kinds of modes that bonding agent sticks on mode on glass as follows mode and (2) of polaroid with (1).

In (1) only in the mensuration of polaroid, with clip between 2 polarizers said 60 ℃, relative humidity 95%, through the time moisture permeability when handling 24 hours be 500g/m ²More than and 2000g/m ²The mode of following polaroid protective film makes up, and prepares the polaroid of 2 absorption axes mutually orthogonals.

In (2) polaroid is sticked on via bonding agent in the mensuration under the mode on glass, make 2 samples (about 5cm * 5cm), this sample through with said 60 ℃, relative humidity 95%, through the time moisture permeability when handling 24 hours be 500g/m ²More than and 2000g/m ²Following polaroid protective film obtains at stickup polaroid on glass in the mode of glass side.In veneer quadrature transmissivity is measured, the film side of this sample is measured towards the light source setting.Measure 2 samples respectively, its mean value is made as veneer quadrature transmissivity.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)～(0255) of TOHKEMY 2007-086748 communique, preferably satisfy these characteristics.

< shape formation >

The shape of polaroid of the present invention not only comprises the polaroid of the diaphragm form that is cut to the size that can directly be assembled into liquid crystal indicator, also comprises through continuous system as strip and be wound as the polaroid of the form (for example long or the mode that 3900m above above for 2500m of reel) of drum.In order to be used for big picture liquid crystal indicator, the width of polaroid preferably is made as more than the 1470mm.

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

Said protective film and said stripping film are that purpose is used with protection polaroid such as when the polaroid shipment, during product examination.At this moment, be purpose applying protective film with the surface of protecting polaroid, use it for opposed faces side to the face of liquid crystal board applying polaroid.In addition, stripping film is that purpose is used to cover the adhesion layer of fitting to liquid crystal board, uses it for the face side to liquid crystal board applying polaroid.

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

< polarizer >

At first, the polarizer that uses in the polaroid of the present invention is described.

As the said polarizer that can in polaroid of the present invention, use; Preferably constitute by polyvinyl alcohol (PVA) (PVA) and dichroic molecules; But also can be of japanese kokai publication hei 11-248937 communique; Use is through generating polyene structure with PVA or PVC dehydration, dechlorination, and the polyvinylene (Polyvinylene) that its orientation is obtained is the polarizer.

(1-1)PVA

As said PVA, the polymer raw materials that preferably the polyvinyl acetate saponification is obtained, but for example can contain unsaturated carboxylic acid, unsaturated sulfonic acid, olefines, vinyl ethers such can with the composition of vinyl acetate copolymerization.In addition, also can use the modified PVA that contains acetoacetyl, sulfonic group, carboxyl, oxyalkylene (Oxyalkylene) base etc.

Other; In polaroid of the present invention; Can preferably use 1 of record in No. the 3021494th, the Jap.P., 2-monoethylene glycol binding capacity is that the above optics impurity of putting down in writing in the PVA film, TOHKEMY 2001-316492 communique below 1.5 moles of % of 5 μ m is every 100cm ²In in the PVA film, TOHKEMY 2002-030163 number below 500 hot water of the TD direction of the film of record cut off temperature and be not PVA film below 1.5 ℃, also have or be mixed with the PVA film that the solution more than the plastifier 15 quality % that put down in writing in the japanese kokai publication hei 06-289225 communique makes by the solution of polyvalent alcohol 1～100 weight % that is mixed with 3～6 yuan of glycerine etc.

(1-2) dichroic molecules

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

In the present invention, especially preferably use the iodide ion of high order.The iodide ion of high order can as " application of polaroid " forever the field very compile, CMC publication or industrial materials, the 28th volume, No. 7, p.39～p.45 described in; PVA is immersed in iodine is dissolved in potassium iodide aqueous solution and/or the boric acid aqueous solution and in the liquid that obtains, with absorption, be oriented in the state on the PVA and generate.

When using dichroic dye as dichroic molecules, preferred azo is a pigment, and preferred especially bisdiazo system and trisazo-are pigment.Therefore the preferred water miscible dyestuff of dichroic dye preferably imports water wettability substituting groups such as sulfonic group, amino, hydroxyl in dichroic molecules, use as the salt of free acid or alkali metal salt, ammonium salt, amine.As the object lesson of such dichroic dye, can enumerate the dichroic dye of putting down in writing in the TOHKEMY 2007-086748 communique.

(1-3) boric acid

Polaroid of the present invention contains boric acid as crosslinking chemical in the polarizer.Through by the crosslinked polarizer of boric acid, the stability of the complex compound that is then formed by dichroic molecules and PVA improves, and can suppress the polarization property deterioration under the 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 with respect to the polarizer 100 mass parts and below 100 mass parts, and more preferably 5 mass parts are above and below 50 mass parts.Be controlled at above-mentioned scope through containing ratio, just can make the balanced polarizer of tone boric acid.

Polaroid of the present invention 60 ℃, relative humidity 95%, through the time handle 800 hours before with afterwards the polarizer in the slip of boric acid be below 30%.The slip of this boric acid is preferably below 25%, more preferably below 20%.

(1-4) organic acid

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

At this moment; Said organic acid content is preferably 0.01～10 mass parts with respect to resin (" constituting the resin of the major component of the polarizer " is meant the resin that contains the quality ratio maximum in the contained resin of the polarizer, is preferably polyvinyl alcohol (PVA)) 100 mass parts of the major component that constitutes the polarizer.If be more than 0.01 mass parts, then obtain polarizer permanance improved effect easily, in addition,, then be difficult to take place the white casse that causes by being separated in the polarizer if be below 10 mass parts.Said organic acid content is 0.1～8 mass parts more preferably, is preferably 0.1～5 mass parts especially.

In addition, polaroid of the present invention after when containing said organic acid in the polaroid protective film stated, even in the polarizer, do not comprise organic acid, also can fully obtain the effect of polaroid of the present invention.

(1-5) thickness of the polarizer

The thickness of the film before the polarizer stretching is not special to be limited, but from the stability of film maintenance, the homogeneous viewpoint of stretching, preferred 1 μ m～1mm, preferred especially 20～200 μ m.In addition, of TOHKEMY 2002-236212 communique, also can use the stress that produces when in water, carrying out 4 times～6 times stretching to be thin PVA film such below the 10N.

< polaroid protective film >

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

(2-1) characteristic of polaroid protective film

Said polaroid protective film 60 ℃, relative humidity 95%, through the time moisture permeability when handling 24 hours be 500g/m ²More than and 2000g/m ²Below.

(moisture permeability of polaroid protective film)

Polaroid protective film of the present invention 60 ℃, relative humidity 95%, through the time moisture permeability when handling 24 hours be 500g/m ²More than and 2000g/m ²Below.The moisture permeability of polaroid protective film of the present invention is 800～1800g/m more preferably ²My god, be preferably 1000～1600g/m especially ²My god.Moisture permeability through with polaroid protective film is made as 500g/m ²More than, can suppress the polarizer performance degradation under the high temperature low humidity condition.In addition, through moisture permeability is made as 2000g/m ²Below, can suppress the polarization property deterioration under the hot and humid condition.

The moisture permeability of film can reduce through the thickness that increases film.In addition, hydrophilic and resin that free volume is big has the higher tendency of moisture permeability, when using acylated cellulose as the resin of polaroid protective film, can reduce moisture permeability through hydrophobing agent or the polarizer permanance modifying agent of stating after adding.

The value of the moisture permeability in this instructions is the moisture permeability test (cup type method) according to JISZ0208, and in the atmosphere of 60 ℃ of temperature, relative humidity 95%, measuring 24 hours is 1m through area 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 ³More than, 1.294g/cm more preferably ³More than, be preferably 1.295g/cm especially ³More than.Density is big more, and then the part of the free volume in the film is few more, and the boric acid that can suppress in the polaroid protective film sees through, and the boric acid content that can suppress in the polarizer reduces.The density of polaroid protective film can increase through in molecule, adding the rigidization compound with ring texture.Particularly, can increase the density of film effectively through the polarizer permanance modifying agent below adding.In addition, the carbohydrate derivates of in the project of following hydrophobing agent, mentioning with pyranose ring or furanose ring also has the effect of the density that increases film, can preferably use.

Density can be measured through commercially available automatic densitometer (for example the MINIDENS of iPros society system etc.).

(thickness of polaroid protective film)

Said 60 ℃, relative humidity 95%, through the time moisture permeability when handling 24 hours be 500g/m ²More than and 2000g/m ²Below the preferred 30 μ m of the thickness～100 μ m of polaroid protective film, more preferably 30 μ m～80 μ m, preferred especially 35 μ m～65 μ m.

On the other hand, the thickness that does not satisfy the polaroid protective film of said characteristic is preferably 30 μ m～100 μ m, and more preferably 35～80 μ m are preferably 35～65 μ m especially.

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

When the polaroid protective film of the characteristic that satisfies said (1) and (2) is merely 1; As the polaroid protective film of the characteristic that does not satisfy said (1) and (2), can use 60 ℃, relative humidity 90%, through the time after handling 24 hours moisture permeability for said 60 ℃, relative humidity 95%, through the time moisture permeability when handling 24 hours be 500g/m ²More than and 2000g/m ²The film of the amount of the equilibrium of following polaroid protective film.

In addition, in addition, consider preferably that water percentage, spring rate wait to select said other polaroid protective film.

Polaroid protective film as the characteristic that does not satisfy said (1) and (2); Can preferably use the acrylic resin put down in writing in the fluoropolymer resin film that contains the ester ring type structure put down in writing in commercially available three cellulose acetate membrane (Fujitac TD80UF, Fujiphoto (strain) system), the TOHKEMY 2006-58322 communique, the TOHKEMY 2009-122644 communique etc.

Below, the employed resin of said polaroid protective film, polarizer permanance modifying agent are described.

(2-2) resin

Then, the resin as the film substrate that uses in the said polaroid protective film is described.

As the employed resin of said polaroid protective film, can use known resin, only otherwise violate that purport of the present invention is just not special to be limited.As said film substrate, can enumerate acylated cellulose, acryl resin, cyclic olefine resin, wherein preferred acylated cellulose resin.That is, said polaroid protective film preferably comprises acylated cellulose.

(acylated cellulose)

Below, the acylated cellulose that can use among the present invention is elaborated.

The degree of substitution of acylated cellulose means that 3 hydroxyls that are present in the cellulosic formation unit ((β) 1, the glucose of 4-glycoside link) are by the ratio of acidylate.Degree of substitution (acidylate degree) can be calculated through the conjugated fatty acid amount in the cellulosic formation unit of measuring per unit mass.In the present invention, the degree of substitution of cellulose bodies can be measured through cellulose bodies being dissolved in by in the substituted dimethyl sulfoxide (DMSO) equal solvent of deuterium ¹³The C-NMR spectrogram, the peak intensity ratio of the carbonyl carbon from acyl group is tried to achieve and is calculated.After the remaining hydroxyl of acylated cellulose is substituted by other different acyl groups of the acyl group that has with acylated cellulose itself, can pass through ¹³C-NMR measures and tries to achieve.About the detailed content of assay method, on the books in the paper of (Carbohydrate.Res., 273 (1995) 83-91) such as Zai Shou mound.

Total acyl substituted degree of the acylated cellulose that can use among the present invention is preferably 2.0～2.97, and more preferably 2.2～2.95, be preferably 2.3～2.95 especially.Polarizer permanance modifying agent used in the present invention particularly with the acylated cellulose and time spent of the scope of such total acyl substituted degree, the polaroid permanance is improved the effect height.

As the acyl group of the acylated cellulose that can use among the present invention, preferred especially acetyl group, propiono, bytyry, more preferred acetyl group.

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

In the present invention, can and with, mix to use substituting group and/or 2 kinds of different acylated celluloses of degree of substitution, also can through after the common The tape casting stated etc., form a plurality of layers that constitute by different acylated celluloses and the film that constitutes.

In addition, the mixed acid ester with fatty acid acyl and replacement or unsubstituted aromatic acyl of record also can preferably use in the present invention in (0023) of TOHKEMY 2008-20896 communique～(0038).

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

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

In said method, the such cellulose of cotton linter or wood pulp is after the organic acid activate such with acetate handled, and in the presence of sulfuric acid catalyst, it is more to use the mixed liquor of the organic acid composition of above-mentioned that kind to carry out the situation of esterification.The organic acid anhydride composition uses with excess quantity with respect to the amount of the hydroxyl that exists in the cellulose usually.In this esterification treatment, outside esterification, also carry out cellulosic backbone (β) 1,4-glycosidic bond) hydrolysis reaction (depolymerization reaction).If the hydrolysis reaction of main chain carries out, then the degree of polymerization of cellulose esters reduces, thereby the rerum natura of the cellulose ester membrane of making reduces.Therefore, the reaction conditions of temperature of reaction and so on considers that preferably the degree of polymerization of resulting cellulose esters and molecular weight decide.

(2-3) polarizer permanance modifying agent

< particular polymers >

Polaroid protective film among the present invention (preferred cellulose acylate film) preferably contains the polymkeric substance that comprises from the repetitive of the monomer shown in the formula (1) as polarizer permanance modifying agent.

Chemical formula 10

·R ¹

In the formula, R ¹Expression hydrogen atom or carbon number are 1～4 fatty group.R ¹Not special the qualification, but be preferably hydrogen atom, methyl or ethyl.

·R ²

R ²The expression substituting group is as substituting group aliphatic base or aromatic series base.

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

·n

N representes 0～4 integer, and is preferred 0～2, more preferably 0～1.In addition, be 0 o'clock at n, substituent R ²Do not exist, but in chemical formula, hydrogen atom is arranged here as long as mean.In other chemical formulas of this instructions with above-mentioned same explanation.

·(A)

(A) expression is used to form 5 or 6 yuan of needed atom groups of ring, is preferably 5 or 6 yuan aromatic rings.Aromatic rings is meant and does not contain heteroatomic aromatic ring and the notion with heteroatomic saturated, undersaturated heterocycle in this manual.

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

Chemical formula 11

·R ¹⁰～R ¹⁹

In the formula, R ¹⁰～R ¹⁹Represent substituting group respectively independently.Substituting group is not special to be limited, but can enumerate following substituting group T, its preferable range same meaning.

·n1～n10

N1, n2, n5, n6, n8 and n10 represent 0～4 integer, preferred 0～2 respectively independently.N3 and n7 represent 0～2 respectively independently, preferred 0～1.N4 and n9 represent 0 or 1, preferred 0 respectively independently.

·R ^1A

R ^1AExpression hydrogen atom or carbon number are 1～4 fatty group.R ^1ANot special the qualification, but be preferably hydrogen atom, methyl or ethyl.

In the present invention, said particular polymers is preferably and contains the coumarone resin of 3 compositions shown in the formula (P-1) as repetitive.Wherein coumarone resin is meant the resin with specific copolymerization ratio that synthesizes from petroleum residue, in addition, also mean by in coumarone-indenes-styrene any or by the general name of its multipolymer that all constitutes.Therefore, the multipolymer shown in the formula (P-1) is included in the category of coumarone resin.

Chemical formula 12

formula P-1

In the formula, R ²¹, R ²², R ²³, and R ²⁴Represent substituting group respectively independently.X, y, z represent the molar ratio of the total repetition unit contained with respect to polymkeric substance, and x representes 1～40%, and y representes 5～95%, and z representes 1～70%.M1, m2 represent 0～4 integer.M3 representes 0～2 integer.M4 representes 0～5 integer.R ¹⁰¹, R ¹⁰², R ¹⁰³Expression hydrogen atom or carbon number are 1～4 fatty group.

·R ²¹～R ²⁴

R ²¹, R ²², R ²³, R ²⁴Represent substituting group respectively independently.Substituting group is not special to be limited, but can enumerate following substituting group T, and its preferable range is same meaning also.

·R ¹⁰¹～R ¹⁰³

R ¹⁰¹～R ¹⁰³Expression hydrogen atom or carbon number are 1～4 fatty group.R ¹¹～R ¹³Not special the qualification, but be preferably hydrogen atom, methyl or ethyl.

·x，y，z

X representes 1～40% with molar ratio, and is preferred 1～30%, more preferably 1～20%.

Y representes 5～95% with molar ratio, and is preferred 10～90%, more preferably 30～90%.

Z representes 1～70% with molar ratio, and is preferred 1～60%, more preferably 1～50%.

X+y+z can not be 100 (%) also, but less than 100 o'clock, means the copolymer composition that contains other.As other copolymer composition, can enumerate vinyltoluene, isopropenyl toluene, AMS, alkyl indenes, dicyclopentadiene etc.

The copolymerization ratio of other copolymer compositions (molar ratio) t is preferred 0～30%, and more preferably 0～20%.

·m1～m4

M1, m2 represent 0～4 integer, preferred 0～2.M3 representes 0～2 integer, preferred 0.M4 representes 0～5 integer, and is preferred 0～3, more preferably 0～1.

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

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

Chemical formula 13

(matter average molecular weight)

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

The short of special instruction of molecular weight and dispersion degree just is made as uses GPC (gel filtration chromatography) method to measure the value that obtains, and molecular weight is made as the matter average molecular weight with polystyrene conversion.The gel of in post, filling that uses in the GPC method is preferably the gel that in repetitive, has aromatics, for example can enumerate the gel that is made up of styrene diethylene benzene copoly mer.Preferred 2～6 of post connects use.The solvent that uses can be enumerated acid amides series solvents such as ether series solvent, N-Methyl pyrrolidone such as tetrahydrofuran.The flow velocity of measuring preferred solvent carries out 0.1～2mL/ minute scope, most preferably carries out 0.5～1.5mL/ minute scope.Through in this scope, measuring, can not apply load and more effectively measure to device.For measuring temperature, preferably under 10～50 ℃, carry out, most preferably under 20～40 ℃, carry out.In addition, the post of use and carrier can suitably be selected according to the rerum natura as the macromolecular compound of determination object.

(addition)

The addition of said particular polymers is not special to be limited, but with respect to the resin that forms polaroid protective film (preferred acylated cellulose) 100 mass parts, is preferably 0.1～100 mass parts, and more preferably 0.5～50 mass parts is preferably 1.0～30 mass parts especially.If what above-mentioned addition more than said lower limit, then can be expected film can suppress the moisture permeability of film and the effect of water percentage effectively,, then can expect to keep high transparent if be below the higher limit.

In this manual, condensate or polymkeric substance be meant except the condensate of the macromolecular compound of the routine that is polymerized in a large number as monomer, means that also comprising monomer is that compound about hundreds of is an oligomer for for example several molecular weight that are polymerized.In addition, when being called condensate or polymkeric substance, short of special instruction just means to comprise interpolymer or multipolymer.

In addition, when in this manual " compound " being added in the suffix address, during perhaps with specific title or by chemical formulation, except this compound itself, also be used to comprise the meaning of its salt, complex compound, its ion.In addition, in the scope of the desired effect of performance, mean to comprise the derivant that forms with the form modification of stipulating.And in this manual, when for substituting group " base " being added in the specific atom group of suffix address, meaning on this group to have substituting group arbitrarily.This replaces for clearly not putting down in writing, unsubstituted compound, and it is also identical to look like.As preferred substituted, can enumerate following substituting group T.

As substituting group T, can enumerate following radicals.

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

< organic acid >

At least 1 in the polaroid protective film that can use in the polaroid of the present invention preferably contains resin, and contain acid ionization constant in the mixed solvent of volume ratio of tetrahydrofuran/water=6/4 under 25 ℃ with respect to these resin 100 mass parts be that 2～7 organic acid 0.1～20 mass parts is as polarizer permanance modifying agent.Through using such organic acid, said polaroid protective film can not make the polarizer permanance under the high temperature low humidity worsen and improve the polarizer permanance under hot and humid.

If use said specific organic acid with said specific content; Then can not cause the acid hydrolysis spinoffs such as (causing that the moisture permeability rising of polaroid protective film, the diffusion of boric acid promote) of the main resin (acylated cellulose etc.) of polaroid protective film; And it is can regulate the pH of the polarizer, so preferred.

(solubleness)

Said organic acid is below the 0.1 quality % in the solubleness with respect to water under 25 ℃ preferably from the acid-hydrolyzed viewpoint of the main resin of polaroid protective films such as inhibition acylated cellulose.Said organic acid, is being more preferably below the 0.03 quality % more preferably below the 0.06 quality % with respect to the solubleness of water under 25 ℃.

As the assay method of the said solubleness among the present invention, adopt the method for record in 153 pages～156 pages of experimental chemistry lecture the 4th edition of ball kind (strain) periodical.

(acid ionization constant)

Said organic acid is 2～7 organic acid for the acid ionization constant in the mixed solvent of the volume ratio of THF/ water=6/4 under 25 ℃.The acid ionization constant of said organic acid in the mixed solvent of the volume ratio of tetrahydrofuran (THF)/water=6/4 is from suppressing the acid-hydrolyzed viewpoint of the employed resins of polaroid protective film such as acylated cellulose; Be preferably 2.5～7; More preferably 2.5～6.5, be preferably 3～5 especially.

As the assay method of the said acid ionization constant among the present invention, adopt the alkali titration of record in 215 pages～217 pages of experimental chemistry lecture the 2nd edition of ball kind (strain) periodical.

(molecular weight)

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

(structure)

Said organic acid preferably contains aromatic ring structure from the viewpoint of the density of film, preferably contains carbon number and be 6～12 aryl, especially preferably contains phenyl.Said organic acid aromatic ring structure also can form condensed ring with other ring.Said organic acid aromatic ring structure also can have substituting group; As this substituting group, only otherwise violate the just not special restriction of purport of the present invention, but be preferably halogen atom or alkyl; More preferably halogen atom or carbon number are 1～6 alkyl, are preferably chlorine atom or methyl especially.

Said organic acid is preferably by shown in the formula (3).

General formula (3)

Chemical formula 14

Said R ²⁶Be preferably carbon number and be 6～18 aryl, more preferably carbon number is 6～12 aryl, is preferably phenyl especially.

Said R ²⁷And R ²⁸Preferred is that 1～12 alkyl (also comprising naphthenic base) or carbon number are 6～12 aryl for hydrogen atom, carbon number respectively independently; More preferably hydrogen atom, carbon number are 1～6 alkyl (also comprising naphthenic base) or phenyl, are preferably hydrogen atom, methyl, ethyl, cyclohexyl or phenyl especially.

As said R ²⁶The substituting group that can have only otherwise violate the just not special restriction of purport of the present invention, but is preferably halogen atom or alkyl, and more preferably halogen atom or carbon number are 1～6 alkyl, are preferably chlorine atom or methyl especially.

As said R ²⁷The substituting group that can have, only otherwise violate the just not special restriction of purport of the present invention, but preferred carbon number is 6～12 aryl, more preferably phenyl.

Below, the organic acid object lesson shown in the illustration 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 synthetic through known method.

(organic acid content)

Said organic acid is preferably 1～20 quality % with respect to the resin (resin of major component is meant the resin that contains the quality ratio maximum in the contained resin of polaroid protective film) of the major component that constitutes polaroid protective film.If be more than the 1 quality %, then obtain polarizer permanance improved effect easily, in addition,, then when making polaroid protective film, be difficult to ooze out or seepage if be below the 20 quality %.Said organic acid content is 1～15 quality % more preferably, is preferably 1～10 quality % especially.

(organic acid acid ionization constant)

The said organic acid preferably acid ionization constant in the mixed solvent of the volume ratio of the tetrahydrofuran/water under 25 ℃=6/4 is 2～7, more preferably 3～6.

< phenol system compound >

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

Chemical formula 16

In the general formula (4), R ¹Expression hydrogen atom or substituting group, R ²Substituting group shown in the expression formula (5); N1 representes 0～4 integer, and n1 is 2 when above, a plurality of R ¹Can be identical mutually also can be different; N2 representes 1～5 integer, and n2 is 2 when above, a plurality of R ²Can be identical mutually also can be different.

Chemical formula 17

Chemical formula 18

In the general formula (6), X representes to replace or unsubstituted aromatic ring; R ⁶, R ⁷, R ⁸And R ⁹Represent independently that respectively hydrogen atom or carbon number are 1～5 alkyl; N5 representes 1～11 integer, and n5 is 2 when above, a plurality of R ⁶, R ⁷, R ⁸, R ⁹With X can be identical mutually also can be different.

R ¹Expression hydrogen atom or substituting group.As substituent example; Not special restriction; (preferred carbon number is 1～10 alkyl can to enumerate alkyl; For example methyl, ethyl, isopropyl, the tert-butyl group, amyl group, heptyl, 1-ethyl pentyl group, benzyl, 2-ethoxyethyl group, 1-ethyloic etc.), (preferred carbon number is 2～20 alkenyl to alkenyl; For example vinyl, allyl, oleyl etc.), (preferred carbon number is 2～20 alkynyl to alkynyl; For example ethinyl, butynyl, phenylacetylene base etc.), (preferred carbon number is 3～20 naphthenic base to naphthenic base; For example cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl etc.), (preferred carbon number is 6～26 aryl to aryl; For example phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorphenyl, 3-aminomethyl phenyl etc.), (preferred carbon number is 2～20 heterocyclic radical to heterocyclic radical; For example 2-pyridine radicals, 4-pyridine radicals, 2-imidazole radicals, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl etc.), alkoxy (preferred carbon number is 1～20 alkoxy, for example methoxyl, ethoxy, isopropoxy, benzyloxy etc.), aryloxy group (preferred carbon number is 6～26 aryloxy group, for example phenoxy group, 1-naphthoxy, 3-methylphenoxy, 4-methoxyl phenoxy group etc.), (preferred carbon number is 2～20 alkoxy carbonyl group to alkoxy carbonyl group; For example carbethoxyl group, the own oxygen carbonyl of 2-ethyl etc.), (preferred carbon number is 0～20 amido to amido; For example amino, N, N-dimethyl amido, N, N-diethyl amido, N-ethyl amido, anilino-etc.), (preferred carbon number is 0～20 sulfoamido to sulfoamido; N for example; N-dimethyl methyl acid amides, N-phenyl-sulfamide etc.), acyloxy (preferred carbon number is 1～20 acyloxy, for example acetoxyl group, benzoyloxy group etc.), (preferred carbon number is 1～20 carbamyl, for example N to carbamyl; N-formyl-dimethylamino, N-phenyl amino formoxyl etc.), amide group (preferred carbon number is 1～20 amide group, for example acetamido, benzamido etc.), cyanic acid or halogen atom (for example fluorine atom, chlorine atom, bromine atoms, iodine atom etc.), hydroxyl.R ¹Preferred hydrogen atom, carbon number are 1～20 alkyl, hydroxyl, more preferably hydrogen atom, hydroxyl, methyl.In addition, R ¹At the said substituting group that also can have on the substituting group more than 1.

N1 representes 0～4 integer, preferred 2～4.

N2 representes 1～5 integer, preferred 1～3.

R2 representes the substituting group shown in the formula (5).

Chemical formula 19

In the general formula (5), A representes to replace or unsubstituted aromatic ring; R ³And R ⁴Represent independently that respectively hydrogen atom, carbon number are 1～5 alkyl, the substituting group shown in the general formula (6); R ⁵Expression singly-bound or carbon number are 1～5 alkylidene; X representes to replace or unsubstituted aromatic ring; N3 representes 0～10 integer, and n3 is 2 when above, a plurality of R ⁵With X can be identical mutually also can be different.

A representes to replace or unsubstituted aromatic ring.Aromatic ring also can be for comprising heteroatomic heterocycles such as nitrogen-atoms, oxygen atom, sulphur atom.As the example of A, can enumerate 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.In addition, other 6 yuan of rings or 5 yuan of rings also can condensations.The preferred phenyl ring of A.As the substituting group that A can have, can enumerate halogen atom (for example fluorine atom, chlorine atom, bromine atoms, iodine atom etc.), alkyl, hydroxyl etc.

R ³And R ⁴Represent independently that respectively hydrogen atom or carbon number are 1～5 alkyl, the substituting group shown in the formula (6).R ³And R ⁴Preferred hydrogen atom, carbon number are 1～3 alkyl, the substituting group shown in the general formula (6), the more preferably substituting group shown in hydrogen atom, methyl, the general formula (6).

Chemical formula 20

R ⁶, R ⁷, R ⁸And R ⁹Represent independently that respectively hydrogen atom or carbon number are 1～5 alkyl.R ³And R ⁴Preferred hydrogen atom, carbon number are 1～3 alkyl, more preferably hydrogen atom, methyl.

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

N5 representes 1～11 integer, and is preferred 1～9, more preferably 1～7.

Said general formula (6) is preferably by shown in the formula (6 ').

Chemical formula 21

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

Said general formula (6) is preferably by shown in the formula (6 ").

Chemical formula 22

General formula (6 ") in, n4 representes 0～10 integer.

N4 representes 0～10 integer, and is preferred 0～8, more preferably 0～6.

In the general formula (5), R ⁵Expression singly-bound or carbon number are 1～5 alkylidene, can have substituting group.R ⁵Preferred carbon number is 1～4 alkylidene, and more preferably carbon number is 1～3 alkylidene.As R ⁵The substituting group that can have can be enumerated carbon number and be 1～5 alkyl (for example methyl, ethyl, isopropyl, the tert-butyl group), halogen atom (for example fluorine atom, chlorine atom, bromine atoms, iodine atom etc.), hydroxyl etc.

In the general formula (5), X representes to replace or unsubstituted aromatic ring.Aromatic ring can be for containing heteroatomic heterocycles such as nitrogen-atoms, oxygen atom, sulphur atom.As the example of X, can enumerate 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.In addition, also can other 6 yuan the ring or 5 yuan of cyclic condensations.The preferred phenyl ring of X.As the substituting group that X can have, identical with the example of enumerating as the substituting group of A.

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

Said general formula (5) is preferably by shown in the formula (5 ').

Chemical formula 23

In the general formula (5 '), R ³Expression hydrogen atom, carbon number are 1～5 alkyl or the substituting group shown in the said general formula (1-3); R ⁵Expression singly-bound or carbon number are 1～5 alkylidene; X representes to replace or unsubstituted aromatic ring; N3 representes 0～5 integer, and n3 is 2 when above, a plurality of R ⁵With X can be identical mutually also can be different.

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

Said general formula (5) is preferably by shown in the formula (5 ").

Chemical formula 24

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

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

Compound shown in the general formula (4) is preferably following mode: R ¹For hydrogen atom or carbon number are 1～5 alkyl, R ²Shown in general formula (5 "), n1 representes 2～4 integer, and n2 representes 1～3 integer, and n3 representes 0～2 integer.

Below, the object lesson of the compound shown in the expression 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 the general formula (4) is preferably 200～1200, and more preferably 250～1000, be preferably 300～800 especially.

Become problem if molecular weight less than 200, then spreads from the volatilization of film sometimes, if surpass 1200, then mist degree raises sometimes.

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

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

In addition, for make the different styrenated phenol of hydroxyl value can be in many places hydrogen bonding, also can be made as the potpourri that contains the compound shown in the different mutually general formulas more than 2 kinds (4).As an example, can enumerate the potpourri of the styrenated phenol that obtains with respect to phenol, 1～3 mole of styrene of alkylation, the styrenated phenol that further obtains at alkylating cinnamic phenyl position and the oligomer styrenated phenol that alkylation obtains on phenol about cinnamic 2～4 aggressiveness with alkylated styrene.

Compound shown in the general formula (4) can also can use commercially available article through in the phenol of 1 equivalent, synthesizing at the phenylethylene that adds more than 1 equivalent in the presence of the acid catalyst usually.In addition, also can directly use the potpourri that obtains by above-mentioned synthetic method.

(acyl modified phenolic varnish type phenolics)

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

Chemical formula 27

(in the general formula (I), R ₁The replacement or the unsubstituted alkyl carbonyl of expression formoxyl or carbon number 2～15, R ₂, R ₃, R ₄The alkyl of representing carbon number 1～4 respectively independently, m, n are represented the integer more than 0 respectively independently, but can not be 0 simultaneously.R ₁, R ₂, R ₃, R ₄Can distinguish during a plurality of the existence identical also can be different.)

Acyl modified phenolic varnish type phenolics (below be sometimes referred to as " novolaks based compound ") is represented by above-mentioned general formula (I).In the present invention, acyl modified be meant phenolic varnish type phenolics hydroxyl by acylated.As acyl group, the replacement or the unsubstituted alkyl carbonyl of preferred formoxyl, carbon number 2～15, wherein preferred especially acetyl group, propiono, bytyry, pivaloyl group.

Cellulose acylate film among the present invention can make against dispersiveness is big, mist degree is low, moisture permeability is low through containing the acyl modified phenolic varnish type phenolics shown in the general formula (I).

Acyl modified phenolic varnish type phenolics among the present invention need carry out acylated with the hydroxyl of phenolic varnish type phenolics, preferably with 50～100% acylated of this hydroxyl.As acylated rate more preferably 70～100%, further preferred 85～100%, preferred especially 90～100%.If this acylated rate is in above-mentioned scope, even can prevent also under hot and humid environment that then the film that has added the phenolic varnish type compound is colored as yellow.

As long as the acylated of the hydroxyl of phenolic varnish type phenolics can be with the hydroxyl acylated of phenolics, then not restriction of its manufacturing approach.When acetyl group, the method for routine that can be through using acetic anhydride method etc. is carried out.For example can be through phenolics is made with acetyl chloride or acetic anhydride reaction (japanese kokai publication hei 9-40608 number etc.) in the presence of alcohols and alkali metal hydroxide.

As the phenolic varnish type phenolics of the raw material of acylated, can be that phenol and aldehyde (formalin) react the common phenolic varnish type phenolics that obtains usually in the presence of acidic catalysts such as oxalic acid.As the raw material of this phenol, not special restriction for example can be used phenol, orthoresol, paracresol, metacresol, p-t-butyl phenol, nonyl phenol, octyl phenol etc. and their potpourri.In addition, as the raw material of aldehyde, can use formaldehyde, paraformaldehyde, acetaldehyde etc. and their potpourri.

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

Chemical formula 28

Chemical formula 29

< molar absorptivity >

Acyl modified phenolic varnish type phenolics among the present invention is that the absorbance of the 230nm～700nm wavelength coverage in the solution of 0.01g/L is below 0.05 in concentration preferably, more preferably below 0.03, further is preferably below 0.02.

If the absorbance in the 230nm of acyl modified phenolic varnish type phenolics～700nm wavelength coverage is above-mentioned scope; Then because the wavelength dispersion variation that the delay of acyl modified phenolic varnish type phenolics performance causes is little, so can obtain the cellulose acylate film that contrary dispersiveness is bigger, mist degree is lower, moisture permeability is lower.

Molar absorptivity can be through measuring regulation by commercially available spectrophotometer (for example the UV3150 of society of (strain) Hitachi system etc.) mass concentration solution absorbency and the absorbance that obtains measured divided by number-average molecular weight.

< number-average molecular weight >

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

< dispersion degree >

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

< addition >

The addition of acyl modified phenolic varnish type phenolics of the present invention preferably is made as 1～30 mass parts with respect to acylated cellulose 100 mass parts, more preferably is made as 2～25 mass parts, further preferably is made as 5～20 mass parts.If addition is below 30 mass parts, mist degree such advantage that do not rise is then arranged, if addition is more than 1 mass parts, then there is moisture permeability to reduce the big such advantage of effect.

In the present invention, acyl modified phenolic varnish type phenolics can cooperate separately, also can be also with more than 2 kinds.

(2-4) hydrophobing agent

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

(carbohydrate derivates is a plastifier)

As said hydrophobing agent, preferred monose or contain the derivant (below be called carbohydrate derivates be plastifier) of the carbohydrates of 2～10 monosaccharide units.

The said carbohydrate derivates of preferred formation is that the monose or the polysaccharide of plastifier is characterised in that can be substituted by substituted group (for example hydroxyl, carboxyl, amino, sulfydryl etc.) in the molecule.As replacing formed example of structure, can enumerate alkyl, aryl, acyl group etc.In addition, can enumerate and replace formed ether structure thus, hydroxyl replaced formed ester structure, replace formed amide structure or imide structure etc. by amino by acyl group.

As said monose or comprise the example of the carbohydrates of 2～10 monosaccharide units, for example can enumerate erythrose, threose, ribose, arabinose, wood sugar, lyxose, allose, altrose, glucose, fructose, mannose, gulose, idose, galactose, talose, trehalose, isotrehalose, neotrehalose, mycosamine, kojibiose, nigerose, maltose, maltitol, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, lactose, lactose amine, lactitol, 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; More preferably arabinose, wood sugar, glucose, fructose, mannose, galactose, maltose, cellobiose, sucrose, beta-schardinger dextrin-, gamma-cyclodextrin are preferably wood sugar, glucose, fructose, mannose, galactose, maltose, cellobiose, sucrose, xylitol, sorbierite especially.

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

Among them, more preferably alkyl, aryl or acyl group are preferably acyl group especially.

As said carbohydrate derivates is the preferred example of plastifier, can enumerate following material.The carbohydrate derivates that but, can use among the present invention be plastifier do not receive these limit.

Preferred wood sugar tetracetate; Alpha-glucose pentaacetate; The fructose pentaacetate; The mannose pentaacetate; The galactose pentaacetate; The maltose octaacetate; The cellobiose octaacetate; Sucrose octaacetate; The xylitol pentaacetate; Sorbitol hexaacetate; Wood sugar four propionic esters; Glucose five propionic esters; Fructose five propionic esters; Mannose five propionic esters; Galactose five propionic esters; Maltose eight propionic esters; Cellobiose eight propionic esters; Sucrose eight propionic esters; Xylitol five propionic esters; Sorbierite six propionic esters; Wood sugar four butyric esters; Glucose five butyric esters; Fructose five butyric esters; Mannose five butyric esters; Galactose five butyric esters; Maltose eight butyric esters; Cellobiose eight butyric esters; Sucrose eight butyric esters; Xylitol five butyric esters; Sorbierite six butyric esters; Wood sugar four benzoic ethers; Glucose pentaphene formic ether; Fructose pentaphene formic ether; Mannose pentaphene formic ether; Galactose pentaphene formic ether; Maltose eight benzoic ethers; Cellobiose eight benzoic ethers; Sucrose eight benzoic ethers; Xylitol pentaphene formic ether; Sorbierite six benzoic ethers etc.More preferably wood sugar tetracetate; Alpha-glucose pentaacetate; The fructose pentaacetate; The mannose pentaacetate; The galactose pentaacetate; The maltose octaacetate; The cellobiose octaacetate; Sucrose octaacetate; The xylitol pentaacetate; Sorbitol hexaacetate; Wood sugar four propionic esters; Glucose five propionic esters; Fructose five propionic esters; Mannose five propionic esters; Galactose five propionic esters; Maltose eight propionic esters; Cellobiose eight propionic esters; Sucrose eight propionic esters; Xylitol five propionic esters; Sorbierite six propionic esters; Wood sugar four benzoic ethers; Glucose pentaphene formic ether; Fructose pentaphene formic ether; Mannose pentaphene formic ether; Galactose pentaphene formic ether; Maltose eight benzoic ethers; Cellobiose eight benzoic ethers; Sucrose eight benzoic ethers; Xylitol pentaphene formic ether; Sorbierite six benzoic ethers etc.Preferred especially maltose octaacetate; The cellobiose octaacetate; Sucrose octaacetate; Wood sugar four propionic esters; Glucose five propionic esters; Fructose five propionic esters; Mannose five propionic esters; Galactose five propionic esters; Maltose eight propionic esters; Cellobiose eight propionic esters; Sucrose eight propionic esters; Wood sugar four benzoic ethers; Glucose pentaphene formic ether; Fructose pentaphene formic ether; Mannose pentaphene formic ether; Galactose pentaphene formic ether; Maltose eight benzoic ethers; Cellobiose eight benzoic ethers; Sucrose eight benzoic ethers; Xylitol pentaphene formic ether; Sorbierite six benzoic ethers etc.

Said carbohydrate derivates is that hydrophobing agent preferably has pyranose structure or furanose structure.

As carbohydrate derivates used in the present invention, preferred especially below shown in compound.But the carbohydrate derivates that can use among the present invention is not limited to this.In addition, in the following structural formula, R representes hydrogen atom or substituting group arbitrarily respectively independently, and a plurality of R can be identical, also can be different.In following structure, substituting group 1,2 is represented R arbitrarily respectively.In addition, degree of substitution representes that R is with the number shown in this substituting group." nothing " expression R is a hydrogen atom.

Chemical formula 31

Chemical formula 32

Chemical formula 33

Chemical formula 34

(preparation method)

Preparation method as said carbohydrate derivates; Can be used as commercially available article and change into the product of system, the acquisitions such as product of Aldrich system from (strain) Tokyo, maybe can come synthetic through commercially available carbohydrates being carried out known ester derivant method (method of for example putting down in writing in the japanese kokai publication hei 8-245678 communique).

As said carbohydrate derivates is the preparation method of plastifier; Can be used as commercially available article and change into the product of system, the acquisitions such as product of Aldrich system from (strain) Tokyo, maybe can come synthetic through commercially available carbohydrates being carried out known ester derivant method (method of for example putting down in writing in the japanese kokai publication hei 8-245678 communique).

Hydrophobing agent of the present invention is preferably 1～30 quality % with respect to the resin (resin of major component is meant the resin that contains the quality ratio maximum in the contained resin of polaroid protective film) of the major component that constitutes polaroid protective film.If be more than the 1 quality %, then obtain polarizer permanance improved effect easily, in addition,, then when making polaroid protective film, be difficult to ooze out or seepage if be below the 30 quality %.The content of said hydrophobing agent is preferably 5～20 quality %, is preferably 5～15 quality % especially.

[manufacturing approach of polaroid]

Below, about the manufacturing approach of polaroid of the present invention, describe with the order of the functionalization of the laminating method of manufacturing approach, polaroid protective film and the polarizer of the manufacturing approach of polaroid protective film, the polarizer, polaroid.

< manufacturing approach of polaroid protective film >

Said 60 ℃, relative humidity 95%, through the time moisture permeability when handling 24 hours be 500g/m ²More than and 2000g/m ²Following polaroid protective film can pass through the solution casting manufactured.Below, for said 60 ℃, relative humidity 95%, through the time moisture permeability when handling 24 hours be 500g/m ²More than and 2000g/m ²Below the manufacturing approach of polaroid protective film, describe as example as the mode of base material to use acylated cellulose, contain said organic acid polaroid protective film but also can make equally when using other resin.In solution casting method, use and in organic solvent, be dissolved with the big solution of acylated cellobiose (dope) manufacturing film.

Said organic solvent comprises preferably that to be selected from carbon number be that 3～12 ether, carbon number are that 3～12 ketone, carbon number are that 3～12 ester and carbon number are the solvent in 1～6 the halogenated hydrocarbon.

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

At said carbon number is in the example of 3～12 ethers, comprises diisopropyl ether, dimethoxymethane, dimethoxy-ethane, 1,4-diox, 1,3-dioxolane, tetrahydrofuran, anisole and phenetol.

At said carbon number is in the example of 3～12 ketone, comprises acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methyl cyclohexanone.

At said carbon number is in the example of 3～12 ester class, comprises ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate and pentyl acetate.

In addition, have in the representative examples of organic of the functional group more than 2 kinds, comprise acetate 2-ethoxy ethyl ester, 2-methyl cellosolve and butoxy ethanol.

Carbon number be the carbon number of 1～6 halogenated hydrocarbon for being preferably 1 or 2, most preferably be 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 moles of %, and more preferably 30～70 moles of % further are preferably 35～65 moles of %, are preferably 40～60 moles of % especially.Methylene chloride is representational halogenated hydrocarbon.

In addition, also can mix the organic solvent that uses 2 kinds above.

Acylated cellobiose cellulose solution (dope) can be through carrying out the method preparation of the routine that processed steps constitutes under the temperature more than 0 ℃ (normal temperature or high temperature).The preparation of acylated cellobiose cellulose solution can use the preparation method of the dope in the common solution casting method and device to implement.In addition, when the method for routine, preferably use halogenated hydrocarbon (particularly methylene chloride) as organic solvent.

The amount of the acylated cellulose in the acylated cellobiose cellulose solution is adjusted into and in resulting solution, contains 10～40 quality %.The amount of acylated cellulose is more preferably 10～30 quality %.The adjuvant of stating after also can adding in advance in the organic solvent (main solvent) arbitrarily.

The acylated cellobiose cellulose solution can prepare through stirring acylated cellulose and organic solvent down at normal temperature (0～40 ℃).The solution of high concentration also can stir under pressurization and heating condition.Particularly, acylated cellulose and organic solvent are added in the pressurizing vessel airtight, heating while stirring more than the boiling point that adds the normal temperature of depressing solvent and under the temperature of the solvent scope of not seething with excitement.Heating-up temperature is generally more than 40 ℃, is preferably 60～200 ℃, more preferably 80～110 ℃.

Also can in advance the thick mixing of each composition be added in the container then.In addition, can drop in the container in order.Container need constitute with the mode that can stir.Can nitrogen injection etc. inactive gas pressurize to container.In addition, also can utilize the rising of the vapor pressure of the solvent that causes by heating.Perhaps, also can under pressure, add each composition after container is airtight.

When heating, preferably from the external heating of container.For example can use the heating arrangement of chuck tubular type.In addition, also can be through at the outer setting heating plate of container, make the liquid circulation and heating container is whole via pipe arrangement.

Stir and preferably paddle is set, use paddle to carry out at internal tank.Paddle preferably has near the length the arrival chamber wall.In order to upgrade the liquid film of chamber wall, terminal preferred setting of paddle scraped oar.

In container, also gauging instrument classes such as pressure gauge, thermometer can be set.In container, each composition is dissolved in solvent.Take out from container the dope cooling back for preparing, and perhaps takes out the back and use coolings such as heat exchanger.

Also can pass through the hot-cold lysis method, preparation acylated cellobiose cellulose solution.About the detailed content of hot-cold lysis method, can use the technology of putting down in writing in (0115)～(0122) of TOHKEMY 2007-86748 communique.

From the acylated cellobiose cellulose solution (dope) of preparation, through solution casting manufactured cellulose acylate film.The preferred interpolation postpones to realize agent in dope.Dope is at cylinder or be with curtain coating, makes solvent evaporation and forms film.Dope before the curtain coating is that 18～35% mode is adjusted concentration with the solid constituent amount preferably.The surface of cylinder or band preferably is processed as mirror status in advance.Dope preferably is the cylinder below 10 ℃ or is with curtain coating in surface temperature.

About the drying means in the solution casting method, on the books in each communique of each instructions of No. the 736892nd, No. the 640731st, each instructions, the BrP of No. the 2739070th, No. the 2336310th, United States Patent (USP), No. the 2367603rd, United States Patent (USP), No. the 2492078th, United States Patent (USP), No. the 2492977th, United States Patent (USP), No. the 2492978th, United States Patent (USP), No. the 2607704th, United States Patent (USP), No. the 2739069th, United States Patent (USP) and United States Patent (USP) and BrP and special public clear 45-4554 number of Japan, special public clear 49-5614 number of Japan, japanese kokai publication sho 60-176834 number, japanese kokai publication sho 60-203430 number and japanese kokai publication sho 62-115035 number.Drying on band or cylinder can be carried out through sending into inactive gass such as air, nitrogen.

In addition, also can be with the film that obtains from cylinder or be with and peel off, carry out drying with the high temperature wind that changes temperature to 100 ℃～160 ℃ gradually again, make evaporate residual solvent.Above method is on the books in the special fair 5-17844 communique of Japan.If according to this method, then can shorten from curtain coating to the time of peeling off.In order to implement this method, make the dope gelation under the cylinder that need be when curtain coating or the surface temperature of band.

The curtain coating that also can use the acylated cellobiose cellulose solution (dope) of preparation to carry out more than 2 layers is come filmization.At this moment, preferably make cellulose acylate film through solution casting method.Dope is at cylinder or be with curtain coating, makes solvent evaporation form film.Dope before the curtain coating is that the mode of the scope of 10～40 quality % is adjusted concentration with the solid constituent amount preferably.The surface of cylinder or band preferably is processed as mirror status in advance.

When a plurality of acylated cellobiose cellulose solution of curtain coating more than 2 layers; Can a plurality of acylated cellobiose cellulose solutions of curtain coating; Make the solution casting that contains acylated cellulose respectively from a plurality of curtain coating mouths in the travel direction devices spaced apart setting of supporter, the limit makes its range upon range of limit make film.These for example can use the method for putting down in writing in each communique of japanese kokai publication sho 61-158414 number, japanese kokai publication hei 1-122419 number and japanese kokai publication hei 11-198285 number.In addition, also can carry out membranization through from 2 curtain coating mouth curtain coating acylated cellobiose cellulose solutions.The method of putting down in writing in each communique of this for example can use Japan special public clear 60-27562 number, japanese kokai publication sho 61-94724 number, japanese kokai publication sho 61-947245 number, japanese kokai publication sho 61-104813 number, japanese kokai publication sho 61-158413 number and japanese kokai publication hei 6-134933 number.And, also can use the casting method of putting down in writing in the japanese kokai publication sho 56-162617 communique that the flow of high viscosity acylated cellobiose cellulose solution is wrapped up the cellulose acylate film of the acylated cellobiose cellulose solution of also extruding this high and low viscosity simultaneously by low viscous acylated cellobiose cellulose solution.

In addition, also can will peel off through the film that the first curtain coating mouth is formed on the supporter through using 2 curtain coating mouths, with support the dignity side of joining and carry out second curtain coating, thereby make film.For example, can enumerate the method for putting down in writing in the special public clear 44-20235 communique of Japan.

The acylated cellobiose cellulose solution of curtain coating can use same solution, also can use acylated cellobiose cellulose solutions different more than 2 kinds.In order to give a plurality of acylated cellulose layer functions, will extrude acylated cellobiose cellulose solution that should function from each curtain coating mouth and get final product.And, acylated cellobiose cellulose solution of the present invention also can with other functional layer (for example adhesion layer, dye coating, antistatic backing, antihalation layer, UV-absorbing layer, polarization layer etc.) curtain coating simultaneously.

(interpolation of polarizer permanance modifying agent)

Manufacturing approach as polaroid of the present invention; Preferably include: in the said polaroid protective film at least 1 operation of using combinations thing system film, said composition comprise resin and with respect to these resin 100 mass parts be 0.1～20 mass parts the said organic acid as polarizer permanance modifying agent, the particular polymers shown in the general formula (1), and general formula (4) shown in compound at least a kind.With respect to acylated cellobiose cellulose solution as the resin raw material of polaroid protective film; Add at least a kind opportunity in the compound shown in particular polymers shown in said organic acid, the general formula (1) and the general formula (4), as long as during the system film, add just not special the qualification.For example can between the synthesis phase of acylated cellulose, add, also can when dope prepares, mix with acylated cellulose.

(interpolation of ultraviolet light absorber)

In the acylated cellobiose cellulose solution,, also can add preferred use ultraviolet light absorber among the present invention from preventing the viewpoint of deteriorations such as polaroid or liquid crystal.As ultraviolet light absorber, be the viewpoint of the liquid crystal expressivity that ultraviolet absorption below the 370nm can be excellent and good from wavelength, preferably use wavelength to be the few ultraviolet light absorber of the absorption of visible light more than the 400nm.The object lesson of the ultraviolet light absorber that preferably uses as the present invention for example can be enumerated 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, can enumerate 2, (3-(3 for 6-di-t-butyl-paracresol, pentaerythrite-four; The 5-di-tert-butyl-hydroxy phenyl) propionic ester), N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide), 1; 3,5-trimethyl-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-isocyanates etc.As the example of benzotriazole based compound, can enumerate 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2, (4-(1 for the 2-di-2-ethylhexylphosphine oxide; 1,3,3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol), (2; 4-pair-(n-octyl sulfo-)-6-(4-hydroxyl-3,5-di-tert-butyl amido)-1,3; 5-triazine, triethylene glycol-two (3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester), N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide), 1; 3,5-trimethyl-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 2 (2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole, (2 (2 '-hydroxyls-3 '; 5 '-di-tert-pentyl-phenyl)-and 5-chlorobenzotriazole, 2,6-di-t-butyl-paracresol, pentaerythrite-four (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester) etc.These ultraviolet rays prevent that the addition of agent is preferably 0.1 mass parts～10.0 mass parts with respect to blooming 100 mass parts.

(interpolation of other adjuvant)

In polaroid protective film, also can add anti-deterioration agent (for example anti-oxidant, peroxide decomposer, free radical inhibitors, metal passivator, sour trapping agent, amine etc.).About anti-deterioration agent, on the books in each communique of japanese kokai publication hei 3-199201 number, japanese kokai publication hei 5-1907073 number, japanese kokai publication hei 5-194789 number, japanese kokai publication hei 5-271471 number, japanese kokai publication hei 6-107854 number.In addition, the addition of said anti-deterioration agent is preferably 0.01～1 quality % of the solution of preparation (dope), more preferably 0.01～0.2 quality %.If addition is more than the 0.01 quality %, so then because can to give full play to the effect of anti-deterioration agent preferred, if addition is below the 1 quality %, then owing to be difficult to produce anti-deterioration agent to the oozing out of the surface of film (bleed out) etc., so preferred.As the example of preferred especially anti-deterioration agent, can enumerate Yoshinox BHT (BHT), tribenzyl amine (TBA).

In addition, in polaroid protective film, preferably add particulate as matting agent.As particulate used in the present invention, can enumerate silicon dioxide, titania, aluminium oxide, zirconia, lime carbonate, talcum, clay, calcined kaolin, calcining calcium silicate, afwillite, alumina silicate, magnesium silicate and calcium phosphate.Consider that from the low aspect of mist degree preferred particulate is the particulate that contains silicon, preferred especially silicon dioxide.Preferred 1 mean grain size of the particulate of silicon dioxide is below the 20nm, and apparent specific gravity is more than 70g/ rises.More than the preferred 90～200g/ of apparent specific gravity rises, more than more preferably 100～200g/ rises.Apparent specific gravity is big more, then can make the dispersion liquid of high concentration more, and mist degree, agglutinator optimization, so preferred.

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

The particulate of silicon dioxide for example can use Aerosil R972, R972V, R974, R812,200,200V, 300, R202, OX50, TT600 commercially available article such as (the above Japanese Aerosil (strain) of being systems).Zirconic particulate for example can use the commercially available particulate of ProductName with Aerosil R976 and R811 (above is Japanese Aerosil (strain) system).

In them; Aerosil 200V, Aerosil R972V are that 1 mean grain size is below the 20nm and apparent specific gravity is the particulate that 70g/ rises above silicon dioxide; Because it is lower that the mist degree of blooming keeps, and the effect of reduction friction factor is big, so preferred especially.

In order to obtain having the polaroid protective film of the little particle of 2 mean grain sizes, when the dispersion liquid of preparation particulate, can consider the whole bag of tricks among the present invention.Following method is for example arranged: preparation in advance mixes the particle dispersion liquid of solvent and particulate, in a spot of acylated cellobiose cellulose solution of preparing in addition, adds this particle dispersion liquid, and stirring and dissolving is mixed with main acylated cellobiose cellulose solution (dope liquid) again.This method good dispersion, the silicon dioxide microparticle of silicon dioxide microparticle be difficult to further aggegation again aspect be preferred manufacturing procedure.In addition; Also have in solvent, to add a spot of cellulose esters, after the stirring and dissolving, add particulate therein and disperse by dispersion machine; With it as the particulate annex solution, with this particulate annex solution by line mixer (In-line mixer) and the well-mixed method of dope liquid.The present invention is not limited to these methods, but silicon dioxide microparticle is mixed preferred 5～30 quality % of concentration of silicon dioxide when disperseing, more preferably 10～25 quality %, most preferably 15～20 quality % with solvent etc.Owing to disperse concentration Gao Ze low with respect to the liquid mist degree of addition, so mist degree, agglutinator optimization are preferred.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.

Employed solvent is preferably enumerated methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols etc. as lower alcohols.Do not limit as the solvent beyond the lower alcohol is special, but employed solvent when preferably using the system film of cellulose esters.

Operation till drying can also can be under inactive gas atmosphere such as nitrogen under air atmosphere to the back from curtain coating for these.The coiling machine that uses in the manufacturing of the polaroid protective film among the present invention is that common employed coiling machine gets final product, and can be batched by permanent tensammetry, permanent torque method, tapering tensammetry, the constant method for coiling such as program Tension Control method of internal stress.

(stretch processing)

Also can carry out stretch processing to said polaroid protective film.Can give required delay to polaroid protective film through stretch processing.The draw direction of cellulose acylate film is preferably any direction in Width, the length direction.

In the method that Width stretches, for example be recorded in japanese kokai publication sho 62-115035 number, japanese kokai publication hei 4-152125 number, japanese kokai publication hei 4-284211 number, japanese kokai publication hei 4-298310 number, japanese kokai publication hei 11-48271 number etc. in each communique.

Being stretching under the heating condition of film implemented.Film can stretch through the processing in the drying, is effective especially when solvent is remaining.When length direction stretches, make the peeling rate of the coiling speed of film if for example regulate the speed of the carrying roller of film greater than film, then film is stretched.When Width stretched, the width of slowly expanding stenter through kept the width edge of film to carry by the stenter limit also can oriented film.Behind film drying, also can use drawing machine stretch the uniaxial tension of long drawing machine (preferred use).

The vitrifacation transition temperature Tg of said polaroid protective film is preferably used in the stretching of said polaroid protective film, under the temperature of (Tg-5 ℃)～(Tg+40 ℃), carries out, and more preferably Tg～(Tg+35 ℃) is preferably (Tg+10 ℃)～(Tg+30 ℃) especially.During dry film, preferred 130 ℃～200 ℃.

In addition, when after curtain coating, stretching, can under the temperature lower, stretch than dry film with the remaining state of dope solvent, at this moment, preferred 100 ℃～170 ℃.

The stretching ratio of said polaroid protective film (with respect to the length growth rate of the film before stretching) is preferred 1%～200%, and more preferably 5%～150%.Particularly preferably stretch with 1%～200% at Width, more preferably 5%～150%, be preferably 30～45% especially.

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

In addition, said polaroid protective film is preferably after being stretched to the maximum tension multiplying power, through keeping the operation (following be also referred to as sometimes " mitigation operation ") of certain hour with the stretching ratio that is lower than the maximum tension multiplying power and making.Relax 50%～99% of the preferred maximum tension multiplying power of stretching ratio in the operation, more preferably 70%～97%, most preferably 90%～95%.In addition, relax preferred 1 second～120 seconds of the time of operation, more preferably 5 seconds～100 seconds.

And said polaroid protective film can make the contraction process of its contraction and manufacturing well in Width clamping film side through comprising the limit.

At the stretching process that stretches with the Width that is included in film, to make the contraction process of its contraction in the carrying direction (length direction) of film be in the manufacturing approach of characteristic; Can keep through the stenter of bow collector (Pantograph) formula or linear electric machine formula; The limit slowly dwindles the interval of folder on the carrying direction on the Width stretching limit of film, film is shunk.

The method of said explanation can be carried out at least a portion in stretching process and the contraction process simultaneously.

In addition; As the stretching device that specifically carries out stretching process; Can hope to use the FITZ machine of city metal working industry society system etc.; In the said stretching process length direction of the film of above-mentioned that kind or any direction in the Width are stretched, and another direction is shunk, the thickness of film is increased.About this device, be recorded in (TOHKEMY 2001-38802 communique).

As stretching ratio in the stretching process and the shrinkage factor in the contraction process; Can be according to value as the delay Rth of delay Re in the face of target and thickness direction; Select suitable value arbitrarily; But the stretching ratio of preferred stretching process is more than 10%, and the shrinkage factor in the contraction process is located at more than 5%.

The Width that is preferably included in film especially stretch 10% or more stretching process and make the contraction process of carrying direction contraction more than 5% of film in the Width limit clamping film side of film.

Wherein, said shrinkage factor is meant length that the film after the contraction the shrinks meaning with respect to the ratio of the length of the perisystolic film in the shrinkage direction among the present invention.

As shrinkage factor preferred 5～40%, preferred especially 10～30%.

(saponification processing)

Said polaroid protective film is given the adaptation with the material of the such polarizer of polyvinyl alcohol (PVA) through carrying out the alkali soap processing, can use as polaroid protective film.

About the method for saponification, the method that can use (0211) and (0212) of TOHKEMY 2007-86748 communique to be put down in writing.

For example preferably carry out to neutralize, to wash also dry circulation by acid solution behind the dipping film surface in aqueous slkali for the alkali soap processing of said polaroid protective film.As said aqueous slkali, can enumerate potassium hydroxide solution, sodium hydroxide solution, the concentration of hydroxide ion is preferably in the scope of 0.1～5.0mol/L, more preferably in the scope of 0.5～4.0mol/L.The aqueous slkali temperature is the scope in room temperature～90 ℃ preferably, more preferably 40～70 ℃ scope.

Also can replace the alkali soap processing, implement the easy adhesion processing of being put down in writing like japanese kokai publication hei 6-94915 communique, japanese kokai publication hei 6-118232 communique.

< manufacturing approach of the polarizer >

As the manufacturing approach of the said polarizer in the manufacturing approach of polaroid of the present invention, not special restriction, but for example preferably with after the said PVA membranization, import dichroic molecules and constitute the polarizer.The manufacturing of PVA film can be logined No. 3342516 instructions, japanese kokai publication hei 09-328593 communique, TOHKEMY 2001-302817 communique, TOHKEMY 2002-144401 communique etc. with reference to method, the Jap.P. of record in (0213)～(0237) of TOHKEMY 2007-86748 communique and carried out.

Particularly, be that preparation section, curtain coating operation, swelling operation, dyeing process, dura mater operation, the stretching process of resin solution, the order of drying process are carried out the manufacturing approach of the said polarizer successively especially preferably with record PVA.In addition, also can be in described operation or online planar inspection operation is set afterwards.

(PVA is the preparation of resin solution)

At said PVA is in the preparation section of resin solution, and preferred for preparation is with the PVA stoste that to be resin dissolves obtain in water or organic solvent.The concentration of the polyvinyl alcohol resin in the stoste is preferably 5～20 quality %.For example preferred following method: the wet cake of PVA is put into dissolving tank, add plastifier, water as required, the limit blasts the water vapor limit from bottom land and stirs.The internal resin temperature preferably is warmed to 50～150 ℃, also can give pressurization in the system.

In addition, can in the said polarizer, not add acid, also can add acid, but when adding, preferably in this operation, add.In addition, when in the polarizer, adding acid, also can use the said organic acid identical acid contained with said polaroid protective film.

(curtain coating)

Said curtain coating operation is usually preferred, and to use PVA with above-mentioned preparation be resin solution stoste curtain coating and the method for film forming.As the method for curtain coating, not special restriction is supplied with double screw extrusion machine but the said PVA that preferably will heat is a resin solution stoste, to supporter, makes film from deliverying unit (preferred mold, more preferably T type slit die) hydrostomia through gear-type pump.In addition, about the not special restriction of temperature of the resin solution of discharging from mould.

As said supporter, preferred curtain coating cylinder, about diameter, width, rotating speed, the surface temperature of cylinder, not special restriction.

Then, preferably make the inside of resulting reel and Surface Edge alternately pass through dryer roll, drying is carried out on the limit.

(swelling)

Said swelling operation is preferably only undertaken by water; But such as japanese kokai publication hei 10-153709 communique record; For the stabilization of optical property with avoid the polaroid base material generation fold on the production line; Also can make polaroid base material swelling, the swellbility of managing the polaroid base material through boric acid aqueous solution.

In addition, though the temperature of swelling operation, time can be set arbitrarily preferred 10 ℃～60 ℃, 5 seconds～2000 seconds.

In addition, when the swelling operation, also can carry out a little and stretch, for example preferably be stretched to the mode about 1.3 times.

(dyeing)

Said dyeing process can use the method for putting down in writing in the TOHKEMY 2002-86554 communique.In addition, not only dipping can be, arbitrary method such as the coating of iodine or dye solution or spraying can also be as colouring method.In addition, also can such as TOHKEMY 2002-290025 communique record, use concentration, the dye bath temperature of iodine, the stretching ratio in bathing and limit to stir the method that body lotion limit in bathing makes its dyeing.

During as dichroic molecules, in order to obtain the polaroid of high-contrast, dyeing process preferably uses iodine is dissolved in the solution that obtains in the potassium iodide aqueous solution at the iodide ion that uses high order.Can use the mode of putting down in writing in the TOHKEMY 2007-086748 communique about the iodine of the IKI WS at this moment and the mass ratio of potassium iodide.

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

(dura mater)

Said dura mater operation preferably in cross-linking agent solution, is flooded or coating solution makes it contain crosslinking chemical.In addition, also can such as japanese kokai publication hei 11-52130 communique record, the dura mater operation is divided into carries out for several times.

As said crosslinking chemical; Can use the U.S. to re-issue the crosslinking chemical of putting down in writing in No. 232897 instructions of patent, such as No. 3357109 instructions of Jap.P. record, in order to improve dimensional stability; Also can use polyaldehyde as crosslinking chemical, but most preferably use the boric acid class.When the crosslinking chemical that uses boric acid to use in as the dura mater operation, can in boric acid-potassium iodide aqueous solution, add metallic ion.As the preferred zinc chloride of metallic ion, but also can such as TOHKEMY 2000-35512 communique record, replace zinc chloride, and use zinc salts such as zinc halide, zinc sulfate, zinc acetate such as zinc iodide.

In addition, can make the boric acid-potassium iodide aqueous solution that is added with zinc chloride, make its dipping PVA film carry out dura mater, can use the method for putting down in writing in the TOHKEMY 2007-086748 communique.

In addition, wherein, both can carry out dip treating, also can not carry out this processing by known acid solution as the raising permanance method under the hot environment.As said processing, can enumerate the method for record in TOHKEMY 2001-83329 communique, japanese kokai publication hei 6-254958 communique, the International Publication WO2006/095815 communique etc. by acid solution.

(stretching)

Said stretching process can preferably use as No. 2454515 instructionss of United States Patent (USP) etc. the stenter mode of that kind put down in writing of vertical uniaxial tension mode or the TOHKEMY 2002-86554 communique putting down in writing.Preferred stretching ratio is 2 times～12 times, more preferably 3 times～10 times.In addition; The relation that also can preferably carry out stretching ratio, raw thickness and polarizer thickness is made as (the polarizer thickness/raw material thickness after diaphragm is fitted) * (total stretching ratio)＞0.17 of putting down in writing in the TOHKEMY 2002-040256 communique, and the relation of the polarizer width the when width of the polarizer that maybe will be when final bath is come out is fitted with diaphragm is made as 0.80≤(width of the polarizer of the polarizer width during the diaphragm applying/when final bath is come out)≤0.95 of putting down in writing the TOHKEMY 2002-040247 communique.

(drying)

Said drying process can use known method in TOHKEMY 2002-86554 communique, but preferred range is 30 ℃～100 ℃, and be 30 seconds～60 minutes preferred drying time.In addition; Also can preferably carry out such as Jap.P. login No. 3148513 instructions record; Carry out the temperature of fading in the water is made as the thermal treatment more than 50 ℃; Perhaps such as japanese kokai publication hei 07-325215 communique or japanese kokai publication hei 07-325218 communique record, under the atmosphere of temperature and humidity management, wear out.

Preferably through such operation, making thickness is the polarizer of 10～200 μ m.In addition, the control of thickness can be through known method control, for example can control through the mould slit width in the said curtain coating operation or stretching condition are set at suitable value.

< laminating method of the polarizer and polaroid protective film >

The manufacturing approach of polaroid of the present invention is 2 polaroid protective films of laminated on the two sides of the above-mentioned said polarizer that obtains.In addition, preferably as stated, a slice in the employed polaroid protective film of polaroid of the present invention be said 60 ℃, relative humidity 95%, through the time moisture permeability when handling 24 hours be 500g/m ²More than and 2000g/m ²Following diaphragm, another sheet does not satisfy said characteristic.

In the manufacturing approach of polaroid of the present invention; Preferably through polaroid protective film is carried out alkali treatment, use the complete saponified polyvinyl alcohol WS that it is fitted in and polyvinyl alcohol film is flooded the method that stretches and make on the two sides of the polarizer that obtains make in iodine solution.

As being used to the fit treated side of said polaroid protective film and the adhesive of the polarizer, for example can enumerate ethene base system latexes such as polyethenol series adhesives such as polyvinyl alcohol (PVA), polyvinyl butyral or butyl acrylate etc.

The polaroid protective film of polaroid of the present invention is preferably fitted with the parallel in fact mode of the slow axis of said polaroid protective film with the axis of homology of the polarizer to the applying method of the said polarizer.

Wherein, parallel in fact be meant said 60 ℃, relative humidity 95%, through the time moisture permeability when handling 24 hours be 500g/m ²More than and 2000g/m ²Below the deviation of direction of the axis of homology of direction and polaroid of principal refractive index nx of polaroid protective film be in 5 °, be preferably in 1 °, more preferably in 0.5 °.If deviation is in 1 °, then the degree of polarization performance under the polaroid Nicol crossed is difficult to reduce, and leaks thereby be difficult to take place light, so preferred.

< functionalization of polaroid >

Polaroid of the present invention also can be preferably used as antireflection film, the brightness enhancement film of the observability that is used to improve display or the functionalization polaroid that is 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, the antiglare layer that is used for functionalization; Record in (0257)～(0276) of TOHKEMY 2007-86748 communique can be made the polaroid of functionalization according to these records.

(3-1) antireflection film

Polaroid of the present invention can use with the antireflection film combination.Antireflection film can use and only give the individual layer fluorine is that raw-material reflectivity of low-refraction such as condensate are that the reflectivity of about 1.5% film or the multi-coated interference that has utilized film is any in the film below 1%.In the present invention, the preferred use in the transparent supporting body laminated has low-index layer and has the formation than the layer (that is, high refractive index layer, middle index layer) of one deck at least of the refractive index of low-refraction floor height.In addition, also can preferably use day eastern skill newspaper, vol.38, No.1, May, 2000,26 pages～28 pages antireflection films of being put down in writing with TOHKEMY 2002-301783 communique etc.

Relation below the refractive index of each layer satisfies.

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

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

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

As said fluorochemicals, for example can preferably use the compound of record in japanese kokai publication hei 9-222503 communique [0018]～[0026], japanese kokai publication hei 11-38202 communique [0019]～[0030], TOHKEMY 2001-40284 communique [0027]～[0028], the TOHKEMY 2000-284102 communique etc.

Saidly contain the compound that silicone compounds preferably has polysiloxane structure, but (the Silaplane (Chisso (strain) system) or contain polysiloxane (japanese kokai publication hei 11-258403 communique) of silanol base etc. at two ends for example that also can use reactive silicone.Make organometallics and specific fluorine-containing silane coupling agent curing (the japanese kokai publication sho 58-142958 communiques that contain alkyl such as silane coupling agent down through condensation reaction in catalyzer coexistence; Japanese kokai publication sho 58-147483 communique; Japanese kokai publication sho 58-147484 communique; Japanese kokai publication hei 9-157582 communique; Japanese kokai publication hei 11-106704 communique; TOHKEMY 2000-117902 communique; TOHKEMY 2001-48590 communique; The compound of TOHKEMY 2002-53804 communique record etc.).

In low-index layer, also can preferably make it contain filling agent (for example silicon dioxide (Silica), fluorine-containing particle primary particle mean grain sizes such as (magnesium fluoride, calcium fluoride, barium fluorides) are the organic fine particles of record in the low-refraction mineral compound of 1～150nm, [0020] of japanese kokai publication hei 11-3820 communique～[0038] etc.), silane coupling agent, lubricant, surfactant etc. as the adjuvant beyond above-mentioned.

Said low-index layer also can pass through vapor phase method (vacuum vapour deposition, sputtering method, ion plating method, plasma CVD method etc.) and form, but considers from the viewpoint that can make at an easy rate, is preferably formed by rubbing method.As rubbing method, can preferably use dip coating, airblade coating method, curtain coating method, rolling method, coiling rod rubbing method, gravure rubbing method, little gravure rubbing method.

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

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

Such ultra micron can use as follows: particle surface is handled (silane coupling agent etc.: japanese kokai publication hei 11-295503 communique through surface conditioning agent; Japanese kokai publication hei 11-153703 communique; TOHKEMY 2000-9908 communique; Anionic property compound or organic metal coupling agent: TOHKEMY 2001-310432 communique etc.); Or with the core shell structure (TOHKEMY 2001-166104 communique etc.) of high index of refraction particle as core; And with particular dispersing agent (japanese kokai publication hei 11-153703 communique for example; United States Patent (USP) 6210858B1 instructions; TOHKEMY 2002-2776069 communique etc.) etc.

Use material as said matrix; Can use existing known thermoplastic resin, curable resin epithelium etc., but also can use the curable film that obtains by the metal alkoxide compositions of putting down in writing in multi-functional material of putting down in writing in TOHKEMY 2000-47004 communique, TOHKEMY 2001-315242 communique, TOHKEMY 2001-31871 communique, the TOHKEMY 2001-296401 communique etc. or the TOHKEMY 2001-293818 communique etc.

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

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

The mist degree of said antireflection film is preferably below 5%, more preferably below 3%.In addition, the intensity of film is preferably more than the H in the pencil hardness test according to JISK5400, more preferably more than the 2H, most preferably is more than the 3H.

(3-2) brightness enhancement film

Polaroid of the present invention can use with the brightness enhancement film combination.Brightness enhancement film has the separation function of circularly polarized light or rectilinearly polarized light, is configured between polaroid and the backlight, at backreflection of backlight side or backward scattering one side's circularly polarized light or rectilinearly polarized light.Reflected light again from backlight portion partly changes polarized light state, reentering when being mapped in brightness enhancement film and the polaroid, and the part transmission, therefore through repeating this process, light utilization efficiency improves, and front face brightness is brought up to about 1.4 times.As brightness enhancement film is known anisotropic emission mode and anisotropic scattering mode arranged, all can with polaroid combination of the present invention.

In the anisotropic emission mode; Known laminate multilayer monadic stretching membrane and unstretching film; Have the anisotropic brightness enhancement film of reflectivity and transmissivity, known multilayer film mode (each instructions record of No. 95/17691 pamphlet of International Publication, No. 95/17692 pamphlet of International Publication, No. 95/17699 pamphlet of International Publication) or the cholesteric crystal mode (Europe patent 606940A2 instructions, the record of japanese kokai publication hei 8-271731 communique) that the principle of having used dielectric mirror is arranged through the refringence that enlarges draw direction.As the brightness enhancement film of the multilayer mode of the principle of having used dielectric mirror, the preferred DBEF-E of use among the present invention, DBEF-D, DBEF-M (being the 3M corporate system), as the preferred NIPOCS (a day eastern electrician (strain) system) that uses among brightness enhancement film the present invention of cholesteric crystal mode.About NIPOCS, can be with reference to day east skill newspaper, vol.38, No.1, May, 2000,19 pages～21 pages etc.

In addition; In the present invention, also preferably use with the brightness enhancement film combination of the positive intrinsic birefringence condensate of putting down in writing in each communique of each instructions of No. 97/32223 pamphlet of International Publication, No. 97/32224 pamphlet of International Publication, No. 97/32225 pamphlet of International Publication, No. 97/32226 pamphlet of International Publication and japanese kokai publication hei 9-274108 number, japanese kokai publication hei 11-174231 number and negative intrinsic birefringence condensate blend being carried out the anisotropic scattering mode that uniaxial tension obtains.As anisotropic scattering mode brightness enhancement film, preferred DRPF-H (3M corporate system).

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

(3-3) hard conating

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

Said hard conating preferably forms through cross-linking reaction or polyreaction by light and/or the hot curable compound that causes.As curable functional group, preferred light polymerism functional group, in addition, the organometallics that contains water-disintegrable functional group is preferably organoalkoxysilane base (Alkoxysilyl) compound.As the concrete formation composition of hard conating, for example can preferably use the composition of records such as TOHKEMY 2002-144913 communique, TOHKEMY 2000-9908 communique, No. 00/46617 pamphlet of International Publication.

The thickness of hard conating is preferably 0.2 μ m～100 μ m.

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

The material that forms hard conating can use the compound that contains the olefinic unsaturated group, the compound that contains ring-opening polymerization property base, and these compounds can be used alone or in combination.As the preferred example of the compound that contains the olefinic unsaturated group, can enumerate the polyacrylate of polyvalent alcohols such as glycol diacrylate, trimethylolpropane triacrylate, two trimethylolpropane tetra-acrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylic ester, dipentaerythritol acrylate; The diacrylate of bisphenol A diglycidyl ether, the epoxy acrylate classes such as diacrylate of hexanediol diglycidyl ether; React resulting urethane acrylate etc. as preferred compound by hydroxy acryl acid esters such as polyisocyanate and hydroxyethylmethacry,ate.In addition; As the commercial compound; Can enumerate EB-600, EB-40, EB-140, EB-1150, EB-1290K, IRR214, EB-2220, TMPTA, TMPTMA (more than, Daicel-UCB (strain) system), UV-6300, UV-1700B (more than, Japanese synthetic chemical industry (strain) system) etc.

In addition; Preferred example as the compound that contains ring-opening polymerization property base; Can enumerate the polyglycidyl ether of ethylene glycol diglycidylether, bisphenol A diglycidyl ether, trimethylolethane trimethacrylate glycidol ether, trihydroxymethylpropanyltri diglycidyl ether, glycerine triglycidyl ether, triglycidyl group trihydroxyethyl isocyanates, sorbierite four glycidol ethers, pentaerythrite four glycidol ethers, cresols novolac resin, the polyglycidyl ether of phenol novolac resin etc. as the diglycidyl ethers; Gather cyclohexyl epoxy methyl ether etc. as what the ester ring type epoxies can be enumerated CELLOXIDE 2021P, CELLOXIDE 2081, EPOLEAD GT-301, EPOLEAD GT-401, EHPE 3150CE (above be Daicel chemical industry (strain) system), phenol novolac resin, can enumerate OXT-121, OXT-221, OX-SQ, PNOX-1009 (above make) etc. for East Asia synthetic (strain) as the oxetanes class.The multipolymer of other polymkeric substance or (methyl) glycidyl acrylates that also can in hard conating, use (methyl) glycidyl acrylate and monomer that can copolymerization.

For the adaptation of the cure shrinkage, raising and the base material that reduce hard conating, reduce and be coated with the curl of handling article among the present invention firmly, preferably carry out in hard conating, adding crosslinked particulates such as organic fine particles such as cross-linked rubber particulate such as oxide fine particle or tygon, the polystyrene of silicon, titanium, zirconium, aluminium etc., the crosslinked particle that gathers (methyl) esters of acrylic acid, dimethyl silicone polymer etc., SBR, NBR.The mean grain size of these crosslinked particulates is preferably 1nm～20000nm.In addition, the shape of crosslinked particulate can not especially restrictedly not used spherical, bar-shaped, needle-like, tabular etc.The addition of particulate is preferably below the 60 volume % of the hard conating after the curing, more preferably below the 40 volume %.

When being added on the inorganic particles of above-mentioned record; Because usually and the compatibility of binder polymer poor, so the surface conditioning agent that also preferably uses metals such as containing silicon, aluminium, titanium and have functional groups such as alkoxy, carboxylic acid group, sulfonic group, phosphonate group 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 especially preferably use electron ray, ultraviolet ray.When it is solidified, consider the thermotolerance of plastics itself, heating-up temperature is preferably below 140 ℃, more preferably below 100 ℃.

(3-4) forward scattering layer

The forward scattering layer is used for improveing the viewing angle characteristic (form and aspect and Luminance Distribution) of the direction up and down when the polaroid with the present invention is applied to liquid crystal indicator.In the present invention; Preferably that refractive index is the different particulate of forward scattering layer carries out bonding agent (Binder) and disperses the formation obtain, for example can use the TOHKEMY 11-38208 communique of forward scattering coefficient specialization, the relative index of refraction of transparent resin and particulate is made as the TOHKEMY 2000-199809 communique of particular range, haze value is defined as the formation of TOHKEMY 2002-107512 communique more than 40% etc.In addition, in order to control the viewing angle characteristic of mist degree, can preferably carry out 31 pages～39 pages " Lumisty " combinations of being put down in writing of technical report " exhibiting optical function film " of polaroid and Sumitomo Chemical (strain) among the present invention and use.

(3-5) antiglare layer

Anti-dazzle (anti-dizzy) layer is used to make reflection light diffusing and prevents to reflect.Anti-dazzle function can form concavo-convex the acquisition through the surface (demonstration side) at liquid crystal indicator.Mist degree with blooming of anti-dazzle function is preferably 3～30%, and more preferably 5～20%, most preferably be 7～20%.

Film surface form concavo-convex method for example can preferably use add particulate and form concavo-convex method (for example TOHKEMY 2000-271878 communique etc.) at film surface, method (for example TOHKEMY 2000-281410 communique, TOHKEMY 2000-95893 communique, TOHKEMY 2001-100004 communique, TOHKEMY 2001-281407 communique etc.) that the bigger particle (particle size is 0.05～2 μ m) that adds a small amount of (0.1～50 quality %) forms uneven-surface film, in the film surface method of transfer printing concaveconvex shape (for example as the embossing job operation, records such as japanese kokai publication sho 63-278839 communique, japanese kokai publication hei 11-183710 communique, TOHKEMY 2000-275401 communiques) etc. physically.

[liquid crystal indicator]

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

Liquid crystal indicator of the present invention is characterised in that and contains 1 polaroid of the present invention at least.

Fig. 1 is the skeleton diagram of the example of expression liquid crystal indicator of the present invention.In Fig. 1, liquid crystal indicator 10 comprises upside polaroid 1 and the downside polaroid 8 that has liquid crystal layer 5 and the liquid crystal cells that is configured in its liquid crystal cells top electrode substrate 3 and liquid crystal cells bottom electrode substrate 6 up and down, is configured in the both sides of liquid crystal cells.Also can between liquid crystal cells and each polaroid, dispose color filter.When using said liquid crystal indicator 10, be configured to cold cathode or thermic cathode fluorimetric pipe or light emitting diode, field emission component, electroluminescent cell backlight overleaf as light source as transmission-type.

Upside polaroid 1 and downside polaroid 8 have constituting that the mode that clips the polarizer by 2 polaroid protective films cascades respectively, and in liquid crystal indicator 10 of the present invention, preferably at least one polaroid is a polaroid of the present invention.Liquid crystal indicator of the present invention 10 preferably from the outside (away from the side of liquid crystal cells) of device with the sequential cascade of the transparent protective film of routine, the polarizer, said polaroid protective film.

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

(VA pattern)

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

In the VA pattern, through the liquid crystal of dielectric anisotropy between upper and lower base plate about for negative, Δ n=0.0813, Δ ε=-4.6 carried out friction orientation, with about 89 ° of sensing, so-called arrow pitch angle that make the direction of orientation that shows liquid crystal molecules.The thickness d of the liquid crystal layer 5 of Fig. 1 is preferably set to about 3.5 μ m.Wherein, according to the size of the long-pending Δ nd of thickness d and refractive index anisotropy Δ n, the brightness when showing in vain changes.Therefore, in order to obtain maximum brightness, the thickness of liquid crystal layer is set with the mode of the scope that reaches 0.2 μ m～0.5 μ m.

The absorption axes 2 of the upside polaroid 1 of liquid crystal cells and the absorption axes 9 of downside polaroid 8 be the quadrature laminated roughly.Inboard in each alignment films of liquid crystal cells top electrode substrate 3 and liquid crystal cells bottom electrode substrate 6 forms transparency electrode (not shown); But do not applying on the electrode under the non-driven state of driving voltage; Liquid crystal molecule in the liquid crystal layer 5 generally perpendicularly is orientated with respect to real estate; Consequently, the polarized state of light through liquid crystal panel does not almost change.That is, in liquid crystal indicator, the black demonstration of in non-driven state, realizing ideal.Relative therewith, under driving condition, liquid crystal molecule tilts in parallel direction at real estate, and the light through liquid crystal panel changes polarization state by the liquid crystal molecule of said inclination.In other words, in liquid crystal indicator, can obtain white demonstration under the driving condition.In addition, in Fig. 1,

symbol

4 and 7 is orientation control direction.

Wherein, owing between upper and lower base plate, apply electric field, be negative liquid crystal material so preferably use liquid crystal molecule on direction of an electric field, vertically to respond such dielectric constant anisotropy.In addition, electrode is being configured on the substrate and when transversely applying electric field, is using liquid crystal material parallel with positive dielectric constant anisotropy at real estate.

In addition, in the liquid crystal indicator of VA pattern, in the liquid crystal indicator of TN pattern the interpolation of common employed chirality agent owing to can make the dynamic response characteristic deterioration and less use, but bad and add in order to reduce orientation sometimes.

The VA pattern to be characterized as high-speed response and contrast high.But, though contrast has the problem in the vergence direction deterioration positive high.Liquid crystal molecule is vertical orientated at real estate when black the demonstration.If from top view, then the birefringence of liquid crystal molecule so transmissivity is low, can obtain high-contrast owing to almost do not have.But, when vergence direction is observed, liquid crystal molecule generation birefringence.In addition, the angle of reporting to the leadship after accomplishing a task of polaroid absorption axes up and down is 90 ° quadrature in the front, but when vergence direction is observed just greater than 90 °.Because these two main causes produce light at vergence direction and leak, thereby contrast descend.Said 60 ℃, relative humidity 95%, through the time moisture permeability when handling 24 hours be 500g/m ²More than and 2000g/m ²When following polaroid protective film is phase retardation film, can dispose said polaroid protective film in order to address this problem as optical compensating gage (phase retardation film).

In addition, when white the demonstration, liquid crystal molecules tilt, but reverse at vergence direction and its, the birefringent of liquid crystal molecule when vergence direction is observed varies in size, and brightness and tone also create a difference.In order to address this problem, also preferably be made as the structure that is called as multidomain that a pixel segmentation of liquid crystal indicator is become a plurality of zones.

(multidomain)

For example in the VA mode through applying electric field, thereby liquid crystal molecule averages out at different a plurality of regional dip viewing angle characteristics in a pixel.For division alignment in a pixel, slit is set on electrode, or projection is set and changes direction of an electric field, thereby make electric field density have deviation.In order to obtain impartial visual angle, increase this and cut apart number and get final product, but cut apart or 8 cut apart the above almost visual angle of equalization that just can obtain through being made as 4 in whole directions.Particularly 8 can the polaroid absorption axes be set at angle arbitrarily when cutting apart, so preferred.

In the zone boundary that orientation is cut apart, liquid crystal molecule is difficult to response in addition.Therefore, in normal black the demonstration, owing to keep black demonstration the, the problem that causes brightness to reduce.Therefore, can in liquid crystal material, add the chirality agent reduces borderline region.

Embodiment

Below, enumerate embodiment, the present invention is explained more specifically.Below embodiment in material, reagent, amount and ratio, the operation etc. represented only otherwise breaking away 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) the system film of cellulose acylate film

< preparation of acylated cellulose >

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

(making of polaroid protective film)

< the air side top layer is with the preparation of dope 101 liquid >

(preparation of acylated cellobiose cellulose solution)

Following composition is added stirred pot, stir with each composition dissolving preparation acylated cellobiose cellulose solution 1.

It is that average substitution degree is 5～6 sucrose benzoate that sucrose benzoate uses the degree of substitution of benzoyl, and promptly 8 substituents are below 15%, and 7,6 substituents add up to below 70%, and 5～3 substituents add up to below 40%.

(preparation of matting agent solution 2)

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

Add above-mentioned matting agent solution 2 of 1.3 mass parts and 98.7 mass parts acylated cellobiose cellulose solutions 1, use line mixer to mix, preparation air side top layer is with solution 101.

(preparation of acylated cellobiose cellulose solution)

Following composition is added stirred pot, stir each composition dissolving, preparation basic unit is with dope 101.

Ultraviolet light absorber C

Chemical formula 35

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

Use line mixer to be blended in air layer side top layer with mixed 1.3 mass parts matting agent solution 2 and the 99.3 mass parts acylated cellobiose cellulose solutions 1 that get in dope 101 liquid, preparation is supported the top layer, side with solution 101.

< curtain coating >

Use the cylinder casting device, with the dope (basic unit use dope) of said preparation and in its both sides with the top layer with dope with 3 layers of while on the curtain coating supporter (the supporter temperature is-9 ℃) of stainless steel from curtain coating mouth curtain coating equably.Peeling off under the state of residual solvent amount in the dope of each layer for 70 quality % roughly, the two ends of the Width of film are fixed by pin stenter, is the state of 3～5 quality % in the residual solvent amount, 1.28 times of cross directional stretchs and carry out drying.Then, further dry through between the roller of annealing device, carrying, obtain the polaroid protective film (cellulose acylate film) of embodiment 101.The thickness of resulting cellulose acylate film is 60 μ m (the air side top layer is 3 μ m, and basic unit is 54 μ m, and supporting the top layer, side is 3 μ m), and width is 1480mm.

(saponification of polaroid protective film is handled)

The polaroid protective film of the embodiment that makes 101 was flooded 3 minutes down at 55 ℃ in the sodium hydrate aqueous solution of 2.3mol/L.In the washing bath of room temperature, clean, 30 ℃ of sulfuric acid neutralizations of using 0.05mol/L down.In the washing bath of room temperature, clean once more, again warm air-dry dry with 100 ℃.Like this, the polaroid protective film of embodiment 101 is carried out the saponification processing on surface.

(making of polaroid)

With average degree of polymerization is that about 2400, saponification degree is after polyvinyl alcohol film that 99.9 moles of thickness that are made up of polyvinyl alcohol (PVA) more than the % are 75 μ m is immersed in 30 ℃ the pure water, and the weight ratio that under 30 ℃, is immersed in iodine/potassium iodide/water is in 0.02/2/100 the WS.Then, the weight ratio that under 56.5 ∑s, is immersed in potassium iodide/boric acid/water is in 12/5/100 the WS.Then, dry under 65 ℃ after 8 ℃ pure water cleaning, obtain the polarizing coating that absorption orientation iodine forms on polyvinyl alcohol film.Stretch and mainly carry out with iodine staining and boric acid treatment procedures, total stretching ratio is 5.3 times.

Use the polyethenol series adhesive, the polaroid protective film of the embodiment 101 that saponification is handled is pasted on a side of the above-mentioned polarizer that makes.Commercially available three cellulose acetate membrane (Fujitac TD80UF, FUJIFILM (strain) system) is carried out same saponification to be handled.Use the polyethenol series adhesive, on the face of the polarizer of the opposite side of the polaroid protective film side of the embodiment 101 that stickup makes, paste the three cellulose acetate membrane after saponification is handled.Wherein, the thickness of commercially available three cellulose acetate membrane is 80 μ m, and moisture permeability is 400g/m ²My god.

At this moment, so that the axis of homology of the polarizer mode parallel with the slow axis of the polaroid protective film of the embodiment that makes 101 be configured.In addition, so that the slow axis of the axis of homology of the polarizer and commercially available three cellulose acetate membrane dispose with the mode of quadrature.

Like this, make the polaroid of embodiment 101.

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

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

Except in the making of the polaroid protective film of embodiment 101 with record is changed in the kind of the kind addition of the degree of substitution of acylated cellulose, hydrophobing agent, polarizer permanance modifying agent and addition, thickness such as the below table 1; Same operation, the polaroid protective film of manufacturing embodiment 102～119 and comparative example 201～202.Wherein, the kind of the kind of the degree of substitution of cellulosic acylate, hydrophobing agent and addition, adjuvant and addition all are made as identical in air side top layer, basic unit, top layer, support side 3 layers.

(the saponification processing 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 carry out saponification processing and polaroid making with embodiment 101 same operations respectively, make the polaroid of each embodiment and comparative example.

[comparative example 203]

(making of 203 polaroid)

Use the polyethenol series adhesive, the commercially available three cellulose acetate membrane (Fujitac TD80UF, FUJIFILM (strain) system) that saponification was handled sticks on the 1 same side of operating the polarizer that makes with embodiment.Again with the face of the polarizer of the opposite side of pasting commercially available three cellulose acetate membrane side on, use the SK adhesion sheet that always grinds chemistry (strain) system to paste commercially available ZEONOR film (ZF14 of Japanese Zeon system), make the polaroid of comparative example 203.

[evaluation]

(mensuration of the moisture permeability of polaroid protective film)

According to the moisture permeability test (cup type method) of JISZ0208, in the atmosphere of 60 ℃ of temperature, relative humidity 95%, measuring 24 hours is 1m through area ²The weight (g) of water vapor of sample, calculate moisture permeability.

(density measurement of polaroid protective film)

Measure the density of film by automatic densitometer (ProductName: MINIDENS, the iPros of Co., Ltd. system).

(polaroid Evaluation of Durability)

To above-mentioned each embodiment that makes and the polaroid of comparative example, measuring wavelength through the method for this instructions record is that 410nm and wavelength are the quadrature transmissivity of the polarizer of 510nm.

Then, 60 ℃, the environment of relative humidity 95% are preserved down after 800 hours and 105 ℃, no damping are preserved each polaroid after 50 hours down, with same gimmick mensuration quadrature transmissivity.Obtain through the time before with the variation of afterwards quadrature transmissivity, it is put down in writing its result as polarizer permanance in below table 1.In addition, the relative humidity under the environment of no damping is 0%～20% scope.

(the mensuration in the polarizer) from the boron content slip of boric acid

Through the time before the polarizer in the boron content quantitative from boric acid

Polaroid is stamped into 1cm * 1cm, add nitric acid 3cc after, under 230 ℃ of maximum temperatures, carry out ashing treatment with microwave.After adding entry total amount being made as 50g, use the ICP-OES (Optima7300DV) of PerkimElmer society system to measure the boron amount.

Under 60 ℃, 95%, 800 hour through the time after boric acid content quantitative

From through the time after polaroid peel off polaroid protective film, only take out the polarizer.Through it is carried out with through the time before same processing, quantitatively the boron amount in the polarizer.

Formula below utilizing calculate 60 ℃, relative humidity 95%, 800 hours through the time before with the slip of afterwards boric acid content.

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

Acid ionization constant in the mixed solvent of the volume ratio of the tetrahydrofuran/water under 25 ℃=6/4 that is 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 each repetitive right side.

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)

Can know through moisture permeability from the result of table 1 and to be made as 500g/m polaroid protective film ²More than, the wavelength that can suppress under the condition of 105 ℃ of no damping is the rising of the intersection transmissivity of 510nm.In addition, can know and use the moisture permeability of polaroid protective film to be made as 2000g/m ²Film is following, the density of film is 1.293g/cm ³60 ℃ of the polaroid of above polaroid protective film, relative humidity 95%, through the time handle 800 hours after before with afterwards 410nm to intersect transmission change little, so preferred.

[embodiment 301]

(making of liquid crystal indicator)

2 polaroids of commercially available liquid crystal TV set (BRAVIAJ5000 of SONY (strain)) are peeled; To use as the polaroid of the present invention of the polaroid protective film of the embodiment 101 of polaroid of the present invention with the polaroid protective film of embodiment 101 respectively in the mode of liquid crystal cell side looking the person's of recognizing side and backlight side, pasted a slice respectively in observer's side and backlight side via bonding agent.So that the axis of homology of the polaroid of observer's side is at above-below direction, and so that the axis of homology of the polaroid of backlight side in the mode of left and right directions, is made as the cross Nicols configuration.With respect to commercially available liquid crystal TV set; Even the liquid crystal indicator of the present invention that makes like this changes ambient humidity; Contrast when being observed by vergence direction changes with tonal variation also little, and hot and humid down and under high temperature low humidity two kinds of situation down, even use for a long time; The reduction of contrast is also little, so preferred.

Symbol description

1 upside polaroid

The direction of 2 upside polaroid absorption axes

3 liquid crystal cells top electrode substrates

The orientation control direction of 4 upper substrates

5 liquid crystal layers

6 liquid crystal cells bottom electrode substrates

The orientation control direction of 7 infrabasal plates

8 downside polaroids

The direction of 9 downside polaroid absorption axes

10 liquid crystal indicators

Claims

1. polaroid, it comprises and contains from the polarizer of the boron of boric acid and be disposed at 2 polaroid protective films of the both sides of this polarizer, wherein,

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

3. polaroid according to claim 1 and 2, wherein, the polaroid protective film that satisfies said characteristic contains the polymkeric substance that comprises from the repetitive of the monomer shown in the formula (1),

In the general formula (1), R ¹Expression hydrogen atom or carbon number are 1～4 fatty group, R ²The expression substituting group, (A) expression is used to form 5 or 6 yuan of needed atom groups of ring, and n representes 0～4 integer.

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

5. polaroid according to claim 3, wherein, the R in the said general formula (1) ¹Be hydrogen atom, (A) 5 yuan of rings of expression, R ²Be hydrogen atom, methyl or hydroxyl.

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

In the formula, R ¹⁰～R ¹⁹Represent substituting group respectively independently, n1, n2, n5, n6, n8 and n10 represent 0～4 integer respectively independently, and n3, n7 and n9 represent 0～2 respectively independently, and n4 representes 0 or 1 respectively independently, R ^1AExpression hydrogen atom or carbon number are 1～4 fatty group.

7. polaroid according to claim 3, wherein, said polymkeric substance is to contain the coumarone resin of 3 compositions shown in the formula (P-1) as repetitive,

formula P-1

In the formula, R ²¹, R ²², R ²³And R ²⁴Represent substituting group respectively independently, x, y, z represent the molar ratio of the total repetition unit contained with respect to polymkeric substance, and x representes 1～40%; Y representes 5～95%, and z representes 1～70%, and m1, m2 represent 0～4 integer respectively independently; M3 representes 0～2 integer, and m4 representes 0～5 integer, R ¹⁰¹, R ¹⁰², R ¹⁰³Represent independently that respectively hydrogen atom or carbon number are 1～4 fatty group.

8. polaroid according to claim 3, wherein, the weight-average molecular weight of said polymkeric substance is 200～10000.

9. polaroid according to claim 1, wherein, it is 2～7 organic acid that the polaroid protective film that satisfies said characteristic contains acid ionization constant in the mixed solvent of volume ratio of a kind of tetrahydrofuran/water=6/4 under 25 ℃ at least.

10. according to claim 1,2 or 9 described polaroids, wherein, the polaroid protective film that satisfies said characteristic comprises the compound shown in the formula (3),

General formula (3)

In the general formula (3), R ²⁶The expression aryl, R ²⁷And R ²⁸Represent hydrogen atom, alkyl, aryl, R respectively independently ²⁶And R ²⁷Can have substituting group respectively.

11. polaroid according to claim 1 and 2, wherein, the polaroid protective film that satisfies said characteristic comprises the compound shown in the formula (4),

In the general formula (6), X representes to replace or unsubstituted aromatic ring; R ⁶, R ⁷, R ⁸And R ⁹Represent independently that respectively hydrogen atom or carbon number are 1～5 alkyl; N5 representes 1～11 integer, and n5 is 2 when above, a plurality of R ⁶, R ⁷, R ⁸With X can be identical mutually also can be different.

12. polaroid according to claim 11, wherein, A and X in said general formula (5) and the said general formula (6) are phenyl ring.

13. polaroid according to claim 11, wherein, said general formula (5) is by shown in the formula (5 "),

General formula (5 ") in, n3 representes 0～5 integer.

14. polaroid according to claim 11, wherein, said general formula (6) is by shown in the formula (6 "),

General formula (6 ") in, n4 representes 0～10 integer.

15. polaroid according to claim 11, wherein, the R in the said general formula (4) ¹For hydrogen atom or carbon number are 1～8 alkyl, R ²Shown in general formula (5 "), n1 representes 2～4 integer, and n2 representes 1～3 integer, and n3 representes 0～2 integer.

16. polaroid according to claim 11, wherein, the compound as shown in the said general formula (4) contains at least 2 kinds of mutual different compounds.

17. polaroid according to claim 11, wherein, the weight-average molecular weight of the compound shown in the said general formula (4) is 200～1200.

18. according to claim 1,2 or 9 described polaroids, wherein, the polaroid protective film that satisfies said characteristic is a cellulose acylate film.

19. a liquid crystal indicator, it comprises 1 claim 1,2 or 9 described polaroids at least.