CN1957273A - Optical compensating polarizing plate, image display device and liquid crystal display device - Google Patents

Optical compensating polarizing plate, image display device and liquid crystal display device Download PDF

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CN1957273A
CN1957273A CN 200580016089 CN200580016089A CN1957273A CN 1957273 A CN1957273 A CN 1957273A CN 200580016089 CN200580016089 CN 200580016089 CN 200580016089 A CN200580016089 A CN 200580016089A CN 1957273 A CN1957273 A CN 1957273A
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polarizing plate
optical compensating
film
rth
transparent protective
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CN100443933C (en
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西浦阳介
中山元
伊藤忠
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Fujifilm Corp
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Fujifilm Corp
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Abstract

An optical compensation polarizing plate comprising: a first transparent protective film; a polarizer; a second transparent protective film; and an optical compensation layer in this order, wherein at least one of the first and second transparent protective films is a cellulose acylate film having a retardation value in plane Re (nm) and a retardation value in film thickness direction Rth (nm) which fulfill the following formulae (I) and (II), and Nz and Re1 defined by the following formulae (III) and (IV), of the optical compensation layer fulfill the following formulae (V) and (VI): (I) |Re|<=10, (II) |Rth|<=25, (III) NZ=(nx1-nz1)/(nx1-ny1), (IV) Re1=(nx1-ny1) x d1, (V) 0.4<=Nz<=0.6 (VI) 100<=Re1<=350, wherein RE1 is a retardation value in plane (nm) at a wavelength of 590 nm; Nz is an Nz factor at a wavelength of 590 nm; nx1 is a refractive index along a slow axis in a film plane; ny1 is a refractive index along a direction perpendicular to the slow axis in a film plane; nz1 is a refractive index along a thickness direction of the film; and d1 is a thickness of the film (nm).

Description

Optical compensating polarizing plate, image-display units and liquid crystal display
Technical field
The present invention relates to a kind of optical compensating polarizing plate, comprise polarizer, its upper strata is pressed with transparent protective film and optical compensating layer.In addition, the present invention relates to use the image-display units of above-mentioned optical compensating polarizing plate.Optical compensating polarizing plate of the present invention is specially adapted to be known as the liquid crystal display of IPS pattern operation.
Background technology
In the liquid crystal display of main use at present, the TN pattern that is known as of use, the liquid crystal molecule that wherein has positive dielectric anisotropy is arranged with about 90 ° distortion attitude.The liquid crystal display of TN pattern comprises the substrate with a pair of transparency electrode, comprises the liquid crystal cell that is encapsulated in the nematic liquid crystal between substrate and establishes polarizing plate with its both sides.Compare with the LCD of other patterns, the advantage of the liquid crystal display of TN pattern is, shows higher relatively reaction velocity, is a few tens of milliseconds, and has the high contrast that shows.Yet they have the problem of some viewing angle characteristics, thereby Show Color and demonstration contrast change with view direction, and therefore, display performance is still poor than CRT.
In the liquid crystal display of TN pattern, show by the electric field that applies perpendicular to substrate.By applying/close electric field, the arrangement of liquid crystal molecule main shaft is almost perpendicular to substrate/almost be parallel to substrate.Therefore, owing to, produce demonstration in variation perpendicular to the liquid crystal molecule major axes orientation on the substrate surface.Therefore, the delay of liquid crystal layer changes with view direction to a great extent, and therefore, great changes have taken place for Show Color and demonstration contrast.For improving these viewing angle characteristics, having proposed provides optical compensating layer between polarizer and the brilliant unit of TN mode liquid crystal, and has proposed various optical compensating gages.Although by providing this optical compensating gage to enlarge the visual angle to a certain extent, this can't obtain the wide visual angle as the CRT replacement in the practical application.
A kind of display system has also been proposed, be not the electric field that applies as in these cases perpendicular to substrate wherein, (JP-A-7-261152 and ASIA DISPLAY ' 95 are (at The Institute of Television Engineers of Japan ﹠amp but apply the electric field that almost is parallel to substrate; The Society for Information Display, open in 577～580 pages and 707～710 pages)).This display system that wherein applies the electric field that almost is parallel to substrate is called IPS (plane switching) pattern.In the liquid crystal display of IPS pattern, liquid crystal molecule does not have almost parallel and even orientation substrate surface when driving attitude.Therefore, when the less variation of plane of polarisation, light can see through liquid crystal layer.Therefore, by polarizing plate being set, when not driving attitude, can realize almost complete black the demonstration in the substrate above and below.
In the IPS pattern, can realize almost complete black the demonstration in dull and stereotyped normal direction.Yet; watching from the direction of off-normal under the dull and stereotyped situation; the problem that causes is; owing to the reason visual angle of the light leak and the phase differential of different ignorance is narrower; and because in the polarizing plate characteristic of the direction that departs from the polarizing plate optical axis that the liquid crystal cell above and below is provided with; light leak is inevitably, and phase differential to be liquid crystal and transparent protective film by even orientation cause.
For overcoming this problem, used polarizing plate, wherein watch the polarizing plate geometrical axis that causes to depart from and compensate by optical compensating gage from certain angle.Polarizing plate with this effect for example is disclosed among the JP-A-4-305602 and JP-A-4-371903.Yet, use known optical compensating gage in actual applications, almost can not obtain enough wide visual angle.
In the polarizing plate of JP-A-4-305602 report, optical compensating gage is as the diaphragm of polarizer.Although this polarizing plate provides favourable viewing angle characteristic in environment commonly used, change in size can take place in this polarizer under high-temperature or high humility, thereby the diaphragm that is laminated directly on it also deforms.Therefore, the problem that causes is that the phase differential that is used as the optical compensating gage of diaphragm has departed from required scope, thereby can not stably keep its effect.
In JP-A-4-371903, use tri acetyl cellulose film (TAC film) that optical compensating gage is laminated on the polarizing plate, this film is commonly used for diaphragm.Owing to do not have stress directly to be carried on the optical compensating gage in this case, the phase differential of optical compensating gage keeps stablizing.Yet the TAC film has the phase differential that can not be ignored, and makes it be difficult to be designed to compensate the optical compensating layer of usefulness.In addition, similar to above-mentioned situation, owing to the change in size of polarizer under high-temperature or high humility, the TAC film is stretched, thereby causes that phase differential changes, and makes it can not realize required purpose.
In JP-A-2004-4641 and JP-A-2004-4642, contain the film of norbornene resin and contain the film of resin with inferior acylamino-and have phenyl and the resin of nitrile group by the lamination cuticula of going bail for.Because phase differential is lowered in these cases, therefore design optical compensating layer easily.Yet these synthetic resin have hydrophobicity usually, and this usually can often cause problem when bonding with polarizer.That is, these resins are easy to peel off.In addition, in these cases, wish that hardly any moisture content sees through polarizer, and thereby be retained in wherein because this can cause the problem of polarizing plate mis-behave.In addition, similar to above-mentioned situation, the problem that phase differential changes in synthetic resin film is more serious than TAC film, makes it can not realize required purpose.
Summary of the invention
The present invention relates to a kind of optical compensating polarizing plate, have polarizing plate and the optical compensating layer that is laminated on it.An object of the present invention is to provide a kind of optical compensating polarizing plate,, can improve the demonstration contrast and the viewing angle characteristic of Show Color, and can not reduce the forward contrast when it being used in image-display units particularly in the liquid crystal display time.
Another object of the present invention provides a kind of image-display units with above-mentioned optical compensating polarizing plate, particularly has excellent viewing angle characteristic and can be used as the liquid crystal display that CRT replaces.
Another object of the present invention provide a kind of in wide region, have high-contrast than and can the IPS pattern operation and the liquid crystal display of visual display easily is provided.
The present inventor has carried out broad research and has overcome the problems referred to above.Therefore, they have invented optical compensating polarizing plate described below, image-display units and liquid crystal display, thus finished the present invention.
Therefore, by following every the present invention that realized is provided.
(1) a kind ofly obtains polarizing plate and the further optical compensating polarizing plate of laminated optical layer of compensation structure on one face by lamination transparent protective film on two surfaces of polarizer; wherein at least one in the transparent protective film is cellulose acylate film; its plane length of delay Re (by nm) and film thickness direction length of delay Rth (by nm) satisfy following formula (I) and (II) and respectively by following formula (III) and (IV) Nz and the Re of the optical compensating layer of definition 1Satisfy following formula (V) and (VI):
(I)|Re|≤10
(II)|Rth|≤25
(III)Nz＝(nx 1-nz 1)/(nx 1-ny 1)
(IV)Re 1＝(nx 1-ny 1)×d 1
(V)0.4≤Nz≤0.6
(VI)100≤Re 1≤350
Re wherein 1It is the plane length of delay (by nm) under the wavelength 590nm; Nz is the Nz factor under the wavelength 590nm; Nx 1It is refractive index along the membrane plane slow axis; Ny 1Be the refractive index of edge perpendicular to the direction of membrane plane slow axis; Nz 1It is refractive index along film thickness direction; And d 1Be the thickness (by nm) of film.
(2) as above-mentioned (1) described optical compensating polarizing plate, wherein transparent protective film satisfies following formula (VII):
(VII) | Re (400)-Re (700)|≤10 Hes | Rth (400)-Rth (700)|≤35,
Wherein Re (λ) is the plane length of delay (by nm) under the wavelength X mn; And Rth (λ) is the film thickness direction length of delay (by nm) under the wavelength X mn.
(3) as above-mentioned (1) or (2) described optical compensating polarizing plate, wherein the film thickness of transparent protective film is 10～120 μ m.
(4) as each described optical compensating polarizing plate in above-mentioned (1)～(3), wherein transparent protective film satisfies following formula (VIII):
(VIII) | Re (MAX)-Re (MIN) |≤6 Hes | Rth (MAX)-Rth (MIN) |≤10
Wherein Re (MAX) and Rth (MAX) are the 1m that downcuts at random 2The maximum delay value of diaphragm (by nm); Re (MIN) and Rth (MIN) are its minimum delay values (by nm).
(5) as each described optical compensating polarizing plate in above-mentioned (1)～(4), wherein transparent protective film contains and at least aly the length of delay Rth of film thickness direction can be reduced to the compound (can reduce the compound of film thickness direction length of delay Rth) that satisfies following formula (IX) and scope (X):
(IX)(Rth(A)-Rth(0))/A≤1.0
(X)0.1≤A≤30
Rth (A) is the Rth (nm) of film that contains the compound that can reduce Rth of A%; Rth (0) is the Rth (nm) that does not contain the film of the compound that can reduce Rth; A be the polymer quality as membrane material be 100 o'clock compounds quality (weight) (%).
(6) as above-mentioned (5) described optical compensating polarizing plate, the compound that wherein can reduce Rth is that octanol-water partition coefficient (LogP) is 0～7 compound.
(7) as above-mentioned (5) or (6) described optical compensating polarizing plate; it contains at least a following formula (13) that is selected from; (18) and the compound of (19) representative as the compound that reduces Rth, be 0.01～30wt.% by its amount of solid cellulose acylate content:
R wherein 1Represent alkyl or aryl, R 2And R 3Each represents hydrogen atom independently, alkyl or aryl, and condition is R 1, R 2And R 3Middle carbon atom summation is 10 or bigger;
Figure A20058001608900112
R wherein 1Represent alkyl or aryl, R 2And R 3Each represents hydrogen atom, alkyl or aryl independently;
Figure A20058001608900113
R wherein 4, R 5And R 6Each represents alkyl or aryl independently.
(8) as each described optical compensating polarizing plate in above-mentioned (1)～(7), wherein transparent protective film contains at least a can the reduction | Re (400)-Re (700)| and | Rth (400)-Rth (700)| compound, be 0.01～30wt.% by its amount of solid cellulose acylate content.
(9) as each described optical compensating polarizing plate in above-mentioned (1)～(8), wherein transparent protective film has slow axis on the horizontal direction (TD) perpendicular to film machine direction (MD).
(10) as each described optical compensating polarizing plate in above-mentioned (1)～(9), wherein transparent protective film is 55 ° or littler by its contact angle of the film of alkali-saponification surface.
(11) as each described optical compensating polarizing plate in above-mentioned (1)～(10), wherein transparent protective film is handled after 240 hours under 60 ℃ and 90%RH, and the variation of Re and Rth is 15nm or littler.
(12) as each described optical compensating polarizing plate in above-mentioned (1)～(11), wherein processing is after 240 hours down at 80 ℃ for transparent protective film, and the variation of Re and Rth is 15nm or littler.
(13) as each described optical compensating polarizing plate in above-mentioned (1)～(12), wherein transparent protective film is the film that stretches, and after stretching the laminated optical layer of compensation.
(14) as each described optical compensating polarizing plate in above-mentioned (1)～(12), wherein transparent protective film is the film that stretches, and stretches behind the laminated optical layer of compensation.
(15) as above-mentioned (13) or (14) described optical compensating polarizing plate, wherein before stretching and afterwards, the plane length of delay of transparent protective film satisfies following formula (XI):
(XI)|Re(n)-Re(0)|/n≤1.0
Wherein Re (n) is the plane length of delay (by nm) of the film of stretching n (%); And Re (0) is the plane length of delay (by nm) of the film that do not stretch.
(16) as each described optical compensating polarizing plate in above-mentioned (1)～(15), wherein transparent protective film comprises that the acyl substituted degree is 2.70～3.00 cellulose ethanoate.
(17) as each described optical compensating polarizing plate in above-mentioned (1)～(15), wherein transparent protective film comprises the cellulose acylate that satisfies following formula (XII)～(XIV):
(XII)2.50≤SA+SB≤3.00
(XIII)0≤SA≤2.5
(XIV)0.5≤SB≤3.00
Wherein SA is the degree of substitution of acetyl group; With SB be the degree of substitution of acyl group with replacement of 3～22 carbon atoms.
(18) as each described optical compensating polarizing plate in above-mentioned (1)～(17), wherein optical compensating layer is an optical compensating layer wherein bar-shaped or that discotic compound is orientated perpendicular to the surface of transparent protective film.
(19) as each described optical compensating polarizing plate in above-mentioned (1)～(17), wherein optical compensating layer contains and has just intrinsic birefringence value and be selected from polyamide, polyimide, polyester, polyetherketone, the polymkeric substance of polyamidoimide and polyester-imide.
(20) as each described optical compensating polarizing plate in above-mentioned (1)～(17), wherein optical compensating layer contains the polymkeric substance with negative intrinsic birefringence value.
(21) as each described optical compensating polarizing plate in above-mentioned (1)～(20), it is bonding that wherein transparent protective film passes through adhesive phase or pressure sensitive adhesive layer and optical compensating layer.
(22) as each described optical compensating polarizing plate in above-mentioned (1)～(21), it also comprises and is selected from hard conating, the one deck at least in anti-flash layer and the anti-reflecting layer.
(23) a kind of image-display units, it comprises as each described optical compensating polarizing plate in above-mentioned (1)～(22).
(24) a kind of liquid crystal display that comprises the image-display units of IPS pattern; wherein be arranged on brilliant first substrate of watching side as each described optical compensating polarizing plate in above-mentioned (1)～(22); comprise that being arranged on brilliant first substrate as the polarizing plate that is laminated at least one lip-deep transparent protective film of polarizer in above-mentioned (1)～(17) as described in each watches on that side of side dorsad, the major axes orientation of liquid crystal molecule is not parallel to the absorption axes direction of polarizing plate in the liquid crystal cell when applying voltage.
(25) a kind of liquid crystal display that comprises the image-display units of IPS pattern; comprising being arranged on brilliant first substrate of watching side as the polarizing plate that is laminated at least one lip-deep transparent protective film of polarizer in above-mentioned (1)～(17) as described in each; be arranged on brilliant first substrate as each described optical compensating polarizing plate in above-mentioned (1)～(22) and watch dorsad on that side of side, when not applying voltage in the liquid crystal cell major axes orientation of liquid crystal molecule perpendicular to the absorption axes direction of polarizing plate.
In the optical compensating polarizing plate of the invention described above, passing through to arrange under quadrature Niccol (Nicol) attitude that the light leak on the direction of off-normal can be compensated by the particular optical layer of compensation under the situation of liquid crystal cell and polarizing plate.Especially, optical compensating polarizing plate of the present invention has the compensation function that the contrast certain angle reduces in the liquid crystal layer of the liquid crystal display of IPS pattern.The above-mentioned Nz value of optical compensating layer is 0.4～0.6, and plane phase differential (Rel) is 100～350nm.From the angle of compensate function, Nz value preferably 0.45 or bigger, more preferably 0.48 or bigger.On the other hand, further preferably the Nz value is 0.55 or littler, more preferably 0.52 or littler.From the angle of compensate function, plane phase retardation Rel is 230nm or bigger, more preferably 250nm or bigger.
In optical compensating polarizing plate of the present invention; at least one transparent protective film that is laminated on two faces of polarizer is to have less optical anisotropy (Re; Rth) cellulose acylate film; promptly | Re|≤10 Hes | Rth|≤25; preferably | Re|≤5 Hes | Rth|≤10, more preferably | and Re|≤2 Hes | Rth|≤5.By the optical compensating layer of specific birefringence rate being arranged having less optically anisotropic cellulose acylate film upper strata pressing element, can bring into play the optical compensation function of optical compensating layer effectively.
Preferably, used transparent protective film has the optical anisotropy distribution of less plane among the present invention.Particularly preferably be | Re (MAX)-Re (MIN) |≤6 Hes | Rth (MAX)-Rth (MIN) |≤10, preferred | Re (MAX)-Re (MIN) |≤3 Hes | Rth (MAX)-Rth (MIN) |≤5.
In following formula, Re (MAX) and Rth (MAX) are the 1m that downcuts at random 2The maximum delay value of diaphragm (by nm); Re (MIN) and Rth (MIN) are its minimum delay values (by nm).
By regulating the plane optical anisotropy of transparent protective film, can also regulate the optical anisotropy of the optical compensating polarizing plate that uses its manufacturing.Thereby, can reduce the demonstration degree of irregularity of the liquid crystal flat-panel that uses it.
The film with less Re and Rth (that is, the optical isotropy film) used among the present invention shows less Re in the stretching attitude, and can keep low-level in-plane scatter, stretches even occur various transmission aborning.Therefore, showing less membrane plane optical anisotropy distributes.
In the present invention, the also preferred cellulose acylate film that uses with less Wavelength distribution.Preferably | Re (400)-Re (700)|≤10 Hes | Rth (400)-Rth (700)|≤35, preferred | Re (400)-Re (700)|≤5 Hes | Rth (400)-Rth (700)|≤25, preferred especially | Re (400)-Re (700)|≤3 Hes | Rth (400)-Rth (700)|≤15.
Preferably above-mentioned transparent protective film is the film that stretches.Stretching can be by uniaxial tension or biaxial stretch-formed carrying out.Biaxial stretch-formed film is particularly preferred.
Usually, the intensity of the membrane material that can improve by stretching provides to have the mechanical property of improving toughness.Yet many materials produce phase differential because of stretching.This film can not be used as the diaphragm that polarizer is used.
On the other hand, transparent protective film of the present invention is a kind of changes in optical properties that causes because of stretching less cellulose acylate film of change in size less or that cause in conjunction with the back stress.Therefore, this film is suitable for use as the diaphragm that polarizer is used.Preferably | Re (n)-Re (0) |/n≤1.0, more preferably | and Re (n)-Re (0) |/n≤0.5.
In following formula, Re (n) is the plane length of delay (by nm) of the film of stretching n (%); And Re (0) is the plane length of delay (by nm) of the film that do not stretch.
Further preferably, the film thickness of transparent protective film is 10～120 μ m among the present invention, more preferably 40～100 μ m, preferred especially 60～80 μ m.
The optical property of transparent protective film changes with environmental change among the present invention, preferably handles under 60 ℃ and 90%RH after 240 hours, and Re and Rth change and be 15nm or littler, more preferably 10nm or littler, more preferably 5nm or littler.Further preferably processing is after 240 hours down at 80 ℃, and the Re of transparent protective film and Rth variation are 15nm or littler, more preferably 5nm or littler.
By regulating the optical anisotropy and the dispersiveness of the transparent protective film that above-mentioned polarizer uses, can easily design the optical compensating layer of lamination thereon, and the optical compensating polarizing plate with high compensation effect is provided.
Although be not particularly limited the thickness of optical compensating layer in the present invention, scope is about 2～200 μ m usually, preferred 10～100 μ m.
The invention still further relates to a kind of image-display units that uses above-mentioned optical compensating polarizing plate.
As image-display units of the present invention, the liquid crystal display of IPS pattern is fit to.By the optical compensating layer of the invention described above is provided, can reduce the light leak that in the black demonstration of the liquid crystal display of IPS pattern, occurs on the surface of the liquid crystal cell of IPS pattern.The liquid crystal display of this IPS pattern all has the high-contrast ratio in all directions, thereby easily realizes having the visual display at wide visual angle.
Below, the preferred embodiment of the liquid crystal display of the IPS pattern of using optical compensating polarizing plate of the present invention is described.
(1) a kind of liquid crystal display; optical compensating polarizing plate wherein of the present invention is arranged on brilliant first substrate of watching side; polarizing plate is arranged on brilliant first substrate dorsad on that side of liquid crystal cell; this polarizing plate has and is laminated to polarizer at least on the one side | Re|≤10 Hes | and the above-mentioned transparent protective film of Rth|≤25, the extraordinary refractive index direction of liquid crystal material is not parallel to the absorption axes direction of polarizing plate in the liquid crystal cell when applying voltage.
(2) a kind of liquid crystal display; wherein polarizing plate is arranged on brilliant first substrate of watching side; this polarizing plate has on the one side at least that is laminated to polarizer | Re|≤10 Hes | and the above-mentioned transparent protective film of Rth|≤25; optical compensating polarizing plate of the present invention is arranged on brilliant first substrate and watches dorsad on that side of side, and the extraordinary refractive index direction of the liquid crystal material when not applying voltage in the liquid crystal cell is perpendicular to the absorption axes direction of polarizing plate.
By the transparent protective film that will use in the optical compensating polarizing plate of the present invention as being arranged on the present invention's at least one in two transparent protective films of the polarizing plate in the liquid crystal cell side of optical compensating polarizing plate dorsad, thereby easily be implemented in all directions all have high-contrast than and the visual display at wide visual angle.
By optical compensating polarizing plate of the present invention is applied to image-display units, particularly liquid crystal display can improve demonstration contrast and viewing angle characteristic, and can not reduce the forward contrast, favourable picture characteristics is provided, thereby has obtained having the picture characteristics of wide visual angle and high-contrast.Optical compensating polarizing plate of the present invention is useful in the liquid crystal display of operating with the IPS pattern.In addition, optical compensating polarizing plate of the present invention optical property under high-temperature and high humility worsens less.
Embodiment
Below, optical compensating polarizing plate of the present invention and image-display units are described.Optical compensating polarizing plate of the present invention is a kind ofly to obtain polarizing plate by lamination transparent protective film on two surfaces of polarizer; and further laminated optical layer of compensation and the optical compensating polarizing plate that is configured on the one side; wherein at least one transparent protective film is a cellulose acylate film; the length of delay Rth (by nm) of its plane length of delay Re (by nm) and film thickness direction satisfies following formula (I) and (II) (hereinafter is called " cellulose acylate film of the present invention ") and respectively by the following formula (III) and (IV) Nz and the Re of optical compensating layer of definition 1Satisfy following formula (V) and (VI):
(I)|Re|≤10
(II)|Rth|≤25
(III)Nz＝(nx 1-nz 1)/(nx 1-ny 1)
(IV)Re 1＝(nx 1-ny 1)×d 1
(V)0.4≤Nz≤0.6
(VI)100≤Re 1≤350
Re wherein 1It is the plane length of delay (by nm) under the wavelength 590nm; Nz is the Nz factor under the wavelength 590nm; Nx 1It is refractive index along the membrane plane slow axis; Ny 1Be the refractive index of edge perpendicular to the direction of membrane plane slow axis; Nz 1It is refractive index along film thickness direction; And d 1Be the thickness (by nm) of film.
In addition, carry out lamination and make the absorption axes of polarizer, the slow axis of optical compensating layer is perpendicular to one another with the slow axis of transparent protective film or is parallel.The angle of the continuous rolling cohesive process from lamination step considers, preferably makes the absorption axes of polarizer be parallel to the slow axis of optical compensating layer.
Next, describe cellulose acylate film of the present invention in detail.
[the raw material cotton that is used for the synthetic cellulose acylate]
The example that is used for the raw cellulose of synthetic cellulose acylate in the present invention comprises velveteen and wood pulp (hard wood pulp and soft wood pulp).Can use from any cellulosic material and obtain cellulose acylate, also can use potpourri in some cases.The cotton write up of these raw materials is at for example Purasuchikku Zairyo Koza (17), Senisokei Jushi (Marusawa and Uda, TheNikkan Kogyo Shinbun, Ltd., 1970) and Japan Institute of Invention andInnovation Journal of Technical Disclosure No.2001-1745, in 7～8 pages.That is, can use wherein the cellulosic material of report, the material of cellulose acylate film of the present invention is not particularly limited.
Below, illustrate from the cellulose acylate film of the present invention of above-mentioned cellulosic material preparation.In cellulose acylate of the present invention, the hydroxyl in the cellulose is by acidylate.As substituting group, can use acyl group with 2～22 carbon atoms.In cellulose acylate of the present invention, the degree of substitution of the hydroxyl in the cellulose is not particularly limited.The combination degree of acetate that can be by measuring hydroxyl in the substituted cellulose or the fatty acid with 3～22 carbon atoms is also determined degree of substitution by calculating.Can measure according to ASTM D-817-91.
As mentioned above, in cellulose acylate of the present invention, the degree of substitution of hydroxyl is not particularly limited in the cellulose.Preferably acyl group is 2.70～3.00 to the degree of substitution of hydroxyl, more preferably 2.85～3.00, more preferably 2.90～3.00.
The acyl group of substituted hydroxy can be aliphatic group or the allyl with 2～22 carbon atoms.Can use for example cellulosic alkyl-carbonyl ester, the alkenyl carbonyl ester, fragrant carbonyl ester and aromatic alkyl carbonyl ester, each randomly has other substituting group.The preferred example of acyl group comprises acetyl group, propiono, bytyry; heptanoyl group, caproyl, caprylyl; capryl, dodecane acyl group, tridecane acyl group; tetradecane acyl group, hexadecane acyl group, octadecanoyl; isobutyryl, uncle's bytyry, cyclohexane carbonyl; oleoyl, benzoyl, naphthyl carbonyl and cinnamoyl.Wherein, acetyl group, propiono, bytyry, dodecane acyl group, octadecanoyl, uncle's bytyry, oleoyl, benzoyl, naphthyl carbonyl, cinnamoyl are preferred, acetyl group, and propiono and bytyry are preferred.
Further preferably use the cellulose acylate potpourri, the cellulose acylate that satisfies all qualifications of following formula (XII)～(XIV) is particularly preferred.
Formula (XII) 2.50≤SA+SB≤3.00
Formula (XIII) 0≤SA≤2.5
Formula (XIV) 0.5≤SB≤3.00.
In following formula, SA is the degree of substitution of acetyl group; With SB be the degree of substitution of acyl group with replacement of 3～22 carbon atoms.
Herein, term " degree of substitution of acetyl group " refers to that at cellulose 2-the acidylate of 3-and 6-position is than sum (that is, degree of substitution 1 shows 100% acidylate).In the present invention, preferably 2.60≤SA+SB≤3.00, more preferably 2.67≤SA+SB≤2.97.About SA, further preferably 0≤SA≤2.20, more preferably 0≤SA≤2.0.About SB, further preferably 0.80≤SB≤2.97, more preferably 1.25≤SB≤2.97.Although in the present invention to cellulose 2-, the hydroxyl degree of substitution of 3-and 6-position is not particularly limited, the hydroxyl degree of substitution of 6-position preferably 0.7 or bigger, more preferably 0.8 or bigger, more preferably 0.85 or bigger.Because this structure not only can prevent to degrade because of the cellulose acylate that the electron beam irradiation causes, can also improve solubleness and improve moisture-proof and thermotolerance.
In cellulose acylate of the present invention, the acyl group with 3～22 carbon atoms of substituent B representative can be aliphatic acyl radical or aromatic acyl.Acyl group in cellulose acylate of the present invention is under the situation of aliphatic acyl radical, and it preferably has 3～18 carbon atoms, more preferably 3～12 carbon atoms, more preferably 3～8 carbon atoms.The example of this aliphatic acyl radical comprises alkyl-carbonyl, alkenyl carbonyl and alkynyl carbonyl.Acyl group in cellulose acylate of the present invention is under the situation of aromatic acyl, and it preferably has 6～22 carbon atoms, more preferably 6～18 carbon atoms, more preferably 6～12 carbon atoms.
The preferred example of cellulose acylate of the present invention comprises cellulose ethanoate; cellulose propionate; cellulose butylate; the cellulose ethanoate propionic ester; cellulose acetate butyrate, cellulose propionate butyric ester, cellulose ethanoate propionic ester butyric ester; the cellulose ethanoate capronate; the cellulose ethanoate caprylate, cellulose ethanoate cyclohexanoate ester, cellulose ethanoate decylate; cellulose ethanoate adamantanecarboxylic acid ester; cellulose acetate acid sulfuric ester, cellulose ethanoate carbamate, cellulose propionate sulfuric ester; cellulose ethanoate propionic ester sulfuric ester, cellulose ethanoate phthalic ester etc.More preferably example comprises cellulose ethanoate, cellulose propionate, cellulose butylate, cellulose ethanoate propionic ester, cellulose acetate butyrate, cellulose propionate butyric ester, cellulose ethanoate capronate, cellulose ethanoate caprylate etc.Its more preferably example comprise cellulose ethanoate, cellulose propionate, cellulose butylate, cellulose ethanoate propionic ester and cellulose acetate butyrate.In this case, acetyl group and degree of substitution with acyl group of 3 or more a plurality of carbon atoms fall into respectively in the above-mentioned scope.Can obtain required characteristic according to degree of substitution.
[degree of polymerization of cellulose acylate]
The degree of polymerization of cellulose acylate of the present invention (expressing with viscosity-average degree of polymerization) is preferably 180～700.In cellulose ethanoate, the degree of polymerization is preferably 180～550, and more preferably 180～400, preferred especially 180～350.Under the too high situation of the degree of polymerization, the dope of cellulose acylate has high viscosity, therefore, almost can not form film by casting.Can be by restriction viscosimetry (KazuoUda ﹠amp; Hideo Saito, SFN-I GAKKAISHI, Vol.18, No.1,105-120 page or leaf, 1962) the measurement average degree of polymerization.The method is documented among the JP-A-9-95538 in more detail.
Analyze the molecular weight distribution of cellulose acylate of the present invention by gel permeation chromatography.Less polydispersity index Mw/Mn (Mw: weight-average molecular weight, Mn: number-average molecular weight) and narrower molecular weight distribution be preferred.More specifically, Mw/Mn is preferably 1.0～3.0, and more preferably 1.0～2.0, most preferably 1.0～1.6.
When removing low molecular weight compositions, mean molecular weight (degree of polymerization) increases, but viscosity is lower than the plain acylate of general fibre, thereby can use.By from the cellulose acylate that synthesizes with conventional method, removing the cellulose acylate that low molecular weight compositions can obtain containing a small amount of low molecular weight compositions.Can be by removing low molecular weight compositions with the organic solvent washing cellulose acylate that is fit to.Contain in preparation under the situation of cellulose acylate of less low molecular weight compositions, preferably the amount with sulfuric acid catalyst in the acetylation controls to 0.5～25 mass parts/100 mass parts cellulose acylates.Consider (that is, having uniform molecular weight distribution) from the angle that helps molecular weight distribution, be controlled in the above-mentioned scope by amount with sulfuric acid catalyst, can the synthetic cellulose acylate.In making cellulose acylate process of the present invention, liquid water content is than 2 quality % or littler preferably, more preferably 1 quality % or littler, preferred especially 0.7 quality % or littler.Usually, cellulose acylate contains water, is known that the liquid water content ratio is 2.5～5 quality %.For regulating the liquid water content ratio of cellulose acylate of the present invention, need the plain acylate of dried fibres.Drying means is not particularly limited, as long as can reach required liquid water content ratio.As the cotton and employed synthetic method of raw material that is used to obtain cellulose acylate; can use write up at Japan Institute ofInvention and Innovation Journal of Technical Disclosure No.2001-1745 (2001.03.15; Japan Institute of Invention and Innovation), raw material cotton and the synthetic method in 7～12 pages.
As cellulose acylate of the present invention, can also use the potpourri of two or more cellulose acylates, as long as these cellulose acylates satisfy above-mentioned substituting group, degree of substitution, the degree of polymerization, the demand of molecular weight distribution etc.
[adjuvant of cellulose acylate]
Can according to purpose in each step of producing in cellulose acylate solution of the present invention (dope), add various adjuvants and (for example, reduce optically anisotropic compound; the wavelength dispersion correctives, UV-blocking agent, plastifier; antidegradant, fine particle, optical characteristics-controlling agent etc.).Below these adjuvants will be described.These adjuvants can add in the step of preparation dope.Selectively, the step that in the final step of preparation dope, adds adjuvant.
Cellulose acylate film preferably of the present invention contains at least aly can reduce optically anisotropic compound, particularly the length of delay Rth of film thickness direction is reduced to and satisfies following formula (IX) and scope (X):
(IX) (Rth(A)-Rth(0))/A≤1.0
(X) 0.1≤A≤30
Preferably, following formula (IX) and (X) be:
(IX) (Rth(A)-Rth(0))/A≤-2.0
(X) 0.05≤A≤25。
Following formula (IX) and (X) be preferably:
(IX) (Rth(A)-Rth(0))/A≤-3.0
(X) 0.1≤A≤20。
In following formula, Rth (A) is the Rth (nm) of film that contains the compound that can reduce Rth of A%; Rth (0) is the Rth (nm) that does not contain the film of the compound that can reduce Rth; A is that the polymer quality as membrane material is the quality (%) of 100 o'clock compounds.
[reducing the architectural characteristic of the optically anisotropic compound of cellulose acylate film]
Below, the optically anisotropic compound that reduces cellulose acylate film is described.
The present inventor has carried out broad research, suppresses the compound of cellulose acylate in the orientation of membrane plane and film thickness direction by using, and has fully reduced optical anisotropy, thereby Re is reduced to 0, Rth is reduced to approaches 0.For this reason, advantageously use and reduce optically anisotropic compound, itself and cellulose acylate are fully compatible, and itself have club shaped structure or planar structure.Under the situation with a plurality of plane functional groups such as aromatic group, more specifically, having not, the nonplanar structure of these functional groups in a plane is favourable.
As the example of the optically anisotropic compound that reduces cellulose acylate film, can use the compound of following formula (1)～(19) representative.
Formula (1)
In following formula, R 11～R 13Each represents the aliphatic group with 1～20 carbon atom independently.R 11～R 13Can be bonded to and form ring together.
Formula (2) formula (3)
In formula (2) and (3), Z represents carbon atom, oxygen atom, sulphur atom or-NR 25-, R wherein 25Represent hydrogen atom or alkyl.The 5-or the 6-unit ring that contain Z can have substituting group.Y 21And Y 22Each represents the ester group with 1～20 carbon atom independently, alkoxy carbonyl, acylamino-or carbamyl.Y 21And Y 22Can be bonded to and form ring together.M is 1～5 integer, and n is 1～6 integer.
Figure A20058001608900241
In formula (4)～(12), Y 31～Y 70Each represents the ester group with 1～20 carbon atom independently, has 1～20 carbon atom alkoxy carbonyl, has the acylamino-of 1～20 carbon atom, has the carbamyl or the hydroxyl of 1～20 carbon atom.V 31～V 43The aliphatic group that each is represented hydrogen atom independently or has 1～20 carbon atom.L 31～L 80Each represents the divalence saturated linker group that has 0～40 atom, comprises 0～20 carbon atom independently.L with 0 atom 31～L 80Refer to that the group that is positioned at the linking group two ends directly forms singly-bound.V 31～V 43And L 31～L 80Can also have substituting group.
Formula (13)
In following formula, R 1Represent alkyl or aryl.R 2And R 3Each represents hydrogen atom, alkyl or aryl independently.R 1, R 2And R 3Have 10 or more a plurality of carbon atom altogether, each in these groups can have substituting group.
Formula (14)
Figure A20058001608900252
In following formula, R 4And R 5Each represents alkyl or aryl independently.R 4And R 5Have 10 or more a plurality of carbon atom altogether, each in these groups can have substituting group.
Formula (15)
In following formula, R 1, R 2And R 3Each represents hydrogen atom or alkyl independently.The divalent linker that the X representative is formed by following group 1 one or more group that is selected from linking group.Y represents alkyl, aryl or aralkyl.
(group 1 of linking group) singly-bound ,-O-,-CO-,-NR 4-, alkylidene and arlydene, wherein R 4Represent hydrogen atom, alkyl, aryl or aralkyl.
Formula (16)
Figure A20058001608900254
In following formula, Q 1, Q 2And Q 3Each represents 5-or 6-unit ring independently.X represents B, C-R (wherein R represents hydrogen atom or substituting group), N, P or P=O.
Formula (17)
In following formula, X 2Represent B, C-R (wherein R represents hydrogen atom or substituting group) or N.R 11, R 12, R 13, R 14, R 15, R 21, R 22, R 23, R 24, R 25, R 31, R 32, R 33, R 34And R 35Each represents hydrogen atom or substituting group.
Formula (18)
Figure A20058001608900262
In following formula, R 1Represent alkyl or aryl.R 2And R 3Each represents hydrogen atom, alkyl or aryl independently.Alkyl and aryl can have substituting group.
The preferred example of formula (18) representative compound is the compound of formula (19) representative.
Formula (19)
Figure A20058001608900263
In following formula (19), R 4, R 5And R 6Each represents alkyl or aryl independently.Alkyl can be straight chain, side chain or naphthenic base.Alkyl preferably has 1～15, and more preferably 1～15,1～12 carbon atom most preferably.As naphthenic base, cyclohexyl is particularly preferred.Aryl preferably has 6～36, more preferably 6～24 carbon atoms.
Abovementioned alkyl and aryl can also have substituting group.The example of preferred substituents comprises halogen atom (for example, chlorine, bromine, fluorine and iodine), alkyl, aryl, alkoxy, aryloxy group, acyl group, alkoxy carbonyl, aryloxycarbonyl, acyloxy, sulfuryl amino, hydroxyl, cyano group, amino and acyl amino.Its more preferably example comprise halogen atom, alkyl, aryl, alkoxy, aryloxy group, sulfuryl amino and acyl amino.Its particularly preferred example comprises alkyl, aryl, sulfuryl amino and acyl amino.
In above-claimed cpd, formula (13), the compound of (18) and (19) representative is preferred.Preferably use at least a compound wherein.
(LogP value)
For preparing cellulose acylate film of the present invention, thereby cellulose acylate reduces in membrane plane and film thickness direction orientation that the preferred octanol-water partition coefficient (logP value) of using is 0～7 compound in the optically anisotropic compound from prevent film.It is relatively poor with the compatibility of cellulose acylate that the logP value surpasses 7 compound, therefore often makes the film muddiness or haze.The logP value has high-hydrophilic less than 0 compound, destroys the water tolerance of cellulose acylate film sometimes.More preferably the logP value is 1～6, preferred especially 1.5～5.
Octanol-water partition coefficient (logP value) can be measured with the flask succusion according to JIS Z7260-107 (2000).Can also be without actual measurement but with calculating or empirical method estimation octanol-water partition coefficient (logP value).As computing method, the preferred Crippen cracking process (J.Chem.Inf.Comput.Sci. that uses, 27,21 (1987)), Viswanadhan cracking process (J.Chem.Inf.Comput.Sci., 29,163 (1989)), Broto cracking process (Eur.J.Med.Chem.-Chim.Theor., 19,71 (1984)) etc.More preferably use Crippen cracking process (J.Chem.Inf.Comput.Sci., 27,21 (1987)).When the logP value of the compound of measuring by measuring method is different from its calculated value, advantageously use the Crippen cracking process to judge whether compound falls in the required scope.
[reducing the physical property of optically anisotropic compound]
Reducing optically anisotropic compound can contain aromatic group or do not contain.Preferably reducing optically anisotropic compound molecular weight is 150 or bigger, but is no more than 3000, more preferably 170 or bigger but be no more than 2000, more preferably 200 or bigger but be no more than 1000.As long as molecular weight falls into this scope, oligomer or polymer architecture that compound can have the specific monomer structure or be linked together and constituted by a plurality of monomeric units.
Preferably reducing optically anisotropic compound is that liquid or fusing point are 25～250 ℃ solid under 25 ℃.Preferred compound is that liquid or fusing point are 25～200 ℃ solid under 25 ℃.Further preferably reducing optically anisotropic compound does not evaporate in dope casting that forms cellulose acylate film and dry run.
By solid cellulose acylate content, the preferred addition that reduces optically anisotropic compound is 0.01～30 quality %, more preferably 1～25 quality %, preferred especially 5～20 quality %.
Can use the simplification compound as reducing optically anisotropic compound.Selectively, can use the potpourri of two or more compounds of any ratio.
Reducing optically anisotropic compound can add in any step of preparation dope.Can add in the final step of dope preparation.
Reducing optically anisotropic compound, to begin to the average content corresponding to total film thickness 10% part from the surface of at least one side be 80～99% of cellulose acylate film center compound average content.Can by use the infrared spectrum method quantitative measurement for example be documented among the JP-A-8-57879 from the teeth outwards with the compound of center, measure compounds content.
Below, the object lesson of the optically anisotropic compound of reduction cellulose acylate film used among the present invention is described, but the invention is not restricted to these compounds.
At first, the compound of formula (1).
In formula (1), R 11～R 13Each represents the aliphatic group with 1～20 carbon atom independently.R 11～R 13Can be bonded to and form ring together.
Below, illustrate in greater detail R 11～R 13R 11～R 13Each is represented independently has 1～20, preferred 1～16, more preferably the aliphatic group of 1～12 carbon atom.Term " aliphatic group " preferably refers to aliphatic alkyl herein, more preferably alkyl (comprising straight chain, side chain and naphthenic base), alkenyl or alkynyl.The example of alkyl comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, tertiary pentyl, n-hexyl, n-octyl, decyl, dodecyl, eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, suberyl, 2,6-Dimethylcyclohexyl, 4-tert-butylcyclohexyl, cyclopentyl, 1-adamantyl, 2-adamantyl, dicyclo [2.2.2] octane-3-base etc.The example of thiazolinyl comprises vinyl, allyl, prenyl, geranyl, oil base, 2-cyclopentene-1-base, 2-cyclohexene-1-base etc.The example of alkynyl comprises ethinyl and propargyl etc.
R 11～R 13The aliphatic group of representative can replace.Substituent example comprises halogen atom (for example, chlorine, bromine; fluorine and iodine), alkyl (comprises straight chain; side chain and naphthenic base, bicyclic alkyl and active methylene); thiazolinyl, alkynyl, aryl; heterocyclic radical (at any the position of substitution), acyl group, alkoxy carbonyl; aryloxycarbonyl, heterocycle oxygen carbonyl, carbamyl; N-acyl amino formoxyl, N-sulfuryl amino formoxyl, N-carbamyl carbamyl; N-sulfamoyl carbamyl, carbazole group, carboxyl or its salt; the oxalyl group, oxamoyl group, cyano group; the inferior acylamino-of carbon, formoxyl, hydroxyl; alkoxy (comprising inferior ethoxyl group or inferior propoxyl group group repetitive), aryloxy group, heterocyclic oxy group group; acyloxy, (alkoxy or aryloxy group) carbonyl oxygen base, carbamoyloxy; sulfonyloxy, amino, (alkyl; aryl or heterocycle) amino, acyl amino, sulfonamido; urea groups, ghiourea group, inferior acylamino-; (alkoxy or aryloxy group) carbonylamino, sulfamoyl amino, semicarbazides group; the group that ammonia is molten; oxamoyl base amino, N-(alkyl or aryl) sulfonyl urea groups, N-acyl group urea groups; N-acyl group sulfamoyl; heterocyclic radical (for example, pyridine group, imidazoline group with season nitrogen-atoms; quinoline group and isoquinoline group); isocyano group, imino group, (alkyl or aryl) sulfonyl; (alkyl or aryl) sulfenyl group; sulfonic group or its salt, sulfamoyl, N-acyl group sulfamoyl; N-Herbicidal sulphonylamino sulfonyl or its salt; phosphino-, phosphinyl, phosphinyl oxygen groups; phosphinyl amino, silicyl etc.
In addition, these groups can be grouped together and form compound substituting group.This substituent example comprises the ethoxy ethoxy ethyl, hydroxyl ethoxy ethyl, ethoxy carbonyl ethyl etc.R 11～R 13Can also have bound phosphate groups as substituting group.Each molecule of compound of formula (1) can have a plurality of bound phosphate groups.
Next, the compound of formula (2) and (3).In formula (2) and (3), Z represents carbon atom, oxygen atom, sulphur atom or-NR 25, R wherein 25Represent hydrogen atom or alkyl.The 5-or the 6-unit ring that contain Z can have substituting group.A plurality of substituting groups can be bonded to and form ring together.Contain the 5-of Z or the example of 6-unit ring and comprise tetrahydrofuran, oxinane, thiophane, thia cyclohexane (thiane), pyrrolidine, piperidines, indoline, isoindoline, benzodihydropyran, isochroman, tetrahydrochysene-2-furanone, tetrahydrochysene-2-pyrone, 4-butane lactams, 6-hexanol lactams etc.
The 5-or the 6-unit ring that contain Z comprise lactone structure or lactams structure promptly having the cyclic ester or the cyclic amides structure of oxygen groups on the carbon atom adjacent with Z.This cyclic ester or cyclic amides example of structure comprise 2-Pyrrolidone, 2-piperidones, 5-valerolactone (pentanolide) and 6-caprolactone (hexanolide).
R 25Represent hydrogen atom or preferably have 1～20 carbon atom, more preferably 1～16 carbon atom, the alkyl of preferred especially 1～12 carbon atom (comprising straight chain, side chain and naphthenic base).R 25The example of the alkyl of representative comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, tertiary pentyl, n-hexyl, n-octyl, decyl, dodecyl, eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, suberyl, 2,6-Dimethylcyclohexyl, 4-tert-butylcyclohexyl, cyclopentyl, 1-adamantyl, 2-adamantyl, dicyclo [2.2.2] octane-3-base etc.R 25The alkyl of representative can replace.As substituent example, can use R 11～R 13Substituent example described those.
Y 21And Y 22Each represents ester group independently, alkoxy carbonyl, acylamino-or carbamyl.Ester group preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom.Its example comprises acetoxyl group, ethyl oxy carbonyl, carbonyl propyl oxygen base, normal-butyl carbonyl oxygen base, isobutyl carbonyl oxygen base, tert-butyl group carbonyl oxygen base, sec-butyl carbonyl oxygen base, n-pentyl carbonyl oxygen base, tertiary pentyl carbonyl oxygen base, n-hexyl carbonyl oxygen base, cyclohexyl carbonyl oxygen base, 1-ethyl pentyl group carbonyl oxygen base, n-heptyl carbonyl oxygen base, n-nonyl carbonyl oxygen base, n-undecane base carbonyl oxygen base, benzyl carbonyl oxygen base, 1-naphthalene carbonyl oxygen base, 2-naphthalene carbonyl oxygen base, 1-diamantane carbonyl oxygen base etc.Alkoxy carbonyl preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom.Its example comprises methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, n-butoxy carbonyl, tert-butoxycarbonyl, isobutoxy carbonyl, sec-butoxy carbonyl, n-pentyloxy carbonyl, tert-pentyloxy carbonyl, positive hexyloxy carbonyl, cyclohexyloxy carbonyl, 2-ethyl hexyl oxy carbonyl, 1-ethyl propoxycarbonyl, n-octyloxy carbonyl, 3,7-dimethyl-3-carbonyl octyloxy, 3,5,5-trimethyl hexyloxy carbonyl, 4-tert-butyl group cyclohexyloxy carbonyl, 2,4-dimethyl amyl group-3-oxygen carbonyl, 1-Buddha's warrior attendant alkoxy carbonyl group, 2-Buddha's warrior attendant alkoxy carbonyl group, dicyclopentadienyl oxygen carbonyl, positive decyl oxygen carbonyl, dodecyl oxygen carbonyl, n-tetradecane base oxygen carbonyl, n-hexadecyl oxygen carbonyl etc.Acylamino-preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom.Its example comprises acetylamino, ethyl acylamino-, n-pro-pyl acylamino-, the isopropyl acylamino-, normal-butyl acylamino-, tert-butyl group acylamino-, the isobutyl acylamino-, the sec-butyl acylamino-, n-pentyl acylamino-, tertiary pentyl acylamino-, the n-hexyl acylamino-, the cyclohexyl acylamino-, 1-ethyl pentyl group acylamino-, 1-ethyl propyl acylamino-, the n-heptyl acylamino-, the n-octyl acylamino-, 1-diamantane acylamino-, 2-diamantane acylamino-, the n-nonyl acylamino-, the dodecyl acylamino-, n-pentane acylamino-, n-hexadecyl acylamino-etc.Carbamyl preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom.Its example comprises the methylamino formoxyl, formyl-dimethylamino, ethylamino formoxyl; the diethylamino formoxyl; the n-pro-pyl carbamyl, isopropyl carbamyl, normal-butyl carbamyl; tert-butyl group carbamyl; the isobutylamino formoxyl, sec-butyl carbamyl, n-pentyl carbamyl; the tertiary pentyl carbamyl; the n-hexyl carbamyl, cyclohexyl carboxyamide base, 2-ethylhexyl carbamyl; 2-ethyl-butyl carbamyl; uncle's octyl group carbamyl, n-heptyl carbamyl, n-octyl carbamyl; 1-diamantane carbamyl; 2-diamantane carbamyl, positive decyl carbamyl, dodecyl carbamyl; n-tetradecane base carbamyl, n-hexadecyl carbamyl etc.Y 21And Y 22Can be bonded to and form ring together.Y 21And Y 22Can also have substituting group.As substituent example, can use R 11～R 13Substituent example described those.M is 1～5, preferred 1～3.N is 1～6, preferred 1～3.
Next, the compound of formula (4)～(12).
In formula (4)～(13), Y 31～Y 70Each represents ester group independently, alkoxy carbonyl, acylamino-, carbamyl or hydroxyl.Ester group preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom.Its example comprises acetoxyl group, ethyl oxy carbonyl, carbonyl propyl oxygen base, normal-butyl carbonyl oxygen base, isobutyl carbonyl oxygen base, tert-butyl group carbonyl oxygen base, sec-butyl carbonyl oxygen base, n-pentyl carbonyl oxygen base, tertiary pentyl carbonyl oxygen base, n-hexyl carbonyl oxygen base, cyclohexyl carbonyl oxygen base, 1-ethyl pentyl group carbonyl oxygen base, n-heptyl carbonyl oxygen base, n-nonyl carbonyl oxygen base, n-undecane base carbonyl oxygen base, benzyl carbonyl oxygen base, 1-naphthalene carbonyl oxygen base, 2-naphthalene carbonyl oxygen base, 1-diamantane carbonyl oxygen base etc.Alkoxy carbonyl preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom.Its example comprises methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, n-butoxy carbonyl, tert-butoxycarbonyl, isobutoxy carbonyl, sec-butoxy carbonyl, n-pentyloxy carbonyl, tert-pentyloxy carbonyl, positive hexyloxy carbonyl, cyclohexyloxy carbonyl, 2-ethyl hexyl oxy carbonyl, 1-ethyl propoxycarbonyl, n-octyloxy carbonyl, 3,7-dimethyl-3-carbonyl octyloxy, 3,5,5-trimethyl hexyloxy carbonyl, 4-tert-butyl group cyclohexyloxy carbonyl, 2,4-dimethyl amyl group-3-oxygen carbonyl, 1-Buddha's warrior attendant alkoxy carbonyl group, 2-Buddha's warrior attendant alkoxy carbonyl group, dicyclopentadienyl oxygen carbonyl, positive decyl oxygen carbonyl, dodecyl oxygen carbonyl, n-tetradecane base oxygen carbonyl, n-hexadecyl oxygen carbonyl etc.Acylamino-preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom.Its example comprises acetylamino, ethyl acylamino-, n-pro-pyl acylamino-, the isopropyl acylamino-, normal-butyl acylamino-, tert-butyl group acylamino-, the isobutyl acylamino-, the sec-butyl acylamino-, n-pentyl acylamino-, tertiary pentyl acylamino-, the n-hexyl acylamino-, the cyclohexyl acylamino-, 1-ethyl pentyl group acylamino-, 1-ethyl propyl acylamino-, the n-heptyl acylamino-, the n-octyl acylamino-, 1-diamantane acylamino-, 2-diamantane acylamino-, the n-nonyl acylamino-, the dodecyl acylamino-, n-pentane acylamino-, n-hexadecyl acylamino-etc.Carbamyl preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom.Its example comprises the methylamino formoxyl, formyl-dimethylamino, ethylamino formoxyl; the diethylamino formoxyl; the n-pro-pyl carbamyl, isopropyl carbamyl, normal-butyl carbamyl; tert-butyl group carbamyl; the isobutylamino formoxyl, sec-butyl carbamyl, n-pentyl carbamyl; the tertiary pentyl carbamyl; the n-hexyl carbamyl, cyclohexyl carboxyamide base, 2-ethylhexyl carbamyl; 2-ethyl-butyl carbamyl; uncle's octyl group carbamyl, n-heptyl carbamyl, n-octyl carbamyl; 1-diamantane carbamyl; 2-diamantane carbamyl, positive decyl carbamyl, dodecyl carbamyl; n-tetradecane base carbamyl, n-hexadecyl carbamyl etc.Y 31～Y 70Can also have substituting group.As substituent example, can use R 11～R 13Substituent example described those.
V 31～V 43Each is represented independently has 1～20, preferred 1～16, more preferably the aliphatic group of 1～12 carbon atom.Term " aliphatic group " preferably refers to aliphatic alkyl herein, more preferably alkyl (comprising straight chain, side chain and naphthenic base), alkenyl or alkynyl.The example of alkyl comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, tertiary pentyl, n-hexyl, n-octyl, decyl, dodecyl, eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, suberyl, 2,6-Dimethylcyclohexyl, 4-tert-butylcyclohexyl, cyclopentyl, 1-adamantyl, 2-adamantyl, dicyclo [2.2.2] octane-3-base etc.The example of thiazolinyl comprises vinyl, allyl, prenyl, geranyl, oil base, 2-cyclopentene-1-base, 2-cyclohexene-1-base etc.The example of alkynyl comprises ethinyl and propargyl etc.V 31～V 43Can also have substituting group.As substituent example, can use R 11～R 13Substituent example described those.
L 31～L 80Each represents the divalence saturated linker group that has 0～40 atom, comprises 0～20 carbon atom independently.
L with 0 atom 31～L 80Refer to that the group that is positioned at the linking group two ends directly forms singly-bound.L 31～L 80Preferred example comprise alkylidene (for example, methylene, ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene, hexa-methylene, methyl ethylidene, ethyl ethylidene etc.), ring divalent group (for example, cis-1,4-cyclohexylene, anti-form-1,4-cyclohexylene, 1,3-ring pentylidene etc.), ether, thioether, ester, acid amides, sulfone, sulfoxide, sulfide, sulfanilamide (SN), ureilene, thioureilene etc.These divalent groups can be bonded to and form the compound group of divalence together.This compound substituent example comprises-(CH 2) 2O (CH 2) 2-,-(CH 2) 2O (CH 2) O (CH 2)-,-(CH 2) 2S (CH 2) 2-,-(CH 2) 2O 2C (CH 2) 2-etc.L 31～L 80Can also have substituting group.As substituent example, can use R 11～R 13Substituent example described those.
In formula (4)～(12), pass through combination Y 31～Y 70, V 31～V 43And L 31～L 80The preferred example of the compound that forms comprises that citrate (for example; triethyl o-acetyl group citrate; tributyl o-acetyl group citrate; acetyl triethyl citrate; acetyl tributyl citrate; three (ethoxy carbonyl methylene) o-acetyl group citrate etc.); oleate (for example; the ethyl oleate; the butyl oleate; 2-ethylhexyl oleate; the phenyl oleate; the cyclohexyl oleate; octoil acid esters etc.); ricinoleate ester (for example; methyl acetyl ricinoleate ester etc.); sebacate (for example; dibutyl sebacate etc.); the glycerine carboxylate (for example; glyceryl acetate; glycerol butyrate etc.); ethyl glycolate (for example; butyl phthalyl butyl alcohol acid esters; ethyl phthalyl ethyl hexanol acid esters; methyl phthalyl ethyl hexanol acid esters; butyl phthalyl butyl alcohol acid esters; methyl phthalyl methyl ethanol acid esters; propyl group phthalyl propyl group ethyl glycolate; butyl phthalyl butyl alcohol acid esters; octyl group phthalyl octyl group ethyl glycolate etc.); the pentaerythrite carboxylate (for example; pentaerythrite tetra-acetate; pentaerythrite four butyric esters etc.); the dipentaerythritol carboxylate (for example; dipentaerythritol six acetic acid esters; dipentaerythritol six butyric esters; dipentaerythritol tetracetate etc.); the trimethylolpropane carboxylate (for example; the trimethylolpropane tris acetic acid esters; trimethylolpropane diacetate esters mono-propionate; the trimethylolpropane tris propionic ester; the trimethylolpropane tris butyric ester; the trimethylolpropane tris valerate; trimethylolpropane tris (tertiary butyl acetate); trimethylolpropane two-2 ethyl hexanoic acid ester; trimethylolpropane four-2 ethyl hexanoic acid ester; trimethylolpropane diacetate esters list caprylate, trimethylolpropane tris caprylate, trimethylolpropane tris (cyclohexane carboxylate) etc.); be documented in the glyceride among the JP-A-11-246704; be documented in two glyceride among the JP-A-2000-63560, be documented in the citrate among the JP-A-11-92574,2-pyrrolidone-5-carboxylic acid's ester (2-Pyrrolidone-5-carboxylic acid methyl ester; 2-Pyrrolidone-5-carboxylic acid ethyl ester; 2-Pyrrolidone-5-carboxylic acid butyl ester, 2-Pyrrolidone-5-carboxylic acid 2-ethylhexyl), cyclohexanedicarboxyester ester (cis-1; 2-cyclohexane dicarboxylic acid dibutyl ester; anti-form-1,2-cyclohexane dicarboxylic acid dibutyl ester, cis-1; 4-cyclohexane dicarboxylic acid dibutyl ester; anti-form-1,4-cyclohexane dicarboxylic acid dibutyl ester etc.), xylitol carboxylate (xylitol pentaacetate; the xylitol tetracetate, xylitol five propionic esters etc.) etc.
Next, list the example of the compound of formula used among the present invention (1)～(12) representative, but the invention is not restricted to this.(C-1～C-76) is the example of formula (1) compound to compound, and (C-201～C-231 and C-401～C-448) are the examples of formula (2)～(12) compound to compound.Shown in the table or the logP value that provides in the bracket be to measure by Crippen cracking process (J.Chem.Inf.Comput.Sci., 27,21 (1987)).
Figure A20058001608900351
In following formula, R 1～R 3With the R in (1) in the following formula 11～R 13Have identical meanings, its object lesson is by shown in following Compound C-1～C-76.
Compound R 1 R 2 R 3 logP
C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14 C-15 C-16 C-17 C-18 C-19 C-20 CH 3 C 2H 5 C 3H 7Different-C 3H 7 C 4H 9Different-C 4H 9The second month in a season-C 4H 9Uncle-C 4H 9 C 5H 11 CH 2C(CH 3) 3Ring-C 5H 91-ethyl propyl C 6H 13Ring-C 6H 11 C 7H 154-methylcyclohexyl 4-tert-butylcyclohexyl C 8H 172-ethylhexyl 3-methyl butyl C 2H 5 C 2H 5 C 3H 7Different-C 3H 7 C 4H 9Different-C 4H 9The second month in a season-C 4H 9Uncle-C 4H 9 C 5H 11 CH 2C(CH 3) 3Ring-C 5H 91-ethyl propyl C 6H 13Ring-C 6H 11 C 7H 154-methylcyclohexyl 4-tert-butylcyclohexyl C 8H 172-ethylhexyl 3-methyl butyl C 2H 5 C 2H 5 C 3H 7Different-C 3H 7 C 4H 9Different-C 4H 9The second month in a season-C 4H 9Uncle-C 4H 9 C 5H 11 CH 2C(CH 3) 3Ring-C 5H 91-ethyl propyl C 6H 13Ring-C 6H 11 C 7H 154-methylcyclohexyl 4-tert-butylcyclohexyl C 8H 172-ethylhexyl 3-methyl butyl 1.24 1.58 2.99 2.82 4.18 4.2 4.23 3.06 5.37 5.71 4.12 5.63 6.55 5.31 7.74 6.3 9.78 8.93 8.95 5.17
C-21 C-22 C-23 C-24 C-25 C-26 C-27 C-28 C-29 C-30 C-31 C-32 C-33 C-34 C-35 C-36 C-37 C-38 C-39 C-40 1,3-dimethylbutyl 1-isopropyl-2-methyl-propyl 2-ethyl-butyl 3,5,5-trimethyl hexyl cyclohexyl methyl CH 3 CH 3 CH 3 C 2H 5 C 2H 5 C 2H 5 C 4H 9 C 4H 9 C 4H 9 C 4H 9 C 4H 9 C 4H 9 C 4H 9 C 4H 9 C 4H 9 1,3-dimethylbutyl 1-isopropyl-2-methyl-propyl 2-ethyl-butyl 3,5,5-trimethyl hexyl cyclohexyl methyl CH 3 CH 3 CH 3 C 2H 5 C 2H 5 C 2H 5 C 4H 9 C 4H 9 C 4H 9 C 4H 9 C 4H 9 C 4H 9 C 4H 9 C 4H 9 C 4H 9 1,3-dimethylbutyl 1-isopropyl-2-methyl-propyl 2-ethyl-butyl 3,5,5-trimethyl hexyl cyclohexyl methyl 2-ethylhexyl 1-adamantyl C 12H 252-ethylhexyl 1-adamantyl C 12H 25Cyclohexyl C 6H 13 C 8H 172-ethylhexyl C 10H 21 C 12H 251-adamantyl C 16H 33Dicyclopentadienyl 6.41 8.05 6.57 9.84 6.25 3.35 2.27 4.93 4.04 2.96 5.62 4.55 4.97 5.76 5.77 6.55 7.35 4.69 8.93 4.68
C-41 C-42 C-43 C-44 C-45 C-46 C-47 C-48 C-49 C-50 C-51 C-52 C-53 C-54 C-55 C-56 C-57 C-58 C-59 C-60 C 6H 13 C 6H 13 C 6H 13 C 6H 13 C 6H 13 C 6H 134-chlorobutyl 4-chlorine hexyl 4-brombutyl 4-bromine hexyl (CH 2) 2OCH 2CH 3 C 8H 17 C 6H 13 C 4H 9 C 4H 9 C 6H 13 C 8H 17 C 4H 9 C 4H 9 C 4H 9 C 6H 13 C 6H 13 C 6H 13 C 6H 13 C 6H 13 C 6H 134-chlorobutyl 4-chlorine hexyl 4-brombutyl 4-bromine hexyl (CH 2) 2OCH 2CH 3 C 8H 17 C 6H 13 C 4H 9 C 4H 9 C 6H 13 C 8H 17 (CH 2) 2O(CH 2) 2OCH 2OH C 4H 9 CH 2CH＝CH 2 C 14H 29 C 8H 172-ethylhexyl C 10H 21 C 12H 251-adamantyl 4-chlorobutyl 4-chlorine hexyl 4-brombutyl 4-bromine hexyl (CH 2) 2OCH 2CH 3 (CH 2) 2O(CH 2) 2OCH 2CH 3 (CH 2) 2O(CH 2) 2OCH 2CH 3 (CH 2) 2O(CH 2) 2OCH 2CH 3 (CH 2) 2O(CH 2) 2OCH 2OH (CH 2) 2O(CH 2) 2OCH 2OH (CH 2) 2O(CH 2) 2OCH 2OH (CH 2) 2O(CH 2) 2OCH 2OH CH 2CH＝CH 2 CH 2CH＝CH 2 9.72 7.35 7.35 8.14 8.93 6.27 4.18 6.55 4.37 6.74 1.14 6.55 4.96 3.38 2.59 4.18 5.76 2.2 4.19 3.64
C-61 C-62 C-63 C-64 C-65 C-66 C-67 C-68 C-69 C-70 C-71 C-72 C-73 C-74 C-75 C-76 (CH 2) 2CO 2CH 2CH 3 (CH 2) 2CO 2(CH 2) 3CH 3 (CH 2) 2CONH(CH 2) 3CH 3 C 4H 9 C 4H 9 C 4H 9 C 4H 9 C 6H 13 C 6H 13Ring-C 6H 13 C 6H 12Cl C 4H 8Cl C 4H 8Cl C 4H 9 C 4H 9The 2-tetrahydrofuran base (CH 2) 2CO 2CH 2CH 3 (CH 2) 2CO 2(CH 2) 3CH 3 (CH 2) 2CONH(CH 2) 3CH 3 C 4H 9 C 4H 9 C 4H 9 C 4H 9 C 6H 13 C 6H 13Ring-C 6H 13 C 6H 12Cl C 4H 8Cl C 4H 8Cl C 4H 92-tetrahydrofuran base 2-tetrahydrofuran base (CH 2) 2CO 2CH 2CH 3(CH 2) 2CO 2(CH 2) 3CH 3(CH 2) 2CONH(CH 2) 3CH 3(CH 2) 4OP＝O(OC 4H 9) 2(CH 2) 4OP＝O(OC 4H 9) 2(CH 2) 4OP＝O(OC 4H 9) 2(CH 2) 2O(CH 2) 2OP＝O(OC 4H 9) 2(CH 2) 2O(CH 2) 2OP＝O(OC 4H 9) 2(CH 2) 4OP＝O(OC 4H 9) 2(CH 2) 2O(CH 2) 2OP＝O(OC 4H 9) 2(CH 2) 2O(CH 2) 2OP＝O(OC 4H 9) 2(CH 2) 2O(CH 2) 2OP＝O(OC 4H 9) 2(CH 2) 2O(CH 2) 2OP＝O(OC 4H 8Cl) 22-2-tetrahydrofuran base 2-2-tetrahydrofuran base 2-2-tetrahydrofuran base 1.1 3.69 1.74 6.66 6.21 6.16 5.99 7.58 8.25 6.35 7.18 5.6 5.59 3.27 2.36 1.45
Figure A20058001608900411
Figure A20058001608900421
Figure A20058001608900441
Below, the compound of formula (13) and (14).
In following formula (13), R 1Represent alkyl or aryl.R 2And R 3Each represents hydrogen atom, alkyl or aryl independently.Particularly preferably be R 1, R 2And R 3Middle carbon atom summation is 10 or bigger.In formula (14), R 4And R 5Each represents alkyl or aryl independently.R 4And R 5Middle carbon atom summation is 10 or bigger.Alkyl and aryl can have substituting group.The example of preferred substituents comprises fluorine atom, alkyl, aryl, alkoxy, sulfuryl group and sulfonamido.Wherein, alkyl, aryl, alkoxy, sulfuryl group and sulfonamido are particularly preferred.Alkyl can be straight chain, side chain or ring-type.Preferably alkyl has 1～25 carbon atom, and more preferably 6～25, preferred especially 6～20 carbon atoms (for example, methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, tertiary pentyl, hexyl, cyclohexyl, heptyl, octyl group, dicyclo octyl group, nonyl, adamantyl, decyl, uncle's octyl group, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl and eicosyl).Aryl preferably has 6～30 carbon atoms, more preferably 6～24 carbon atoms (for example, phenyl, xenyl, terphenyl, naphthyl, binaphthyl and triphenyl phenyl).Next, list the preferred example of the compound of formula (13) or formula (14) representative, but the invention is not restricted to these object lessons.
Figure A20058001608900451
Figure A20058001608900461
Figure A20058001608900471
Figure A20058001608900491
Next, the compound of formula (15) representative.
In following formula (15), R 1, R 2And R 3Each represents hydrogen atom or alkyl independently.As alkyl, the alkyl (for example, methyl, ethyl, propyl group, isopropyl, butyl, amyl group or isopentyl) with 1～5 carbon atom is preferred.Particularly preferably be R 1, R 2And R 3In at least one be alkyl (for example, methyl, ethyl, propyl group or isopropyl) with 1～3 carbon atom.X preferably represents by being selected from singly-bound ,-O-,-CO-,-NR 4-(R wherein 4Represent hydrogen atom, alkyl, aryl or aralkyl), alkylidene (preferably has 1～6 carbon atom, more preferably 1～3 carbon atom, as methylene, ethylidene or propylidene), or arlydene (preferably has 6～24 carbon atoms, more preferably 6～12 carbon atoms, as phenylene, diphenylene or naphthylene) the divalent linker that forms of one or more group.Y preferably represents hydrogen atom, and alkyl (preferably has 2～25 carbon atoms, more preferably 2～20 carbon atoms, as ethyl, isopropyl, the tert-butyl group, hexyl, the 2-ethylhexyl, uncle's octyl group, dodecyl, cyclohexyl, dicyclohexyl or adamantyl), aryl (preferably has 6～24 carbon atoms, more preferably 6～18 carbon atoms, as phenyl, xenyl or naphthyl), or aralkyl (preferably has 7～30 carbon atoms, more preferably 7～20 carbon atoms, as benzyl, tolyl, tert-butyl-phenyl, diphenyl methyl or trityl group).Alkyl, aryl or aralkyl are preferred.About combination-Y-Y, preferably-carbon atom summation among the X-Y is 0～40, more preferably 1～30, most preferably 1～25.Next, list the preferred example of the compound of formula (14) representative, but the invention is not restricted to these object lessons.
Figure A20058001608900511
Below, the compound of formula (15).
General formula (16)
Q 1, Q 2And Q 3Each represents 5-or 6-unit ring independently, can be hydrocarbon ring or heterocycle.This ring can be monocycle or form condensed ring with another ring.The preferred example of hydrocarbon ring comprises and replacing or unsubstituted cyclohexane ring, replaces or unsubstituted cyclopentane ring and aromatic hydrocarbon ring, more preferably aromatic hydrocarbon ring.The preferred example of heterocycle comprises having oxygen, and 5-and 6-unit at least a in nitrogen and the sulphur atom encircle.As heterocycle, have oxygen, at least a aromatic heterocycle is preferred in nitrogen and the sulphur atom.
Q 1, Q 2And Q 3Preferred example comprise aromatic hydrocarbon ring and aromatic heterocycle.The preferred example of aromatic hydrocarbon ring comprises monocycle with 6～30 carbon atoms and di-aromatics ring (phenyl ring for example, naphthalene nucleus etc.), aromatic hydrocarbon ring with 6～20 carbon atoms is preferred, and the aromatic hydrocarbon ring with 6～12 carbon atoms is preferred, and phenyl ring is preferred..
As aromatic heterocycle, have oxygen atom, the aromatic heterocycle of nitrogen-atoms or sulphur atom is preferred.The object lesson of heterocycle comprises furans, pyrroles, thiophene, imidazoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole, purine, thiazoline, thiazole, thiadiazoles,  azoles quinoline,  azoles, the  diazole, quinoline, isoquinoline, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthridines, azophenlyene, tetrazolium, benzimidazole, benzoxazol, benzothiazole, benzotriazole, four benzazoles etc.The preferred example of aromatic heterocycle comprises pyridine, triazine and quinoline.Q preferably 1, Q 2And Q 3Be aromatic hydrocarbon ring, more preferably phenyl ring.Q 1, Q 2And Q 3Can have substituting group, substituent example comprises below with the substituting group T that illustrates.
X represents B, C-R (wherein R represents hydrogen atom or substituting group), N, P or P=O.The preferred example of X comprises B, and (wherein R preferably represents aryl to C-R, replaces or unsubstituted amino alkoxy, aryloxy group; acyl group, alkoxy carbonyl, aryloxycarbonyl, acyloxy, acyl amino; alkoxycarbonyl amino, aryloxycarbonyl amino, sulfuryl amino, hydroxyl; sulfydryl, halogen atom such as fluorine atom, chlorine atom, bromine atoms or iodine atom; and carboxyl, more preferably aryl, alkoxy, aryloxy group; hydroxyl or halogen atom, more preferably alkoxy or hydroxyl, especially preferably hydroxyl), and N.C-R is particularly preferred.
The preferred example of formula (16) compound is the compound of following formula (17) representative.
Formula (17)
Figure A20058001608900531
In following formula, X 2Represent B, C-R (wherein R represents hydrogen atom or substituting group), N, P or P=O.R 11, R 12, R 13, R 14, R 15, R 21, R 22, R 23, R 24, R 25, R 31, R 32, R 33, R 34And R 35Each represents hydrogen atom or substituting group.
X 2Represent B, C-R (wherein R represents hydrogen atom or substituting group), N, P or P=O.X 2Preferred example comprise B, (wherein R preferably represents aryl to C-R, replaces or unsubstituted amino alkoxy, aryloxy group; acyl group, alkoxy carbonyl, aryloxycarbonyl, acyloxy, acyl amino; alkoxycarbonyl amino, aryloxycarbonyl amino, sulfuryl amino, hydroxyl; sulfydryl, halogen atom such as fluorine atom, chlorine atom, bromine atoms or iodine atom; and carboxyl, more preferably aryl, alkoxy, aryloxy group; hydroxyl or halogen atom, more preferably alkoxy or hydroxyl, especially preferably hydroxyl), N and P=O.C-R and N are preferred, and C-R is particularly preferred..
R 11, R 12, R 13, R 14, R 15, R 21, R 22, R 23, R 24, R 25, R 31, R 32, R 33, R 34And R 35Each represents hydrogen atom or substituting group.As substituent example, can use below with the substituting group T that illustrates.R 11, R 12, R 13, R 14, R 15, R 21, R 22, R 23, R 24, R 25, R 31, R 32, R 33, R 34And R 35Preferred example comprise alkyl, thiazolinyl, thiazolinyl, alkynyl; aryl replaces or unsubstituted amino alkoxy, aryloxy group; acyl group, alkoxy carbonyl, aryloxycarbonyl, acyloxy; acyl amino, alkoxycarbonyl amino, aryloxycarbonyl amino, sulfuryl amino; sulfamoyl, carbamyl, alkyl sulfide, aryl sulphur; sulfonyl, sulfinyl, urea groups, phosphinylidyne amino; hydroxyl, sulfydryl, halogen atom such as fluorine atom, chlorine atom; bromine atoms and iodine atom, cyano group, sulfonic group; carboxyl, nitro, hydroximic acid ester group (hydroxamate); sulfino, diazanyl, imino group; heterocyclic radical (preferably have 1～30 carbon atom, more preferably 1～12 carbon atom, and have for example nitrogen-atoms; oxygen atom or sulphur atom be as heteroatoms, as imidazole radicals, and pyridine radicals; quinolyl, furyl, piperidyl; morpholinyl, benzoxazol base, benzimidazolyl and benzothiazolyl) and silicyl.Its more preferably example comprise alkyl, aryl replaces or unsubstituted amino, alkoxy and aryloxy group.Wherein, alkyl, aryl and alkoxy are particularly preferred.
These substituting groups can further be replaced.Have under two or more substituent situations, substituting group can be identical or different.If possible, these substituting groups can form ring by bonding.
Below, above-mentioned substituting group T is described.The example of substituting group T comprises that alkyl (preferably has 1～20 carbon atom, more preferably 1～12 carbon atom, preferred especially 1～8 carbon atom; as methyl, ethyl, isopropyl; the tert-butyl group, n-octyl, positive decyl; n-hexadecyl, cyclopropyl, cyclopentyl and cyclohexyl); thiazolinyl (preferably has 2～20 carbon atoms; more preferably 2～12 carbon atoms, preferred especially 2～8 carbon atoms are as vinyl; allyl; 2-butenyl group and the second month in a season-pentenyl), alkynyl (preferably has 2～20 carbon atoms, more preferably 2～12 carbon atoms; preferred especially 2～8 carbon atoms; as propargyl and 3-pentynyl), aryl (preferably has 6～30 carbon atoms, more preferably 6～20 carbon atoms; preferred especially 6～12 carbon atoms; as phenyl, right-aminomethyl phenyl and naphthyl), replacement or unsubstituted amino (preferably have 0～20 carbon atom; more preferably 0～10 carbon atom; preferred especially 0～6 carbon atom, as amino, methylamino; dimethylamino; diethylamino and dibenzyl amino), alkoxy (preferably has 1～20 carbon atom, more preferably 1～12 carbon atom; preferred especially 1～8 carbon atom; as methoxyl, ethoxy and butoxy), aryloxy group (preferably has 6～20 carbon atoms; more preferably 6～16 carbon atoms; preferred especially 6～12 carbon atoms are as phenoxy group and 2-naphthoxy), acyl group (preferably has 1～20 carbon atom; more preferably 1～16 carbon atom; preferred especially 1～12 carbon atom, as acetyl group, benzoyl; formoxyl and valeryl); alkoxy carbonyl (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～12 carbon atoms; as methoxycarbonyl and ethoxy carbonyl); aryloxycarbonyl (preferably has 7～20 carbon atoms, more preferably 7～16 carbon atoms, preferred especially 7～10 carbon atoms; as carbobenzoxy); acyloxy (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～10 carbon atoms; as acetoxyl group and benzoyloxy); acyl amino (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～10 carbon atoms; as acetyl-amino and benzoyl-amido); alkoxycarbonyl amino (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～12 carbon atoms; as methoxycarbonyl amino); aryloxycarbonyl amino (preferably has 7～20 carbon atoms, more preferably 7～16 carbon atoms, preferred especially 7～12 carbon atoms; as phenyloxycarbonyl amino); sulfuryl amino (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; amino and the benzenesulfonyl amino as methane sulfonyl); sulfamoyl (preferably has 0～20 carbon atom, more preferably 0～16 carbon atom, preferred especially 0～12 carbon atom; as sulfamoyl; the methyl sulfamoyl, dimethylamino sulfonyl and phenyl sulfamoyl base), carbamyl (preferably has 1～20 carbon atom; more preferably 1～16 carbon atom; preferred especially 1～12 carbon atom, as carbamyl, the methylamino formoxyl; diethylamino formoxyl and phenyl amino formoxyl); alkyl sulfide (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; as methyl sulphur and ethyl sulphur); aryl sulphur (preferably has 6～20 carbon atoms, more preferably 6～16 carbon atoms, preferred especially 6～12 carbon atoms; as phenyl sulphur); sulfonyl (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; as mesyl and tosyl); sulfinyl (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; as methanesulfinyl and benzene sulfinyl); urea groups (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; as urea groups; methyl urea groups and phenyl urea groups), phosphinylidyne amino (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom; preferred especially 1～12 carbon atom; amino and the phenyl phosphinylidyne amino as the diethyl phosphinylidyne), hydroxyl, sulfydryl; halogen atom (for example; fluorine atom, chlorine atom, bromine atoms and iodine atom); cyano group; sulfonic group, carboxyl, nitro; the hydroximic acid ester group; sulfino, diazanyl, imino group; heterocyclic radical (preferably has 1～30 carbon atom; more preferably 1～12 carbon atom, and have nitrogen-atoms, oxygen atom or sulphur atom are as heteroatoms; as imidazole radicals; pyridine radicals, quinolyl, furyl; piperidyl; morpholinyl, benzoxazol base, benzimidazolyl and benzothiazolyl); silicyl (preferably has 3～40 carbon atoms; more preferably 3～30 carbon atoms, preferred especially 3～24 carbon atoms are as trimethyl silyl and triphenyl silicyl) etc.
These substituting groups can further be replaced.Have under two or more substituent situations, substituting group can be identical or different.If possible, these substituting groups can be bonded together and form ring.
Next, in conjunction with the object lesson compound of Ming Dynasty style (16) representative in more detail.Yet, should be appreciated that to the invention is not restricted to these object lessons.
Figure A20058001608900561
Figure A20058001608900581
Figure A20058001608900591
Next, the preferred example of the compound of formula (16) or formula (19) representative.Yet, should be appreciated that to the invention is not restricted to these object lessons.
Figure A20058001608900621
Figure A20058001608900641
Figure A20058001608900651
Next, list octanol-water partition coefficient (logP value) and be 0～7 Rth-and reduce the example of compound, but the invention is not restricted to these object lessons.
(polyol ester compound)
Polyol ester compound dibasic alcohol or more higher alcohol and one or more monocarboxylic ester.Next, list the example of polyol ester compound, but the invention is not restricted to these object lessons.
(polyvalent alcohol)
The preferred example of polyvalent alcohol comprises ribitol, arabite, ethylene glycol, diethylene glycol, triethylene glycol, TEG, 1, the 2-propane diol, 1,3-propane diol, dipropylene glycol, tripropylene glycol, 1, the 2-butylene glycol, 1,3 butylene glycol, 1,4-butylene glycol, dibutylene glycol, 1,2,4-butane triol, 1,5-pentane diol, 1, the 6-hexane diol, hexane triol, galactitol, mannitol, 3-methylpentane-1,3, the 5-triol, pinacol, D-sorbite, trimethylolpropane, trimethylolethane, xylitol etc.Its particularly preferred example is a triethylene glycol, TEG, dipropylene glycol, tripropylene glycol, D-sorbite, trimethylolpropane and xylitol.
(monocarboxylic acid)
As the monocarboxylic acid in the polyol ester, can use known aliphatics monocarboxylic acid, alicyclic monocarboxylic acid, aromatic series monocarboxylic acids etc. are not particularly limited.From improving the vapour transmission rate, the angle of the confining force of water content and cellulose acylate film is preferably used alicyclic monocarboxylic acid or aromatic series monocarboxylic acid.
Next, list monocarboxylic preferred example, but the invention is not restricted to this.
As the aliphatics monocarboxylic acid, the preferred use has 1～32 carbon atom, more preferably 1～20 carbon atom, the straight or branched fatty acid of preferred especially 1～10 carbon atom.Preferably use acetate, with the compatibility of improvement with cellulose esters.Further preferably use acetate and other monocarboxylic potpourris.
The monocarboxylic preferred example of aliphatics comprises saturated fatty acid, as acetate, and propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, n-nonanoic acid, sad, 2-ethyl-cyclohexane carboxylic-acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, Heptadecanoic acide, stearic acid, nonadecylic acid, arachic acid, mountain Yu acid, lignoceric acid, hexacosoic acid, carboceric acid, montanic acid, melissic acid and lacceroic acid, unsaturated fatty acid, as undecenoic acid, oleic acid, sorbic acid, linoleic acid, leukotrienes and arachidonic acid etc.These fatty acid can have substituting group.
Alicyclic monocarboxylic preferred example comprises cyclopentane-carboxylic acid, cyclohexane-carboxylic acid, cyclooctane carboxylic acid and its derivant.
The monocarboxylic preferred example of aromatic series comprises benzoic acid, have the benzoic acid derivative of introducing the alkyl in the phenyl ring,, have the aromatic series monocarboxylic acid of two or more phenyl ring as toluic acid, as the xenyl carboxylic acid, naphthalene-carboxylic acid and tetralin carboxylic acid and its derivant.Wherein, benzoic acid is preferred.
In polyol ester, can use the potpourri of carboxylic acid or two or more carboxylic acids.OH group in the polyvalent alcohol can be by whole esterifications.Selectively, some of them can remain-the OH group.Preferably have three or more aromatic rings or cycloalkyl ring in each molecule of polyol ester.
Below, list the example of polyol ester compound, but the invention is not restricted to this.
(carbonate)
Next, list the example of carbonate.Yet, the invention is not restricted to this.That is, its object lesson comprises phthalic ester, citrate etc.The example of phthalic ester comprises the phthalic acid dimethyl esters, phthalic acid diethyl ester, dicyclohexyl phthalate, phthalic acid dioctyl ester, phthalic acid diethylhexyl ester etc.The example of citrate comprises acetyl triethyl citrate and acetyl tributyl citrate.In addition, can use the oleic acid butyl ester, methyl acetyl licinolate, decanedioic acid dibutyl ester, acetin, trimethylolpropane tris benzoic ether etc.In addition, preferably use alkyl phthalic acyl group alkyl alcohol acid esters for this purpose.Alkyl in the alkyl phthalic acyl group alkyl alcohol acid esters is the alkyl with 1～8 carbon atom.The example of alkyl phthalic acyl group alkyl alcohol acid esters comprises methyl phthalyl methyl ethanol acid esters; ethyl phthalyl ethyl hexanol acid esters; propyl group phthalyl propyl group ethyl glycolate; butyl phthalyl butyl alcohol acid esters; octyl group phthalyl octyl group ethyl glycolate; methyl phthalyl ethyl hexanol acid esters; ethyl phthalyl methyl ethanol acid esters; ethyl phthalyl propyl group ethyl glycolate; propyl group phthalyl ethyl hexanol acid esters; methyl phthalyl propyl group ethyl glycolate; methyl phthalyl butyl alcohol acid esters; ethyl phthalyl butyl alcohol acid esters; butyl phthalyl methyl ethanol acid esters; butyl phthalyl ethyl hexanol acid esters; propyl group phthalyl butyl alcohol acid esters; butyl phthalyl propyl group ethyl glycolate; methyl phthalyl octyl group ethyl glycolate; ethyl phthalyl octyl group ethyl glycolate; octyl group phthalyl methyl ethanol acid esters, methyl phthalyl ethyl hexanol acid esters etc.Preferably use methyl phthalyl methyl ethanol acid esters, ethyl phthalyl ethyl hexanol acid esters, propyl group phthalyl propyl group ethyl glycolate, butyl phthalyl butyl alcohol acid esters or octyl group phthalyl octyl group ethyl glycolate.Ethyl phthalyl ethyl hexanol acid esters is particularly preferred.Can also use two or more the potpourri in these alkyl phthalic acyl group alkyl alcohol acid esters.
Next, list the example of carbonate.Yet, the invention is not restricted to this.
Figure A20058001608900731
Figure A20058001608900741
(many novel cycloalkenycarboxyliacid acids)
Preferably used many novel cycloalkenycarboxyliacid acids molecular weight is 3000 or littler among the present invention, more preferably 250～2000.About ring structure, preferably by the ring of 3～8 atomic buildings, 6-unit ring and/or 5-unit ring are preferred, but the ring size is not particularly limited.These rings can also contain carbon, oxygen, nitrogen, silicon or other atoms.Ring can have the part of unsaturated link as it.For example, 6-unit ring can be phenyl ring or cyclohexane ring.Used compound has a plurality of these ring structures among the present invention.That is, can use the compound that in a molecule, has phenyl ring and cyclohexane ring, have the compound of two cyclohexane rings, naphthalene derivatives, anthracene derivant etc.The preferred compound that has three or more this ring structures in each molecule that is to use.Further preferably at least one ring structure does not have unsaturated link.Its exemplary comprises colophonic acid and rosin acid derivative, as dihydro colophonic acid and palustric acid.Next, list the general formula of these compounds, but the invention is not restricted to this.
Figure A20058001608900751
(bisphenol derivative)
Used bisphenol derivative preferred molecular weight is 10000 or littler among the present invention.Can use monomer, oligomer or polymkeric substance in this scope.In addition, can use with another kind of polymkeric substance or use the multipolymer of the compound of reactive substituents modification endways.Next, list the example of carbonate.Yet, the invention is not restricted to this.
In the example of above-mentioned bisphenol derivative, R 1～R 4Each represents the alkyl of hydrogen atom or 1～10 carbon atom.L, each represents the quantity of corresponding repetitive m and n.L preferably, each is 1～100 for m and n, more preferably 1～20 integer, but the invention is not restricted to this.
[wavelength dispersion correctives]
Next, the compound (below be called the wavelength dispersion correctives) of the wavelength dispersion that reduces cellulose acylate film of the present invention is described.For improving the wavelength dispersion Rth of cellulose acylate film, preferably add at least a compound, the wavelength dispersion Rth of following formula (XXI) representative is reduced to (Δ Rth) satisfies in following formula (XKX) and the scope (XX).
(XIX) (ΔRth(B)-ΔRth(0))/B≤-2.0
(XX) 0.01≤B≤30
(XXI) ΔRth＝|Rth (400)-Rth (700)|
In following formula, Δ Rth (B) is the Δ Rth (nm) of film of compound that contains the reduction Δ Rth of B%; Δ Rth (0) is the Δ Rth (nm) that does not contain the film of the compound that reduces Δ Rth.B is that the polymer quality as membrane material is the quality (%) of 100 o'clock compounds.
About following formula (XIX) and (XX), more preferably:
(XXII) (ΔRth(B)-ΔRth(0))/B≤-3.0
(XXIII) 0.05≤B≤25；
More preferably:
(XXIV) (ΔRth(B)-ΔRth(0))/B≤-4.0
(XXV) 0.1≤B≤20。
Above-mentioned wavelength dispersion correctives has absorption in the ultraviolet range of 200～400nm.By adding wavelength dispersion correctives by solid cellulose acylate content 0.01～30 quality %, wavelength dispersion Re and Rth that can the plain acylate film of controlling fiber.
Usually, the Re of cellulose acylate film and Rth value are bigger than short wavelength side at long wavelength side.Therefore, need to enlarge, make wavelength dispersion level and smooth in short wavelength side less relatively Re and Rth value.On the other hand, the compound that absorbs in the ultraviolet range of 200～400nm has the wavelength dispersion characteristic, and wherein the absorptance of long wavelength side is bigger than short wavelength side.When this compound itself is present in the cellulose acylate film with the isotropy form, similar to the wavelength dispersion of absorptance, therefore seem birefringenct property and the wavelength dispersion of Re and Rth is bigger at short wavelength side.
By using the compound that absorbs and show at short wavelength side as mentioned above Re and the bigger wavelength dispersion of Rth in the ultraviolet range of 200～400nm, the wavelength dispersion that can regulate cellulose acylate film.For this reason, it is compatible full and uniformly to be used to regulate the compound and the cellulose acylate of wavelength dispersion.The uptake zone of this compound in the ultraviolet range is preferably 200～400nm, more preferably 220～395nm, more preferably 240～390nm.
In recent years, liquid crystal display is used in televisor, kneetop computer, the mobile phone etc. needs to have excellent transmissivity optical element, thereby can increase brightness under less electric power.Have absorption in the ultraviolet range that is added in 200～400nm and can reduce cellulose acylate film | Re (400)-Re (700)| and | Rth (400)-Rth (700)| the situation of compound under, consider from this viewpoint, need this compound to have excellent spectral-transmission favtor.In cellulose acylate film of the present invention, preferably the spectral-transmission favtor under the wavelength 380nm is 45% or bigger but be no more than 95%, and the spectral-transmission favtor under the wavelength 350nm is 10% or still less.
Consider that from the viewpoint of volatility the molecular weight of the wavelength dispersion correctives that the invention described above is preferably used is preferably 250～1000, more preferably 260～800, more preferably 270～800, preferred especially 300～800.As long as molecular weight falls into this scope, can use the oligomer or the polymer architecture that have the specific monomer structure or link together and constitute by a plurality of monomeric units.
Preferably the wavelength dispersion correctives does not evaporate in dope casting of making cellulose acylate film and dry run.
(the adding level of compound)
By solid cellulose acylate content, the preferred addition of the wavelength dispersion correctives that the present invention preferably uses is 0.01～30 quality %, more preferably 0.1～20 quality %, preferred especially 0.2～10 quality %.
(method that adds compound)
As the wavelength dispersion correctives, can use the simplification compound.Selectively, can use the potpourri of two or more compounds of any ratio.
The wavelength dispersion correctives can add in any step of preparation dope.Can add in the final step of dope preparation.
The object lesson of the preferred wavelength dispersion correctives that uses comprises benzotriazole cpd, benzophenone cpd, cyano-containing compound among the present invention, oxo Benzophenone compound, the salicylate compound, nickel complex salt compound etc., but the invention is not restricted to these compounds.
As benzotriazole cpd, those of formula (101) representative are preferably used as wavelength dispersion correctives of the present invention.
Formula (101): Q 1-Q 2-OH
In following formula, Q 1Represent nitrogenous aromatic heterocycle, Q 2Represent aromatic ring.
Q 1Represent nitrogenous aromatic heterocycle, the preferred 5-～nitrogenous aromatic heterocycle of 7-unit, the more preferably nitrogenous aromatic heterocycle of 5-or 6-unit, as imidazoles, pyrazoles, triazole, tetrazolium, thiazole,  azoles, selenazoles, benzotriazole, benzothiazole, benzoxazol, benzo selenazoles, thiadiazoles, the  diazole, aphthothiazoles, naphtho- azoles, azepine benzimidazole, purine, pyridine, pyrazine, pyrimidine, pyridazine, triazine, three benzazoles, four benzazoles etc.More preferably, Q 1Represent the nitrogenous aromatic heterocycle of 5-unit, as imidazoles, pyrazoles, triazole, tetrazolium, thiazole, the  azoles, benzotriazole, benzothiazole, benzoxazol, thiadiazoles or  diazole, benzotriazole is particularly preferred.
Q 1The nitrogenous aromatic heterocycle of representative can have substituting group, and substituent example comprises below with the substituting group T that illustrates.Have under a plurality of substituent situations, these substituting groups can be fused to and form other ring together.
Q 2The aromatic ring of representative can be aromatic hydrocarbon ring or aromatic heterocycle.It can be that monocycle or its form condensed ring with another ring.
The preferred example of aromatic hydrocarbon ring comprises monocycle with 6～30 carbon atoms or di-aromatics ring (for example phenyl ring, naphthalene nucleus etc.), more preferably has the aromatic hydrocarbon ring of 6～20 carbon atoms, more preferably has the aromatic hydrocarbon ring of 6～12 carbon atoms.Phenyl ring is most preferred.
The preferred example of aromatic heterocycle comprises the aromatic heterocycle that contains nitrogen-atoms or contain sulphur atom.The object lesson of heterocycle comprises thiophene, imidazoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole, purine, thiazoline, thiazole, thiadiazoles,  azoles quinoline,  azoles,  diazole, quinoline, isoquinoline, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthridines, azophenlyene, tetrazolium, benzimidazole, benzoxazol, benzothiazole, benzotriazole, four benzazoles etc.The preferred example of aromatic heterocycle comprises pyridine, triazine and quinoline.
Q 2The aromatic ring of representative is the aromatic hydrocarbon ring preferably, more preferably naphthalene nucleus or phenyl ring, especially preferably phenyl ring.Q 2Can have substituting group, substituent example comprises below with the substituting group T that illustrates.
The example of substituting group T comprises that alkyl (preferably has 1～20 carbon atom, more preferably 1～12 carbon atom, preferred especially 1～8 carbon atom; as methyl, ethyl, isopropyl; the tert-butyl group, n-octyl, positive decyl; n-hexadecyl, cyclopropyl, cyclopentyl and cyclohexyl); thiazolinyl (preferably has 2～20 carbon atoms; more preferably 2～12 carbon atoms, preferred especially 2～8 carbon atoms are as vinyl; allyl; 2-butenyl group and the second month in a season-pentenyl), alkynyl (preferably has 2～20 carbon atoms, more preferably 2～12 carbon atoms; preferred especially 2～8 carbon atoms; as propargyl and 3-pentynyl), aryl (preferably has 6～30 carbon atoms, more preferably 6～20 carbon atoms; preferred especially 6～12 carbon atoms; as phenyl, right-aminomethyl phenyl and naphthyl), replacement or unsubstituted amino (preferably have 0～20 carbon atom; more preferably 0～10 carbon atom; preferred especially 0～6 carbon atom, as amino, methylamino; dimethylamino; diethylamino and dibenzyl amino), alkoxy (preferably has 1～20 carbon atom, more preferably 1～12 carbon atom; preferred especially 1～8 carbon atom; as methoxyl, ethoxy and butoxy), aryloxy group (preferably has 6～20 carbon atoms; more preferably 6～16 carbon atoms; preferred especially 6～12 carbon atoms are as phenoxy group and 2-naphthoxy), acyl group (preferably has 1～20 carbon atom; more preferably 1～16 carbon atom; preferred especially 1～12 carbon atom, as acetyl group, benzoyl; formoxyl and valeryl); alkoxy carbonyl (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～12 carbon atoms; as methoxycarbonyl and ethoxy carbonyl); aryloxycarbonyl (preferably has 7～20 carbon atoms, more preferably 7～16 carbon atoms, preferred especially 7～10 carbon atoms; as carbobenzoxy); acyloxy (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～10 carbon atoms; as acetoxyl group and benzoyloxy); acyl amino (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～10 carbon atoms; as acetyl-amino and benzoyl-amido); alkoxycarbonyl amino (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～12 carbon atoms; as methoxycarbonyl amino); aryloxycarbonyl amino (preferably has 7～20 carbon atoms, more preferably 7～16 carbon atoms, preferred especially 7～12 carbon atoms; as phenyloxycarbonyl amino); sulfuryl amino (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; amino and the benzenesulfonyl amino as methane sulfonyl); sulfamoyl (preferably has 0～20 carbon atom, more preferably 0～16 carbon atom, preferred especially 0～12 carbon atom; as sulfamoyl; the methyl sulfamoyl, dimethylamino sulfonyl and phenyl sulfamoyl base), carbamyl (preferably has 1～20 carbon atom; more preferably 1～16 carbon atom; preferred especially 1～12 carbon atom, as carbamyl, the methylamino formoxyl; diethylamino formoxyl and phenyl amino formoxyl); alkyl sulfide (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; as methyl sulphur and ethyl sulphur); aryl sulphur (preferably has 6～20 carbon atoms, more preferably 6～16 carbon atoms, preferred especially 6～12 carbon atoms; as phenyl sulphur); sulfonyl (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; as mesyl and tosyl); sulfinyl (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; as methanesulfinyl and benzene sulfinyl); urea groups (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; as urea groups; methyl urea groups and phenyl urea groups), phosphinylidyne amino (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom; preferred especially 1～12 carbon atom; amino and the phenyl phosphinylidyne amino as the diethyl phosphinylidyne), hydroxyl, sulfydryl; halogen atom (for example; fluorine atom, chlorine atom, bromine atoms and iodine atom); cyano group; sulfonic group, carboxyl, nitro; the hydroximic acid ester group; sulfino, diazanyl, imino group; heterocyclic radical (preferably has 1～30 carbon atom; more preferably 1～12 carbon atom, and have nitrogen-atoms, oxygen atom or sulphur atom are as heteroatoms; as imidazole radicals; pyridine radicals, quinolyl, furyl; piperidyl; morpholinyl, benzoxazol base, benzimidazolyl and benzothiazolyl); silicyl (preferably has 3～40 carbon atoms; more preferably 3～30 carbon atoms, preferred especially 3～24 carbon atoms are as trimethyl silyl and triphenyl silicyl) etc.These substituting groups can further be replaced.Have under two or more substituent situations, substituting group can be identical or different.If possible, these substituting groups can be bonded to and form ring together.
As the compound of formula (101) representative, the compound of following formula (101-A) representative is preferred.
Formula (101-A):
In following formula, R 1, R 2, R 3, R 4, R 5, R 6, R 7And R 8Each represents hydrogen atom or substituting group independently.
R 1, R 2, R 3, R 4, R 5, R 6, R 7And R 8Each represents hydrogen atom or substituting group independently.As substituting group, can use above-mentioned substituting group T.These substituting groups can further be replaced by other substituting group, and substituting group can be fused to and forms ring structure together.
R 1And R 3Preferably each represents hydrogen atom, alkyl, and thiazolinyl, alkynyl, aryl replaces or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom.More preferably represent hydrogen atom, alkyl, aryl, aryloxy group or halogen atom, more preferably hydrogen atom or have the alkyl of 1～12 carbon atom especially preferably has the alkyl of the individual carbon atom in 1～12 (preferred 4～12).
R 2And R 4Preferably each represents hydrogen atom, alkyl, and thiazolinyl, alkynyl, aryl replaces or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom.More preferably represent hydrogen atom, alkyl, aryl, alkoxy, aryloxy group or halogen atom, more preferably hydrogen atom or have the alkyl of 1～12 carbon atom, preferred especially hydrogen atom or methyl, most preferably hydrogen atom.
R 5And R 8Preferably each represents hydrogen atom, alkyl, and thiazolinyl, alkynyl, aryl replaces or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom.More preferably represent hydrogen atom, alkyl, aryl, alkoxy, aryloxy group or halogen atom, more preferably hydrogen atom or have the alkyl of 1～12 carbon atom, preferred especially hydrogen atom or methyl, most preferably hydrogen atom.
R 6And R 7Preferably each represents hydrogen atom, alkyl, and thiazolinyl, alkynyl, aryl replaces or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom.More preferably represent hydrogen atom, alkyl, aryl, alkoxy, aryloxy group or halogen atom, more preferably hydrogen atom or halogen atom, especially preferably hydrogen atom or chlorine atom.
As the compound of formula (101) representative, the compound of following formula (101-B) representative is preferred.
Formula (101-B):
Figure A20058001608900831
In following formula, R 1, R 3, R 6And R 7The identical meanings that has with definition in the formula (101-A).Its preferable range is also identical.
Next, list the preferred example of the compound of formula (101) representative, but the invention is not restricted to these object lessons.
Figure A20058001608900832
Figure A20058001608900841
Verified, from the angle of confining force, in above-mentioned benzotriazole cpd, contain molecular weight and be 320 or the cellulose acylate film of the present invention of littler benzotriazole cpd be favourable.
As the benzophenone cpd of one of wavelength dispersion correctives that uses in the present invention, preferably use the compound of following formula (102) representative.
In following formula, Q 1, Q 2And Q 3Each represents aromatic ring independently.X represents NR (wherein R represents hydrogen atom or substituting group).
Q 1And Q 2The aromatic ring of representative can be aromatic hydrocarbon ring or aromatic heterocycle.They can be monocycles or form condensed ring with another ring.
Q 1And Q 2The aromatic hydrocarbon ring preferred example of representative comprises monocycle with 6～30 carbon atoms or di-aromatics ring (for example phenyl ring, naphthalene nucleus etc.), more preferably has the aromatic hydrocarbon ring of 6～20 carbon atoms, more preferably has the aromatic hydrocarbon ring of 6～12 carbon atoms.Phenyl ring is most preferred.
Q 1And Q 2The preferred example of the aromatic heterocycle of representative comprises and contains aerobic, the aromatic heterocycle of at least one in nitrogen and the sulphur atom.The object lesson of heterocycle comprises furans, pyrroles, thiophene, imidazoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole, purine, thiazoline, thiazole, thiadiazoles,  azoles quinoline,  azoles, the  diazole, quinoline, isoquinoline, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthridines, azophenlyene, tetrazolium, benzimidazole, benzoxazol, benzothiazole, benzotriazole, four benzazoles etc.The preferred example of aromatic heterocycle comprises pyridine, triazine and quinoline.
Q 1And Q 2The aromatic ring of representative is the aromatic hydrocarbon ring preferably, more preferably has the aromatic hydrocarbon ring of 6～12 carbon atoms, more preferably replaces or unsubstituted phenyl ring, preferred especially phenyl ring.
Q 1And Q 2Can have substituting group, substituent example comprises below with the substituting group T that illustrates, as long as this substituting group does not contain carboxylic acid, sulfonic acid or quaternary ammonium salt.If possible, substituting group can be bonded to and form ring structure together.
X represents NR (wherein R represents hydrogen atom or substituting group, comprises below with the substituting group T that illustrates), oxygen atom or sulphur atom.Preferably, X is NR (wherein R preferably represents acyl group or sulfonyl, and this substituting group can also have substituting group) or oxygen atom.Oxygen atom is particularly preferred.
The example of substituting group T comprises that alkyl (preferably has 1～20 carbon atom, more preferably 1～12 carbon atom, preferred especially 1～8 carbon atom; as methyl, ethyl, isopropyl; the tert-butyl group, n-octyl, positive decyl; n-hexadecyl, cyclopropyl, cyclopentyl and cyclohexyl); thiazolinyl (preferably has 2～20 carbon atoms; more preferably 2～12 carbon atoms, preferred especially 2～8 carbon atoms are as vinyl; allyl; 2-butenyl group and the second month in a season-pentenyl), alkynyl (preferably has 2～20 carbon atoms, more preferably 2～12 carbon atoms; preferred especially 2～8 carbon atoms; as propargyl and 3-pentynyl), aryl (preferably has 6～30 carbon atoms, more preferably 6～20 carbon atoms; preferred especially 6～12 carbon atoms; as phenyl, right-aminomethyl phenyl and naphthyl), replacement or unsubstituted amino (preferably have 0～20 carbon atom; more preferably 0～10 carbon atom; preferred especially 0～6 carbon atom, as amino, methylamino; dimethylamino; diethylamino and dibenzyl amino), alkoxy (preferably has 1～20 carbon atom, more preferably 1～12 carbon atom; preferred especially 1～8 carbon atom; as methoxyl, ethoxy and butoxy), aryloxy group (preferably has 6～20 carbon atoms; more preferably 6～16 carbon atoms; preferred especially 6～12 carbon atoms are as phenoxy group and 2-naphthoxy), acyl group (preferably has 1～20 carbon atom; more preferably 1～16 carbon atom; preferred especially 1～12 carbon atom, as acetyl group, benzoyl; formoxyl and valeryl); alkoxy carbonyl (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～12 carbon atoms; as methoxycarbonyl and ethoxy carbonyl); aryloxycarbonyl (preferably has 7～20 carbon atoms, more preferably 7～16 carbon atoms, preferred especially 7～10 carbon atoms; as carbobenzoxy); acyloxy (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～10 carbon atoms; as acetoxyl group and benzoyloxy); acyl amino (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～10 carbon atoms; as acetyl-amino and benzoyl-amido); alkoxycarbonyl amino (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～12 carbon atoms; as methoxycarbonyl amino); aryloxycarbonyl amino (preferably has 7～20 carbon atoms, more preferably 7～16 carbon atoms, preferred especially 7～12 carbon atoms; as phenyloxycarbonyl amino); sulfuryl amino (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; amino and the benzenesulfonyl amino as methane sulfonyl); sulfamoyl (preferably has 0～20 carbon atom, more preferably 0～16 carbon atom, preferred especially 0～12 carbon atom; as sulfamoyl; the methyl sulfamoyl, dimethylamino sulfonyl and phenyl sulfamoyl base), carbamyl (preferably has 1～20 carbon atom; more preferably 1～16 carbon atom; preferred especially 1～12 carbon atom, as carbamyl, the methylamino formoxyl; diethylamino formoxyl and phenyl amino formoxyl); alkyl sulfide (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; as methyl sulphur and ethyl sulphur); aryl sulphur (preferably has 6～20 carbon atoms, more preferably 6～16 carbon atoms, preferred especially 6～12 carbon atoms; as phenyl sulphur); sulfonyl (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; as mesyl and tosyl); sulfinyl (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; as methanesulfinyl and benzene sulfinyl); urea groups (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom; as urea groups; methyl urea groups and phenyl urea groups), phosphinylidyne amino (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom; preferred especially 1～12 carbon atom; amino and the phenyl phosphinylidyne amino as the diethyl phosphinylidyne), hydroxyl, sulfydryl; halogen atom (for example; fluorine atom, chlorine atom, bromine atoms and iodine atom); cyano group; sulfonic group, carboxyl, nitro; the hydroximic acid ester group; sulfino, diazanyl, imino group; heterocyclic radical (preferably has 1～30 carbon atom; more preferably 1～12 carbon atom, and have nitrogen-atoms, oxygen atom or sulphur atom are as heteroatoms; as imidazole radicals; pyridine radicals, quinolyl, furyl; piperidyl; morpholinyl, benzoxazol base, benzimidazolyl and benzothiazolyl); silicyl (preferably has 3～40 carbon atoms; more preferably 3～30 carbon atoms, preferred especially 3～24 carbon atoms are as trimethyl silyl and triphenyl silicyl) etc.These substituting groups can further be replaced.Have under two or more substituent situations, substituting group can be identical or different.If possible, these substituting groups can be bonded to and form ring together.
As the compound of formula (102) representative, the compound of following formula (102-A) representative is preferred.
Formula (102-A):
Figure A20058001608900881
In following formula, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8And R 9Each represents hydrogen atom or substituting group independently.
R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8And R 9Each represents hydrogen atom or substituting group independently.As substituting group, can use above-mentioned substituting group T.These substituting groups can further be replaced by another substituting group, and substituting group can be fused to and form ring structure together.
R 1, R 3, R 4, R 5, R 6, R 8And R 9Preferably each represents hydrogen atom, alkyl, and thiazolinyl, alkynyl, aryl replaces or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom.More preferably represent hydrogen atom, alkyl, aryl, alkoxy, aryloxy group or halogen atom, more preferably hydrogen atom or have the alkyl of 1～12 carbon atom, preferred especially hydrogen atom or methyl.Hydrogen atom is most preferred.
R 2Preferably represent hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl replaces or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom.More preferably represent hydrogen atom, alkyl with 1～20 carbon atom, amino with 0～20 carbon atom, alkoxy with 1～12 carbon atom, aryloxy group or hydroxyl with 6～12 carbon atoms, the alkoxy that more preferably has 1～20 carbon atom especially preferably has the alkoxy of 1～12 carbon atom.
R 7Preferably represent hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl replaces or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom.More preferably represent hydrogen atom, alkyl with 1～20 carbon atom, amino with 0～20 carbon atom, alkoxy with 1～12 carbon atom, aryloxy group or hydroxyl with 6～12 carbon atoms, more preferably hydrogen atom or have the alkyl (preferred 1～12 carbon atom, more preferably 1～8 carbon atom, more preferably methyl) of 1～20 carbon atom.Methyl or hydrogen atom are particularly preferred.
As the compound of formula (102) representative, the compound of following formula (102-B) representative also is preferred.
Formula (102-B):
Figure A20058001608900891
In following formula, R 10Represent hydrogen atom, replace or unsubstituted alkyl, replace or unsubstituted thiazolinyl, replace or unsubstituted alkynyl or replacement or unsubstituted aryl.
R 10Represent hydrogen atom, replace or unsubstituted alkyl, replace or unsubstituted thiazolinyl, replace or unsubstituted alkynyl or replacement or unsubstituted aryl.As substituting group, can use above-mentioned substituting group T.
R 10Preferred representative replaces or unsubstituted alkyl, more preferably replaces or unsubstituted alkyl with 5～20 carbon atoms, more preferably replace or unsubstituted alkyl with 5～12 carbon atoms (for example, n-hexyl, the 2-ethylhexyl, n-octyl, positive decyl, dodecyl or benzyl), preferred especially the replacement or unsubstituted alkyl (for example, 2-ethylhexyl, n-octyl with 5～12 carbon atoms, positive decyl, dodecyl or benzyl).
The compound of formula (102) representative can be synthetic with the known method of JP-A-11-12219 record.
Next, list the object lesson of the compound of formula (102) representative, but the invention is not restricted to these object lessons.
Figure A20058001608900901
Figure A20058001608900911
In the present invention, can also use the cyano-containing compound as the wavelength dispersion correctives.As the cyano-containing compound, the compound of formula (103) representative is preferred.
Formula (103):
Figure A20058001608900912
In following formula, Q 1And Q 2Each represents aromatic ring independently.X 1And X 2Each represents hydrogen atom or substituting group, as long as wherein at least one represents cyano group, and carbonyl, sulfonyl or aromatic heterocycle.Q 1And Q 2The aromatic ring of representative can be aromatic hydrocarbon ring or aromatic heterocycle.They can be monocycles or form condensed ring with another ring.
The preferred example of aromatic hydrocarbon ring comprises monocycle with 6～30 carbon atoms or di-aromatics ring (for example phenyl ring, naphthalene nucleus etc.), more preferably has the aromatic hydrocarbon ring of 6～20 carbon atoms, more preferably has the aromatic hydrocarbon ring of 6～12 carbon atoms.Phenyl ring is most preferred.
The preferred example of aromatic heterocycle comprises the aromatic heterocycle that contains nitrogen-atoms or sulphur atom.The object lesson of heterocycle comprises thiophene, imidazoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole, purine, thiazoline, thiazole, thiadiazoles,  azoles quinoline,  azoles,  diazole, quinoline, isoquinoline, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthridines, azophenlyene, tetrazolium, benzimidazole, benzoxazol, benzothiazole, benzotriazole, four benzazoles etc.The preferred example of aromatic heterocycle comprises pyridine, triazine and quinoline.
Q 1And Q 2The aromatic ring of representative each preferably aromatic hydrocarbon ring, more preferably phenyl ring.
Q 1And Q 2Can have substituting group, substituent example comprises below with the substituting group T that illustrates.The example of substituting group T comprises that alkyl (preferably has 1～20 carbon atom, more preferably 1～12 carbon atom, preferred especially 1～8 carbon atom, as methyl, ethyl, isopropyl, the tert-butyl group, n-octyl, positive decyl, n-hexadecyl, cyclopropyl, cyclopentyl and cyclohexyl), thiazolinyl (preferably has 2～20 carbon atoms, more preferably 2～12 carbon atoms, preferred especially 2～8 carbon atoms are as vinyl, allyl, 2-butenyl group and the second month in a season-pentenyl), alkynyl (preferably has 2～20 carbon atoms, more preferably 2～12 carbon atoms, preferred especially 2～8 carbon atoms, as propargyl and 3-pentynyl), aryl (preferably has 6～30 carbon atoms, more preferably 6～20 carbon atoms, preferred especially 6～12 carbon atoms, as phenyl, right-aminomethyl phenyl and naphthyl), replacement or unsubstituted amino (preferably have 0～20 carbon atom, more preferably 0～10 carbon atom, preferred especially 0～6 carbon atom, as amino, methylamino, dimethylamino, diethylamino and dibenzyl amino), alkoxy (preferably has 1～20 carbon atom, more preferably 1～12 carbon atom, preferred especially 1～8 carbon atom, as methoxyl, ethoxy and butoxy), aryloxy group (preferably has 6～20 carbon atoms, more preferably 6～16 carbon atoms, preferred especially 6～12 carbon atoms are as phenoxy group and 2-naphthoxy), acyl group (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom, as acetyl group, benzoyl, formoxyl and valeryl), alkoxy carbonyl (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～12 carbon atoms, as methoxycarbonyl and ethoxy carbonyl), aryloxycarbonyl (preferably has 7～20 carbon atoms, more preferably 7～16 carbon atoms, preferred especially 7～10 carbon atoms, as carbobenzoxy), acyloxy (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～10 carbon atoms, as acetoxyl group and benzoyloxy), acyl amino (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～10 carbon atoms, as acetyl-amino and benzoyl-amido), alkoxycarbonyl amino (preferably has 2～20 carbon atoms, more preferably 2～16 carbon atoms, preferred especially 2～12 carbon atoms, as methoxycarbonyl amino), aryloxycarbonyl amino (preferably has 7～20 carbon atoms, more preferably 7～16 carbon atoms, preferred especially 7～12 carbon atoms, as phenyloxycarbonyl amino), sulfuryl amino (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom, amino and the benzenesulfonyl amino as methane sulfonyl), sulfamoyl (preferably has 0～20 carbon atom, more preferably 0～16 carbon atom, preferred especially 0～12 carbon atom, as sulfamoyl, the methyl sulfamoyl, dimethylamino sulfonyl and phenyl sulfamoyl base), carbamyl (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom, as carbamyl, the methylamino formoxyl, diethylamino formoxyl and phenyl amino formoxyl), alkyl sulfide (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom, as methyl sulphur and ethyl sulphur), aryl sulphur (preferably has 6～20 carbon atoms, more preferably 6～16 carbon atoms, preferred especially 6～12 carbon atoms, as phenyl sulphur), sulfonyl (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom, as mesyl and tosyl), sulfinyl (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom, as methanesulfinyl and benzene sulfinyl), urea groups (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom, as urea groups, methyl urea groups and phenyl urea groups), phosphinylidyne amino (preferably has 1～20 carbon atom, more preferably 1～16 carbon atom, preferred especially 1～12 carbon atom, amino and the phenyl phosphinylidyne amino as the diethyl phosphinylidyne), hydroxyl, sulfydryl, halogen atom (for example, fluorine atom, chlorine atom, bromine atoms and iodine atom), cyano group, sulfonic group, carboxyl, nitro, the hydroximic acid ester group, sulfino, diazanyl, imino group; Heterocyclic radical (preferably have 1～30 carbon atom, more preferably 1～12 carbon atom, and have nitrogen-atoms, oxygen atom or sulphur atom be as heteroatoms, as imidazole radicals, and pyridine radicals, quinolyl, furyl, piperidyl, morpholinyl, benzoxazol base, benzimidazolyl and benzothiazolyl), silicyl (preferably has 3～40 carbon atoms, more preferably 3～30 carbon atoms, preferred especially 3～24 carbon atoms are as trimethyl silyl and triphenyl silicyl) etc.These substituting groups can further be replaced.Have under two or more substituent situations, substituting group can be identical or different.If possible, these substituting groups can be bonded to and form ring together.
X 1And X 2Each represents hydrogen atom or substituting group, as long as wherein at least one represents cyano group, and carbonyl, sulfonyl or aromatic heterocycle.X 1And X 2The substituting group of representative can be above-mentioned substituting group T.X 1And X 2The substituting group of representative can be by substituting group replacement in addition.X 1And X 2Can be fused to and form ring structure together.
X 1And X 2Preferred example comprise hydrogen atom, alkyl, aryl; cyano group, nitro, carbonyl; sulfonyl and aromatic heterocycle; more preferably cyano group, carbonyl, sulfonyl and aromatic heterocycle; more preferably cyano group and carbonyl; preferred especially cyano group and alkoxy carbonyl (C (=O) OR, wherein the R representative has the alkyl of 1～20 carbon atom, has aryl or its combination of 6～12 carbon atoms).
As the compound of formula (103) representative, the compound of following formula (103-A) representative is preferred.
Formula (103-A):
Figure A20058001608900941
In following formula, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9And R 10Each represents hydrogen atom or substituting group independently.X 1And X 2Have identical meanings with formula (20), its preferable range is also identical.
R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9And R 10Each represents hydrogen atom or substituting group independently.As substituting group, can use above-mentioned substituting group T.These substituting groups can further be replaced by other substituting group, and substituting group can be fused to and form ring structure together.
R 1, R 2, R 4, R 5, R 6, R 7, R 9And R 10Preferably each represents hydrogen atom, alkyl, and thiazolinyl, alkynyl, aryl replaces or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom.More preferably represent hydrogen atom, alkyl, aryl, alkoxy, aryloxy group or halogen atom, more preferably hydrogen atom or have the alkyl of 1～12 carbon atom, preferred especially hydrogen atom or methyl.Hydrogen atom is most preferred.
R 3And R 8Preferably each represents hydrogen atom, alkyl, and thiazolinyl, alkynyl, aryl replaces or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom.More preferably represent hydrogen atom, alkyl with 1～20 carbon atom, amino with 0～20 carbon atom, alkoxy with 1～12 carbon atom, aryloxy group or hydroxyl with 6～12 carbon atoms, more preferably hydrogen atom has the alkyl of 1～12 carbon atom or has the alkoxy of 1～12 carbon atom, preferred especially hydrogen atom.
As the compound of formula (103) representative, the compound of following formula (103-B) representative also is preferred.
Formula (103-B):
Figure A20058001608900951
In following formula, R 3And R 8(103-A) has identical meanings with formula, and its preferable range is also identical.X 3Represent hydrogen atom or substituting group.
X 3Represent hydrogen atom or substituting group, above-mentioned substituting group T can be used as substituting group.If possible, it can further be replaced by other substituting group.X 3Preferably represent hydrogen atom, alkyl, aryl, cyano group; nitro, carbonyl, sulfonyl or aromatic heterocycle, more preferably cyano group or carbonyl; preferred especially cyano group or alkoxy carbonyl (C (=O) CR, wherein the R representative has the alkyl of 1～20 carbon atom, has aryl or its combination of 6～12 carbon atoms).
As the compound of formula (103) representative, the compound of following formula (103-C) representative also is preferred.
Formula (103-C):
Figure A20058001608900961
In following formula, R 3And R 8Have the identical meanings formula with (103-A), its preferable range is also identical.R 21Representative has the alkyl of 1～20 carbon atom.
At R 3And R 8All be under the situation of hydrogen atom, R 21Preferred representative has the alkyl of 2～12 carbon atoms, more preferably has the alkyl of 4～12 carbon atoms, more preferably has the alkyl of 6～12 carbon atoms, preferred especially n-octyl, uncle's octyl group, 2-ethylhexyl, positive decyl or dodecyl.The 2-ethylhexyl is most preferred.
At R 3And R 8Not under the situation of hydrogen atom, R 21Preferred representative has the alkyl that is no more than 20 carbon atoms, makes that the compound molecular weight of formula (103-C) is 300 or bigger.
The compound of formula (103) representative can be by being documented in Journal of AmericaChemical Society, Vo1.63, and the method in 3452 pages (1941) is synthetic.
Next, list the object lesson of the compound of formula (103) representative, but the invention is not restricted to these object lessons.
[fine particle matting agent]
Cellulose acylate film of the present invention preferably contains fine particle as matting agent.The example of used fine particle comprises silicon dioxide among the present invention, titania, aluminium oxide, zirconia, lime carbonate, talcum, clay, calcined kaolin, calcining calcium silicate, afwillite, alumina silicate, magnesium silicate and calcium phosphate.The fine particle that contains silicon is preferred, because turbidity is low.Silicon dioxide is particularly preferred.The average one-level granularity of preferred fine particles of silica is 20nm or littler, and apparent specific gravity is a 70g/ liter or bigger.The fine particle that average one-level granularity is 5～16nm is preferred, because the turbidity of the film that obtains can reduce.Apparent specific gravity preferably 90～200g/ rises or is bigger, and more preferably 100～200g/ rises or be bigger.Higher apparent specific gravity can prepare the dispersion with higher concentration, thereby improves turbidity and aggregation.
The aggregation that it is 0.1～3.0 μ m that these fine particles form average secondary granularity.In film, these particles occur with the form of the aggregation of one-level particle, form the high rough degree of 0.1～3.0 μ m on the film surface.The secondary particle mean size is 0.2～1.5 μ m preferably, more preferably 0.4～1.2 μ m, most preferably 0.6～1.1 μ m.Watch particle in the film by scanning electron microscope, the circumscribed diameter of particle is defined by granularity, thereby measures one-level or secondary granularity.Observe 200 particles of diverse location, its mean value is called particle mean size.
As fine particles of silica, can use the commercially available prod, as AEROSIL R972, R972V, R974, R812,200,200V, 300, R202, OX50 and TT600 (all being to make) by NIPPON AEROSIL.As the zirconia fine particle, can use with the trade name commercially available product of AEROSIL R976 or R811 (making) for example by NIPPON AEROSIL.
In these products, AEROSIL 200V and AEROSIL R972 are particularly preferred, because their to be average one-level granularities be 20nm or littler and apparent specific gravity are that 70g/ rises or bigger fine particles of silica, when keeping the low turbidity of blooming, can reduce friction factor efficiently.
In the present invention, for obtaining containing the cellulose acylate film of particle, when the present invention prepares the dispersion of fine particle, several technology have been used with less average secondary granularity.For example, stir mixed solvent and fine particle down, at first prepare the dispersion of fine particle.Then, the dispersion of the fine particle that obtains is added to a small amount of separately in the cellulose acylate solution of preparation, and under agitation dissolves.Then, the solution that obtains is further mixed with main cellulose acylate dope.This preparation method is preferred, because wherein the dispersiveness of fine particles of silica is high, and fine particles of silica reassociates hardly.In another approach, comprise the plain ester of small amount of fibers is added in the solvent, stir dissolving down, then to wherein adding fine particle, disperse with decollator, obtain the solution of fine particle adjuvant, fully mix with dope with the solution of online mixer then the fine particle adjuvant.Although the invention is not restricted to these methods, when fine particles of silica mixed in solvent for example and disperses, concentration of silicon dioxide is 5～30 quality % preferably, more preferably 10～25 quality %, most preferably 15～20 quality %.Higher dispersion concentration is preferred, because solution turbidity is lower, thereby improves turbidity and aggregation.The final content of cellulose acylate in dope is 0.01～1.0g/m preferably 2, more preferably 0.03～0.3g/m 2, 0.08～0.16g/m most preferably 2
The preferred example that is used as the lower alcohol of solvent comprises methylol, ethyl alcohol, propyl group alcohol, isopropyl alcohol and butyl alcohol.Solvent outside the lower alcohol is not particularly limited, but used solvent is preferred the use when forming cellulose ester membrane.
[plastifier, antidegradant and peel off promoter]
Except optically anisotropic compound of above-mentioned reduction and wavelength dispersion correctives; cellulose acylate film of the present invention (for example can contain the various adjuvants that add according to various objectives in each stage of preparation; plastifier; UV blockers; antidegradant is peeled off promoter and infrared absorbent).These adjuvants can be solid matter or oily mater.That is, fusing point or boiling point are not particularly limited.For example, can use fusing point is that 20 ℃ or lower ultraviolet light absorber and fusing point are the potpourri of 20 ℃ or higher another kind of ultraviolet light absorber.Similarly, can use the potpourri of the plastifier of for example in JP-A-2001-151901, putting down in writing.The example of infrared ray absorbing dyestuff for example is documented among the JP-A-2001-194522.Although these adjuvants can add in any stage of dope preparation, the preparation process that adds adjuvant can be the final step of dope preparation process.The adding level of various materials is not particularly limited, as long as can realize required effect.In addition, under the situation of the plain film of multi-layer fiber, each layer can contain the adjuvant of the different amounts of variety classes.These technology are conventional known, for example are documented among the JP-A-2001-151902.In addition, about adjuvant, the optional write up that uses is at JapanInstitute of Invention and Innovation Journal of Technical Disclosure No.2001-1745 (2001.03.15, Japan Institute of Invention and Innovation), the material in 16 pages.
[the adding ratio of compound]
In cellulose acylate film of the present invention, by the cellulose acylate quality, molecular weight be 3000 or the content summation of littler compound be preferably 5～45%, more preferably 10～40%, more preferably 15～30%.As mentioned above, these compounds comprise the optically anisotropic compound of reduction, the wavelength dispersion correctives, and UV blockers, plastifier, antidegradant, fine particle is peeled off promoter, infrared absorbent etc.Preferably the molecular weight of these compounds is 3000 or littler, more preferably 2000 or littler, more preferably 1000 or littler.The total content of these compounds less than 5% situation under, the performance of cellulose acylate itself is obviously showed, the problem of generation is that optical property and physical strength often change with the variation of temperature and humidity.Total content at these compounds surpasses under 45% the situation, and compound is no longer compatible with cellulose acylate.Therefore, often make these compound sedimentations, thereby film becomes muddy (that is, from film, flowing out).
[organic solvent of cellulose acylate solution]
The above-mentioned cellulose acylate solution of preferred use obtains cellulose acylate film of the present invention by film forming.About film build method, can use solvent cast to become embrane method, wherein use the cellulose acylate solution (dope) that is dissolved in the organic solvent.As the preferred example that is used as the organic solvent of primary solvent in the present invention, the preferred use is selected from the ester with 3～12 carbon atoms, ketone, ether, pure and mild hydrocarbon and the solvent with halogenated hydrocarbons of 1～7 carbon atom.These esters, ketone, ether and alcohol can have ring structure.As primary solvent can also use and have two or more functional groups (that is, and-O-,-CO-and-COO-) ester, the compound of ketone and ether, these compounds can have other functional group simultaneously, as alcoholic extract hydroxyl group.When primary solvent had two or more functional groups, carbon number fell into above-mentioned in the compound restricted portion with a functional group.
As mentioned above; cellulose acylate film of the present invention can comprise as the chloro halogenated hydrocarbons of primary solvent or not have the chlorine organic solvent; this is documented in Japan Institute of Invention andInnovation Journal of Technical Disclosure No.2001-1745 (2001.03.15; Japan Institute of Invention and Innovation), in 12～16 pages.The invention is not restricted to this.
Other solvents and dissolving method that cellulose acylate solution of the present invention and film are used are disclosed in the following patent, and are embodiment preferred: for example, and JP-A-2000-95876; JP-A-12-95877; JP-A-10-324774, JP-A-8-152514, JP-A-10-330538; JP-A-9-95538; JP-A-9-95557, JP-A-10-235664, JP-A-12-63534; JP-A-11-21379; JP-A-10-182853, JP-A-10-278056, JP-A-10-279702; JP-A-10-323853; JP-A-10-237816, JP-A-11-60807, JP-A-11-152342; JP-A-11-292988, JP-A-11-60752 etc.According to these patents, not only reported preferred solvent, and reported the material of its solution property and coexistence, from but the preferred embodiments of the invention.
[method for preparing cellulose acylate film]
[dissolving step]
Next, preparation cellulose acylate solution (dope) is described.With any means dissolving cellulos acylate, without limits, i.e. room temperature dissolving, hot-cold lysis, heat of solution or its combination.About preparing cellulose acylate solution of the present invention; the concentration of solution when dissolving and filtration; the preferred use is documented in for example Japan Institute of Invention and Innovation Journal ofTechnical Disclosure No.2001-1745 (2001.03.15; Japan Institute ofInvention and Innovation), the method in 22～25 pages.
(transparency of dope)
The dope transparency of cellulose acylate solution preferably of the present invention is 85% or higher, more preferably 88% or higher, more preferably 90% or higher.In the present invention, verified various adjuvants are dissolved in the cellulose acylate rich liquor solution fully.In the reality by dope being poured into glass chamber (among the 1cm * 1cm), (UV-3150, Shimadzu makes) measures the absorptance under the 550nm with spectrophotometer, and the independent measurement solvent is as blank, calculate transparency according to ratio then, thereby measure the dope transparency with blank absorptance.
[casting, dry and coiling step]
Can obtain cellulose acylate film of the present invention by using above-mentioned cellulose acylate solution to carry out film forming.About film build method and device, can use routine to be used to form the solvent cast film build method and the solvent cast film formation device of cellulose acylate film.The dope (cellulose acylate solution) that will prepare in dissolving machine (still) is stored in to be stored in the still, behind the froth breaking, dope is finally prepared.Emit dope from the dope escape hole then, and be added in the pressurizing mold by for example constant pressure pump (thereby supplying dope accurately with constant rate of speed) according to rotating speed.From the pipe box (slit) of pressurizing mold, dope evenly casts on the metal support of the continuous running in the cast part.In metal support almost is circular pick-up point place, peels off half-dried dope film (being also referred to as tablet) from metal support.Clamp the two ends of gained tablet, the maintenance width is a constant level, with the tentering machine transmission, thus dry.Roller with drying device transmits then, thereby the drying of finishing is batched predetermined length with coiling machine.The combination of the roller of tentering machine and drying device can change according to purpose.Cellulose acylate film preferably of the present invention has slow axis on the horizontal direction (TD) perpendicular to film machine direction (MD).At the solvent cast film build method that is used for making the function and protecting film that electronic console or photosensitive silve halide material use (promptly; the main application of cellulose acylate film of the present invention); except the solvent cast film formation device; also often use spreader; thereby by for example undercoat is provided; antistatic layer, anti-halation layer or protective seam and processing of films surface.These layers write up is at Japan Institute of Invention and Innovation Journal ofTechnical Disclosure No.2001-1745 (2001.03.15, Japan Institute ofInvention and Innovation), in 25～30 pages.Technological selection described in the document is used for the present invention, comprises casting (comprising common casting), metal support, and drying is peeled off etc.
The thickness of cellulose acylate film is preferably 10～120 μ m, more preferably 40～100 μ m, more preferably 60～80 μ m.
[optical compensating layer]
As optical compensating layer, can use satisfy above-mentioned to Nz value and plane phase differential Re 1Any layer of the requirement of value is not particularly limited.For example, can use birefringence heavy polymer film, the combinations of low molecular weight liquid crystals film of the liquid crystalline polymer film of orientation and orientation.
The example of heavy polymer comprises acrylic polymers, as polymethylmethacrylate, and styrene polymer, as polystyrene and vinyl cyanide/styrol copolymer (AS resin), polyolefin is as polycarbonate and polypropylene, polyester, as polyethylene terephthalate and PEN, alicyclic polyolefin, as polynorbornene, polyvinyl alcohol (PVA), polyvinyl butyral, polymethyl vinyl ether, polyacrylic acid hydroxyethyl ester, hydroxy ethyl cellulose, hydroxy propyl cellulose, methylcellulose, polyene propyl ester, polysulfones, polyethersulfone, polyphenylene sulfide, polyphenylene oxide, polyene propyl group sulfone, polyvinyl alcohol (PVA), polyamide, polyimide, Polyvinylchloride, cellulosic polymer, various multipolymers (binary/ternary system), graft copolymer and its blend.Wherein, it is preferred having the polymkeric substance of negative intrinsic birefringence value such as polystyrene and polymethylmethacrylate.Preferred especially the use has the polymkeric substance (being called (A)) of unsaturated double-bond and the graft copolymer (being called (C)) that at least a styrene monomer (being called (B)) obtains by addition polymerization.Polymkeric substance (A) can have unsaturated double-bond on its main chain or side chain.
Further preferably use polymkeric substance with just intrinsic birefringence value, as polyamide, polyimide, polyester, polyetherketone, polyamidoimide or polyester-imide.
Next, the polymkeric substance (A) that constitutes the main chain backbone that b referred to as graft copolymer (C) is described.
More specifically, polymkeric substance (A) is the polymkeric substance that has the unsaturated link repetitive at its main chain or side chain.Preferably, this repetitive obtains by the monomer that polymerization has the conjugated diolefine structure.
Preferred example with monomer of conjugated diolefine structure comprises 1,3-butadiene, isoprene, 1, the 3-pentadiene, 2-ethyl-1,3-butadiene, 2-n-pro-pyl-1, the 3-butadiene, 2,3-dimethyl-1,3-butadiene, the 2-methyl isophthalic acid, 3-pentadiene, 1-phenyl-1,3-butadiene, 1-Alpha-Naphthyl-1,3-butadiene, 1-betanaphthyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1-bromo-1, the 3-butadiene, 1-chlorbutadiene, 2-fluoro-1, the 3-butadiene, 2,3-two chloro-1, the 3-butadiene, 1,1,2-three chloro-1,3-butadienes and 2-cyano group-1,3-butadiene.In these compounds, 1,3-butadiene, isoprene and 2-chloro-1,3-butadiene are particularly preferred.
The polymkeric substance (A) that constitutes the main chain backbone b referred to as graft copolymer (C) can be a monomer with above-mentioned diene structure and the multipolymer of different hydrophobic monomer.
The example of hydrophobic monomer comprises ethene, propylene, 1-butylene, isobutylene, styrene, α-Jia Jibenyixi, vinyl ketone, single ethylenic unsaturated hydrocarbon (alkene) ester of aliphatic acid (for example, vinylacetate and allyl acetic acid ester), ethylenic unsaturated monocarboxylic acid or dicarboxylic ester are (for example, methyl methacrylate, Jia Jibingxisuanyizhi, the just own ester of n-BMA, methacrylic acid, cyclohexyl methacrylate, the methacrylic acid benzyl ester, the just own ester of n-butyl acrylate, acrylic acid, 2-ethylhexyl acrylate, the methacrylic acid tertiary butyl ester, lauryl methacrylate, acrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxy-propyl ester), ethylenic unsaturated monocarboxylic acid or dicarboxylic acid acid amides (for example, tert-butyl group acrylamide, 7-butyl methyl acrylamide), single ethylenically unsaturated compounds (for example, vinyl cyanide, methacrylonitrile) etc.In these monomers, ethene, propylene, styrene, α-Jia Jibenyixi, the acrylic or methacrylic acid esters, vinyl cyanide and methacrylonitrile are particularly preferred.
As mentioned above, can use above-mentioned two or more to have the monomer hydrophobic monomer different of conjugated structure with two or more.Polymerization has the unsaturated structure that the monomer of conjugated structure introduces in the polymkeric substance (A) can have cis as known in the art-1,4-key, anti-form-1,4-key or anti-form-1, any in the 2-key.
At the biaxial stretch-formed heavy polymer film of in-plane or at in-plane single shaft or biaxially-stretched film, stretch at thickness direction then, the refractive index of regulating thickness direction can obtain optical compensating layer by for example.Selectively, by making heat shrink films and heavy polymer film bonding, stretching and/or shrinkable polymer film come tilted alignment under the effect of thermal shrinkage force then, can obtain optical compensating layer.
The example of liquid crystal polymer comprises various backbone chain types and side chain type, wherein provides the conjugation straight chain atomic group (liquid crystal is former) of liquid crystal aligning performance to be incorporated in main chain or the side chain.The object lesson of main chain liquid crystalline polymer comprises polyester liquid crystal polymer, plate-like polymkeric substance and the cholesteric polymkeric substance to the row orientation.The example of side chain liquid crystalline polymer comprises having polysiloxane, polyacrylate, polymethacrylate or poly-malonate are as main chain backbone and have and can provide to cyclic compound unit that the contraposition of row orientation characteristic replaces as those of side chain by the former part of the liquid crystal that comprises the conjugation atomic group.In the liquid crystalline polymer film of these orientations, by (for example for example liquid crystal polymer solution being deployed on the alignment surfaces, be formed on the polyimide that the surface on the glass plate rubbed or the film of polyvinyl alcohol (PVA), or has a face of the inclination evaporation of monox), heating then makes liquid crystal polymer orientation (particularly tilted alignment).
As the example of combinations of low molecular weight liquid crystals, can use bar-shaped and plate-like (discotic) liquid-crystal compounds.Preferably, bar-shaped or disc liquid-crystal compounds and transparent protective film are vertical orientated.
(disc liquid-crystal compounds)
The example of used disc liquid-crystal compounds comprises compound (people such as C.Destrade, Mol.Crysr.Liq.Cryst., vol.71,111 pages (1981 of putting down in writing in the various documents) among the present invention; Japan Society of Chemistry, Kikan Kagaku Sosetsu, No.22, Ekisho noKagaku, the 5th chapter, the 10th chapter (2) (1994); People such as B.Kohne, Angew.Chem.Soc.Chem.Comm., 1794 pages (1985); With people such as J.Zhang, J.Am.Chem.Soc., Vol.116,2655 pages (1994)).
In optical compensating layer, preferably, discotic liquid-crystalline molecules is fixed on alignment state, most preferably fixes by polymerization.Preferably, discotic liquid-crystalline molecules is oriented and fixes perpendicular to the transparent protective film surface among the present invention.The polymerization of discotic liquid-crystalline molecules is documented among the JP-A-8-27284.For fixing discotic liquid-crystalline molecules, need make as substituent polymerisable group to combine with discotic liquid-crystalline molecules disk center by polymerization.Yet, when polymerisable group directly combines with disk center, in polymerization, almost can not keep alignment state.Therefore, linking group is introduced between disk center and the polymerisable group.Discotic liquid-crystalline molecules with polymerizable groups is disclosed among the JP-A-2001-4387.
(rod shaped liquid crystal compound)
The example of used rod shaped liquid crystal compound comprises azomethine among the present invention, azoxy class (azoxys), the cyanobiphenyl base, cyano-phenyl ester, benzoic ether, the cyclohexane-carboxylic acid phenylester, the cyano-phenyl cyclohexane, the phenyl pyrimidine of cyano group-replacement, the phenyl pyrimidine of alkoxy-replacement, phenyl dioxane, diaryl replaced acetylene class (tolans) and thiazolinyl cyclohexyl benzene formonitrile HCN.Except these combinations of low molecular weight liquid crystals compounds, can also use the high molecular liquid-crystal compounds.
In optical compensating layer, preferably, rod shaped liquid crystal molecule is fixed on alignment state, most preferably fixes by polymerization.Preferably, rod shaped liquid crystal molecule is oriented and fixes perpendicular to the transparent protective film surface among the present invention.The example of used polymerisable rod shaped liquid crystal compound comprises and is documented in Makromol.Chem. among the present invention, vol.190,255 pages (1989), AdvancedMaterials, Vol.5,107 pages (1993), US patent 4683327, US patent 5622648, US patent 5770107, WO 95/22586, WO 95/24455, WO 97/00600, WO98/23580, and WO 98/52905, JP-A-1-272551, JP-A-6-16616, JP-A-7-110469, the compound among JP-A-11-80081 and the JP-A-2001-328973.
(polarizer)
As polarizer, can use all kinds, be not particularly limited.The example of polarizer comprises the product that obtains by following process: by making hydrophilic polymer film (for example, the polyvinyl alcohol (PVA) basement membrane, the formalized polyvinyl alcohol (PVA) basement membrane of part or partly-hydrolysed vinyl/vinyl acetate copolymer basement membrane) the absorption dichroic substance, as iodine or dichroic dye, monadic stretching membrane and the polyenoid alkyl alignment films that constitutes by the Polyvinylchloride of for example dewater polyvinyl alcohol (PVA) or dehydrochlorination then.In these polarizers, comprise that the polarizer of polyvinyl alcohol (PVA) basement membrane and dichroic substance such as iodine is fit to.The common thickness of this polarizer is about 5～80 μ m, but the invention is not restricted to this.
Comprise with the polarizer of the polyvinyl alcohol (PVA) basement membrane of iodine staining and uniaxial tension and for example can construct as follows: make polyvinyl alcohol (PVA) dyeing by dipping in iodine aqueous solution, be stretched to 3-～7-then doubly.When needing, film can be immersed in and randomly contain boric acid, and zinc sulfate is in the aqueous solution of the potassium iodide of zinc chloride etc.When needing, can wash the polyvinyl alcohol (PVA) basement membrane with water by in water, flooding after dyeing.By washing the polyvinyl alcohol (PVA) basement membrane with water, remaining dust and fragment and stop inhibitor on can flush away film surface.In addition, can prevent the unevenness such as the roughness that produce because of polyvinyl alcohol (PVA) basement membrane swelling.Stretching can be carried out make film dyeing with iodine after.Selectively, stretch and dye and carry out simultaneously, or after finishing stretching, dye.Can also in the aqueous solution of boric acid or potassium iodide or in water-bath, stretch to film.
Can transparent protective film not processed in conjunction with the surface (that is, not having the surface of above-mentioned coating) of polarizer, form hard conating or prevent reflection, viscosity, diffusion or flash of light (anti-flash of light).Preferably form hard conating among the present invention, at least a in anti-flash layer and the anti-reflecting layer.
Be coated with firmly to handle and prevent the polarizer galled spots.Can form hard conating by form cured film on the surface of transparent protective film, cured film is by being suitable for UV cured and having excellent hardness, the resin formation (for example, acrylic compounds or siloxane resin) of sliding etc.Carry out anti-reflex treated to prevent the lip-deep outside of polarizer reflection of light, can be undertaken, for example form anti-reflective film by method commonly used in this area.Carry out release treatment to prevent the close adhesion with adjacent layer.
Resist flash of light to handle to prevent reflecting the phenomenon that suppresses to watch by the light of polarizer because of the lip-deep outer sidelight of polarizer; can be by on the transparent protective film surface, forming thin peak in the mode that is fit to and paddy constitutes, for example by sandblast or embossing or add thin transparent particles and make rough surface.
Be used on the transparent protective film surface, forming the fine particle of thin peak and paddy as adding; can use transparent fine particles; as fine inorganic particle; optional have electric conductivity and particle mean size is 0.5～50 μ m; constitute every, antimony oxide etc. by monox, aluminium oxide, titanium dioxide, zirconia, tin oxide, indium oxide, oxidation, or the organic fine particle that constitutes by crosslinked or uncrosslinked polymkeric substance etc.Under the situation that forms thin peak and paddy from the teeth outwards, form the transparent resin of thin peak and paddy on it by per 100 mass parts, the common addition of these fine particles is 2～50 mass parts, preferred 5～25 mass parts.Anti-flash layer can also pass through the diffusion layer of the light of polarizing plate as propagation, thereby enlarges visual angle (visual angle expansion effect etc.).
Above-mentioned anti-reflecting layer, adherent layer, diffusion layer, anti-flash layer etc. can be formed on transparent protective film originally on one's body.Selectively, these layers can form as the optical layers of separating with transparent protective film.
[surface treatment]
When needing, cellulose acylate film of the present invention can carry out surface treatment, thereby can strengthen bonding with each functional layer (for example, undercoat and backing layer).As surface treatment, can use glow discharge to handle ultraviolet treatment with irradiation, Corona discharge Treatment, flame treatment and acid or alkali treatment.It can be 10 that glow discharge is herein handled -3Low Temperature Plasma Treating under the infrabar of～20Torr or the Cement Composite Treated by Plasma under the atmospheric pressure.Plasma exciatiaon gas is meant the gas of the plasma that is excited under these conditions, and its example comprises argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, chlorofluorocarbons such as tetrafluoromethane and its potpourri.Preferred these gas write ups that use in the present invention are at Japan Institute of Invention andInnovation Journal of Technical Disclosure No.2001-1745 (2001.03.15, Japan Institute of Invention and Innovation), in 30～32 pages.
[by the contact angle on alkali soap processing film surface]
The alkali soap processing can be used as a kind of effective means of surface treatment transparent protective film of the present invention.In this case, preferred 55 ° or littler of its contact angle of the film of alkali-saponification surface, more preferably 50 ° or littler, more preferably 45 ° or littler.Use conventional method to measure contact angle and estimate hydrophilic/hydrophobic, be included on the film surface of alkali-saponification and drip the water droplet of 3mm diameter, and measure the angle between film surface and water droplet.
After finishing above-mentioned surface treatment, use the isocyanates based adhesive, polyvinyl alcohol-based adhesives, the gel based adhesive, vinyl latex, polyester aqueous solution etc. are adhered on the transparent protective film polarizer.
Can by any method optical compensating layer be laminated on the polarizing plate, without limits.That is, can carry out lamination on the transparent protective film by using adhesive phase or pressure sensitive adhesive layer that optical compensating layer is adhered to.The contact adhesive that constitutes pressure sensitive adhesive layer compatibly is selected from those that for example have base polymer, as acrylic polymers, and silicon resin copolymer, polyester, polyurethane, polyethers, fluoropolymer or rubber, but the invention is not restricted to this.Especially, preferably use acrylic psa,, show suitable pressure-sensitive adhesion performance, comprise wettability, cohesive performance and viscosity, weatherability and excellent heat resistance because it has excellent optical clarity.
[structure of polarizing plate]
Can obtain polarizing plate by lamination transparent protective film on two faces of polarizer.The lamination of transparent diaphragm is not particularly limited by any method.Above-mentioned transparent protective film and polarizer when bonding, can used bonding agent or contact adhesive.As bonding agent or contact adhesive, consider that water content changes and the polarizing plate characteristic, what preferably use is to contain a small amount of volatile ingredient, does not need high warm hardening and drying, those that can handle at short notice.
As bonding agent or contact adhesive, preferably use aqueous binder.For example, can use the isocyanates based adhesive, polyvinyl alcohol-based adhesives, gel based adhesive, vinyl latex, polyester aqueous solution etc.Aqueous binder uses with the bonding agent of aqueous solution form usually, contains the solid matter of 0.5～60wt.%.
Can handle the surface for the treatment of, thereby promote bonding with the bonding transparent protective film of polarizer.Therefore, can strengthen bounding force.Promote that by dry or coating bonding material promotes bonding processing.The example of dried comprises corona treatment, and gas is dizzy to be handled, Cement Composite Treated by Plasma, low pressure UV processing etc.Promote that bonding examples of material comprises cellulose ester-based resin, carbamate-modified copolymer vibrin, silane coupling agent etc.Also can promote bonding combination of materials to use dried and coating.In addition, can use for example sodium hydrate aqueous solution saponification transparent protective film, thereby strengthen bounding force.Can also promote to carry out saponification after the bonding processing.
Can make transparent protective film and polarizer bonding by using roll-type laminating machine etc.Bonding agents etc. can be coated on transparent protective film or the polarizing plate.Can be coated with the two simultaneously.After bonding, the dry adhesive phase that comprises dry coating layer that forms.The thickness of adhesive phase is generally 0.1～5 μ m, but the invention is not restricted to this.
Behind bonding transparent protective film and optical compensating layer on two faces of polarizer, the polarizing plate of dry the invention described above.Baking temperature is generally 20～100 ℃, and preferred 30～80 ℃, but can be according to variations such as adhesive type.Be 1～30 minute drying time, preferred 1～15 minute.Under this drying condition, can make the bonding agent sclerosis, and remove moisture content.
Optical compensating polarizing plate and can have the function that absorbs ultraviolet light such as each layers such as adhesive phases, this produces by handling ultraviolet light absorber, as salicylate compound, oxybenzene compound, benzotriazole cpd, alpha-cyanoacrylate ester compounds or nickel complex salt compound.
Optical compensating polarizing plate of the present invention is useful in the liquid crystal display of IPS pattern.The liquid crystal display of IPS pattern has the liquid crystal cell that has a pair of substrate (fixing liquid crystal layer therebetween), be formed on an electrode on the substrate, be retained on the liquid-crystal composition layer that has dielectric anisotropy between substrate, be used to arrange the orientation regulating course of liquid-crystal composition molecule, it is relative with substrate and apply the drive unit of driving voltage to electrode.Electrode has such alignment structures, makes to apply the electric field almost parallel with the interface of liquid-crystal composition interlayer with being orientated regulating course.
Optical compensating polarizing plate of the present invention is arranged on watches side or light incident side.Preferably the optical compensating layer side of optical compensating polarizing plate is positioned at the liquid crystal cell side.On the liquid crystal cell side of optical compensating polarizing plate dorsad, polarizing plate is set.The absorption axes that is arranged on the absorption axes of the polarizing plate on brilliant first substrate both sides and optical compensating polarizing plate is vertical mutually.As polarizing plate, can use with optical compensating polarizing plate to have the polarizer that is laminated to the transparent protective film on the both sides equally.As transparent protective film, preferably use cellulose acylate film, the cellulosic triacetate film is particularly preferred.Preferably use at least one side of polarizer and in optical compensating polarizing plate of the present invention, to use | Re|≤10 Hes | the cellulose acylate film of Rth|≤25.
When the liquid crystal cell of IPS pattern watch side that optical compensating polarizing plate is set the time, preferably the polarizing plate in brilliant first substrate of opposite side (light incident side) is navigated to and watch side, make that when not applying voltage the major axes orientation of liquid crystal molecule is perpendicular to the absorption axes direction of polarizing plate in the liquid crystal cell.
When the light incident side in the liquid crystal cell of IPS pattern is provided with optical compensating polarizing plate, preferably the polarizing plate in brilliant first substrate of side is watched in the location, makes the major axes orientation of when the not applying voltage liquid crystal molecule in the liquid crystal cell perpendicular to the absorption axes direction of polarizing plate.
When reality was used, other optical layers can be laminated on optical compensating polarizing plate and the polarizing plate.Although this optical layers is not particularly limited, can use one or more kinds to be used to form optical layers in liquid crystal display etc., reflecting plate for example, half transmitting plate, polarizer (comprising 1/2 and 1/4 wavelength plate) etc.The polarizing plate that has the reflective polarizer vibration plate or the half transmitting polarizing plate of the reflecting plate that is laminated on the polarizing plate or half transmitting plate and have a film of the raising brightness that is laminated on the polarizing plate is preferred.
Reflective polarizer vibration plate with the reflecting plate that is laminated on the polarizing plate is used to form liquid crystal display, owing to show from watching side (demonstration side) reflection incident light to produce.Its advantage is, do not need internal light source (backlight etc.), can reduce the thickness of unit like this.When needed, can form the reflective polarizer vibration plate, for example on a face of polarizing plate, form the reflection horizon that constitutes by metal etc. by protective clear layer etc. with the method that is fit to.
The object lesson of reflective polarizer vibration plate comprises the polarizing plate with reflection horizon; the reflection horizon is formed by the paper tinsel or the deposited film that are constituted by the reflective metals on face of the transparent protective film of delustring such as aluminium when needed; with polarizing plate with transparent protective film and reflection horizon; transparent protective film has by fine particle being added to the thin peak that forms on the above-mentioned transparent protective film and the surface structure of paddy, and the reflection horizon has the surface structure which is provided with thin peak and paddy.The advantage in reflection horizon with surface structure of thin peak and paddy is can reduce directionality and prevent the outward appearance of glistening by diffusion into the light emitted, and reduce the irregular of brightness.The advantage that contains the transparent protective film of fine particle is that incident light and reflected light are spread after the transmission, thereby reduce the irregular of brightness.This reflection horizon with surface structure (coming from the surface structure with the thin peak of transparent protective film and paddy) of thin peak and paddy can be by suitable method (for example; vacuum deposition method; sputtering method, ion plating method etc.) directly the formation metal level forms on protective clear layer.
As substituting of the system that on the transparent protective film of above-mentioned polarizing plate, directly forms reflecting plate, can also use the reflecting plate of the suitable film that comprises corresponding hyaline membrane that forms thereon and reflection horizon.Because the reflection horizon is made of metal usually, preferably uses transparent protective film, coating such as polarizing plate reflecting surface, thus prevent to reduce because of oxidation makes reflectivity, therefore, in long-time, keep initial reflectance, and need not be by means of any independent protective seam.
By using the Transflective layer can obtain the half transmitting polarizing plate as half minute surface, as above-mentioned reflection horizon, it allows light reflection and transmission.This half transmitting polarizing plate is located at the dorsal part of liquid crystal cell usually.In relative brighter atmosphere, use under the situation of liquid crystal display etc., owing to produce the image demonstration from the incident light reflection of watching side (demonstration side).On the other hand, in darker relatively atmosphere, use internal light source such as generation image backlight to show.That is, the half transmitting polarizing plate is used to form liquid crystal display, wherein can save light source such as energy backlight in the brighter atmosphere relatively, and in darker relatively atmosphere, use internal light source to produce image and show.
Next, illustrate to have the optical compensating polarizing plate that is laminated to the optical compensating layer on the polarizing plate.Use optical compensating layer that linearly polarized photon is changed into ellipse or circularly polarized light, ellipse or circularly polarized light are changed into linearly polarized photon, or change the polarization direction of linearly polarized photon.As linearly polarized photon being changed into circularly polarized light or circularly polarized light being changed into the optical compensating layer of linearly polarized photon, particularly use so-called 1/4 wavelength plate (being also referred to as λ/4 plates).1/2 wavelength plate (being also referred to as λ/2 plates) is generally used for changing the polarization direction of linearly polarized photon.
Optical compensating polarizing plate is used for painted (indigo plant, the Huang etc.) that compensation (preventing) causes because of the liquid crystal layer birefringence of liquid crystal display effectively, to obtain not having painted monochrome to show.More preferably regulate three-dimensional refractive index because can compensate (preventing) from certain angle watch and produce painted.Optical compensating polarizing plate is used for for example controlling the tone of the image of the reflective liquid crystal display unit with multicolor image demonstration effectively.Also has the function of reflecting of preventing.
Comprise that the polarizing plate of the film of polarizing plate and the raising brightness bonding with it is located at the dorsal part of liquid crystal cell usually.When natural light incident, the film reflection that improves brightness has the linearly polarized photon of certain polarization angle or the circularly polarized light of certain orientation, and allows other transmittance.Have this polarizing plate that is laminated to the film of the raising brightness on the polarizing plate by use, can obtain polarized light in certain polarization state from light source such as incident light backlight, reflection simultaneously is not at the light of certain polarization state.The further counter-rotatings such as reflection horizon of the light that on the face of this raising brightness, reflects by being located at dorsal part, and then enter the film that improves brightness.Make the light of incident once more partly or entirely with the light transmission of certain polarization state.Therefore, can increase light quantity, thereby the polarized light that is absorbed by polarizer is provided almost not and increases the light quantity that can be used for liquid crystal display etc., improve brightness by the film that improves brightness.In other words, using under the situation of the film that improves brightness by polarizer etc. from the incident light that comes backlight that for example is arranged on the liquid crystal cell dorsal part, the wide part that the polarization direction is different from the polarization axle of polarizer is absorbed by polarizer, and can not pass through polarizer.That is, about 50% light is absorbed by polarizer, although can change according to the characteristic of used polarizer.Therefore, the light quantity that can be used in the liquid crystal image display etc. descends the image blackening that obtains.When use improving the film of brightness, the light with the polarization direction that can be absorbed by polarizer does not enter, but reflects on the film that improves brightness.Light is by being located at the reflection horizon isoinversion of dorsal part then, and then enters the film that improves brightness.By repeating these processes, only allow to have the polarized light that can see through the polarization direction of polarizer and pass through, and offer polarizer.Because this system can be used for the image demonstration of liquid crystal display effectively from the light of grade backlight, and can the blast screen.
Can also between film that improves brightness and reflection horizon, provide diffuser plate.The light that reflects on the film that improves brightness is shifted to reflection horizon etc.Diffuser plate makes it possible to even diffused transmission light, and removes polarization state, thereby produces unpolarized attitude.That is to say that diffuser plate changes into natural light with polarized light.(that is, natural mode) light is shifted to the reflection horizon to unpolarized attitude, secondary reflection again on the reflection horizon.Subsequently, light enters the film that improves brightness once more once more by diffuser plate.Repeat these processes.By between the film of above-mentioned raising brightness and reflection horizon etc., providing the diffusion layer that polarized light is changed into natural light, the brightness of display screen can be remained on certain level, simultaneously, can reduce the inhomogeneous of display screen brightness.Therefore, can obtain all even shinny display screen.Obviously,, can suitably improve the multiplicity of original incident light, thereby play the synergy that all even shinny display screen is provided with the diffusion function of diffuser plate by this diffuser plate is provided.
Film as above-mentioned raising brightness, can use the film that makes the linear polarization transmittance of certain polarization axle still reflect other light, laminated (for example as the multilayer that dielectric multilayer film or the different film of reflection anisotropy constitute, the D-BEF that 3M makes), with can reflect clockwise or anticlockwise round polymerization light and allow other light transmissive films, alignment films as cholesteric liquid crystal polymers, with the film that in the film substrate, has this aligned liquid-crystal layer (for example, the Transmax of the PCF350 of NITTO DENKO manufacturing and Merck manufacturing).
Therefore, in the film of the raising brightness of the linear polarization transmittance of the certain polarization axle of above-mentioned permission, by the control polarization axle, transmitted light enters polarizer.Therefore, by regulating the absorption of polarizing plate, light can see through effectively.In the film such as cholesteric liquid crystal layers that allow the light transmissive raising brightness of circular polarization, light can enter polarizing plate equally.Yet, consider from the angle of regulating absorption loss, preferably before inciding polarizing plate, circularly polarized light is changed into linearly polarized photon by polarizer.As polarizer, can use 1/4 wavelength plate, thereby circularly polarized light is changed into rectilinearly polarized light.
By at the phase separation layer that shows out of phase difference characteristic as stacked as the light light phase separation layer of 1/4 wavelength plate of 550nm for example on the phase separation layer of 1/2 wavelength plate, can obtain in wide wavelength coverage polarizer as 1/4 wavelength plate.That is, the intermembranous polarizer that provides in polarizing plate and raising brightness can comprise one or more phase separation layer.
Under the situation of cholesteric liquid crystal layers, different two or more of reflection wavelength layer is stacked mutually.Because this structure can reflect the circularly polarized light in the wide wavelength coverage (for example, the visible region), therefore, can obtain the transmission circularly polarized light in the wide wavelength coverage.
As the above-mentioned polarizing plate that separates polarized light, polarizing plate can comprise that two or more are laminated to optical layers together.Therefore, can use the oval polarizing plate of oval polarizing plate of reflection or half transmitting, comprise the combination of above-mentioned reflective polarizer vibration plate or half transmitting polarizing plate and polarizer.
By in the process of preparation liquid crystal display etc. continuously and separately lamination can form optical compensating layer.Replacedly, can mainly be laminated to and obtain optical compensating polarizing plate on the transparent protective film.The advantage of this method is, quality stability and manufacturing property excellence, thereby help to improve the manufacture method of liquid crystal display etc.Use the bonding mode such as the pressure sensitive adhesive layer that are fit to carry out lamination.
Can construct liquid crystal display in the usual way.Generally speaking, construct liquid crystal display by compatibly assembling required parts such as illuminator and integrated drive electronics.In the present invention, can construct liquid crystal display in the usual way, be not particularly limited, but use above-mentioned blooming.Can at random use various types of liquid crystal cell, as above-mentioned a kind of IPS pattern, a kind of VA type and a kind of π type.
As liquid crystal display, can use suitable liquid crystal display, for example have the sort of of illuminator or reflecting plate.In the structure liquid crystal display, suitable parts (for example, diffuser plate, anti-flash layer, anti-reflective film, fender, prism array, lens array sheet, light diffusing sheet, backlight etc.) can be set, in suitable position so that one deck or more multi-layered to be provided.
The Japanese patent application JP2004-148335 that the application submitted to based on May 18th, 2004, the Japanese patent application JP 2005-68096 that the Japanese patent application JP 2004-380722 that on Dec 28th, 2004 submitted to and on March 10th, 2005 submit to, be incorporated herein by reference at this full content, describe in detail with regard to liking with them.
Embodiment
Now, illustrate in greater detail the present invention in conjunction with the following examples.Yet, should be appreciated that to the invention is not restricted to these embodiment.
(plane length of delay Re)
With sample (30mm * 40mm) under 25 ℃ of 60%RH, regulate 2 hours.Use the Re value under automatic birefringence meter KOBRA 21 ADH (OJI KEISOKU KIKI manufacturing) the measurement normal direction 590nm.Measuring wavelength dispersion | Re (400)-Re (700)| under the situation about waiting, under different wave length, measure.
(film thickness direction postpones Rth)
With sample (30mm * 40mm) under 25 ℃ of 60%RH, regulate 2 hours.Use the Rth value under automatic birefringence meter KOBRA 21 ADH (OJI KEISOKU KIKI manufacturing) the measurement 590nm, use normal direction and tilt 10 ° under 590nm with respect to the normal direction of film, 20 °, 30 °, the length of delay that the incident light of 40 ° and 50 ° directions is measured uses mean refractive index and the film thickness of plane slow axis as pitch angle (rotation angle) and supposition.As the mean refractive index of supposition, can use POLYMER HANDBOOK, JOHN WILEY ﹠amp; SONS, data that provide among the INC and various optical film products catalogue.Under the mean refractive index condition of unknown, can use the Abbe refractometer to measure.The mean refractive index of main optical film is as follows: cellulose acylate (1.48), cyclic olefin polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49), polystyrene (1.59).
Measuring wavelength dispersion | Rth (400)-Rth (700)| when waiting, different wave length is measured.
(measuring N z)
By using automatic birefringence meter KOBRA 21 ADH (OJI KEISOKU KIKI manufacturing) to measure nx, ny and nz calculate Nz=(nx-nz)/(nx-ny), use normal direction and tilt 10 ° under 590nm with respect to the normal direction of film, 20 °, 30 °, the length of delay that the incident light of 40 ° and 50 ° directions is measured uses mean refractive index and the film thickness of plane slow axis as pitch angle (rotation angle) and supposition.
(turbidity of film)
Use nephelometer (NIPPON DENSHOKU manufacturing) to measure turbidity.
(measuring the water content of film)
Measure water content with Karl Fisher method.
(measuring the vapour transmission rate)
Measure the vapour transmission rate by the cup method.
[embodiment 1]
(manufacturing transparent protective film)
In having the stainless steel dissolving tank (4000L) of stirring vane, cellulose ethanoate powder (thin slice) is added in the solvent mixture solution that comprises following composition gradually, fully stir and disperse, reach 2000kg up to total amount.Add the present invention respectively and reduce optically anisotropic compound and wavelength dispersion correctives of the present invention (as listed in the table 1), obtain sample 101～106.
Cellulosic triacetate (degree of substitution shown in the table 1) 17.0 mass parts
Methylene chloride 70.5 mass parts
Methyl alcohol 10.5 mass parts
Provide optically isotropic compound (as listed in the table 1) 2.0 mass parts
Regulate compound (as listed in the table 1) 0 or 8 mass parts of wavelength dispersion
The plane phase difference value of transparent protective film is | Re|≤10nm, thickness direction phase differential be | and Rth|≤25nm.
Simultaneously, | Re (400)-Re (700)|≤10nm and | Rth (400)-Rth (700)|≤35nm.
(laminated optical layer of compensation)
Behind the above-mentioned cellulose acylate sample 101～106 of surface-saponification, the contact angle that confirms these samples is 38 °.Next, with the coating solution of the alignment films of following composition with line bar coating machine with 20ml/m 2Speed be coated on each film, under 60 ℃ of thermal currents dry 60 seconds, under 100 ℃ of thermal currents dry 120 seconds then.Next, the film that friction so forms on the direction that is parallel to the film slow-axis direction.
The composition of the coating solution that alignment films is used
Modified polyvinylalcohol 15 mass parts of showing down
Water 334 mass parts
Methyl alcohol 100 mass parts
Glutaraldehyde 1 mass parts
P-toluenesulfonic acid 0.3 mass parts
Modified polyvinylalcohol:
Figure A20058001608901191
On the film that is orientated like this, with the disc liquid-crystal compounds of #3.4 line bar coating below dissolving 1.8g in the 3.9g methyl ethyl ketone, 0.2g the trimethylolpropane triacrylate (V#360 of oxirane-modification, OSAKA ORGANIC CHEMICAL INDUSTRIES makes), 0.06g (Irgacure 907 for Photoepolymerizationinitiater initiater, Ciba-Geigy makes), 0.02g emulsion (Kayacure DETX, NIPPON KAYAKU Co., Ltd. makes) and 0.01g below the vertical-tropism agent of air-interface side and the solution for preparing.The product and the metal frame that obtain are bonding, and heat 3 minutes down at 125 ℃ in thermostat, make the disc liquid-crystal compounds orientation.Subsequently, use 120W/cm high-pressure sodium lamp UV irradiation 30 seconds down, make disc liquid-crystal compounds crosslinked, leave standstill cool to room temperature then at 100 ℃.Therefore, optical compensating layer is by lamination.
Disc liquid-crystal compounds:
Figure A20058001608901192
The vertical-tropism agent of air-interface side:
Figure A20058001608901193
When calculating the optical characteristics of discotic mesogenic phase separation layer only, Re 1Be 200nm, the Nz value is 0.54.Therefore, confirmed that the orientation of discotic mesogenic is perpendicular to face.Slow-axis direction is parallel to frictional direction.
(structure of optical compensating polarizing plate 1～6)
Each the transparent protective film film (sample 101～106) and adhesive film TD80UF (the Fuji Photo Film Co. that will have the optical compensating layer that is laminated on it; Ltd. make; 80 μ m) be laminated to (polarizer: 20 μ m) on the two sides of film; this film absorbs iodine by the polyvinyl alcohol (PVA) basement membrane and orientation obtains, and uses bonding agent to obtain optical compensating polarizing plate 1～6.
(structure of polarizing plate 1～6)
With above-mentioned each transparent protective film (sample 101～106) and adhesive film TD80UF (Fuji PhotoFilm Co.; Ltd. make; be laminated on the film two sides 80 μ m) that (polarizer: 20 μ m), this film obtains by making the polyvinyl alcohol (PVA) basement membrane absorb iodine, uses bonding agent to obtain polarizing plate 1～6.
(structure of liquid crystal display 1)
Optical compensating polarizing plate 1 is laminated in the brilliant unit of IPS mode liquid crystal, makes the optical compensating layer side watch the surface of side as liquid crystal cell.On that side of liquid crystal cell dorsad,, thereby provide liquid crystal display with contact adhesive lamination polarizing plate 1.The polarizing plate 1 of watching side is by lamination, makes that when not applying voltage the extraordinary refractive index direction of liquid-crystal composition is perpendicular to the absorption axes of optical compensating polarizing plate in the liquid crystal cell.Polarizing plate 1 is set makes the absorption axes of its absorption axes perpendicular to optical compensating polarizing plate.
(evaluation)
Use contrast instrument (EZ-Contrast, ELDIM makes), under 45 ° of visual angles, on the plane with from the contrast ratio of this liquid crystal display of 70 ° of pitch angle measurements of normal direction with respect to vertical polarizing plate optical axis.When as a result, contrast ratio in plane is 370,70 ° is 35.In black the demonstration, with the plane degree of staining with under 45 ° of visual angles, from the degree of staining comparison at 70 ° of pitch angle of normal direction with respect to vertical polarizing plate optical axis.As a result, observe less variation.When this liquid crystal display was exposed among 60 ℃ and the 95%RH after 200 hours, check the plane unevenness with bore hole.As a result, observe less unevenness.Similarly, polarization property variation not almost.
(structure of liquid crystal display 2～6)
By the single 1 structure liquid crystal display 2～6 of liquid crystal display, but use polarizing plate 2～6 to replace used polarizing plate 1 in structure liquid crystal display 1, use optical compensating polarizing plate 2～6 to replace optical compensating polarizing plate 1.Therefore, obtain similar performance.
[embodiment 2]
(manufacturing transparent protective film)
Preparation cellulosic triacetate solution is pressed embodiment 1 perparation of specimen 114, but composition below using.
Cellulosic triacetate (powder, degree of substitution 2.86, viscosity-average degree of polymerization are 320, water content 0.4 quality %, viscosity in the 6 quality % dichloromethane solutions is 305mPas, particle mean size 1.5mm and standard deviation 0.5mm) 17.0 mass parts
Methylene chloride 67.4 mass parts
Methyl alcohol 12.7 mass parts
Butanols 0.5 mass parts
Triphenyl (TPP) 1.3 mass parts
Xenyl-diphenyl phosphoester (BDP) 0.7 mass parts
Provide optically isotropic compound (as listed in the table 1) 2.0 mass parts
Regulate compound (as listed in the table 1) 0.8 mass parts of wavelength dispersion
(structure of polarizing plate 7)
Above-mentioned transparent protective film is laminated on the film two sides (polarizer: 20 μ m), this film obtains by making the polyvinyl alcohol (PVA) basement membrane absorb iodine, uses bonding agent to obtain polarizing plate 7.
(laminated optical layer of compensation)
By the OPS oriented polystyrene film, obtaining thickness is 60 μ m, Re 1It for 260nm and Nz value 0.50 optical compensating layer.With contact adhesive this optical compensating layer is laminated on the polarizing plate 7, makes slow axis be parallel to the absorption axes of polarizing plate.Therefore, obtain optical compensating polarizing plate 7.
(structure of liquid crystal display 7)
Optical compensating polarizing plate 7 is laminated in the brilliant unit of IPS mode liquid crystal, makes the optical compensating layer side watch the surface of side as liquid crystal cell.On that side of liquid crystal cell dorsad,, thereby provide liquid crystal display 7 with contact adhesive lamination polarizing plate 7.The polarizing plate 7 of watching side is by lamination, makes that when not applying voltage the extraordinary refractive index direction of liquid-crystal composition is perpendicular to the absorption axes of optical compensating polarizing plate 7 in the liquid crystal cell.Polarizing plate 7 is set makes the absorption axes of its absorption axes perpendicular to optical compensating polarizing plate.
(evaluation)
Under 45 ° of visual angles, on the plane with measure the contrast ratio of this liquid crystal display from 70 ° of pitch angle of normal direction with respect to vertical polarizing plate optical axis.As a result, contrast ratio in plane is 370, and is 35 during 70 ° of visual angles.In black the demonstration, with the plane degree of staining with under with respect to 45 ° of visual angles of vertical polarizing plate optical axis from the degree of staining comparison at 70 ° of pitch angle of normal direction.As a result, observe less variation.When this liquid crystal display was exposed among 60 ℃ and the 95%RH after 200 hours, check the plane unevenness with bore hole.Therefore, observe less unevenness.Similarly, polarization property variation not almost.
[embodiment 3]
(manufacturing transparent protective film)
Preparation cellulosic triacetate solution is pressed embodiment 2 perparations of specimen 114, but composition below using.
(powder has degree of substitution 2.86 to cellulosic triacetate, and viscosity-average degree of polymerization is 320, water content is 0.4 quality %, viscosity in the 6 quality % dichloromethane solutions is 305mPas, particle mean size 1.5mm and standard deviation 0.5mm) 17.0 mass parts
Methyl acetate 62.4 mass parts
Ethanol 5.7 mass parts
Butanols 6.5 mass parts
Triphenyl (TPP) 1.3 mass parts
Xenyl-diphenyl phosphoester (BDP) 0.7 mass parts
Provide optically isotropic compound (as listed in the table 1) 2.0 mass parts
Regulate compound (as listed in the table 1) 0.8 mass parts of wavelength dispersion
(structure of polarizing plate 8)
Above-mentioned transparent protective film is laminated on the film two sides (polarizer: 20 μ m), this film obtains by making the polyvinyl alcohol (PVA) basement membrane absorb iodine, uses bonding agent to obtain polarizing plate 8.
(laminated optical layer of compensation)
Behind the above-mentioned cellulose acylate sample 115 of surface-saponification, the contact angle that confirms these samples is 38 °.Next, with the coating solution of the alignment films of following composition with line bar coating machine with 20ml/m 2Speed be coated on each film, under 60 ℃ of thermal currents dry 60 seconds, under 100 ℃ of thermal currents dry 120 seconds then.Next, the film that friction forms on the direction that is parallel to the film slow-axis direction.
(composition of the coating solution that alignment films is used)
Modified polyvinylalcohol 15 mass parts of showing down
Water 334 mass parts
Methyl alcohol 100 mass parts
Glutaraldehyde 1 mass parts
P-toluenesulfonic acid 0.3 mass parts
Modified polyvinylalcohol:
Figure A20058001608901231
On the film that is orientated like this, with the disc liquid-crystal compounds of #3.4 line bar coating below dissolving 1.8g in the 3.9g methyl ethyl ketone, 0.2g the trimethylolpropane triacrylate (V#360 of oxirane-modification, OSAKA ORGANIC CHEMICAL INDUSTRIES makes), 0.06g (Irgacure 907 for Photoepolymerizationinitiater initiater, Ciba-Geigy makes), 0.02g emulsion (Kayacure DETX, NIPPON KAYAKU Co., Ltd. makes) and 0.01g below the solution for preparing of the vertical-tropism agent of air-interface side.The product and the metal frame that obtain are bonding, and heat 3 minutes down at 125 ℃ in thermostat, thereby make the disc liquid-crystal compounds orientation.Subsequently, use 120W/cm high-pressure sodium lamp UV irradiation 30 seconds down, make disc liquid-crystal compounds crosslinked, leave standstill cool to room temperature then at 100 ℃.Thereby optical compensating layer is by lamination.
Disc liquid-crystal compounds:
The vertical-tropism agent of air-interface side:
Figure A20058001608901242
When calculating the optical characteristics of discotic mesogenic phase separation layer only, Re 1Be 200nm, the Nz value is 0.54.Therefore, confirmed that the orientation of discotic mesogenic is perpendicular to face.Slow-axis direction is parallel to frictional direction.
(structure of liquid crystal display 8)
Optical compensating polarizing plate 8 is laminated in the brilliant unit of IPS mode liquid crystal, makes the optical compensating layer side watch the surface of side as liquid crystal cell.On that side of liquid crystal cell dorsad,, thereby provide liquid crystal display 8 with contact adhesive lamination polarizing plate 8.The polarizing plate 8 of watching side is by lamination, makes that when not applying voltage the extraordinary refractive index direction of liquid-crystal composition is perpendicular to the absorption axes of optical compensating polarizing plate 8 in the liquid crystal cell.Polarizing plate 8 is set makes the absorption axes 8 of its absorption axes perpendicular to optical compensating polarizing plate.
(evaluation)
Under 45 ° of visual angles, on the plane with measure the contrast ratio of this liquid crystal display from 70 ° of pitch angle of normal direction with respect to vertical polarizing plate optical axis.Therefore, contrast ratio in plane is to be 35 under 370,70 ° of visual angles.In black the demonstration, with the plane degree of staining with under with respect to 45 ° of visual angles of vertical polarizing plate optical axis from the degree of staining comparison at 70 ° of pitch angle of normal direction.As a result, observe less variation.When this liquid crystal display was exposed among 60 ℃ and the 95%RH after 200 hours, check the plane unevenness with bore hole.Therefore, observe less unevenness.Similarly, polarization property variation not almost.
[embodiment 4]
(manufacturing transparent protective film)
By by embodiment 1 but use cellulosic triacetate to prepare cellulosic triacetate solution with big degree of substitution (degree of substitution 2.94, viscosity-average degree of polymerization are 320), thus the perparation of specimen 116.The transparent protective film that obtains is cut into slices (10cm * 2cm), and use Tensilon (Orientec, Co. makes) to stretch 5% with speed 1cm/min.5% the orientation before and afterwards, the plane length of delay of transparent protective film | Re (5)-Re (0)|/5=0.5nm.
(structure of polarizing plate 9) (laminated optical layer of compensation) (structure of liquid crystal display 9)
By embodiment 1 but use above-mentioned transparent protective film to obtain polarizing plate 9, the liquid crystal display 9 of optical compensating polarizing plate 9 and IPS pattern.
(evaluation)
Under 45 ° of visual angles, from the contrast ratio of 70 ° of these liquid crystal displays 9 of incline measurement of normal direction with respect to vertical polarizing plate optical axis.As a result, the contrast ratio is 35.In black the demonstration, with the plane degree of staining with under with respect to 45 ° of visual angles of vertical polarizing plate optical axis from the degree of staining comparison at 70 ° of pitch angle of normal direction.As a result, observe less variation.When this liquid crystal display was exposed among 60 ℃ and the 95%RH after 200 hours, check the plane unevenness with bore hole.
As a result, observe less unevenness.Similarly, polarization property variation not almost.
[embodiment 5]
(manufacturing transparent protective film)
By by embodiment 1 but use cellulose acylate SEF-1 described below, SEF-2 and SEF-3 replace cellulosic triacetate to prepare cellulosic triacetate solution, thus the perparation of specimen 117.Assess performance then.
(cellulose acylate SEF-1)
With the cellulose that obtains from cotton is raw material, synthetic cellulose acylate SEF-1.Cellulose acylate SEF-1 is a kind of powder; its degree of substitution with acetyl group is 1.20; the bytyry degree of substitution is 1.50; total degree of substitution is 2.70; viscosity-average degree of polymerization is 280; water content is 0.2 quality %, and the viscosity in the 6 quality % dichloromethane solutions is 235mPas, particle mean size 1.5mm and standard deviation 0.6mm.In solid cellulose acylate inclusions, remaining acetic acid content is 0.1 quality % or littler, and remaining butyric acid content is 0.1 quality % or littler.Ca content is 85ppm, and Mg content is 30ppm, and Fe content is 0.3ppm, is 130ppm as the sulfur content of sulfate.The degree of substitution of 6-position acetyl group be 0.40 and 6-position bytyry degree of substitution be 0.48.Weight-average molecular weight/number-average molecular weight is 2.6 than (measuring by GPC).
(cellulose acylate SEF-2)
Cellulose acylate SEF-2 is a kind of powder; its degree of substitution with acetyl group is 2.58; the bytyry degree of substitution is 1.30; total degree of substitution is 2.88; viscosity-average degree of polymerization is 365; water content is 0.2 quality %, and the viscosity in the 6 quality % dichloromethane solutions is 290mPas, particle mean size 1.4mm and standard deviation 0.6mm.
(cellulose acylate SEF-3)
Cellulose acylate SEF-3 is a kind of powder; degree of substitution with acetyl group is 1.00; the propiono degree of substitution is 1.85; total degree of substitution is 2.85; viscosity-average degree of polymerization is 280; water content is 0.19 quality %, and the viscosity in the 6 quality % dichloromethane solutions is 105mPas, particle mean size 1.5mm and standard deviation 0.4mm.
The transparent protective film that obtains is cut into slices (10cm * 2cm), and use Tensilon (Orientec, Co. makes) to stretch 5% with speed 1cm/min.5% the orientation before and afterwards, the plane length of delay of transparent protective film | Re (5)-Re (0)|/5=0.5nm.
(structure of polarizing plate 10) (laminated optical layer of compensation) (structure of liquid crystal display 10)
By embodiment 1 but use above-mentioned transparent protective film to obtain polarizing plate 10, the liquid crystal display 10 of optical compensating polarizing plate 10 and IPS pattern.
(evaluation)
Under 45 ° of visual angles, from the contrast ratio of 70 ° of incline measurement liquid crystal displays 9 of normal direction with respect to vertical polarizing plate optical axis.As a result, the contrast ratio is 35.In black the demonstration, with the plane degree of staining with under with respect to 45 ° of visual angles of vertical polarizing plate optical axis from the degree of staining comparison at 70 ° of pitch angle of normal direction.As a result, observe less variation.When this liquid crystal display was exposed among 60 ℃ and the 95%RH after 200 hours, check the plane unevenness with bore hole.As a result, observe less unevenness.Similarly, polarization property variation not almost.Therefore, should be appreciated that the plain acylate of special fiber is preferred among the present invention.
[embodiment 6]
(manufacturing transparent protective film)
In having the stainless steel dissolving tank (4000L) of stirring vane, cellulose ethanoate powder (thin slice) is added in the solvent mixture solution that comprises following composition gradually, fully stir and disperse, reach 2000kg up to total amount.Add the present invention respectively and reduce optically anisotropic compound and wavelength dispersion correctives of the present invention (as listed in the table 1), obtain sample 107～113 and sample 118～121.
Cellulosic triacetate (degree of substitution 2.94, viscosity-average degree of polymerization are 320)
17.0 mass parts
Methylene chloride 70.5 mass parts
Methyl alcohol 10.5 mass parts
Provide optically isotropic compound (as listed in the table 1) 2.0 mass parts
Regulate compound (as listed in the table 1) 0 or 8 mass parts of wavelength dispersion
When at arbitrary region (1m 2) when measuring, plane phase difference value Re is 1 ± 1nm, thickness direction phase difference value Rth is 0 ± 1nm.Handle transparent protective film after 240 hours under 60 ℃ and 90%RH, Re and Rth show the variation of 3nm and 5nm respectively.Handle transparent protective film down after 240 hours at 80 ℃, Re and Rth show the variation of 2nm and 5nm respectively.
(structure of polarizing plate 11～21)
With above-mentioned each transparent protective film (107～113 and 118～121) and anti-reflective film CV02L80 (Fuji Photo Film Co.; Ltd. make; 80 μ m) be laminated to (polarizer: 20 μ m) on the film two sides; this film makes it absorb iodine then by the saponified polyvinyl alcohol basement membrane and obtains, use bonding agent to obtain polarizing plate 11～21.
(laminated optical layer of compensation)
By the stretching polycarbonate membrane, its thickness of the optical compensating layer that obtains is 60 μ m, Re 1Be 210nm, the Nz value is 0.48.This optical compensating layer is laminated on the polarizing plate 11～17 of sample 107～113 sides with contact adhesive, the feasible slow axis of optical compensating layer in each case is parallel to the absorption axes of polarizing plate.Therefore, obtain optical compensating polarizing plate 11～21.
(structure of liquid crystal display 11)
Optical compensating polarizing plate 11 is laminated in the brilliant unit of IPS mode liquid crystal, makes the optical compensating layer side watch the surface of side as liquid crystal cell.On that side of liquid crystal cell dorsad,, thereby provide liquid crystal display 11 with contact adhesive lamination polarizing plate 11.The polarizing plate 11 of watching side is by lamination, makes that when not applying voltage the extraordinary refractive index direction of liquid-crystal composition is perpendicular to the absorption axes of optical compensating polarizing plate 11 in the liquid crystal cell.Polarizing plate 11 is set makes the absorption axes of its absorption axes perpendicular to optical compensating polarizing plate.
(evaluation)
Use contrast instrument (EZ-Contrast, ELDIM makes), under 45 ° of visual angles, on the plane with from the contrast ratio of this liquid crystal display of 70 ° of pitch angle measurements of normal direction with respect to vertical polarizing plate optical axis.Therefore, contrast ratio in plane is to be 35 under 370,70 ° of visual angles.In black the demonstration, with the plane degree of staining with under 45 ° of visual angles, from the degree of staining comparison at 70 ° of pitch angle of normal direction with respect to vertical polarizing plate optical axis.As a result, observe less variation.When this liquid crystal display was exposed among 60 ℃ and the 95%RH after 200 hours, check the plane unevenness with bore hole.As a result, observe less unevenness.Similarly, polarization property variation not almost.
(structure of liquid crystal display 12～21)
Press the structure construction liquid crystal display 12～21 of liquid crystal display 11, but use polarizing plate 12～21 to replace polarizing plate 11, use optical compensating polarizing plate 12～21 to replace optical compensating polarizing plate 21.As a result, obtain similar performance.
[embodiment 7]
(manufacturing transparent protective film)
By under 140 ℃, being stretched across stiff end with sample 118～121 stretching 1.1-times that obtain among the embodiment 6, in 10% sodium hydrate aqueous solution, flooded 1 minute down then at 75 ℃, carry out hydrophilicity-imparting treatment.Use the pure water washing sample then, carried out hydrophiling in dry 3 minutes down, obtain transparent protective film 122～125 at 70 ℃.
(structure of polarizing plate 22～25)
With above-mentioned each transparent protective film (122～125) and anti-reflective film CV02L80 (Fuji PhotoFilm Co.; Ltd. make; 80 μ m) be laminated to (polarizer: 20 μ m) on the film two sides; this film is by the saponified polyvinyl alcohol basement membrane and its absorption iodine is obtained, and uses bonding agent to obtain polarizing plate 22～25.
(laminated optical layer of compensation)
By pressing embodiment 6 stretching polycarbonate membranes, obtain optical compensating layer, this optical compensating layer is laminated on the polarizing plate 22～25 of sample 122～125 sides with contact adhesive, the feasible slow axis of optical compensating layer in each case is parallel to the absorption axes of polarizing plate.As a result, obtain optical compensating polarizing plate 22～25.
(structure of liquid crystal display 22)
Optical compensating polarizing plate 22 is laminated in the brilliant unit of IPS mode liquid crystal, makes the optical compensating layer side watch the surface of side as liquid crystal cell.On that side of liquid crystal cell dorsad,, thereby provide liquid crystal display 22 with contact adhesive lamination polarizing plate 22.The polarizing plate 22 of watching side is by lamination, makes that when not applying voltage the extraordinary refractive index direction of liquid-crystal composition is perpendicular to the absorption axes of optical compensating polarizing plate 22 in the liquid crystal cell.Polarizing plate 22 is set makes the absorption axes of its absorption axes perpendicular to optical compensating polarizing plate.
(evaluation)
Use contrast instrument (EZ-Contrast, ELDIM makes), under 45 ° of visual angles, on the plane with from the contrast ratio of this liquid crystal display of 70 ° of pitch angle measurements of normal direction with respect to vertical polarizing plate optical axis.As a result, contrast ratio in plane is to be 35 under 370,70 ° of visual angles.In black the demonstration, with the plane degree of staining with under 45 ° of visual angles, from the degree of staining comparison at 70 ° of pitch angle of normal direction with respect to vertical polarizing plate optical axis.As a result, observe less variation.When this liquid crystal display was exposed among 60 ℃ and the 95%RH after 200 hours, check the plane unevenness with bore hole.As a result, observe less unevenness.Similarly, polarization property variation not almost.
(structure of liquid crystal display 23～25)
Press the structure construction liquid crystal display 23～25 of liquid crystal display 22, but use polarizing plate 13～25 to replace polarizing plate 22, use optical compensating polarizing plate 13～25 to replace optical compensating polarizing plate 21.Therefore, obtain similar performance.
[embodiment 8]
(laminated optical layer of compensation)
On the sample 118～121 that in embodiment 6, obtains, by the alignment films laminated optical layer of compensation of embodiment 1.Next,, in 10% sodium hydrate aqueous solution, flooded 1 minute down then, carry out hydrophilicity-imparting treatment at 75 ℃ by under 140 ℃, vertically sample being stretched 1.05-doubly.Use the pure water washing sample then, carried out hydrophiling down in dry 3 minutes at 70 ℃.Use contact adhesive to carry out lamination, make the slow axis of optical compensating layer be parallel to the absorption axes of polarizing plate, obtain having the optical compensating layer 26～29 of diaphragm.
(optical compensating polarizing plate 26～29)
With above-mentioned optical compensating layer (26～29) and anti-reflective film CV02L80 (the Fuji Photo Film Co. that respectively has diaphragm; Ltd. make; 80 μ m) be laminated to (polarizer: 20 μ m) on the film two sides; this film is by the saponified polyvinyl alcohol basement membrane and its absorption iodine is obtained, and uses bonding agent to obtain polarizing plate 26～29.
(structure of liquid crystal display 26)
Optical compensating polarizing plate 26 is laminated in the brilliant unit of IPS mode liquid crystal, makes the optical compensating layer side watch the surface of side as liquid crystal cell.On that side of liquid crystal cell dorsad,, thereby provide liquid crystal display 26 with contact adhesive lamination polarizing plate 26.The polarizing plate 26 of watching side is by lamination, makes that when not applying voltage the extraordinary refractive index direction of liquid-crystal composition is perpendicular to the absorption axes of optical compensating polarizing plate 26 in the liquid crystal cell.Polarizing plate 26 is set makes the absorption axes of its absorption axes perpendicular to optical compensating polarizing plate.
(evaluation)
Use contrast instrument (EZ-Contrast, ELDIM makes), under 45 ° of visual angles, on the plane with from the contrast ratio of this liquid crystal display of 70 ° of pitch angle measurements of normal direction with respect to vertical polarizing plate optical axis.As a result, contrast ratio in plane is to be 35 under 370,70 ° of visual angles.In black the demonstration, with the plane degree of staining with under 45 ° of visual angles, from the degree of staining comparison at 70 ° of pitch angle of normal direction with respect to vertical polarizing plate optical axis.As a result, observe less variation.When this liquid crystal display was exposed among 60 ℃ and the 95%RH after 200 hours, check the plane unevenness with bore hole.Therefore, observe less unevenness.Similarly, polarization property variation not almost.
(structure of liquid crystal display 27～29)
Press the structure construction liquid crystal display 27～29 of liquid crystal display 26, but use polarizing plate 27～29 to replace polarizing plate 26, use optical compensating polarizing plate 27～29 to replace optical compensating polarizing plate 26.As a result, obtain similar performance.
[comparative example 1]
By make the polyvinyl alcohol (PVA) basement membrane absorb iodine and the two sides of the film that obtains of stretching on (polarizer: 20 μ m); use the contact adhesive lamination as the cellulosic triacetate film of transparent protective film (T80UZ, by Fuji Photo Film Co., Ltd. makes; 80 μ m), obtain polarizing plate.The cellulosic triacetate film thickness is 80 μ m, and plane phase differential Re is 4nm, and thickness direction phase differential Rth is 45nm.
By embodiment 1 this polarizing plate is laminated on the liquid crystal cell two sides of IPS pattern, obtains liquid crystal display.Arrangement is arranged on the polarizing plate on the liquid crystal cell two sides, makes that their polarization axle is vertical mutually.
Under 45 ° of visual angles, on the plane with measure the contrast ratio of this liquid crystal display from 70 ° of pitch angle of normal direction with respect to vertical polarizing plate optical axis.As a result, contrast ratio in plane is to be 9 under 370,70 ° of visual angles.In black the demonstration, under 45 ° of visual angles, observe from 70 ° of pitch angle of normal direction and seriously to become blueness.
[comparative example 2]
Use contact adhesive with film (TAC TD80U; Fuji Photo Film Co.; Ltd. make; 80 μ m) be laminated to by make the polyvinyl alcohol (PVA) basement membrane absorb iodine and a face of the film that obtains of stretching on (polarizer: 20 μ m); simultaneously ZEONOR film (ZEON Co. preparation) is laminated on the another side as transparent protective film, obtains polarizing plate.The ZEONOR film thickness is 80 μ m, and plane phase differential Re is 1nm, and thickness direction phase differential Rth is 4nm.
By embodiment 1 this polarizing plate is laminated on the liquid crystal cell two sides of IPS pattern, obtains liquid crystal display.Arrangement is arranged on the polarizing plate on the liquid crystal cell two sides, makes that their polarization axle is vertical mutually.
Under 45 ° of visual angles, on the plane with measure the contrast ratio of this liquid crystal display from 70 ° of pitch angle of normal direction with respect to vertical polarizing plate optical axis.As a result, contrast ratio in plane is to be 10 under 360,70 ° of visual angles.In black the demonstration, under 45 ° of visual angles, observe from 70 ° of pitch angle of normal direction and seriously to become blueness.When this liquid crystal display is exposed among 60 ℃ and the 95%RH 200 hours, when taking out then, observe polarizer and ZEONOR occur at the interface peel off, occur inhomogeneously simultaneously, and contrast reduces.
[comparative example 3]
Use contact adhesive with film (TAC TD80U; Fuji Photo Film Co.; Ltd. make; 80 μ m) be laminated to by make the polyvinyl alcohol (PVA) basement membrane absorb iodine and a face of the film that obtains of stretching on (polarizer: 20 μ m); phase retardation film (the plane phase differential 100nm that the while lamination obtains by the stretching polycarbonate membrane; Nz=0.5) as transparent protective film, make the slow axis of phase retardation film be parallel to the absorption axes of polarizing plate, obtain optical compensating polarizing plate 17.By embodiment 1 optical compensating polarizing plate that forms is laminated in the brilliant unit of IPS mode liquid crystal, makes the optical compensating layer side watch the surface of side as liquid crystal cell.On that side of liquid crystal cell dorsad, press the polarizing plate 1 that uses among the embodiment 1 with pressure sensitive adhesive layer, thereby liquid crystal display 17 is provided.
Under 45 ° of visual angles, on the plane with measure the contrast ratio of this liquid crystal display from 70 ° of pitch angle of normal direction with respect to vertical polarizing plate optical axis.As a result, contrast ratio in plane is to be 15 under 360,70 ° of visual angles.In black the demonstration, under 45 ° of visual angles, observe from 70 ° of pitch angle of normal direction and seriously to become blueness.When this liquid crystal display is exposed among 60 ℃ and the 95%RH 200 hours, when taking out then, observe polarizer and ZEONOR occur at the interface peel off, occur inhomogeneously simultaneously, and contrast reduces.
[comparative example 4]
Use contact adhesive with film (TAC TD80U; Fuji Photo Film Co.; Ltd. make; 80 μ m) be laminated to by make the polyvinyl alcohol (PVA) basement membrane absorb iodine and a face of the film that obtains of stretching on (polarizer: 20 μ m); phase retardation film (the plane phase differential 120nm that the while lamination obtains by the stretching polycarbonate membrane; Nz=1.0) as transparent protective film, make the slow axis of phase retardation film be parallel to the absorption axes of polarizing plate, obtain optical compensating polarizing plate 18.By embodiment 1 optical compensating polarizing plate that forms is laminated in the brilliant unit of IPS mode liquid crystal, makes the optical compensating layer side watch the surface of side as liquid crystal cell.On that side of liquid crystal cell dorsad, press the polarizing plate 1 that uses among the embodiment 1 with pressure sensitive adhesive layer, thereby liquid crystal display is provided.
Under 45 ° of visual angles, on the plane with measure the contrast ratio of this liquid crystal display from 70 ° of pitch angle of normal direction with respect to vertical polarizing plate optical axis.As a result, contrast ratio in plane is to be 8 under 370,70 ° of visual angles.In black the demonstration, under 45 ° of visual angles, observe from 70 ° of pitch angle of normal direction and seriously to become blueness.When this liquid crystal display is exposed among 60 ℃ and the 95%RH 200 hours, when taking out then, observe polarizer and ZEONOR occur at the interface peel off, take place inhomogeneously simultaneously, and contrast reduces.
The optical property of table 1 sample 101～116
Sample Embodiment Film thickness μ m The cellulose ethanoate degree of substitution Reduce optically anisotropic reagent (LogP) Re (590) nm Rth (590) m Wavelength dispersion correctives (LogP) |Re (400) -Re (700)| nm |Rth (400) -Rth (700)| nm Dope transparency % Film Tg ℃ Film turbidity % ΔRth nm (10％RH -80％ RH) H 2O content % (%RH) Vapour transmission rate (being scaled 80 μ m) g/m 2My god
101 1 80 2.86 A-19 (5.9% pair of cellulose) 2.9 1.8 23.8 Do not have - 6.0 23.1 93.4 138.4 0.33 27.7 3.4 1482
102 1 80 2.86 A-19 (12% pair of cellulose) 2.9 1.9 7.2 Do not have - 5.2 24.4 93.2 138.5 0.35 26.5 3.2 1346
103 1 80 2.86 A-19 (12% pair of cellulose) 2.9 1.0 14.9 UV-102 (1.8% pair of cellulose) 5.6 1.1 14.7 92.1 134.2 0.42 25.4 3.1 1152
104 1 60 2.86 A-19 (12% pair of cellulose) 2.9 2.0 12.3 UV-102 (1.8% pair of cellulose) 5.6 0.8 14.2 92.4 134.0 0.35 24.8 3.0 1164
105 1 40 2.86 A-19 (12% pair of cellulose) 2.9 1.3 8.2 UV-102 (1.8% pair of cellulose) 5.6 0.1 13.8 91.8 133.9 0.32 23.9 3.1 1158
106 1 80 2.86 C-1 (12% pair of cellulose) 1.2 1.3 -22.5 Do not have - 9.0 21.5 90.3 132.4 0.31 - 2.7 1688
107 5 80 2.94 A-7 (12% pair of cellulose) 6.4 0.5 -2.1 Do not have - 3.2 13.0 91.4 136.2 0.33 - 3.0 1584
108 5 80 2.94 B-30 (12% pair of cellulose) 3.1 1.1 5.1 Do not have - 3.4 14.2 92.3 138.1 0.32 - 3.1 1543
109 5 80 2.94 PL-1 (12% pair of cellulose) 1.2 0.8 -7.6 Do not have - 4.0 14.5 90.7 137.4 0.34 - 3.4 1538
110 5 80 2.94 PL-19 (12% pair of cellulose) 2.4 1.0 7.3 Do not have - 5.0 11.0 89.4 124.5 0.24 - 3.6 1595
111 5 80 2.94 D-7 (12% pair of cellulose) 3.7 1.7 -9.9 Do not have - 5.0 18.1 92.2 138.0 0.27 - 3.2 1405
112 5 80 2.94 E-1 (12% pair of cellulose) 2.8 0.8 6.5 Do not have - 6.0 17.4 93.0 133.0 0.23 - 2.8 1438
113 5 80 2.94 I-10 (12% pair of cellulose) 3.0 0.2 17.1 UV-21+ UV-22 (total 1.8% pair of cellulose) 10.1 0 4.8 14.8 89.4 132.8 0.36 - 2.7 1128
114 2 80 2.86 L-1 (12% pair of cellulose) 4.0 0.4 11.4 UV-21+ UV-22 (total 1.8% pair of cellulose) 10.1 0 4.4 13.2 90.2 131.3 0.32 - 2.9 1178
115 3 40 2.86 A-19 (12% pair of cellulose) 2.9 0.3 3.2 UV-102 (3.6% pair of cellulose) 5.6 1.2 7.5 93.3 134.3 0.34 24.9 3.3 1063
116 4 40 2.94 A-19 (12% pair of cellulose) 2.9 0.5 0.2 UV-102 (3.6% pair of cellulose) 5.6 1.0 2.8 93.1 133.8 0.36 23.7 3.2 958
Table 2
Sample Embodiment Film thickness The TAC-degree of substitution The Rth-depressant Re Rth The wavelength dispersion correctives ΔRe ΔRth Transparency Tg Turbidity The humidity correlativity H 2O content The vapour transmission rate
118 5，6，7 80 2.94 A-19 0.8 -1.1 UV-102 (1.8％) 1.0 10.0 93.1 134 0.20 - 2.8 1020
119 5，6，7 90 2.94 A-19 1.0 -2.1 UV-102 (1.8％) 1.2 12.1 92.8 134 0.23 - 2.8 952
120 5，6，7 80 2.94 D-7 1.1 -1.5 UV-21-22 (1.8％) 1.4 11.7 93.1 137 0.28 - 2.9 1120
121 5，6，7 90 2.94 D-7 1.5 -2.4 UV-21-22 (1.8％) 1.9 13.8 92.0 137 0.32 - 2.9 980

Claims (25)

1. an optical compensating polarizing plate comprises: first transparent protective film in order; Polarizer; Second transparent protective film; And optical compensating layer; wherein at least one in first and second transparent protective films is cellulose acylate film; its plane length of delay Re (nm) and film thickness direction length of delay Rth (nm) satisfy following formula (I) and (II) with by the following formula (III) and (IV) Nz and the Re of optical compensating layer of definition 1Satisfy following formula (V) and (VI):
(I)|Re|≤10
(II)|Rth|≤25
(III)Nz＝(nx 1-nz 1)/(nx 1-ny 1)
(IV)Re 1＝(nx 1-ny 1)×d 1
(V)0.4≤Nz≤0.6
(VI)100≤Re 1≤350
Re wherein 1It is the plane length of delay (nm) under the wavelength 590nm; Nz is the Nz factor under the wavelength 590nm; Nx 1It is refractive index along the membrane plane slow axis; Ny 1Be the refractive index of edge perpendicular to the direction of membrane plane slow axis; Nz 1It is refractive index along film thickness direction; And d 1Be the thickness (nm) of film.
2. optical compensating polarizing plate as claimed in claim 1, wherein at least one in first and second transparent protective films satisfies following formula (VII):
(VII) | Re (400)-Re (700)|≤10 Hes | Rth (400)-Rth (700)|≤35,
Wherein Re (λ) is the plane length of delay (nm) under the wavelength X mn; And Rth (λ) is the film thickness direction length of delay (nm) under the wavelength X mn.
3. optical compensating polarizing plate as claimed in claim 1, wherein at least one thickness in first and second transparent protective films is 10～120 μ m.
4. optical compensating polarizing plate as claimed in claim 1, wherein at least one in first and second transparent protective films satisfies following formula (VIII):
(VIII) | Re (MAX)-Re (MIN) |≤6 Hes | Rth (MAX)-Rth (MIN) |≤10
Wherein Re (MAX) and Rth (MAX) are the 1m that downcuts at random 2The maximum delay value of diaphragm (nm); Re (MIN) and Rth (MIN) are its minimum delay values (nm).
5. optical compensating polarizing plate as claimed in claim 1, wherein at least one in first and second transparent protective films contains at least a length of delay Rth of film thickness direction can being reduced to and satisfies following formula (IX) and scope (X):
(IX) (Rth(A)-Rth(0))/A≤1.0
(X) 0.1≤A≤30
Rth (A) is the Rth (nm) of film that contains the compound that can reduce Rth of A%; Rth (0) is the Rth (nm) that does not contain the film of the compound that can reduce Rth; A is that the polymer quality as membrane material is the quality (%) of 100 o'clock compounds.
6. optical compensating polarizing plate as claimed in claim 5, the compound that wherein can reduce Rth are that octanol-water partition coefficient (LogP) is 0～7 compound.
7. optical compensating polarizing plate as claimed in claim 5, it contains at least a following formula (13) that is selected from, and the compound of (18) and (19) representative is 0.01～30wt.% as the compound that reduces Rth by its amount of solid cellulose acylate content:
R wherein 1Represent alkyl or aryl, R 2And R 3Each represents hydrogen atom independently, alkyl or aryl, and condition is R 1, R 2And R 3Middle carbon atom summation is 10 or bigger;
Figure A2005800160890003C2
R wherein 1Represent alkyl or aryl, R 2And R 3Each represents hydrogen atom, alkyl or aryl independently;
Figure A2005800160890003C3
R wherein 4, R 5And R 6Each represents alkyl or aryl independently.
8. optical compensating polarizing plate as claimed in claim 1, wherein at least one in first and second transparent protective films contains at least a can the reduction | Re (400)-Re (700)| and | Rth (400)-Rth (700)| compound, be 0.01～30wt.% by its amount of solid cellulose acylate content.
9. optical compensating polarizing plate as claimed in claim 1, wherein at least one in first and second transparent protective films has a slow axis in a lateral direction perpendicular to the film machine direction.
10. optical compensating polarizing plate as claimed in claim 1, wherein at least one in first and second transparent protective films is by alkali-saponification, and its contact angle of the film of alkali-saponification surface is 55 ° or littler.
11. optical compensating polarizing plate as claimed in claim 1, wherein at least one in first and second transparent protective films handled after 240 hours under 60 ℃ and 90%RH, and the variation of Re and Rth is 15nm or littler.
12. optical compensating polarizing plate as claimed in claim 1, wherein processing is after 240 hours down at 80 ℃ at least one in first and second transparent protective films, and the variation of Re and Rth is 15nm or littler.
13. optical compensating polarizing plate as claimed in claim 1, wherein at least one in first and second transparent protective films is the film that stretches, and optical compensating layer is provided after stretching.
14. optical compensating polarizing plate as claimed in claim 1, wherein at least one in first and second transparent protective films is the film that stretches, and stretches after optical compensating layer is provided.
15. optical compensating polarizing plate as claimed in claim 13, wherein before stretching and afterwards, the plane length of delay of at least one in first and second transparent protective films satisfies following formula (XI):
(XI) |Re(n)-Re(0)|/n≤1.0
Wherein Re (n) is the plane length of delay (nm) of the film of stretching n (%); And Re (0) is the plane length of delay (nm) of the film that do not stretch.
16. optical compensating polarizing plate as claimed in claim 1, wherein at least one in first and second transparent protective films comprises that the acyl substituted degree is 2.70～3.00 cellulose ethanoate.
17. optical compensating polarizing plate as claimed in claim 1, wherein at least one in first and second transparent protective films comprises the cellulose acylate that satisfies following formula (XII)～(XIV):
(XII) 2.50≤SA+SB≤3.00
(XIII) 0≤SA≤2.5
(XIV) 0.5≤SB≤3.00
Wherein SA is the degree of substitution of acetyl group; With SB be the degree of substitution of acyl group with replacement of 3～22 carbon atoms.
18. optical compensating polarizing plate as claimed in claim 1, wherein optical compensating layer be wherein bar-shaped or discotic compound perpendicular in first and second transparent protective films at least one the surface and the optical compensating layer that is orientated.
19. optical compensating polarizing plate as claimed in claim 1, wherein optical compensating layer contains and has just intrinsic birefringence value and be selected from polyamide, polyimide, polyester, polyetherketone, the polymkeric substance of polyamidoimide and polyester-imide.
20. optical compensating polarizing plate as claimed in claim 1, wherein optical compensating layer contains the polymkeric substance with negative intrinsic birefringence value.
21. optical compensating polarizing plate as claimed in claim 1, it is bonding that wherein at least one in first and second transparent protective films passed through adhesive phase or pressure sensitive adhesive layer and optical compensating layer.
22. optical compensating polarizing plate as claimed in claim 1, it also comprises and is selected from hard conating, the one deck at least in anti-flash layer and the anti-reflecting layer.
23. an image-display units, it comprises optical compensating polarizing plate as claimed in claim 1.
24. liquid crystal display that comprises the image-display units of IPS pattern; optical compensating polarizing plate wherein as claimed in claim 1 is arranged on brilliant first substrate of watching side; the polarizing plate that comprises transparent protective film as claimed in claim 1 and polarizer is arranged on brilliant first substrate and watches dorsad on that side of side, and the major axes orientation of liquid crystal molecule is not parallel to the absorption axes direction of polarizing plate in the liquid crystal cell when applying voltage.
25. liquid crystal display that comprises the image-display units of IPS pattern; polarizing plate comprising transparent protective film as claimed in claim 1 and polarizer is arranged on brilliant first substrate of watching side; optical compensating polarizing plate as claimed in claim 1 be arranged on brilliant first substrate watch dorsad side that side on, when not applying voltage in the liquid crystal cell major axes orientation of liquid crystal molecule perpendicular to the absorption axes direction of polarizing plate.
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