CN101617250B

CN101617250B - Retardation film, process for production thereof and polarizer

Info

Publication number: CN101617250B
Application number: CN2008800055914A
Authority: CN
Inventors: 田中圭; 牛野卓浩; 桑原和雄; 关口正之
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2007-03-02
Filing date: 2008-02-25
Publication date: 2011-05-04
Anticipated expiration: 2028-02-25
Also published as: WO2008108199A1; KR20090127331A; CN101617250A; JPWO2008108199A1; TW200846385A; TWI425024B

Abstract

The invention aims at providing a retardation film which exhibits an NZ near 1 and which little warps after it has been laminated with a polarizer; a process for the production thereof; and a polarizer made by using the film. The retardation film is made from a cyclic olefin polymer and satisfies the following requirements (1) to (5): (1) 70nm <= Re <= 300nm, (2) 1.1<= NZ <= 1.7, (3) Alpha(MD) <=90ppm/ DEG C, (4) Alpha(TD) <= 90ppm/ DEG C, and (5) |Alpha(MD) - Alpha(TD)| <= 30ppm/ DEG C.

Description

Phase retardation film, its manufacture method and polaroid

Technical field

The present invention relates to the phase retardation film and the manufacture method thereof that form by the cyclic olefin based polymer and the polaroid that has used this phase retardation film.

Background technology

Annular ethylene series resin has as inferior characteristics, promptly, the glass transition temperature height owing to the outspoken nature of backbone structure, owing to the group that has large volume in backbone structure is amorphism and transmittance height, and, thereby receive publicity as the transparent thermoplastic resin of thermotolerance, the transparency, optical characteristics excellence owing to the little low-birefringence that shows of anisotropy of refractive index.

In recent years, carried out above-mentioned annular ethylene series resin is applied to for example research in the fields such as encapsulant of optical materials such as CD, optical lens, optical fiber, optical semiconductor sealing etc.In addition, be applied to optical film, as follows, carried out improveing the trial of the problem of optical film in the past.

The film of polycarbonate, polyester or the cellulose triacetate etc. that use as optical film in the past, exist because photoelastic coefficient is big and therefore can present the problem that phase differential or phase differential change because of small STRESS VARIATION, in addition, also have problems such as thermotolerance, suction deformability deterioration, so proposed the various films that to use as optics by the film that annular ethylene series resin forms.For example, in patent documentation 1～2, record film formed polarizer by annular ethylene series resin.In addition, in patent documentation 3～5, record the diaphragm that the annular ethylene series resin film is used for polaroid.

In these communiques, the water-intake rate that records the annular ethylene series resin film is below 0.05%, the main points that its low water absorbable is outstanding.But, under with the annular ethylene series resin film of such low water absorbable situation as for example polarizer, used for liquid crystal display element substrate, can the adaptation of hard conating, antireflection film, transparency conducting layer or aspect the cementability of polaroid, glass the generation problem.In addition, under the situation as the diaphragm of polaroid, the same with water-intake rate except the problems referred to above, its moisture permeability is also low, so also can occur in the problem of the shipwreck of normally used water system bonding agent in the applying with polarizing coating with drying.

On the other hand, as annular ethylene series resin, known have various materials, and the water-intake rate that is not limited to all annular ethylene series resin is below 0.05%.In order to make water-intake rate is below 0.05%, and annular ethylene series resin must be the polyolefin structure that only is made of carbon atom and hydrogen atom, or part contains the structure of halogen.

Therefore, in order to solve the above-mentioned problem that is derived from low water absorbable, in patent documentation 6～7 grades, record the optical film that contains the annular ethylene series resin that in molecule, has imported polar group.These optical films have advantage as follows, promptly outstanding aspect the low phase differential of high transparent, transmitted light and then the even and stable optical characteristics such as phase differential when being stretched orientation, thermotolerance, good with the adaptation of other materials or cementability etc., and the suction distortion is little, and it is used to most liquid crystal display cells.

But,,,, require further homogeneity, stability in order not upset the identification of image for employed optical film along with the maximization of in recent years liquid crystal display cells, the raising of brightness contrast rate, the high-definitions such as raising of visual angle identity.For this reason, further require and the outstanding phase retardation film of the applying of polarizing coating and the appearance of polaroid.For example; in patent documentation 8 grades, record the polaroid of the warpage after having reduced the applying diaphragm; described warpage becomes problem on making and to installing of liquid crystal display cells, but the combination of the diaphragm on the two sides of polarizing coating is limited, requires further to improve.

Patent documentation 1: Japanese kokai publication hei 5-2108 communique

Patent documentation 2: Japanese kokai publication hei 5-64865 communique

Patent documentation 3: Japanese kokai publication hei 5-212828 communique

Patent documentation 4: Japanese kokai publication hei 6-51117 communique

Patent documentation 5: Japanese kokai publication hei 7-77608 communique

Patent documentation 6: Japanese kokai publication hei 7-287122 communique

Patent documentation 7: Japanese kokai publication hei 7-287123 communique

Patent documentation 8: TOHKEMY 2005-215700 communique

Summary of the invention

The invention provides a kind of NZ coefficient near 1 and after fitting with polarizing coating few phase retardation film and the manufacture method thereof of warpage, and the polaroid that has used this film.

Phase retardation film of the present invention is characterized in that, is formed by the cyclic olefin based polymer, satisfies following formula (1)～(5).

(1)70nm≤Re≤300nm

(2)1.1≤NZ≤1.7

(in formula (1)～(2), Re is the interior phase differential of face of the film at wavelength 589nm place, represents that with Re=(nx-ny) * d NZ is the coefficient with NZ=(nx-nz)/(nx-ny) expression.Here, nx represents the largest refractive index in the face, and ny is illustrated in the face refractive index with the direction of nx quadrature, and nz represents and the refractive index of the film thickness direction of nx and ny quadrature that d represents the thickness (nm) of film.)

(3)α(MD)≤90ppm/℃

(4)α(TD)≤90ppm/℃

(5)|α(MD)-α(TD)|≤30ppm/℃

(in formula (3)～(5), the average coefficient of linear expansion of α (MD) expression film length direction, the average coefficient of linear expansion of α (TD) expression film Width.But, above-mentioned average coefficient of linear expansion all is the values under-40 ℃～85 ℃.)

Phase retardation film of the present invention, preferred above-mentioned cyclic olefin based polymer has the formation unit shown in the following formula (I).

[in formula (I), m is the integer more than 1, and p is the integer more than 0 or 1; D is-CH=CH-or-CH ₂CH ₂-shown in group; R ¹～R ⁴Represent independently of one another that from hydrogen atom halogen atom contains the binding group of oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, replace or unsubstituted carbon number is 1～30 alkyl, atom of selecting in the polar group or group; R ¹And R ²Can be integrated and form bivalent hydrocanbon radical, R ³And R ⁴Can be integrated and form bivalent hydrocanbon radical.R ¹And R ²Can mutually combine and form carbocyclic ring or heterocycle, R ³And R ⁴Can mutually combine and form carbocyclic ring or heterocycle, this carbocyclic ring or heterocycle can be monocycle, also can be many rings.]

Phase retardation film of the present invention, preferred thickness is 20～100 μ m, the maximum ga(u)ge of film and the difference of minimum thickness are in the 3 μ m.

The manufacture method of phase retardation film of the present invention, it is characterized in that, to thickness is that the difference of the maximum ga(u)ge of 100～250 μ m and film and minimum thickness be 3 μ m with interior cycloolefin polymer film (original membrane (former anti-Off イ Le system)) is that 2.5～5.5 times mode is carried out horizontal uniaxial tension with stretching ratio, obtains above-mentioned phase retardation film.

Polaroid of the present invention is characterized in that, forms at the one-sided at least stacked above-mentioned phase retardation film of polarizing coating.

If be 2.5～5.5 times the phase retardation film that is formed by the cyclic olefin based polymer of the present invention implemented cross directional stretch with stretching ratio, then obtain the NZ coefficient near 1 and after fitting with polarizing coating the few film of warpage, it is suitable for vertical alignment-type liquid crystal display device.

Embodiment

Below, the present invention is specifically described.

＜phase retardation film 〉

Phase retardation film of the present invention is formed by the cyclic olefin based polymer, satisfies following formula (1)～(5).

(1)70nm≤Re≤300nm

(2)1.1≤NZ≤1.7

(3)α(MD)≤90ppm/℃

(4)α(TD)≤90ppm/℃

(5)|α(MD)-α(TD)|≤30ppm/℃

(1) and (2) be the influential optical characteristics of viewing angle compensation performance to liquid crystal cell, according to the kind of the liquid crystal that in liquid crystal cell, uses, display format etc. and also difference of preferred value, but Re value about (1), light leak when preventing that liquid crystal cell is black and show during, obtain aspect the good viewing angle compensation from oblique the observation, be preferably 75nm～200nm, more preferably 75nm～150nm.(2) NZ value near 1 viewing angle compensation that helps the vertical alignment-type liquid crystal element more, is preferably 1.1～1.5 more, and more preferably 1.1～1.4.

In addition, using polaroid of the present invention to carry out under the situation of viewing angle compensation of vertical alignment-type liquid crystal element, in a side of paired polaroid the phase separation layer of Re≤60nm, NZ 〉=3 is being set, this is preferred carrying out aspect the good viewing angle compensation.(definition of phase differential Re and NZ as previously shown in the face of this phase separation layer, nx represents the largest refractive index in this phase differential aspect, ny is illustrated in this phase differential aspect and the refractive index of the direction of nx quadrature, nz represents and the refractive index of the thickness direction of this phase separation layer of nx and ny quadrature that d (nm) represents the thickness of this phase separation layer.)

About (3) and (4), mean that all the more little change in size that is then caused by temperature variation of α value is more little.But except polyimide, polyethersulfone, the contour heat stable resin of polyphenylene sulfide etc., the linear expansion coefficient of thermoplastic resin is bigger than glass, metal usually, and when using resin separately, linear expansion coefficient can be near 0.In addition, the polyvinyl alcohol (PVA) that constitutes polaroid etc. and the unbalance possibility of the change in size of other resins being arranged also, is not that linear expansion coefficient is low more good more.But, certain above change in size, warpage, ripple take place in the heating when understanding because of the polaroid drying, so not preferred.Thus, about α (MD) and α (TD), say more realistically to be 30ppm/ ℃～90ppm/ ℃.

(5) anisotropy of the change in size that causes by temperature variation of expression.The difference that means α (MD) and α (TD) is big more, and the difference of the change in size amount of film direction is big more, becomes warpage takes place easily.Preferably | α (MD)-α (TD) |≤25ppm/ ℃, more preferably | and α (MD)-α (TD) |≤20ppm/ ℃.

＜cyclic olefin based polymer 〉

As the cyclic olefin based polymer that uses in the present invention, be not particularly limited, can enumerate the addition copolymer etc. of hydride, addition (being total to) polymkeric substance, cycloolefin monomer and alpha-olefin of open loop (being total to) polymkeric substance, this open loop (being total to) polymkeric substance of the cycloolefin monomer of formula described later (I ') and formula (II ') expression.Wherein, the hydride of preferred open loop (being total to) polymkeric substance especially preferably has the polymkeric substance of the structural unit shown in the following general formula (I).This polymkeric substance can be the homopolymer with the structural unit shown in the following general formula (I), can also be the multipolymer with the structural unit shown in structural unit shown in the formula (I) and the following general formula (II).

[in formula (II), E is independently-CH=CH-or-CH ₂CH ₂-shown in group; R ⁵～R ⁸Represent hydrogen atom independently of one another, halogen atom contains the binding group of oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, replaces or unsubstituted carbon number is 1～30 alkyl, polar group; R ⁵And R ⁶Can be integrated and form bivalent hydrocanbon radical, R ⁷And R ⁸Can be integrated and form bivalent hydrocanbon radical.R ⁵Or R ⁶, and R ⁷Or R ⁸Can mutually combine and form carbocyclic ring or heterocycle, this carbocyclic ring or heterocycle can be single ring architecture, also can be multiring structure.]

For the glass transition temperature that makes the cyclic olefin based polymer is the zone that is suitable for film processing, guarantee that simultaneously birefringence is controlled, the m in the above-mentioned general formula (I) is preferably 1～5, and more preferably 1～3, more preferably 1～2; P is preferably 0～4, and more preferably 0～2, more preferably 0～1.In addition, R ¹～R ⁴Carbon number be preferably 1～25, more preferably 1～20, more preferably 1～10, and then, the R in the above-mentioned general formula (II) ⁵～R ⁸Carbon number be preferably 1～25, more preferably 1～20, more preferably 1～10.

Manufacture method

Cyclic olefin based polymer of the present invention has the structural unit shown in structural unit shown in the above-mentioned formula (I) and the above-mentioned formula (II) as required.

Structural unit shown in the above-mentioned formula (I) by open loop (being total to) polymerization by the cycloolefin monomer derived shown in the following formula (I ').

(in formula (I '), m, p and R ¹～R ⁴Identical with above-mentioned formula (1).)

In formula (I) or (I '); as polar group, for example can enumerate hydroxyl, carbon number and be 1～10 alkoxy, carbon acyloxy (carbonyloxy group), alkoxy carbonyl, aryloxycarbonyl, cyano group, amide group, imide, three organic siloxies, three Organosilyls, amino, acyl group, alkoxysilyl, sulfonyl and carboxyl etc.More particularly, as above-mentioned alkoxy, can enumerate for example methoxyl, ethoxy etc.; As the carbon acyloxy, can enumerate for example aryl-carbonyl oxygen such as alkyl such as acetoxyl group, propionyloxy carbon acyloxy and benzoyloxy; As alkoxy carbonyl, can enumerate for example methoxycarbonyl, ethoxy carbonyl etc.; As aryloxycarbonyl, can enumerate for example phenyloxycarbonyl, naphthoxy carbonyl, fluorenes oxygen base carbonyl, biphenylyloxy carbonyl etc.; As three organic siloxies, can enumerate for example trimethylsiloxy, silicohetane alcoxyl base etc.; As three Organosilyls, can enumerate trimethyl silyl, triethylsilyl etc.; As amino, can enumerate primary amine groups; As alkoxysilyl, can enumerate for example trimethoxysilyl, triethoxysilyl etc.

As halogen atom, can enumerate fluorine atom, chlorine atom and bromine atoms.

As carbon number is 1～10 alkyl, can enumerate for example alkyl such as methyl, ethyl, propyl group; Naphthenic base such as cyclopentyl, cyclohexyl; Alkenyls such as vinyl, allyl, propenyl etc.

And replacement or unsubstituted alkyl can directly be combined on the ring structure, perhaps can be by linking group (linkage) combination.As linking group, can enumerate carbon number for example and be 1～10 bivalent hydrocanbon radical and (for example use-(CH ₂) _mThe alkylidene of-(in the formula, m is 1～10 integer) expression); Binding group (carbonyl (CO-), oxygen carbonyl (O (CO)-), the sulfo group (SO for example that contains aerobic, nitrogen, sulphur or silicon ₂-), ehter bond (O-), thioether bond (S-), imino group (NH-), amido link (NHCO-,-CONH-), siloxane bond (OSi (R) ₂-(in the formula, R is alkyl such as methyl, ethyl)) etc., can be the binding group that contains a plurality of these groups.

As cycloolefin monomer (I '), specifically can enumerate compound as follows.

Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

Five rings [6.5.1.1 ^3,6.0 ^2,7.0 ^9,13]-4-ten pentaenes,

8-methyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-ethyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-methoxycarbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-ethoxy carbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-positive propoxy carbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-isopropoxy carbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-n-butoxy carbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-methyl-8-methoxycarbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-methyl-8-ethoxy carbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-methyl-8-positive propoxy carbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-methyl-8-isopropoxy carbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-methyl-8-n-butoxy carbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-cyano group Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-cyano group-8-methyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-ethidine Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-phenyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-fluorine Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-methyl fluoride Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-difluoromethyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-trifluoromethyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-pentafluoroethyl group Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8,8-difluoro Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8,9-difluoro Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8, two (trifluoromethyl) Fourth Ring [4.4.0.1 of 8- ^2,5.1 ^7,10]-3-dodecene,

8, two (trifluoromethyl) Fourth Ring [4.4.0.1 of 9- ^2,5.1 ^7,10]-3-dodecene,

8-methyl-8-trifluoromethyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8,8,9-trifluoro Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8,8,9-three (trifluoromethyl) Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8,8,9,9-tetrafluoro Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8,8,9,9-four (trifluoromethyl) Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8,8-two fluoro-9, two (trifluoromethyl) Fourth Ring [4.4.0.1 of 9- ^2,5.1 ^7,10]-3-dodecene,

8,9-two fluoro-8, two (trifluoromethyl) Fourth Ring [4.4.0.1 of 9- ^2,5.1 ^7,10]-3-dodecene,

8,8,9-three fluoro-9-trifluoromethyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8,8,9-three fluoro-9-trifluoromethoxy Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8,8,9-three fluoro-9-five fluorine propoxyl group Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-fluoro-8-pentafluoroethyl group-9, two (trifluoromethyl) Fourth Ring [4.4.0.1 of 9- ^2,5.1 ^7,10]-3-dodecene,

8,9-two fluoro-8-seven fluorine isopropyl-9-trifluoromethyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-chloro-8,9,9-trifluoro Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8,9-two chloro-8, two (trifluoromethyl) Fourth Ring [4.4.0.1 of 9- ^2,5.1 ^7,10]-3-dodecene,

8-(2,2,2-trifluoro ethoxy carbonyl) Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene,

8-methyl-8-(2,2,2-trifluoro ethoxy carbonyl) Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecene.

They can use separately, or and with more than 2 kinds.

In the present invention, the structural unit shown in the preferred above-mentioned formula (I) has polar group, the group shown in the preferably following formula of this polar group (III).That is, the cycloolefin monomer shown in structural unit shown in the above-mentioned formula (I) or the above-mentioned formula (I '), preferred R ¹～R ⁴In at least one be the group shown in the following formula (III).

-(CH ₂) _nCOOR’…(III)

(in formula (III), n is 0 or 1～5 integer, and R ' is that carbon number is 1～15 alkyl.)

In above-mentioned formula (III), the n value is more little, and the carbon number of R ' is few more in addition, and the glass transition temperature of the multipolymer that obtains is high more, and thermotolerance improves, so preferred.That is, n is 0 or 1～5 integer normally, but is preferably 0 or 1, is preferably 0 especially.In addition, R ' normally carbon number is 1～15 alkyl, but preferred carbon number is 1～3 alkyl, and more preferably carbon number is 1～2 alkyl.

And then in above-mentioned formula (I) or (I '), when also being combined with alkyl on the carbon atom of the polar group combination shown in the above-mentioned general formula (III), the balance of the thermotolerance of the multipolymer that obtains and suction (wetting) property is accomplished, so preferred.In addition, the carbon number of alkyl is preferably 1～5, and more preferably 1～2, be preferably 1 especially.

Structural unit shown in the above-mentioned formula (II) by ring opening copolymer, is derived by the cycloolefin monomer (II) shown in the following formula (II ').

(formula (II ') in, R ⁵～R ⁸(II) is identical with above-mentioned formula.)

As such cycloolefin monomer, specifically can enumerate compound as follows.

Three ring [4.3.0.1 ^2,5] last of the ten Heavenly stems-3, the 7-diene,

Dicyclo [2.2.1] hept-2-ene",

Dicyclo [2.2.1] heptan-2, the 5-diene,

5-methyl bicycle [2.2.1] hept-2-ene",

5-ethyl dicyclo [2.2.1] hept-2-ene",

5-propyl group dicyclo [2.2.1] hept-2-ene",

5-butyl dicyclo [2.2.1] hept-2-ene",

5-amyl group dicyclo [2.2.1] hept-2-ene",

5-hexyl dicyclo [2.2.1] hept-2-ene",

5-heptyl dicyclo [2.2.1] hept-2-ene",

5-octyl group dicyclo [2.2.1] hept-2-ene",

5-nonyl dicyclo [2.2.1] hept-2-ene",

5-decyl dicyclo [2.2.1] hept-2-ene",

5-undecyl dicyclo [2.2.1] hept-2-ene",

5-dodecyl dicyclo [2.2.1] hept-2-ene",

5-tridecyl dicyclo [2.2.1] hept-2-ene",

5-myristyl dicyclo [2.2.1] hept-2-ene",

5-pentadecyl dicyclo [2.2.1] hept-2-ene",

5-cetyl dicyclo [2.2.1] hept-2-ene",

5-heptadecyl dicyclo [2.2.1] hept-2-ene",

5-octadecyl dicyclo [2.2.1] hept-2-ene",

5-nonadecyl dicyclo [2.2.1] hept-2-ene",

5-eicosyl dicyclo [2.2.1] hept-2-ene",

5-phenyl dicyclo [2.2.1] hept-2-ene",

5-cyano-bicyclo [2.2.1] hept-2-ene",

5-methoxycarbonyl dicyclo [2.2.1] hept-2-ene",

5-ethoxy carbonyl dicyclo [2.2.1] hept-2-ene",

5-methoxycarbonyl-5-methyl bicycle [2.2.1] hept-2-ene",

5-ethoxy carbonyl-5-methyl bicycle [2.2.1] hept-2-ene",

5-cyano group-5-methyl bicycle [2.2.1] hept-2-ene",

5-ethidine dicyclo [2.2.1] hept-2-ene" spiral shell [fluorenes-9,8 '-three ring [4.3.0.1 ^2,5] [3] decene].

They can use separately, or and with more than 2 kinds.In the present invention, wherein preferably use dicyclo [2.2.1] hept-2-ene", three ring [4.3.0.1 ^2,5] last of the ten Heavenly stems-3, the 7-diene.

Cyclic olefin based polymer of the present invention, can by make separately more than one, cycloolefin monomer (I ') and cycloolefin monomer (II ') carry out ring opening copolymer and make.Cyclic olefin based polymer of the present invention is in order to make its water absorptivity with thermotolerance and appropriateness, so especially preferably by 8-methyl-8-methoxycarbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10The multipolymer that]-3-dodecene and dicyclo [2.2.1] hept-2-ene" forms.

In the present invention; about the compound shown in the cycloolefin monomer (formula (I ')) and cycloolefin monomer (formula (II ') shown in compound) the copolymerization ratio; be made as in total under the situation of 100 weight portions them; common cycloolefin monomer (II ') be 0～40 weight portion, be preferably the scope of 3～30 weight portions.If the copolymerization ratio of cycloolefin monomer (II ') surpasses 30 weight portions, glass transition temperature is reduced, the heat-resistant stability of all characteristics of films such as phase differential or size is reduced.In addition, less than 3 weight portions the time, have the situation of sliding, toughness, stretch process and the reduction of presenting property of phase differential of resulting formed body, film or sheet.

In the present invention, except these cycloolefin monomers (I ') and (II '), also can in the scope of not damaging purpose of the present invention, use other cycloolefin monomers or other monomers that can copolymerization as the copolymerization starting monomer on a small quantity, cyclic olefin based polymer of the present invention can contain above-mentioned formula (I) and (II) shown in structural unit beyond structural unit.This structural unit for example can be by making cyclic olefine monomers such as cyclobutane, cyclopentene, cycloheptene, cyclooctene, carries out ring opening copolymer and form with above-mentioned cycloolefin monomer (I ') and (II ').In addition, making above-mentioned cycloolefin monomer (I ') and (II ') carry out ring opening copolymer in the presence of the unsaturated hydrocarbon based polymers that also can be by having the alkene unsaturated link in main chain at polybutadiene, polyisoprene, Styrene-Butadiene, ethene-non-conjugated diene multipolymer, polynorbornene etc. etc. forms, under situation, there is the improved trend of resistance to impact of multipolymer of the present invention with such structural unit.

But, in the present invention, preferably only use cycloolefin monomer (I ') and (II ') to carry out copolymerization.Promptly, cyclic olefin based polymer of the present invention, except above-mentioned formula (I) and the structural unit (II), can in the scope of not damaging purpose of the present invention, have other structural units, but preferably not have except that above-mentioned formula (I) and the structural unit the structural unit (II).

The ring opening copolymer thing that each cycloolefin monomer ring opening copolymer is obtained only, in its molecule, has the alkene unsaturated link, and have heat-resisting problem such as painted, and so preferably this alkene unsaturated link is hydrogenated, the method that this hydrogenation also can application of known.

For example, open clear 63-218726 communique, spy and open flat 1-132626 communique, spy and open catalyzer, solvent and the temperature conditions etc. that flat 1-240517 communique, spy are opened record in the flat 2-10221 communique etc. by being applied in the spy, can implement ring-opening polymerization and hydrogenation.

As the hydrogenation ratio of alkene unsaturated link, be generally 80 moles more than the %, preferred 90 moles more than the %, further preferred 95 moles more than the %, preferred especially 99 moles more than the %.In addition, hydrogenation of the present invention as mentioned above, intramolecular alkene unsaturated link is carried out, when cyclic olefin based polymer of the present invention has aromatic group, this aromatic group also has favourable effect aspect optical characteristics such as refractive index, the thermotolerance, therefore not necessarily will carry out hydrogenation.

As the molecular weight of cyclic olefin based polymer of the present invention, the number-average molecular weight by polystyrene conversion (Mn) of preferably using gel permeation chromatography (GPC) to measure is generally 3 * 10 ³～5 * 10 ⁵, be preferably 5 * 10 ³～3 * 10 ⁵, more preferably 1 * 10 ⁴～2 * 10 ⁵, and be generally 5 * 10 by the weight-average molecular weight (Mw) of polystyrene conversion ³～1 * 10 ⁶, be preferably 1 * 10 ⁴～5 * 10 ⁵, more preferably 2 * 10 ⁴～4 * 10 ⁵Scope.

When molecular weight was too small, resulting sometimes film strength can reduce, or the presenting property of phase differential during stretch process can reduce.On the other hand, when molecular weight was excessive, solution viscosity, melt viscosity became too high, and throughput rate, the processability of multipolymer of the present invention worsen sometimes.

In addition, the molecular weight distribution of cyclic olefin based polymer of the present invention (Mw/Mn) is generally 1.5～10, is preferably 2～7, and more preferably 2～5.

Cyclic olefin based polymer of the present invention is generally 0.05～1 weight % at 23 ℃ saturated water absorption, preferred 0.07～0.8 weight %, more preferably 0.1～0.7 weight %.As long as the saturated water absorption of cyclic olefin based polymer of the present invention is in above-mentioned scope, even then under high temperature wets such condition more, also can stably keep various optical characteristics, the transparency, phase differential and the phase differential homogeneity or the dimensional accuracy of resulting film, and with the adaptation of other materials, excellent in adhesion, therefore can in use not peel off etc., and, also good with the intermiscibility of adjuvant such as antioxidant, so the selection degree of freedom of the kind of adjuvant and addition becomes big.

At this saturated water absorption during less than 0.05 weight %, the film of gained and the adaptation of other materials, cementability are low, in use peel off easily, and the addition of adjuvant such as antioxidant are restricted sometimes.On the other hand, when this saturated water absorption surpasses 1 weight %, because of suction causes change of optical property, change in size easily.

Here, saturated water absorption is according to ASTM D570, measures the value of gaining in weight and obtaining by dipping in 23 ℃ water after 1 week.

The glass transition temperature of cyclic olefin based polymer of the present invention (Tg) is generally 70～250 ℃, is preferably 90～200 ℃, further preferred 100～180 ℃.At Tg is more than 120 ℃ the time, preferred owing to have excellent thermotolerance.,, therefore might aspect thermotolerance, have problems during at Tg because heat distortion temperature reduces less than 90 ℃, and, the problem that change of optical property that the film Yin Wendu of gained causes increases and so on produced sometimes.On the other hand, when Tg surpassed 200 ℃, processing temperature was too high when carrying out stretch process, and hot deterioration takes place multipolymer of the present invention sometimes, or throughput rate, processability worsen.

Here, the Tg of cyclic olefin based polymer is following to be obtained, promptly, use differential scanning calorimeter (DSC), under 20 ℃/minute of programming rates, nitrogen atmosphere, measure, the maximum peak temperature (A point) of the differential differential scanning heat curve that obtains when so measuring and deduct 20 ℃ temperature (B point) from the maximum peak temperature and depict at the differential scanning heat curve, will with the B point be on the baseline of starting point tangent line be that the intersection point of tangent line of starting point is as Tg with the A point.

Polymerization catalyst

As the catalyzer that in the manufacturing of cyclic olefin based polymer of the present invention, uses, for example preferably use at Olefin Metathesis and Metathesis Polymerization (K.J.IVIN, J.C.MOL, Academic Press 1997) the middle catalyzer of putting down in writing etc.As such catalyzer, for example can enumerate (i) by (a) and transposition (Metathesis) catalyzer that (b) is combined to form, described (a) is at least a kind that is selected from the compound of W, Mo, Re, V and Ti; Described (b) is the compound of alkali metal (for example Li, Na, K), alkaline-earth metal element (for example Mg, Ca), the 12nd family's element (for example Zn, Cd, Hg), the 13rd family's element (for example B, Al), the 14th family's element (for example Si, Sn, Pd) etc. and is at least a kind of compound that is selected from the compound with at least one this element-carbon bond or this element-hydrogen bond.In order to improve this activity of such catalysts, can add (c) described later adjuvant.

As the object lesson of above-mentioned (a) composition, for example can enumerate WCl ₆, MoCl ₅, ReOCl ₃, VOCl ₃, TiCl ₄Deng open the compound of putting down in writing in the flat 1-240517 communique the spy.They may be used alone, can also be used in combination of two or more kinds.

As the object lesson of above-mentioned (b) composition, for example can enumerate n-C ₄H ₉Li, (C ₂H ₅) ₃Al, (C ₂H ₅) ₂AlCl, (C ₂H ₅) _1.5AlCl _1.5, (C ₂H ₅) AlCl ₂, MAO, LiH etc. open the compound of putting down in writing in the flat 1-240517 communique the spy.They may be used alone, can also be used in combination of two or more kinds.

As the adjuvant of above-mentioned (c) composition, for example can suitably use alcohols, aldehydes, ketone, amine etc., and then can use the spy and open the compound of putting down in writing in the flat 1-240517 communique.They may be used alone, can also be used in combination of two or more kinds.

Above-mentioned about making up (a) becomes the use amount of the metathesis catalyst that forms of grading, above-mentioned (a) composition and all the mol ratio of " (a) composition: all monomers " of monomers be generally 1: 500～1: 500000 scope, be preferably 1: 1000～1: 100000 scope.And then, about above-mentioned (a) composition and (b) components in proportions, the metallic atom of " (a): (b) " (mole) than be generally 1: 1～1: 50, preferred 1: 2～1: 30 scope.Under the situation of in this metathesis catalyst, adding above-mentioned (c) adjuvant, about (a) composition and (c) components in proportions, the mol ratio of " (c): (a) " is generally 0.005: 1～and 15: 1, preferred 0.05: 1～7: 1 scope.

In addition, as other catalyzer, can use (ii) the metathesis catalyst that forms by the transition metal-arbine complex of periodic table the 4th family～the 8th family, becket butane complex etc.

As above-mentioned catalyzer object lesson (ii), for example can enumerate W (=N-2,6-C ₆H ₃ ⁱPr ₂) (=CH ^TertBu) (O ^TertBu) ₂, Mo (=N-2,6-C ₆H ₃ ⁱPr ₂) (=CH ^TertBu) (O ^TertBu) ₂, Ru (=CHCH=CPh ₂) (PPh ₃) ₂Cl ₂, Ru (=CHPh) [P (C ₆H ₁₁) ₃] ₂Cl ₂Deng.They may be used alone, can also be used in combination of two or more kinds.

About above-mentioned catalyzer use amount (ii), the mol ratio of " catalyzer (ii): all monomers " is generally 1: 500～1: 50000 scope, is preferably 1: 100～1: 10000 scope.

Wherein, can make up above-mentioned catalyzer (i) and (ii) use.

The adjusting of the molecular weight of the multipolymer of Shi Yonging in the present invention also can wait and carry out, but preferably regulate by the reaction system that makes molecular weight regulator coexist as ring opening copolymer by adjustment polymerization temperature, the kind of catalyzer, solvent types.As molecular weight regulator, for example alpha-olefines and styrene such as optimal ethylene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, wherein, preferred especially 1-butylene and 1-hexene.These molecular weight regulators may be used alone, can also be used in combination of two or more kinds.About the use amount of this molecular weight regulator, be generally 0.005～0.6 mole with respect to per 1 mole of whole monomer, be preferably 0.02～0.5 mole.

As the solvent (promptly dissolving the solvent of monomer, ring-opening polymerization catalyst, molecular regulation agent etc.) that in the ring opening copolymer reaction, uses, for example can enumerate paraffinics such as pentane, hexane, heptane, octane, nonane, decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, naphthalane, norbornane; Aromatic hydrocarbons such as benzene,toluene,xylene, ethylbenzene, isopropyl benzene; Chlorobutane, bromohexane, methylene chloride, ethylene dichloride, 1, compounds such as halogenation alkane, halogenated aromatic such as 6-dibromo-hexane, chlorobenzene, chloroform, zellon; Saturated carboxylic acid ester classes such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate; Ethers such as dibutyl ethers, tetrahydrofuran, dimethoxy-ethane.Optimization aromatic hydrocarbon wherein.They may be used alone, can also be used in combination of two or more kinds.About this ring-opening polymerization use amount with solvent, the weight ratio of " solvent: all monomers " is generally 1: 1～10: 1 amount, is preferably 1: 1～5: 1 amount.

The temperature of the monomer solution when adding catalyzer is preferably 30～200 ℃, more preferably 50 ℃～180 ℃.Under less than 30 ℃ situation, the yield of polymkeric substance can reduce sometimes, surpassing under 200 ℃ the situation, is difficult to control molecular weight sometimes.

Reaction time when carrying out the ring opening copolymer reaction is generally 0.1～10 hour, but preferred 0.1～9 hour, more preferably 0.1～8 hour.

Only with each cycloolefin monomer ring opening copolymer and the ring opening copolymer thing, in its molecule, have the alkene unsaturated link, and have heat-resisting problem such as painted, so preferably with this alkene unsaturated link hydrogenation.The method of hydrogenation, preferred hydrogenation ratio are as previously mentioned.

＜adjuvant 〉

In cyclic olefin based polymer of the present invention, can add various adjuvants as required.For example, in order to improve oxidation stability, prevent painted and deterioration, can cooperate from phenol is that antioxidant, lactone are that antioxidant, phosphorous antioxidant and sulphur are the antioxidant of selecting the antioxidant.Above-mentioned antioxidant can cooperate with the ratio that is 0.001～5 weight portion with respect to above-mentioned polymkeric substance 100 weight portions.As the object lesson of antioxidant, can be exemplified below:

1) 2,6-di-tert-butyl-4-methy phenol, 4,4 '-thiobis-(the 6-tert-butyl group-3-methyl-phenyl), 1,1-bis(4-hydroxyphenyl)cyclohexane, 2, [methylene-3-(3 for 2 '-methylene-bis(4-ethyl-6-t-butyl phenol), four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane, 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearate, 2, [phenol such as 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester is that antioxidant or quinhydrones are antioxidant to 5-di-tert-butyl hydroquinone and pentaerythrite-four;

2) two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, three (2, the 4-di-tert-butyl-phenyl) phosphite ester, four (2,4-di-t-butyl-5-aminomethyl phenyl) 4,4 '-biphenylene, two phosphinates, 3, phosphorus such as 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids-diethylester, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, three (4-methoxyl-3,5 diphenyl) phosphite esters and three (nonyl phenyl) phosphite ester are secondary antioxidant; And

3) dilauryl-3, sulphur such as 3 '-thiodipropionate and 2-mercaptobenzimidazole are secondary antioxidant etc.

In addition, also can in cyclic olefin based polymer of the present invention, cooperate fire retardant.As fire retardant, can use known material, for example can enumerate halogenated flame retardant, Sb system fire retardant, phosphate flame retardant and metal hydroxides etc.Wherein, preferably just demonstrate effect and can make water absorptivity with a spot of cooperation; the deterioration of the low-dielectric and the transparency is the phosphate flame retardant of irreducible minimum; more preferably 1; two (phenyl phosphoryl) benzene of 3-; 1; two (diphenylphosphine acyl group) benzene of 3-; 1; two [two (alkyl phenyl) phosphoryl] benzene of 3-; 1; 3-two [two (2 '; 6 '-3,5-dimethylphenyl) phosphoryl] benzene; 1; 3-two [two (2 '; 6 '-diethyl phenyl) phosphoryl] benzene; 1; 3-two [two (2 '; 6 '-diisopropyl phenyl) phosphoryl] benzene; 1; 3-two [two (2 '; 6 '-dibutyl phenyl) phosphoryl] benzene; 1; two [two (2 '-tert-butyl-phenyl) phosphoryl (ホス Off ホリ the Le)] benzene of 3-; 1; two [two (2 '-isopropyl phenyl) phosphoryl] benzene of 3-; 1; two [two (2 '-aminomethyl phenyl) phosphoryl] benzene of 3-; 1; two (diphenylphosphine acyl group) benzene of 4-; 1; 4-two [two (2 '; 6 '-3,5-dimethylphenyl) phosphoryl] benzene; 1; 4-two [two (2 '; 6 '-diethyl phenyl) phosphoryl] benzene; 1; 4-two [two (2 '; 6 '-diisopropyl phenyl) phosphoryl] benzene; 1; two [two (2 '-tert-butyl-phenyl) phosphoryl] benzene of 4-; 1, two [two (2 '-isopropyl phenyl) phosphoryl] benzene of 4-; 1, two [two (2 '-aminomethyl phenyl) phosphoryl] benzene and 4 of 4-; 4 '-two [two (2 ", 6 "-3,5-dimethylphenyl) the phosphoryl phenyl] condensed type phosphate flame retardant such as dimethylmethane.Use level is decided by the degree of the anti-flammability of selected fire retardant and requirement, but is 0.5～40 weight portion with respect to cyclic olefin polymer 100 weight portions preferably, and more preferably 2～30 weight portions are preferably 4～20 weight portions especially.Use level at above-mentioned fire retardant is less than under the situation of 0.5 weight portion, and effect is insufficient, on the other hand, uses if surpass 40 weight portions, and the transparency is impaired, and electrical characteristics such as specific inductive capacity worsen, or the water-intake rate increase, or thermotolerance worsens.

In cyclic olefin based polymer of the present invention, in the scope of not damaging the invention effect, can also add known adjuvants such as antioxidant, thermal stabilizer, light stabilizer, phase differential adjustment agent, ultraviolet light absorber, antistatic agent, spreading agent, processability improver, chlorine agent for capturing, fire retardant, crystallization nucleating agent, anti blocking agent, antifoggant, release agent, pigment, organic or inorganic packing material, neutralizing agent, lubricant, distintegrant, metal passivator, anti-pollution material, antiseptic, other resins, thermoplastic elastomer as required.

The manufacturing of＜original membrane 〉

The original membrane of using in the making of phase retardation film of the present invention is following to be obtained, that is, by with the cycloolefin polymer dissolution in suitable solvent and cast, be shaped to film or sheet etc. thus.In addition, also can obtain by known method systems such as extrusion by melting film.

The original membrane that obtains has outstanding balance at aspects such as optical characteristics such as the transparency, resistance to chemical reagents, thermotolerance, water tolerance and moisture-proofs.

About original membrane, film thickness is 100～250 μ m, is preferably 120～200 μ m, and the maximum ga(u)ge of film and the difference of minimum thickness are in 3 μ m, preferably in 2 μ m.

The manufacturing of＜phase retardation film 〉

Phase retardation film of the present invention is fit to obtain by with above-mentioned stretching ratio original membrane being implemented horizontal uniaxial tension.

In order to obtain phase retardation film of the present invention, need implement the operation of heating stretch processing to original membrane.

About heating the temperature of stretch processing, glass transition temperature (Tg) with the original membrane that is formed by the cyclic olefin based polymer used in the present invention is benchmark, be generally (Tg-10 ℃)～scope of (Tg+70 ℃), be preferably (Tg ± 0 ℃)～scope of (Tg+50 ℃).In above-mentioned scope, the hot deterioration of film can not take place, in addition, can under the situation that film can not rupture, stretch, so preferred.Here, Tg is to use the value that above-mentioned differential scanning calorimeter (DSC) is obtained.

Stretching is preferably the horizontal uniaxial tension of stenter (uniaxial tension of Width).By horizontal uniaxial tension, the largest refractive index in the face becomes the film Width,, can carry out roller and fit to roll-type, so throughput rate improves when bonding with polarizer.From optical characteristics such as accurate control Re, NZ and optical axises, preferred laterally uniaxial tension Temperature Distribution be controlled in design temperature ± 0.5 ℃ with interior, preferably set temperature ± 0.3 ℃ with interior, more preferably carry out in ℃ with interior stove design temperature ± 0.2.

Here, laterally the design temperature of uniaxial tension can be the temperature that the All Ranges in stove all equates, also can be stage or gradient be provided with the temperature of distribution.Under the situation of design temperature for the temperature that has been provided with distribution, the actual temperature in the preferred stove distribute and the Temperature Distribution that sets ± 0.5 ℃ with interior, preferred ± 0.3 ℃ with interior, more preferably ± 0.2 ℃ in.

Laterally the draw speed of uniaxial tension for example is the scope of 2～100m/ minute, preferred 5～50m/ minute.Stretching ratio and drawing numbers etc. are suitably selected according to needed phase difference value.Stretching ratio is 2.5～5.5 times, preferred 2.8～5.4 times, and preferred especially 3.0～5.3 times.

Drawing numbers is 1 time～2 times.

In the present invention, at stretching ratio is that high magnification surpasses 4 times situation etc. down, the thickness after guarantee to stretch and the homogeneity aspect of phase differential, preferably carry out horizontal uniaxial tension twice, but just can obtain through one-off drawing under the inhomogeneity situation of thickness and phase differential, more preferably making drawing numbers is 1 time.It should be noted that stretching ratio when carrying out twice horizontal uniaxial tension is with the stretching ratio and the product representation of stretching ratio for the first time for the second time.

The thickness of phase retardation film of the present invention is 20～100 μ m, preferred 25～90 μ m.In addition, the difference of the maximum ga(u)ge of this film and minimum thickness is in the 3 μ m.

More than, the adjusting of molecular weight, Tg, film thickness and the stretching ratio of multipolymer are above-mentioned preferable range in selection by making comonomer (I ') and (II ') and copolymerization ratio, the polyreaction, the α (MD) and the α (TD) of phase retardation film can be controlled at preferred range, the excessive change in size and the anisotropy of change in size in the time of can preventing to heat reduce making this phase retardation film be layered in warpage, the ripple of the one-sided at least polaroid that obtains of polarizing coating.

＜purposes 〉

Phase retardation film of the present invention has the outstanding transparency, thermotolerance and low water absorbable, in addition, warpage, the ripple of the polaroid that stacked this phase retardation film forms are less, so on polaroid is made and the liquid crystal display cells processing of making easy, and the homogeneity of liquid crystal display cells, stability and high-resolution are outstanding.Thus, be suitable for various liquid crystal display cells, especially vertical alignment-type liquid crystal display device etc. can be realized good viewing angle compensation.

Embodiment

Below, specific embodiments of the invention are described, but the present invention is not limited to these embodiment.It should be noted that followingly, unless otherwise specified, " part ", " % " are meant " weight portion ", " weight % ".

In addition, each assessment item among the following embodiment is measured by following method.

＜glass transition temperature (Tg) 〉

Use the differential scanning calorimeter (DSC) of SEIKO INSTRUMENTS corporate system, under being 20 ℃/minute, nitrogen atmosphere, programming rate measures, on the differential scanning heat curve, depict the maximum peak temperature (A point) of the differential differential scanning heat curve that mensuration like this obtains and deduct 20 ℃ temperature (B point), being that tangent line on the baseline of starting point is obtained as Tg with the intersection point that is the tangent line of starting point with the B point with the A point from the maximum peak temperature.

＜saturated water absorption 〉

According to ASTM D570, in one week of impregnated sample in 23 ℃ water, the weight change of the sample before and after the mensuration dipping is obtained saturated water absorption by this value.

＜total light transmittance 〉

Use the haze meter " HGM-2DP type " of SUGA TEST INSTRUMENTS corporate system to measure.

The phase differential of＜transmitted light 〉

Use " KOBRA-21ADH " of prince's instrumentation machine (strain) system, measure the phase differential Re and the NZ at wavelength 589nm place.

＜logarithm viscosity 〉

Use Ubbelohde viscometer, (sample solution concentration: 0.5g/dL), measure under 30 ℃ in chloroform or cyclohexane.

＜weight-average molecular weight and number-average molecular weight 〉

By gel permeation chromatography (GPC) (HLC-8020, eastern Cao (strain) system), use tetrahydrofuran (THF) solvent, measure weight-average molecular weight (Mw), number-average molecular weight (Mn), molecular weight distribution (Mw/Mn) by polystyrene conversion.

＜average coefficient of linear expansion 〉

Use " TMA-SS6000 " of SEIKO INSTRUMENTS (strain) system, under elongation pattern, load 1g, film width 4mm, chuck (chuck) spacing 20mm, 10 ℃/minute the condition of heating up, measure-40 ℃～85 ℃ average coefficient of linear expansion (α (MD) and α (TD)).

＜synthesis example 1 〉

With 8-methyl-8-methoxycarbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,10250 parts of]-3-dodecenes (specific monomer), 18 parts of 1-hexenes (molecular weight regulator) and toluene (ring-opening polymerization solvent) are encased in the reaction vessel of nitrogen displacement for 750 parts, and this solution is heated to 60 ℃.Then, add in the solution in reaction vessel as 0.62 part of the toluene solution (1.5 mol) of the aluminium triethyl of polymerization catalyst with through the tungsten hexachloride (tert-butyl alcohol: methyl alcohol: tungsten=0.35mol: 0.3mol: 3.7 parts of toluene solutions 1mol) (concentration 0.05 mol) of the tert-butyl alcohol and methyl alcohol modification, under 80 ℃, this solution carried out 3 hours heated and stirred, make it that ring-opening polymerization takes place thus, obtain ring-opening polymerization polymer solution.Polymerisation conversion in this polyreaction is 97%.

In the 1000 parts of reactors of packing into of ring-opening polymerization polymer solution that so obtain, in this ring-opening polymerization polymer solution, add RuHCl (CO) [P (C ₆H ₅) ₃] ₃0.12 part, at hydrogen-pressure 100kg/cm ², 165 ℃ of temperature of reaction condition under, heated and stirred 3 hours is carried out hydrogenation.After reaction solution (hydrogenated polymer solution) cooling that obtains, the releasing hydrogen gas decompression.This reaction solution is injected in a large amount of methyl alcohol, coagulum is separated recovery, it is carried out drying, obtain hydropolymer (below, be called " Resin A ").

The Resin A that so obtains is passed through ¹The hydrogenation ratio that H-NMR measures is 99.9%, the glass transition temperature of measuring by the DSC method (Tg) is 165 ℃, the number-average molecular weight of measuring by the GPC method based on polystyrene conversion (Mn) is 32000, weight-average molecular weight (Mw) be 137000 and molecular weight distribution (Mw/Mn) be 4.29, at 23 ℃ saturated water absorptions is 0.3%, and the logarithm viscosity in 30 ℃ chloroform is 0.78dl/g.

＜synthesis example 2 〉

Use 8-methyl-8-methoxycarbonyl Fourth Ring [4.4.0.1 ^2,5.1 ^7,1035 parts of 215 parts of]-3-dodecenes and dicyclo [2.2.1] hept-2-ene"s, the addition that makes the 1-hexene is 30 parts, in addition similarly obtains hydropolymer (below, be called " resin B ") with synthesis example 1.

The resin B that so obtains is passed through ¹The hydrogenation ratio that H-NMR measures is 99.9%, the Tg that measures by the DSC method is 125 ℃, the Mn based on polystyrene conversion that measures by the GPC method is 46000, Mw be 190000 and Mw/Mn be 4.15, at 23 ℃ saturated water absorptions is 0.18%, and the logarithm viscosity in 30 ℃ chloroform is 0.53dl/g.

＜synthesis example 3 〉

Use Fourth Ring [4.4.0.1 ^2,5.1 ^7,1053 parts of]-3-dodecenes, 8-ethidine Fourth Ring [4.4.0.1 ^2,5.1 ^7,1046 parts of]-3-dodecenes and three ring [4.3.0.1 ^2,5]-the last of the ten Heavenly stems-3,66 parts of 7-diene, the addition that makes the 1-hexene is 18 parts, uses cyclohexane to replace toluene as the ring-opening polymerization solvent, in addition similarly obtains hydropolymer (below, be called " resin C ") with synthesis example 1.

The hydrogenation ratio of the resin C that obtains is 99.9%, the Tg that measures by the DSC method is 137 ℃, by the GPC method (solvent: o-dichlorobenzene) Mn of Ce Dinging be 39000, Mw be 158000 and Mw/Mn be 4.05, at 23 ℃ saturated water absorptions is 0.01%, and the logarithm viscosity in 30 ℃ chloroform is 0.70dl/g.

＜Production Example 1 〉

The manufacturing of resin molding (A-1)

Above-mentioned Resin A is dissolved in toluene, make that concentration is 30% (solution viscosity under the room temperature is 30000mPas), [3-(3 to add pentaerythrite four as antioxidant with respect to resin 100 weight portions, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] 0.1 weight portion, use the metallic fiber sintered filter of the aperture 5 μ m that Japanese PALL company makes, limit control solution flow rate makes pressure differential remain on 0.4MPa and filters with inner edge.Use is arranged at the aboveground metal industry system " INVEX labocoater " in 1000 grades the toilet, on the base material PET film that has carried out the thick 100 μ m of hydrophiling (easy bondingization) surface-treated with acrylic acid series (east beautiful (strain) system " Lumirror U94 "), be coated with resulting solution, making dried thickness is 130 μ m.It after carrying out primary drying under 50 ℃, is carried out redrying under 90 ℃.Obtain resin molding (A-1) after peeling off the PET film.The total light transmittance of the resin molding that obtains (A-1) is 93%.

＜Production Example 2 〉

The manufacturing of resin molding (B-1)

Except using resin B to replace the Resin A,, obtain the resin molding (B-1) of thick 150 μ m according to the method same with Production Example 1.The total light transmittance of the resin molding that obtains (B-1) is 93%.

＜Production Example 3 〉

The manufacturing of resin molding (C-1)

Use resin C to replace Resin A, and replace toluene,, obtain the resin molding (C-1) of thick 150 μ m in addition according to the method same with Production Example 1 with cyclohexane.The total light transmittance of the resin molding that obtains (C-1) is 93%.

＜Production Example 4 〉

The manufacturing of resin molding (B-2)

Use biaxial extruder (TEM-48, Toshiba Machinery Co., Ltd.'s system) and pass through gear-type pump extrusion resin A downstream, using the aperture of nominal is the metallic fiber sintered filter of the Japanese smart line corporate system of 10 μ m, carry out melt filteration, use the T mould (width is 650mm) of clothes hanger type, making the gap of T mould outlet is 0.5mm, under 280 ℃, be extruded into membranaceously, be crimped on the chill roll, obtain the film (B-2) of thick 150 μ m thus.The total light transmittance of the film that obtains (B-2) is 93%.

＜Production Example 5 〉

The manufacturing of resin molding (C-2)

Use resin C to replace Resin A,, obtain the resin molding (C-2) of thick 150 μ m in addition according to the method same with Production Example 4.The total light transmittance of the resin molding that obtains (C-2) is 93%.

[embodiment 1]

The manufacturing of phase retardation film (A-11)

Use the cross directional stretch machine of tentering formula, under 180 ℃, 2.5 times settings, (A-1) carries out horizontal uniaxial tension to above-mentioned resin molding, obtains the phase retardation film that thickness is 51～53 μ m (A-11) thus.The Re of the stretched film that obtains is 155nm, and NZ is 1.40.In addition, the average coefficient of linear expansion of draw direction (film Width) (α (TD)) is 60ppm/ ℃, with the average coefficient of linear expansion (α (MD)) of the direction (film length direction) of draw direction quadrature be 72ppm/ ℃.

[embodiment 2]

The manufacturing of phase retardation film (B-11)

Under 147 ℃, 3.0 times settings, (B-1) carries out horizontal uniaxial tension to above-mentioned resin molding, obtains the phase retardation film that thickness is 47～50 μ m (B-11) thus.The Re of the stretched film that obtains is 105nm, and NZ is 1.35.In addition, α (TD) is 74ppm/ ℃, and α (MD) is 85ppm/ ℃.

[embodiment 3]

The manufacturing of phase retardation film (B-21)

Use resin molding (B-2) to replace resin molding (B-1), in addition, obtain the phase retardation film that thickness is 48～51 μ m (B-21) according to similarly to Example 2 method.In addition, the Re of the stretched film that obtains is 155nm, and NZ is 1.35.α (TD) is 72ppm/ ℃, and α (MD) is 86ppm/ ℃.

[embodiment 4]

The manufacturing of phase retardation film (B-22)

Under 133 ℃, 2.0 times settings, (B-2) carries out horizontal uniaxial tension to above-mentioned resin molding, and then under 147 ℃, 2.4 times settings, this film is carried out horizontal uniaxial tension, obtaining 4.8 times of essence stretchings and thickness thus is the phase retardation film (B-22) of 30～33 μ m.The Re of the stretched film that obtains is 150nm, and NZ is 1.20.In addition, α (TD) is 74ppm/ ℃, and α (MD) is 87ppm/ ℃.

[embodiment 5]

The manufacturing of phase retardation film (C-11)

Under 157 ℃, 3.0 times settings, (C-1) carries out cross directional stretch to above-mentioned resin molding, obtains the stretched film that thickness is 49～52 μ m (C-11) thus.The Re of the stretched film that obtains is 160nm, and NZ is 1.33.In addition, α (TD) is 63ppm/ ℃, and α (MD) is 70ppm/ ℃.

[embodiment 6]

The manufacturing of phase retardation film (C-21)

Use resin molding (C-2) to replace resin molding (C-1), under 160 ℃, 3.0 times settings, carry out cross directional stretch, obtain the phase retardation film that thickness is 48～51 μ m (C-21) thus.The Re of the stretched film that obtains is 142nm, and NZ is 1.34.In addition, α (TD) is 68ppm/ ℃, and α (MD) is 74ppm/ ℃.

[comparative example 1]

The manufacturing of stretched film (A-12)

Under 185 ℃,, obtain the stretched film that thickness is 75～77 μ m (A-12) thus with 2.7 times of above-mentioned resin molding (A-1) longitudinal stretchings.The Re of the stretched film that obtains is 400nm, and NZ is 1.03.In addition, α (TD) is 92ppm/ ℃, and α (MD) is 58ppm/ ℃.

＜Production Example 6 〉

The manufacturing of polarizing coating

By iodine concentration be 0.03% and potassium iodide concentration be in the dye bath that forms of 0.5% aqueous solution (30 ℃ of temperature), with 3 times stretching ratios polyvinyl alcohol (PVA) (hereinafter referred to as " PVA ") is carried out preceding stretch process, subsequently, by boric acid concentration be 5% and potassium iodide concentration be in the crosslinked bath that forms of 8% aqueous solution (55 ℃ of temperature), carry out after stretching processing with 2 times stretching ratios, implement dried, obtain polarizing coating (below be also referred to as " polarizer ") thus.

＜preparation example 〉

The preparation of water system bonding agent

Preparation PVA is 4% aqueous solution of resin (trade name: 163-03045 (molecular weight 500, the about 88mol% of saponification degree) and the pure medicine of light (strain) system).On the other hand, (cooperating poly-epoxy among 100 parts of trade name: the WLS-201 (nonvolatile component 35%, big Japanese ink chemical industry (strain) system) is 5 parts in hardening agent (trade name: CR-5L (effective constituent 100% product), big Japanese ink chemical industry (strain) are made) at urethane adhesive.Is that aqueous solution and polyurethane series resin mix to count 20: 80 ratio in the solid constituent weight ratio with the PVA that obtains, and water dilutes then, the mixed aqueous solution (water system bonding agent) of preparation 15%

＜embodiment 7 〉

The making of polaroid (A-111)

To a face of the phase retardation film (A-11) of A4 size, with power 60W/m ²/ minute carry out corona treatment, so that the mode of draw direction quadrature separately, use above-mentioned water system bonding agent fit this corona treatment face and polarizer, under state with the draw direction of molding box fixed polarizer, 50 ℃ of dryings 3 minutes, then 80 ℃ of dryings 20 minutes.Then, using PVA is bonding agent another face applying cellulose triacetate (TAC) film at above-mentioned polarizer, similarly carries out drying, has obtained polaroid (A-111).

The transmissivity of the polaroid that obtains is 43.7%, and degree of polarization is 99.9%.When being statically placed in tabular surface from the molding box dismounting and with this polaroid, about 7mm is floated in the film end.

[embodiment 8]

The making of polaroid (B-111)

Use stretched film (B-11) to replace stretched film (A-11), in addition, adopt the method identical, obtained polaroid (B-111) with embodiment 7.

The transmissivity of the polaroid that obtains is 43.5%, and degree of polarization is 99.9%.When being statically placed in tabular surface from the molding box dismounting and with this polaroid, about 8mm is floated in the film end.

[embodiment 9]

The making of polaroid (B-211)

Use stretched film (B-21) to replace stretched film (A-11), in addition, adopt the method identical, obtained polaroid (B-211) with embodiment 7.

The transmissivity of the polaroid that obtains is 43.6%, and degree of polarization is 99.9%.When being statically placed in tabular surface from the molding box dismounting and with this polaroid, about 10mm is floated in the film end.

[embodiment 10]

The making of polaroid (B-221)

Use stretched film (B-22) to replace stretched film (A-11), in addition, adopt and the identical method of polaroid (A-111), obtained polaroid (B-221).

The transmissivity of the polaroid that obtains is 43.6%, and degree of polarization is 99.9%.When being statically placed in tabular surface from the molding box dismounting and with this polaroid, about 15mm is floated in the film end.

[embodiment 11]

The making of polaroid (C-111)

Use stretched film (C-11) to replace stretched film (A-11), in addition, adopt the method identical, obtained polaroid (C-111) with embodiment 7.

The transmissivity of the polaroid that obtains is 43.4%, and degree of polarization is 99.9%.When being statically placed in tabular surface from the molding box dismounting and with this polaroid, about 7mm is floated in the film end.

[embodiment 12]

The making of polaroid (C-211)

Use stretched film (C-21) to replace stretched film (A-11), in addition, adopt the method identical, obtained polaroid (C-211) with embodiment 7.

The transmissivity of the polaroid that obtains is 43.6%, and degree of polarization is 99.9%.When being statically placed in tabular surface from the molding box dismounting and with this polaroid, about 7mm is floated in the film end.

[comparative example 2]

The making of polaroid (A-121)

Use stretched film (A-12) to replace stretched film (A-11), in addition, adopt the method identical, obtained polaroid (A-121) with embodiment 7.

The transmissivity of the polaroid that obtains is 43.7%, and degree of polarization is 99.9%.When being statically placed in tabular surface from the molding box dismounting and with this polaroid, film curls becomes tubular.

Industrial utilizability

Phase retardation film of the present invention, uniformity and stability are outstanding, warpage after fitting with polarizing coating etc. is few, so be suitable for making polarizer, can be suitable for mobile phone, notebook computer, auto navigation, portable game machine, LCD TV, possess the various liquid crystal indicators such as LCD monitor of giant display.

Claims

1. a phase retardation film is characterized in that,

Form by the cyclic olefin based polymer, satisfy following formula (1)～(5),

(1)70nm≤Re≤300nm

(2)1.1≤NZ≤1.7

In formula (1)～(2), Re is the interior phase differential of face of the film at wavelength 589nm place, represent with Re=(nx-ny) * d, NZ is the coefficient with NZ=(nx-nz)/(nx-ny) expression, and here, nx represents the largest refractive index in the face, ny is illustrated in the face and the refractive index of the direction of nx quadrature, nz represents and the refractive index of the film thickness direction of nx and ny quadrature that d represents the thickness of film, and unit is nm;

(3)α(MD)≤90ppm/℃

(4)α(TD)≤90ppm/℃

(5)|α(MD)-α(TD)|≤30ppm/℃

In formula (3)～(5), the average coefficient of linear expansion of α (MD) expression film length direction, the average coefficient of linear expansion of α (TD) expression film Width, but, described average coefficient of linear expansion all is the values under-40 ℃～85 ℃.

2. phase retardation film according to claim 1 is characterized in that,

Described cyclic olefin based polymer has the formation unit shown in the following formula (I),

In formula (I), m is the integer more than 1, and p is the integer more than 0 or 1; D is-CH=CH-or-CH ₂CH ₂-shown in group; R ¹～R ⁴Represent independently of one another that from hydrogen atom halogen atom contains the binding group of oxygen atom, sulphur atom, nitrogen-atoms or silicon atom, replace or unsubstituted carbon number is 1～30 alkyl, atom of selecting in the polar group or group; R ¹And R ²Can be integrated and form bivalent hydrocanbon radical, R ³And R ⁴Can be integrated and form bivalent hydrocanbon radical; R ¹And R ²Can mutually combine and form carbocyclic ring or heterocycle, R ³And R ⁴Can mutually combine and form carbocyclic ring or heterocycle, this carbocyclic ring or heterocycle can be monocycle, also can be many rings.

3. phase retardation film according to claim 1 is characterized in that,

Thickness is 20～100 μ m, and the maximum ga(u)ge of film and the difference of minimum thickness are in the 3 μ m.

4. a polaroid is characterized in that,

Any described phase retardation film forms in the one-sided at least stacked claim 1～3 of polarizing coating.