CN101140334B

CN101140334B - Optical compensation film and retardation film

Info

Publication number: CN101140334B
Application number: CN2007101497755A
Authority: CN
Inventors: 土井亨; 下里伸治; 小原直人
Original assignee: Tosoh Corp
Current assignee: Tosoh Corp
Priority date: 2006-09-05
Filing date: 2007-09-05
Publication date: 2011-04-20
Anticipated expiration: 2027-09-05
Also published as: JP4697098B2; CN101140334A; JP2008064817A

Abstract

To provide a retardation film and an optical compensation film which have excellent optical properties and are useful as a compensation film for compensating the contrast and viewing-angle characteristics of liquid-crystal displays and as an antireflection film. The invention provides: an optical compensation film or optical compensation layer which is a film or layer comprising a fumaric ester resin, the film or layer having three-dimensional refractive indexes satisfying the relationship nz>ny x, wherein nx is the refractive index in a fast-axis direction of the film plane or layer plane, ny is the refractive index in an in-plane direction perpendicular to the fast-axis direction, and nz is the refractive index in an out-of-plane vertical direction, the ratio of the retardation as measured at a wavelength of 450 nm to the retardation as measured at a wavelength of 550 nm (R450/R550) being 1.1 or lower (film (A)) ; an optical compensation film which comprises the film (A) and a film (B) which has three-dimensional refractive indexes satisfying the relationship ny>nx z, wherein nx is the refractive index in a fast-axis direction of the film plane, ny is the refractive index in an in-plane direction perpendicular to the fast-axis direction, and nz is the refractive index in an out-of-plane vertical direction, and which has an in-plane retardation (Re) as measured at a wavelength of 550 nm of 50 nm or larger; a retardation film which is a film comprising a fumaric ester resin and in which when the refractive index in a fast-axis direction of the film plane, the refractive index in an in-plane direction perpendicular to the fast-axis direction, and the refractive index in an out-of-plane vertical direction are expressed by nx, ny, and nz, respectively, the refractive indexes satisfy the relationship nx<ny nz.

Description

Optical compensation films and phase retardation film

Technical field

The refractive index that the present invention relates to film thickness direction is big, the interior phase differential of face is big, wavelength dependency is little etc., the optical characteristics excellence, and to the contrast of LCD or the effective optical compensation films of improvement and the phase retardation film of viewing angle characteristic.

Technical background

LCD is being used with monitor, notebook computer, TV from the portable phone to the computing machine widely as most important display device in the multimedia society.In order to improve display characteristic, LCD has been used many bloomings.Especially phase retardation film improves very big effects such as contrast, compensation tone when bringing into play from positive or oblique watching.As phase retardation film in the past, use polycarbonate or cyclic polyolefin, but these macromolecules are and have positive birefringent macromolecule.Here, define as described below birefringent positive and negative.

Adopting stretches waits the optical anisotropy of the polymeric membrane that carries out molecular orientation can use indicatrix shown in Figure 1 to represent.Here, the refractive index of the leading phase shaft direction in the face during stretched film is expressed as nx, and the refractive index of direction in the perpendicular face is expressed as ny, and the refractive index of the outer vertical direction of face is expressed as nz.Moreover so-called leading phase shaft is the low direction of principal axis of refractive index in the face.

In addition, so-called negative birefringence is the birefringence that draw direction becomes the leading phase shaft direction, and so-called positive birefringence is the birefringence that the direction vertical with draw direction becomes the leading phase shaft direction.

Promptly, has negative birefringent macromolecule when unilateral stretching, the axial refractive index that stretches little (leading phase shaft: draw direction), when having positive birefringent macromolecule unilateral stretching, the little (leading phase shaft: the direction vertical) of the axial refractive index vertical with draw direction with the tensile axis direction.

In addition, phase differential (Re) can be used following value representation in the face: the refractive index (nx) of the leading phase shaft direction in the face vertical with the leading phase shaft direction in refractive index (the ny)-face of direction, multiply by the value that film thickness obtains again.

Many macromolecules have positive birefringence.As having negative birefringent macromolecule, acrylic resin or polystyrene are arranged, but the expression power of the phase differential of acryl resin is little, insufficient as the characteristic of optical compensation films.There is following problem in polystyrene: the photoelasticity modulus in room temperature region is big, only just can make the change problem of stability of equiphase difference of phase differential with small stress, problem on the big such optical characteristics of the wavelength dependency of phase differential, also has heat-resisting problem of hanging down in such practicality, therefore, do not use at present.

Here, the wavelength dependency of so-called phase differential is meant that phase differential changes owing to measuring wavelength.Can be used in the phase differential (R450) of wavelength 450nm place mensuration and the ratio R450/R550 of the phase differential (R550) that wavelength 550nm place measures represents.Usually, the trend that high molecular this R450/R550 change of aromatic structure is big is big, in the contrast or the reduction of field angle characteristic of low wavelength region may.

Show negative birefringent high molecular stretched film because the refractive index height of film thickness direction, become unexistent in the past optical compensation films, therefore, can be as the optical compensation films that compensates the optical compensation films of display viewing angles characteristic or be used for the compensation polarizing plate visual angle of being used to of alignment-type liquid crystal (IPS-LCD), reflection LCD, semi-transmission type LCD etc. in super-twist nematic liquid crystal (STN-LCD) for example or vertical alignment-type liquid crystal (VA-LCD), the face, market is big to the demand with negative birefringent optical compensation films.Proposed to use and had the method that positive birefringent macromolecule raising film thickness direction refractive index is made film.One of them is a kind of disposal route, and this method comprises, at the bonding heat-shrinkable film of the one or both sides of polymeric membrane, this laminated body is heated stretch processing, and the thickness direction of polymeric membrane is applied convergent force (for example, with reference to patent documentation 1～3).In addition, propose the limit polymeric membrane has been applied electric field, carried out the method (for example with reference to patent documentation 4) of unilateral stretching in the opposite, limit.Also proposed by having the phase retardation film (for example with reference to patent documentation 5) that negative optically anisotropic particulate and transparent macromolecule constitute.Propose coating fluid crystallinity polymeric membrane, made it the optical compensation films or the optical compensating layer (for example with reference to patent documentation 6) of axial pole-face vertical (homeo tropic) orientation.The optical compensation films (for example with reference to patent documentation 7, non-patent literature 1) of aromatic polymers such as painting polyethylene base naphthalene or polyvinyl biphenyl has been proposed again.

In addition, also proposed to use the blooming (for example, with reference to patent documentation 8) of Polyvinyl carbazole family macromolecule.

The scheme (for example referring to patent documentation 9,10) of relevant use dimethyl ester resinoid, the resinoid plastic substrate for display of crosslinked dimethyl ester, blooming, phase retardation film has been proposed.

Patent documentation 1: No. 2818983 communiques of patent

Patent documentation 2: the spy opens flat 05-297223 communique

Patent documentation 3: the spy opens flat 05-323120 communique

Patent documentation 4: the spy opens flat 06-088909 communique

Patent documentation 5: the spy opens the 2005-156862 communique

Patent documentation 6: the spy opens the 2002-333524 communique

Patent documentation 7: the spy opens the 2006-221116 communique

Patent documentation 8: the spy opens the 2001-91746 communique

Patent documentation 9: the spy opens the 2005-97544 communique

Patent documentation 10: the spy opens the 2006-249318 communique

Non-patent literature 1: Japanese Society of Rheology will, vol.22, No.2, pp129-134 (1994)

Summary of the invention

The problem that invention will solve

Yet the method that proposes in the patent documentation 1～4 is because manufacturing process is very complicated, so there is the low problem of production efficiency.And the control of phase differential homogeneity etc. is also difficult than employing stretching control in the past significantly.In addition, when using polycarbonate as basement membrane (base film), the photoelastic constant under the room temperature is big, and the stability that small stress will make phase differential change etc. at phase differential also has problems.In addition, also have problems such as the wavelength dependency of phase differential is big.

In addition, the phase retardation film that makes in the patent documentation 5 has negative birefringent phase retardation film for have negative optically anisotropic particulate by interpolation, considers from the simplification of manufacture method and the viewpoint of economy, requires not need to add the phase retardation film of particulate.In the patent documentation 6 described methods, exist to be difficult to make the axial equably vertical orientated problem of pole-face of liquid crystal liquid crystal property macromolecule.In addition, in patent documentation 7, the 8 described methods, problem such as exist the film make to break easily or the wavelength dispersibility of phase differential is big.

Patent documentation 9 has proposed to use the scheme of the resinoid plastic substrate for display of dimethyl ester, but does not propose relevant optical compensation films and phase retardation film.

Patent documentation 10 makes phase retardation film by the dimethyl ester resinoid is carried out crosslinked stretching, and still, phase differential is little, uses also existing problems as phase retardation film in fact.

Therefore, order of the present invention is, optical compensation films or the optical compensating layer and the phase retardation film of optical characteristics, mechanical property excellence is provided.

Solve the method for problem

The present inventor found that in view of above-mentioned problem further investigation, comprises the film of specific resin or the three-dimensional refractive index of layer and satisfies the optical compensation films of particular kind of relationship and the requirement that phase retardation film satisfies the problems referred to above, thereby finished the present invention.

That is, the present invention relates to:

Optical compensation films or optical compensating layer (film (A)), it comprises the fumarate resinoid, in the three-dimensional refractive index of film or layer, if face refractive index interior or the leading phase shaft direction that aspect is interior is nx, if perpendicular face is interior or the refractive index of the interior direction of aspect is ny, if face is outer or the refractive index (refractive index that also claims film thickness direction) of the vertical direction that aspect is outer during for nz, the relation that has nz＞ny 〉=nx, the phase differential of measuring at wavelength 450nm place is below 1.1 with the ratio (R450/R550) of the phase differential of measuring at wavelength 550nm place;

Optical compensation films, this film comprises film (A) and film (B), wherein, described film (B) is, in the three-dimensional refractive index of film, if the refractive index of the leading phase shaft direction in the face is nx, if the refractive index of direction is ny in the perpendicular face, when the refractive index of establishing the outer vertical direction of face is nz, there is the relation of ny＞nx 〉=nz, when the thickness of film was designated as d, phase differential (Re) was more than the 50nm in the face that wavelength 550nm place measures;

Phase retardation film, it comprises the fumarate resinoid, wherein, if this face to the refractive index of leading phase shaft direction be nx, if the refractive index of direction is ny in the perpendicular face, when the refractive index of establishing the outer vertical direction of face was nz, the pass of each refractive index was nx＜ny≤nz;

Phase retardation film, it comprises the fumarate resinoid, wherein, this film comprises film (C) and film (D), described film (C) is, the refractive index of establishing the leading phase shaft direction in this face is nx, and the refractive index of establishing direction in the perpendicular face is ny, if when the refractive index of the vertical direction that face is outer was nz, the pass of each refractive index was nx＜ny≤nz; Described film (D) is that in the three-dimensional refractive index of film, the refractive index of establishing the leading phase shaft direction in the face is nx, if the refractive index of direction is ny in the perpendicular face, when if the refractive index of the vertical direction that face is outer is nz, have ny＞nx 〉=nz, or the relation of ny＞nz 〉=nx.

The invention effect

According to the present invention, can provide contrast or the compensate film of viewing angle characteristic or the optical compensation films and the phase retardation film of the optical characteristics excellence that antireflection film uses as LCD.

Description of drawings

The variation of the indicatrix that Fig. 1 stretching causes.

Symbol description

Nx: the refractive index of the leading phase shaft direction in the expression face.

Ny: the refractive index of representing direction in the face vertical with nx.

Nz: the refractive index of the vertical direction that the expression face is outer.

Embodiment

Below, optical compensation films of the present invention and phase retardation film are at length described.

Optical compensation films of the present invention is described.

Optical compensation films of the present invention or optical compensating layer, it comprises the fumarate resinoid, wherein, in the three-dimensional refractive index of film or layer, the refractive index of the leading phase shaft direction in the face or in the aspect is designated as nx, with in the perpendicular face or the refractive index in the aspect be designated as ny, when refractive index face is outer or the vertical direction that aspect is outer is designated as nz, the relation that has nz＞ny 〉=nx, the relation that especially preferably has nz＞ny ≈ nx, the phase differential of measuring at wavelength 450nm place is below 1.1 with the ratio (R450/R550) of the phase differential of measuring at wavelength 550nm place.Here, in the said face or the refractive index n x of the leading phase shaft direction in the aspect, be in the face or the minimum axial refractive index of refractive index in the aspect.In addition, these nx, ny and nz can obtain by for example using the automatic birefringence meter of sample apsacline.

In addition, optical compensation films of the present invention is optical compensation films or the layer that comprises the fumarate resinoid, and so-called this comprises the layer of fumarate resinoid, is the fumaric acid esters resin part when for example representing the above-mentioned fumarate resinoid of on base material applying.

Moreover usually, the stretching of the control of the three-dimensional refractive index of film by film etc. carried out, so that the management of manufacturing process or quality becomes is complicated, the film that comprises the fumarate resinoid demonstrates the specific phenomenon that the refractive index of film thickness direction uprises when not stretching.

In addition, in optical compensation films of the present invention or the optical compensating layer, when the thickness of film is designated as d, use the outer phase differential (Rth) of face of following formula (1) expression preferred-30～-2000nm, preferred especially-50～-1000nm, further preferred-100～-500nm.

Rth＝[(nx+ny)/2-nz]×d (1)

The ratio R450/550 of the phase differential (R550) that the wavelength dependency of phase differential can be measured with the phase differential (R450) and the wavelength 550nm place of wavelength 450nm place mensuration represents.In optical compensation films of the present invention or optical compensating layer, this R450/550 is preferred below 1.1, and is preferred especially below 1.08, further preferred below 1.05.

As the fumarate resinoid that uses among the present invention, can enumerate the polymkeric substance of fumarate, the dimethyl ester residue unit that wherein preferably comprises above general formula (a) expression of 50 moles of %, be more preferably 70 moles more than the %, particularly, from the optical compensation films that becomes thermotolerance and mechanical property excellence or the viewpoint of optical compensation films, preferred 80 moles more than the % of dimethyl ester residue unit is more preferably 90 moles more than the %.

[changing 1]

(in the formula, R ₁, R ₂Represent C respectively independently _3～12Branched-chain alkyl or cyclic alkyl).

Here, as the ester substituent R of dimethyl ester residue unit ₁, R ₂, be C independently respectively _3～12Branched-chain alkyl or cyclic alkyl, can be by halogen radicals such as fluorine, chlorine; Ether; Ester group or amino the replacement, for example can enumerate isopropyl, sec-butyl, the tert-butyl group, sec-amyl, tertiary pentyl, Sec-Hexyl, uncle's hexyl, cyclopropyl, cyclopentyl, cyclohexyl etc., especially, consider from the viewpoint of the optical compensation films that becomes thermotolerance, mechanical property excellence or optical compensating layer, preferred isopropyl, sec-butyl, the tert-butyl group, cyclopentyl, cyclohexyl etc., consider further preferred isopropyl from the viewpoint of the balance good optical compensate film that becomes thermotolerance, mechanical property or optical compensating layer.

Dimethyl ester residue unit as general formula (a) expression, particularly, can enumerate, fumaric acid diisopropyl ester residue, fumaric acid di-secondary butyl ester residue, fumaric acid di tert butyl carbonate residue, fumaric acid di-secondary pentyl ester residue, fumaric acid two tert-pentyl ester residues, the own ester residue of fumaric acid di-secondary, the own ester residue of fumaric acid two uncles, fumaric acid two ring propyl ester residues, fumaric acid two ring pentyl ester residues, fumaric acid two cyclohexyl residues etc., wherein preferred fumaric acid diisopropyl ester residue, fumaric acid di-secondary butyl ester residue, fumaric acid di tert butyl carbonate residue, fumaric acid two ring pentyl ester residues, fumaric acid two cyclohexyl residues etc., preferred especially fumaric acid diisopropyl ester residue.

Preferably the fumarate resinoid that uses as the present invention uses comprises 50 moles of fumarate resinoids with the dimethyl ester residue unit of general formula (a) expression more than the %, be comprise the dimethyl ester residue unit of general formula (a) expression more than 50% mole and 50 moles of % following comprise can with the resin of the residues of monomers unit of dimethyl ester class copolymerization, as comprise can with the residues of monomers unit of dimethyl ester class copolymerization, for example can enumerate phenylethylene residues such as styrene residue, α-Jia Jibenyixi residue; The acrylic acid residue; The esters of acrylic acid residue of methyl acrylate residue, ethyl acrylate residue, butyl acrylate residue, acrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters residue, tetrahydrofurfuryl acrylate residue etc.; Methyl acrylic ester residues such as methacrylic acid residue, methyl methacrylate residue, Jia Jibingxisuanyizhi residue, butyl methacrylate residue, methacrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters residue, tetrahydrofurfuryl methacrylate residue; Vinyl esters residues such as vinyl acetate residue, propionate residue; The vinyl cyanide residue; The methacrylonitrile residue; In the olefines residues such as ethene residue, propylene residues etc. more than a kind or 2 kinds, wherein preferred acrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters residue, methacrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters residue, preferred especially acrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters residue.

The fumarate resinoid that uses as the present invention, preferably the number-average molecular weight (Mn) of the polystyrene standard conversion that obtains of the stripping curve of measuring by gel permeation chromatography (to call GPC in the following text) is 1 * 10 ³Above resin, good from becoming mechanical property, the optical compensation films that processing and forming is good during the system film or the viewpoint of optical compensating layer are considered, are preferably 2 * 10 especially ⁴～2 * 10 ⁵

Manufacture method as the fumarate resinoid that constitutes optical compensation films of the present invention or optical compensating layer, as long as can obtain this fumarate resinoid, then can adopt any method to make, for example can use simultaneously the dimethyl ester class, optional can with the monomer of dimethyl ester class copolymerization, carry out free radical polymerization or free-radical polymerized the manufacturing.Dimethyl ester class as this moment, for example can enumerate fumaric acid diisopropyl ester, fumaric acid di-secondary butyl ester, fumaric acid di tert butyl carbonate, fumaric acid di-secondary pentyl ester, fumaric acid two tert-pentyl esters, the own ester of fumaric acid di-secondary, the own ester of fumaric acid two uncles, fumaric acid two ring propyl ester, fumaric acid two ring pentyl esters, fumaric acid two cyclohexyls etc., as can with the monomer of dimethyl ester copolymerization, for example can enumerate phenylethylenes such as styrene, α-Jia Jibenyixi; Acrylic acid; Esters of acrylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters, tetrahydrofurfuryl acrylate; Methacrylic acid; Methyl acrylic esters such as methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters, tetrahydrofurfuryl methacrylate; Vinyl esters such as vinyl acetate, propionate; Vinyl cyanide; Methacrylonitrile; In the olefines such as ethene, propylene etc. more than a kind or 2 kinds, wherein preferred acrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters, methacrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters, preferred especially acrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters.

In addition, the radical polymerization as using can adopt known polymerization to carry out, and for example can adopt any methods such as mass polymerization, solution polymer, suspension polymerization, precipitation polymerization method, emulsion polymerization.

As carrying out the fashionable polymerization initiator of radical polymerization, for example can enumerate organic peroxides such as benzoyl peroxide, lauroyl peroxide, peroxidating decoyl, acetyl peroxide, di-t-butyl peroxide, tert-butyl peroxide isopropyl benzene, cumyl peroxide, peroxide acetic acid butyl ester, peroxidized t-butyl perbenzoate, the peroxidating trimethylace tonitric tert-butyl ester; 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-butyronitrile), 2,2 '-azoisobutyronitrile, dimethyl-2,2 '-azoisobutyronitrile, 1, the two azo-initiators such as (cyclohexanes-1-nitrile) of 1 '-azo.

In addition, do not have particular restriction, for example can enumerate aromatic solvents such as benzene,toluene,xylene as spendable solvent in solution polymerization process, suspension polymerization, precipitation polymerization method, the emulsion polymerization; Alcohols solvents such as methyl alcohol, ethanol, propyl alcohol, butanols; Cyclohexane; Two

Alkane; Tetrahydrofuran (THF); Acetone; MEK; Dimethyl formamide; Isopropyl acetate; Water etc. also can be enumerated their mixed solvent.

In addition, carry out the fashionable polymerization temperature of radical polymerization, can suitably set according to the decomposition temperature of polymerization initiator, general preferred scope at 40～150 ℃ is carried out polymerization.

Optical compensation films of the present invention or optical compensating layer (film (A)), it can also be the optical compensation films (film (E)) that comprises film (B), described film (B) is, in the three-dimensional refractive index of film, if the refractive index of the leading phase shaft direction in the face is nx, if the refractive index of direction is ny in the perpendicular face, when if the refractive index of the vertical direction that face is outer is nz, the relation that has ny＞nx 〉=nz, when the thickness of film was d, the phase differential (Re) in the face that wavelength 550nm place measures of following formula (2) expression was preferably more than the 50nm.

Re＝(ny-nx)×d (2)

In addition, aforementioned films (B) for example can be carried out unilateral stretching etc. by the polymkeric substance that will have positive bijectivity, makes the film that there is ny＞nx 〉=nz relation in three-dimensional refractive index.

In addition, polymkeric substance as film (B), so long as have the polymkeric substance of positive birefringence, then there is not particular restriction, wherein consider from the viewpoint of the thermotolerance or the transparency, as preferred example, can enumerate polycarbonate resin, polyethersulfone resin, cyclic polyolefin resin, N-substituted maleimide resin.And, more than the preferred 50nm of phase differential (Re), more than the preferred especially 100nm, be more preferably more than the 120nm in the face of film (B).

In addition, in the film (E), the three-dimensional refractive index of film, if the refractive index of the leading phase shaft direction in the face is nx, if the refractive index of direction is ny in the perpendicular face, if the refractive index of the vertical direction that face is outer is nz, when the thickness of film was d, the orientation parameter (Nz) of following formula (3) expression was preferred-0.1～0.95, particularly at STN-LCD, IPS-LCD, reflection type LCD, in the field angle compensation of semi-transmission type LCD, Nz is preferred 0.40～0.60, and is further preferred 0.45～0.55, in the field angle compensation of polaroid, Nz preferred-0.10～0.10, preferred especially-0.05～0.05, further preferred 0～0.05.

Nz＝(ny-nz)/(ny-nx) (3)

In addition, in the film (E), phase differential (Re) is 50～1000nm, is preferably 100～500nm especially in the face of preferred aforementioned formula (2) expression, in addition, when using 1/4 wavelength plate, preferred 130～140nm, when using 1/2 wavelength plate, preferred 270～280nm.

Manufacture method as the optical compensation films that comprises the fumarate resinoid in the optical compensation films of the present invention does not have particular restriction, for example, can adopt methods such as solution casting method, fusion The tape casting to make.

Solution casting method is solution that the fumaric acid esters resin dissolves is obtained in solvent (below, claim a rubber cement) curtain coating after on the support substrate, waits by heating that removing desolvates obtains the method for film.With the method for rubber cement curtain coating on support substrate, for example, can adopt T pattern method, scraper rubbing method, rod to be coated with method, rolling method, lip Tu Fa etc. as at this moment.The most general industrial method is the method that rubber cement is extruded at banded or support substrate cylindraceous continuously from die head.Support substrate as using for example has glass substrate; Metal substrate such as stainless steel or iron plate; Plastic bases such as polyethylene terephthalate (PET), cellulose triacetate celluosic resins such as (TAC) etc.The film that comprises the fumarate resinoid that makes like this can be peeled off the back from support substrate and use, and in addition, as support substrate, when using glass substrate, plastic base, also can not peel off and directly uses as laminated body.The solution casting manufactured has high transparent, and during the film of thickness accuracy, surface smoothing excellence, the solution viscosity of rubber cement is epochmaking factor, preferred 700～30000cps, preferred especially 1000～10000cps.In addition, the fusion The tape casting is with the fusion in extruder of fumarate resinoid, from the narrow slit of T pattern be extruded into membranaceous after, the limit uses roller or air etc. to cool off the method for forming of limit traction.

The manufacture method of the optical compensation films that comprises optical compensation films or optical compensating layer (film (A)) and film (B) that preferably uses as optical compensation films of the present invention does not have particular restriction, for example can adopt the unstretching film that will comprise the fumarate resinoid and have the method that the unilateral stretching film of the film of positive birefringence fits (below, as manufacture method 1), resin-coated method (below, as manufacture method 2) on the unilateral stretching film of the film with positive birefringence of fumaric acid esters etc. is made.

The film that has positive birefringence in the manufacture method 1,2 for example can be enumerated the film that polycarbonate resin, polyethersulfone resin, cyclic polyolefin resin, N-substituted maleimide resin etc. constitute.By this film with positive birefringence is carried out unilateral stretching, for example adopt 150～200 ℃ of temperature, draw speed 10～30mm/ branch, the condition of stretching ratio 30～70% stretches, and can make the unilateral stretching film of the film with positive birefringence.

Manufacture method 1 can be by will having positive birefringence the unilateral stretching film of film fit with the unstretching film that comprises the fumarate resinoid and make optical compensation films.Applying method as this moment for example can adopt the continuous processing manufacturing of spool (roll to roll).The method of using known bonding agent to fit.

Manufacture method 2 can be by on the unilateral stretching film of the film with positive birefringence, and coating fumarate resinoid is made optical compensation films.The result becomes the unilateral stretching film that comprises the film with positive birefringence and comprises the optical compensation films of the layer of fumarate resinoid.The coating process of this moment is after being coated on the solution (coating solution) that the fumaric acid esters resin dissolves obtains in solvent on the film, removes the method for desolvating by heating.As the coating process of this moment, for example can adopt scraper rubbing method, excellent rubbing method, grooved roller rubbing method (gravure coating), seam die head rubbing method, lip rubbing method, some rubbing method etc.Industrial film coating is generally the grooved roller rubbing method.The thick film coating is generally a rubbing method.In solution coat, in order to have the high transparency, and the coating of thickness accuracy, surface smoothing excellence, coating solution viscosity is epochmaking factor, preferred solution viscosity is 10～10000cps, preferred especially 10～5000cps.The present invention uses the coating thickness (thickness of the layer that is made of the fumarate resinoid) of fumarate resinoid by the decision of the phase differential of film thickness direction, preferred dry back 1～200 μ m, preferred especially 10～100 μ m.In addition, also can in advance easy adhesion process be carried out on the surface of film (B).

In addition, optical compensation films of the present invention can be mutually or is carried out lamination with other optical compensation films.

For the thermal stability that improves optical compensation films of the present invention preferably cooperates antioxidant.As this antioxidant, for example can enumerate Hinered phenols antioxidant, Phosphorus antioxidant, other antioxidant, these antioxidant can be used alone or in combination respectively.In addition, consider, preferably Hinered phenols antioxidant used with Phosphorus antioxidant that this moment, particularly preferred example was used as mixing Phosphorus antioxidant with respect to Hinered phenols antioxidant 100 weight portions by 100～500 weight portions from the viewpoint that improves antioxidant effect synergistically.In addition, as the addition of antioxidant, with respect to fumarate resinoid 100 weight portions that constitute optical compensation films of the present invention, preferred 0.01～10 weight portion, preferred especially 0.5～1 weight portion.

In addition, as ultraviolet light absorber, for example can cooperate ultraviolet light absorbers such as benzotriazole, benzophenone, triazine, benzoic ether as required.

Optical compensation films of the present invention can cooperate other polymkeric substance, surfactant, polyelectrolyte, electric conductivity complex compound, inorganic filler, pigment, dyestuff, antistatic agent, antiblocking agent, slip agent etc. in the scope that does not break away from the invention main idea.

Optical compensation films of the present invention can with the polaroid lamination, and make circle or elliptic polarizing piece uses.In addition, improving optical compensation films such as film or color compensating film as the field angle of liquid crystal display cells is useful, and circular polarizing disk also can be used as antireflection film and uses.In addition, also can be used as the optical compensation films use that the brightness that improves the LCD use improves the viewing angle characteristic of film.

Phase retardation film of the present invention is described.

As the fumarate resinoid that uses in the phase retardation film of the present invention, can enumerate the polymkeric substance of fumarate, the dimethyl ester residue unit that wherein preferably comprises aforementioned formula (a) expression is the above fumarate resinoids of 50 moles of %.

Phase retardation film of the present invention comprises aforementioned fumarate resinoid, is the phase retardation film that does not need to add particulate.

In addition, the feature of phase retardation film of the present invention is, if the refractive index of the leading phase shaft direction in the face is nx, if the refractive index of direction is ny in the perpendicular face, when the refractive index of establishing the outer vertical direction of face was nz, the pass of each refractive index was nx＜ny≤nz, and, owing to satisfy aforementioned nx＜ny≤nz, therefore, become the phase retardation film of the field angle compensation performance excellence of STN-LCD, IPS-LCD, reflection type LCD or semi-transmission type LCD etc.

In addition, become the viewpoint consideration of the better phase retardation film of optical characteristics from phase retardation film of the present invention.The phase differential (Re) in the face that wavelength 550nm place measures of preferred aforementioned formula (2) expression is 50～2000nm, preferred especially 50～1000nm, preferred again 100～500nm.

Phase differential (Re) in the relevant face, more particularly, when phase retardation film of the present invention is used as the phase retardation film at the visual angle of the LCD that is used to compensate TN or VA, IPS or ocb mode, phase differential (Re) is more than the 50nm in the preferred face, more than the preferred especially 100nm, more preferably more than the 135nm.

Preferred 100～the 200nm of phase differential (Re) in the face when using in addition, as the circularly polarized light film of phase retardation film and laminated integratedization of polaroid.The circularly polarized light film is except the compensate film of reflection LCD, and also at the antireflection film of OLED display etc., brightness improves in the film etc. to be used.

In addition, the preferred 200～400nm of phase differential (Re) in the face when phase retardation film of the present invention uses as 1/2 wave film is used for the LCD of STN pattern, the preferred 50～1000nm of phase differential (Re) in the face when being used for brightness and improving the viewing angle compensation of film.

The wavelength dependency of phase differential, the ratio R450/R550 that can be used as the phase differential of measuring at the phase differential (R450) and the wavelength 550nm place of wavelength 450nm place mensuration (R550) represents.In the phase retardation film of the present invention, this R450/R550 is preferred below 1.1, and is preferred especially below 1.08, more preferably below 1.05.

In addition, the thickness of phase retardation film is preferably 10～400 μ m, is preferably 20～150 μ m especially, more preferably the scope of 30～100 μ m.

Manufacture method as phase retardation film of the present invention does not have particular restriction, for example, can adopt the solution casting method that uses when making aforementioned optical compensation films, methods such as fusion The tape casting are carried out membranization, by carrying out unidirectional to this film or two-way stretch control phase difference is made phase retardation film of the present invention.As the unilateral stretching method, for example, can enumerate free width of cloth unilateral stretching, the method of using stenter to stretch, the methods that stretch between roller etc. are as bidirectional extending method, the method of using stenter to stretch is for example arranged, expand into method that tubulose stretches etc.As the stretching condition of film, from difficult uneven thickness takes place, and become mechanical property, the viewpoint of the phase retardation film of optical characteristics excellence considers that preferred 80～250 ℃ of draft temperature is preferably 120～220 ℃ especially, preferred 1.01～5 times of stretching ratio is preferably 1.01～2 times especially.

Phase retardation film of the present invention preferably cooperates antioxidant when the film moulding or for the thermal stability that improves phase retardation film itself.As this antioxidant, for example can enumerate Hinered phenols antioxidant, Phosphorus antioxidant, other antioxidant, these antioxidant can be distinguished use separately or use simultaneously.In addition, consider, preferably Hinered phenols antioxidant and Phosphorus antioxidant used simultaneously that especially preferably by 100～500 weight portions mix and use Phosphorus antioxidant for example with respect to Hinered phenols antioxidant 100 weight portions this moment from the viewpoint that improves antioxidant effect synergistically.In addition, as the addition of antioxidant,, be preferably the scope of 0.5～1 weight portion especially with respect to preferred 0.01～10 weight portion of fumarate resinoid 100 weight portions that constitutes phase retardation film of the present invention.

Phase retardation film of the present invention is in the scope that does not break away from main idea of the present invention, can also cooperate other macromolecule, surfactant, polyelectrolyte, electric conductivity complex compound, inorganic filler, pigment, dyestuff, antistatic agent, antiblocking agent, slip agent etc.

Phase retardation film of the present invention is the film that comprises the fumarate resinoid, it also can be the phase retardation film (film F) that comprises film (C) and film (D), described film (C) is, if the refractive index of the leading phase shaft direction in this face is nx, if the refractive index of direction is ny in the perpendicular face, when if the refractive index of the vertical direction that face is outer is nz, the pass of each refractive index is nx＜ny≤nz, described film (D) is, in the three-dimensional refractive index of film, the refractive index of establishing the leading phase shaft direction in the face is nx, and the refractive index of establishing direction in the perpendicular face is ny, when if the refractive index of the vertical direction that face is outer is nz, there is the relation of ny＞nx 〉=nz or ny＞nz 〉=nx.

As the fumarate resinoid that uses among the film F, can enumerate the polymkeric substance of fumarate, wherein preferably comprise the fumarate resinoid of the dimethyl ester residue unit of above aforementioned formula (a) expression of 50 moles of %.

The film that uses among the film F (C), when establishing film thickness and being d, the phase differential (Re) in the face of wavelength 550nm place mensuration of aforementioned formula (2) expression is preferably 50～2000nm, preferred especially 100～600nm, more preferably 120～300nm.

In addition, the film that uses among the film F (D), the preferred 50～2000nn of phase differential (Re) in the face that the wavelength 550nm place of aforementioned formula (2) expression measures.

Such film (D), for example by the polymkeric substance with positive birefringence is carried out unilateral stretching, perhaps after the two sides of the polymkeric substance with positive birefringence or one side are fitted heat shrink films, carry out unilateral stretching and can make three-dimensional refractive index and have ny＞nx 〉=nz, or the film of ny＞nz 〉=nx relation.As polymkeric substance with positive birefringence, so long as have the polymkeric substance of positive birefringence, then there is not particular restriction, consider from the viewpoint of the thermotolerance or the transparency etc., can enumerate polycarbonate resin, polyethersulfone resin, polyarylate resin, polyimide resin, cyclic polyolefin resin, N-substituted maleimide resin etc. as preferred example.Wherein, consider the big film of wavelength dispersion of optimization polycarbonate resin, polyethersulfone resin etc. from the viewpoint that can obtain the dispersed phase retardation film of head sea length.

Film F is the phase retardation film that comprises film (C) and film (D), the angle that the leading phase shaft of the leading phase shaft of film (C) and film (D) forms can be set as requested, wherein consider to be preferably below 90 degree ± 20 degree from the control of wavelength dispersibility and the viewpoint of production efficiency, be preferably especially below 90 degree ± 5 degree, more preferably 90 degree.

What phase differential (Re) was a film (C) with the phase differential of film (D) in the face of the phase differential that is made of film (C) and film (D) is poor, phase retardation film as phase differential with 1/4 wavelength, it is so-called 1/4 wavelength plate, preferably in the face of the film of measuring at wavelength 550nm place (C) in the face of phase differential (Re) and film (D) difference of phase differential (Re) be 100～160nm, be preferably 130～150nm especially.In addition, as the phase retardation film of the phase differential that 1/2 wavelength is arranged, promptly so-called 1/2 wavelength plate, preferably in the face of the film of measuring at wavelength 550nm place (C) in the face of phase differential (Re) and film (D) difference of phase differential (Re) be 250～300nm.

The wavelength dispersibility of film F can be by adjusting the phase differential control of film (C) and film (D).As 1/4 wavelength plate, when 1/2 wavelength plate uses, the ratio (R450/R550) of the phase differential (R550) that phase differential (R450) that wavelength 450nm place measures and wavelength 550nm place measure is preferably below 1.0, and is preferred especially below 0.99, more preferably below 0.98.In addition, the ratio (R650/R550) of the phase differential (R550) that phase differential (R650) that wavelength 650nm place measures and wavelength 550nm place measure is preferably more than 1.0, is preferably more than 1.01 especially.

The manufacture method of the film that uses among the film F (C) does not have particular restriction.The solution casting method that uses in the time of for example can adopting aforementioned optical compensation films to make, methods such as fusion The tape casting are carried out membranization, poor by the method control phase of this film being carried out unilateral stretching or two-way above stretching, can be made into the film (C) that phase retardation film of the present invention uses.

In addition, the manufacture method of the film (D) that film F uses does not have particular restriction, methods such as the solution casting method that uses in the time of for example can adopting aforementioned optical compensation films to make, fusion The tape casting are carried out membranization, employing to this film carry out unilateral stretching or the two-way above method that stretches, the method control phase of carrying out unilateral stretching behind the one or both sides applying heat shrink films of this film is poor, can be made into the film (D) that phase retardation film of the present invention uses.

Method as unilateral stretching, can enumerate free width of cloth unilateral stretching, the method that the use stenter stretches, the method that stretches between roller etc. are as bidirectional extending method, the method of using stenter to stretch is for example arranged, expand into method that tubulose stretches etc.And as the method for carrying out unilateral stretching behind the applying heat shrink films, for example can enumerate after the two sides of the polymkeric substance with positive birefringence or one side are utilized the bounding force of this film self or used the adhering method applying heat shrink films such as bonding agent of easy fissility and carry out free width of cloth unilateral stretching, use the method that drawing machine stretches, the method that stretches etc. between roller, heat shrink films is peeled off after stretching.As stretching condition,, become mechanical property from being difficult for that uneven thickness takes place, the viewpoint of the phase retardation film of good optical properties is considered, preferred 80～250 ℃ of draft temperature, preferred especially 120～220 ℃, preferred 1.01～5 times of stretching ratio is preferably 1.01～2 times especially.

Do not have particular restriction as the heat shrink films that uses, for example can enumerate biaxial stretching film or unilateral stretching film, can enumerate biaxial stretching film such as polyester, polystyrene, tygon, polypropylene, Polyvinylchloride, Vingon or unilateral stretching film etc. especially.

Film F for example can fit aforementioned films (C) and film (D) and make.The method of fitting is not had particular restriction, can close by putting up, the known sticker of preferred especially use is fitted the package film (roll film) of film (C) and film (D).In addition, during applying, the angle that the leading phase shaft of the leading phase shaft of film (C) and film (D) forms is preferably 90 degree ± 20 degree, but considers to be preferably especially below 90 degree ± 5 degree from the viewpoint that spool is fitted, more preferably 90 degree.

In addition, also can make by the method that stretches after the unstretching film moulding with film (C) and film (D) such as use coextrusion.

Film F preferably cooperates antioxidant when the film moulding or for the thermal stability that improves phase retardation film self.As this antioxidant, for example can enumerate Hinered phenols antioxidant, Phosphorus antioxidant, other antioxidant, these antioxidant can use separately or use simultaneously.In addition, consider, preferably Hinered phenols antioxidant and Phosphorus antioxidant are used simultaneously, at this moment,, preferably mix and use Phosphorus antioxidant by 100～500 weight portions for example with respect to Hinered phenols antioxidant 100 weight portions from the viewpoint that improves anti-oxidant action synergistically.In addition, as the addition of antioxidant, with respect to fumarate resinoid 100 weight portions that constitute phase retardation film of the present invention, preferred 0.01～10 weight portion is preferably the scope of 0.5～1 weight portion especially.

In addition, as ultraviolet light absorber, for example, can cooperate ultraviolet light absorbers such as benzotriazole, benzophenone, triazine, benzoic ether as required.

Film F also can cooperate other macromolecule, surfactant, polyelectrolyte, electric conductivity complex compound, inorganic filler, pigment, dyestuff, antistatic agent, antiblocking agent, slip agent etc. in the scope that does not break away from the invention main idea.

In addition, film F also can be mutually or is carried out lamination with other phase retardation film.

Except the phase retardation film of circularly polarized light film that 1/4 wavelength plate and laminated integratedization of polaroid are obtained, reflection LCD, film F can use the antireflection film at OLED display or touch pad etc., and brightness improves in the aspect such as film.And, also can be by making composite polarizing plate with the polaroid lamination.

Embodiment

By the following examples the present invention is at length described, but the present invention is not subjected to any restriction of these embodiment.Moreover the reagent that short of specified otherwise is then used uses commercially available product.

The composition of dimethyl ester resinoid (Daip)

Use nuclear magnetic resonance measuring device (NEC manufacturing, trade name JNM-GX270), by the proton magnetic resonance (PMR) beam split ( ¹H-NMR) spectral analysis is obtained.

The mensuration of number-average molecular weight

Post has been installed in use, and (TOSOH Co., Ltd makes, trade name TSK-GEL GMH _HR-H) gel permeation chromatograph (GPC) (TOSOH Co., Ltd make, trade name HLC-8020), 40 ℃ of column temperature, under the condition that flow 1.0ml/ divides, THF is a solvent, obtains as the polystyrene standard scaled value.

The mensuration of glass transition temperature (Tg)

Use differential scanning type calorimeter (Seiko electronics industry (strain) is made, and trade name DSC 2000), measure by 10 ℃/minute programming rate.

The mensuration of film light penetration and mist degree

The light penetration of the film that makes and mist degree use haze meter (Japanese electric look industry system, trade name NDH 2000), the mensuration of light penetration is measured by JIS K 7361-1 (version in 1997), and the mensuration of mist degree is measured by JIS K 7136 (version in 2000).

The mensuration of refractive index

Use Abbe refractomecer (love delay (atago) system), measure by JIS K 7142 (1981 editions).

The calculating of phase differential and orientation parameter in the mensuration of three-dimensional refractive index, the outer phase differential of face, the face

Use the automatic birefringence meter of test portion apsacline (prince remembers survey machine (strain) manufacturing, trade name KOBRA-WR), change the elevation measurement three-dimensional refractive index.Calculate the outer phase differential (Rth) of face, phase differential (Re) and orientation parameter (Nz) in the face by three-dimensional refractive index again.

The positive negative judgement of birefringence

The polarizing microscope of the polarizing microscope of use macromolecular material the ABC of (the abundant work in chestnut room, AGNE (アグネ) technique center version, the 5th chapter, pp78～82, (2001)) record carries out the positive negative judgement of birefringence.

The mensuration of photoelasticity modulus

Use light rheometer (light レオメ one タ one) (HRS-100, OAK (オ one Network) makes made) to measure by draw speed 1%/s.

Synthesis example 1 (Production Example of dimethyl ester homopolymer)

The distilled water 18kg that in 30 liters autoclave, adds the partly-hydrolysed polyvinyl alcohol (PVA) that contains 0.2 weight %, fumaric acid diisopropyl ester 3kg, dimethyl-2 as polymerization initiator, 2 '-azo-bis-isobutyrate 7g, 50 ℃ of polymerization temperatures, carry out the suspension free-radical polyreaction under 24 hours the condition of polymerization time.Behind the particulate filter that obtains, use methyl alcohol fully to wash and obtain fumaric acid diisopropyl ester homopolymer 80 ℃ of dryings.The number-average molecular weight of the fumaric acid diisopropyl ester homopolymer that makes is 160,000.

Synthesis example 2 (synthesizing of Daip)

In the autoclave of the 30L that has stirring machine, cooling tube, nitrogen ingress pipe and thermometer, add hydroxypropyl methylcellulose (SHIN-ETSU HANTOTAI's chemistry system, trade name: smear special happy plain (メトロ one ズ) 60SH-50) 48g, distilled water 15601g, fumaric acid diisopropyl ester 8161g, acrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters 240g and as the peroxidating trimethylace tonitric tert-butyl ester 45g of polymerization initiator, carry out nitrogen bubble after 1 hour, the limit is stirred the limit and is kept carrying out in 24 hours free radical suspensioning polymerization at 49 ℃ under 200rpm.Cool to room temperature carries out centrifuging to the suspending liquid of the polymer particle that contains generation.Use distilled water washing 2 times to obtaining polymer particle, use methanol wash 2 times after, carry out drying under reduced pressure (yield: 80%) at 80 ℃.

The number-average molecular weight of the polymer particle that makes is 142,000.By ¹H-NMR measures and confirms that polymer particle is the fumaric acid diisopropyl ester multipolymer of fumaric acid diisopropyl ester residue unit/acrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters residue unit=96/4 (mole %).

Synthesis example 3 (synthesizing of Daip)

In the glass ampule pipe of 75mL, add fumaric acid diisopropyl ester 69.89g, acrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters 0.91g and as the peroxidating trimethylace tonitric tert-butyl ester 0.39g of polymerization initiator, carry out nitrogen replacement after, tube sealing is carried out in decompression.By keeping carrying out in 24 hours free radical polymerization down at 50 ℃.Behind the cool to room temperature, the polymer dissolution that generates in tetrahydrofuran.By the polymer solution that obtains is added to the polymkeric substance that obtains white powder in the excessive methyl alcohol.After the polymkeric substance use methanol wash that obtains 3 times, at 80 ℃ of drying under reduced pressure (yields: 84%).

The number-average molecular weight of the polymkeric substance that makes is 171,000.By ¹H-NMR measures and confirms that polymkeric substance is the fumaric acid diisopropyl ester multipolymer of fumaric acid diisopropyl ester residue unit/acrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters residue unit=98/2 (mole %).

Synthesis example 4 (synthesizing of Daip)

In the glass ampule pipe of 75mL, add fumaric acid diisopropyl ester 68.09g, acrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters 3.06g and as the peroxidating trimethylace tonitric tert-butyl ester 0.39g of polymerization initiator, carry out nitrogen replacement after, tube sealing is carried out in decompression.By keeping carrying out in 24 hours free radical polymerization at 50 ℃.Behind the cool to room temperature, the polymer dissolution that generates in tetrahydrofuran.By the polymer solution that makes is added to the polymkeric substance that obtains white powder in the excessive methyl alcohol.After the polymkeric substance use methanol wash that makes 3 times, under 80 ℃, carry out drying under reduced pressure (yield: 70%).

The number-average molecular weight of the polymkeric substance that makes is 179,000.By ¹H-NMR measures and confirms that polymkeric substance is the fumaric acid diisopropyl ester multipolymer of fumaric acid diisopropyl ester residue unit/acrylic acid 3-ethyl-3-oxa-cyclobutyl methyl esters residue unit=94/6 (mole %).

Film Production Example 1

The fumaric acid diisopropyl ester homopolymer that synthesis example 1 is made is dissolved in and becomes 22% solution in the THF solvent, with respect to fumaric acid diisopropyl ester homopolymer 100 weight portions, interpolation is as the tricresyl phosphate (2 of Hinered phenols antioxidant, the 4-di-tert-butyl-phenyl) ester 0.35 weight portion and as the pentaerythrite four of Phosphorus antioxidant [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] 0.15 weight portion, behind 2-(2H-benzotriazole-2-yl)-paracresol 1 weight portion as ultraviolet light absorber, adopt T pattern method curtain coating on the support substrate of solution casting device, respectively at 40 ℃, drying is after 15 minutes under 80 ℃ and 120 ℃, obtain wide 250mm, the film of thickness 120 μ m.

The light penetration of the film that makes is 93%, and mist degree is 0.3%, and refractive index is 1.470.

Film Production Example 2

The fumaric acid diisopropyl ester homopolymer that synthesis example 1 is made is dissolved in and becomes 22% solution in the THF solvent, with respect to fumaric acid diisopropyl ester homopolymer 100 weight portions, interpolation is as the tricresyl phosphate (2 of Hinered phenols antioxidant, the 4-di-tert-butyl-phenyl) ester 0.35 weight portion and as the pentaerythrite four of Phosphorus antioxidant [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] 0.15 weight portion, behind 2-(2H-benzotriazole-2-yl)-paracresol 1 weight portion as ultraviolet light absorber, adopt T pattern method curtain coating on the support substrate of solution casting device, respectively at 40 ℃, drying is after 10 minutes under 80 ℃ and 120 ℃, obtain wide 250mm, the film of thickness 105 μ m.

Film Production Example 3

Synthesis example 1 is made fumaric acid diisopropyl ester homopolymer is dissolved in and becomes 22% solution in the THF solvent, with film Production Example 1 similarly, adopt T pattern method curtain coating on the support substrate of solution casting device, make wide 250mm, the film of thickness 124 μ m.

Film Production Example 4

Polycarbonate resin (ALDRICH (ア Le De リ Star チ) manufacturing) is dissolved in dichloromethane solution becomes 25% solution, with respect to polycarbonate resin 100 weight portions, interpolation is as the tricresyl phosphate (2 of antioxidant, the 4-di-tert-butyl-phenyl) [3-(3 for ester 0.35 weight portion and pentaerythrite four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] 0.15 weight portion, behind 2-(2H-benzotriazole-2-yl)-paracresol 1 weight portion as ultraviolet light absorber, adopt T pattern method curtain coating on the support substrate of solution casting device, respectively at 40 ℃, 80 ℃, and drying obtained wide 250mm, the film of thickness 100 μ m after 15 minutes under 120 ℃.

The film light penetration that makes is 91%, and mist degree is 0.6%, and refractive index is 1.583.

Film Production Example 5

Cyclic polyolefin resin (polynorbornene with fat base, the ALDRICH manufacturing) being dissolved in methylene chloride becomes 25% solution, again with respect to cyclic polyolefin resin 100 weight portions, interpolation is as the tricresyl phosphate (2 of antioxidant, the 4-di-tert-butyl-phenyl) [3-(3 for ester 0.35 weight portion and pentaerythrite four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] 0.15 weight portion, behind 2-(2H-benzotriazole-2-yl)-paracresol 1 weight portion as ultraviolet light absorber, adopt T pattern method curtain coating on the support substrate of solution casting device, respectively at 40 ℃, 80 ℃, and 120 ℃ down after dry 15 minutes, obtain wide 250mm, the film of thickness 100 μ m.

The light penetration of the film that makes is 92%, and mist degree is 0.4%, and refractive index is 1.510.

Film Production Example 6

Polycarbonate resin (ALDRICH manufacturing) is dissolved in dichloromethane solution becomes 25% solution, similarly makes wide 250mm with film Production Example 2, the film of thickness 85 μ m.

The light penetration of the film that makes is 91%, and mist degree is 0.5%, and refractive index is 1.583.

Embodiment 1

The fumaric acid diisopropyl ester homopolymer that synthesis example 1 is made is dissolved in the THF solvent becomes 22% solution, again with respect to fumaric acid diisopropyl ester homopolymer 100 weight portions, interpolation is as the tricresyl phosphate (2 of Hinered phenols antioxidant, the 4-di-tert-butyl-phenyl) ester 0.35 weight portion and as the pentaerythrite four of Phosphorus antioxidant [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] 0.15 weight portion, behind 2-(2H-benzotriazole-2-yl)-paracresol 1 weight portion as ultraviolet light absorber, adopt T pattern method curtain coating on the support substrate of solution casting device, respectively at 40 ℃, drying is after 15 minutes under 80 ℃ and 120 ℃, obtain wide 250mm, the film of thickness 21 μ m.

The film light penetration that makes is 93%, and mist degree is 0.3%, and the photoelasticity modulus is 5 * 10 ^-12Pa ^-1, film three-dimensional refractive index be nx=1.4689, ny=1.4689, nz=1.4723 (nz＞ny=nx).In addition, phase differential (Re) is 0nm in the face that makes, and the outer phase differential (Rth) of face is-71nm.The ratio (R450/R550) (wavelength dependency) of phase differential is 1.02.In addition, the pulling strengrth of the film that makes is 50MPa, and tensile elongation is 12%, has the mechanical property of abundant practicality.

Find out that by these results because the refractive index of the film thickness direction that obtains is big, wavelength dependency is little so be applicable to optical compensation films.

Embodiment 2

Make wide 250mm with embodiment 1 same method, the film of thickness 30 μ m.

The film light penetration that makes is 93%, and mist degree is 0.4%, and the three-dimensional refractive index of film is nx=1.4690, ny=1.4690, nz=1.4721 (nz＞ny=nx).Phase differential (Re) is 0nm in the face that makes, and the outer phase differential (Rth) of face is-93nm.The ratio (R450/R550) (wavelength dependency) of phase differential is 1.02.

Find out that by these results because the refractive index of the film thickness direction that makes is big, wavelength dependency is little, so be applicable to optical compensation films.

Embodiment 3

The fumaric acid diisopropyl ester multipolymer that synthesis example 2 is made is dissolved in toluene: the MEK weight ratio is to become 20% solution in 1: 1 the solution, adopt T pattern method curtain coating on the support substrate of solution casting device, respectively 80 ℃ and 120 ℃ of dryings after 10 minutes, make wide 250mm, the film of thickness 23 μ m.

The light penetration of the film that makes is 94%, and mist degree is 0.3%, and the photoelasticity modulus is 5 * 10 ^-12Pa ^-1, film three-dimensional refractive index be nx=1.4689, ny=1.4690, nz=1.4721 (nz＞ny ≈ nx).Phase differential (Re) is 1nm in the face that makes, and the outer phase differential (Rth) of face is-87nm.The ratio (R450/R550) (wavelength dependency) of phase differential is 1.02.In addition, the pulling strengrth of the film that makes is 50MPa, and tensile elongation is 11%, has the mechanical property of abundant practicality.

Found out that by these results the refractive index of the film thickness direction that makes is big, wavelength dependency is little, so be applicable to optical compensation films.

Embodiment 4

Synthesis example 3 is made fumaric acid diisopropyl ester multipolymer be dissolved in toluene: the MEK weight ratio is to become 20% solution in 1: 1 the solution, adopt T pattern method curtain coating on the support substrate of solution casting device, respectively 80 ℃ and 120 ℃ of dryings after 10 minutes, make wide 250mm, the film of thickness 31 μ m.

The light penetration of the film that makes is 94%, and mist degree is 0.3%, and the photoelasticity modulus is 5 * 10 ^-12Pa ^-1, film three-dimensional refractive index be nx=1.4686, ny=1.4687, nz=1.4727 (nz＞ny ≈ nx).In addition, phase differential (Re) is 1nm in the face that makes, and the outer phase differential (Rth) of face is-127nm.The ratio (R450/R550) (wavelength dependency) of phase differential is 1.02.In addition, the pulling strengrth of the film that makes is 50MPa, and tensile elongation 11% has the mechanical property of abundant practicality.

Embodiment 5

The fumaric acid diisopropyl ester multipolymer that synthesis example 4 is made is dissolved in toluene: the MEK weight ratio is to become 20% solution in 1: 1 the solution, adopt T pattern method curtain coating on the support substrate of solution casting device, respectively 80 ℃ and 120 ℃ of dryings after 10 minutes, make wide 250mm, the film of thickness 27 μ m.

The film light penetration that makes is 94%, and mist degree is 0.3%, and the photoelasticity modulus is 5 * 10 ^-12Pa ^-1, film three-dimensional refractive index be nx=1.4687, ny=1.4687, nz=1.4726 (nz＞ny=nx).Phase differential (Re) is 1nm in the face that makes, and the outer phase differential (Rth) of face is-104nm.The ratio (R450/R550) (wavelength dependency) of phase differential is 1.02.In addition, the pulling strengrth 50MPa of the film that makes, tensile elongation 12% has the mechanical property of abundant practicality.

Comparative example 1

Preparation polycarbonate (Supreme Being people's (strain) system, trade name panlite (パ Application ライト) L1225) 25 weight %, the dichloromethane solution of methylene chloride 75 weight %, this dichloromethane solution curtain coating on the polyethylene terephthalate film, solidify after making solvent evaporates, obtain film by peeling off.To obtain again peel off after film 100 ℃ of dryings 4 hours, at 110 ℃～130 ℃, by 10 ℃ respectively dry 1 hour at interval, use vacuum drier 120 ℃ of dryings 4 hours then, obtain having the film (below, claim film (1)) of about 90 μ m thickness.

The glass transition temperature (Tg) of the film that makes (1) is 150 ℃.Light penetration is 90.0%, and mist degree is 0.6%, and the three-dimensional refractive index of film is nx=1.5830, ny=1.5830, nz=1.5830.The outer phase differential (Rth) of phase differential (Re) and face is 0nm in the face that makes.

Find out that by these results the refractive index of the film thickness direction that makes is little, is not suitable for optical compensation films.

Embodiment 6

The film that comparative example 1 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 170 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 10mm/ divides, and stretches+50%.The film that stretches (claiming film 1 (a)) shows positive birefringence.The three-dimensional refractive index of the film 1 (a) that makes is nx=1.5826, ny=1.5842, and (ny＞nx＞nz), phase differential (Re) is 125nm to nz=1.5822 in the face.

In addition, go up the film that applying embodiment 1 makes, make thickness 97 μ m films at this film 1 (a).The three-dimensional refractive index of this film is nx=1.5593, ny=1.5606, and phase differential (Re) is 126nm in the nz=1.5600, face, orientation parameter (Nz) is 0.5.

Find out that by these results the film that makes is applicable to optical compensation films.

Embodiment 7

The film that comparative example 1 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 170 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 10mm/ divides, and stretches+33%.The film that stretches (claiming film 1 (b)) shows positive birefringence.The three-dimensional refractive index of the film 1 (b) that makes is nx=1.5826, ny=1.5839, and (ny＞nx＞nz), phase differential (Re) is 113nm to nz=1.5825 in the face.

In addition, go up the film that applying embodiment 2 makes, make thickness 113 μ m films at this film 1 (b).The three-dimensional refractive index of this film is nx=1.5494, ny=1.5504, and phase differential (Re) is 113nm in the nz=1.5502, face, orientation parameter (Nz) is 0.20.

Coating solution Production Example 1

The fumaric acid diisopropyl ester homopolymer that synthesis example 1 is made is dissolved in toluene: the MEK weight ratio is to become 10% solution in 1: 1 the solution, again with respect to fumaric acid diisopropyl ester homopolymer 100 weight portions, interpolation is as the tricresyl phosphate (2 of antioxidant, the 4-di-tert-butyl-phenyl) [3-(3 for ester 0.35 weight portion and pentaerythrite four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] 0.15 weight portion, as 2-(2H-benzotriazole-2-yl)-paracresol 1 weight portion of ultraviolet light absorber, make coating solution.

Embodiment 8

Use aforementioned coating solution to adopt the scraper rubbing method to be coated with on the film 1 (a) that embodiment 6 makes, making dried thickness (thickness that comprises the layer of fumarate resinoid) is 21 μ m, makes film (film thickness: 96 μ m).The three-dimensional refractive index that comprises the layer of fumarate resinoid is nx=1.4689, ny=1.4689, nz=1.4723 (nz＞ny=nx).

The three-dimensional refractive index of this film is nx=1.5593, ny=1.5606, and phase differential (Re) is 125nm in the nz=1.5600, face, orientation parameter (Nz) is 0.5.

Embodiment 9

Use aforementioned coating solution to adopt the scraper rubbing method to be coated with on the film 1 (b) that embodiment 7 makes, making coating dry thickness (thickness that comprises the layer of fumarate resinoid) is 30 μ m, makes film (film degree: 112 μ m).The three-dimensional refractive index that comprises the layer of fumarate resinoid is nx=1.4690, ny=1.4690, nz=1.4721 (nz＞ny=nx).

The three-dimensional refractive index of this film is nx=1.5494, ny=1.5504, and phase differential (Re) is 112nm in the nz=1.5502, face, orientation parameter (Nz) is 0.20.

Embodiment 10

The film that comparative example 1 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 165 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 20mm/ divides, and stretches+50%.The film that stretches (claiming film 1 (c)) shows positive birefringence.The three-dimensional refractive index of the film 1 (c) that makes is nx=1.5820, ny=1.5851, and (ny＞nx＞nz), phase differential (Re) is 263nm to nz=1.5819 in the face.

In addition, use aforementioned coating solution to adopt the scraper rubbing method to go up coating and obtain film (film thickness: 94 μ m) at film 1 (c).The three-dimensional refractive index that comprises the layer of fumarate resinoid is nx=1.4678, ny=1.4678, nz=1.4744 (nz＞ny=nx).

The three-dimensional refractive index of this film is nx=1.5089, ny=1.5117, and phase differential (Re) is 263nm in the nz=1.5094, face, orientation parameter (Nz) is 0.82.

Embodiment 11

The film that comparative example 1 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 160 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 20mm/ divides, and stretches+50%.The film that stretches (claiming film 1 (d)) shows positive birefringence.The thickness of the film 1 (d) that makes is 83 μ m, and three-dimensional refractive index is nx=1.5813, ny=1.5865, and (ny＞nx＞nz), phase differential (Re) is 429nm to nz=1.5812 in the face.

In addition, use aforementioned coating solution to adopt the scraper rubbing method on film 1 (d), to be coated with and make film (film thickness: 113 μ m).The thickness that comprises the layer of fumarate resinoid is 30 μ m, and three-dimensional refractive index is nx=1.4690, ny=1.4690, nz=1.4721 (nz＞ny=nx).

The three-dimensional refractive index of this film is nx=1.5484, ny=1.5522, and phase differential (Re) is 429nm in the nz=1.5494, face, orientation parameter (Nz) is 0.74.

Embodiment 12

The film that comparative example 1 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 170 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 10mm/ divides, and stretches+60%.The film that stretches (claiming film 1 (e)) shows positive birefringence.The thickness of the film 1 (e) that obtains is 70 μ m, and three-dimensional refractive index is: nx=1.5824, and ny=1.5843, (ny＞nx＞nz), phase differential (Re) is 133nm to nz=1.5823 in the face.

In addition, use aforementioned coating solution to adopt the scraper rubbing method on film 1 (e), to be coated with and make film (film thickness: 113 μ m).The three-dimensional refractive index of this film is nx=1.5493, ny=1.5503, and phase differential (Re) is 131nm in the nz=1.5504, face, orientation parameter (Nz) is-0.10.

Embodiment 13

The film that comparative example 1 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 170 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 10mm/ divides, and stretches+65%.The film that stretches (claiming film 1 (f)) shows positive birefringence.The three-dimensional refractive index of the film 1 (f) that makes is nx=1.5825, ny=1.5843, and (ny＞nx＞nz), phase differential (Re) is 137nm to nz=1.5821 in the face.

In addition, go up the film that applying embodiment 3 makes, obtain thickness 99 μ m films at this film 1 (f).The three-dimensional refractive index of this film is nx=1.5523, ny=1.5537, and phase differential (Re) is 137nm in the nz=1.5530, face, orientation parameter (Nz) is 0.5.

Comparative example 2

The film that comparative example 1 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 165 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 10mm/ divides, and+50% (film thickness: 85 μ m) stretches.The film that stretches shows positive birefringence, and phase differential (Re) is 264nm in the face.Three-dimensional refractive index is nx=1.5820, ny=1.5851, and nz=1.5819, orientation parameter (Nz) is 1.02.

Comparative example 3

Under nitrogen environment atmosphere, use small-sized decollator, (the ALDRICH system, weight-average molecular weight: 17.5 ten thousand) 9.0g, under 2500rpm, room temperature was dissolved 1 hour to add poly-(2-vinyl naphthalene) in methylene chloride 49.6g.Use 25 μ m filtrators that the polymer solution that makes is filtered.Then, after using rod to be coated with method to be coated on this polymer solution on the thickness 188 μ m PET films, flow down at nitrogen and on pet substrate, to form the film that gathers (2-vinyl naphthalene) an air-dry night.

Peel the part that this gathers (2-vinyl naphthalene) film off from pet substrate, measure thickness and optical characteristics.Dried thickness is 58 μ m.Moreover when peeling off, film becomes fragile, and it is damaged that part takes place.

The three-dimensional refractive index of the film that makes is nx=1.6557, ny=1.6558, nz=1.6578.The outer phase differential (Rth) of face is-120.2nm that the ratio (R450/R550) (wavelength dependency) of phase differential is 1.12.

Though find out that by these results there is the relation of nz＞ny 〉=nx in the film that makes, because wavelength dependency is big, so be not suitable for optical compensation films.

Comparative example 4

Use small-sized decollator, (ALDRICH makes, weight-average molecular weight: about 1,100,000) 13.2g, under 6000rpm, room temperature was dissolved 1 hour to add poly-(9-vinylcarbazole) in N-N-methyl-2-2-pyrrolidone N-(NMP).The polymer solution that makes uses 25 μ m filtrators to filter.Then, adopt rod to be coated with method behind this polymer solution of coating on the PET film of thickness 188 μ m, by 60 ℃ of heated-air dryings 1 hour, 100 ℃ of following heated-air dryings 15 minutes.On pet substrate, form poly-(9-vinylcarbazole) film.

Peel the part that this gathers (9-vinylcarbazole) film off from pet substrate, measure thickness and optical characteristics.Dried thickness is 33 μ m.Moreover, film trichorrhexis first portion breakage when peeling off.

The three-dimensional refractive index of the film that makes is nx=1.6819, ny=1.6820, nz=1.6926.The outer phase differential (Rth) of face is-350.0nm that the ratio (R450/R550) (wavelength dependency) of phase differential is 1.14.

Embodiment 14

The film that film Production Example 1 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 140 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 10mm/ divides, and stretches 1.125 times.Measure the result of the three-dimensional refractive index of the film that stretches, because the axial refractive index that stretches is little, the film that makes has negative birefringence.

(nx=1.4681, ny=1.4692 nz=1.4727) find out that obtaining film is nx＜ny＜nz to the result who measures from three-dimensional refractive index, and the refractive index of film thickness direction is big.And phase differential Re=(ny-nx) in the face * d is greatly to 131nm.The ratio (R450/R550) (wavelength dependency) of phase differential is low to moderate 1.02 in addition.

Find out that from these results the film that obtains is owing to there is negative birefraction, the refractive index of thickness direction is big, and phase differential is big in the face in addition, and wavelength dependency is little, so be applicable to phase retardation film.

Embodiment 15

The film that film Production Example 1 is obtained is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 140 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 10mm/ divides, and stretches 1.25 times.The result of the three-dimensional refractive index that measure to stretch and since tensile axis to refractive index little, so the film that obtains has negative birefringence.

Because (nz=1.4729), so the film nx＜ny＜nz that makes, the refractive index of film thickness direction is big for nx=1.4667, ny=1.4704 for the result that three-dimensional refractive index is measured.And phase differential Re=(ny-nx) in the face * d is greatly to 418nm.Phase differential is low to moderate 1.02 than (R450/R550) (wavelength dependency) in addition.

Found out that by these results because the film that makes has negative birefraction, the refractive index of thickness direction is big, phase differential is big in this outside, and wavelength dependency is little, so be applicable to phase retardation film.

Embodiment 16

The film that film Production Example 1 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 140 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 10mm/ divides, and stretches 1.375 times.The result of the three-dimensional refractive index of the film that measure to stretch and since tensile axis to refractive index little, so the film that makes has negative birefringence.

The result who measures by three-dimensional refractive index (nx=1.4653, ny=1.4714 nz=1.4733) find out, the film nx＜ny＜nz that makes, and the refractive index of film thickness direction is big.And phase differential Re=(ny-nx) in the face * d is greatly to 636nm.The ratio (R450/R550) (wavelength dependency) of phase differential is low to moderate 1.02 in addition.

Found out that by these results because the film that makes has negative birefraction, the refractive index of thickness direction is big, in addition, phase differential is big in the face, and wavelength dependency is little, so be applicable to phase retardation film.

Comparative example 5

The film that film Production Example 4 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 170 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 10mm/ divides, and stretches 1.10 times.Measure the result of the three-dimensional refractive index of the film that stretches, because the axial refractive index vertical with the tensile axis direction is little, so the film that obtains has positive birefringence.

(nx=1.5844, ny=1.5823 find out that nz=1.5823) film that makes is nx＞ny=nz to the result who is measured by three-dimensional refractive index, and the refractive index of the thickness direction of film is little.

Find out that by these results the film that makes is not suitable for the phase retardation film of the field angle compensation performance of STN-LCD or IPS-LCD.

Comparative example 6

The film that film Production Example 5 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 180 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 15mm/ divides, and stretches 2.0 times.Measure the result of the three-dimensional refractive index of the film that stretches, because the axial refractive index vertical with the tensile axis direction is little, so the film that obtains has positive birefringence.

The result who measures by three-dimensional refractive index (nx=1.5124, ny=1.5090 nz=1.5090) find out, the film nx＞ny=nz that makes, and the refractive index of the thickness direction of film is little.

Embodiment 17

The film that film Production Example 2 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 140 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 10mm/ divides, and stretches 1.2 times (claiming film A-1 later on).From the result of the three-dimensional refractive index of the film that measure to stretch (nx=1.4673, ny=1.4702, nz=1.4725) (nx＜ny＜nx) find out, the axial refractive index that stretches is little, the film that makes has negative birefringence.Phase differential Re=(ny-nx) * d is 283nm in the face in addition.

The polycarbonate membrane that film Production Example 4 is made is cut into the square of a slice 50mm, use two-way stretch device (well unit makes made) 170 ℃ of temperature, implement free width of cloth unilateral stretching under the condition that draw speed 10mm/ divides, stretch 1.5 times (claiming film B-1 later on).The three-dimensional refractive index nx=1.5827 of the film that makes, ny=1.5842, nz=1.5827 (ny＞nz=nx), show positive birefringence.And phase differential (Re) is 130nm in the face.

The leading phase shaft that makes here the film A-1 that makes is fitted with the leading phase shaft of film B-1 is vertical (90 ° of angles).The thickness of stack membrane is 186 μ m.Phase differential (Re) is 153nm in the face.The phase differential (R450) of wavelength 450nm place mensuration is 0.98 with the ratio (R450/R550) of the phase differential (R550) of wavelength 550nm place mensuration in addition.In addition, the phase differential (R650) of wavelength 650nm place mensuration is 1.01 with the ratio (R650/R550) of the phase differential (R550) of wavelength 550nm place mensuration.

Find out that by these results the film that makes is controlled because of wavelength dispersibility, have the long dispersiveness of head sea, so be applicable to phase retardation film.And also be suitable as the film of the phase differential with 1/4 wavelength, promptly so-called 1/4 wavelength plate uses.

Embodiment 18

The film that film Production Example 3 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 160 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 10mm/ divides, and stretches 1.25 times (claiming film A-2 later on).The result who measures by the three-dimensional refractive index of the film that stretches (nx=1.4660, ny=1.4709, nz=1.4731) (nx＜ny＜nx) find out, the axial refractive index that stretches is little, and the film that makes has negative birefringence.Phase differential Re=(ny-nx) * d is 531nm in the face in addition.

The polycarbonate membrane that film Production Example 6 is made is cut into the square of a slice 50mm, use two-way stretch device (well unit makes made) 160 ℃ of temperature, implement free width of cloth unilateral stretching under the condition that draw speed 20mm/ divides, stretch 1.5 times (claiming film B-2 later on).The three-dimensional refractive index nx=1.5811 of the film that makes, ny=1.5863, nz=1.5819 (ny＞nz＞nx), show positive birefringence.Phase differential Re is 395nm in the face in addition.

The leading phase shaft that makes the film A-2 that makes is here fitted with the leading phase shaft of film B-2 is vertical (90 ° of angles).The thickness of stack membrane is 185 μ m.Phase differential (Re) is 136nm in the face.The phase differential (R450) of wavelength 450nm place mensuration is 0.91 with the ratio (R450/R550) of the phase differential (R550) of wavelength 550nm place mensuration in addition.The phase differential (R650) of wavelength 650nm place mensuration is 1.07 with the ratio (R650/R550) of the phase differential (R550) of wavelength 550nm place mensuration in addition.

Find out that by these results the film that makes is controlled because of wavelength dispersibility, have the long dispersiveness of head sea.So be applicable to phase retardation film.And also be suitable as the film of the phase differential of 1/4 wavelength, promptly so-called 1/4 wavelength plate uses.

Embodiment 19

The film that film Production Example 6 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 165 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 20mm/ divides, and stretches 1.5 times (claiming film B-3 later on).The three-dimensional refractive index nx=1.5820 of the film that makes, ny=1.5849, nz=1.5819 (ny＞nx＞nz), show positive birefringence.And phase differential (Re) is 261nm in the face.

Make that the leading phase shaft of the leading phase shaft of the film A-2 that embodiment 18 makes and the film B-3 of manufacturing here is vertical fits (90 ° of angles).The thickness of stack membrane is 199 μ m.Phase differential (Re) is 270nm in the face.In addition, the phase differential (R450) of wavelength 450nm place mensuration is 0.97 with the ratio (R450/R550) of the phase differential (R550) of wavelength 550nm place mensuration.In addition, the phase differential (R650) of wavelength 650nm place mensuration is 1.03 with the ratio (R650/R550) of the phase differential (R550) of wavelength 550nm place mensuration.

Find out, to have the long dispersiveness of head sea because the film wavelength dispersibility that makes is controlled by these results.So be applicable to phase retardation film.And also be suitable as the film of the phase differential of 1/2 wavelength, promptly so-called 1/2 wavelength plate.

Embodiment 20

The commercially available PES film (husky (lonza of dragon, ロ Application ザ) make) be cut into the square of a slice 50mm, use two-way stretch device (well unit makes made) 245 ℃ of temperature, implement free width of cloth unilateral stretching under the condition that draw speed 20mm/ divides, stretch 1.5 times (claiming film B-4 later on).The three-dimensional refractive index nx=1.6587 of the film that makes, ny=1.6611, nz=1.6587 (ny＞nz=nx), show positive birefringence.And phase differential (Re) is 149nm in the face.

Make that the leading phase shaft of the leading phase shaft of the film A-1 that embodiment 17 makes and the film B-4 of manufacturing here is vertical fits (90 ° of angles).The thickness of stack membrane is 161 μ m.Phase differential (Re) is 134nm in the face.In addition, the phase differential (R450) of wavelength 450nm place mensuration is 0.94 with the ratio (R450/R550) of the phase differential (R550) of wavelength 550nm place mensuration.In addition, the phase differential of measuring at wavelength 650nm place (R650) is 1.03 with the ratio (R650/R550) of the phase differential of measuring at wavelength 550nm place (R550).

Find out, to have the long dispersiveness of head sea because the film wavelength dispersibility that makes is controlled by these results.So be applicable to phase retardation film.And also be suitable as the phase retardation film of phase differential, promptly so-called 1/4 wavelength plate with 1/4 wavelength.

Embodiment 21

The film that film Production Example 3 is made is cut into the square of a slice 50mm, uses two-way stretch device (well unit makes made) 140 ℃ of temperature, implements free width of cloth unilateral stretching under the condition that draw speed 10mm/ divides, and stretches 1.21 times (claiming film A-3 later on).By the result of the three-dimensional refractive index of the film that measure to stretch (nx=1.4671, ny=1.4702, nz=1.4725) (nx＜ny＜nz) find out, tensile axis to refractive index little, the film that makes has negative birefringence.And phase differential Re=(ny-nx) * d is 312nm in the face.

The polycarbonate membrane that film Production Example 4 is made is cut into the square of a slice 50mm, use two-way stretch device (well unit makes made) 170 ℃ of temperature, implement free width of cloth unilateral stretching under the condition that draw speed 10mm/ divides, stretch 1.5 times (claiming film B-5 later on).The three-dimensional refractive index nx=1.5827 of the film that makes, ny=1.5842, nz=1.5827 (ny＞nz=nx), show positive birefringence.And phase differential Re is 130nm in the face.

The leading phase shaft that makes here the film A-3 that makes is fitted with the leading phase shaft of film B-5 is vertical (90 ° of angles).The thickness of stack membrane is 177 μ m.Phase differential (Re) is 183nm in the face.The phase differential of measuring at wavelength 450nm place (R450) is 0.96 with the ratio (R450/R550) of the phase differential of measuring at wavelength 550nm place (R550) in addition.In addition, the phase differential (R650) of wavelength 650nm place mensuration is 1.06 with the ratio (R650/R550) of the phase differential (R550) of wavelength 550nm place mensuration.

Find out, to have the long dispersiveness of head sea, so be applicable to phase retardation film because the film wavelength dispersibility that makes is controlled by these results.And also be suitable as the phase retardation film of the phase differential of 1/4 wavelength, promptly so-called 1/4 wavelength plate uses.

Embodiment 22

Make the leading phase shaft of the film A-3 that embodiment 21 makes become 80 degree ground to fit with the leading phase shaft of film B-5.Phase differential (Re) is 181nm in the face.In addition, the phase differential (R450) of wavelength 450nm place mensuration is 0.97 with the ratio (R450/R550) of the phase differential (R550) of wavelength 550nm place mensuration.In addition, the phase differential (R650) of wavelength 650nm place mensuration is 1.03 with the ratio (R650/R550) of the phase differential (R550) of wavelength 550nm place mensuration.

Find out because the film wavelength dispersibility that makes is controlled to have the long dispersiveness of head sea by these results.So be applicable to phase retardation film.And also be suitable as the phase retardation film of the phase differential of 1/4 wavelength, promptly so-called 1/4 wavelength plate uses.

Embodiment 23

Make the leading phase shaft of the film A-3 that embodiment 21 makes become 70 degree ground to fit with the leading phase shaft of film B-5.Phase differential (Re) is 181nm in the face.In addition, the phase differential (R450) of wavelength 450nm place mensuration is 0.98 with the ratio (R450/R550) of the phase differential (R550) of wavelength 550nm place mensuration.In addition, the phase differential (R650) of wavelength 650nm place mensuration is 1.02 with the ratio (R650/R550) of the phase differential (R550) of wavelength 550nm place mensuration.

Find out, to have the long dispersiveness of head sea because the film wavelength dispersibility that makes is controlled by these results.So be applicable to phase retardation film.And also be suitable as the phase retardation film of the phase differential of 1/4 wavelength, promptly so-called 1/4 wavelength plate uses.

Comparative example 7

Phase differential (Re) is 130nm in the face of the film B-1 that embodiment 15 makes.In addition, the phase differential of measuring at wavelength 450nm place (R450) is 1.08 with the ratio (R450/R550) of the phase differential (R550) of wavelength 550nm place mensuration.The phase differential (R650) that wavelength 650nm place measures is 0.96 with the ratio (R650/R550) of the phase differential (R550) that wavelength 550nm place measures.

Owing to do not use film (A), so the long bad dispersibility of head sea.

Though use specific mode that the present invention at length is illustrated, can not break away from the intent of the present invention and scope, carry out various changes and distortion, this is clearly to those skilled in the art.

In addition, the Japanese patent application that the application filed an application according on September 5th, 2006 (special hope 2006-239767), the Japanese patent application of filing an application on October 4th, 2006 (special hope 2006-273046), the Japanese patent application of filing an application on November 22nd, 2006 (special hope 2006-316322), reach the Japanese patent application (the special 2007-195756 of hope) of filing an application on July 27th, 2007, quoted its full content.

Claims

1. optical compensation films, this optical compensation films comprises the fumarate resinoid, wherein, in the three-dimensional refractive index of described film, the refractive index of the leading phase shaft direction in the face is designated as nx, and the refractive index of direction is designated as ny in the perpendicular face, when the refractive index of the vertical direction that face is outer is designated as nz, the relation that has nz＞ny 〉=nx, the ratio R450/R550 of the phase differential that phase differential of measuring at wavelength 450nm place and wavelength 550nm place measure is below 1.1.

2. the described optical compensation films of claim 1, wherein, when the thickness of film was designated as d, the outer phase differential Rth of the face of the film of following formula (1) expression was-30～-2000nm,

Rth＝[(nx+ny)/2-nz]×d (1)。

3. claim 1 or 2 described optical compensation films, it is used for liquid crystal display cells.

4. optical compensating layer, this optical compensating layer comprises the fumarate resinoid, wherein, in the three-dimensional refractive index of described layer, the refractive index of the leading phase shaft direction in the aspect is designated as nx, and the refractive index of direction is designated as ny in the perpendicular aspect, when the refractive index of the vertical direction that aspect is outer is designated as nz, the relation that has nz＞ny 〉=nx, the ratio R450/R550 of the phase differential that phase differential of measuring at wavelength 450nm place and wavelength 550nm place measure is below 1.1.

5. the described optical compensating layer of claim 4, wherein, when the thickness of layer was designated as d, the outer phase differential Rth of the face of the layer of following formula (1) expression was-30～-2000nm,

Rth＝[(nx+ny)/2-nz]×d (1)。

6. claim 4 or 5 described optical compensating layers, it is used for liquid crystal display cells.

7. optical compensation films; This film comprises that optical compensation films claimed in claim 1 or optical compensating layer claimed in claim 4 are film A and film B; Described film B is; In the three-dimensional refractive index of film; The refractive index of the leading phase shaft direction in the face is designated as nx; The refractive index of direction is designated as ny in the perpendicular face; When the refractive index of the vertical direction that face is outer is designated as nz; The relation that has ny＞nx 〉=nz; When the thickness of film is designated as d; Phase difference Re in the face that wavelength 550nm place measures shown in the following formula (2) is more than the 50nm

Re＝(ny-nx)×d (2)。

8. the described optical compensation films of claim 7, wherein, the orientation parameter Nz of following formula (3) expression is in-0.1～0.95 the scope,

Nz＝(ny-nz)/(ny-nx) (3)。

9. claim 7 or 8 described optical compensation films, wherein, phase differential Re is 50～1000nm in the face of aforementioned formula (2) expression.

10. claim 7 or 8 described optical compensation films, it is used for liquid crystal display cells.

11. phase retardation film, this film comprises the fumarate resinoid, wherein, the refractive index of the leading phase shaft direction in this face is designated as nx, the refractive index of direction is designated as ny in the perpendicular face, and when the refractive index of the vertical direction that face is outer was designated as nz, the pass of each refractive index was nx＜ny≤nz, and phase differential R450 that wavelength 450nm place measures and the ratio R450/R550 of the phase differential R550 that wavelength 550nm place measures are below 1.1.

12. the described phase retardation film of claim 11, wherein, the phase differential Re in the face that wavelength 550nm place measures shown in the following formula (2) is 50～2000nm,

Re＝(ny-nx)×d (2)。

13. a phase retardation film, this film comprises the fumarate resinoid, and wherein, this film comprises film C and film D,

Described film C is, the refractive index of the leading phase shaft direction in this face is designated as nx, and the refractive index of direction is designated as ny in the perpendicular face, and when the refractive index of the vertical direction that face is outer was designated as nz, the pass of each refractive index was nx＜ny≤nz;

Described film D is, in the three-dimensional refractive index of film, the refractive index of the leading phase shaft direction in the face is designated as nx, the refractive index of direction is designated as ny in the perpendicular face, when the refractive index of the vertical direction that face is outer is designated as nz, there is ny＞nx 〉=nz or ny＞nz 〉=nx relation

Phase differential R450 that this phase retardation film is measured at wavelength 450nm place and the ratio R450/R550 of the phase differential R550 that measures at wavelength 550nm place are below 1.0.

14. the described phase retardation film of claim 13, this film comprise that with the phase differential Re in the face that wavelength 550nm place measures shown in the following formula (2) be the film D of 50～2000nm,

Re＝(ny-nx)×d (2)。

15. claim 13 or 14 described phase retardation films wherein, are 50～2000nm with phase differential Re in the face of the film C that measures at wavelength 550nm place shown in the aforementioned formula (2).

16. the described phase retardation film of claim 13, wherein, the leading phase shaft angulation of the leading phase shaft of film C and film D is 90 degree ± 20 degree.

17. claim 13 or 16 described phase retardation films, wherein, in the face of the film C that measures at wavelength 550nm place in the face of phase differential Re and film D the difference of phase differential Re be 100～160nm.

18. claim 13 or 16 described phase retardation films, wherein, in the face of the film C that measures at wavelength 550nm place in the face of phase differential Re and film D the difference of phase differential Re be 250～300nm.

19. the described phase retardation film of claim 13, wherein, phase differential R650 that measures at wavelength 650nm place and the ratio R650/R550 of the phase differential R550 that measures at wavelength 550nm place are more than 1.

20. a composite polarizing plate, it is stacked in any one described phase retardation film in the claim 11,12,13,14,16 on the polaroid and forms.

21. a composite polarizing plate, it is stacked in the described phase retardation film of claim 15 on the polaroid and forms.

22. a composite polarizing plate, it is stacked in the described phase retardation film of claim 17 on the polaroid and forms.

23. a composite polarizing plate, it is stacked in the described phase retardation film of claim 18 on the polaroid and forms.

24. a composite polarizing plate, it is stacked in the described phase retardation film of claim 19 on the polaroid and forms.