KR101112443B1 - Cellulose film, polarizing film and liquid crystal display - Google Patents

Abstract

(Problem) The present invention provides a cellulose film having a small change in optical compensation ability due to heat and humidity.

(Solution means) A polarizing plate and a liquid crystal display device using a cellulose film containing at least two kinds of retardation regulators and the film.

Description

Cellulose film, polarizer and liquid crystal display device {CELLULOSE FILM, POLARIZING FILM AND LIQUID CRYSTAL DISPLAY}

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing which shows the structural example which combined the polarizing plate and functional optical film of this invention, Example (A) which adhered the functional optical film and polarizer through an adhesive as one protective film of a polarizing plate, and a protective film on both surfaces of a polarizer. The example (B) which adhered the functional optical film to the polarizing plate which formed this through the adhesive is shown, respectively.

It is explanatory drawing which shows an example of the liquid crystal display device in which the polarizing plate of this invention is used.

* Explanation of symbols for the main parts of the drawings *

1, 1a, 1b: protective film

2: polarizer

3: functional optical film

4: adhesive layer

11: upper polarizer

12: upper polarizer absorption axis

13: upper optically anisotropic layer (viewing angle expanding film)

14: Upper optically anisotropic layer orientation control direction                 

15: liquid crystal cell upper electrode substrate

16: Upper substrate orientation control direction

17: liquid crystal layer

18: liquid crystal cell lower electrode substrate

19: Lower substrate orientation control direction

20: lower optically anisotropic layer (viewing angle expanding film)

21: Lower optically anisotropic layer orientation control direction

22: lower polarizer

23: lower polarizer absorption axis

This invention relates to the cellulose film useful as retardation film, etc., and the polarizing plate and liquid crystal display device which use this film.

Background Art [0002] Liquid crystal display devices have been widely used year by year as small-size image display devices with small power consumption. Conventionally, a large drawback of a liquid crystal display device is that a large dependence of the viewing angle of an image is a disadvantage, but recently, a high viewing angle liquid crystal mode such as a VA mode, an IPS mode, and the like has been put into practical use. Demand is growing rapidly.

Accordingly, even higher performance has started to be required for retardation films used in liquid crystal displays and polarizing plates using the same. In particular, the improvement of the durability with respect to temperature and humidity is a big subject of a polarizing plate.

Particularly problematic in the durability test of the polarizing plate is a decrease in the degree of polarization, but since this is caused by the decomposition of iodine adsorbed by the polarizer due to the action of water, it is effective to reduce the water permeability of the protective film of the polarizing plate. Known. However, since the cellulose acylate itself used for the protective film of a polarizing plate is a very hydrophilic polymer, and high water permeability is high, the method of adding a various hydrophobic agent and reducing water permeability is proposed. Patent Document 1 discloses a method of adding a rosin derivative and an epoxy resin to a cellulose acylate film to reduce the moisture permeability. However, the improvement effect was not enough with these methods.

On the other hand, the cellulose acetate film has been conventionally used in a polarizing plate protective film on the advantage of having a small optical anisotropy, but in recent years, the cellulose acetate film has been used in combination with a function as a retardation film by providing a phase difference by biaxial stretching or the like. Patent Document 2 discloses a method of adding a high planar compound to a cellulose acylate film. However, these methods have a problem that it is difficult to achieve both the optical properties required for the retardation film and the water permeability required for the polarizing plate protective film, and the humidity dependency of the optical properties of the retardation film itself is also large.

(Patent Document 1) Japanese Unexamined Patent Publication No. 2002-146044

(Patent Document 2) Japanese Unexamined Patent Publication No. 2001-166144

An object of the present invention is to provide a cellulose film useful as a retardation film, for example, in which a change in optical compensation ability due to heat and humidity is small.

Another object of the present invention is to provide a polarizing plate with a small change in transmittance and polarization degree due to heat and humidity.

Still another object of the present invention is to use a polarizing plate having a retardation film having excellent viewing angle compensability and / or a protective film having low moisture permeability on both sides of the polarizer in a liquid crystal display, so that problems such as light leakage do not occur, It is to provide a liquid crystal display device having a wide viewing angle and high display quality.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, when adding both the compound of the high planarity and the compound which has an aromatic ring but the compound of low planarity to a cellulose acylate film, the water permeability of the cellulose acylate film obtained will fall remarkably, and the cellulose The humidity dependence of the optical characteristic of an acylate film was found to become small. In addition, it was found that by adjusting the ratio of the disk-shaped compound and the compound having low planarity, a wide range of optical characteristics can be adjusted while maintaining the humidity dependence of moisture permeability and optical characteristics. The former has the effect of raising the retardation, and the latter has the effect of decreasing the retardation.

That is, this invention provides the following means.

1) A cellulose film comprising at least two kinds of retardation regulators.

2) The cellulose film of 1) containing at least one kind of retardation increasing agent and a retardation lowering agent, respectively.

3) At least 1 type of the compound represented by the following general formula (I) and at least 1 type of the compound represented by the following general formula (II), (III) or (IV) are contained, The cellulose film characterized by the above-mentioned.

General formula (Ⅰ)

(Wherein X ¹ is a single bond, -NR ^4- , -O- or -S-; X ² is a single bond, -NR ^5- , -O- or -S-; X ³ is, A single bond, -NR ^6- , -O- or -S-, R ¹ , R ² and R ³ are each independently an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; and R ⁴ , R ⁵ And R ⁶ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. The alkyl group, alkenyl group, aryl group, and heterocyclic group may each have a substituent.)

General formula (Ⅱ)

[In formula, R <^21> , R <^22> and R <^23> respectively independently represents a hydrogen atom or an alkyl group. X ²¹ represents a divalent linking group formed from at least one group selected from the linking group group 1 below. Y ²¹ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

(Connection gigun 1) a single ^{bond, -O-, -CO-, -NR 24 -} , represents an alkylene group or arylene group. R ²⁴ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.]

General formula (Ⅲ)

[Wherein, R ³¹ represents an alkyl group or an aryl group, and R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group or an aryl group. The total number of carbon atoms of R ³¹ , R ³² and R ³³ is 10 or more, and the alkyl group and the aryl group may each have a substituent. R ³¹ and R ³² may combine to form a ring.]

General formula (Ⅳ)

(Wherein, X ⁴² represents B, CR ⁷⁰ (R ⁷⁰ represents a hydrogen atom or a substituent.), N, P or P = O. R ⁴⁰ , R ⁵⁰ and R ⁶⁰ are each independently aryl. (R ⁴⁰ , R ⁵⁰ and R ⁶⁰ preferably each independently represent a substituted or unsubstituted phenyl group.) The aryl group, cycloalkyl group and heterocyclic group each represent a substituent. R ⁴⁰ and R ⁵⁰ may combine to form a ring.)

4) Rth [nm] and Re [nm] defined by the following formulas (A) and (B)

30 nm ≤ Rth ≤ 300 nm,

2nm≤Re≤80nm

And Rth / Re ratio is 1-6, The cellulose film in any one of 1) -3) characterized by the above-mentioned.

(A) Formula Re [nm] = (nx-ny) × d

(B) Formula Rth [nm] = {(nx + ny) / 2-nz} × d

[Wherein, nx is a refractive index in the slow axis direction in the film plane; ny is the refractive index of the fast-axis direction in a film plane; nz is a refractive index in the thickness direction of the film; And d is the thickness [nm] of the film.]

5) The cellulose film according to any one of 1) to 4), wherein the water vapor transmission rate at 60 ° C. 95% RH 24hr is 400 g / m 2 · 24 hr or more and 2000 g / m 2 · 24 hr or less.

6) The equilibrium moisture content of 25 ° C 80% RH is 3.0% or less, and the ratio of the equilibrium moisture content of 25 ° C 80% RH to the equilibrium moisture content of 25 ° C 10% RH is 3 or more and 10 or less. Cellulose film of any one of).

7) The cellulose film according to any one of 1) to 6), wherein a ratio of Rth of 25 ° C to 80% RH to Rth of 25 ° C of 10% RH is 0.65 or more.

8) The cellulose film according to any one of 1) to 7), wherein the ratio of Re at 25 ° C to 80% RH to Re at 25 ° C for 10% RH is 0.65 or more.

9) The polarizing plate which sticks a protective film on both sides of a polarizer, WHEREIN: At least 1 piece of the protective film is a cellulose film in any one of 1) -8), The polarizing plate characterized by the above-mentioned.

10) The polarizing plate which provided the adhesion layer in the polarizing plate of 9).

11) The polarizing plate of 9), wherein an antiglare layer is formed on the air side protective film.

12) The polarizing plate of 9) characterized by having a reflective layer or a transflective reflective layer.

13) The polarizing plate of 9) characterized by having a retardation layer or (lambda) / 4 layer.

14) The polarizing plate of 9) characterized by having a viewing angle compensation film (viewing angle compensation layer).

15) The polarizing plate of 9) characterized by having a brightness enhancement layer.

16) The liquid crystal display device which consists of a liquid crystal cell and two polarizing plates arrange | positioned at both sides, and at least 1 polarizing plate is a polarizing plate in any one of 9) -15).

In the present invention, the retardation regulator is to change the retardation of the cellulose film, and when it contains at least two kinds thereof, an excellent effect can be obtained, and at least one of each of the retardation increasing agent and the retardation lowering agent is included. desirable.

Here, the retardation increasing agent is a Rita of a cellulose acylate film compared with retardation when it is not added, when 0.1-30 mass parts, Preferably 1-10 mass parts is added with respect to 100 mass parts of cellulose acylates. The compound which raises a date by 10 nm or more, Preferably it is 50 nm or more and 250 nm or less.

In addition, when retardation lowering agent is 0.1-30 mass parts with respect to 100 mass parts of cellulose acylates, Preferably 0.5-10 mass parts is added, the retarder of a cellulose acylate film compared with the retardation when it is not added The compound which lowers a date by 5 nm or less, Preferably 5 nm or less and 100 nm or more is said.

Moreover, 1/10-10 are preferable and, as for ratio (mass ratio) with respect to the retardation increasing agent of a retardation lowering agent, 1/10-1 are more preferable.

In addition, retardation is measured by the following method. The in-plane retardation Re (0) of a cellulose film is measured at 25 degreeC 10% RH using an ellipsometer (M-150, Nippon Spectrum Co., Ltd. product (brand name)). In addition, the retardation Re (40) and Re (-40) are measured by turning the in-plane slow axis by 40 ° and -40 °. Using the film thickness and the refractive index in the slow axis direction (nx) as parameters, the refractive index in the fast axis direction (ny) and the refractive index in the thickness direction so as to fit to the measured values Re (0), Re (40) and Re (-40). (nz) is calculated by calculation to determine the Rth retardation value. The measurement wavelength is 632.8 nm. In addition, it measures similarly also in 25 degreeC 80% RH.

Best Mode for Carrying Out the Invention

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, when the disk compound and the aromatic ring which have high planarity but the compound with low planarity are added to a cellulose acylate film simultaneously, the water permeability of the cellulose acylate film obtained will fall remarkably, and the cellulose acylate It was found that the humidity dependence of the optical properties of the film is reduced. In addition, it was found that by controlling the ratio of the disk-shaped compound and the compound having low planarity, a wide range of optical properties can be adjusted while maintaining the humidity dependence of moisture permeability and optical properties. The former has the effect of raising the retardation, for example, is represented by the general formula (I) described above, and the latter has the effect of reducing the retardation, for example, the general formulas (II) and (III) described above. Or (IV). However, in the cellulose acylate film containing these at the same time, it was found that an effect much more unexpected than that expected from the effect of adding each compound alone was unexpectedly obtained. That is, the outstanding cellulose acylate film which brings about the fall of moisture permeability more than what is expected from addition alone, and which has the effect that the temperature dependency of an optical characteristic is small is obtained, and this film can be used as retardation film etc.

In the present invention, by adding both of the retardation increasing agent and the retardation lowering agent to the cellulose acylate film, the above-mentioned unexpected effect can be exhibited by these interactions. That is, in this invention, the retardation raise agent and the retardation lowering agent of the combination which show an interaction action are used together.

First, the compound which has a 1,3,5-triazine ring represented by the said General formula (I) used by this invention is demonstrated.

(I)

In the formula, X ¹ is a single bond, -NR ^4- , -O- or -S-; X ² is a single bond, -NR ^5- , -O- or -S-; X ³ is a single bond, -NR ^6- , -O- or -S-; R ¹ , R ² and R ³ are each independently an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; And R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. It is especially preferable that the compound represented by Formula (I) is a melamine compound. In a melamine compound, in formula (I), X <^1> , X <^2> and X <^3> are -NR <^4> -, -NR <^5> -and -NR <^6> -or X <^1> , X <^2> and X <^3> are respectively, It is a single bond, and R <^1> , R <^2> and R <^3> are heterocyclic groups which have a free valency at a nitrogen atom. -X ¹ -R ¹ , -X ² -R ^2, and -X ³ -R ³ are preferably the same substituent. It is particularly preferable that R ¹ , R ² and R ³ are aryl groups. R ⁴ , R ⁵ and R ⁶ are particularly preferably hydrogen atoms.

It is preferable that the said alkyl group is a chain alkyl group rather than a cyclic alkyl group. The linear alkyl group is more preferable than the branched chain alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 10, still more preferably 1 to 8, and most preferably 1 to 6 carbon atoms. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (eg methoxy, ethoxy, epoxyethyloxy) and an acyloxy group (eg acryloyloxy, methacryloyloxy). It is preferable that the said alkenyl group is a linear alkenyl group rather than a cyclic alkenyl group. The linear alkenyl group is more preferable than the branched chain alkenyl group. The number of carbon atoms of the alkenyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 10, still more preferably 2 to 8, and most preferably 2 to 6 carbon atoms. . The alkenyl group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (eg methoxy, ethoxy, epoxyethyloxy) and an acyloxy group (eg acryloyloxy, methacryloyloxy).                     

It is preferable that it is phenyl or naphthyl, and, as for the said aryl group, it is especially preferable that it is phenyl. The aryl group may have a substituent. Examples of the substituent include a halogen atom, hydroxyl, cyano, nitro, carboxyl, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, alkoxycarbonyl group, alkenyloxycarbonyl group, Aryloxycarbonyl group, sulfamoyl, alkyl substituted sulfamoyl group, alkenyl substituted sulfamoyl group, aryl substituted sulfamoyl group, sulfonamide group, carbamoyl, alkyl substituted carbamoyl group, alkenyl substituted carbamoyl group, aryl substituted carbyl Bamoyl group, amide group, alkylthio group, alkenylthio group, arylthio group and acyl group are included. The said alkyl group has the same definition as the alkyl group mentioned above. The alkyl portion of the alkoxy group, acyloxy group, alkoxycarbonyl group, alkyl substituted sulfamoyl group, sulfonamide group, alkyl substituted carbamoyl group, amide group, alkylthio group and acyl group is also the same as the alkyl group mentioned above.

The alkenyl group has the same definition as the alkenyl group described above. Alkenyl moieties of alkenyloxy group, acyloxy group, alkenyloxycarbonyl group, alkenyl substituted sulfamoyl group, sulfonamide group, alkenyl substituted carbamoyl group, amide group, alkenylthio group and acyl group Same as the group. Examples of the aryl group include phenyl, α-naphthyl, β-naphthyl, 4-methoxyphenyl, 3,4-diethoxyphenyl, 4-octyloxyphenyl and 4-dodecyloxyphenyl. Examples of the aryloxy group, acyloxy group, aryloxycarbonyl group, aryl substituted sulfamoyl group, sulfonamide group, aryl substituted carbamoyl group, amide group, arylthio group and acyl group moiety are the same as the examples of the aryl group. .                     

It is preferable that the heterocyclic group when X <^1> , X <^2> or X <^3> is -NR-, -O-, or -S- has aromaticity. The heterocycle having aromaticity is generally an unsaturated heterocycle, preferably a heterocycle having the largest double bond. It is preferable that a heterocyclic ring is a 5-membered ring, a 6-membered ring, or a 7-membered ring, It is more preferable that it is a 5-membered ring or a 6-membered ring, It is most preferable that it is a 6-membered ring. The heteroatom of the heterocycle is preferably N, S or O, and particularly preferably N. As a heterocyclic ring which has aromaticity, a pyridine ring (as a heterocyclic group, 2-pyridyl or 4-pyridyl) is especially preferable. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as those of the substituent of the aryl moiety. It is preferable that the heterocyclic group in the case where X ¹ , X ² or X ³ is a single bond is a heterocyclic group having a free valency at a nitrogen atom. It is preferable that the heterocyclic group which has a free valency in a nitrogen atom is a 5-membered ring, a 6-membered ring, or a 7-membered ring, It is more preferable that it is a 5-membered ring or a 6-membered ring, It is most preferable that it is a 5-membered ring. The heterocyclic group may have a plurality of nitrogen atoms. Moreover, the heterocyclic group may have hetero atoms (for example, 0, S) other than a nitrogen atom. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as those of the substituent of the aryl moiety. Below, the example of the heterocyclic group which has a free valency in a nitrogen atom is shown.

It is preferable that the molecular weight of the compound which has a 1,3,5-triazine ring represented by the said General formula (I) is 300-2000. It is preferable that the boiling point of a compound is 260 degreeC or more. A boiling point can be measured using a commercially available measuring apparatus (for example, TG / DTA100, a brand name, and the Seiko electronics industry make). Below, the specific example of the compound which has a 1,3,5-triazine ring represented by the said General formula (I) is shown. In addition, the some R shown by each example means the same group. The definition of R is shown later in the formula together with the specific example number.

(1)-(12)

(1) butyl

(2) 2-methoxy-2-ethoxyethyl

(3) 5-undecenyl

(4) phenyl                     

(5) 4-ethoxycarbonylphenyl

(6) 4-butoxyphenyl

(7) p-biphenylyl

(8) 4-pyridyl

(9) 2-naphthyl

(10) 2-methylphenyl

(11) 3,4-dimethoxyphenyl

(12) 2-furyl

(13)

(14)-(79)

(14) phenyl

(15) 3-ethoxycarbonylphenyl

(16) 3-butoxyphenyl

(17) m-biphenylyl

(18) 3-phenylthiophenyl                     

(19) 3-chlorophenyl

(20) 3-benzoylphenyl

(21) 3-acetoxyphenyl

(22) 3-benzoyloxyphenyl

(23) 3-phenoxycarbonylphenyl

(24) 3-methoxyphenyl

(25) 3-anilinophenyl

(26) 3-isobutyrylaminophenyl

(27) 3-phenoxycarbonylaminophenyl

(28) 3- (3-ethylureido) phenyl

(29) 3- (3,3-diethylureido) phenyl

(30) 3-methylphenyl

(31) 3-phenoxyphenyl

(32) 3-hydroxyphenyl

(33) 4-ethoxycarbonylphenyl

(34) 4-butoxyphenyl

(35) p-biphenylyl

(36) 4-phenylthiophenyl

(37) 4-chlorophenyl

(38) 4-benzoylphenyl                     

(39) 4-acetoxyphenyl

(40) 4-benzoyloxyphenyl

(41) 4-phenoxycarbonylphenyl

(42) 4-methoxyphenyl

(43) 4-anilinophenyl

(44) 4-isobutyrylaminophenyl

(45) 4-phenoxycarbonylaminophenyl

(46) 4- (3-ethylureido) phenyl

(47) 4- (3,3-diethylureido) phenyl

(48) 4-methylphenyl

(49) 4-phenoxyphenyl

(50) 4-hydroxyphenyl

(51) 3,4-diethoxycarbonylphenyl

(52) 3,4-dibutoxyphenyl

(53) 3,4-diphenylphenyl

(54) 3,4-diphenylthiophenyl

(55) 3,4-dichlorophenyl

(56) 3,4-dibenzoylphenyl

(57) 3,4-diacetoxyphenyl

(58) 3,4-dibenzoyloxyphenyl                     

(59) 3,4-diphenoxycarbonylphenyl

(60) 3,4-dimethoxyphenyl

(61) 3,4-dianilinophenyl

(62) 3,4-dimethylphenyl

(63) 3,4-diphenoxyphenyl

(64) 3,4-dihydroxyphenyl

(65) 2-naphthyl

(66) 3,4,5-triethoxycarbonylphenyl

(67) 3,4,5-tributoxyphenyl

(68) 3,4,5-triphenylphenyl

(69) 3,4,5-triphenylthiophenyl

(70) 3,4,5-trichlorophenyl

(71) 3,4,5-tribenzoylphenyl

(72) 3,4,5-triacetoxyphenyl

(73) 3,4,5-tribenzoyloxyphenyl

(74) 3,4,5-triphenoxycarbonylphenyl

(75) 3,4,5-trimethoxyphenyl

(76) 3,4,5-trianilinophenyl

(77) 3,4,5-trimethylphenyl

(78) 3,4,5-triphenoxyphenyl                     

(79) 3,4,5-trihydroxyphenyl

80-145

80 phenyl

(81) 3-ethoxycarbonylphenyl

(82) 3-butoxyphenyl

(83) m-biphenylyl

(84) 3-phenylthiophenyl

(85) 3-chlorophenyl

(86) 3-benzoylphenyl

(87) 3-acetoxyphenyl

(88) 3-benzoyloxyphenyl

(89) 3-phenoxycarbonylphenyl

(90) 3-methoxyphenyl

(91) 3-anilinophenyl

(92) 3-isobutyrylaminophenyl

(93) 3-phenoxycarbonylaminophenyl

(94) 3- (3-ethylureido) phenyl

(95) 3- (3,3-diethylureido) phenyl                     

(96) 3-methylphenyl

(97) 3-phenoxyphenyl

(98) 3-hydroxyphenyl

(99) 4-ethoxycarbonylphenyl

(100) 4-butoxyphenyl

(101) p-biphenylyl

(102) 4-phenylthiophenyl

(103) 4-chlorophenyl

(104) 4-benzoylphenyl

(105) 4-acetoxyphenyl

(106) 4-benzoyloxyphenyl

(107) 4-phenoxycarbonylphenyl

(108) 4-methoxyphenyl

(109) 4-anilinophenyl

(110) 4-isobutyrylaminophenyl

(111) 4-phenoxycarbonylaminophenyl

(112) 4- (3-ethylureido) phenyl

(113) 4- (3,3-diethylureido) phenyl

(114) 4-methylphenyl

(115) 4-phenoxyphenyl                     

(116) 4-hydroxyphenyl

(117) 3,4-diethoxycarbonylphenyl

(118) 3,4-dibutoxyphenyl

(119) 3,4-diphenylphenyl

(120) 3,4-diphenylthiophenyl

(121) 3,4-dichlorophenyl

(122) 3,4-dibenzoylphenyl

(123) 3,4-diacetoxyphenyl

(124) 3,4-dibenzoyloxyphenyl

(125) 3,4-diphenoxycarbonylphenyl

(126) 3,4-dimethoxyphenyl

(127) 3,4-dianilinophenyl

(128) 3,4-dimethylphenyl

(129) 3,4-diphenoxyphenyl

(130) 3,4-dihydroxyphenyl

(131) 2-naphthyl

(132) 3,4,5-triethoxycarbonylphenyl

(133) 3,4,5-tributoxyphenyl

(134) 3,4,5-triphenylphenyl

(135) 3,4,5-triphenylthiophenyl                     

(136) 3,4,5-trichlorophenyl

(137) 3,4,5-tribenzoylphenyl

(138) 3,4,5-triacetoxyphenyl

(139) 3,4,5-tribenzoyloxyphenyl

(140) 3,4,5-triphenoxycarbonylphenyl

(141) 3,4,5-trimethoxyphenyl

(142) 3,4,5-trianilinophenyl

(143) 3,4,5-trimethylphenyl

(144) 3,4,5-triphenoxyphenyl

(145) 3,4,5-trihydroxyphenyl

(146)-(164)

(146) phenyl

(147) 4-ethoxycarbonylphenyl

(148) 4-butoxyphenyl

(149) p-biphenylyl

(150) 4-phenylthiophenyl

(151) 4-chlorophenyl

(152) 4-benzoylphenyl                     

(153) 4-acetoxyphenyl

(154) 4-benzoyloxyphenyl

(155) 4-phenoxycarbonylphenyl

(156) 4-methoxyphenyl

(157) 4-anilinophenyl

(158) 4-isobutyrylaminophenyl

(159) 4-phenoxycarbonylaminophenyl

(160) 4- (3-ethylureido) phenyl

(161) 4- (3,3-diethylureido) phenyl

(162) 4-methylphenyl

(163) 4-phenoxyphenyl

(164) 4-hydroxyphenyl

(165)-(183)

(165) phenyl

(166) 4-ethoxycarbonylphenyl

(167) 4-butoxyphenyl

(168) p-biphenylyl

(169) 4-phenylthiophenyl                     

(170) 4-chlorophenyl

(171) 4-benzoylphenyl

(172) 4-acetoxyphenyl

(173) 4-benzoyloxyphenyl

(174) 4-phenoxycarbonylphenyl

(175) 4-methoxyphenyl

(176) 4-anilinophenyl

(177) 4-isobutyrylaminophenyl

(178) 4-phenoxycarbonylaminophenyl

(179) 4- (3-ethylureido) phenyl

(180) 4- (3,3-diethylureido) phenyl

(181) 4-methylphenyl

(182) 4-phenoxyphenyl

(183) 4-hydroxyphenyl

(184)-(202)

(184) phenyl

(185) 4-ethoxycarbonylphenyl

(186) 4-butoxyphenyl                     

(187) p-biphenylyl

(188) 4-phenylthiophenyl

(189) 4-chlorophenyl

(190) 4-benzoylphenyl

(191) 4-acetoxyphenyl

(192) 4-benzoyloxyphenyl

(193) 4-phenoxycarbonylphenyl

(194) 4-methoxyphenyl

(195) 4-anilinophenyl

(196) 4-isobutyrylaminophenyl

(197) 4-phenoxycarbonylaminophenyl

(198) 4- (3-ethylureido) phenyl

(199) 4- (3,3-diethylureido) phenyl

(200) 4-methylphenyl

(201) 4-phenoxyphenyl

(202) 4-hydroxyphenyl

(203)-(221)

(203) phenyl

(204) 4-ethoxycarbonylphenyl

(205) 4-butoxyphenyl

(206) p-biphenylyl

(207) 4-phenylthiophenyl

(208) 4-chlorophenyl

(209) 4-benzoylphenyl

(210) 4-acetoxyphenyl

(211) 4-benzoyloxyphenyl

(212) 4-phenoxycarbonylphenyl

(213) 4-methoxyphenyl

(214) 4-anilinophenyl

(215) 4-isobutyrylaminophenyl

(216) 4-phenoxycarbonylaminophenyl

(217) 4- (3-ethylureido) phenyl

(218) 4- (3,3-diethylureido) phenyl

(219) 4-methylphenyl

(220) 4-phenoxyphenyl

(221) 4-hydroxyphenyl                     

(222)-(419)

(222) phenyl

(223) 4-butylphenyl

(224) 4- (2-methoxy-2-ethoxyethyl) phenyl

(225) 4- (5-nonenyl) phenyl

(226) p-biphenylyl

(227) 4-ethoxycarbonylphenyl

(228) 4-butoxyphenyl

(229) 4-methylphenyl

(230) 4-chlorophenyl

(231) 4-phenylthiophenyl

(232) 4-benzoylphenyl

(233) 4-acetoxyphenyl

(234) 4-benzoyloxyphenyl

(235) 4-phenoxycarbonylphenyl

(236) 4-methoxyphenyl

(237) 4-anilinophenyl

(238) 4-isobutyrylaminophenyl                     

(239) 4-phenoxycarbonylaminophenyl

(240) 4- (3-ethylureido) phenyl

(241) 4- (3,3-diethylureido) phenyl

(242) 4-phenoxyphenyl

(243) 4-hydroxyphenyl

(244) 3-butylphenyl

(245) 3- (2-methoxy-2-ethoxyethyl) phenyl

(246) 3- (5-nonenyl) phenyl

(247) m-biphenylyl

(248) 3-ethoxycarbonylphenyl

(249) 3-butoxyphenyl

(250) 3-methylphenyl

(251) 3-chlorophenyl

(252) 3-phenylthiophenyl

(253) 3-benzoylphenyl

(254) 3-acetoxyphenyl

(255) 3-benzoyloxyphenyl

(256) 3-phenoxycarbonylphenyl

(257) 3-methoxyphenyl

(258) 3-anilinophenyl                     

(259) 3-isobutyrylaminophenyl

(260) 3-phenoxycarbonylaminophenyl

(261) 3- (3-ethylureido) phenyl

(262) 3- (3,3-diethylureido) phenyl

(263) 3-phenoxyphenyl

(264) 3-hydroxyphenyl

(265) 2-butylphenyl

(266) 2- (2-methoxy-2-ethoxyethyl) phenyl

(267) 2- (5-nonenyl) phenyl

(268) o-biphenylyl

(269) 2-ethoxycarbonylphenyl

(270) 2-butoxyphenyl

(271) 2-methylphenyl

(272) 2-chlorophenyl

(273) 2-phenylthiophenyl

(274) 2-benzoylphenyl

(275) 2-acetoxyphenyl

(276) 2-benzoyloxyphenyl

(277) 2-phenoxycarbonylphenyl

(278) 2-methoxyphenyl                     

(279) 2-anilinophenyl

(280) 2-isobutyrylaminophenyl

(281) 2-phenoxycarbonylaminophenyl

(282) 2- (3-ethylureido) phenyl

(283) 2- (3,3-diethylureido) phenyl

(284) 2-phenoxyphenyl

(285) 2-hydroxyphenyl

(286) 3,4-dibutylphenyl

(287) 3,4-di (2-methoxy-2-ethoxyethyl) phenyl

(288) 3,4-diphenylphenyl

(289) 3,4-diethoxycarbonylphenyl

(290) 3,4-didodecyloxyphenyl

(291) 3,4-dimethylphenyl

(292) 3,4-dichlorophenyl

(293) 3,4-dibenzoylphenyl

(294) 3,4-diacetoxyphenyl

(295) 3,4-dimethoxyphenyl

(296) 3,4-di-N-methylaminophenyl

(297) 3,4-diisobutyrylaminophenyl

(298) 3,4-diphenoxyphenyl                     

(299) 3,4-dihydroxyphenyl

(300) 3,5-dibutylphenyl

(301) 3,5-di (2-methoxy-2-ethoxyethyl) phenyl

(302) 3,5-diphenylphenyl

(303) 3,5-diethoxycarbonylphenyl

(304) 3,5-didodecyloxyphenyl

(305) 3,5-dimethylphenyl

(306) 3,5-dichlorophenyl

(307) 3,5-dibenzoylphenyl

(308) 3,5-diacetoxyphenyl

(309) 3,5-dimethoxyphenyl

(310) 3,5-di-N-methylaminophenyl

(311) 3,5-diisobutyrylaminophenyl

(312) 3,5-diphenoxyphenyl

(313) 3,5-dihydroxyphenyl

(314) 2,4-dibutylphenyl

(315) 2,4-di (2-methoxy-2-ethoxyethyl) phenyl

(316) 2,4-diphenylphenyl

(317) 2,4-diethoxycarbonylphenyl

(318) 2,4-didodecyloxyphenyl                     

(319) 2,4-dimethylphenyl

(320) 2,4-dichlorophenyl

(321) 2,4-dibenzoylphenyl

(322) 2,4-diacetoxyphenyl

(323) 2,4-dimethoxyphenyl

(324) 2,4-di-N-methylaminophenyl

(325) 2,4-diisobutyrylaminophenyl

(326) 2,4-diphenoxyphenyl

(327) 2,4-dihydroxyphenyl

(328) 2,3-dibutylphenyl

(329) 2,3-di (2-methoxy-2-ethoxyethyl) phenyl

(330) 2,3-diphenylphenyl

(331) 2,3-diethoxycarbonylphenyl

(332) 2,3-didodecyloxyphenyl

(333) 2,3-dimethylphenyl

(334) 2,3-dichlorophenyl

(335) 2,3-dibenzoylphenyl

(336) 2,3-diacetoxyphenyl

(337) 2,3-dimethoxyphenyl

(338) 2,3-di-N-methylaminophenyl                     

(339) 2,3-diisobutyrylaminophenyl

(340) 2,3-diphenoxyphenyl

(341) 2,3-dihydroxyphenyl

(342) 2,6-dibutylphenyl

(343) 2,6-di (2-methoxy-2-ethoxyethyl) phenyl

(344) 2,6-diphenylphenyl

(345) 2,6-diethoxycarbonylphenyl

(346) 2,6-didodecyloxyphenyl

(347) 2,6-dimethylphenyl

(348) 2,6-dichlorophenyl

(349) 2,6-dibenzoylphenyl

(350) 2,6-diacetoxyphenyl

(351) 2,6-dimethoxyphenyl

(352) 2,6-di-N-methylaminophenyl

(353) 2,6-diisobutyrylaminophenyl

(354) 2,6-diphenoxyphenyl

(355) 2,6-dihydroxyphenyl

(356) 3,4,5-tributylphenyl

(357) 3,4,5-tri (2-methoxy-2-ethoxyethyl) phenyl

(358) 3,4,5-triphenylphenyl                     

(359) 3,4,5-triethoxycarbonylphenyl

(360) 3,4,5-tridodecyloxyphenyl

(361) 3,4,5-trimethylphenyl

(362) 3,4,5-trichlorophenyl

(363) 3,4,5-tribenzoylphenyl

(364) 3,4,5-triacetoxyphenyl

(365) 3,4,5-trimethoxyphenyl

(366) 3,4,5-tri-N-methylaminophenyl

(367) 3,4,5-triisobutyrylaminophenyl

(368) 3,4,5-triphenoxyphenyl

(369) 3,4,5-trihydroxyphenyl

(370) 2,4,6-tributylphenyl

(371) 2,4,6-tri (2-methoxy-2-ethoxyethyl) phenyl

(372) 2,4,6-triphenylphenyl

(373) 2,4,6-triethoxycarbonylphenyl

(374) 2,4,6-tridodecyloxyphenyl

(375) 2,4,6-trimethylphenyl

(376) 2,4,6-trichlorophenyl

(377) 2,4,6-tribenzoylphenyl

(378) 2,4,6-triacetoxyphenyl                     

(379) 2,4,6-trimethoxyphenyl

(380) 2,4,6-tri-N-methylaminophenyl

(381) 2,4,6-triisobutyrylaminophenyl

(382) 2,4,6-triphenoxyphenyl

(383) 2,4,6-trihydroxyphenyl

(384) pentafluorophenyl

(385) pentachlorophenyl

(386) pentamethoxyphenyl

(387) 6-N-methylsulfamoyl-8-methoxy-2-naphthyl

(388) 5-N-methylsulfamoyl-2-naphthyl

(389) 6-N-phenylsulfamoyl-2-naphthyl

(390) 5-ethoxy-7-N-methylsulfamoyl-2-naphthyl

(391) 3-methoxy-2-naphthyl

(392) 1-ethoxy-2-naphthyl

(393) 6-N-phenylsulfamoyl-8-methoxy-2-naphthyl

(394) 5-methoxy-7-N-phenylsulfamoyl-2-naphthyl

(395) 1- (4-methylphenyl) -2-naphthyl

(396) 6,8-di-N-methylsulfamoyl-2-naphthyl

(397) 6-N-2-acetoxyethylsulfamoyl-8-methoxy-2-naphthyl

(398) 5-acetoxy-7-N-phenylsulfamoyl-2-naphthyl                     

(399) 3-benzoyloxy-2-naphthyl

(400) 5-acetylamino-1-naphthyl

(401) 2-methoxy-1-naphthyl

(402) 4-phenoxy-1-naphthyl

(403) 5-N-methylsulfamoyl-1-naphthyl

(404) 3-N-methylcarbamoyl-4-hydroxy-1-naphthyl

(405) 5-methoxy-6-N-ethylsulfamoyl-1-naphthyl

(406) 7-tetradecyloxy-1-naphthyl

(407) 4- (4-methylphenoxy) -1-naphthyl

(408) 6-N-methylsulfamoyl-1-naphthyl

(409) 3-N, N-dimethylcarbamoyl-4-methoxy-1-naphthyl

(410) 5-methoxy-6-N-benzylsulfamoyl-1-naphthyl

(411) 3,6-di-N-phenylsulfamoyl-1-naphthyl

(412) methyl

(413) ethyl

(414) Butyl

(415) octyl

(416) Dodecyl

(417) 2-butoxy-2-ethoxyethyl

(418) benzyl                     

(419) 4-methoxybenzyl

(424)-(426)

(424) methyl

(425) phenyl

(426) Butyl

(430)-(437)

(430) methyl

(431) ethyl

(432) Butyl

(433) octyl

(434) Dodecyl

(435) 2-butoxy-2-ethoxyethyl

(436) benzyl

(437) 4-methoxybenzyl

(446)

As a compound which has a 1,3,5-triazine ring represented by the said General formula (I), you may use a melamine polymer. It is preferable to synthesize | combine a melamine polymer by the polymerization reaction of a melamine compound and a carbonyl compound represented by a following formula (IA).

In formula, R <^11> , R <^12> , R <^13> , R <^14> , R <^15> and R <^16> are respectively independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. The definition and substituents of the alkyl group, alkenyl group, aryl group and heterocyclic group are the same as the definitions and substituents of the groups described in the formula (I). Polymerization reaction of a melamine compound and a carbonyl compound is the same as that of the synthesis | combining method of normal melamine resin (for example, melamine formaldehyde resin). You may use a commercially available melamine polymer (melamine resin). It is preferable that the molecular weight of a melamine polymer is 2000 or more and 400,000 or less. Examples of the repeating unit of the melamine polymer are shown below.

(MP-1)-(MP-50)

(MP-51)-(MP-100)

(MP-101)-(MP-150)

(MP-151)-(MP-200)

You may use the copolymer which combined two or more types of repeating units. You may use together 2 or more types of homopolymers or copolymers. You may use together the compound which has a 1,3,5-triazine ring represented by two or more types of said general formula (I). You may use together 2 or more types of disk-shaped compounds (for example, the compound which has a 1,3,5-triazine ring represented by the said General formula (I), and a compound which has a porphyrin skeleton).

Next, the compound represented by general formula (II) used by this invention is demonstrated in detail.

General formula (Ⅱ)

In the general formula (II), R ²¹ , R ^22, and R ²³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl). , Amyl, isoamyl), and particularly preferably at least one of R ²¹ , R ²² and R ²³ is an alkyl group having 1 to 3 carbon atoms (eg, methyl, ethyl, propyl, isopropyl). Do. X ²¹ is a single bond, -O-, -CO-, an alkylene group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, for example, methylene, ethylene, propylene) or an arylene group ( Preferably it is 6-24 carbon atoms, More preferably, it is 6-12. For example, it is preferable that it is a bivalent coupling group formed from 1 or more types chosen from phenylene, biphenylene, naphthylene), It is particularly preferable that it is a divalent linking group formed of at least one group selected from -O-, an alkylene group or an arylene group. Y ²¹ is a hydrogen atom, an alkyl group (preferably having 2 to 25 carbon atoms, more preferably 2 to 20. For example, ethyl, isopropyl, t-butyl, hexyl, 2-ethylhexyl, t- Octyl, dodecyl, cyclohexyl, dicyclohexyl, adamantyl), aryl groups (preferably having 6 to 24 carbon atoms, more preferably 6 to 18. For example, phenyl, biphenyl, terphenyl (terphenyl), naphthyl) or an aralkyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20. For example, benzyl, credyl, t-butylphenyl, diphenylmethyl, triphenyl Methyl), and particularly preferably an alkyl group, an aryl group or an aralkyl group. A combination of -X ²¹ -Y ²¹ is preferably a total number of carbon atoms of -X ²¹ -Y ²¹ is 0 to 40, and 1 to 30 is more preferable, most preferably 1-25.

Although the preferable example of the compound represented by these general formula (II) is shown below, this invention is not limited to these specific examples.                     

Next, the compound represented by general formula (III) used by this invention is demonstrated in detail.

General formula (Ⅲ)

In General Formula (III), R ³¹ represents an alkyl group or an aryl group, and R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group or an aryl group. Moreover, it is especially preferable that the sum total of carbon ^number of R <^31> , R <^32> and R < ³³ > is 10 or more. As the substituent, a fluorine atom, an alkyl group, an aryl group, an alkoxy group, a sulfone group and a sulfonamide group are preferable, and an alkyl group, an aryl group, an alkoxy group, a sulfone group and a sulfonamide group are particularly preferable. In addition, the alkyl group may be linear, branched, or cyclic, preferably having 1 to 25 carbon atoms, more preferably 6 to 25, and having 6 to 20 (eg, methyl, ethyl, propyl). Isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, bicyclooctyl, nonyl, adamantyl, decyl, t-octyl, undecyl, Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, didecyl) are particularly preferred. The aryl group preferably has 6 to 30 carbon atoms, and particularly preferably 6 to 24 carbon atoms (for example, phenyl, biphenyl, terphenyl, naphthyl, binaphthyl and triphenylphenyl). R ³¹ and R ³² may be bonded to each other to form a ring.

Moreover, it is preferable that the addition amount of the modifier of this invention is 2-30 mass% with respect to cellulose acylate, It is more preferable that it is 2-25 mass%, It is especially preferable that it is 2-20 mass%.

Although the preferable example of a compound represented by general formula (III) is shown below, this invention is not limited to this specific example.

Next, the compound of general formula (IV) used by this invention is demonstrated in detail.

General formula (Ⅳ)

(Wherein, X ⁴² represents B, CR ⁷⁰ (R ⁷⁰ represents a hydrogen atom or a substituent.), N, P or P = O. R ⁴⁰ , R ⁵⁰ and R ⁶⁰ each independently represents an aryl group. (For example, a phenyl group), a cycloalkyl group (for example, cyclohexyl group), or a heterocyclic group (for example, 4-pyridyl group), and these aryl group, cycloalkyl group, and heterocyclic group are respectively on a ring. It may have a substituent, R ⁴⁰ and R ⁵⁰ may combine with each other to form a ring.)

The compound of the general formula (IV) used in the present invention is preferably a compound represented by the following general formula (IVA).                     

General formula (IVA)

Wherein X ⁴² represents B, CR ⁷⁰ (R ⁷⁰ represents a hydrogen atom or a substituent.), N, P, or P═O. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ to R ⁶⁵ each independently represent a hydrogen atom or a substituent, if possible, the above R ⁴¹ to R ⁶⁵ Two groups (for example, R ⁴¹ and R ^51, etc.) may combine with each other to form a ring.)

In General Formulas (IV) and (IVA), X ⁴² represents B, CR ⁷⁰ (R ⁷⁰ represents a hydrogen atom or a substituent.), N, P, P═O, and X ⁴² is preferably B, CR ⁷⁰ (R ⁷⁰ is preferably an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxy Carbonylamino group, sulfonylamino group, hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group, more preferably aryl group, alkoxy group, aryloxy group, to a hydroxy group, a halogen atom, more preferably an alkoxy group, a hydroxy group, and particularly preferably a hydroxy group.), and N, P = O, and more preferably from CR ^70, N, and particularly preferably CR ^70.

R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ to R ⁶⁵ represent a hydrogen atom or a substituent The substituent (T) mentioned later is applicable as a substituent. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ to R ⁶⁵ , preferably an alkyl group, Alkenyl group, alkynyl group, aryl group, substituted or unsubstituted amino group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group , Sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, ureido group, phosphate amide group, hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine) Atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably Is 1 to 12, and as a hetero atom, for example, a nitrogen atom, an oxygen atom, Sulfur atoms, and specific examples thereof include imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzooxazolyl, benzimidazolyl, benzthiazolyl, and the like. More preferably, they are an alkyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, and an aryloxy group, More preferably, they are an alkyl group, an aryl group, and an alkoxy group.

These substituents may be further substituted. In addition, when there are two or more substituents, they may be same or different. In addition, if possible, they may be linked to each other to form a ring.

The substituent T mentioned above is demonstrated below. As the substituent (T), for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms), for example methyl, ethyl, iso-propyl, tert- Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably C2-C20, more preferably C2-C12) Especially preferably, it is C2-C8, For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc. are mentioned.), An alkynyl group (preferably C2-C20, More preferably, C2-C12, Especially preferably, it is C2-C8, For example, propargyl, 3-pentynyl, etc. are mentioned.), An aryl group (preferably C6-C30, More preferably, carbon number) 6-20, Especially preferably, it is C6-C12, For example, phenyl, p-methylphenyl, naphthyl, etc. are mentioned. ), A substituted or unsubstituted amino group (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example, amino, methylamino, dimethylamino, diethylamino , Dibenzylamino, etc.), alkoxy group (preferably C1-C20, More preferably, it is C1-C12, Especially preferably, it is C1-C8, For example, methoxy, ethoxy , Butoxy, etc.), an aryloxy group (preferably C6-C20, More preferably, it is C6-C16, Especially preferably, it is C6-C12, For example, phenyloxy, 2- Naphthyloxy, etc.), acyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, acetyl, benzoyl, formyl , Pivaloyl, etc.), alkoxycarbonyl group (wind Preferably it is C2-C20, More preferably, it is C2-C16, Especially preferably, it is C2-C12, For example, methoxycarbonyl, ethoxycarbonyl, etc. are mentioned.), An aryloxycarbonyl group ( Preferably it is C7-20, More preferably, it is C7-16, Especially preferably, it is C7-10, For example, Phenyloxycarbonyl etc. are mentioned.), Acyloxy group (Preferably carbon number 2-20, More preferably, it is C2-C16, Especially preferably, it is C2-C10, For example, an acetoxy, benzoyloxy, etc. are mentioned.), Acylamino group (Preferably C2-C20, More preferably, it is C2-C16, Especially preferably, it is C2-C10, For example, acetylamino, benzoylamino etc. are mentioned.), The alkoxycarbonylamino group (Preferably C2-C20, More preferably Preferably 2 to 16 carbon atoms It is preferably 2 to 12 carbon atoms, for example, methoxycarbonylamino and the like.), An aryloxycarbonylamino group (preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, especially Preferably it is C7-12, For example, a phenyloxycarbonylamino etc. are mentioned.) A sulfonylamino group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, C1-C12, for example, methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl group (preferably C0-20, More preferably, C0-16, Especially preferably, Has 0 to 12 carbon atoms, and examples thereof include sulfamoyl, methyl sulfamoyl, dimethyl sulfamoyl, phenyl sulfamoyl and the like.), Carbamoyl group (preferably C1-20, more preferably C1) ～ 16, particularly preferably 1 to 12, and carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like.), An alkylthio group (preferably 1 to 20 carbon atoms), more preferred. Preferably it is C1-C16, Especially preferably, it is C1-C12, For example, methylthio, ethylthio, etc. are mentioned.), An arylthio group (preferably C6-C20, More preferably, carbon number) 6-16, Especially preferably, it is C6-C12, For example, a phenylthio etc. are mentioned.), A sulfonyl group (Preferably C1-C20, More preferably, C1-C16, Especially preferably, Is C1-C12, and mesyl, tosyl, etc. are mentioned, for example, sulfinyl group (preferably C1-C20, More preferably, C1-C16, Especially preferably, it is C1-C12 For example, methane sulfinyl, benzene sulfinyl, etc. are mentioned.), A ureido group (Preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, ureido, methylureido, phenylureido, etc. are mentioned.), Phosphoric acid Amide group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, a diethyl phosphate amide, a phenyl phosphate amide, etc. are mentioned), A hydroxyl group , Mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group , Heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms), and as a hetero atom, for example, a nitrogen atom, an oxygen atom, a sulfur atom, and specifically, for example, imidazolyl, pyridyl, quinine Teal, furyl, piperidyl, morpholino, ben Oxazolyl, benzimidazolyl, benzthiazolyl, etc.), silyl group (preferably, C3-C40, More preferably, C3-C30, Especially preferably, it is C3-24 For example, trimethylsilyl, triphenylsilyl, etc. can be mentioned), etc. are mentioned. These substituents may be further substituted. In addition, when there are two or more substituents, they may be same or different. In addition, if possible, they may be linked to each other to form a ring.

Although the specific example is given to the compound represented by general formula (IV) below, it demonstrates in detail, but this invention is not limited at all by the following specific examples.                     

The compound represented by general formula (I) and the compound represented by general formula (II), (III) or (IV) are 0.01-20 mass parts in total with respect to 100 mass parts of cellulose esters, Preferably it is 0.5- 10 parts by mass is used. By using the said compound in this range, the retardation and water permeability of a film can be controlled suitably. In use of less than 0.01 mass part, control of retardation and water permeability become inadequate. When used in excess of 20 parts by mass, the additive is not compatible with the cellulose ester and crystallized in the film.

In addition, the compound represented by general formula (I) is 0.1-30 mass parts with respect to 100 mass parts of cellulose esters, Preferably 1-10 mass parts is used. The compound represented by general formula (II), (III) or (IV) is 0.1-10 mass parts with respect to 100 mass parts of cellulose esters, Preferably 0.5-7 mass parts is used.

Next, the cellulose film used preferably in this invention is described in detail. The cellulose used for the cellulose film of this invention is a compound which has a cellulose skeleton obtained by using a cellulose compound and cellulose as a raw material, and introducing a functional group biologically or chemically. Especially, a cellulose ester is preferable and a cellulose acylate is more preferable.

The cellulose acylate film used by this invention is demonstrated.

[Manufacture of Cellulose Acylate and Cellulose Acylate Film]

Although the acyl group of this cellulose acylate film is not specifically limited, It is preferable to use an acetyl group, a propionyl group, butyryl group, and especially an acetyl group is preferable. 2.7-3.0 are preferable and, as for the substitution degree of all acyl groups, 2.8-2.95 are more preferable. When using the cellulose acetate whose all acyl group is an acetyl group, acetyl substitution degree is preferable in 2.7-2.95, More preferably, 2.8-2.95, Most preferably 2.84-2.89. Moreover, the acetyl substitution degree of 2.50 or more and 2.86 or less described in Unexamined-Japanese-Patent No. 13-356214, and 2.75 or more and 2.86 or less described in Unexamined-Japanese-Patent No. 13-226495 can also be used preferably. When too low, Re tends to be larger than a desired value by the conveyance tension at the time of casting | flow_spread, and there exists a problem that an in-plane deviation also tends to occur. In addition, as for substitution degree of the 6th-position acyl group, 0.9 or more are used preferably. When the degree of substitution is 0.9 or less, variations in Re and Rth are likely to occur. In addition, the substitution degree of the acyl group in this invention adopts the value computed according to ASTMD817.

In this invention, it is preferable to use the cellulose acetate whose acetylation degree exists in the range of 59.0 to 61.5%.

The degree of acetylation means the amount of bound acetic acid per cellulose unit mass. Acetylation degree is based on the measurement and calculation of the acetylation degree in ASTM: D-817-91 (test methods, such as a cellulose acetate).

It is preferable that it is 250 or more, and, as for the viscosity average polymerization degree (DP) of a cellulose acylate, it is more preferable that it is 290 or more.

Moreover, it is preferable that the cellulose acylate used for this invention has a narrow molecular weight distribution of Mw / Mn (Mw is mass mean molecular weight, Mn is number average molecular weight) by gel permeation chromatography. It is preferable that the value of specific Mw / Mn exists in the range of 1.0-1.7, It is more preferable to exist in the range of 1.3-1.65, It is most preferable to exist in the range of 1.4-1.6.

As a cellulose acetate of this invention, it is described in the synthesis example 1 described in Paragraph No. 0043-0044 of Unexamined-Japanese-Patent No. 11-5851, the synthesis example 2 described in Paragraph No. 0048-0049, and Paragraph No. 0051-0402. The cellulose acetate obtained by the synthesis method of the synthesis example 3 currently used can be used.

[Production of Cellulose Acylate Film]

It is preferable to manufacture the cellulose acylate film of this invention by the solvent cast method. In the solvent cast method, a film is manufactured using the solution (dope) which melt | dissolved cellulose acylate in the organic solvent.

 The organic solvent preferably includes a solvent selected from ethers having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and halogenated hydrocarbons having 1 to 6 carbon atoms. .                     

Ethers, ketones, and esters may have a cyclic structure. Compounds having two or more of any of the functional groups of ethers, ketones and esters (ie -0-, -CO- and -CO0-) can also be used as organic solvents. The organic solvent may have other functional groups, such as an alcoholic hydroxyl group. In the case of the organic solvent which has two or more types of functional groups, it is preferable that the carbon atom number exists in the above-mentioned preferable carbon atom number range of the solvent which has any one functional group.

Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phentol This includes.

Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexanone.

Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.

Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

 The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, most preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. It is preferable that the ratio in which the hydrogen atom of a halogenated hydrocarbon is substituted by halogen is 25-75 mol%, It is more preferable that it is 30-70 mol%, It is further more preferable that it is 35-65 mol%, 40-60 mol% Is most preferred. Methylene chloride is a representative halogenated hydrocarbon.

You may use it in mixture of 2 or more types of organic solvent.

A cellulose acylate solution can be prepared by the general method which consists of processing at 0 degreeC or more (normal temperature or high temperature). Preparation of a solution can be performed using the conventional method and apparatus of preparation of dope by the solvent casting method. Moreover, in the case of a general method, it is preferable to use a halogenated hydrocarbon (especially methylene chloride) as an organic solvent.

The quantity of cellulose acylate is adjusted so that 10-40 mass% may be contained in the solution obtained. The amount of cellulose acylate is more preferably 10 to 30% by mass. In an organic solvent (main solvent), arbitrary additives (plasticizer, antidegradant, etc.) mentioned later can also be added.

A solution can be prepared by stirring a cellulose acylate and an organic solvent at normal temperature (0-40 degreeC). The high concentration solution may be stirred under pressurized and heated conditions. Specifically, the cellulose acylate and the organic solvent are placed in a pressurized container and sealed, and the mixture is stirred while heating to a temperature within a range where the solvent is not boiled while the pressure is at or above the normal temperature of the solvent.

Heating temperature is 40 degreeC or more normally, Preferably it is 60-200 degreeC, More preferably, it is 80-110 degreeC.

Each component may be premixed beforehand and then placed in a container. Moreover, you may inject into a container one by one. The vessel should be configured to be agitable. The vessel can be pressurized by injecting an inert gas such as nitrogen gas. Moreover, you may use the raise of the vapor pressure of a solvent by heating. Or after sealing a container, you may add each component under pressure.

When heating, it is preferable to heat from the exterior of a container. For example, a jacket type heating device can be used. Moreover, the whole container can also be heated by installing a plate heater outside the container, piping, and circulating a liquid.

It is preferable to provide a stirring blade inside a container and to stir using this. It is preferable that the stirring blade has a length reaching the vicinity of the wall of the container. It is preferable to form a scraper blade at the end of the stirring blade in order to update the liquid film on the container wall.

The container may be provided with measuring instruments such as a pressure gauge and a thermometer. Each component is dissolved in a solvent in a container. The prepared dope is taken out of the container after cooling, or it is cooled using a heat exchanger or the like after taking out.

A solution can also be prepared by a cooling dissolution method. In the cooling dissolution method, the cellulose acylate can be dissolved in an organic solvent which is difficult to dissolve by the usual dissolution method. Moreover, even if it is a solvent which can melt | dissolve a cellulose acylate by a normal dissolution method, there exists an effect that a uniform solution can be obtained quickly by a cooling dissolution method.

In the cooling dissolution method, first, the cellulose acylate is slowly added while stirring in an organic solvent at room temperature.

It is preferable to adjust the quantity of a cellulose acylate so that 10-40 mass% may be contained in this mixture. The amount of cellulose acylate is more preferably 10 to 30% by mass. Moreover, arbitrary additives mentioned later can also be added to a mixture.

Next, the mixture is cooled to -100 to -10 占 폚 (preferably -80 to -10 占 폚, more preferably -50 to -20 占 폚, most preferably -50 to -30 占 폚). Cooling can be performed, for example in a dry ice methanol bath (-75 degreeC) or a cooled diethylene glycol solution (-30--20 degreeC). The mixture of cellulose acylate and an organic solvent solidifies by cooling.

The cooling rate is preferably 4 ° C / minute or more, more preferably 8 ° C / minute or more, and most preferably 12 ° C / minute or more. The faster the cooling rate is, the better, but 10000 ° C / sec is the theoretical upper limit, 1000 ° C / sec is the technical upper limit, and 100 ° C / sec is the practical upper limit. The cooling rate is a value obtained by dividing the difference between the temperature at the start of cooling and the final cooling temperature by the time from the start of cooling to the final cooling temperature.

And when this is heated to 0-200 degreeC (preferably 0-150 degreeC, more preferably 0-120 degreeC, most preferably 0-50 degreeC), a cellulose acylate will melt | dissolve in an organic solvent. An elevated temperature may be left to stand only at room temperature and may be heated in a warm bath.                     

The heating rate is preferably 4 ° C / minute or more, more preferably 8 ° C / minute or more, and most preferably 12 ° C / minute or more. The higher the heating rate is, the better, but 10000 ° C / sec is the theoretical upper limit, 1000 ° C / sec is the technical upper limit, and 100 ° C / sec is the practical upper limit. The heating rate is a value obtained by dividing the difference between the temperature at the start of heating and the final heating temperature by the time from the start of heating to the final heating temperature.

A uniform solution can be obtained by the above method. Moreover, when melt | dissolution is inadequate, cooling and a heating operation can also be repeated. Whether or not dissolution is sufficient can be judged only by observing the appearance of the solution by visual observation.

In the cooling dissolution method, it is preferable to use an airtight container in order to avoid moisture mixing due to condensation during cooling. In the cooling warming operation, the dissolution time can be shortened by pressurizing during cooling and depressurizing during heating. In order to perform pressurization and pressure reduction, it is preferable to use a pressure-resistant container.

In addition, 20 mass% of the solution which melt | dissolved cellulose acetate (acetylation degree: 60.9%, viscosity average degree of polymerization: 299) in methyl acetate by the cooling dissolution method was sol at 33 degreeC according to the measurement by a differential scanning calorimeter (DSC). A similar phase transition point exists between a state and a gel state, and below this temperature, a uniform gel state is obtained. Therefore, this solution needs to be stored at a temperature above the pseudo phase transition temperature, preferably at a gel phase transition temperature of about 10 ° C. However, this pseudo phase transition temperature changes with acetylation degree of a cellulose acetate, viscosity average polymerization degree, solution concentration, and the organic solvent to be used.                     

The cellulose acylate film is manufactured from the prepared cellulose acylate solution (dope) by the solvent cast method. It is preferable to add the said retardation raising agent and the retardation lowering agent to dope.

The dope is flexible on a drum or band and evaporates the solvent to form a film. It is preferable to adjust the density | concentration of the dope before casting | flow_spread so that solid content may be 18 to 35%. It is preferable to finish the surface of a drum or a band in a mirror surface state. It is preferable that dope is cast | flow_spreaded on the drum or band whose surface temperature is 10 degrees C or less.

In the present invention, when the dope (cellulose acylate solution) is cast on the band, it is dried in a substantially airless state for a time of 10 seconds or more and 90 seconds or less, preferably 15 seconds or more and 90 seconds or less in the first half of drying before peeling. A process to make it carry out. In the case of casting on the drum, a step of drying in a substantially airless state for a time of 1 second or more and 10 seconds or less, preferably 2 seconds or more and 5 seconds or less is performed in the first half of drying before peeling.

In the present invention, "drying before peeling" refers to drying from peeling off as a film after dope is applied on a band or drum. In addition, a "half part" shall refer to a previous process on the basis of half of the whole time from application | coating of dope to peeling. "Substantially non-wind" means that a wind speed of 0.5 m / s or more is not detected at a distance within 200 mm from the band surface or the drum surface.

The first half of the drying prior to peeling is usually about 30 to 300 seconds in the case of the band, but is dried in a windless state for 10 seconds to 90 seconds, preferably 15 seconds to 90 seconds. In the case of a drum, the time is usually about 5 to 30 seconds, but it is dried in a windless state for 1 to 10 seconds, preferably 2 to 5 seconds. 0 to 180 degreeC is preferable and 40 to 150 degreeC of atmosphere temperature is more preferable. The operation of drying in a non-winding state can be carried out at any stage of the first half of drying before peeling, but is preferably performed immediately after casting. If the drying time in a non-winding state is less than 10 seconds, the retardation increasing agent and the retardation lowering agent are less likely to be uniformly distributed in the film. If the drying time exceeds 90 seconds, the retardation increasing agent and the retardation lowering agent are peeled off in an insufficient state of drying, and the surface shape of the film is deteriorated.

The time other than drying in the airless state in drying before peeling can be dried by blowing an inert gas. At this time, the temperature of the wind is preferably 0 ° C to 180 ° C, more preferably 40 ° C to 150 ° C.

As for the drying method in the solvent cast method, US Patents 2336310, 2367603, 2492078, 2492977, 2492978, 2607704, 2739069, 2739070, British Patent 640731, and Each specification of 736892, Unexamined-Japanese-Patent No. 45-4554, 49-5614, 60-176834, 60-203430, 62-115035 is described. Drying on a band or drum can be performed by blowing inert gas, such as air and nitrogen.

The obtained film may be peeled off from the drum or the band, and dried again by hot air having gradually changed the temperature from 100 to 160 ° C to evaporate the residual solvent. The above method is described in JP-A-5-17844. According to this method, it is possible to shorten the time from casting to peeling. In order to carry out this method, the dope must be gelated at the surface temperature of the drum or band during casting.

It can also form into a film by carrying out casting | flow_spread 2 or more layers using the adjusted cellulose acylate solution (dope). In this case, it is preferable to produce a cellulose acylate film by the solvent cast method. The dope is flexible on a drum or band and evaporates the solvent to form a film. It is preferable to adjust density | concentration for the dope before casting | flow_spread so that solid content may be 10 to 40% of range. It is preferable that the surface of a drum or a band is finished to a mirror surface state.

When plural cellulose acylate liquids of two or more layers are cast, it is possible to cast a plurality of cellulose acylate solutions and a solution containing cellulose acylate from a plurality of oils formed at intervals in the advancing direction of the support. It is also possible to produce a film while flexibly laminating each other. For example, the method described in each of Unexamined-Japanese-Patent No. 61-158414, Unexamined-Japanese-Patent No. 1-22419, and Unexamined-Japanese-Patent No. 11-198285 can be used. Moreover, it can also form into a film by casting a cellulose acylate solution from two oil studies. For example, JP-A-60-27562, JP-A-61-94724, JP-A-61-947245, JP-A-61-104813, JP-A-61- The method described in each of 158413 and Unexamined-Japanese-Patent No. 6-134933 can be used. Moreover, the cellulose acylate film which wraps the flow of the high viscosity cellulose acylate solution of Unexamined-Japanese-Patent No. 56-162617 with the low viscosity cellulose acylate solution, and simultaneously extrudes the high / low viscosity cellulose acylate solution Flexible methods can also be used.

Moreover, using two oil studies, the film shape | molded by the support body by 1st oil study is peeled off, and a film can also be produced by performing 2nd casting | flow_spread to the side which contacted the support body surface. For example, the method of Unexamined-Japanese-Patent No. 44-20235 is mentioned.

The same solution may be used for the flexible cellulose acylate solution, and different cellulose acylate solutions may be used. In order to provide a function to a some cellulose acylate layer, the cellulose acylate solution according to the function may be extruded from each oil research. Moreover, the cellulose acylate solution of this invention can also be flexible simultaneously with another functional layer (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, an ultraviolet absorbing layer, a polarizing layer, etc.).

In the conventional monolayer liquid, in order to make the required film thickness, the cellulose acylate solution of high concentration and high viscosity must be extruded. In this case, the stability of the cellulose acylate solution is poor, and solids are generated, and swelling occurs in some places, or the planarity is poor, which is often a problem. As a solution to this problem, by casting a plurality of cellulose acylate solutions from oil studies, a solution of high viscosity can be extruded on a support at the same time, the planarity is improved, and a film having excellent planar shape can be produced as well as thick. Reduction of a dry load can be achieved by using a cellulose acylate solution, and the production speed of a film can be raised.

The following plasticizers can be used for the cellulose acylate film in order to improve mechanical properties. Phosphoric acid ester or carboxylic acid ester is used as a plasticizer. Examples of the phosphate ester include triphenyl phosphate (TPP) and tricredyl phosphate (TCP). Phthalic acid ester and citric acid ester are typical as carboxylic acid ester. Examples of phthalate esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and diethylhexyl phthalate (DEHP). . Examples of citric acid ester include O-acetyl citrate triethyl (OACTE) and O-acetyl citrate tributyl (OACTB). Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Phthalate ester plasticizers (DMP, DEP, DBP, DOP, DPP, DEHP) are preferably used. DEP and DPP are particularly preferred.

It is preferable that the addition amount of a plasticizer is 0.1-25 mass% of the amount of cellulose acylate, It is more preferable that it is 1-20 mass%, It is most preferable that it is 3-15 mass%.

A deterioration inhibitor (for example, antioxidant, a peroxide decomposer, a radical inhibitor, a metal deactivator, an acid trapping agent, and an amine) can also be added to a cellulose acylate film. The deterioration inhibitor is described in Japanese Unexamined Patent Publications No. 3-199201, 5-1907073, 5-194789, 5-271471, and 6-107854. It is preferable that it is 0.01-1 mass% of the solution (dope) to prepare, and, as for the addition amount of a deterioration inhibitor, it is more preferable that it is 0.01-0.2 mass%. If the amount is less than 0.01% by mass, the effect of the deterioration inhibitor is hardly recognized. When addition amount exceeds 1 mass%, the bleeding-out of the deterioration inhibitor with respect to the film surface may be recognized. Examples of particularly preferred deterioration inhibitors include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).

These steps from casting to post-drying may be carried out in an air atmosphere, or may be carried out in an inert gas atmosphere such as nitrogen gas. The winding machine used for manufacture of the cellulose acylate film used by this invention should just be what is generally used, and winding methods, such as the static tensioning method, the static torque method, the taper tensioning method, the program tension control method with constant internal stress, etc. I can wind it up.

[Surface Treatment of Cellulose Acylate Film]

It is preferable that a cellulose acylate film performs surface treatment. Specific methods include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment or ultraviolet irradiation treatment. Moreover, as described in Unexamined-Japanese-Patent No. 7-333433, it is also preferable to form a undercoat layer.

From the viewpoint of maintaining the flatness of the film, in these treatments, the temperature of the cellulose acylate film is preferably set to Tg (glass transition temperature) or lower, specifically 150 ° C or lower.

When using as a transparent protective film of a polarizing plate, it is especially preferable to perform acid treatment or alkali treatment, ie, saponification process with respect to a cellulose acylate, from a viewpoint of adhesiveness with a polarizer.

It is preferable that surface energy is 55 mN / m or more, and it is more preferable that they are 60 mN / m or more and 75 mN / m or less.

Hereinafter, it demonstrates concretely, taking an alkali saponification process as an example.

The alkali saponification treatment of the cellulose acylate film is preferably carried out in a cycle in which the film surface is immersed in an alkaline solution, neutralized with an acidic solution, washed with water and dried.

Examples of the alkali solution include potassium hydroxide solution and sodium hydroxide solution, and the prescribed concentration of the hydroxide ions is preferably in the range of 0.1 to 3.0 N, more preferably in the range of 0.5 to 2.0 N. It is preferable to exist in the range of room temperature to 90 degreeC, and, as for alkaline solution temperature, it is more preferable to exist in the range which is 40-70 degreeC.

The surface energy of a solid can be calculated | required by the contact angle method, the wet heat method, and the adsorption method, as described in "The basis and application of a wet" (Israise Co., Ltd. issue of December 10, 1989). In the case of the cellulose acylate film of this invention, it is preferable to use a contact angle method.

Specifically, two kinds of solutions of which surface energy is already known are added dropwise to the cellulose acylate film, and the droplet is included at the angle formed by the tangent drawn on the droplet and the film surface at the intersection of the surface of the droplet and the film surface. The angle of the side is defined as the contact angle, and the surface energy of the film can be calculated by calculation.

[Water vapor transmission rate]

The water vapor transmission rate measures the water vapor transmission rate of each sample according to the method described in JIS Z 0208, and calculates the moisture content (g) evaporated in 24 hours per 1 m ^{2 of} area.

The water vapor transmission rate of the cellulose acylate film can be adjusted by various methods.

The water vapor transmission rate can be reduced by adding a hydrophobic compound to a cellulose acylate film and reducing the water absorption of a cellulose acylate film. In this case, the additive which has low compatibility with a cellulose acylate and a small plasticizing effect is especially preferable.

The compound represented by said general formula (I)-(IV) can be used suitably as a hydrophobization agent.

The water absorption of the cellulose acylate film can be evaluated by measuring the equilibrium moisture content at a constant temperature and humidity. 5 mass% or less is preferable and, as for the equilibrium moisture content in 25 degreeC 80% RH of a cellulose acylate film, 3 mass% or less is more preferable. The equilibrium moisture content is calculated by dividing the moisture content (g) by the sample mass (g) by measuring the moisture content of the sample that has reached equilibrium after leaving it at the temperature and humidity for 24 hours.                     

In addition, the water vapor transmission rate can also be reduced by stretching in the conveyance direction and / or the width direction during film formation, and by densifying the orientation of the molecular chain of the cellulose acylate.

Stretching can be performed in both uniaxial stretching and biaxial stretching.

Although biaxial stretching has the simultaneous biaxial stretching method and the sequential biaxial stretching method, the sequential biaxial stretching method is preferable from a continuous manufacture viewpoint, and after peeling a dope, peeling a film from a band or a drum and extending width direction (stretch method After extending | stretching in), it extends in a longitudinal direction (width direction).

The method of extending | stretching in the width direction is Unexamined-Japanese-Patent No. 62-115035, Unexamined-Japanese-Patent No. 4-152125, 4-284211, 4298310, 11-48271, etc., for example. Each publication is described. Stretching of a film is performed under normal temperature or heating conditions. It is preferable that heating temperature is below the glass transition temperature of a film. The film can be stretched in the treatment during drying, and is particularly effective when a solvent remains. In the case of stretching in the longitudinal direction, for example, the film is stretched when the speed of the conveying roller of the film is adjusted to make the winding speed of the film faster than the peeling speed of the film. In the case of extending | stretching of the width direction, conveying, maintaining the width of a film in a tenter, and extending | stretching a film can also extend | stretch the width of a tenter gradually. After drying of the film, stretching using a stretching machine (preferably uniaxial stretching using a long stretching machine) is also possible. It is preferable that the draw ratio of the film (the ratio of the increase by stretching to the original length) is in the range of 5 to 50%, more preferably in the range of 10 to 40%, and is in the range of 15 to 35%. Most preferably in the range.

Moreover, water permeability can also be reduced by processing a cellulose acylate film at high temperature and increasing crystallinity. The treatment needs to be carried out at a temperature and time such that the volatilization of the low molecular weight compound and the thermal decomposition of the cellulose acylate film itself are not a problem. 160 degreeC or more and 260 degrees C or less are preferable, and 180 degreeC or more and 240 degrees C or less are more preferable. 5 minutes or more and 2 hours or less are preferable, and, as for processing time, 10 minutes or more and 1 hour or less are more preferable.

[Hygroscopic expansion coefficient]

The hygroscopic expansion coefficient indicates the amount of change in the sample length when the relative humidity is changed under a constant temperature.

In order to prevent an increase in the transmittance of the frame shape, the moisture absorption expansion coefficient of the cellulose acylate film is preferably 30 × 10 ⁻⁵ /% RH or less, more preferably 15 × 10 ⁻⁵ /% RH or less, Most preferably, it is 10x10 <^-5> % or less RH. In addition, although the smaller one is preferable, the hygroscopic expansion coefficient is a value more than 1.0x10 <^-5> % RH.

It shows below about the measuring method of a moisture absorption expansion coefficient. The sample of width 5mm and length 20mm was cut out from the produced polymer film (retardation plate), one end was fixed, and it hanged in 25 degreeC and 20% RH (R0) atmosphere. A 0.5 g weight was attached to the other end and left for 10 minutes to measure the length (L0). Next, length L1 was measured by making humidity 80% RH (R1), with temperature being 25 degreeC. The hygroscopic expansion coefficient was calculated by the following equation. The measurement employ | adopted the average value by measuring 10 samples about the same sample.

Hygroscopic expansion coefficient [/% RH] = {(L1-L0) / L0} / (R1-R0)

In order to reduce the dimensional change by moisture absorption, it is preferable to reduce the amount of residual solvent at the time of film forming and to reduce the free volume in a polymer film.

A general technique for reducing residual solvents is to dry them at high temperatures for a long time, but if they are dried for too long, productivity is naturally deteriorated. Therefore, it is preferable that the amount of the residual solvent with respect to a cellulose acylate film exists in the range of 0.01-1 mass%, It is more preferable to exist in the range of 0.02-0.07 mass%, It is most preferable to exist in the range of 0.03-0.05 mass% desirable.

By controlling the amount of the residual solvent, a polarizing plate having an optical compensating ability can be produced at a low cost and with high productivity.

The amount of residual solvent was melt | dissolved a fixed amount of sample in chloroform, and measured using the gas chromatograph (GC18A, Shimadzu Corporation make).

In the solution casting method, a film is produced using a solution (dope) in which a polymer material is dissolved in an organic solvent. Drying in the solution casting method is largely divided into drying on the drum (or band) surface and drying at the time of film conveyance, as will be described later. In the case of drying on the drum (or band) surface, it is preferable to dry slowly at a temperature not exceeding the boiling point of the solvent used (if it exceeds the boiling point, bubbles are formed). In addition, it is preferable to perform drying at the time of film conveyance at the glass transition point +/- 30 degreeC of a polymeric material, More preferably, it is +/- 20 degreeC.

Moreover, it is preferable to add the compound which has a hydrophobic group as another method of making the dimensional change by the said moisture absorption small. The material having a hydrophobic group is not particularly limited as long as it is a material having a hydrophobic group such as an alkyl group or a phenyl group in the molecule, but a material corresponding to the plasticizer or the deterioration inhibitor added to the cellulose acylate film is particularly preferably used. Examples of these preferred materials include triphenylphosphate (TPP), tribenzylamine (TBA), and the like.

It is preferable to exist in the range of 0.01-30 mass% with respect to the solution (dope) to adjust, and, as for the addition amount of the compound which has these hydrophobic groups, it is more preferable to exist in the range of 0.1-20 mass%.

[Retardation of Film]

Re retardation value [nm] and Rth retardation value [nm] of a film are respectively defined by following formula (A) and (B).

(A) Re = (nx-ny) × d

(B) Rth = {(nx + ny) / 2-nz} × d

In Formula (A) and (B), nx is the refractive index of the slow-axis direction (direction in which a refractive index becomes largest) in a film plane.

In Formulas (A) and (B), ny is a refractive index in the fast axis direction (direction in which the refractive index becomes minimum) in the film plane.                     

In Formula (B), nz is the refractive index of the thickness direction of a film.

In Formula (A) and (B), d is the thickness of the film which makes a unit nm.

The cellulose acylate film of this invention can be used suitably as retardation film corresponding to various liquid crystal modes.

Preferred optical properties of the cellulose acylate film depend on the liquid crystal mode.

It is preferable that Re is 10-100, and, as for OCB mode, it is more preferable that it is 20-70. It is preferable that Rth is 50-300, and it is more preferable that it is 100-250.

It is preferable that it is 20-100, and, as for VA mode, it is more preferable that it is 30-70. It is preferable that Rth is 50-250, and it is more preferable that it is 80-180.

Moreover, for TN, it is preferable that Re is 0-50, and it is more preferable that it is 2-30. It is preferable that Rth is 10-200, and it is more preferable that it is 30-150.

In OCB mode and TN mode, an optically anisotropic layer is apply | coated on the cellulose acylate film which has the said retardation value, and can be used as an optical compensation film.

Moreover, it is preferable that birefringence ((DELTA) n: nx-ny) of a cellulose acylate film exists in the range of 0.00-0.002. Moreover, it is preferable that birefringence {(nx + ny) / 2-nz} of the thickness direction of a support film and an opposing film exists in the range of 0.00-0.04.

Moreover, as for the thickness (dry film thickness) of a cellulose acylate film, 20-110 micrometers is preferable and 40-100 micrometers is more preferable.

[Photoelasticity]

The photoelastic coefficient of the protective film of the present invention is preferably 60 × 10 ^-8 cm 2 / N or less, more preferably 20 × 10 ^-8 cm 2 / N or less. The photoelastic coefficient can be obtained by ellipsometer.

[Glass transition temperature]

120 degreeC or more is preferable and, as for the glass transition temperature of the protective film of this invention, 140 degreeC or more is more preferable. The glass transition temperature is the average value of the temperature at which the baseline derived from the glass transition of the film starts to change when measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC) and the temperature returns to the baseline again. As obtained.

1. Composition of Polarizer

First, the protective film and polarizer which comprise the polarizing plate of this invention are demonstrated.

The polarizing plate of this invention may have an adhesive layer, a separate film, and a protective film as a component other than a polarizer and a protective film.

(1) protective film                     

Although the polarizing plate of this invention has two protective films in total, one on both sides of a polarizer, it is preferable that at least one of these has a function as retardation film together.

The protective film of the present invention is preferably a polymer film made of norbornene resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyallylate, polysulfone, cellulose acylate and the like.

Among these, the said cellulose acylate is the most preferable.

(2) polarizer

The polarizer of the present invention is preferably composed of polyvinyl alcohol (PVA) and dichroic molecules. However, as described in Japanese Patent Laid-Open No. 11-248937, the polarizer is dehydrated and dechlorinated. The polyvinylene polarizer which produced the yen structure and orientated this can also be used.

Although PVA is a polymer material which saponified polyvinyl acetate, it may contain the component copolymerizable with vinyl acetate, such as unsaturated carboxylic acid, unsaturated sulfonic acid, olefins, and vinyl ether, for example. Moreover, modified PVA containing acetoacetyl group, sulfonic acid group, carboxyl group, oxyalkylene group, etc. can also be used.

Although the saponification degree of PVA is not specifically limited, From a viewpoint of solubility, etc., 80-100 mol% is preferable and 90-100 mol% is especially preferable. Moreover, although the polymerization degree of PVA is not specifically limited, 1000-10000 are preferable and 1500-5000 are especially preferable.                     

The syndiotacticity of PVA is preferably 55% or more in order to improve durability as described in Japanese Patent No. 2978219, but 45 to 52.5% described in Japanese Patent No. 3317494 can also be preferably used.

After PVA film-forming, it is preferable to introduce | transduce a dichroic molecule and to comprise a polarizer. As the manufacturing method of a PVA film, the method of cast | flow_spreading the stock solution which melt | dissolved PVA system resin in water or an organic solvent, and forming a film is generally used preferably. The density | concentration of polyvinyl alcohol-type resin in a stock solution is 5-20 mass% normally, and a PVA film with a film thickness of 10-200 micrometers can be manufactured by forming this stock solution by the casting method. PVA film can be manufactured with reference to Unexamined-Japanese-Patent No. 3342516, Unexamined-Japanese-Patent No. 9-328593, Unexamined-Japanese-Patent No. 13-302817, and Unexamined-Japanese-Patent No. 14-144401.

Although the crystallinity degree of a PVA film is not specifically limited, 50-75 mass% of average crystallization degrees (Xc) described in Japanese Patent No. 3,325,73, and in order to reduce in-plane color deviation, are disclosed by Unexamined-Japanese-Patent No. 14-236214. PVA films of 38% or less crystallinity as described can be used.

It is preferable that birefringence ((DELTA) n) of a PVA film is small, and the PVA film whose birefringence described in Unexamined-Japanese-Patent No. 3342516 is 1.0x10 <^-3> or less can be used preferably. However, as described in Japanese Patent Application Laid-Open No. 14-228835, the birefringence of the PVA film may be 0.02 or more and 0.01 or less, in order to obtain a high degree of polarization while avoiding cutting during stretching of the PVA film. As described in Patent Publication No. Hei 14-060505, the value of (nx + ny) / 2-nz may be 0.0003 or more and 0.01 or less. The retardation (in-plane) of the PVA film is preferably Onm or more and 100 nm or less, more preferably 0 nm or more and 50 nm or less. Moreover, 0 nm or more and 500 nm or less are preferable, and, as for Rth (film thickness direction) of a PVA film, 0 nm or more and 300 nm or less are more preferable.

In addition to the polarizing plate of the present invention, a PVA film having a 1,2-glycol bond amount described in Japanese Patent No. 301494 or less and 1.5 mol% or less, and an optical foreign material of 5 μm or more described in JP-A-13-316492 PVA films of 500 or less per 100 cm 2, PVA films having a hydrothermal cleavage temperature nonuniformity in the TD direction of the film described in JP-A-H14-030163, 1.5 ° C. or lower, and 3 to 6-valent polyhydric alcohols such as glycerin and the like. PVA film manufactured from the solution which mixed -100 mass parts or mixed the plasticizer of Unexamined-Japanese-Patent No. 6-289225 with 15 mass% or more can be used preferably.

Although the film film thickness before extending | stretching of a PVA film is not specifically limited, 1 micrometer-1 mm are preferable from a viewpoint of the stability of film retention and the homogeneity of extending | stretching, and 20-200 micrometers is especially preferable. As described in JP-A-H14-236212, a thin PVA film in which the stress generated when stretching from 4 to 6 times in water is 10 N or less may be used.

The dichroic molecule can preferably use higher order iodine ions such as I ₃ -or I ₅ -or a dichroic dye. In the present invention, higher order iodine ions are particularly preferably used. The higher iodine ions may be a liquid obtained by dissolving iodine in an aqueous solution of potassium iodide, as described in "Application of Polarizing Plates", Nagata, CMC Publications and Industrial Materials, Vol. 28, No. 7, p39 to p45. PVA is immersed in boric-acid aqueous solution, and it can produce | generate in the state made to adsorb | suck and oriented to PVA.

When a dichroic dye is used as a dichroic molecule, an azo dye is preferable, and a bis azo dye and a tris azo dye are especially preferable. It is preferable that a dichroic dye is water-soluble, and for this reason, hydrophilic substituents, such as a sulfonic acid group, an amino group, and a hydroxyl group, are introduce | transduced into a dichroic molecule, and it is used preferably as a free acid or a salt of an alkali metal salt, ammonium salt, and amines.

Specific examples of such dichroic dyes include, for example, C.I. Direct Red 37, Congo Red (C.I.Direct Red 28), C.I. Direct Violet 12, C.I. Direct Blue 90, C.I. Direct Blue 22, C.I. Direct Blue 1, C.I. Direct Blue 151, C.I. Benzidine series such as Direct Green 1, C.I. Direct Yellow 44, C.I. Direct Red 23, C.I. Diphenylurea type, such as Direct Red 79, C.I. Stilbene systems such as Direct Yellow 12, C.I. Dinaphthylamines such as Direct Red 31, C.I. Direct Red 81, C.I. Direct Violet 9, C.I. J mountain systems, such as Direct Blue 78, are mentioned.

In addition to this, C.I. Direct Yellow 8, C.I. Direct Yellow 28, C.I. Direct Yellow 86, C.I. Direct Yellow 87, C.I. Direct Yellow 142, C.I. Direct Orange 26, C.I. Direct Orange 39, C.I. Direct Orange 72, C.I. Direct Orange 106, C.I. Direct Orange 107, C.I. Direct Red 2, C.I. Direct Red 39, C.I. Direct Red 83, C.I. Direct Red 89, C.I. Direct Red 240, C.I. Direct Red 242, C.I. Direct Red 247, C.I. Direct Violet 48, C.I. Direct Violet 51, C.I. Direct Violet 98, C.I. Direct Blue 15, C.I. Direct Blue 67, C.I. Direct Blue 71, C.I. Direct Blue 98, C.I. Direct Blue 168, C.I. Direct Blue 202, C.I. Direct Blue 236, C.I. Direct Blue 249, C.I. Direct Blue 270, C.I. Direct Green 59, C.I. Direct Green 85, C.I. Direct Brown 44, C.I. Direct Brown 106, C.I. Direct Brown 195, C.I. Direct Brown 210, C.I. Direct Brown 223, C.I. Direct Brown 224, C.I. Direct Black 1, C.I. Direct Black 17, C.I. Direct Black 19, C.I. Direct Black 54 and the like, and also JP-A-62-70802, JP-A-1-11202202, JP-A-172906, JP-A-172907 and JP-A-172907. The dichroic dye described in each of Unexamined-Japanese-Patent No. 1-183602, Unexamined-Japanese-Patent No. 1-248105, Unexamined-Japanese-Patent No. 1-265205, and Unexamined-Japanese-Patent No. 7-261024, etc. can also be used preferably. In order to manufacture the dichroic molecule which has various colors, these dichroic dye may mix | blend 2 or more types. When using a dichroic dye, adsorption thickness may be 4 micrometers or more, as described in Unexamined-Japanese-Patent No. 14-082222.

When the content of the dichroic molecule in the film is too small, the polarization degree is low, and even when the content of the dichroic molecule is excessively large, the single plate transmittance decreases, so that it is usually from 0.01% by mass to 0.01 with respect to the polyvinyl alcohol-based polymer constituting the matrix of the film. It adjusts to the range of 5 mass%.

As a preferable film thickness of a polarizer, 5 micrometers-40 micrometers are preferable, More preferably, they are 10 micrometers-30 micrometers. It is also preferable to make ratio of the thickness of a polarizer and the thickness of the protective film mentioned later into the range of 0.01 <= A (polarizer film thickness) / B (protective film film thickness) <= 0.16 described in Unexamined-Japanese-Patent No. 14-174727. .

Although the crossing angle of the slow axis of a protective film and the absorption axis of a polarizer can be made into arbitrary values, it is preferable that they are parallel or an azimuth angle of 45 +/- 20 degrees.

2. Manufacturing Process of Polarizing Plate

Next, the manufacturing process of the polarizing plate of this invention is demonstrated.

It is preferable that the manufacturing process of the polarizing plate in this invention consists of a swelling process, a dyeing process, a hard film process, an extending process, a drying process, a protective film adhesion process, and a post-adhesion drying process. The order of a dyeing process, the film-forming process, and an extending process may be changed arbitrarily, or you may carry out combining several processes simultaneously. And, as described in Japanese Patent No. 3316515, washing with water after the dura film step can also be preferably performed.

In this invention, it is especially preferable to sequentially perform a swelling process, a dyeing process, a film-forming process, an extending process, a drying process, a protective film adhesion process, and a drying process after adhesion in the order described. In addition, you may provide an online surface shape inspection process during or after the process mentioned above.

Although it is preferable to perform a swelling process only with water, as described in Unexamined-Japanese-Patent No. 10-153709, in order to stabilize optical performance and to avoid wrinkles in the polarizing plate base material in a manufacturing line, a polarizing plate The substrate may be swollen with an aqueous boric acid solution and the degree of swelling of the polarizing plate substrate may be managed.

In addition, although the temperature and time of a swelling process can be arbitrarily determined, 10 second or more and 60 degrees C or less, 5 second or more and 2000 second or less are preferable.

The dyeing process can use the method of Unexamined-Japanese-Patent No. 2002-86554. In addition, the dyeing method may be any means such as application or spraying of iodine or dye solution as well as dipping. Moreover, as described in Unexamined-Japanese-Patent No. 13-290025, you may use the method of dyeing, stirring, the density | concentration of iodine, dyeing bath temperature, the draw ratio in a bath, and the bath liquid in a bath.

When using higher order iodine ion as a dichroic molecule, in order to obtain a high contrast polarizing plate, it is preferable to use the liquid which melt | dissolved iodine in the aqueous solution of potassium iodide for a dyeing process. In this case, 0.05-20 g / L of iodine of an aqueous solution of potassium iodide in aqueous solution, 3-200 g / L of potassium iodide, and the mass ratio of iodine and potassium iodide are 1-2000 in the preferable range. 10-1200 second of dyeing time is preferable, and 10-60 degreeC of liquid temperature is preferable. More preferably, iodine is 0.5-2 g / L, potassium iodide is 30-120 g / L, mass ratio of iodine and potassium iodide is 30-120, the dyeing time is 30-600 second, and liquid temperature is 20-50 degreeC. Is good.

Further, as described in Japanese Patent No. 3145747, boron-based compounds such as boric acid and borax may be added to the dyeing solution.

It is preferable that a film formation process is immersed in a crosslinking agent solution, or apply | coats a solution and contains a crosslinking agent. Moreover, as described in Unexamined-Japanese-Patent No. 11-52130, a dura film process can also be performed in several times.

As the crosslinking agent, those described in US Reissue Patent No. 232897 may be used. As described in Japanese Patent No. 3357109, polyhydric aldehyde may be used as the crosslinking agent to improve dimensional stability, but boric acid is most preferably used. do.

When boric acid is used as a crosslinking agent used for a film-forming process, metal ion can also be added to boric-acid potassium iodide aqueous solution. Although zinc chloride is preferable as the metal ion, zinc salts such as zinc halides such as zinc iodide, zinc sulfate, and zinc acetate may be used in place of zinc chloride, as described in JP-A-2000-35512.

In this invention, it is preferable to produce the boric-acid potassium iodide aqueous solution which added zinc chloride, and to immerse a PVA film, and to harden a film | membrane. The boric acid is preferably 1 to 100 g / L, the potassium iodide is 1 to 120 g / L, the zinc chloride is preferably 0.01 to 10 g / L, the film formation time is 10 to 1200 seconds, and the liquid temperature is preferably 10 to 60 ° C. More preferably, boric acid is 10-80 g / L, potassium iodide is 5-100 g / L, zinc chloride is 0.02-8 g / L, film-forming time is 30-600 second, and liquid temperature is 20-50 degreeC.

As the stretching step, the longitudinal uniaxial stretching method described in US Pat. No. 2,454,515 or the like, or the tenter method described in JP-A-2002-86554 can be preferably used. Preferable draw ratio is 2 times or more and 12 times or less, More preferably, they are 3 times or more and 10 times or less. In addition, the relationship between the draw ratio, the disk thickness, and the polarizer thickness is described in JP-A-H14-040256 (Polarizer film thickness / disk thickness after protective film) × (total draw ratio)> 0.17 The relationship between the width of the polarizer after the final bath and the width of the polarizer at the time of attaching the protective film is 0.80 ≤ (polarizer after passing through the polarizer width / final bath with the protective film) described in JP-A-H14-040247. Can be preferably performed.

Although the method of Unexamined-Japanese-Patent No. 2002-86554 can be used for a drying process, the preferable temperature range is 30 degreeC-100 degreeC, and a preferable drying time is 30 second-60 minutes. In addition, as described in Japanese Patent No. 3148513, a heat treatment is performed in which the water color fading temperature is 50 ° C or higher, or described in Japanese Patent Application Laid-Open No. 7-325215 or Japanese Patent Laid-Open No. 7-325218. As described above, aging in an atmosphere in which temperature and humidity are managed can also be preferably performed.

A protective film adhesion process is a process of sticking two protective films on both surfaces of the above-mentioned polarizer which passed through the drying process. The method of supplying an adhesive liquid just before adhesion, laminating | stacking a polarizer and a protective film, and sticking by a pair of rolls is used preferably. In addition, as described in Japanese Unexamined Patent Application Publication Nos. 2001-296426 and 2002-86554, in order to suppress groove-shaped unevenness of a record resulting from elongation of a polarizer, the moisture content of the polarizer at the time of attachment is adjusted. It is preferable. In this invention, the moisture content of 0.1%-30% is used preferably.

Although the adhesive agent of a polarizer and a protective film is not specifically limited, PVA system resin (it contains modified PVA, such as an acetoacetyl group, a sulfonic acid group, a carboxyl group, an oxyalkylene group), aqueous solution of a boron compound, etc. are mentioned, Especially, a PVA system Resin is preferable. 0.01-5 micrometers is preferable and, as for the thickness of an adhesive bond layer, 0.05-3 micrometers is especially preferable.

Moreover, in order to improve the adhesive force of a polarizer and a protective film, it is preferable to surface-treat a protective film, to make it hydrophilic, and to adhere. The surface treatment method is not particularly limited, but any method such as saponification using an alkaline solution or corona treatment can be used. It is also possible to form a layer which facilitates adhesion such as a gelatin undercoat after surface treatment. As described in JP 14-267839 A, the contact angle with water on the surface of the protective film is preferably 50 ° or less.

Although the drying conditions after adhesion are based on the method of Unexamined-Japanese-Patent No. 2002-86554, the preferable temperature range is 30 degreeC-100 degreeC, and a preferable drying time is 30 second-60 minutes. Moreover, it is also preferable to age in the atmosphere which controlled temperature-humidity as described in Unexamined-Japanese-Patent No. 7-325220.

It is preferable that element content in a polarizer is 0.1-3.0 g / m <2> of iodine, 0.1-5.0 g / m <2> of boron, 0.1-2.0 g / m <2> of potassium, and 0-2.0 g / m <2> of zinc. In addition, potassium content may be 0.2 mass% or less, as described in Unexamined-Japanese-Patent No. 13-166143, and zinc content in a polarizer is 0.04 mass%-0.5 described in Unexamined-Japanese-Patent No. 12-035512. It can also be set as mass%.

As described in Japanese Patent No. 3323255, in order to increase the dimensional stability of the polarizing plate, an organic titanium compound and / or an organic zirconium compound are added and used in any one of a dyeing step, an extending step, and a film forming step, and the organic titanium It may also contain at least one compound selected from compounds and organic zirconium compounds. Moreover, in order to adjust the color of a polarizing plate, you may add a dichroic dye.

3. Characteristics of polarizer

(1) transmittance and polarization degree

Although the preferable single plate transmittance of the polarizing plate of this invention is 42.5% or more and 49.5% or less, More preferably, they are 42.8% or more and 49.0% or less. The preferable ranges of polarization degree defined by Formula 4 are 99.900% or more and 99.999% or less, More preferably, they are 99.940% or more and 99.995% or less. The preferred range of parallel transmittance is 36% or more and 42% or less, and the preferred range of orthogonal transmittance is 0.001% or more and 0.05% or less. Although the preferable range of the dichroic ratio defined by Formula 5 is 48 or more and 1215 or less, More preferably, they are 53 or more and 525 or less.

The above-mentioned transmittance is based on JIS Z 8701,

(Equation 1)

.

Here, K, S (λ), y (λ), τ (λ) are as follows.

(Equation 2)                     

(식3)

(Eq. 3)

S (λ): Spectral distribution of standard light used for color display

y (λ): equivalence function in XYZ system

τ (λ): spectral transmittance

λ: measurement wavelength [nm]

(Equation 3)

(식4)

(Eq. 4)

(Equation 4)

(식5)

(Eq. 5)

The iodine concentration and the single plate transmittance may be in the range described in Japanese Patent Application Laid-Open No. 14-258051.

The parallel transmittance may have a small wavelength dependency as described in Japanese Patent Application Laid-Open No. Hei 13-083328 and Japanese Patent Application Laid-Open No. 14-022950. The optical characteristic in the case of arrange | positioning a cross nicol polarizing plate may be the range described in Unexamined-Japanese-Patent No. 13-091736, and the relationship between parallel transmittance and orthogonal transmittance is the range described in Unexamined-Japanese-Patent No. 14-174728. You may pay it.

As described in Japanese Patent Application Laid-Open No. Hei 14-221618, the standard deviation of parallel transmittance every 10 nm between wavelengths of light is between 420 and 700 nm is 3 or less, and the wavelength of light is between 420 and 700 nm. The minimum value of (parallel transmittance / orthogonal transmittance) every 10 nm may be 300 or more.

Parallel transmittance and orthogonal transmittance at wavelength 440 nm of the polarizing plate, parallel transmittance and orthogonal transmittance at wavelength 550 nm, parallel transmittance and orthogonal transmittance at wavelength 610 nm are disclosed in Japanese Patent Application Laid-Open No. 14-258042 and The range described in 14-258043 can also be preferably performed.

(2) color

The color of the polarizing plate of the present invention can be preferably evaluated by using the brightness index L * and chromaticity index a * and b * in the L * a * b * color system which is recommended as a CIE equal perceptual space. L *, a *, b * is defined by Formula 6 using X, Y, Z mentioned above.

(5)

(식6)

(Eq. 6)

Where X _O , Y _O and Z _O represent the three stimulus values of the illumination light source, in the case of standard light C, X _O = 98.072, Y _O = 100, Z _O = 118.225, and in the case of standard light D ₆₅ , X _O = 95.045, Y ₀ = 100, Z ₀ = 108.892.

The range of preferable a * of one polarizing plate is -2.5 or more and 0.2 or less, More preferably, it is -2.0 or more and 0 or less. The range of preferable b * of one polarizing plate is 1.5 or more and 5 or less, More preferably, it is 2 or more and 4.5 or less. The preferable range of a * of the parallel transmitted light of two polarizing plates is -4.0 or more and 0 or less, More preferably, they are -3.5 or more and -0.5 or less. The range with preferable b * of parallel transmitted light of two polarizing plates is 2.0 or more and 8 or less, More preferably, it is 2.5 or more and 7 or less. The preferable range of a * of orthogonal transmission light of two polarizing plates is -0.5 or more and 2 or less, More preferably, they are 0 or more and 1.0 or less. The preferable range of b * of the orthogonal transmitted light of two polarizing plates is -2.0 or more and 2 or less, More preferably, they are -1.5 or more and 0.5 or less.

The color may be evaluated by the chromaticity coordinates (x, y) calculated from the above-described X, Y, and Z, for example, the chromaticity (x _P , y _P ) of the parallel transmitted light of the two polarizing plates and the chromaticity (x) of the orthogonal transmitted light. _C , y _C ) is defined in Japanese Unexamined Patent Publication No. Hei 14-214436, Japanese Unexamined Patent Application Publication No. Hei 13-166136 and Japanese Unexamined Patent Application Publication No. 14-169024, or the relationship between color and absorbance in Japan. It can also implement suitably in the range described in Unexamined-Japanese-Patent No. 13-311827.

(3) viewing angle characteristics

Transmittance ratio and xy chromaticity difference between the case where the vertical polarized light is incident and the incident light is incident at an angle of 40 degrees with respect to the normal line at 45 degrees with respect to the polarization axis in the case of cross nicol arrangement of the polarizing plates and incident light of 550 nm It is also preferable to set it as the range of Unexamined-Japanese-Patent No. 13-166135 and Unexamined-Japanese-Patent No. 13-166137. In addition, as described in Japanese Patent Application Laid-Open No. 10-068817, the light transmittance (T _O ) in the vertical direction of the polarizing plate laminate arranged with cross nicol and the light transmittance in the direction inclined by 60 ° from the normal of the laminate ( T ₆₀₎ ratio (as described in T ₆₀ / T ₀₎ to less than 10000, or are described in Japanese Kokai Publication Hei-14-139625 call, the natural light incident from the normal to the polarizer at an angle of elevation to 80 degrees In the case where it is made, the transmittance | permeability difference of the transmitted light within a wavelength range of 20 nm in the wavelength range of 520-640 nm of the transmission spectrum shall be 6% or less, or the film described in Unexamined-Japanese-Patent No. 8-248201. It is also preferable to set the luminance difference of the transmitted light in a place 1 cm away from above within 30%.

(4) durability

(4-1) damp heat durability

As described in Japanese Patent Application Laid-Open No. Hei 13-116922, when left for 500 hours in an atmosphere at 60 ° C. and 90% RH for 500 hours, the rate of change of light transmittance and polarization degree before and after is 3% or less based on absolute values. It is preferable. In particular, it is more preferable that the change rate of light transmittance is 2% or less, and the change rate of polarization degree is 1.0% or less, or 0.1% or less based on an absolute value. Moreover, as described in Unexamined-Japanese-Patent No. 7-077608, it is also preferable that polarization degree after 80 degreeC, 90% RH, and 500 hours leaving is 95% or more, and single transmittance is 38% or more.

(4-2) dry durability

When it is left to stand in 80 degreeC and dry atmosphere for 500 hours, it is preferable that the change rate of the light transmittance and polarization degree before and after that is also 3% or less based on an absolute value. In particular, it is more preferable that the change rate of light transmittance is 2% or less, and the change rate of polarization degree is 1.0% or less and 0.1% or less based on an absolute value.

(4-3) other durability

And as described in Unexamined-Japanese-Patent No. 6-167611, the shrinkage rate after leaving at 80 degreeC for 2 hours is made into 0.5% or less, or the polarizing plate laminated body arrange | positioned cross nicol on both surfaces of a glass plate is carried out in 69 degreeC atmosphere. X value and y value after leaving for 750 hours fall within the range described in JP-A-10-068818, or 105 cm ^-1 by Raman spectroscopy after 200 hours in 80 ° C and 90% RH atmosphere. It is also preferable to make the change of the spectral intensity ratio of 157cm <^-1> into the range as described in Unexamined-Japanese-Patent No. 8-094834 and 9-197127.

(5) orientation

The higher the degree of orientation of the PVA, the better polarization performance can be obtained, but 0.2 to 1.0 is a preferred range as an order parameter value calculated by means such as polarized Raman scattering or polarized light FT-IR. Further, as described in Japanese Patent Laid-Open No. 59-133509, the difference between the orientation coefficient of the polymer segment in the entire amorphous region of the polarizer and the orientation coefficient (0.75 or more) of the occupying molecule is at least 0.15, or As described in Japanese Patent Application Laid-Open No. 4-204907, the orientation coefficient of the amorphous region of the polarizer is preferably 0.65 to 0.85, or the degree of orientation of the higher order iodine ions of I ₃ or I ₅ is 0.8 to 1.0 as the order parameter value. It can be carried out.

(6) Other characteristics

As described in Japanese Patent Application Laid-Open No. 14-006133, the shrinkage force in the absorption axis direction per unit width when heated at 80 ° C. for 30 minutes is set to 4.0 N / cm or less, or Japanese Patent Laid-Open No. 14-236213 As described in the following, when the polarizing plate is left for 120 hours under a heating condition of 70 ° C., both the dimensional change rate in the absorption axis direction and the dimensional change rate in the polarization axis direction of the polarizing plate are set to within ± 0.6%, or the moisture content of the polarizing plate is disclosed in Japanese Patent Application. As described in Japanese Patent Application Laid-Open No. 14-090546, it can also be preferably set to 3% by mass or less. And as described in Unexamined-Japanese-Patent No. 12-249832, the surface roughness of the direction perpendicular | vertical to a stretch axis is made into 0.04 micrometer or less based on a center line average roughness, or described in Unexamined-Japanese-Patent No. 10-268294. Refractive index in the transmission axis direction (n ₀ ) It can also be preferably performed to make larger than 1.6, or to make the relationship between the thickness of a polarizing plate and the thickness of a protective film into the range of Unexamined-Japanese-Patent No. 10-111411.

4. Functionalization of Polarizer

The polarizing plate of the present invention is a magnification film of an LCD, a λ / 4 plate for application to a reflective LCD, an antireflection film for improving the visibility of a display, a brightness enhancement film, a hard coat layer, a front scattering layer, and an antiglare. It is preferably used as a functionalized polarizing plate in combination with an optical film having a functional layer such as an (antiglare) layer.

The cross-sectional schematic diagram of the structural example which combined the polarizing plate of this invention and the functional optical film mentioned above is shown in FIG. As one protective film 1 of a polarizing plate, the functional optical film 3 and the polarizer 2 can also be adhere | attached through an adhesive agent (FIG. 1 (A)), and protective films 1a and 1b are formed on both surfaces of the polarizer 2, respectively. The functional optical film 3 can also be adhere | attached to one polarizing plate through the adhesive layer 4 (FIG. 1 (B)). In the former case, any transparent protective film can be used for the other protective film. It is also preferable to make each interlayer peeling strength, such as a functional layer and a protective film, into 4.0N / 25mm or more as described in Unexamined-Japanese-Patent No. 14-311238. It is preferable to arrange | position a functional optical film in the liquid crystal module side according to the function made into the objective, or arrange | positioning on the opposite side to a liquid crystal module, ie, a display side or a backlight side.

Below, the functional optical film used in combination with the polarizing plate of this invention is demonstrated.

(1) viewing angle magnification film (optical compensation film)

The polarizing plate of the present invention is a viewing angle magnification film proposed in display modes such as twisted nematic (TN), in-plane switching (IPS), optimally compensated bend (OCB), vertically aligned (VA), and electrically controlled controlled wire (ECB). It can be used in combination with.                     

As a viewing angle expansion film for TN mode, Japanese Journal of Printing Journal No. 36, No. 3 (1999) p40-44, Monthly Display August issue (2002) p20-24, Japanese Patent Application Laid-Open No. 4-229828, Japanese Unexamined Patent WV films (manufactured by Fuji Photographic Film Co., Ltd.) described in JP-A-6-75115, JP-A-6-214116, JP-A-8-50206 and the like can be preferably used in combination.

The preferable structure of the viewing angle expansion film for TN mode is to have an orientation layer and an optically anisotropic layer in this order on the above-mentioned transparent polymer film. Although the viewing angle magnification film can also be attached to the polarizing plate by an adhesive, it is particularly preferable from the viewpoint of thinning that it is also used as one of the protective films of the polarizer as described in SID'OO Dig., P551 (2000).

The alignment layer can be formed by means such as rubbing treatment of an organic compound (preferably a polymer), evaporation of an inorganic compound, formation of a layer having micro groups. Moreover, although the orientation layer which generate | occur | produces an orientation function by provision of an electric field, provision of a magnetic field, or light irradiation is known, the orientation layer formed by the rubbing process of a polymer is especially preferable. The rubbing treatment is preferably carried out by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth. It is preferable that the absorption axis direction of a polarizer and a rubbing direction are substantially parallel. As a kind of polymer used for an orientation layer, the polymer etc. which have a polymerizable group of polyimide, polyvinyl alcohol, Unexamined-Japanese-Patent No. 9-152509, etc. can be used preferably. It is preferable that it is 0.01-5 micrometers, and, as for the thickness of an orientation layer, it is more preferable that it is 0.05-2 micrometers.                     

It is preferable that an optically anisotropic layer contains a liquid crystalline compound. It is especially preferable that the liquid crystalline compound used for this invention has a discotic compound (discotic liquid crystal). The discotic liquid crystal molecule has a disk-like core portion like the triphenylene derivative of D-1, and has a structure in which side chains extend radially therefrom. Further, in order to impart stability over time, it is also preferable to further introduce a group reacting with heat, light, or the like. Preferable examples of the discotic liquid crystal are described in Japanese Patent Laid-Open No. 8-50206.

D-1

The discotic liquid crystal molecules are oriented substantially parallel to the film plane with a pretilt angle in the rubbing direction in the vicinity of the alignment layer, and the discotic liquid crystal molecules are oriented so as to be perpendicular to the plane on the opposite air surface side. The entire discotic liquid crystal layer has a hybrid orientation, and by this layer structure, the viewing angle of the TFT-LCD in the TN mode can be realized.

In general, the optically anisotropic layer is applied by applying a solution in which a discotic compound and other compounds (for example, a polymerizable monomer, a photopolymerization initiator) are dissolved in a solvent, onto an alignment layer, and then drying to a discotic nematic phase forming temperature. After heating, it is superposed | polymerized by irradiation of UV light etc., and obtained by cooling again. As discotic nematic liquid crystal phase-solid-state transition temperature of the discotic liquid crystalline compound used for this invention, 70-300 degreeC is preferable, and 70-170 degreeC is especially preferable.

Moreover, as a compound other than the discotic compound added to the said optically anisotropic layer, it is compatible with a discotic compound, and unless a liquid crystal discotic compound changes a preferable inclination-angle or impairs orientation, Compounds can also be used. Among them, cellulose acetate and cellulose acetate as additives for controlling the orientation of the air interface such as a polymerizable monomer (eg, a compound having a vinyl group, a vinyloxy group, an acryloyl group and a methacryloyl group) and a fluorine-containing triazine compound And polymers such as propionate, hydroxypropyl cellulose, and cellulose acetate butyrate. These compounds are generally used in an amount of 0.1 to 50% by mass, preferably 0.1 to 30% by mass, based on the discotic compound.

It is preferable that it is 0.1-10 micrometers, and, as for the thickness of an optically anisotropic layer, it is more preferable that it is 0.5-5 micrometers.

The preferable aspect of a viewing angle expansion film consists of the cellulose acylate film as a transparent base film, the orientation layer formed on it, and the optically anisotropic layer which consists of a discotic liquid crystal formed on the orientation layer, and an optically anisotropic layer is made to UV light irradiation. It is bridge | crosslinked by.

In addition to the above, in the case of combining the viewing angle expanding film and the polarizing plate of the present invention, for example, as described in Japanese Patent Application Laid-open No. Hei 7-198942, it has an optical axis in a direction intersecting the plate surface and has a birefringence. It can also be preferably carried out by laminating with a retardation plate exhibiting anisotropy, or substantially equalizing the dimensional change rate of the protective film and the optically anisotropic layer, as described in JP-A-14-258052. Further, as described in JP-A-12-258632, the water content of the viewing angle-expanded film and the polarizing plate to be adhered is set to 2.4% or less, or as described in JP-A-H14-267839. It is also preferable to set the contact angle with water on the film surface to 70 degrees or less.

The viewing angle magnification film for IPS mode liquid crystal cells is used for the optical compensation of the liquid crystal molecules oriented parallel to the substrate surface and the viewing angle characteristic of the orthogonal transmittance of the polarizing plate at the time of black display of an electric field-free state. In the IPS mode, black display is performed in a state where no electric field is applied, and the transmission axes of the upper and lower pairs of polarizing plates are perpendicular to each other. However, when observed in an oblique direction, the crossing angle of the transmission axis is not 90 degrees, and light leaks and contrast decreases. In the case of using the polarizing plate of the present invention in an IPS mode liquid crystal cell, in order to reduce the leakage light, the in-plane retardation is made close to zero and the retardation is made in the thickness direction as described in JP-A-10-54982. It is used in combination with the viewing angle magnification film which has.

The viewing angle magnification film for liquid crystal cells of the OCB mode is used to optically compensate the liquid crystal layer vertically aligned at the center of the liquid crystal layer and obliquely aligned near the substrate interface by applying an electric field, thereby improving the viewing angle characteristic of the black display. When the polarizing plate of the present invention is used in an OCB mode liquid crystal cell, the polarizing plate of the present invention is preferably used in combination with a viewing angle magnification film in which the disk-shaped liquid crystalline compound described in US Patent 5805253 is hybrid-oriented.

The viewing angle magnification film for liquid crystal cells of VA mode improves the viewing angle characteristic of the black display of the state in which the liquid crystal molecule was orientated perpendicularly to the board | substrate surface in the no field applied state. Such a viewing angle expanding film is a film in which the in-plane retardation described in Japanese Patent No. 2866372 is close to zero and has a retardation in the thickness direction, or a film in which discoid compounds are arranged in parallel to the substrate, or the same in-plane retardation. In order to prevent the deterioration of orthogonal transmittance of the polarizing plate in the oblique direction of the stretched film which has a value, or the slow axis orthogonally crosses, it is used combining suitably what was laminated | stacked.

(2) λ / 4 plate

The polarizing plate of the present invention can be used as a circular polarizing plate laminated with a λ / 4 plate. The circularly polarizing plate has a function of converting incident light into circularly polarized light, and is preferably used for a semi-transmissive liquid crystal display device such as a reflective liquid crystal display device, an ECB mode, or an organic EL element.

It is preferable that the λ / 4 plate used in the present invention is a retardation film having a retardation (Re) of approximately 1/4 of the wavelength in the visible light wavelength range in order to obtain almost complete circularly polarized light in the visible light wavelength range. Do. The term "retardation of approximately 1/4 in the wavelength range of visible light" means that the longer the wavelength is, the larger the retardation is at wavelength 400 to 700 nm, and the retardation value (Re450) measured at the wavelength of 450 nm is 80 to 125 nm. Moreover, the range which satisfy | fills the relationship whose retardation value Re590 measured at the wavelength of 590 nm is 120-160 nm is shown. It is more preferable that it is Re590-Re450≥5 nm, and it is especially preferable that Re590-Re450≥10 nm.

The λ / 4 plate used in the present invention is not particularly limited as long as the above conditions are satisfied. For example, JP-A-5-27118, JP-A-10-68816, JP-A-JP (Lambda) / 4 board which laminated | stacked the some polymer film of 10-90521, (lambda) / 4 board which extended | stretched one polymer film of WO00 / 65384, WO 00/26705, Unexamined-Japanese-Patent No. 2000-284126 Arbitrary (lambda) / 4 boards, such as a (lambda) / 4 board in which at least 1 or more layers of optically anisotropic layers were formed on the polymer film of Unexamined-Japanese-Patent No. 2002-31717, can be used. In addition, the slow-axis direction of a polymer film and the orientation direction of an optically anisotropic layer can be arrange | positioned in arbitrary directions according to a liquid crystal cell.

In the circular polarizing plate, the slow axis of the λ / 4 plate and the transmission axis of the polarizer may cross at any angle, but are preferably crossed in the range of 45 ° ± 20 °. However, the slow axis of the λ / 4 plate and the transmission axis of the polarizer may cross each other in the ranges other than the above.

When the λ / 4 plate is formed by laminating the λ / 4 plate and the λ / 2 plate, as described in Japanese Patent No. 3236304 and Japanese Patent Application Laid-open No. Hei 10-68816, the λ / 4 plate and λ / It is preferable that the angle between the in-plane slow axis of the two plates and the transmission axis of the polarizing plate is substantially 75 degrees and 15 degrees.

(3) antireflection film

The polarizing plate of this invention can be used in combination with an antireflection film. As the antireflection film, a film having a reflectance of only about 1.5% or a film having a reflectance of 1% or less using multilayer interference of a thin film can be used. In this invention, the structure which laminated | stacked the low refractive index layer and the at least 1 layer (namely, the high refractive index layer and the medium refractive index layer) which has higher refractive index than the low refractive index layer on a transparent support body is used preferably. Moreover, the anti-reflective film of Nitto Kibo, vol. 38, No. 1, may, 2000, pages 26-28, Unexamined-Japanese-Patent No. 2002-301783, etc. can also be used preferably.

The refractive index of each layer satisfies the following relationship.

Refractive Index of High Refractive Index Layer> Refractive Index of Middle Refractive Index Layer> Refractive Index of Transparent Support> Refractive Index of Low Refractive Index Layer

As a transparent support body used for an antireflection film, the transparent polymer film used for the protective film of the polarizing layer mentioned above can be used preferably.

The refractive index of the low refractive index layer is 1.20 to 1.55, preferably 1.30 to 1.50. It is preferable to use a low refractive index layer as an outermost layer which has scratch resistance and antifouling property. In order to improve scratch resistance, it is also preferable to impart slipperiness to the surface by using a silicon group or a fluorine-containing material.

As a fluorine-containing compound, Unexamined-Japanese-Patent No. 9-222503 specification paragraphs [0018]-[0026], the 11-38202 specification paragraphs [0019]-[0030], Unexamined-Japanese-Patent No. The compound described in 2001-40284 specification paragraphs [0027]-[0028], Unexamined-Japanese-Patent No. 2000-284102, etc. can be used preferably.                     

The silicon-containing compound is preferably a compound having a polysiloxane structure, but is preferably a reactive silicone (e.g., cyraprene (manufactured by Chisso Co., Ltd.)) or a polysiloxane containing silanol groups at both ends (Japanese Patent Laid-Open No. 11-258403). Etc. can also be used. An organometallic compound such as a silane coupling agent and a silane coupling agent containing a specific fluorine-containing hydrocarbon group can also be cured by a condensation reaction in the presence of a catalyst (JP-A-58-142958, 58-147483, 58). -147484, Japanese Patent Application Laid-Open Nos. 9-157582, 11-106704, Japanese Patent Laid-Open Nos. 2000-117902, 2001-48590, 2002-53804 and the like.

In the low refractive index layer, as an additive other than the above, a low refractive index having an average diameter of primary particles such as fillers (for example, silicon dioxide (silica) and fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride)) is 1 to 150 nm. It is also preferable to contain an inorganic compound, organic fine particles described in paragraphs [0020] to [0038] of JP-A-11-3820), a silane coupling agent, a lubricant, a surfactant, and the like.

The low refractive index layer may be formed by a vapor phase method (vacuum deposition method, sputtering method, ion plating method, plasma CVD method, etc.), but is preferably formed by a coating method in that it can be manufactured at low cost. As the coating method, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, and a micro gravure method can be preferably performed.

The film thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm, and most preferably 60 to 120 nm.                     

It is preferable to make the medium refractive index layer and the high refractive index layer into the structure which disperse | distributed the high refractive index inorganic compound ultrafine particle of an average particle diameter of 100 nm or less in the matrix material. Examples of the high refractive index inorganic compound fine particles include inorganic compounds having a refractive index of 1.65 or more, for example, oxides such as Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, In, composite oxides containing these metal atoms, and the like. Can be preferably used.

Such ultra-fine particles can be treated with a surface treatment agent (such as a silane coupling agent: Japanese Patent Laid-Open No. 11-295503, Japanese Patent Laid-Open No. 11-153703, Japanese Patent Laid-Open No. 2000-9908, an anionic compound or an organic metal couple). Ring agent: Japanese Laid-Open Patent Publication No. 2001-310432, etc.), a core shell structure having high refractive index particles as a core (Japanese Laid-Open Patent Publication No. 2001-166104, etc.), or using a specific dispersant in combination (for example, Japanese Patent Laid-Open No. 11). -153703, Patent No. US 6210858 B1, Japanese Laid-Open Patent Publication No. 2002-2776069 and the like.

Arbitrary thermoplastic resin, (thermo) curable resin film, etc. can be used as a matrix material, However, Unexamined-Japanese-Patent No. 2000-47004, 2001-315242, 2001-31871, 2001-296401, etc. are described. The curable film obtained from a polyfunctional material and the metal alkoxide composition of Unexamined-Japanese-Patent No. 2001-293818 etc. can also be used.

It is preferable that the refractive index of a high refractive index layer is 1.70-2.20. It is preferable that it is 5 nm-10 micrometers, and, as for the thickness of a high refractive index layer, it is more preferable that it is 10 nm-1 micrometer.

The refractive index of the medium refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. It is preferable that the refractive index of a medium refractive index layer is 1.50-1.70.

It is preferable that it is 5% or less, and, as for the haze of an antireflection film, 3% or less is more preferable. Moreover, it is preferable that it is H or more by the pencil hardness test according to JISK5400, and, as for the intensity | strength of a film, it is more preferable that it is 2H or more, and it is most preferable that it is 3H or more.

(4) brightness enhancement film

The polarizing plate of this invention can be used in combination with a brightness improving film. The brightness enhancement film has a separation function of circularly polarized light or linearly polarized light, and is disposed between the polarizing plate and the backlight, so that one circularly polarized light or linearly polarized light is reflected back or scattered back toward the backlight side. Since the re-reflected light from the backlight part partially changes the polarization state and is partially transmitted when reentering the brightness enhancing film and the polarizing plate, by repeating this process, the light utilization is improved and the front brightness is improved by about 1.4 times. . Anisotropic reflection system and anisotropic scattering system are known as a brightness enhancement film, and both can be combined with the polarizing plate of this invention.

In the anisotropic reflection method, a luminance improving film having anisotropy of reflectance and transmittance is known by laminating a uniaxially stretched film and an unstretched film multiplely and increasing the refractive index difference in the stretching direction, and a multilayer film method using the principle of dielectric mirror (WO 95/17691, WO 95/17692, WO 95/17699, and the cholesteric liquid crystal system (European Patent 606940 A2 specification, Japanese Unexamined Patent Application, First Publication No. Hei 8-271731) are known. DBEF-E, DBEF-D, DBEF-M (all manufactured by 3M) as the multilayer brightness enhancement film using the principle of dielectric mirror, and NIPOCS as the brightness enhancement film of the cholesteric liquid crystal type (Nitto Electric Co., Ltd.) Production) is preferably used in the present invention. For NI and POCS, refer to Nitto Kibo, vol. 38, No. 1, may, 2000, pages 19 to 21, and the like.

Moreover, in this invention, each specification of WO 97/32223, WO 97/32224, WO 97/32225, WO 97/32226, and each of Unexamined-Japanese-Patent No. 9-274108, 11-174231 is described. It is preferable to use it in combination with the brightness enhancement film of the anisotropic scattering system which uniaxially stretched and blended the positive intrinsic birefringent polymer and the negative intrinsic birefringent polymer. As an anisotropic scattering system brightness improvement film, DRPF-H (made by 3M company) is preferable.

It is preferable to use the polarizing plate of this invention and a brightness improving film as an integrated form which attached | attached through the adhesive or the one protective film of a polarizing plate as a brightness improving film.

(5) other functional optical films

In addition to the polarizing plate of this invention, it uses in combination with the functional optical film which provided the hard-coat layer, the front-scattering layer, the antiglare (anti-glare) layer, the gas barrier layer, the slip layer, the antistatic layer, the undercoat layer, the protective layer, etc. It is also preferable to. It is also preferable to use these functional layers in combination with each other and in the same layer as the above-described antireflection layer, optically anisotropic layer and the like.                     

(5-1) Hard Coat Layer

In order to provide mechanical strength, such as abrasion resistance, in the polarizing plate of this invention, combining a hard coat layer with the functional optical film formed in the surface of a transparent support body is performed preferably. In the case where the hard coat layer is applied to the antireflection film described above and used, the hard coat layer is preferably formed between the transparent support and the high refractive index layer.

It is preferable to form a hard-coat layer by crosslinking reaction of a curable compound by light and / or heat, or a polymerization reaction. As the curable functional group, a photopolymerizable functional group is preferable, and the organoalkoxysilyl compound is preferably an organometallic compound containing a hydrolyzable functional group. As a specific structural composition of a hard-coat layer, the thing of Unexamined-Japanese-Patent No. 2002-144913, 2000-9908, WO 0/46617, etc. can be used preferably, for example.

It is preferable that the film thickness of a hard-coat layer is 0.2-100 micrometers.

It is preferable that the intensity | strength of a hard-coat layer is H or more by the pencil hardness test according to JISK5400, It is more preferable that it is 2H or more, It is most preferable that it is 3H or more. And in the taper test based on JISK5400, it is more preferable that the amount of abrasion of the test piece before and behind a test is small.

As the material for forming the hard coat layer, a compound containing an ethylenically unsaturated group and a compound containing a ring-opening polymerizable group can be used, and these compounds can be used alone or in combination. Preferable examples of the compound containing an ethylenically unsaturated group include ethylene glycol diacrylate, trimethylol propane triacrylate, ditrimethyl all propane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol pentaacryl. Polyacrylates of polyols such as latex and dipentaerythritol hexaacrylate; Epoxy acrylates, such as the diacrylate of bisphenol A diglycidyl ether, the diacrylate of hexanediol diglycidyl ether, etc .: Urethane obtained by reaction of hydroxyl-containing acrylate, such as polyisocyanate and hydroxyethyl acrylate. Acrylate etc. are mentioned as a preferable compound. Moreover, as a commercial compound, EB-600, EB-40, EB-140, EB-1150, EB-1290K, IRR214, EB-2220, TMPTA, TMPTMA (above, manufactured by Daicel UBC Co., Ltd.), UV-6300, UV-1700B (above, Nippon Synthetic Chemical Co., Ltd. make (all brand name)), etc. are mentioned.

Preferable examples of the compound containing a ring-opening polymerizable group include ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, trimethylol ethane triglycidyl ether, and trimethylol propane triglycidyl as glycidyl ethers. Ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, sorbitol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, polyglycidyl ether of cresol novolac resin, phenol novolak resin As cycloaliphatic epoxy, such as polyglycidyl ether, Celoxide 2021P, Celoxide 2081, Eporide GT-301, Eporide GT-401, and EHPE 3150CE (all are manufactured by Daicel Chemical Industries, Ltd. (all brand names)) ), OXT-121, OXT-221, OX-SQ, PNOX-1009 (above, manufactured by Dong-A Synthetic Co., Ltd.) as oxetanes, such as polycyclohexyl epoxy methyl ether of phenol novolak resin )), And the like. In addition, the polymer of glycidyl (meth) acrylate or the copolymer with the monomer copolymerizable with glycidyl (meth) acrylate can also be used for a hard-coat layer.

The hard coat layer includes oxide fine particles such as silicon, titanium, zirconium, aluminum, polyethylene, polystyrene, etc., in order to reduce hardening shrinkage of the hard coat layer, to improve adhesion to the substrate, and to reduce curl of the hard coat processed article of the present invention. It is also preferable to add crosslinked fine particles such as crosslinked particles such as poly (meth) acrylic acid esters and polydimethylsiloxane, and organic fine particles such as crosslinked rubber fine particles such as SBR (styrene butadiene rubber) and NBR (nitrile rubber). It is preferable that the average particle diameters of these crosslinked microparticles | fine-particles are 1 nm-20000 nm. In addition, the shape of crosslinked microparticles | fine-particles can be used without a restriction | limiting, such as spherical shape, rod shape, needle shape, and plate shape. It is preferable that it is 60 volume% or less of the hard-coat layer after hardening, and, as for the addition amount of microparticles | fine-particles, 40 volume% or less is more preferable.

In the case of adding the inorganic fine particles described above, since affinity with the binder polymer is generally poor, it contains metals such as silicon, aluminum and titanium, and further contains alkoxide groups, carboxylic acid groups, sulfonic acid groups and phosphonic acid groups. Surface treatment using the surface treating agent which has a functional group is also performed preferably.

It is preferable to harden a hard coat layer using heat or an active energy ray, and it is more preferable to use active energy rays, such as a radiation, a gamma ray, an alpha ray, an electron beam, and an ultraviolet-ray among these, and when considering safety and productivity, an electron beam It is particularly preferable to use ultraviolet rays. When hardening with heat, in consideration of the heat resistance of plastic itself, 140 degreeC or less of heating temperature is preferable, More preferably, it is 100 degrees C or less.

(5-2) Forward Scattering Layer

The front scattering layer is used to improve the viewing angle characteristics (color and luminance distribution) in the vertical and horizontal directions when the polarizing plate of the present invention is applied to a liquid crystal display device. In this invention, the structure which binder disperse | distributed the microparticles from which refractive index differs is preferable, For example, Unexamined-Japanese-Patent No. 11-38208 which specified the forward scattering coefficient, Japan which made the relative refractive index of a transparent resin and microparticles into the specific range The structure of Unexamined-Japanese-Patent No. 2000-199809, Unexamined-Japanese-Patent No. 2002-107512 which prescribed | regulated haze value 40% or more can be used. Moreover, in order to control the viewing angle characteristic of haze, it is also preferable to use the polarizing plate of this invention in combination with "Lumisti" described in the technical report "optical functional film" pages 31-39 of Sumitomo Chemical Industries, Ltd. can do.

(5-3) Antiglare Layer

The antiglare (anti-glare) layer is used to scatter the reflected light to prevent reflection. The antiglare function is obtained by forming irregularities on the outermost surface (display side) of the liquid crystal display device. The haze of the optical film having an antiglare function is preferably 3 to 30%, more preferably 5 to 20%, and most preferably 7 to 20%.

As for the method of forming irregularities on the surface of the film, for example, a method of forming irregularities on the surface of a film by adding fine particles (for example, JP 2000-271878, etc.), relatively large particles (particle diameter of 0.05 to 2 µm) ) To form a surface uneven film by adding a small amount (0.1-50 mass%) (for example, JP 2000-281410, 2000-95893, 2001-100004, 2001-281407, etc.). ), A method of physically transferring an uneven shape to the surface of a film (for example, as an embossing method, JP-A-63-278839, JP-A-11-183710, JP-2000-275401 Etc.) etc. can be used preferably.

These functional layers can be formed and used on either or both surfaces of a polarizer side and a surface opposite to a polarizer.

5. Liquid Crystal Display Using Polarizer

Next, the liquid crystal display device using the polarizing plate of this invention is demonstrated.

2 is an example of a liquid crystal display device in which the polarizing plate of the present invention is used.

The liquid crystal display device shown in FIG. 2 has the upper polarizing plate 11 and the lower polarizing plate 22 arrange | positioned through the liquid crystal cell 15-19 and the liquid crystal cell 15-19. Although the polarizing plate is sandwiched by a polarizer and a pair of transparent protective films, it is shown as an integrated polarizing plate in FIG. 2, and detailed structure is abbreviate | omitted. The liquid crystal cell is composed of a liquid crystal layer formed from the upper substrate 15 and the lower substrate 18 and the liquid crystal molecules 17 sandwiched therebetween. The liquid crystal cell has TN (Twisted Nematic), IPS (In-Plane Switching), OCB (Optically Compensatory Bend), VA (Vertically Aligned), ECB ( Although classified as a display mode such as Electrically Controlled Birefringence, the polarizing plate of the present invention can be used for all display modes regardless of transmission and reflection type.

An alignment film (not shown) is formed on the surface (hereinafter may be referred to as "inner surface") in contact with the liquid crystal molecules 17 of the substrates 15 and 18, and by rubbing treatment or the like performed on the alignment film, The orientation of the liquid crystal molecules 17 in the non-field applied state or low applied state is controlled. Moreover, the transparent electrodes (not shown) which can apply an electric field to the liquid crystal layer which consists of liquid crystal molecules 17 are formed in the inner surface of the board | substrates 15 and 18. FIG.

The rubbing direction in the TN mode is performed in the direction perpendicular to each other on the upper and lower substrates, and the magnitude of the tilt angle can be controlled by the strength, the number of rubbings, and the like. The alignment film is formed by applying a polyimide film and baking it. The magnitude of the twist angle (twist angle) of the liquid crystal layer is determined by the crossing angle of the rubbing direction of the upper and lower substrates and the chiral agent added to the liquid crystal material. In this case, a chiral agent with a pitch of about 60 μm was added so that the twist angle was 90 °.

The twist angle is set at around 90 ° (85 to 95 °) for notebook PCs, PC monitors, and television liquid crystal displays, and from 0 to 70 ° when used as a reflective display device such as a mobile phone. do. In addition, in the IPS mode or the ECB mode, the twist angle is 0 °. In the IPS mode, the electrode is disposed only on the lower substrate 18, and an electric field parallel to the substrate surface is applied. In addition, in the OCB mode, the tilt angle is increased without the twist angle, and in the VA mode, the liquid crystal molecules 17 are oriented perpendicular to the upper and lower substrates.

The magnitude of the product (Δnd) of the thickness (d) of the liquid crystal layer and the refractive index anisotropy (Δn) changes the brightness at the time of white display. For this reason, the range is set for each display mode to obtain the maximum brightness.

High contrast can be obtained by laminating so that the crossing angle of the absorption axis 12 of the upper polarizing plate 11 and the absorption axis 23 of the lower polarizing plate 22 is generally orthogonal. The crossing angle between the absorption axis 12 of the upper polarizing plate 11 of the liquid crystal cell and the rubbing direction of the upper substrate 15 varies depending on the liquid crystal display mode, but is generally set parallel or vertical in the TN and IPS modes. It is often set to 45 ° in OCB and ECB modes. However, the optimum value is different in each display mode for the adjustment of the color tone and the viewing angle of the display color, but is not limited to this range.

The liquid crystal display device in which the polarizing plate of this invention is used is not limited to the structure of FIG. 2, and may contain the other member. For example, a color filter may be disposed between the liquid crystal cell and the polarizer. Moreover, the above-mentioned viewing angle expansion films 13 and 20 can also be arrange | positioned between a liquid crystal cell and a polarizing plate. The polarizing plates 11 and 22 and the viewing angle magnification films 13 and 20 may be arranged in a laminated form attached with an adhesive, or may be arranged as a so-called integrated elliptical polarizing plate using one protective film on the liquid crystal cell side for expanding the viewing angle.

Moreover, when using as a transmission type, the backlight which uses a cold cathode or a hot cathode fluorescent tube, or a light emitting diode, a field emission element, an electroluminescent element as a light source can be arrange | positioned at the back surface. In addition, the liquid crystal display device in which the polarizing plate of the present invention is used may be a reflection type, and in this case, it is sufficient to arrange one polarizing plate on the observation side, and a reflective film is provided on the rear surface of the liquid crystal cell or the lower substrate of the liquid crystal cell. do. Of course, the front light using the light source may be formed on the liquid crystal cell observation side.

(Example)

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited at all by these.

Example 1

(Production of cellulose acylate film (1))

The following composition was put into the mixing tank, it stirred while heating, each component was melt | dissolved, and the cellulose acylate solution A was prepared.

<Cellulose Acylate Solution A Composition>

100 parts by mass of cellulose acetate having a degree of acetylation of 60.9%

Triphenyl phosphate (plasticizer) 7.8 parts by mass

3.9 parts by mass of biphenyldiphenyl phosphate (plasticizer)

300 parts by mass of methylene chloride (first solvent)

54 parts by mass of methanol (second solvent)

11 parts by mass of 1-butanol

The following composition was put into another mixing tank, it stirred while heating, each component was melt | dissolved, and additive solution B-1-B-6 were prepared.

<Additive solution B-1-B-6 composition>                     

Dope Methylene chloride
(Mass part) Methanol
(Mass part) UV absorbers (A)
(Mass part) UV absorbers (B)
(Mass part) compound
(446)
(Mass part) compound
(F-7)
(Mass part) B-1 80 20 2 4 none none B-2 Homology Homology Homology Homology 30 none B-3 Homology Homology Homology Homology none 30 B-4 Homology Homology Homology Homology 10 20 B-5 Homology Homology Homology Homology 20 10 B-6 Homology Homology Homology Homology 15 15

<Production of Cellulose Acetate Film 1>

40 mass parts of additive solutions B-1 were added to 474 mass parts of cellulose acylate solution A, and it fully stirred, and dope was prepared. The dope was cast on a drum cooled to 0 ° C. from oil studies. It peels off outside of 70 mass% of solvent content rates, The both ends of the width direction of a film are fixed with a pin tenter (pin tenter of FIG. 3 of Unexamined-Japanese-Patent No. 4-1009), and a solvent content rate is 3-5 mass%. It dried while maintaining the space | interval which the elongation of a horizontal direction (direction perpendicular | vertical to a machine direction) becomes 3% in a state. Then, it dried further by conveying between the rolls of a heat processing apparatus, and produced the cellulose acetate film 1 of thickness 80micrometer.

<Production of Cellulose Acetate Films (2) to (8)>

In the preparation of the cellulose acetate film 1, cellulose acetate films 2 to 8 were produced in the same manner as in the cellulose acetate film 1 except that the additive solution and the thickness were changed to the contents of Table 2.

Sample Number Additive solution thickness
(Μm) Additive amount
(Mass%, large cellulose acetate) Moisture permeability
(g / m ² ㆍ 24hr) Remarks compound
(446) compound
(F-7) (One) B-1 80 0 0 1950 Comparative example (2) B-2 80 8.8 0 1530 Comparative example (3) B-3 80 0 8.8 1610 Comparative example (4) B-4 80 2.9 5.9 1100 Invention (5) B-5 80 5.9 2.9 1040 Invention (6) B-6 80 4.4 4.4 810 Invention (7) B-6 60 4.4 4.4 1080 Invention (8) B-6 40 4.4 4.4 1340 Invention

[Example 2]

(Saponification)

The cellulose acetate films (1)-(8) were immersed for 2 minutes in 55 degreeC sodium hydroxide aqueous solution at 55 degreeC. It wash | cleaned in the water bath of room temperature, and it neutralized using 0.1 N sulfuric acid at 30 degreeC. Again, it wash | cleaned in the water washing bath of room temperature, and dried again by the warm air of 100 degreeC. In this way, the surface of the cellulose acetate film was saponified.

And the WV film of FUJIFILM film manufacture was saponified on the same conditions, and it used for producing the following sample.

Example 3

Iodine was adsorbed to the stretched polyvinyl alcohol film to produce a polarizer, and the cellulose acetate film 1 produced in Example 1 was attached to one of the polarizers using a polyvinyl alcohol-based adhesive. The transmission axis of the polarizer and the slow axis of the cellulose acetate film were arranged to be parallel to each other.

And the WV film saponified in Example 2 was affixed on the opposite side of the polarizer using the polyvinyl alcohol-type adhesive agent. In this way, the polarizing plate 1 was produced.

Example 4

The polarizing plates (2)-(8) were produced with the combination of the cellulose acetate film shown in Table 3 by the method similar to Example 3.

Example 5

The polarizing plate thus prepared was attached to the glass plate so that the WV film was on the glass side, and the resultant was passed for 1000 hours at 60 ° C. and 90% RH. Was calculated. The results are shown in Table 3.

From the result of Table 3, it turns out that the polarizing plate of this invention is small in the change of the polarization degree with respect to heat and humidity, and excellent in durability.

Polarizer Air interface side protective film Polarization degree Remarks (One) Cellulose Acylate Film (1) 97.4 Comparative example (2) Cellulose Acylate Film (2) 98.1 Comparative example (3) Cellulose Acylate Film (3) 98.4 Comparative example (4) Cellulose Acylate Film (4) 99.1 Invention (5) Cellulose Acylate Film (5) 99.3 Invention (6) Cellulose Acylate Film (6) 99.7 Invention (7) Cellulose Acylate Film (7) 99.0 Invention (8) Cellulose Acylate Film (8) 98.9 Invention

[Example 6]                     

A pair of polarizing plates formed on a 20-inch liquid crystal display device (LC-20V1, manufactured by Sharp Co., Ltd.) using a TN-type liquid crystal cell was peeled off, and instead of the polarizing plate produced in Example 5, the optical compensation sheet was a liquid crystal. It adhere | attached one by one to the observer side and the backlight side through an adhesive so that it might become a cell side. It was arrange | positioned so that the transmission axis of the polarizing plate of an observer side, and the transmission axis of the polarizing plate of a backlight side may orthogonally cross. The light leakage was evaluated by continuously lighting the backlight for 100 hours under an environmental condition of a temperature of 25 ° C. and a relative humidity of 60%, and visually observing the front black display state in the dark room. As a result, it was not observed in the liquid crystal display device using the polarizing plate of this invention with respect to the frame-shaped light leakage observed on the display screen of a liquid crystal display device in the polarizing plate of a comparative example.

Example 7

(Preparation of cellulose acetate solution)

The following composition was thrown into the mixing tank, it stirred, each component was melt | dissolved, and the cellulose acetate solution was prepared.

Cellulose Acetate Solution A1 Composition

100.0 parts by mass of cellulose acetate having a degree of acetylation of 60.9%

Methylene chloride (first solvent) 402.0 parts by mass

60.0 parts by mass of methanol (second solvent)

(Preparation of Matte Solution)

The following composition was put into the disperser, and it stirred and dissolved each component, and prepared the mat solution.                     

Matte solution composition

Silica particles with an average particle diameter of 16 nm

(AEROSIL R972, brand name, Nippon Aerosil Co., Ltd.) 2.0 parts by mass

Methylene chloride (first solvent) 76.3 parts by mass

11.4 parts by mass of methanol (second solvent)

10.3 parts by mass of cellulose acetate solution A1

(Preparation of additive solution)

The following composition was put into a mixing tank, stirred while heating to dissolve each component to prepare an additive (retardation increasing agent) solution.

Additive solution composition

19.8 parts by mass of additive (446)

Methylene chloride (first solvent) 58.4 parts by mass

8.7 parts by mass of methanol (second solvent)

Cellulose acetate solution A1 12.8 parts by mass

(Production of Cellulose Acetate Film 11)                     

94.6 parts by mass of the cellulose acetate solution A1 and 1.3 parts by mass of the mat agent solution and 4.1 parts by mass of the retardation synergist solution were mixed after filtration and cast using a band softener. The mass ratio of the retardation increasing agent to cellulose acetate was 4.6%. The film was peeled off from the band with a residual solvent amount of 30%, and the film having a residual solvent amount of 13% by mass under a condition of 130 ° C was transversely stretched at a draw ratio of 28% using a tenter, and then the width after stretching was 30 at 140 ° C as it is. Hold for seconds. Then, the clip was peeled off and dried at 140 degreeC for 40 minutes, and the cellulose acetate film was produced. The amount of residual solvent of the completed cellulose acetate film was 0.2%, and the film thickness was 92 micrometers.

The cellulose acetate films (12)-(18) were produced by the same method except having changed the kind and quantity of the additive in the additive solution to the content of Table 4.

(Measurement of optical characteristics)

About the produced cellulose acetate film, the retardation value was measured by the following method.

Measurement method of Rth retardation value

The in-plane retardation Re (O) was measured at 25 degreeC 10% RH using the ellipsomter (N4-15O, Nippon Spectrometer). In addition, the retardation Re (40) and Re (-40) were measured by turning 40 degrees and -40 degrees with the in-plane slow axis as a turning axis. Using the film thickness and the refractive index (nx) in the slow axis direction as parameters, the refractive index (ny) in the fast axis direction and the thickness direction so as to fit to the measured values Re (0), Re (40) and Re (-40). The refractive index (nz) was calculated | required by calculation and Rth retardation value was determined. The measurement wavelength was 632.8 nm. In addition, it measured similarly also in 25 degreeC 80% RH. The results are shown in Table 5.

Moreover, it was confirmed that Rth increased when Compound 446 and Compound 250 were added, and Rth decreased when A-4, PL-29, and F-2 were added.

Sample Number additive Remarks Kinds amount
(mass%) Kinds amount
(mass%) Cellulose Acetate Film (11) (446) 4.6 - 0 Comparative example Cellulose Acetate Film (12) (250) 7 - 0 Comparative example Cellulose Acetate Film (13) (250) 3 - 0 Comparative example Cellulose Acetate Film (14) (250) 5 (A · 4) 2 Invention Cellulose Acetate Film (15) (250) 6 (A · 4) 3 Invention Cellulose Acetate Film (16) (250) 7 (A · 4) 2 Invention Cellulose Acetate Film (17) (446) 7 (PL, 29) 2 Invention Cellulose Acetate Film (18) (446) 7 (F, 2) 2 Invention

Sample number Measured value at 25 ° C 10% RH Measured value at 25 ° C 80% RH The ratio of the measured value at 25 ° C 80% RH with the measured value at 25 ° C 10% RH Remarks Re
(Nm) Rth
(Nm) Re
(Nm) Rth
(Nm) Rth / Re Rain of Re Rth's Rain Cellulose Acetate Film (11) 46 210 39 176 4.5 0.61 0.65 Comparative example Cellulose Acetate Film (12) 54 240 43 186 4.3 0.63 0.68 Comparative example Cellulose Acetate Film (13) 35 172 28 146 5.2 0.59 0.61 Comparative example Cellulose Acetate Film (14) 48 152 38 138 3.6 0.74 0.71 Invention Cellulose Acetate Film (15) 51 159 43 156 3.6 0.72 0.73 Invention Cellulose Acetate Film (16) 55 170 47 150 3.2 0.77 0.78 Invention Cellulose Acetate Film (17) 53 177 48 162 3.4 0.78 0.75 Invention Cellulose Acetate Film (18) 54 173 48 153 3.2 0.75 0.73 Invention

From the results of Table 5, it can be seen that the cellulose acylate film of the present invention can realize a wide range of optical properties, and the humidity dependency of the optical properties is small and is a preferable retardation film.

Example 8

(Saponification)

5.2 ml / m <2> of the following composition was apply | coated on the cellulose acetate film 11 produced in Example 7, and it dried at 60 degreeC for 10 second. The surface of the film was washed with running water for 10 seconds, and the film surface was dried by blowing air at 25 ° C.

Saponified liquid composition

Isopropyl Alcohol 818 parts by mass

167 parts by mass of water

187 parts by mass of propylene glycol

68.3 parts by mass of potassium hydroxide

(Formation of alignment film)

On the saponified cellulose acetate film 11, the coating liquid of the following composition was apply | coated 24 ml / m <2> with the wire bar coater of # 14. It dried for 60 second with the warm air of 60 degreeC, and 150 second with the warm air of 90 degreeC again.

Next, the rubbing process was performed to the formed film | membrane in the direction which is 45 degrees with the extending direction (nearly coinciding with the ground axis) of a cellulose acetate film (transparent support body).

Alignment film coating liquid composition

20 parts by mass of the following modified polyvinyl alcohol

360 parts by mass of water

120 parts by mass of methanol

Glutalaldehyde (crosslinking agent) 1.0 parts by mass                     

Modified polyvinyl alcohol

(Formation of Optically Anisotropic Layer (Optical Compensation Sheet))

91 parts by mass of discotic liquid crystalline molecules (I) of the following formula, 9 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, trade name, manufactured by Osaka Organic Chemical Co., Ltd.), cellulose acetate butyl 1.5 mass parts of rates (CAB 531-1, a brand name, Eastman Chemical Co., Ltd.), a photoinitiator (Irugacure 907, a brand name, the Chiba Corporation company) 3 mass parts, a sensitizer (Kayacure DETX, a brand name, Nippon Kayaku Co., Ltd.) ) Production) 1 mass part and the coating liquid which melt | dissolved 1.0 mass part of citrate ester mixtures of the following formula in 214.2 mass parts methyl ethyl ketone were apply | coated 6.2 ml / m <2> by the wire bar coater of # 3.6 in 25 degreeC atmosphere. This was attached to a metal mold and heated in a thermostat at 140 ° C. for 2 minutes to orient the discotic liquid crystalline molecules. Next, UV irradiation was carried out at 90 ° C. for 1 minute using a 120 W / cm high-pressure mercury lamp to polymerize the discotic liquid crystal molecules. Thereafter, the mixture was allowed to cool to room temperature.

R ₁ = H or C ₂ H ₅

R ₂ = H or C ₂ H ₅

R ₃ = H or C ₂ H ₅

Citrate Ester Mixtures

(Production of polarizing plate)

Iodine was adsorbed on the stretched polyvinyl alcohol film to prepare a polarizing film.

Next, the transparent support side of the produced optical compensation sheet was affixed to one side of the polarizing film using the polyvinyl alcohol-type adhesive agent. It was arrange | positioned so that the slow axis of a transparent support body and the transmission axis of a polarizing film may become parallel.

A commercially available cellulose triacetate film (Fuji-Tak TD80UF, trade name, manufactured by Fuji Photo Film Co., Ltd.) was saponified in the same manner as in Example 2, and the polyvinyl alcohol-based adhesive was used on the opposite side of the polarizing film (no optical compensation sheet was attached). Side).

In this way, the polarizing plate 11 was produced.

(Production of bend alignment liquid crystal cell)

A polyimide film was formed as an orientation film on the glass substrate with an ITO electrode, and the orientation film was rubbed. The obtained two glass substrates were opposed by the arrangement | positioning which a rubbing direction becomes parallel, and the cell gap was set to 5.7 micrometers. A liquid crystal compound (ZLI1132, trade name, manufactured by Merck Co., Ltd.) having Δn of 0.1396 was injected into the cell gap to prepare a bend alignment liquid crystal cell.

(Production of liquid crystal display device)

Two polarizing plates produced so that the produced bend alignment cell were sandwiched between were attached. The optically anisotropic layer of the polarizing plate faced the cell substrate, and the rubbing direction of the liquid crystal cell and the rubbing direction of the optically anisotropic layer facing it were arranged so as to be antiparallel.

Example 9

In the polarizing plate 11 of Example 8, the polarizing plates 12-18 were produced by the same method except having changed the cellulose acylate film into (12)-(18).

The backlight was turned on continuously for 500 hours under the environmental conditions of the temperature of 25 degreeC and 60% of a relative humidity, and light leakage was evaluated by visually observing the front black display state in a dark room. As a result, it was not observed in the liquid crystal display device using the polarizing plate of this invention about the frame-shaped light leakage observed on the display screen of a liquid crystal display device in the polarizing plate of a comparative example.

Example 10

The cellulose acylate produced in Example 7 by peeling off a pair of polarizing plates formed on a 22-inch liquid crystal display device (manufactured by Sharp Co., Ltd.) using a VA type liquid crystal cell, and instead fabricating the polarizing plate produced in Example 9. The film was attached one by one to the observer side and the backlight side through the pressure-sensitive adhesive so that the film was the liquid crystal cell side. It was arrange | positioned so that the transmission axis of the polarizing plate of an observer side, and the transmission axis of the polarizing plate of a backlight side may orthogonally cross.

It was found that the polarizing plate of the present invention has a wide contrast viewing angle and is preferable.

ADVANTAGE OF THE INVENTION According to this invention, the cellulose film excellent in the durability with respect to heat | fever and humidity, and useful as a protective film, retardation film, etc. of a polarizing plate, Preferably, a cellulose acylate film can be provided.

According to the present invention, it is possible to provide a polarizing plate having excellent durability against heat and humidity.

The polarizer has an optical compensation function, a liquid crystal display of twisted nematic (TN) type, optically compensated bend (OCB) type, electrically controlled birefringence (ECB) type, vertically aligned (VA) type, and in-plane switching (IPS) type It can be used advantageously in the apparatus.

Claims (12)

At least 1 type of the compound represented by the following general formula (I), and at least 1 type of the compound represented by the following general formula (III) or (IVA) are contained, The cellulose film characterized by the above-mentioned. General formula (Ⅰ)

(Wherein X ¹ is a single bond, -NR ^4- , -O- or -S-; X ² is a single bond, -NR ^5- , -O- or -S-; X ³ is, A single bond, -NR ^6- , -O- or -S-, R ¹ , R ² and R ³ are each independently an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; and R ⁴ , R ⁵ And R ⁶ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. The alkyl group, alkenyl group, aryl group, and heterocyclic group may each have a substituent.) General formula (Ⅲ)

[Wherein, R ³¹ represents an alkyl group or an aryl group, and R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group or an aryl group. The total number of carbon atoms of R ³¹ , R ³² and R ³³ is 10 or more, and the alkyl group and the aryl group may each have a substituent. R ³¹ and R ³² may combine to form a ring.] General formula (IVA)

Wherein X ⁴² represents C-OH. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ to R ⁶⁵ each independently represent a hydrogen atom or a substituent, two groups in the above R ⁴¹ to R ⁶⁵ may be bonded to each other to form a ring.) The compound represented by the said general formula (I) is a compound which raises the retardation of a cellulose film, The compound represented by the said general formula (III) or (IVA) is a retardation of a cellulose film. Cellulose film, characterized in that the compound for lowering. The Rth [nm] and Re [nm] according to claim 1 or 2, which are defined by the following formulas (A) and (B): 30 nm ≤ Rth ≤ 300 nm, 2nm≤Re≤80nm And Rth / Re ratio is 1 or more and 6 or less. (A) Formula Re [nm] = (nx-ny) × d (B) Formula Rth [nm] = {(nx + ny) / 2-nz} × d [Wherein, nx is a refractive index in the slow axis direction in the film plane; ny is the refractive index of the fast-axis direction in a film plane; nz is a refractive index in the thickness direction of the film; And d is the thickness [nm] of the film.] The cellulose film according to claim 1 or 2, wherein the water vapor transmission rate at 60 ° C. 95% RH 24 hr is 400 g / m 2 · 24 hr or more and 2000 g / m 2 · 24 hr or less. The equilibrium moisture content of 25 ° C 80% RH is 3.0% or less, and the ratio of the equilibrium moisture content of 25 ° C 80% RH to the equilibrium moisture content of 25 ° C 10% RH is 3 or more and 10 or less. Cellulose film, characterized in that. The cellulose film according to claim 1 or 2, wherein the ratio of Rth of 25 ° C to 80% RH to Rth of 25 ° C of 10% RH is 0.65 or more. The cellulose film according to claim 1 or 2, wherein the ratio of Re of 25 ° C to 80% RH to Re of 25 ° C to 10% RH is 0.65 or more. The polarizing plate which sticks a protective film on both sides of a polarizer, WHEREIN: At least 1 piece of the protective film is a cellulose film of Claim 1 or 2, The polarizing plate characterized by the above-mentioned. The polarizing plate according to claim 8, wherein at least one of an adhesive layer, an antiglare layer, a reflective layer, a transflective reflective layer, a retardation layer, a viewing angle compensation layer, and a brightness enhancement layer is formed. The polarizing plate according to claim 9, wherein the retardation layer is a λ / 4 layer. It consists of a liquid crystal cell and two polarizing plates arrange | positioned at both sides, and at least 1 polarizing plate is a polarizing plate of Claim 8, The liquid crystal display device characterized by the above-mentioned. delete

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