CN100468099C

CN100468099C - Optical film, polarizing plate and liquid crystal display

Info

Publication number: CN100468099C
Application number: CNB2005800285787A
Authority: CN
Inventors: 关口正之; 牛野卓浩; 杉山直树; 广野达也; 川岛直之
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2004-08-30
Filing date: 2005-08-25
Publication date: 2009-03-11
Anticipated expiration: 2025-08-25
Also published as: CN101006369A; JP2006065224A

Abstract

The invention provides an optical film for a liquid crystal display, in which a wide range of a retardation of transmitted light can be controlled in manufacturing and good viewing angle compensation effects on such as preventing light leakage or color dropout (coloring) in true black display and achieving a high contrast in all directions can be obtained when used in liquid crystal display. The optical film of the invention includes a film (a) layer made of a cyclic olefin resin and a film (b) layer made of a polyimide resin or a polyetherimide resin, wherein following formulae (1) and (2) are preferably satisfied: (1) 200 nm | Rth | 1,000 nm and (2) 0 | R550 | 200 nm, wherein Rth and R550 represent the retardation in the direction of film thickness and the in-plane retardation of the film, respectively, at wavelength of 550 nm.

Description

Blooming, polaroid and LCD

Technical field

The present invention relates to blooming, polaroid and LCD.The present invention more specifically relates to LCD with cycloolefin resin film and polyimide or polyetherimide resin film with blooming, the LCD that has the polaroid of this blooming and have this blooming or polaroid.

Background technology

That LCD has is extremely thin, volume is little, the advantage of low power consumption, so be used to various products such as mobile phone, notebook computer, auto-navigation system, LCD TV.Wherein, use transmission type lcd device (VA (vertically aligned particularly, vertical orientated) type) LCD TV not only estimate to have in the future more substantial demand, and along with the maximization of display, more in the past than the high meticulous demonstration and the cost degradation that more required wide visual angle, high brightness.

State (the orthogonal state of the axis of homology of polaroid) with Nicol crossed uses in the transmission type lcd device of two polaroids, if the position that makes observation display becomes oblique from the front of display, the axis of homology of then apparent last two polaroids departs from 90 degree, light leak when therefore producing black display and the problem of leaking look (painted).In order to solve such problem, between liquid crystal cell and each polaroid, be situated between and carry out the compensation that exists with ... the visual angle of polaroid with various phase retardation films.

As above-mentioned phase retardation film, known for example contain (for example, with reference to patent documentations 1～3) such as the resinoid bloomings of thermoplastic norbornene.The transparency of the blooming that is formed by norbornene resin like this is high, and the phase differential of transmitted light is low, and it is good to make transmitted light produce the optical characteristics such as phase differential of stable homogeneous.

Yet LCD TV etc. obtain high-contrast in order to prevent light leak, need the high phase retardation film of phase difference value of thickness direction, and above-mentioned existing phase retardation film is difficult to fully satisfy high like this requirement.

In addition, for the phase retardation film of the optical characteristics that obtains to have the character that meets liquid crystal cell, need exploitation can control the structure of multiple optical characteristics and job operation etc.

In addition, in the existing LCD, between liquid crystal cell and two polaroids, be situated between respectively and carry out viewing angle compensation with phase retardation film, therefore use two phase retardation films at least, but, need exploitation can only carry out the phase retardation film of viewing angle compensation with a phase retardation film in order to realize the further slimming and the cost degradation of LCD.

In addition; in the existing polaroid; for the liquid crystal deterioration of the liquid crystal cell part that prevents to produce etc., add use ultraviolet light absorber (UVA) in the diaphragm of polaroid, the membrane portions that for example forms by triacetyl cellulose (TAC) from the ultraviolet ray of light source or environment for use.Yet, cause cost to rise adding ultraviolet light absorber, the durable stable aspect of phase differential during particularly as the diaphragm that has the function of giving phase differential concurrently, also and unsatisfactory, existing problems.

Patent documentation 1: Japanese patent laid-open 5-2108 communique

Patent documentation 2: Japanese patent laid-open 7-287122 communique

Patent documentation 3: Japanese patent laid-open 7-287123 communique

The announcement of invention

Can be when problem of the present invention is to provide and makes at the phase differential of inner control transmitted light in a big way, when being used for LCD, play the light leak when preventing black display long-term and stably and leak the blooming of good viewing angle compensation effect such as look (painted), the omnibearing high-contrast of acquisition, the LCD that has the polaroid of this blooming and have this blooming or polaroid.

In order to solve above-mentioned problem, the inventor has carried out conscientiously research.Found that,, can solve above-mentioned problem, thereby finish the present invention by on specific cycloolefin resin film, having the blooming of the rete that forms by polyimide based resin or polyetherimides resin.

That is, blooming of the present invention is characterised in that, has the film a layer that is made of the cycloolefin resinoid and by the film b layer that polyimide based resin or polyetherimides resin form, better is to satisfy following formula (1) and (2).

(1)200nm≦Rth≦1000nm

(2)0≦R550≦200nm

In the above-mentioned formula, Rth is for the phase differential of wavelength 550nm place film thickness direction, with Rth=[(nx+ny)/2-nz] * d represents, R550 represents the phase differential in the wavelength 550nm place face, represents with R550=(nx-ny) * d.Here, nx is the largest refractive index in the face, ny be in the face with the refractive index of nx vertical direction, nz is the refractive index of the film thickness direction vertical with respect to nx, ny, d is the thickness (nm) of film.

Aforementioned films a layer better is to form with the cycloolefin resinoid of the formation unit of following general formula (II) expression with the formation unit of following general formula (I) expression and 70～0mol% by having 30～100mol%, the thickness of this film a layer is 10000 (nm)～200000 (nm), and it is the rete that obtains through uniaxial tension or biaxial stretch-formed processing that satisfies following formula (3)～(6).

In the formula (I), m is the integer more than 1, and p is the integer more than 0 or 1, D independently be with-CH=CH-or-CH ₂CH ₂The group of-expression, R ¹～R ⁴Independent respectively expression hydrogen atom, halogen atom maybe can have the replacement of the binding group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom or not have the alkyl or the polar group of the carbon number 1～30 of replacement, R ¹With R ²And/or R ³With R ⁴Can be integrated and form the alkyl of divalent, R ¹Or R ²With R ³Or R ⁴Can mutually combine and form carbocyclic ring or heterocycle, this carbocyclic ring or heterocycle can be single ring architecture or multiring structure.

In the formula (II), E independently be with-CH=CH-or-CH ₂CH ₂The group of-expression, R ⁵～R ⁸Independent respectively expression hydrogen atom, halogen atom maybe can have the replacement of the binding group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom or not have the alkyl or the polar group of the carbon number 1～30 of replacement, R ⁵With R ⁶And/or R ⁷With R ⁸Can be integrated and form the alkyl of divalent, R ⁵Or R ⁶With R ⁷Or R ⁸Can mutually combine and form carbocyclic ring or heterocycle, this carbocyclic ring or heterocycle can be single ring architecture or multiring structure.

(3)20nm≦R _ath≦500nm

(4)0≦R _a550≦200nm

(5)1.00≦R _a450/R _a550≦1.30

(6)0.70≦R _a650/R _a550≦1.00

In above-mentioned formula (3)～(6), R _aTh is for the phase differential of the film a of wavelength 550nm place thickness direction, with R _aTh=[(nx _a+ ny _a)/2-nz _a] * d _aExpression, R _a450, R _a550, R _a650 represent the interior phase differential R of film a face at wavelength 450nm, 550nm, 650nm place respectively _a, with R _a=(nx _a-ny _a) * d _aExpression.Here, nx _aBe the largest refractive index in the film a face, ny _aFor in the film a face and nx _aThe refractive index of vertical direction, nz _aFor with respect to nx _a, ny _aThe refractive index of vertical film a thickness direction, d _aThickness (nm) for film a.

Polyimide based resin as constituting aforementioned films b layer can preferably exemplify the polyimide based resin with alicyclic structure, better is the polyimide based resin that has with the structural unit of following formula (III) expression.

In the formula (III), X is 4 valency organic groups with alicyclic structure, and Y is the divalent organic group.

In addition, as the polyetherimide resinoid that constitutes aforementioned films b layer, can exemplify the polyetherimide resinoid that has with the structural unit of following formula (IV) expression.

In the formula (IV), X ' and Y ' can be identical, also can be different, represent saturated or undersaturated alkyl.

In addition, aforementioned films b layer better is to satisfy following formula (7)～(10).

(7)100nm≦R _bth≦1000nm

(8)0≦R _b550≦200nm

(9)1.00≦R _b450/R _b550≦1.30

(10)0.7≦R _b650/R _b550≦1.00

In above-mentioned formula (7)～(10), R _bTh is for the phase differential of the film b of wavelength 550nm place thickness direction, with R _bTh=[(nx _b+ ny _b)/2-nz _b] * d _bExpression, R _b450, R _b550, R _b650 represent the interior phase differential R of film b face at wavelength 450nm, 550nm, 650nm place respectively _b, this R _bWith R _b=(nx _b-ny _b) * d _bExpression.Wherein, aforementioned R _aTh and R _bTh's and below 1000nm, aforementioned R _a550 and R _b550 and below 200nm.Here, nx _bBe the largest refractive index in the film b face, ny _bFor in the film b face and nx _bThe refractive index of vertical direction, nz _bFor with respect to nx _b, ny _bThe refractive index of vertical film b thickness direction, d _bThickness (nm) for film b.

Blooming of the present invention can have acrylic compounds and/or polyurethanes primary coat c layer between aforementioned films a layer and film b layer.The blooming with acrylic compounds and/or polyurethanes primary coat c layer like this can form aforementioned films b layer by lining and obtain then by form aforementioned primary coat c layer by lining on the film a that obtains through uniaxial tension or biaxial stretch-formed processing on this primary coat c layer.In addition, also can on the film that does not stretch that forms by the cycloolefin resinoid, form aforementioned primary coat c layer by lining, on this primary coat c layer by lining formation aforementioned films b layer after, carry out uniaxial tension or biaxial stretch-formed processing again and obtain.

Polaroid of the present invention is characterised in that to have aforesaid blooming of the present invention.

LCD of the present invention is characterised in that to have aforesaid blooming of the present invention or polaroid.

The optical characteristics such as phase differential of the stable homogeneous when blooming of the present invention not only keeps as the high transparent of the speciality of existing cycloolefin resin film, low phase differential and stretch orientation, and thermotolerance, good with the adaptation of other material and connectivity etc., the suction distortion is little, and can control the phase differential of transmitted light during fabrication.In addition, owing to phase differential can easily being produced and controlling, therefore when being used for LCD, can stably obtain good viewing angle compensation effect.

In addition,, then do not need as in the past, to use two bloomings (phase retardation film), can obtain enough viewing angle compensation effects yet by a blooming if use blooming of the present invention (phase retardation film).In addition, the influence that not changed by environment for use, long-term performance goes out stable properties.

The best mode that carries out an invention

Below, blooming of the present invention, polaroid and LCD are elaborated.

[blooming]

＜structure and optical characteristics 〉

Blooming of the present invention is to have the film a layer that is made of the cycloolefin resinoid and the film of the film b layer that formed by polyimide based resin or polyetherimides resin, better is to satisfy following formula (1) and (2).

(1)200nm≦Rth≦1000nm

(2)0≦R550≦200nm

In above-mentioned formula (1) and (2), Rth is for the phase differential of wavelength 550nm place film thickness direction, with Rth=[(nx+ny)/2-nz] * d represents, R550 represents the phase differential in the wavelength 550nm place face, represents with R550=(nx-ny) * d.Here, nx is the largest refractive index in the face, ny be in the face with the refractive index of nx vertical direction, nz is the refractive index of the film thickness direction vertical with respect to nx, ny, d is the thickness (nm) of film.

Shown in above-mentioned formula (1), the Rth of blooming of the present invention at 200～1000nm, better be 200～400nm, be more preferably in 250～300 the scope, and shown in above-mentioned formula (2), the R550 of blooming of the present invention at 0～200nm, better be 10～150nm, good especially be in the scope of 30～100nm, thereby the light leak of LCD can prevent from oblique the observation especially the time, obtain high-contrast.

＜film a 〉

The film a layer that constitutes blooming of the present invention better is the phase retardation film that satisfies following formula (3)～(6) that is formed by the cycloolefin resinoid.

(3)20nm≦R _ath≦500nm

(4)0≦R _a550≦200nm

(5)1.00≦R _a450/R _a550≦1.30

(6)0.70≦R _a650/R _a550≦1.00

Shown in above-mentioned formula (3), the R of film a layer _aTh is 20～500nm, better is 20～200nm, is more preferably 50～150nm.

Shown in above-mentioned formula (4), the R of film a layer _a550 is 0～200nm, better is 5～100nm, is more preferably 20～70nm.

Film a layer shown in above-mentioned formula (5), R _a450/R _a550 value 1.00～1.30, better be 1.00～1.20, good especially be in 1.00～1.10 the scope, and shown in above-mentioned formula (6), R _a650/R _a550 value 0.70～1.00, better be 0.80～1.00, good especially be in 0.90～1.00 the scope, thereby the phase difference value height of short wavelength side, the phase difference value of long wavelength side is low, promptly shows so-called positive wavelength dispersibility, becomes the low film of wavelength interdependence of phase difference value simultaneously.

From the angle of the slimming of LCD, the ideal thickness of aforesaid film a layer be 10000nm～200000nm, better be 30000nm～100000nm, good especially is 40000nm～70000nm.

As the cycloolefin resinoid that constitutes above-mentioned film a layer, because the optical characteristics such as phase differential of the stable homogeneous in the time of not only can obtaining high transparent, low phase differential and stretch orientation, and thermotolerance, good with the adaptation of other material and connectivity etc., suction distortion is little, therefore better is to have 30～100mol% with the formation unit of following general formula (I) expression (below be also referred to as " constituting unit I ") and the 70～0mol% norbornene resin with the formation unit of following general formula (II) expression (below be also referred to as " formation unit II ").

In the above-mentioned formula (I), m is the integer more than 1, and p is the integer more than 0 or 1.

In addition, above-mentioned formula (I) and (II) in, D and E are independent respectively be with-CH=CH-or-CH ₂CH ₂The group of-expression.

R ¹～R ⁸Respectively independent expression hydrogen atom, halogen atoms such as fluorine atom, sulphur atom, bromine atoms can have the replacement of the binding group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom or not have the alkyl of the carbon number 1～30 of replacement, perhaps polar group.

As the alkyl of above-mentioned carbon number 1～30, can exemplify for example alkyl such as methyl, ethyl, propyl group, cyclopentyl such as cyclopentyl, cyclohexyl, alkenyls such as vinyl, allyl, propenyl etc.In addition, above-mentioned alkyl can directly combine with ring structure, perhaps can be situated between to link group (linkage) combination.

As such binding group, the divalent alkyl that can exemplify carbon number 1～10 is (for example with-(CH ₂) _lThe alkylidene of-(l is 1～10 integer) expression), binding group (carbonyl (CO-), oxygen carbonyl (O (CO)-), the sulfonic group (SO for example that contains aerobic, nitrogen, sulphur or silicon ₂-), ehter bond (O-), thioether group (S-), imino group (NH-), amido link (NHCO-,-CONH-), siloxane bond (OSi (R ₂)-(R is alkyl such as methyl, ethyl)) etc., can be the binding group that comprises a plurality of above-mentioned groups.

In addition, R ¹With R ²And/or R ³With R ⁴Can be integrated and form the alkyl of divalent, R ¹Or R ²With R ³Or R ⁴Can mutually combine and form carbonyl ring or heterocycle, this carbocyclic ring or heterocycle can be single ring architecture or multiring structure.R ⁵～R ⁸Also be same.

As polar group, can exemplify hydroxyl; the alkoxy of carbon number 1～10 (methoxyl for example; ethoxy etc.); alkoxy carbonyl group (methoxycarbonyl group for example; carbethoxyl group etc.); aryloxycarbonyl (phenyloxycarbonyl for example; the naphthoxy carbonyl; fluorenes oxygen base carbonyl; biphenylyloxy carbonyl etc.); cyano group; amide group; the group that contains imide ring; trialkyl siloxy group (trimethylsiloxane group for example; the triethyl siloxy group); trialkyl silylation (TMS for example; triethyl silyl); amino (for example primary amino radical); acyl group; alkoxysilane group (trimethoxy silane base for example; the triethoxysilicane alkyl); contain the group of sulfonyl and carboxyl etc.

As the preferred form of above-mentioned norbornene resin used among the present invention, can exemplify:

By the above-mentioned resin that constitutes unit (I) formation of 100mol%;

Constitute unit (I) and the above-mentioned formation of 50～5mol% unit (II) and constitute the R in the above-mentioned formula (I) by 50～95mol% is above-mentioned ¹And R ²Be hydrogen atom, R ³Be methyl, R ⁴Be methoxycarbonyl group, m=1, p=0, the R in the above-mentioned formula (II) ⁵～R ⁸Resin for hydrogen atom or alkyl;

Constitute unit (I) and the above-mentioned formation of 50～5mol% unit (II) and constitute the R in the above-mentioned formula (I) by 50～95mol% is above-mentioned ¹And R ²Be hydrogen atom, R ³Be methyl, R ⁴Be methoxycarbonyl group, m=1, p=0, the R in the above-mentioned formula (II) ⁵Or R ⁶And R ⁷Or R ⁸Be hydrogen atom, and R ⁵～R ⁸The mutually combine resin etc. of the divalent straight chain shape alkyl that forms carbon number 3 of all the other groups.

The monomer that can form above-mentioned formation unit (I) is represented with following general formula (I ').

In the above-mentioned formula (I '), m, p, R ¹～R ⁴With m, p, the R in the above-mentioned formula (I) ¹～R ⁴Implication is identical.Below, the object lesson of the monomer (the following monomer (I ') that also claims) that example is such, but the present invention is not limited to these object lessons.In addition, following monomer (I ') may be used alone, two or more kinds can also be used in combination.

Can exemplify

Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

Five rings [6.5.1.1 ^2.5.0 ^2.7.0 ^9.13]-4-15 carbenes,

Five rings [7.4.0.1 ^2.5.0 ^9.12.0 ^8.12]-3-15 carbenes,

8-methoxycarbonyl group Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-carbethoxyl group Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

The positive third oxygen carbonyl Fourth Ring [4.4.0.1 of 8- ^2.5.1 ^7.10]-3-dodecylene,

The different third oxygen carbonyl Fourth Ring [4.4.0.1 of 8- ^2.5.1 ^7.10]-3-dodecylene,

The positive butoxy carbonyl of 8-Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-phenyloxycarbonyl Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-methyl-8-methoxycarbonyl group Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-methyl-8-carbethoxyl group Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

The positive third oxygen carbonyl Fourth Ring [4.4.0.1 of 8-methyl-8- ^2.5.1 ^7.10]-3-dodecylene,

The different third oxygen carbonyl Fourth Ring [4.4.0.1 of 8-methyl-8- ^2.5.1 ^7.10]-3-dodecylene,

The positive butoxy carbonyl of 8-methyl-8-Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-methyl-8-phenyloxycarbonyl Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

Five rings [8.4.0.1 ^2.5.0 ^9.12.0 ^8.13]-3-cetene,

Seven ring [8.7.0.1 ^3.6.1 ^10.17.1 ^12.15.0 ^2.7.0 ^11.16]-4-eicosylene,

Seven ring [8.8.0.1 ^4.7.1 ^11.18.1 ^13.160 ^3.8.0 ^12.17]-5-heneicosene,

8-ethylidene Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-phenyl Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-methyl-8-phenyl Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-fluorine Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-methyl fluoride Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-difluoromethyl Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-trifluoromethyl Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-pentafluoroethyl group Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8,8-difluoro Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8,9-difluoro Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8,8-two (trifluoromethyl) Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8,9-two (trifluoromethyl) Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-methyl-8-trifluoromethyl Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8,8,9-trifluoro Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8,8,9-three (trifluoromethyl) Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8,8,9,9-tetrafluoro Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8,8,9,9-four (trifluoromethyl) Fourth Ring [4.4.0.1 ^2.51 ^7.10]-3-dodecylene,

8,8-two fluoro-9,9-two (trifluoromethyl) Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8,9-two fluoro-8,9-two (trifluoromethyl) Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8,8,9-three fluoro-9-trifluoromethyl Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8,8,9-three fluoro-9-trifluoromethoxy Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8,8,9-three fluoro-9-five fluorine propoxyl group Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-fluoro-8-pentafluoroethyl group-9,9-two (trifluoromethyl) Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8,9-two fluoro-8-seven fluorine isopropyl-9-trifluoromethyl Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-chloro-8,9,9-trifluoro Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8,9-two chloro-8,9-two (trifluoromethyl) Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-(2,2,2-trifluoro carbethoxyl group) Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene,

8-methyl-8-(2,2,2-trifluoro carbethoxyl group) Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene etc.

In the above-mentioned object lesson, 8-methyl-8-methoxycarbonyl group Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene can improve the glass temperature of the multipolymer that obtains, the harmful effects such as distortion that can be subjected to hardly absorbing water and produce, and can keep water absorptivity with the good degree of the adaptation of other material and connectivity, so be desirable.

The monomer that can form above-mentioned formation unit (II) is represented with following general formula (II ').

In the above-mentioned formula (II '), R ⁵～R ⁸With the R in the above-mentioned formula (II) ⁵～R ⁸Same meaning.Below, the object lesson of the monomer (the following monomer (II ') that also claims) that example is such, but the present invention is not limited to these object lessons.In addition, following monomer (II ') may be used alone, two or more kinds can also be used in combination.

Can exemplify

Two ring [2.2.1] hept-2-ene"s,

Three ring [4.3.0.1 ^2.5]-3-decene,

Three ring [4.3.0.1 ^2.5] last of the ten Heavenly stems-3, the 7-diene,

Three ring [4.4.0.1 ^2.5]-3-undecylene

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

5-ethyl two ring [2.2.1] hept-2-ene"s,

5-methoxycarbonyl group two ring [2.2.1] hept-2-ene"s,

5-methyl-5-methoxycarbonyl group two ring [2.2.1] hept-2-ene"s,

5-phenyloxycarbonyl two ring [2.2.1] hept-2-ene"s,

5-methyl-5-phenyloxycarbonyl two ring [2.2.1] hept-2-ene"s,

5-cyano group two ring [2.2.1] hept-2-ene"s,

5-ethylene ring [2.2.1] hept-2-ene",

5-phenyl two ring [2.2.1] hept-2-ene"s,

5-naphthyl two ring [2.2.1] hept-2-ene"s (α, β two types all can),

5-fluorine two ring [2.2.1] hept-2-ene"s,

5-methyl fluoride two ring [2.2.1] hept-2-ene"s,

5-trifluoromethyl two ring [2.2.1] hept-2-ene"s,

5-pentafluoroethyl group two ring [2.2.1] hept-2-ene"s,

5,5-difluoro two ring [2.2.1] hept-2-ene"s,

5,6-difluoro two ring [2.2.1] hept-2-ene"s,

5,5-two (trifluoromethyl) two ring [2.2.1] hept-2-ene"s,

5,6-two (trifluoromethyl) two ring [2.2.1] hept-2-ene"s,

5-methyl-5-trifluoromethyl two ring [2.2.1] hept-2-ene"s,

5,5,6-trifluoro two ring [2.2.1] hept-2-ene"s,

5,5,6-three (methyl fluoride) two ring [2.2.1] hept-2-ene"s,

5,5,6,6-tetrafluoro two ring [2.2.1] hept-2-ene"s,

5,5,6,6-four (trifluoromethyl) two ring [2.2.1] hept-2-ene"s,

5,5-two fluoro-6,6-two (trifluoromethyl) two ring [2.2.1] hept-2-ene"s,

5,6-two fluoro-5,6-two (trifluoromethyl) two ring [2.2.1] hept-2-ene"s,

5,5,6-three fluoro-5-trifluoromethyls two ring [2.2.1] hept-2-ene"s,

5-fluoro-5-pentafluoroethyl group-6,6-two (trifluoromethyl) two ring [2.2.1] hept-2-ene"s,

5,6-two fluoro-5-seven fluorine isopropyl-6-trifluoromethyl two ring [2.2.1] hept-2-ene"s,

5-chloro-5,6,6-trifluoro two ring [2.2.1] hept-2-ene"s,

5,6-two chloro-5,6-two (trifluoromethyl) two ring [2.2.1] hept-2-ene"s,

5,5,6-three fluoro-6-trifluoromethoxies two ring [2.2.1] hept-2-ene"s,

5,5,6-three fluoro-6-seven fluorine propoxyl group two ring [2.2.1] hept-2-ene"s,

5-(4-phenyl) two ring [2.2.1] hept-2-ene"s,

4-(two rings [2.2.1] heptan-5-alkene-2-yl) benzene sulfonyl benzene etc.

Wherein, the R of general formula (II ') ⁵～R ⁸All be hydrogen atom monomer, other is obvious for effect that the monomer of hydrogen atom or any two monomers that links with the alkylidene of carbon number 3～5 improve the toughness of the optical film that obtains for the alkyl of carbon number 1～30 for any, so be desirable.From stable on heating angle, that good especially is R ⁵～R ⁸All be the monomer of hydrogen atom, all other is the monomer of hydrogen atom, perhaps R for methyl, ethyl or phenyl for any ⁵Or R ⁶And R ⁷Or R ⁸Be hydrogen atom and R ⁵～R ⁸All the other groups mutually combine and form the monomer of the divalent straight chain shape alkyl of carbon number 3～5.In addition, two ring [2.2.1] hept-2-ene"s, 5-phenyl two ring [2.2.1] hept-2-ene"s, three ring [4.3.0.1 ^2.5] last of the ten Heavenly stems-3, synthesizing of 7-diene is easy, so be desirable.

Above-mentioned norbornene resin can obtain by make above-mentioned monomer (I ') and/or monomer (II ') open loop (being total to) polymerization with known method (for example the Jap.P. spy opens the method for putting down in writing in the 2003-14901 communique).In addition, can also make the monomer copolymerization except that above-mentioned monomer (I ') and (II '), for example cycloolefins such as cyclobutane, cyclopentene, cycloheptene, cyclooctene etc.In addition, can use the hydride of open loop (being total to) polymkeric substance that obtains.

The logarithm viscosity that (30 ℃) are measured in the methenyl choloride of above-mentioned norbornene resin is 0.2～5dL/g, better is 0.3～4dL/g, and good especially is 0.5～3dL/g.If exceed above-mentioned scope, then solution viscosity is too high, and processability can worsen, if be lower than above-mentioned scope, then film strength descends.

As the molecular weight of above-mentioned norbornene resin, the number-average molecular weight (Mn) of the polystyrene conversion that records with gel permeation chromatography (GPC) is generally 8000～1000000, better is 10000～500000, and good especially is 20000～100000.In addition, weight-average molecular weight (Mw) common 20000～3000000, better be 30000～1000000, good especially be in 40000～500000 the scope.In addition, about molecular weight distribution, above-mentioned Mw/Mn is generally 1.5～10, better is 2～8, and good especially is 2.5～5.

Saturated water absorption during 23 ℃ of above-mentioned norbornene resin below 1 weight %, better is 005～1 weight % usually, is more preferably 0.1～0.7 weight %, and good especially is 0.1～0.5 weight %.If saturated water absorption is in this scope, then also can keep various optical characteristics such as the homogeneity of for example transparency, phase differential, phase differential and dimensional accuracy under as conditions such as high temperature are how wet, good with the adaptation and the connectivity of other material, thereby can not peel off in using etc., and also good with the intermiscibility of additive such as antioxidant, thereby the degree of freedom of adding is big.In addition, above-mentioned saturated water absorption is measured the value of gaining in weight and trying to achieve for flooded for 1 week in 23 ℃ of water according to ASTMD570 after.

The SP value (solubility parameter) of above-mentioned norbornene resin better is 10～30 (MPa ^1/2), be more preferably 12～25 (MPa ^1/2), good especially is 15～20 (MPa ^1/2).The SP value is in above-mentioned scope, then solvent commonly used can be well norbornene resin be dissolved in, the manufacturing of film can be stably carried out, the characteristic homogeneous of the film that obtains simultaneously, connectivity and good can be made, the water-intake rate appropriateness can also be made with the adaptation of substrate.

The glass temperature of above-mentioned norbornene resin (Tg) is according to the formation unit (I) of norbornene resin and constitute having or not of kind, ratio of components, adjuvant etc. of unit (II) and different, but be generally 80～350 ℃, better be 100～250 ℃, be more preferably 120～200 ℃.If Tg is lower than above-mentioned scope, then heat distortion temperature is low, and thermotolerance can go wrong, and the changes in optical properties that is produced by temperature of the blooming that obtains can increase.In addition, if Tg is higher than above-mentioned scope, then the temperature that is heated near Tg in the stretch process etc. adds man-hour, and hot deterioration takes place resin probably.

In not damaging the transparency and stable on heating scope, can in above-mentioned norbornene resin, mix known thermoplastic resin, thermoplastic elastomer, rubber polymer, organic fine particles, inorganic particles, antioxidant, ultraviolet light absorber, release agent, fire retardant, antiseptic, wood powder, coupling agent, petroleum resin, plastifier, colorant, lubricant, anti-live agent, silicone oil, gas-development agent etc.

＜film b 〉

The film b layer that constitutes blooming of the present invention better is to be made of polyimide based resin or polyetherimide resinoid, satisfies following formula (7)～(10).

(7)100nm≦R _bth≦1000nm

(8)0≦R _b550≦200nm

(9)1.00≦R _b450/R _b550≦1.30

(10)0.7≦R _b650/R _b550≦1.00

Shown in above-mentioned formula (7), the R of film b layer _bTh is 100～1000nm, better is 100～300nm, is more preferably 100～200nm.In addition, shown in above-mentioned formula (8), the R of film b layer _b550 value is 0～200nm, better is 5～100nm, is more preferably 10～30nm.

Film b layer shown in above-mentioned formula (9), R _b450/R _b550 value 1.30～1.00, better be 1.20～1.00, good especially be in 1.10～1.00 the scope, and shown in above-mentioned formula (10), R _b650/R _b550 value 0.70～1.00, better be 0.80～1.00, good especially be in 0.90～1.00 the scope, thereby the phase difference value height of short wavelength side, the phase difference value of long wavelength side is low, promptly shows so-called positive wavelength dispersibility, is the low film of wavelength interdependence of phase difference value simultaneously.

From the angle of the slimming of LCD, the ideal thickness of aforesaid film b layer be 1000nm～20000nm, better be 2000nm～15000nm, good especially is 3000nm～10000nm.

In addition, the light transmittance at the wavelength 360nm place of above-mentioned film b layer it is desirable to below 10%, better is below 5%, to be more preferably below 1%.Light transmittance by making wavelength 360nm place can improve the durable stability of Liquid crystal component in above-mentioned scope.

(polyimide based resin)

As the polyimide based resin that constitutes above-mentioned film b layer, it is desirable to have the polyimide based resin of alicyclic structure, it better is the polyimide that has with the repetitive of following formula (III) expression, because it is not only good with the adaptation of above-mentioned film a layer, and can obtain phase difference characteristics and light transmittance good optical film.In addition, owing to can show required phase differential by film, therefore such polyimide based resin is more preferably to small part and has biphenyl backbone.

Above-mentioned polyimide based resin can synthesizing polyamides acid obtains this polyamic acid imidizate by making tetracarboxylic dianhydride and diamine reactant.In addition, the above-mentioned polyimide based resin with alicyclic structure can obtain by the tetracarboxylic dianhydride that use has an alicyclic structure usually, and the polyimide based resin with biphenyl backbone can obtain by the diamines that use has a biphenyl backbone.The polyimide of particularly preferred polyimide based resin for using tetracarboxylic dianhydride with alicyclic structure and diamines to obtain with biphenyl backbone.

As above-mentioned tetracarboxylic dianhydride, for example can exemplify 1,2,3 with alicyclic structure, 4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 3,3 ', 4,4 '-the dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 3,5,6-three carboxyls norbornane-2-acetate dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5 (tetrahydrochysene-2,5-two oxa-s-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 5-(2,5-two oxa-tetrahydrofuran bases)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid dianhydride, two ring [2,2,2]-Xin-7-alkene-2,3,5,6-tetracarboxylic dianhydride etc.

Used polyimide based resin can contain tetracarboxylic dianhydride except that above-mentioned tetracarboxylic dianhydride with alicyclic structure as the polymerization composition among the present invention.As such tetracarboxylic dianhydride, can exemplify for example butane tetracarboxylic acid dianhydride, pyromellitic acid anhydride, 3,3 ', 4,4 '-the benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) benzene phosphine oxide dianhydride, to phenylene two (triphenyl phthalic acid) dianhydride, metaphenylene two (triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-the diphenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-the diphenyl methane dianhydride, ethylene glycol-two (trimellitate), propylene glycol-two (trimellitate), 1,4-butylene glycol-two (trimellitate), 1,6-hexanediol-two (trimellitate), 1,8-ethohexadiol-two (trimellitate), 2,2-two (4-hydroxyphenyl) propane-two (trimellitate) etc.

Above-mentioned tetracarboxylic dianhydride can be used alone, and also can be used in combination more than 2 kinds.In addition, better be more than the 50mol% by in whole tetracarboxylic dianhydrides, using, be more preferably more than the 70mol%, good especially more than the 90mol% of being, preferably 100mol% has the tetracarboxylic dianhydride of alicyclic structure, the adaptation of not only above-mentioned film b layer and above-mentioned film a layer is good, and can obtain phase difference characteristics and light transmittance good optical film, so be desirable.

As above-mentioned diamines with biphenyl backbone, for example can exemplify 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-two (4-amino-benzene oxygen) biphenyl etc.

In addition, as the diamines except that diamines with biphenyl backbone, can exemplify for example p-phenylenediamine (PPD), m-phenylene diamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diphenyl sulfide, 4,4 '-diamino-diphenyl sulfone, 4,4 '-the diaminobenzene formailide, 4,4 '-diaminodiphenyl ether, 1, the 5-diaminonaphthalene, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 3,4 '-diaminodiphenyl ether, 3,3 '-the diamido benzophenone, 3,4 '-the diamido benzophenone, 4,4 '-the diamido benzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 2, the 7-diamino-fluorene, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-methylene-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamido-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-(to the phenylene isopropylidene) diphenylamine, 4,4 '-(metaphenylene isopropylidene) diphenylamine, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-aromatic diamines such as octafluoro biphenyl, 1, the 1-p dimethylamine, 1, the 3-propane diamine, tetra-methylenedimine, five methylene diamine, hexamethylene diamine, the heptamethylene diamines, eight methylene diamine, nine methylene diamine, 4,4-diamido heptamethylene diamines, 1, the 4-cyclohexanediamine, isophorone diamine, tetrahydrochysene dicyclopentadienyl diamines, six hydrogen-4,7-is to inferior indanyl dimethylene diamines, three ring [6.2.1.0 ^2.7]-Ya undecyl dimethyl diamines, 4,4 '-methylene two aliphatics and ester ring type diamines such as (cyclohexylamine), 2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamido-2,3-diamido pyrazine, 5,6-diamido-2,4-dihydroxy-pyrimidine, 2,4-diamido-6-dimethylamino-1,3, the 5-triazine, 1,4-two (3-aminopropyl) piperazine, 2,4-diamido-6-isopropoxy-1,3, the 5-triazine, 2,4-diamido-6-methoxyl-1,3, the 5-triazine, 2,4-diamido-6-phenyl-1,3, the 5-triazine, 2,4-diamido-6-phenyl s-triazine, 2,4-diaminostilbene, 3, the 5-triazine, 4,6-diamido-2-vinyl s-triazine, 2,4-diamido-5-phenyl thiazole, 2, the 6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3,5-diaminostilbene, 2, the 4-triazole, 6,9-diamido-2-ethoxy acridine propyl alcohol acid esters, 3,8-diamido-6-phenylphenanthridineand, 1,4-diamido piperazine, 3, the 6-proflavin, two (4-aminophenyl) aniline and the diamines that in molecule, has 2 primary amino radicals and the nitrogen-atoms except that this primary amino radical with the compound etc. of following general formula (i) or (ii) expression

(in the formula (i), R ⁹Expression has 1 valency organic group of the ring structure of the nitrogen atom that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, and Z represents the divalent organic group.)

(formula (ii) in, R ¹⁰Expression has the divalent organic group of ring structure of the nitrogen atom that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, and Z represents the divalent organic group, exists a plurality of Z can be identical or different.)

Single-substituted two amines of (iii) representing with following formula,

(formula (iii) in, R ¹¹Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R ¹²Expression have the steroid skeleton 1 valency organic group, have trifluoromethyl or the fluorine-based 1 valency organic group or the alkyl of carbon number 6～30.)

The diamido alkyl siloxane of (iv) representing with following formula,

(formula (iv) in, R ¹³The alkyl of representing carbon number 1～12 respectively independently, q are 1～20 integer, and r is 1～3 integer.)

With following formula (v)～(ix) Biao Shi compound etc.

(in the above-mentioned formula, t is 2～12 integer, and u is 1～5 integer.)

Above-mentioned diamine compound may be used alone, two or more kinds can also be used in combination.Wherein, it better is above-mentioned diamines with biphenyl backbone, p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 4,4 '-(to the phenylene diisopropylidene) diphenylamine, 4,4 '-(metaphenylene diisopropylidene) diphenylamine, 1, the 4-cyclohexanediamine, 4,4 '-methylene two (cyclohexylamine), 1,4-two (4-amino-benzene oxygen) benzene, with above-mentioned formula (v)～(ix) Biao Shi compound, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, with the compound in the compound of above-mentioned formula (i) expression with following formula (i-1) expression, compound in the compound of (iii) representing with the compound of following formula (ii-1) expression with above-mentioned formula in the compound of (ii) representing with above-mentioned formula with following formula (iii-1)～(iii-6) expression.

With with respect to the contained amino of 1 equivalent diamines, the contained anhydride group of tetracarboxylic dianhydride is 0.2～2 equivalent, better is the ratio of 0.3～1.4 equivalent, use tetracarboxylic dianhydride and diamines, in organic solvent, in common 0～150 ℃, better be the reaction of carrying out tetracarboxylic dianhydride and diamines under 0～100 ℃ the temperature conditions.By reacting under such condition, the molecular weight of the polyamic acid that obtains is enough big.

As above-mentioned organic solvent, as long as solubilized is not particularly limited as the tetracarboxylic dianhydride of reaction raw materials and diamines and as the polyamic acid of the polymkeric substance that generates.Specifically, can use gamma-butyrolacton, N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, N, non-proton class polar solvents such as N-dimethyl acetamide, dimethyl sulfoxide, tetramethylurea, HMPA, phenol solvents such as metacresol, xylenol, phenol, halogenated phenol etc.

The use amount of above-mentioned organic solvent better is that making as the total amount of the tetracarboxylic dianhydride of reaction raw materials and diamines is the ratio of 0.1～30 weight % with respect to the total amount of reaction solution.In addition, in the scope that the polyamic acid that generates can not be separated out, above-mentioned organic solvent can also use simultaneously for the polyamic acid that generates and be the alcohols of Weak solvent, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc.

Handle or in the presence of dewatering agent and imidization catalyst, carry out imidizate and handle and make its dehydrocyclization by the imidizate that the above-mentioned polyamic acid that obtains is adopted heating, can obtain above-mentioned polyimide.Adopting the temperature in the imidizate processing of heating to be generally 60～250 ℃, better is 100～170 ℃.Handle by carry out imidizate in such temperature range, the molecular weight of the acid imide polymkeric substance that obtains is enough big.

As above-mentioned dewatering agent, can use for example acetic anhydride, propionic andydride, trifluoroacetic anhydride etc.The use amount of this dewatering agent is preferably 1.6～20 moles with respect to the repetitive of 1 mole of polyamic acid.

As above-mentioned imidization catalyst, can use for example tertiary amines such as pyridine, trimethylpyridine, lutidines, triethylamine, but be not limited to these compounds.The usage ratio of this imidization catalyst is preferably 0.5～10 mole with respect to 1 mole of used dewatering agent.In addition, used organic solvent in handling as this imidizate can exemplify the organic solvent as solvent example used in polyamic acid synthetic.In addition, the temperature that this imidizate is handled is generally 0～180 ℃, better is 60～150 ℃.

In addition, among the present invention used polyimide based resin can be polyamic acid not by the part imide amination polymer of 100% imidizate, but the imidizate rate better is more than 50%, is more preferably more than 80%, good especially is more than 90%, preferably more than 95%.By making the imidizate rate in above-mentioned scope, lining property and the phase differential when making film b layer controlled good is so be desirable.

The value of the logarithm viscosity of the polyimide that obtains as mentioned above is generally 0.05～10dL/g, better is 0.05～5dL/g.In addition, the value of logarithm viscosity is for to using the N-N-methyl-2-2-pyrrolidone N-to measure the value that obtain as the solution of 0.5g/100mL at 30 ℃ as solvent, polymer concentration.

(polyetherimide resinoid)

As the polyetherimide resinoid that constitutes above-mentioned film b layer, because it is not only good with the adaptation of above-mentioned film a layer, and can obtain phase difference characteristics and light transmittance good optical film, so better be the polyetherimide resinoid (following also claim " polyetherimide (IV) ") that has with the formation unit of following general formula (IV) expression.

In the above-mentioned formula (IV), X ' and Y ' can be identical or different, represent saturated or undersaturated alkyl respectively.

In addition, as above-mentioned polyetherimide (IV), owing to can obtain good characteristic, good especially is the polyetherimide resinoid that has with the formation unit of following general formula (V) expression.

Above-mentioned polyetherimide (IV) can be by the synthesizing polyamides acid with the tetracarboxylic dianhydride with ehter bond (following also claim " compound (VI) ") of following general formula (VI) expression and diamine compound reaction, and this polyamic acid is carried out the imidizate processing and obtains.

In the formula (VI), the X ' same meaning in X ' and the above-mentioned formula (IV) for example can exemplify-CH ₂-,-C ₂H ₄-and following group etc.

Above-claimed cpd (VI) can use a kind separately as acid dianhydride, also can be used in combination more than 2 kinds.

In addition, above-mentioned polyetherimide (IV) can use acid dianhydride except that above-claimed cpd (VI) as the polymerization composition.When the summation of the use amount of all acid dianhydrides was made as 100mol%, the usage ratio of above-claimed cpd (VI) was more than the 50mol%, better is more than the 70mol%, is more preferably more than the 90mol%, and good especially is 100mol%.Usage ratio by making compound (VI) is in above-mentioned scope, and is not only good with the adaptation of above-mentioned film a layer, and can obtain phase difference characteristics and light transmittance good optical film.

As the acid dianhydride except that above-claimed cpd (VI), can exemplify for example butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetrabasic carboxylic acid acid dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 3,3 ', 4,4 '-the dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 3,5,6-three carboxyls norbornane-2-acetate dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5 (tetrahydrochysene-2,5-two oxa-s-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 5-(2,5-two oxa-tetrahydrofuran bases)-and 3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid dianhydride, two rings [2,2,2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, pyromellitic acid anhydride, 3,3 ', 4,4 '-the benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) benzene phosphine oxide dianhydride, to phenylene two (triphenyl phthalic acid) dianhydride, metaphenylene two (triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-the diphenyl methane dianhydride, ethylene glycol-two (trimellitate), propylene glycol-two (trimellitate), 1,4-butylene glycol-two (trimellitate), 1,6-hexanediol-two (trimellitate), 1,8-ethohexadiol-two (trimellitate), 2,2-two (4-hydroxyphenyl) propane-two (trimellitate) etc.

As used diamine compound in above-mentioned polyetherimide (IV) synthetic, be not particularly limited, can exemplify for example p-phenylenediamine (PPD), m-phenylene diamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diphenyl sulfide, 4,4 '-diamino-diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-the diaminobenzene formailide, 4,4 '-diaminodiphenyl ether, 1, the 5-diaminonaphthalene, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 3,4 '-diaminodiphenyl ether, 3,3 '-the diamido benzophenone, 3,4 '-the diamido benzophenone, 4,4 '-the diamido benzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 2, the 7-diamino-fluorene, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-methylene-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamido-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-(to the phenylene isopropylidene) diphenylamine, 4,4 '-(metaphenylene isopropylidene) diphenylamine, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-aromatic diamines such as octafluoro biphenyl, 1, the 1-p dimethylamine, 1, the 3-propane diamine, tetra-methylenedimine, five methylene diamine, hexamethylene diamine, the heptamethylene diamines, eight methylene diamine, nine methylene diamine, 4,4-diamido heptamethylene diamines, 1, the 4-cyclohexanediamine, isophorone diamine, tetrahydrochysene dicyclopentadienyl diamines, six hydrogen-4,7-is to inferior indanyl dimethylene diamines, three ring [6.2.1.0 ^2.7]-Ya undecyl dimethyl diamines, 4,4 '-methylene two aliphatics and ester ring type diamines such as (cyclohexylamine), 2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamido-2,3-diamido pyrazine, 5,6-diamido-2, the 4-dihydroxy-pyrimidine, 2,4-diamido-6-dimethylamino-1,3,5-triazines, 1,4-two (3-aminopropyl) piperazine, 2,4-diamido-6-isopropoxy-1,3,5-triazines, 2,4-diamido-6-methoxyl-1,3, the 5-triazine, 2,4-diamido-6-phenyl-1,3, the 5-triazine, 2,4-diamido-6-phenyl s-triazine, 2, the 4-diaminostilbene, 3, the 5-triazine, 4,6-diamido-2-vinyl s-triazine, 2,4-diamido-5-phenyl thiazole, 2, the 6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3, the 5-diaminostilbene, 2, the 4-triazole, 6,9-diamido-2-ethoxy acridine propyl alcohol acid esters, 3,8-diamido-6-phenylphenanthridineand, 1,4-diamido piperazine, 3, the 6-proflavin, two (4-aminophenyl) aniline and in molecule, have the diamines of 2 primary amino radicals and the nitrogen-atoms except that this primary amino radical with the compound etc. of above-mentioned general formula (i) or (ii) expression, single-substituted two amines of (iii) representing with above-mentioned formula, the diamido alkyl siloxane of (iv) representing with above-mentioned formula and with above-mentioned formula (v)～(ix) Biao Shi compound etc.

Above-mentioned diamine compound may be used alone, two or more kinds can also be used in combination.Wherein, it better is p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 4,4 '-(to the phenylene diisopropylidene) diphenylamine, 4,4 '-(metaphenylene diisopropylidene) diphenylamine, 1, the 4-cyclohexanediamine, 4,4 '-methylene two (cyclohexylamine), 1,4-two (4-amino-benzene oxygen) benzene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-two (4-amino-benzene oxygen) biphenyl, with above-mentioned formula (v)～(ix) Biao Shi compound, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, with the compound in the compound of above-mentioned formula (i) expression with above-mentioned formula (i-1) expression, compound in the compound of (iii) representing with the compound of above-mentioned formula (ii-1) expression with above-mentioned formula in the compound of (ii) representing with above-mentioned formula with above-mentioned formula (iii-1)～(iii-6) expression.

In above-mentioned polyetherimide (IV) synthetic, for example with respect to the contained amino of 1 equivalent diamines, the contained anhydride group of compound (VI) be 0.4～2.3 equivalent, better be 0.5～1.9 equivalent, be more preferably the ratio of 0.7～1.5 equivalent, use above-claimed cpd (VI) and diamines, in organic solvent, in common 0～150 ℃, better be to react under 0～100 ℃ the temperature conditions.By reacting under such condition, the molecular weight of the polyamic acid that obtains is enough big.

As above-mentioned organic solvent, as long as solubilized is not particularly limited as the compound (VI) of reaction raw materials and diamines and as the polyamic acid of the polymkeric substance of generation.Specifically, can use gamma-butyrolacton, N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, N, non-proton class polar solvents such as N-dimethyl acetamide, dimethyl sulfoxide, tetramethylurea, HMPA, phenol solvents such as metacresol, xylenol, phenol, halogenated phenol etc.

The use amount of above-mentioned organic solvent better is the total amount that makes compound (VI) as reaction raw materials and diamines with respect to the total amount of reaction solution is the ratio of 0.1～30 weight %.In addition, in the scope that the polyamic acid that generates can not be separated out, above-mentioned organic solvent can also use simultaneously for the polyamic acid that generates and be the alcohols of Weak solvent, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc.

Handle or in the presence of dewatering agent and imidization catalyst, carry out imidizate and handle and make its dehydrocyclization by the imidizate that the polyamic acid that obtains is as mentioned above adopted heating, can obtain above-mentioned polyetherimide (IV).Adopting the temperature in the imidizate processing of heating to be generally 60～250 ℃, better is 100～170 ℃.Handle by carry out imidizate in such temperature range, the molecular weight of the polyetherimide that obtains (IV) is enough big.

In addition, above-mentioned polyetherimide (IV) can be polyamic acid not by the part imide amination polymer of 100% imidizate, but the imidizate rate better is more than 50%, is more preferably more than 80%, good especially is more than 90%, preferably more than 95%.By making the imidizate rate in above-mentioned scope, lining property and the phase differential when making film b layer controlled good is so be desirable.

The value of the logarithm viscosity of the polyetherimide that obtains as mentioned above (IV) is generally 0.05～10dL/g, better is 0.05～5dL/g.In addition, the value of logarithm viscosity is for to using the N-N-methyl-2-2-pyrrolidone N-to measure the value that obtain as the solution of 0.5g/100mL at 30 ℃ as solvent, polymer concentration.

The manufacture method of＜blooming 〉

Blooming of the present invention can be by on the film a that carries out obtaining after uniaxial tension or biaxial stretch-formed processing make it have certain optical properties that is formed by above-mentioned cycloolefin resinoid, is made by above-mentioned polyimide based resin or polyetherimides resin-shaped film forming b layer with lining.

In addition, blooming of the present invention also can form resin molding b layer by above-mentioned polyimide based resin of lining or polyetherimide resinoid on the not stretching resin film that is formed by above-mentioned cycloolefin resinoid, after making laminated film, this laminated film is carried out uniaxial tension or biaxial stretch-formed and make.

(primary coat c layer)

Blooming of the present invention can have at least 1 layer acrylic compounds and/or polyurethanes primary coat c layer between above-mentioned film a layer and film b layer.

The thickness of above-mentioned primary coat c layer is not particularly limited, and better is being 0.01～10 μ m, is being more preferably in the scope of 0.1～3 μ m.Thickness is during less than above-mentioned scope, and the adaptation between film a layer and the film b layer can descend.In addition, during greater than above-mentioned scope, the system film can descend.

(i) acrylic compounds undercoat

As the acrylic polymers that constitutes aforesaid propylene acids undercoat,, be not particularly limited so long as get final product with the acrylate compounds that has 1 (methyl) acryloyl group in the molecule at least polymkeric substance as monomeric unit.As such acrylate compounds, can exemplify for example simple function (methyl) acrylate compounds and multifunctional (methyl) acrylate compounds.Wherein, because phase retardation film formation is improved with the reactivity of composition, so better be multifunctional (methyl) acrylate compounds.

Object lesson as above-mentioned simple function (methyl) acrylate compounds, can exemplify (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) acrylic acid n-pentyl ester, (methyl) acrylic acid isopentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid heptyl ester, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid 11 esters, (methyl) dodecyl acrylate, (methyl) lauryl acrylate, (methyl) octadecyl acrylate, (methyl) alkyl-acrylates such as the different octadecyl ester of (methyl) acrylic acid, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxy alkyl ester classes such as (methyl) acrylic acid hydroxy butyl ester, (methyl) acrylic acid phenoxy ethyl, (methyl) acrylic acid-2-hydroxyl-(methyl) acrylic acid phenoxyalkyl ester classes such as 3-phenoxy group propyl ester, (methyl) acrylic acid methoxyl ethyl ester, (methyl) acrylic acid ethoxy ethyl ester, (methyl) acrylic acid phenoxy ethyl, (methyl) acrylic acid butoxy ethyl ester, (methyl) alkoxyalkyl acrylate classes such as (methyl) acrylic acid methoxyl butyl ester, polyethyleneglycol (methyl) acrylate, ethoxy diethylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group polyglycol (methyl) acrylate, polyglycol (methyl) esters of acrylic acids such as Nonylphenoxy polyglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, methoxyl polypropylene glycol (methyl) acrylate, ethoxy polypropylene glycol (methyl) acrylate, polypropylene glycol (methyl) esters of acrylic acids such as Nonylphenoxy polypropylene glycol (methyl) acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid-4-butyl cyclohexyl, (methyl) acrylic acid two cyclopentyl esters, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentadienyl ester, (methyl) acrylic acid norbornene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid cycloalkyl esters such as (methyl) acrylic acid three ring decyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid tetrahydro furfuryl ester etc.These simple functions (methyl) acrylate compounds can use a kind separately, also can be used in combination more than 2 kinds.

Object lesson as above-mentioned multifunctional (methyl) acrylate compounds, can exemplify two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid binaryglycol ester, two (methyl) acrylic acid TEG ester, polyglycol two (methyl) acrylate, 1,4-butylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, two (methyl) alkyl acrylate diol-lipids such as neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris hydroxyethyl three (methyl) acrylate, two (trihydroxy methyl) propane four (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, many (methyl) esters of acrylic acid of polyvalent alcohols such as hydroxyl trimethylace tonitric neopentyl glycol two (methyl) acrylate, isocyanuric acid ester three (methyl) acrylate, three (2-hydroxyethyl) isocyanuric acid ester two (methyl) acrylate, many (methyl) esters of acrylic acid of isocyanuric acid esters such as three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, many (methyl) esters of acrylic acid of naphthenic hydrocarbon such as tricycloheptane two basic dimethyl two (methyl) acrylate, two (methyl) acrylate of the ethylene oxide adduct of bisphenol-A, two (methyl) acrylate of the propylene oxide adduct of bisphenol-A, (methyl) acrylate of the alkylene oxide addition product of bisphenol-A, two (methyl) acrylate of the ethylene oxide adduct of hydrogenated bisphenol A, two (methyl) acrylate of the propylene oxide adduct of hydrogenated bisphenol A, (methyl) acrylate of the alkylene oxide addition product of hydrogenated bisphenol A, (methyl) acrylate derivative class of the bisphenol-As such as (methyl) acrylate that obtain by bisphenol A diglycidyl ether and (methyl) acrylic acid, 3,3,4,4,5,5,6,6-octafluoro octane two (methyl) acrylate, 3-(2-perfluoro hexyl) ethoxy-1,2-two (methyl) acryloyl propane, N-n-pro-pyl-N-2, fluorine-containing (methyl) esters of acrylic acids such as 3-two (methyl) acryloyl propyl group perfluorinated octyl sulfuryl amine.These multifunctional (methyl) acrylate compounds can use a kind separately, also can be used in combination more than 2 kinds.

In these multifunctional (methyl) acrylate compounds, be that acryloyl radix contained in 1 molecules such as dipentaerythritol acrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate is many well especially, the raising that can realize cross-linking density, multifunctional (methyl) acrylate compounds of giving good film strength.

Among the present invention, can use free radical thermal initiator or free radical photo-initiation when acrylate compounds is solidified, from storage stability and productive angle, better be free radical photo-initiation.

Object lesson as above-mentioned free radical photo-initiation, can exemplify the 1-hydroxycyclohexylphenylketone, 2,2 '-dimethoxy-2-phenyl acetophenone ketone, xanthone, fluorenes, Fluorenone, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methyl acetanilide ketone, the 4-chloro benzophenone, 4,4 '-the dimethoxy benzophenone, 4,4 '-the diamido benzophenone, Michler's keton, the benzoyl propyl ether, the benzoin ethylether, benzyl dimethyl ketal, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, thioxanthones, diethyl thioxanthone, the 2-isopropyl thioxanthone, the 2-clopenthixal ketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl propane-1-ketone etc.These free radical photo-initiations can use a kind separately, also can be used in combination more than 2 kinds.

In these free radical photo-initiations, better be 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide, 1-hydroxycyclohexylphenylketone.

In addition, such free radical photo-initiation can use commercially available product.For example, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone can be bought " ィ Le ガキュァ 907 " (チバスペシャ Le ディケミカ Le ズ Co., Ltd. system), and the 1-hydroxycyclohexylphenylketone can be bought " ィ Le ガキュァ 184 " (チバスペシャ Le ディケミカ Le ズ Co., Ltd. system).

The addition of above-mentioned free radical photo-initiation with respect to 100 parts by weight of acrylic acid ester compounds, it is desirable to 0.1～20 weight portion so long as the amount that enough curing reactions carry out is not particularly limited usually, better is 0.5～10 weight portion.If the addition of free radical photo-initiation is lower than above-mentioned scope, then the curing reaction of acrylate compounds can't fully carry out, and can't obtain to have the primary coat c layer of enough hardness.In addition, if the addition of free radical photo-initiation surpasses above-mentioned scope, then the storage stability of primary coat c layer can reduce.

From the angle of system film, above-mentioned (methyl) acrylate better is to add solvent to use.At this moment, so long as dissolve or disperse the solvent of above-mentioned (methyl) acrylate, be not particularly limited.In addition, (methyl) acrylate composition that has added solvent can be an organic solvent system, also can be water systems such as emulsion, colloidal dispersion, aqueous solution.

As organic solvent, can use for example methyl alcohol, ethanol, isopropyl alcohol, normal butyl alcohol, acetone, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate etc.From with the adaptation of base material and the good angle of system film, good especially alcohols and the ketones such as methyl ethyl ketone, methyl isobutyl ketone such as methyl alcohol, ethanol, isopropyl alcohol of being to use may be used alone, can also be two or more kinds in combination.In addition, above-mentioned organic solvent can contain water.

(ii) polyurethanes undercoat

Above-mentioned polyurethanes undercoat forms by urethane composition being coated on norbornene resin film surface.Comprise urethane resin and solvent in such urethane composition.

As above-mentioned urethane resin, so long as have the resin of a plurality of ammonia ester bonds, be not particularly limited, can exemplify polymkeric substance that for example polyol compound and polyisocyanate reaction obtains etc.The number-average molecular weight of used urethane resin is generally 1000～200000 among the present invention, better is about 30000～100000.

In order to make urethane resin stably be dissolved or dispersed in organic solvent and/or water, and improve the coating of bonding agent and the connectivity of base material and bonding agent, as the polymerization composition,, better be to add the compound that contains hydrophilic radical except polyol compound and polyisocyanate.

As above-mentioned polyol compound, can exemplify polyether glycol, polyester polyol, polyacrylic acid polyvalent alcohol etc.Wherein, good especially is polyether glycol.As such polyether glycol, can exemplify polyether glycol that for example makes photopolymerizable ring compound and polyvalent alcohol ring opening copolymer and obtain etc.

As above-mentioned polyvalent alcohol, can exemplify ethylene glycol, polyglycol, propylene glycol, polypropylene glycol, polytetramethylene glycol, poly-hexanediol, poly-heptandiol, poly-decanediol, glycerine, trimethylolpropane, pentaerythrite, bisphenol-A, Bisphenol F, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F, quinhydrones, naphtho-quinhydrones, anthra quinhydrones, 1,4-cyclohexanediol, tristane glycol, tristane dimethanol, pentacyclopentadecandimethanol glycol, pentacyclopentadecandimethanol dimethanol etc.They can use separately, also can be used in combination.

As above-mentioned photopolymerizable ring compound, can exemplify for example oxirane, epoxypropane, 1, the 2-epoxy butane, butene-1-change oxygen, the isobutyl alkylene oxide, 3,3-dichloromethyl oxetanes, tetrahydrofuran, the 2-methyltetrahydrofuran, 3-methyltetrahydrofuran diox trioxane Si oxane, cyclohexene oxide, styrene oxide, epichlorokydrin, glycidyl methacrylate, allyl glycidyl ether, the allyl glycidyl phosphate, butadiene monoxide, one oxidation isoprene, the vinyl oxetanes, the vinyl tetrahydrofuran, vinyl cyclohexene oxygen, phenyl glycidyl ether, butyl glycidyl ether, ring-type ethers such as benzoic acid ethylene oxidic ester.They can use separately, also can be used in combination.

In addition, the polyether glycol that also can use annular lactone acid such as cyclic imide classes such as above-mentioned photopolymerizable ring compound and ethylene imine, β-propionic acid lactone and glycollic acid lactide or dimethyl cyclo(poly)siloxane class ring opening copolymer to obtain.The ring opening copolymer thing of these photopolymerizable ring compounds can random incorporation, also can be the block-wise combination.As such polyether glycol, better be polytetramethylene glycol, poly-hexanediol etc.

As above-mentioned polyisocyanate, be not particularly limited, can use polyisocyanate used in the manufacturing of common polyurethane.For example can exemplify 2, the 4-toluene diisocyanate, 2, the 6-toluene diisocyanate, 1, the 3-XDI, 1, the 4-XDI, 1, the 5-naphthalene diisocyanate, m-benzene diisocyanate, PPDI, 3,3 '-dimethyl-4,4 '-methyl diphenylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, 3,3 '-the dimethyl benzene diisocyanate, 4,4 '-the xenyl diisocyanate, 1, the 6-hexane diisocyanate, isophorone diisocyanate, methylene two (4-cyclohexyl isocyanate), 2,2, the 4-trimethyl hexamethylene diisocyanate, two (2-isocyanate group ethyl) fumarate, 6-isopropyl-1, the 3-phenyl diisocyanate, 4-diphenyl propane diisocyanate, lysinediisocyanate, hydrogenated diphenyl methane diisocyanate, the hydrogenation of benzene dimethylene diisocyanate, tetramethylxylylene diisocyanate, 2,5 (or 6)-two (isocyanates ylmethyl)-two ring [2.2.1] heptane etc.These polyisocyanates may be used alone, two or more kinds can also be used in combination.Wherein, better be isophorone diisocyanate.

As the above-mentioned compound that contains hydrophilic radical, can exemplify and in molecule, have at least 1 active hydrogen atom, and contain the ionic compound of carboxyl and/or sulfonic functional group.As such compound that contains hydrophilic radical, can exemplify for example 2-isethionic acid, phenolsulfonic acid, sulfosalicylic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine-4,6-disulfonic acid, 2, sulfoacid compound and derivants thereof such as 4-diaminotoluene-5 sulfonic acid, perhaps 2,2-dihydromethyl propionic acid, 2,2-dimethylolpropionic acid, 2,2-dihydroxymethyl valeric acid, dihydroxymaleic acid, 2,6-dihydroxy-benzoic acid, 3,4-two diaminobenzoic acids etc. contain the compound and the derivant thereof of carboxylic acid.

In the reaction of these compounds, total amount with respect to 100 weight portion reactants, usually better be to use 0.01～1 weight portion copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin dilaurate, triethylamine, 1,4-diazabicylo [2.2.2] octane, 2,6,7-trimethyl-1, polyurethane-reinforcement catalyzer such as 4-diazabicylo [2.2.2] octane.In addition, temperature of reaction is generally 10～90 ℃, better is 30～80 ℃.

Used solvent in the urethane composition so long as dissolving or disperse the solvent of above-mentioned urethane resin be not particularly limited.In addition, polyurethane resin composition can be an organic solvent system, also can be water systems such as emulsion, colloidal dispersion, aqueous solution.

As organic solvent, can use for example methyl alcohol, ethanol, isopropyl alcohol, normal butyl alcohol, acetone, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate etc.In addition, under the situation of water system, also can mix for example above-mentioned alcohols or ketone.In addition, under the situation of water system, can use spreading agent, perhaps in urethane resin, introduce functional groups such as carboxyl, sulfonyl, ammonium.

In the combination of above-mentioned solvent, change less and can obtain the angle of good coating from the phase differential of base material, better be to use the solvent that is selected from methyl alcohol, ethanol, isopropyl alcohol, normal butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone and water, may be used alone, can also be two or more kinds in combination.

The solid component concentration of above-mentioned urethane composition is generally 1～60 weight %, better is 1～30 weight %, is more preferably 1～10 weight %.If solid component concentration is lower than above-mentioned scope, then be difficult to make layer of polyurethane to form required thickness.On the other hand, if be higher than above-mentioned scope, then can be difficult to form the layer of polyurethane of homogeneous.

Can mix crosslinking chemical, tackifier, antioxidant, colorant, ultraviolet light absorber, light stabilizer, silane coupling agent, thermal polymerization blocking agent, levelling agent, surfactant, preserving stabilizer, plastifier, lubricant, filler, anti aging dope, wellability modifying agent in the above-mentioned urethane composition again, be coated with face modifying agent etc.When particularly conduct contains the compound introducing carboxyl of hydrophilic radical in urethane composition, better be to use the epoxies crosslinking chemical.

As such crosslinking chemical, so long as have the crosslinking chemical of at least one epoxy radicals in the molecule, be not particularly limited, can exemplify for example bisphenol type epoxy compound, phenolic varnish type epoxy compound, alicyclic epoxy compound, aliphatic epoxy compound, aromatic ring oxygen compound, glycidic amine type epoxy compound, halogenated epoxide etc.

More specifically, can exemplify bisphenol A diglycidyl ether, the Bisphenol F diglycidyl ether, bisphenol type epoxy compounds such as bisphenol-S diglycidyl ether, phenol phenolic varnish type epoxy compound, phenolic varnish type epoxy compounds such as cresols phenolic varnish type epoxy compound, 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3, the 4-epoxy radicals) cyclohexane Jian diox, two (3,4 epoxycyclohexyl methyl) adipate, vinyl cyclohexene oxygen, 4-ethylene oxide cyclohexane, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4 '-epoxy-6 '-the methylcyclohexanecarboxylic acid ester, methylene two (3, the 4-7-oxa-bicyclo[4.1.0), the diepoxy dicyclopentadiene, two (3 of ethylene glycol, 4-epoxycyclohexyl methyl) ether, ethylene (3, the 4-epoxycyclohexane carboxylate), epoxidation tetrabenzyl alcohol, interior ester modified 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, lactone modified epoxy tetrahydrochysene benzyl alcohol, cyclohexene oxide, the hydrogenated bisphenol A diglycidyl ether, A Hydrogenated Bisphenol A F diglycidyl ether, alicyclic epoxy compounds such as bisphenol-A D diglycidyl ether, 1, the 4-butanediol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, T 55, aliphatic epoxy compounds such as trihydroxymethylpropanyltri diglycidyl ether, the bromo bisphenol A diglycidyl ether, bromo Bisphenol F diglycidyl ether, halogenated epoxides such as bromo bisphenol-S diglycidyl ether, glycidic amine type epoxy compounds such as four glycidyl group aminophenyl methane.

In addition, except above-claimed cpd, can also exemplify polyethyleneglycol diglycidylether, poly-alkane glycol such as polypropylene glycol diglycidyl ether 2-glycidyl ethers, to ethylene glycol, propylene glycol, fatty polyol additions such as glycerine more than a kind or 2 kinds alkylene oxide and the polyglycidyl ether class of the polyether glycol that obtains, the 2-glycidyl ethers of aliphatic long-chain dibasic acid, the monoglycidyl ether class of aliphatics higher alcohol, phenol, cresols, the monoglycidyl ether class of butylphenol or Aethoxy Sklerol that their addition alkylene oxides are obtained, the ethylene oxidic ester class and the epoxidised soybean oil of higher fatty acid, butyl epoxy stearate, octyl epoxy stearate, epoxidation linseed wet goods.

In addition, can also use in advance with the epoxy resin that polymerization obtains in suitable preferred range of these compounds more than a kind or 2 kinds.

In addition, as spendable epoxy compound among the present invention, the compound that also can exemplify conjugated diene polymer of monomers, conjugated diene monomer and have multipolymer, the dienes monomer of the compound of ethene unsaturated link and have the multipolymer of the compound of ethene unsaturated link, (being total to) polymer ring oxidations such as natural rubber are obtained.

As the commercially available prod of above-mentioned urethane composition, for example can exemplify " Ha ィ De ラ Application WLS-201 ", " WLS-202 ", " WLS-210 ", " WLS-213 ", " WLS-220 " (big Japanese ィ Application キ chemical industry Co., Ltd. system) etc.

(iii) ultramicron

For cross-linking density and the system film of controlling aforesaid propylene acids and/or polyurethane polymer,, also better be to add ultramicron except acrylic compounds and/or polyurethane polymer.Specifically, the organic ultramicron that better is to use ultrafine inorganic particles such as monox, zirconia, titanium dioxide or tin oxide or forms by acrylic polymers.

(the formation method of primary coat c layer)

Formation method as aforesaid propylene acids and/or polyurethanes primary coat c layer is not particularly limited, and can use for example spin coating, line to be coated with, the whole bag of tricks such as rod is coated with, roller coat, scraper coating, the coating of curtain formula, serigraphy.

In addition, the baking temperature as ground coating composition is not particularly limited, for example 60～150 ℃.Residual solvent amount in the primary coat c layer needs the least possible, below 3 weight %, better is below 1 weight % usually, is more preferably below 0.5 weight %.

Total light transmittance of aforesaid propylene acids and/or polyurethanes primary coat c layer desirable usually more than 80%, better be more than 90%.

By between film a layer and film b layer, forming primary coat c layer like this, when applying film a layer and film b layer, can improve the coating of bonding agent, obtain long-time stable adaptation.

(manufacture method) with blooming of primary coat c layer

Blooming of the present invention has under the situation of above-mentioned primary coat c layer, can form above-mentioned film b layer with lining on this primary coat c layer, thereby make this blooming by carrying out forming above-mentioned primary coat c layer with lining on uniaxial tension or the biaxial stretch-formed film a that obtains.

In addition, also can on the not stretching resin film that forms by above-mentioned cycloolefin resinoid, form aforementioned primary coat c layer with lining, after forming above-mentioned film b layer with lining on this primary coat c layer, the laminated film that obtains is carried out uniaxial tension or biaxial stretch-formed, thereby make blooming with primary coat c layer.

By between film a layer and film b layer, forming primary coat c layer like this, when using bonding agent, can improve its coating, and because the raising of adaptation, the manufacturing property stability in the time of can obtaining film and add man-hour or blooming and use.

(not stretching resin film)

The not stretching resin film that is formed by above-mentioned cycloolefin resinoid obtains by known system embrane method such as melt-shaping method or solution casting method.In addition, because the homogeneity and the surface smoothing of thickness are good, better be solution casting method.In addition, from the angle of productivity and cost, better be the melt-shaping method.

As solution casting method, can exemplify following method: the cycloolefin resinoid is dissolved or dispersed in appropriate solvent, makes the liquid of debita spissitudo, with its cast or coat on the suitable base material and drying after, the resin molding that obtains is peeled off from base material.

As base material used in the solution casting method, can exemplify for example metal drum (drum), steel band, polyethylene terephthalate (PET) or Polyethylene Naphthalate polyester films such as (PEN), teflon system band etc.In addition, as mentioned above, the film b layer that is formed by above-mentioned polyimide based resin can use the film a (also comprising unstretching film) that is formed by above-mentioned cycloolefin resinoid as base material, forms by solution casting method.

When above-mentioned base material uses polyester film, can use surface treated film.As the surface-treated method, can exemplify the method for hydrophilizing of general employing, for example with acrylic resin or the resin that contains sulphonate-base by coating or lamination and the method for lamination, perhaps make method that the water wettability on film surface improves etc. by Cement Composite Treated by Plasma or Corona discharge Treatment.

Resinous principle concentration in the resin solution is generally 0.1～90 weight %, better is 1～50 weight %, is more preferably 5～35 weight %.When resinous principle concentration is lower than above-mentioned scope, the resin molding of adequate thickness be can can't obtain to have, and because foaming that solvent evaporation etc. produces etc., the resin molding that can can't obtain to have good surface smoothness followed.On the other hand, when resinous principle concentration was higher than above-mentioned scope, the viscosity of resin solution was too high, can't obtain the resin molding of thickness and surface state homogeneous.

In addition, the viscosity under the resin solution room temperature is generally 1～1000000mPas, better is 10～100000mPas, is more preferably 100～50000mPas, and good especially is 1000～40000mPas.

As the solvent that is used for the resin solution preparation, for the cycloolefin resinoid, can exemplify for example benzene, toluene, aromatic species solvents such as dimethylbenzene, methyl cellosolve, ethyl cellosolve, 1-methoxyl-cellosolve kind solvents such as 2-propyl alcohol, diacetone alcohol, acetone, cyclohexanone, methyl ethyl ketone, 4-methyl-2 pentanone, cyclohexanone, ethyl cyclohexanone, 1, ketones solvents such as 2-dimethylcyclohexanon, methyl lactate, esters solvents such as ethyl lactate, 2,2,3,3-tetrafluoro-1-propyl alcohol, methylene chloride, halogen-containing solvent such as methenyl choloride, ether solvents such as tetrahydrofuran diox, the 1-amylalcohol, alcohols solvents such as 1-butanols etc.

For polyimide based resin or polyetherimide resinoid, can exemplify for example N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolacton, N, dinethylformamide, N, non-proton class polar solvents such as N-dimethyl acetamide, dimethyl sulfoxide, tetramethylurea, HMPA, phenol solvents such as metacresol, xylenol, phenol, halogenated phenol etc.

Above-mentioned solvent may be used alone, two or more kinds can also be used in combination.

As the method for coating resin solution on base material, can use the method that adopts mould, coating machine, brush etc. and spraying process, rolling method, spin-coating method, infusion process, heliogravure etc.In addition, in order to obtain the optical film of desired thickness, can carry out the coating of resin solution repeatedly.

As making solvent from coating the method for the resin solution evaporation on the base material, be not particularly limited, can use the method for common employing, for example can adopt by a plurality of rollers and make its method of from drying oven, passing through etc.In addition, produce bubble if follow the evaporation of solvent, the characteristic of the optical film that then obtains significantly descends.Therefore, for fear of the generation of bubble, better be when minute multiple working procedure carries out the evaporation process of solvent, temperature in each operation and air quantity are controlled.

Remaining in quantity of solvent in the resin molding usually below 20 weight %, better is below the 5 weight %, is more preferably below the 1 weight %, and good especially is below the 0.5 weight %.The residual solvent amount exceeds under the situation of above-mentioned scope, and is actual when using this resin molding, through the time change in size can increase, and because residual solvent, glass temperature can reduce, thermotolerance can descend.

In addition, in order to carry out stretching process described later well, the quantity of solvent that needs will remain in the resin molding suitably is adjusted in the above-mentioned scope.Specifically, for it being stablized, showing the phase differential that stretch processing produces equably, making residual quantity of solvent be generally 20～0.1 weight %, better is 5～0.1 weight %, is more preferably 1～0.1 weight %.By quantity of solvent being controlled in such scope, can easily carrying out stretch processing, and can easily carry out the control of phase differential.

The quantity of solvent that remains in the resin molding is controlled in such scope, after the stretched operation, stablizes, can reduce the residual solvent amount by drying process again in order to make optical characteristics such as phase differential.At this moment, the residual solvent amount better is 5～0.1 weight %, is more preferably 1～0.1 weight %.

The thickness of resin film that obtains like this is generally 0.1～3000 μ m, better is 0.1～1000 μ m, is more preferably 1～500 μ m, and good especially is 5～300 μ m.This thickness is during less than above-mentioned scope, the difficult treatment of this resin molding in the reality.On the other hand, when this thickness is higher than above-mentioned scope, be difficult to this resin molding is rolled into web-like.

Above-mentioned thickness of resin film distributes with respect to mean value usually in ± 20%, better is in ± 10%, is more preferably in ± 5%, be well especially ± 3% in.In addition, the rate of change of the thickness of every 1cm better is below 5% usually below 10%, is more preferably below 1%, and good especially is below 0.5%.By forming resin molding, when this resin molding is carried out stretch processing, can prevent the generation of the phase differential inequality of transmitted light with such thickness condition.

(stretch processing)

As to the method that the unstretching film that as above obtains carries out stretch processing, using known free end uniaxial tension, wide constraint uniaxial tension or biaxial stretch-formed method in order to obtain above-mentioned optical characteristics.

When uniaxial tension was handled, draw speed was generally 1～5000%/minute, better be 50～1000%/minute, be more preferably 100～1000%/minute.

In the biaxial stretch-formed facture, can adopt simultaneously to both direction carry out stretch processing method, carry out uniaxial tension and handle the method that stretch processing is carried out to the direction different with the draw direction in this stretch processing in the back.At this moment, the angle of 2 tensile axis is not particularly limited, usually in the scope of 120～60 degree according to the desired characteristic decision of objective optics film.In addition, draw speed can be identical at each draw direction, also can be different, be generally 1～5000%/minute, better be 50～1000%/minute, be more preferably 100～1000%/minute, be 100～500% well especially/minute.

The stretch processing temperature is not particularly limited, and is benchmark with the glass temperature Tg of resin, in Tg ± 30 ℃, better be Tg ± 15 ℃, be more preferably in Tg-5～Tg+15 ℃ the scope.By the stretch processing temperature is set in the above-mentioned scope, the generation of phase differential inequality in the stretched film that can suppress to obtain, and also the control of the refractive index of each composition becomes easily, so be desirable.

Draw ratio is not particularly limited according to the desired characteristic decision of objective optics film, is generally 1.01～10 times, better is 1.03～5 times, is more preferably 1.03～3 times.If draw ratio is higher than above-mentioned scope, the phase differential of the stretched film that then obtains is difficult to control.The film that drawn is handled can directly cool off, but better is to keep more than at least 10 seconds under the temperature atmosphere of Tg-20 ℃～Tg of resin molding, better is 30 seconds～60 minutes, be more preferably 1～60 minute after, cool off again.Thus, can obtain transmitted light phase differential through the time phase retardation film with low uncertainty and stable.

Carried out the film of stretch processing as mentioned above, molecule is orientated because of stretch processing, and the result makes transmitted light produce phase differential, and the thickness that this phase differential can be by draw ratio, draft temperature or film etc. is controlled.

＜first way 〉

Blooming of the present invention has above-mentioned optical characteristics, and viewing angle compensation is respond well, so be suitable as the used compensation film for angular field of view of large-scale LCD TV of LCD, particularly VA type.In addition, in addition, can also be used for mobile phone, numerical information terminal, beeper, navigational system, vehicle mounted LCD, LCD monitor, light modulation panel, OA equipment with display, AV equipment with various liquid crystal display cells, electroluminescent display element or touch-screens etc. such as displays.In addition, also can be used as the used wave plate of record regenerator of CDs such as CD, CD-R, MD, MO, DVD.

[polaroid]

The polaroid that polaroid of the present invention obtains for the blooming in one or both sides lamination the invention described above of polariscope (polarizing coating).As the lamination method, can be directly polariscope and blooming is bonding by suitable bonding agent or bonding agent, also can be in lamination bonding blooming on the polariscope of diaphragm.If consider cost etc., better be direct lamination blooming of the present invention on polariscope.

As above-mentioned polariscope (polarizing coating), be not particularly limited, can use for example to make polarized components such as containing iodine or dichroic dye in the film that forms by polyvinyl alcohol resins such as polyvinyl alcohol (PVA) (PVA), polyvinyl formal, polyvinyl acetals and stretch and the film that obtains.

As said protection film; be not particularly limited, can use for example good polymer films such as the transparency, physical strength, thermal stability such as triacetyl cellulose cellulose families such as (TAC) film, polyesters film, polycarbonate-based film, polyether sulfone film, polyamide-based film, polyimide film, polyolefins film.

Used bonding agent or bonding agent when making the diaphragm lamination to above-mentioned polariscope is not particularly limited, and can use the bonding agent or the bonding agent that are for example formed by acrylic polymers or vinyl alcohol polymer.Particularly use the film that forms by PVA as under the polariscopic situation,, better be to use PVA class bonding agent from the angle of connectivity.

Used bonding agent or bonding agent when making the direct lamination of blooming to above-mentioned polariscope is not particularly limited, and for example can use aqueous binder that the water-borne dispersions by acrylic polymer constitutes etc.By using such aqueous binder, adaptation is further improved, durable having good stability is so be desirable.In addition, as make the direct lamination of blooming to lamination used bonding agent or bonding agent on the polariscope of diaphragm the time, be not particularly limited, can suitably use aforesaid bonding agent or bonding agent etc.

The viewing angle compensation of polaroid of the present invention is respond well, thus by this polaroid being configured in the one or both sides of the liquid crystal cell of LCD, the light leak in the time of not only can preventing black display and leak look (painted), and can obtain high-contrast.In addition, even use for a long time under hot conditions, the characteristic variations of polaroid of the present invention is also little, so usable range is wide.

[embodiment]

Below, exemplify embodiment, the present invention is carried out more specific description, but only otherwise exceed its technology contents, the present invention is not limited to following embodiment.In addition, under the situation that does not have in following to specify, " part " and " % " expression " weight portion " and " weight % ".

The assay method of various measured values of the present invention is as described below.

(1) glass temperature (Tg)

Using the differential scanning calorimeter (DSC) of セィコ-ィ Application スッ Le メ Application ッ corporate system, under nitrogen atmosphere, is that 20 ℃/minute condition is measured with programming rate.

(2) saturated water absorption

According to ASTM D570, sample to be carried out for 1 week in 23 ℃ water, mensuration is flooded the weight change of front and back and is tried to achieve.

(3) total light transmittance, mist degree

Use スガ testing machine corporate system haze meter (HGM-2DP type) to measure.

(4) phase differential of transmitted light

Use prince's instrumentation machine Co., Ltd.'s system " KOBRA-21ADH ", with 480,550,590,630, the wavelength of 750nm measures, and for the part beyond these wavelength, uses the phase difference value of aforementioned waves strong point, uses Cauchy's expansion to calculate.

(5) fleck defect is measured

The certifiable part light leak of naked eyes when observing between the polaroid of Nicol crossed state for specimen holder carries out instrumentation to the light leak of size more than 10 μ m on the light source that sample is placed 1000cd/m.

(6) brightness, visual angle and contrast are measured

Use the nitometer " LS-110 " of ミノ Le Co., Ltd. system, in the darkroom, measure brightness, visual angle and the contrast of liquid crystal panel.

(7) residual solvent amount

In the good solvent of non-use solvent, use gas chromatography (Shimadzu Seisakusho Ltd.'s system " GC-7A ") that the solution that obtains is analyzed sample dissolution.

(8) logarithm viscosity

Use Ubbelodhe type viscosity meter, at methenyl choloride, cyclohexane or N-N-methyl-2-2-pyrrolidone N-(sample solution concentration: 0.5g/dL), measure at 30 ℃.

＜synthesis example 1 〉

With 250 parts of 8-methyl-8-methoxycarbonyl group Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene (specific monomer), 18 parts of 1-hexenes (molecular weight regulator) and 750 parts of toluene (ring-opening polymerization solvent) join nitrogen replacement reaction vessel in, this solution is heated to 60 ℃.Then, add in the solution in reaction vessel the toluene solution of 0.62 part of aluminium triethyl (1.5mol/L) and 3.7 parts as polymerization catalyst with the tert-butyl alcohol and methyl alcohol modification the tungsten hexachloride (tert-butyl alcohol: methyl alcohol: the toluene solution (concentration 0.05mol/L) of tungsten=0.35mol:0.3mol:1mol).By with this system 80 ℃ of heated and stirred 3 hours, make it carry out ring-opening polymerization, obtain ring-opening polymerization polymer solution.Polymerisation conversion in this polyreaction is 97%, and the logarithm viscosity that the ring-opening polymerization polymer that obtains records in 30 ℃ is 0.75dL/g.

1000 parts of ring-opening polymerization polymer solution that obtain are like this packed in the reactor, in this ring-opening polymerization polymer solution, add 0.12 part of RuHCl (CO) [P (C ₆H ₅) ₃] ₃, with Hydrogen Vapor Pressure 100kg/cm ², 165 ℃ of temperature of reaction condition under heated and stirred 3 hours, carry out hydrogenation.After reaction solution (hydrogenated polymer solution) cooling that obtains, remove the pressure of hydrogen.This reaction solution is injected a large amount of methyl alcohol, separate and reclaim coagulum, be dried, obtain hydropolymer (hereinafter referred to as " Resin A 1 ").

For the Resin A 1 that obtains like this, use ¹The hydrogenation ratio that H-NMR records is 99.9%, the glass temperature (Tg) that records by the DSC method is 165 ℃, (solvent: the number-average molecular weight of the polystyrene conversion that tetrahydrofuran) records (Mn) is 32000 by the GPC method, weight-average molecular weight (Mw) is 137000, molecular weight distribution (Mw/Mn) is 4.29, saturated water absorption in the time of 23 ℃ is 0.3%, and the SP value is 19 (MPa ^1.2), the logarithm viscosity in 30 ℃ the methenyl choloride is 0.78dL/g.

＜synthesis example 2 〉

Except using 215 parts of 8-methyl-8-methoxycarbonyl group Fourth Ring [4.4.0.1 ^2.5.1 ^7.10The addition of]-3-dodecylene and 35 part of two ring [2.2.1] hept-2-ene", 1-hexene (molecular weight regulator) is outside 18 parts, similarly operates with synthesis example 1, obtains hydropolymer (hereinafter referred to as " Resin A 2 ").

For the Resin A 2 that obtains like this, hydrogenation ratio is 99.9%, the glass temperature (Tg) that records by the DSC method is 125 ℃, (solvent: the Mn of the polystyrene conversion that tetrahydrofuran) records is 46000 by the GPC method, Mw is 190000, saturated water absorption when molecular weight distribution (Mw/Mn) is 4.15,23 ℃ is 0.18%, and the SP value is 19 (MPa ^1/2), the logarithm viscosity in 30 ℃ the methenyl choloride is 0.69dL/g, gel content is 0.2%.

＜synthesis example 3 〉

Except using 53 parts of Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene, 46 parts of 8-ethylidene Fourth Ring [4.4.0.1 ^2.5.1 ^7.10]-3-dodecylene and 66 part of three ring [4.3.0.1 ^2.5]-the last of the ten Heavenly stems-3, the 7-diene, the addition of 1-hexene (molecular weight regulator) is 18 parts, uses cyclohexane to replace similarly operating with synthesis example 1 outside the toluene as ring-opening polymerization with solvent, obtains hydropolymer (hereinafter referred to as " Resin A 3 ").

For the Resin A 3 that obtains like this, hydrogenation ratio is 99.9%, the glass temperature (Tg) that records by the DSC method is 137 ℃, (solvent: the Mn of the polystyrene conversion that cyclohexane) records is 39000 by the GPC method, Mw is 158000, saturated water absorption when molecular weight distribution (Mw/Mn) is 4.05,23 ℃ is 0.01%, and the SP value is 17 (MPa ^1/2), the logarithm viscosity in 30 ℃ the methenyl choloride is 0.70dL/g, gel content is 0.2%.

＜synthesis example 4 〉

Make 18.9141g 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and 31.0859g 4,4 '-two (4-amino-benzene oxygen) biphenyl are dissolved in the 200g N-N-methyl-2-2-pyrrolidone N-, at room temperature react 3 hours.The reaction solution that obtains is injected in the excessive methyl alcohol, make the polyamic acid precipitation, then with washed with methanol, in 40 ℃ of dryings 15 hours, obtaining the logarithm viscosity that 48.2g records in the N-N-methyl-2-2-pyrrolidone N-was the polymkeric substance of 2.45dL/g under reduced pressure.This polymer dissolution of 30.0g in the 270g gamma-butyrolacton, is added 20.0g pyridine and 15.0g acetic anhydride in this solution, carry out imidizate at 120 ℃ and handled 3 hours.The reactant liquor that obtains is injected in the excessive methyl alcohol, makes polymer precipitation, obtain the polyimide (hereinafter referred to as " resin B 1 ") of logarithm viscosity 2.39dL/g.

＜synthesis example 5 〉

Except using 2,2 '-dimethyl-4,4 '-benzidine replacement 4, outside 4 '-two (4-amino-benzene oxygen) biphenyl, with synthesis example 4 synthesis of polyimides (hereinafter referred to as " resin B 2 ") similarly, the logarithm viscosity that the resin B 2 that obtains records in the N-N-methyl-2-2-pyrrolidone N-is 2.10dL/g.

＜synthesis example 6 〉

Except using 4,4 '-diaminodiphenyl-methane replacement 4, outside 4 '-two (4-amino-benzene oxygen) biphenyl, with synthesis example 4 synthesis of polyimides (hereinafter referred to as " resin B 3 ") similarly, the logarithm viscosity that the resin B 3 that obtains records in the N-N-methyl-2-2-pyrrolidone N-is 0.86dL/g.

＜synthesis example 7 〉

Make tetracarboxylic dianhydride with ehter bond shown in the following chemical formula of 43.9302g (VII) and 9.1270g 1, the 3-phenylenediamine is dissolved in the 200g N-N-methyl-2-2-pyrrolidone N-, at room temperature reacts 3 hours.The reactant liquor that obtains is injected in the excessive methyl alcohol, makes polyamic acid precipitation, then with washed with methanol, in 40 ℃ of dryings 15 hours, obtaining the logarithm viscosity that 48.2g records in the N-N-methyl-2-2-pyrrolidone N-was the polymkeric substance of 2.38dL/g under reduced pressure.This polymkeric substance of 30.0g is dissolved in the 270g N-N-methyl-2-2-pyrrolidone N-once more, in this solution, adds 20.0g pyridine and 15.0g acetic anhydride, carry out imidizate at 120 ℃ and handled 3.5 hours.The reactant liquor that obtains is injected in the excessive methyl alcohol, makes polymer precipitation, obtain the polyetherimide (hereinafter referred to as " resin B 4 ") of logarithm viscosity 2.35dL/g.

＜Production Example 1〉resin molding (a1)

Above-mentioned Resin A is dissolved in toluene (solution viscosity under the room temperature is 30000mPas) with 30% concentration, with respect to 100 parts by weight polymer, [3-(3 as the pentaerythrite four of antioxidant to add 0.1 weight portion, 5-di-t-butyl-4-hydroxyphenyl) propionic ester], the solution that the obtains metallic fiber sintered filtrator with the aperture 5 μ m of Japanese Port-Le system is filtered, control the flow velocity of solution simultaneously, make differential pressure in 0.4MPa.Use is arranged at the aboveground metal industry system " INVEX tests coating machine " in 1000 grades the toilet, with the solution coat that obtains with acrylic compounds hydrophiling (easy bondingization) surface treatment the base material PET film (eastern レ Co., Ltd.'s system " Le ミラ-U94 ") of thick 100 μ m on, making dried thickness is 100 μ m, with its 50 ℃ carry out the drying first time after, it is dry to carry out the second time at 90 ℃.Peel off from the PET film, obtain resin molding (a1).The residual solvent amount of the film that obtains is 0.5%, and total light transmittance is 93%.

＜Production Example 2〉resin molding (a2)

Except using Resin A 2 to replace the Resin A 1,, obtain the resin molding (a2) of thick 100 μ m by the method same with Production Example 1.The residual solvent amount of the film that obtains is 0.5%, and total light transmittance is 93%.

＜Production Example 3〉resin molding (a3)

Except using Resin A 3 to replace Resin A 1, use cyclohexane to replace outside the toluene, by the method same, obtain the resin molding (a3) of thick 150 μ m with Production Example 1.The residual solvent amount of the film that obtains is 0.5%, and total light transmittance is 92%.

＜Production Example 4〉resin molding (a4)

With above-mentioned resin molding (a1) biaxial stretch-formed processing when 180 ℃ are carried out 1.72 times in 1.44 times in a direction, the direction vertical with aforementioned direction, obtain the resin molding (a4) of thickness 36 μ m.The R550 of the resin molding that obtains (a4) is 45nm, and Rth is 135nm.

＜Production Example 5〉resin molding (a5)

With above-mentioned resin molding (a2) biaxial stretch-formed processing when 122 ℃ are carried out 1.75 times in 1.49 times in a direction, the direction vertical with aforementioned direction, obtain the resin molding (a5) of thickness 34 μ m.The R550 of the resin molding that obtains (a5) is 67nm, and Rth is 238nm.

＜Production Example 6〉resin molding (a6)

With above-mentioned resin molding (a3) biaxial stretch-formed processing when 145 ℃ are carried out 1.95 times in 1.69 times in a direction, the direction vertical with aforementioned direction, obtain the resin film (a6) of thickness 39 μ m.The R550 of the resin molding that obtains (a6) is 48nm, and Rth is 142nm.

＜Production Example 7〉resin molding (a7)

Go up the composition (solid component concentration: 10 weight %) that obtains with the mixed solvent dilution of methyl ethyl ketone and isopropyl alcohol with 24 microns coiling rod coating uv curing resin " デソラィト Z7524 " (JSR Corp.'s system) at interval at above-mentioned resin molding (a4), 80 ℃ of heating 5 minutes, make solvent evaporates.Then, the coated face side is carried out 250mW/cm with metal halid lamp ², 1J/cm ²Ultraviolet ray irradiation, obtain having the resin molding (a7) of undercoat.

＜Production Example 8〉resin molding (a8)

Go up the composition (solid component concentration: 3 weight %) that obtains with the methyl ethyl ketone dilution with 12 microns coiling rod coating polyether-polyurethane material " Ha ィ De ラ Application WLS-201 " at interval (big Japanese ィ Application キ chemical industry Co., Ltd. system) at resin molding (a5), 80 ℃ of heat dryings 5 minutes, obtain having the resin molding (a8) of undercoat.

＜Production Example 9〉resin molding (a9)

Except using resin molding (a6) to replace similarly operating with Production Example 8 resin molding (a5), obtain having the resin molding (a9) of undercoat.

＜Production Example 10〉resin molding (a10)

Except using resin molding (a1) to replace similarly operating with Production Example 7 resin molding (a4), obtain having the resin molding (a10) of undercoat.

(embodiment 1)

Except using 10% gamma-butyrolacton solution of resin B 1, use the resin molding (a4) that obtains in the Production Example 4 to replace base material PET film, outside film not being peeled off from base material, by the method same, obtain resin molding (a4) and the blooming (1) of the incorporate lamination type of polyimide film (b1) that forms by resin B 1 with Production Example 1.The thickness of polyimide film (b1) layer of the blooming that obtains (1) is 3 μ m, and total light transmittance is 92%.

(embodiment 2)

Except using resin B 2 to replace the resin B 1,, obtain resin molding (a4) and the blooming (2) of the incorporate lamination type of polyimide film (b2) that forms by resin B 2 by method similarly to Example 1.The thickness of polyimide film (b2) layer of the blooming that obtains (2) is 3 μ m, and total light transmittance is 92%.

(embodiment 3)

Except using resin B 3 to replace the resin B 1,, obtain resin molding (a4) and the blooming (3) of the incorporate lamination type of polyimide film (b3) that forms by resin B 3 by method similarly to Example 1.The thickness of polyimide film (b3) layer of the blooming that obtains (3) is 3 μ m, and total light transmittance is 92%.

(embodiment 4)

Except using resin molding (a5) to replace resin molding (a4),, obtain resin molding (a5) and the blooming (4) of the incorporate lamination type of polyimide film (b4) that forms by resin B 1 by method similarly to Example 1 as the base material.The thickness of the polyimide layer of the blooming that obtains (4) is 3 μ m, and total light transmittance is 92%.

(embodiment 5)

Except using resin molding (a1) to replace resin molding (a4),, obtain resin molding (a1) and the resin molding of the incorporate lamination type of polyimide film (b5) that forms by resin B 1 by method similarly to Example 1 as the base material.The thickness of the polyimide layer of the laminated film that obtains is 3 μ m, and total light transmittance is 92%.Then, to laminated film biaxial stretch-formed processing when 180 ℃ are carried out 1.70 times in 1.40 times in a direction, the direction vertical with aforementioned direction, obtain the lamination type blooming (5) that polyimide film (b5 ') that the resin molding (a1 ') that obtained by resin molding (a1) drawn and polyimide film (b5) drawn obtain constitutes.

The optical characteristics and the thickness of the blooming that obtains among the embodiment 1～5 are shown in table 1.

[table 1]

By The above results as can be known, the lamination type blooming that is made of cycloolefin resin film and polyimide layer of the present invention can carry out the control of the optical characteristics in the wider range by the structure of each layer and the selection of job operation.

The preparation example of＜aqueous binder 〉

In reaction vessel, add 250 parts of distilled water, in this reaction vessel, add 90 parts of butyl acrylates, 8 part of 2 hydroxyethyl meth acrylate, 2 parts of divinylbenzenes and 0.1 part of potassium oleate, its stirring fin by Teflon (registered trademark) system is stirred, carry out dispersion treatment.After carrying out nitrogen replacement in this reaction vessel, this system is warming up to 50 ℃, add 0.2 part of potassium persulfate, the beginning polymerization.After 2 hours, add 0.1 part of potassium persulfate again, this system is warming up to 80 ℃, continued polyreaction 1 hour, obtain polymer dispersion liquid.Then, this polymer dispersion liquid is concentrated into 70% solid component concentration, obtains the aqueous binder (bonding agent) that the water-borne dispersions by polyacrylate polymers constitutes with polar group by using evaporator.

For the acrylic polymer that constitutes the aqueous binder that obtains like this, by GPC method (solvent: tetrahydrofuran) number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of mensuration polystyrene conversion, Mn is 69000 as a result, Mw is that the logarithm viscosity in 135000,30 ℃ the methenyl choloride is 1.2dL/g.

(embodiment 6)

After stretching before commercially available polyvinyl alcohol (PVA) (PVA) system film carried out with 3 times draw ratio in the dye bath of 30 ℃ of aqueous solution of iodine concentration 0.03 weight %, potassium iodide concentration 0.5 weight %, draw ratio with 2 times in 55 ℃ crosslinked bath of the aqueous solution of boric acid concentration 5 weight %, potassium iodide concentration 8 weight % carries out after stretching, obtains polariscope after the drying.

Go up with the excellent No.2 (K﹠amp of coiling at resin molding (a4); The K corporate system) composition (solid component concentration: 3 weight %) that obtains with the methyl ethyl ketone dilution of coating polyether-polyurethane material " Ha ィ De ラ Application WLS-201 " (big Japanese ィ Application キ chemical industry Co., Ltd. system), 80 ℃ of heat dryings 50 minutes, obtained forming the film (ac1) of polyurethanes primary coat c layer.The residual solvent amount of the film that obtains (ac1) is 0.5%, and total light transmittance is 93%.The 10% gamma-butyrolacton solution of coating resin B1 on the polyurethanes primary coat c of this film (ac1) layer forms polyimide film (b6) again, obtains lamination type blooming (6).The thickness of polyimide film (b6) layer of the blooming that obtains (6) is 3 μ m, and total light transmittance is 92%.The optical characteristics and the thickness of blooming (6) are shown in table 2.

[table 2]

	Cycloolefin resinoid rete	The polyimide based resin rete	Blooming
	Cycloolefin resinoid rete	The polyimide based resin rete	Blooming	The kind of film	(a4)	(b6)	(6)
Thickness (μ m)	36	3 3	40	The kind of film	(a4)	(b6)	(6)
Thickness (μ m)	36	3 3	40	Rth(nm)	135	137	274
R550(nm)	45	5	51	Rth(nm)	135	137	274
R550(nm)	45	5	51	R450/R550	1.02	1.07	-
R650/R550	0.99	0.97	-	R450/R550	1.02	1.07	-

Then, with the axis of homology of polaroid and the parallel state of axle of the draw direction of blooming (6), attach above-mentioned blooming (6) in above-mentioned polariscopic one side with above-mentioned aqueous binder, on another side, use PVA class bonding agent to attach commercially available triacetyl cellulose (TAC) system film, obtain polaroid (1).The transmissivity and the degree of polarization of the polaroid that investigation obtains (1), the result is respectively 44.0% and 99.9%.

In order to estimate the characteristic of above-mentioned polaroid (1), the polaroid and the phase retardation film in front of observer's side that will be attached at the liquid crystal panel of the Sharp Corporation's system LCD TV (LC-13B1-S) that adopts the black TFT liquid crystal of the low reflection of ASV mode earlier peeled off.Then, attach above-mentioned polaroid (1) in this position of having peeled off, make its axis of homology with the original polaroid that attaches identical, the phase retardation film of this polaroid (1) (blooming (6)) is in the liquid crystal cell side.In addition, the phase retardation film at the back side that is attached at observer's side of liquid crystal panel is peeled off, made it be the state that back side of panel does not have phase retardation film.

Affirmation has position angle 45 degree of the LCD TV of this polaroid (1), the contrast of polar angle 60 degree directions, and the result is 70, is higher numerical value.In addition, in all directions visual angle (zone of contrast more than 10) confirmed, about the results verification, about, oblique all 170 the degree more than.

In addition, as long duration test, polaroid (1) after placing 2000 hours respectively under the environment of 100 ℃ and 60 ℃, 90RH% is similarly estimated, and the rate of change of the above-mentioned characteristic before and after the long duration test as a result [=(before changing-change back) * 100/ change before] is all in 5%.

(comparative example 1)

Except using commercially available TAC film to replace obtaining polaroid (2) similarly to Example 6 the blooming (6).Investigate the transmissivity and the degree of polarization of this polaroid (2), the result is respectively 44.0% and 99.9%.

The polaroid (2) that obtains is attached on the LCD TV similarly to Example 6, confirm the contrast of position angle 45 degree, polar angle 60 degree directions, the result is 3, is lower numerical value.In addition, in all directions visual angle (zone of contrast more than 10) confirmed, about the results verification, about all 170 the degree more than, but oblique only be 80 the degree.

In addition, as long duration test, the polaroid (2) after placing 2000 hours respectively under the environment of 100 ℃ and 60 ℃, 90RH% is confirmed degree of polarization, the results change rate is respectively 10% and 8%.

(comparative example 2)

Except use is carried out biaxial stretch-formed processing and is made its TAC film that has with the same phase differential (Rth, R550) of film (a4) replace obtaining polaroid (3) similarly to Example 6 the cycloolefin resin film (a4).Investigate the transmissivity and the degree of polarization of this polaroid (3), the result is respectively 44.0% and 99.9%.

The polaroid (3) that obtains is attached on the LCD TV similarly to Example 6, confirm the contrast of position angle 45 degree, polar angle 60 degree directions, the result is 40.In addition, in all directions visual angle (zone of contrast more than 10) confirmed, about the results verification, about, oblique all 170 the degree more than, but as long duration test, after placing 2000 hours respectively under the environment of 100 ℃ and 60 ℃, 90RH%, the variation of degree of polarization as a result is respectively difference 10% and 12%, and the variation of the contrast of position angle 45 degree, polar angle 60 degree directions is greatly to 30%.

(embodiment 7)

Except using 5% N-N-methyl-2-2-pyrrolidone N-solution of resin B 4, use the resin molding (a7) that obtains in the Production Example 7 to replace base material PET film, outside film not being peeled off from base material, by the method same, obtain resin molding (a7) and the blooming (7) of the incorporate lamination type of polyetherimde films (b7) that forms by resin B 4 with Production Example 1.In addition, adjust, make polyetherimde films (b7) be formed at the primary coat treated side side of resin molding (a7).The thickness of polyetherimde films (b7) layer of the blooming that obtains (7) is 10 μ m, and total light transmittance is 91%, and the light transmittance of wavelength 360nm is 0.5%.

(embodiment 8)

Except using resin molding (a8) to replace the resin molding (a7),, obtain resin molding (a8) and the blooming (8) of the incorporate lamination type of polyetherimde films (b8) that forms by resin B 4 by method similarly to Example 1.The thickness of polyetherimde films (b8) layer of the blooming that obtains (8) is 5 μ m, and total light transmittance is 91%, and the light transmittance of wavelength 360nm is 8.2%.

(embodiment 9)

Except using resin molding (a9) to replace resin molding (a7), use 5% dichloromethane solution to replace outside the 5% N-N-methyl-2-2-pyrrolidone N-solution, by method similarly to Example 1, obtain resin molding (a9) and the blooming (9) of the incorporate lamination type of polyetherimde films (b9) that forms by resin B 4.The thickness of polyetherimde films (b9) layer of the blooming that obtains (9) is 3 μ m, and total light transmittance is 91%, and the light transmittance of wavelength 360nm is 9.6%.

(embodiment 10)

Except using resin molding (a10) to replace the resin molding (a7),, obtain resin molding (a10) and the resin molding of the incorporate lamination type of polyetherimde films (b10) that forms by resin B 4 by method similarly to Example 1.The thickness of the polyetherimide layer of the laminated film that obtains is 10 μ m, and total light transmittance is 91%, and the light transmittance of wavelength 360nm is 0.6%.

Then, to the biaxial stretch-formed processing when 180 ℃ are carried out 1.70 times in 1.40 times in a direction, the direction vertical with aforementioned direction of the laminated film that obtains, obtain the lamination type blooming (10) that polyimide film (b10 ') that the resin molding (a10 ') that obtained by resin molding (a10) drawn and polyetherimde films (b10) drawn obtain constitutes.

The optical characteristics and the thickness of the blooming that obtains among the embodiment 7～10 are shown in table 3.

[table 3]

(embodiment 11)

After stretching before commercially available PVA system film carried out with 3 times draw ratio in the dye bath of 30 ℃ of aqueous solution of iodine concentration 0.03 weight %, potassium iodide concentration 0.5 weight %, draw ratio with 2 times in 55 ℃ crosslinked bath of the aqueous solution of boric acid concentration 5 weight %, potassium iodide concentration 8 weight % carries out after stretching, obtains polariscope after the drying.

On resin molding (a7) and face primary coat treated side opposition side, be diluted to the composition that 3 weight % obtain with methyl ethyl ketone with 12 microns coiling rod coating polyether-polyurethane material " Ha ィ De ラ Application WLS-201 " at interval (big Japanese ィ Application キ chemical industry Co., Ltd. system), 80 ℃ of heat dryings 5 minutes, obtain having the resin molding (ac2) of polyurethanes primary coat c layer on the two sides.

Then, except using resin molding (ac2) to replace resin molding (a7), use 10% gamma-butyrolacton solution of resin B 4 to replace outside the 5% N-N-methyl-2-2-pyrrolidone N-solution of resin B 4, operate the incorporate lamination type blooming of polyetherimde films (b11) (11) that obtains resin molding (ac2) and form similarly to Example 1 by resin B 4.

The thickness of polyetherimde films (b11) layer of blooming (11) is 3 μ m, and total light transmittance is 91%.In addition, the light transmittance of wavelength 360nm is 9.0%.The optical characteristics and the thickness of blooming (11) are shown in table 4.

[table 4]

	Cycloolefin resinoid rete	The polyetherimides resin film layer	Blooming
	Cycloolefin resinoid rete	The polyetherimides resin film layer	Blooming	The kind of film	(a7)	(b11)	(11)
Thickness (μ m)	36	3 3	39	The kind of film	(a7)	(b11)	(11)
Thickness (μ m)	36	3 3	39	Rth(nm)	135	137	272
R550(nm)	45	5	50	Rth(nm)	135	137	272
R550(nm)	45	5	50	R450/R550	1.02	1.07	-
R650/R550	0.99	0.97	-	R450/R550	1.02	1.07	-

Then, with the axis of homology of polaroid and the parallel state of axle of the draw direction of blooming (11), attach above-mentioned blooming (11) in above-mentioned polariscopic one side with above-mentioned aqueous binder, on another side, use PVA class bonding agent to attach commercially available TAC system film, obtain polaroid (4).The transmissivity and the degree of polarization of the polaroid that investigation obtains (4), the result is respectively 44.0% and 99.9%.

In order to estimate the characteristic of above-mentioned polaroid (4), the polaroid and the phase retardation film in front of observer's side that will be attached at the liquid crystal panel of the Sharp Corporation's system LCD TV (LC-13B1-S) that adopts the black TFT liquid crystal of the low reflection of ASV mode earlier peeled off.Then, attach above-mentioned polaroid (4) in this position of having peeled off, make its axis of homology with the original polaroid that attaches identical, the phase retardation film of this polaroid (4) (blooming (11)) is in the liquid crystal cell side.In addition, the phase retardation film at the back side that is attached at observer's side of liquid crystal panel is peeled off, made it be the state that back side of panel does not have phase retardation film.

Affirmation has position angle 45 degree of the LCD TV of this polaroid (4), the contrast of polar angle 60 degree directions, and the result is 70, is higher numerical value.In addition, in all directions visual angle (zone of contrast more than 10) confirmed, about the results verification, about, oblique all 170 the degree more than.

In addition, as long duration test, polaroid (4) after placing 2000 hours respectively under the environment of 100 ℃ and 60 ℃, 90RH% is similarly estimated, and the rate of change of the above-mentioned characteristic before and after the long duration test as a result [=(before changing-change back) * 100/ change before] is all in 5%.

Claims

1. blooming is characterized in that, has film a layer that is made of the cycloolefin resinoid and the film b layer that is formed by polyimide based resin with alicyclic structure or polyetherimides resin.

2. blooming as claimed in claim 1 is characterized in that, satisfies following formula (1) and (2):

(1)200nm≦Rth≦1000nm

(2)0≦R550≦200nm

In the above-mentioned formula, Rth represents the phase differential of wavelength 550nm place film thickness direction, with Rth=[(nx+ny)/2-nz] * d represents, R550 represents the phase differential in the wavelength 550nm place face, represents with R550=(nx-ny) * d; Wherein, nx is the largest refractive index in the face, ny be in the face with the refractive index of nx vertical direction, nz is the refractive index of the film thickness direction vertical with respect to nx, ny, d is the thickness nm of film.

3. blooming as claimed in claim 1, it is characterized in that, aforementioned films a layer forms with the cycloolefin resinoid of the formation unit of following general formula (II) expression with the formation unit of following general formula (I) expression and 70～0mol% by having 30～100mol%, and the thickness of this film a layer is 10000～200000nm;

In the formula (I), m is the integer more than 1, and p is the integer more than 0 or 1, D independently be with-CH=CH-or-CH ₂CH ₂The group of-expression, R ¹～R ⁴Independent respectively expression hydrogen atom, halogen atom or have or do not have the replacement of the binding group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom or do not have the alkyl or the polar group of the carbon number 1～30 of replacement, R ¹With R ²And/or R ³With R ⁴The integrated alkyl that forms divalent, R ¹Or R ²With R ³Or R ⁴Mutually combining to form carbocyclic ring or heterocycle, and this carbocyclic ring or heterocycle are single ring architecture or multiring structure;

In the formula (II), E independently be with-CH=CH-or-CH ₂CH ₂The group of-expression, R ⁵～R ⁸Independent respectively expression hydrogen atom, halogen atom or have or do not have the replacement of the binding group that contains oxygen atom, sulphur atom, nitrogen-atoms or silicon atom or do not have the alkyl or the polar group of the carbon number 1～30 of replacement, R ⁵With R ⁶And/or R ⁷With R ⁸The integrated alkyl that forms divalent, R ⁵Or R ⁶With R ⁷Or R ⁸Mutually combining to form carbocyclic ring or heterocycle, and this carbocyclic ring or heterocycle are single ring architecture or multiring structure.

4. blooming as claimed in claim 1 is characterized in that, aforementioned films a layer satisfies following formula (3)～(6):

(3)20nm≦R _ath≦500nm

(4)0≦R _a550≦200nm

(5)1.00≦R _a450/R _a550≦1.30

(6)0.70≦R _a650/R _a550≦1.00

In the above-mentioned formula, R _aTh represents the phase differential of the film a of wavelength 550nm place thickness direction, with R _aTh=[(nx _a+ ny _a)/2-nz _a] * d _aExpression, R _a450, R _a550, R _a650 represent the phase differential R of the film a at wavelength 450nm, 550nm, 650nm place respectively _a, with R _a=(nx _a-ny _a) * d _aExpression; Wherein, nx _aBe the largest refractive index in the film a face, ny _aFor in the film a face and nx _aThe refractive index of vertical direction, nz _aFor with respect to nx _a, ny _aThe refractive index of vertical film a thickness direction, d _aThickness nm for film a.

5. blooming as claimed in claim 1 is characterized in that, the rete of aforementioned films a layer for obtaining through uniaxial tension or biaxial stretch-formed processing.

6. blooming as claimed in claim 1 is characterized in that, aforementioned films b layer is formed by the polyimide based resin with structural unit of representing with following formula (III):

7. blooming as claimed in claim 1 is characterized in that, aforementioned films b layer is formed by the polyimide based resin that has biphenyl backbone to small part.

8. blooming as claimed in claim 1 is characterized in that, aforementioned films b layer is formed by the polyetherimides resin with structural unit of representing with following formula (IV):

In the formula (IV), X ＇ and Y ＇ can be identical, also can be different, represent saturated or undersaturated alkyl.

9. blooming as claimed in claim 8 is characterized in that, the structural unit of representing with aforementioned formula (IV) is the structural unit of representing with following general formula (V):

10. blooming as claimed in claim 1 is characterized in that, aforementioned films b layer satisfies following formula (7)～(10):

(7)100nm≦R _bth≦1000nm

(8)0≦R _b550≦200nm

(9)1.00≦R _b450/R _b550≦1.30(10)0.7≦R _b650/R _b550≦1.00

In the above-mentioned formula, R _bTh represents the phase differential of the film b of wavelength 550nm place thickness direction, with R _bTh=[(nx _b+ ny _b)/2-nz _b] * d _bExpression, R _b450, R _b550, R _b650 represent the phase differential R of the film b at wavelength 450nm, 550nm, 650nm place respectively _b, this R _bWith R _b=(nx _b-ny _b) * d _bExpression; Aforementioned R _aTh and R _bTh's and below 1000nm, aforementioned R _a550 and R _b550 and below 200nm; Wherein, nx _bBe the largest refractive index in the film b face, ny _bFor in the film b face and nx _bThe refractive index of vertical direction, nz _bFor with respect to nx _b, ny _bThe refractive index of vertical film b thickness direction, d _bThickness nm for film b.

11. blooming as claimed in claim 1 is characterized in that, has acrylic compounds primary coat c layer between aforementioned films a layer and film b layer.

12. blooming as claimed in claim 11, it is characterized in that, described blooming forms aforementioned acrylic compounds primary coat c layer by lining on the film a that obtains through uniaxial tension or biaxial stretch-formed processing, and lining forms aforementioned films b layer and obtains on this primary coat c layer then.

13. blooming as claimed in claim 11, it is characterized in that, described blooming forms aforementioned acrylic compounds primary coat c layer by lining on the film that does not stretch that is formed by the cycloolefin resinoid, after lining on this primary coat c layer forms aforementioned films b layer, carry out uniaxial tension or biaxial stretch-formed processing and obtain.

14. blooming as claimed in claim 1 is characterized in that, has polyurethanes primary coat c layer between aforementioned films a layer and film b layer.

15. blooming as claimed in claim 14 is characterized in that, described blooming forms aforementioned polyurethanes primary coat c layer by lining on the film a that obtains through uniaxial tension or biaxial stretch-formed processing, and lining forms aforementioned films b layer and obtains on this primary coat c layer.

16. blooming as claimed in claim 14, it is characterized in that, described blooming forms aforementioned polyurethanes primary coat c layer by lining on the film that does not stretch that is formed by the cycloolefin resinoid, after lining on this primary coat c layer forms aforementioned films b layer, carry out uniaxial tension or biaxial stretch-formed processing and obtain.

17. polaroid is characterized in that, has each described blooming in the claim 1～16.

18. LCD is characterized in that, has each described blooming in the claim 1～16.

19. LCD is characterized in that, has the described polaroid of claim 17.