JP2003301049A - Stretched cellulose ester film, method for producing stretched cellulose ester film, elliptically polarizing plate and display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stretched cellulose ester film which improves the visibility and visual field angle even when a cellulose ester film is stretched at a high draw ratio, reduces the increase in haze, and simultaneously reduces the cost of the film for protecting a polarizing plate, its production method, an elliptically polarizing plate and a display which use the stretched cellulose ester film. <P>SOLUTION: The stretched cellulose ester film having secondary particles which have an average particle diameter of 0.1-5 μm and contain primary fine particles having an average particle diameter of 0.001 to smaller than 0.1 μm, is characterized in that the content of an additive in the neighborhood of the secondary particles is higher than the average content of the additive in the stretched cellulose ester film. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a stretched cellulose ester film (hereinafter also simply referred to as a stretched film), a method for producing a stretched cellulose ester film (hereinafter also simply referred to as a production method and method), an elliptical polarizing plate and a display device. Regarding

[0002]

2. Description of the Related Art With the increase in definition of liquid crystal display devices, further improvement in visibility of the display devices is required. In addition, various methods have been proposed to improve the viewing angle of the display device.

For example, a method of using a stretched polycarbonate film as a retardation plate has been proposed, but this requires a retardation plate to be attached separately from the polarizing plate, which is not only complicated but also costly. It was.

It has been confirmed that excellent visibility can be obtained by using a stretched cellulose ester film as a retardation film, and a cellulose ester film can also serve as a polarizing plate protective film. It was thought that it would be possible to reduce the cost. However, when the cellulose ester film was stretched at a ratio of 1.15 times or more, haze was increased, which was a problem. The rise in haze lowers the sharpness of the display device, and therefore its improvement has been required.

[0005]

Therefore, an object of the present invention is to improve the visibility and viewing angle even when the cellulose ester film is stretched at a magnification of 1.15 times or more, and to reduce the haze, An object of the present invention is to provide a stretched cellulose ester film capable of reducing the cost of a protective film for an elliptically polarizing plate, a method for producing the stretched cellulose ester film, and an elliptically polarizing plate and a display device using the stretched cellulose ester film.

[0006]

The above objects of the present invention can be achieved by the following constitutions.

1. Average particle size is 0.001 or more and 0.1 μm
In a stretched cellulose ester film having secondary particles having an average particle size of 0.1 to 5 μm containing primary fine particles of less than, the average content of the additives in the stretched cellulose ester film is A stretched cellulose ester film having a high content.

2. The average content of the additive in the stretched cellulose ester film is 3 to 30%, wherein the stretched cellulose ester film described in 1 above.

3. 3. The stretched cellulose ester film as described in 1 or 2 above, wherein at least one of the additives is an additive having three or more aromatic rings or cycloalkyl rings in the molecule.

4. 1.15-2 in at least one direction
The stretched cellulose ester film according to any one of 1 to 3 above, which has been double-stretched.

5. In-plane retardation R ₀ is 30 to 2
At 00 nm, the retardation R _t in the film thickness direction is 80 to 3
Any one of the above 1 to 4, characterized in that it is 00 nm
The stretched cellulose ester film according to the item.

6. The content of the additive in the vicinity of the secondary particles is 1.1 times or more the average content of the additive in the stretched cellulose ester film. The stretched cellulose ester film described.

7. After casting a dope solution prepared by mixing a cellulose ester solution in which cellulose ester is dissolved in an organic solvent with a fine particle dispersion liquid containing an additive on a support and peeling the solution, a web containing the solvent is prepared from 1. 15-2
A method for producing a stretched cellulose ester film, which comprises double stretching.

8. 8. The method for producing a stretched cellulose ester film as described in 7 above, wherein the content of the additive contained in the fine particle dispersion is higher than the content of the additive contained in the cellulose ester solution.

9. 9. The method for producing a stretched cellulose ester film as described in 7 or 8 above, wherein the fine particle dispersion is mixed in-line with a cellulose ester solution, and the obtained dope solution is cast on a support.

10. A stretched cellulose ester film produced by the method for producing a stretched cellulose ester film according to any one of 7 to 9 above.

11. An elliptically polarizing plate comprising the stretched cellulose ester film according to any one of 1 to 6 and 10.

12. A display device comprising the stretched cellulose ester film according to any one of 1 to 6 and 10.

13. Average particle size 0.001 or more 0.1μ
2 having an average particle size of 0.1 to 5 μm including primary fine particles of less than m
In the method for producing a stretched cellulose ester film having a cellulose ester layer having secondary particles, the web is stretched in a state where the content of the additive in the vicinity of the secondary particles is higher than the average content of the additive in the cellulose ester layer. A method for producing a stretched cellulose ester film, which comprises:

14. 14. The method for producing a stretched cellulose ester film as described in 13 above, wherein at least one of the additives is a plasticizer.

15. 15. The method for producing a stretched cellulose ester film as described in 13 or 14, wherein the web having the cellulose ester layer formed by co-casting is stretched.

16. 16. The method for producing a stretched cellulose ester film according to any one of 13 to 15, wherein the cellulose ester layer is formed of a dope containing substantially no chlorine-based solvent.

The present invention will be described in more detail below. The present inventor has found that an increase in haze can be significantly suppressed by increasing the additive concentration in the vicinity of the secondary particles to 1.1 times or more the average content of the additive in the stretched film. The content of the additive in the vicinity of the secondary particles is more preferably 1.1 to 9 times, and particularly preferably 1.2 to 7 times the average content of the additive in the stretched film. .

In the vicinity of the secondary particles, gaps between the primary particles constituting the secondary particles are also included, and it is particularly preferable that the content of the additive in the gaps is within the above range. .

The additive in the stretched film may be plural kinds, and the total average content thereof is preferably 3 to 30%, more preferably 6 to 25%.

The average content of additives in the stretched film is calculated by the following formula. Average content of additive in stretched film (%) = [mass of additive (excluding cellulose ester and fine particles) (g)
/ (Mass of cellulose ester film)] × 100 The stretched cellulose ester film according to the invention of claims 1 to 6 or 10 has an average primary particle size of 0.001 or more and 0.1 μm or less.
In the stretched cellulose ester film having secondary particles containing fine particles of less than m, the additive content in the vicinity of secondary particles 2'as shown in FIG. 1 is higher than the average content of the additive in the stretched film. It has a feature. The above 1
The average particle size of the secondary particles is preferably 0.01 to less than 0.1 μm. The average particle size of the secondary particles is preferably 0.1 to 5 μm. The thickness is more preferably 0.1 to 3 μm, further preferably 0.1 to 1 μm.

The particle size of the fine particles in the film was taken by taking an electron microscope photograph of the cross section in the thickness direction and in the direction parallel to the slow axis of the stretched film.
The particle diameter of the fine particles in the cross-sectional area of 1000 μm ² at the place within was measured and calculated as the average value of the fine particle diameters at 10 locations. As shown in FIG. 1, the average particle size of the secondary particles is such that, when the secondary particles 1'observed by a scanning electron microscope in a cross section in the thickness direction of the film are sandwiched by two parallel lines, the distance between the parallel lines is The maximum length was defined as the secondary particle diameter L. In addition, in FIG. 1, particles having at least 5 or more primary particles 3'are referred to as secondary particles. The secondary particle size is 10μ
Those exceeding m were considered to be foreign matter defects and were excluded from the calculation of the average particle size.

The fine particles to be added are added mainly for the purpose of imparting slipperiness to the stretched film.

Examples of the additives added to the stretched cellulose ester film include ultraviolet absorbers, plasticizers, and moisture permeability improving agents.

Conventionally, the cellulose ester film is 1.
When stretched at a high draw ratio of 15 times or more, the haze tended to increase remarkably.

Therefore, care must be taken to prevent the haze from rising as much as possible by controlling the temperature, time, or amount of residual solvent during stretching, and the present inventor has conducted extensive studies to solve this point. As a result, the increase in haze of the cellulose ester film stretched at the high magnification is
It was presumed that the shape of the secondary particles contained in the secondary particles was changed when the secondary particles were stretched and stretched, and it was caused by microvoids or cracks formed in the vicinity of the secondary particles, gaps between the primary particles, particle interfaces, or the like.

Therefore, in the present invention, by increasing the content of the additive in the vicinity of the secondary particles higher than the average content of the additive in the stretched cellulose ester film, the stretching ratio can be increased to 1.15 times or more. Even if the stretching is performed, the cellulose resin component in the vicinity of the secondary particles tends to flow, and the occurrence of microvoids or cracks is significantly suppressed, and thus it is considered that the haze is prevented from increasing.

Therefore, as the additive of the present invention, one having a melting point or glass transition point (Tg) of the additive itself lower than the Tg of the cellulose ester, or a cellulose ester film by being contained in the cellulose ester film. Additives that can lower the Tg of are preferably used.

The larger the amount of the additive added, the more the haze increase can be suppressed. However, the amount of the additive added to the entire cellulose ester film depends on the moisture permeability, the ultraviolet absorption property, the optical property (retardation), and the dimensional stability. There are many restrictions because they affect the mechanical properties, mechanical strength, and transport speed.

However, by increasing the amount of the additive in the vicinity of the secondary particles, it is not necessary to greatly change the amount of the additive in the cellulose ester film, and the effect of the present invention is remarkably obtained.

The additive amount in the vicinity of the secondary particles is preferably an amount that lowers the Tg of the cellulose ester film by 3 to 100 ° C., more preferably 5 to 80 ° C.

It is more preferable that the additive has three or more aromatic rings or cycloalkyl rings in the molecule.
More preferably, at least one such additive is included in the cellulose ester film. Here, the aromatic ring is preferably a phenyl ring which may have a substituent or a cyclohexane ring which may have a substituent. Particularly, a plasticizer is preferably used.

The stretched film of the present invention is characterized by being stretched by 1.15 to 2 times in at least one direction.

That is, as described above, in the present invention, even if the cellulose ester film is stretched at a high magnification (high magnification: 1.15 to 2 magnification), the increase in haze is significantly suppressed. preferable.

According to the invention, the in-plane retardation R ₀
A stretched cellulose ester film having a R of 30 to 1000 nm is obtained, and a stretched cellulose ester film having a R ₀ of 30 to 200 nm is preferably obtained. In particular, a stretched cellulose ester film having an in-plane retardation R ₀ of 30 to 200 nm and a retardation R _t in the film thickness direction of 80 to 300 nm is preferable in that the effect of the present invention can be further exhibited.

More preferably, R ₀ is 45 to 100 nm
And the retardation R _t in the film thickness direction is 90 to 200 nm.
Is.

As a more preferred example, R ₀ is 30 to 70.
nm, and the retardation R _{t in the} film thickness direction is 100.
A stretched cellulose ester film having a thickness of ˜160 nm, particularly preferably R ₀ of 40 to 60 nm and a retardation R _{t in the} film thickness direction of 105 to 145 n.
An example of the stretched cellulose ester film is m.

In the present invention, the vicinity of the secondary particles means
As shown in FIG. 1, when the cross section of the stretched film in the thickness direction is observed with an electron microscope and the secondary particles 1'are sandwiched by two parallel lines, the length at which the distance between the parallel lines is maximum is the secondary An area inside a circle having a diameter L and a diameter of L and having the same center is referred to as a secondary particle vicinity 2 '.

Even if the concentration of the additive is constant in this region, the concentration may increase as the concentration becomes closer to the secondary particles. In particular, it is preferable that the content of the additive in the gap between the primary particles 3'constituting the secondary particles is higher than the average content of the additive in the stretched film.

In the present invention, the content of the additive in the vicinity of the secondary particles is higher than the content of the average additive in the stretched cellulose ester film means that the average content of the additive in the stretched cellulose ester film is 1 1. It means more than 1 time.

When the stretched cellulose ester film has a multi-layered structure by a co-casting method or the like, in the layer containing fine particles such as the surface layer, the layer containing fine particles with the additive content near the secondary particles is It is within the scope of the present invention that the additive content is higher than the average content of the additive, and the additive content in the vicinity of the secondary particles is 1.1 times or more the average content of the additive in the layer. The layer containing fine particles is a layer containing 0.03% by mass or more of fine particles. A layer containing 0.03 to 1 mass% of fine particles is preferable, and a layer containing 0.05 to 0.5 mass% is more preferable.

The additive content in the vicinity of the secondary particles can be analyzed by cutting out the layer or secondary particle portion containing fine particles on the surface or cross section of the stretched film under a microscope.

Specifically, the cross section is prepared by embedding a stretched film in an epoxy embedding resin for electron microscope observation pretreatment,
An ultramicrotome equipped with a diamond knife is used to make ultra-thin sections with a thickness of about 0.1 micrometer, or a focused ion beam (Focused Ion) is used.
Beam: FIB) processing device, Ga on the surface of the laminate
It can be obtained by focusing and scanning the ion beam and cutting out a thin section having a thickness of about 0.1 micrometer. The additive content of the obtained slices near the secondary particles can be measured by a known analysis method.

Alternatively, the cross section can be determined from the peak ratios of the additives and the like in the vicinity of the secondary fine particles and the portion apart from the secondary fine particles by using a time-of-flight secondary ion mass spectrometer or electron beam microanalyzer. .

For example, in the case of a phosphoric acid ester type additive, the content of the additive can be analyzed and measured for phosphorus atoms by an electron beam microanalyzer.

The refractive index of the stretched cellulose ester film of the present invention is preferably 1.45 to 1.55, more preferably 1.47 to 1.50.

The refractive index can be measured by using an automatic birefringence meter Abbe's refractometer and a Na light source.

The additives for the stretched cellulose ester film of the present invention will be described below.

The stretched cellulose ester film of the present invention preferably contains a plasticizer or an ultraviolet absorber as an additive.

The plasticizer is not particularly limited, but is a phosphoric acid ester plasticizer, a phthalic acid ester plasticizer, a trimellitic acid ester plasticizer, a pyromellitic acid plasticizer, a glycolate plasticizer, a quencher. Examples thereof include acid ester plasticizers and polyester plasticizers.

Examples of the phosphoric acid ester plasticizers include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc .; phthalic acid ester plasticizers. Examples thereof include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butylbenzyl phthalate, dicyclohexyl phthalate and the like; examples of the trimellitic acid plasticizer include tributyl trimellitate. Tate, triphenyl trimellitate, triethyl trimellitate, etc .; Examples of pyromellitic acid ester plasticizers include: Tiger butyl pyromellitate, tetraphenyl pyromellitate, tetraethyl pyromellitate, etc .; As the glycerin ester based plasticizer, for example,
Triacetin, tributyrin, etc .; glycolic acid ester-based plasticizers include, for example, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, etc .; examples of other carboxylic acid ester plasticizers include: Examples thereof include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, various trimellitic acid esters and the like, trimethylolpropane tribenzoate and the like.

Of these, phosphoric acid ester plasticizers and glycolic acid ester plasticizers are more preferable. It is more preferable to use these plasticizers alone or in combination.

The amount of plasticizer used depends on the film performance,
1 to 30 relative to cellulose ester in terms of processability
It is preferably mass%.

Next, the ultraviolet absorber will be described. From the viewpoint of preventing deterioration of the liquid crystal, an ultraviolet absorber which is excellent in absorption of ultraviolet rays having a wavelength of 370 nm or less and has a small absorption of visible light having a wavelength of 400 nm or more is preferably used from the viewpoint of good liquid crystal display property.

Specific examples of the ultraviolet absorber preferably used in the present invention include, for example, oxybenzophenone compounds, benzotriazole compounds, salicylate compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex salt compounds, inorganic powders. The present invention is not limited thereto.

As the benzotriazole type ultraviolet absorber, a compound represented by the following general formula [1] is preferably used.

[0062]

[Chemical 1]

In the general formula [1], R ₁ , R ₂ , R ₃ ,
R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an acyloxy group, an aryloxy group, an alkylthio group, an arylthio group, Represents a mono- or dialkylamino group, an acylamino group or a 5- or 6-membered heterocyclic group, and R ₄ and R ₅ are ring-closed to form 5
A 6-membered carbocycle may be formed.

Specific examples of the ultraviolet absorber used in the present invention will be given below, but the present invention is not limited thereto.

UV-1-1: 2- (2'-hydroxy-
5'-methylphenyl) benzotriazole UV-1-2: 2- (2'-hydroxy-3 ', 5'-
Di-ter-butylphenyl) benzotriazole UV-1-3: 2- (2'-hydroxy-3'-ter
-Butyl-5'-methylphenyl) benzotriazole UV-1-4: 2- (2'-hydroxy-3 ', 5'-
Di-ter-butylphenyl) -5-chlorobenzotriazole UV-1-5: 2- (2'-hydroxy-3'-
(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole UV-1-6: 2,2-methylenebis (4- (1,1,
3,3-Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol) Further, as a benzophenone-based UV absorber which is one of the UV absorbers preferably used in the present invention, the following general formula [ The compound represented by 2] is more preferably used.

[0066]

[Chemical 2]

In the general formula [2], Y represents a hydrogen atom, a halogen atom or an alkyl group, an alkenyl group, an alkoxy group or a phenyl group, and these alkyl group, alkenyl group and phenyl group have a substituent. Good. A
Is a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group,
It represents a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group or a -CO (NH) _n-1- D group, and D represents an alkyl group, an alkenyl group or a phenyl group which may have a substituent. m and n represent 1 or 2.

In the above, the alkyl group represents, for example, a linear or branched aliphatic group having up to 24 carbon atoms,
The alkoxy group is, for example, an alkoxy group having up to 18 carbon atoms, and the alkenyl group is, for example, an alkenyl group having up to 16 carbon atoms, such as an allyl group and a 2-butenyl group. Further, as a substituent for an alkyl group, an alkenyl group or a phenyl group, a halogen atom such as chlor, bromine or a fluorine atom, a hydroxy group, a phenyl group,
(This phenyl group may be substituted with an alkyl group or a halogen atom) and the like.

Specific examples of the benzophenone compound represented by the general formula [2] are shown below, but the invention is not limited thereto.

UV-3-1: 2,4-dihydroxybenzophenone UV-3-2: 2,2'-dihydroxy-4-methoxybenzophenone UV-3-3: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-3-4: Bis (2-methoxy-4-hydroxy-)
5-benzoylphenylmethane) The above-mentioned ultraviolet absorber preferably used in the present invention is a benzotriazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber that has high transparency and is excellent in the effect of preventing deterioration of an elliptical polarizing plate or a liquid crystal element. Agents are preferred, and benzotriazole-based UV absorbers with less unwanted coloring are particularly preferred.

The ultraviolet absorber may be added by dissolving the ultraviolet absorber in an organic solvent such as alcohol, methylene chloride or dioxolane and then adding it to the dope.
Alternatively, it may be added directly in the dope composition (in-line addition). Those that do not dissolve in organic solvents, such as inorganic powder,
A dissolver or a sand mill is used in an organic solvent and cellulose ester to disperse them and then added to the dope.

The amount of the ultraviolet absorber used is not uniform depending on the type of compound and the use conditions, but is usually 0.2 to 5.0 g per 1 m ^{2 of the} stretched cellulose ester film, and 0.4 to 3. 0 g is more preferable, and 0.6 to
2.0 g is particularly preferred.

Next, the additives of the present invention other than the plasticizer and the ultraviolet absorber will be described. The additive functions as a moisture permeability improving agent or a film physical property improving agent.

A compound having a triphenylene ring is mentioned as one of the specific examples of the additive, and among them, the compound represented by the following general formula (I) is preferable.

[0075]

[Chemical 3]

In the general formula (I), R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom, a halogen atom, nitro, sulfo, an aliphatic group, an aromatic group, a heterocyclic group, —O—
_{R 11, -S-R 12,} -CO-R 13, -O-CO-R 14,
_{-CO-O-R 15, -O} -CO-O-R 16, -NR 17 R
₁₈ , -CO-NR ₁₉ R ₂₀ , -NR ₂₁ -CO-R ₂₂ , -O
-CO-NR ₂₃ R ₂₄ , -SiR ₂₅ R ₂₆ R ₂₇ , -O-Si
_{R 28 R 29 R 30, -S} -CO-R 31, -O-SO 2 -
_{R 32, -SO-R 33,} -NR 34 -CO-O-R 35, -S
O ₂ -R ₃₆ or _{-NR 37 -CO-NR 38 R 39} , R 11, R
₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ ,
R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R
₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ ,
R ₃₆ , R ₃₇ , R ₃₈ and R ₃₉ are a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. In addition, R ¹ and R ² , R ³ and R ⁴
Alternatively, R ⁵ and R ⁶ may combine with each other to form a ring.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are --O.
_{-R 11, -S-R 12,} -O-CO-R 14, -O-CO-
_{O-R 16, -NR 17 R} 18, -NR 21 -CO-R 22 or -
O—CO—NR ₂₃ R ₂₄ is preferred, and —O—R
_{11, -S-R 12, -O} -CO-R 14, -O-CO-O-
R ₁₆ or —O—CO—NR ₂₃ R ₂₄ is more preferred, —O—R ₁₁ or —O—CO—R ₁₄ is even more preferred, and —O—CO—R ₁₄ is preferred. Most preferred.

R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R
₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ ,
R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R
Each of ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ , R ₃₈ and R ₃₉ is preferably a hydrogen atom, an aliphatic group or an aromatic group.
R ₁₄ of -O-CO-R ₁₄ is most preferably an aromatic group.

In the general formula (I), R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ and R ⁶ are preferably the same group.

Examples of the aliphatic group include an alkyl group, an alkenyl group, an alkynyl group, a substituted alkyl group, a substituted alkenyl group and a substituted alkynyl group.

The alkyl group may be cyclic (eg cycloalkyl group etc.), and the alkyl group may be branched. The alkyl group preferably has 1 to 30 carbon atoms, more preferably has 1 to 20 carbon atoms, and most preferably has 1 to 10 carbon atoms.

Specific examples of the alkyl group include, for example, methyl, ethyl, i-propyl, butyl, i-butyl and s-.
Examples thereof include butyl, t-butyl, t-pentyl, hexyl, octyl, t-octyl, dodecyl and tetracosyl groups.

The alkenyl group may be cyclic (cycloalkenyl group), and the alkenyl group may be branched. Further, the alkenyl group may have two or more double bonds.

The alkenyl group has preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and most preferably 2 to 10 carbon atoms.

Specific examples of the alkenyl group include vinyl,
Allyl or 3-heptenyl are mentioned. The alkynyl group may be cyclic (cycloalkynyl group), and the alkynyl group may have a branch.

Further, the alkynyl group may have two or more triple bonds. The alkynyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and most preferably 2 to 10 carbon atoms.

Specific examples of the alkynyl group include ethynyl, 2-propynyl, 1-pentynyl and 2,4-octadiynyl groups.

Substituted alkyl group, substituted alkenyl group and group
Specific examples of the substituent of the substituted alkynyl group include, for example, halo.
Gen atom, nitro, sulfo, aromatic group, heterocyclic group, -O
-R ₄₁, -SR₄₂, -CO-R₄₃, -O-CO-
R₄₄, -CO-OR₄₅, -O-CO-OR₄₆, -N
R₄₇R₄₈, -CO-NR₄₉R₅₀, -NR₅₁-CO-
R₅₂, -O-CO-NR₅₃R₅₄, -SiR₅₅R₅₆R₅₇R
₅₈Or -O-SiR₅₉R₆₀R₆₁R₆₂Are listed.

R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₄₆ , R
₄₇ , R ₄₈ , R ₄₉ , R ₅₀ , R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ ,
R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R ₆₀ , R ₆₁ or R
₆₂ is a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The alkyl part of the substituted alkyl group is the same as the above alkyl group.

Specific examples of the substituted alkyl group include benzyl, phenethyl, 2-methoxyethyl, ethoxymethyl, 2- (2-methoxyethoxy) ethyl, 2-hydroxyethyl, hydroxymethyl, 2-carboxyethyl, carboxymethyl, Ethoxycarbonylmethyl, 4
-Each group such as acryloyloxybutyl, trichloromethyl or perfluoropentyl. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group. Specific examples of the substituted alkenyl group include styryl and 4-methoxystyryl groups.

The alkynyl portion of the substituted alkynyl group is the same as the above alkynyl group. Specific examples of the substituted alkynyl group include 4-butoxyphenylethynyl, 4-propylphenylethynyl and trimethylsilylethynyl groups.

In the present invention, the aromatic group means an aryl group and a substituted aryl group. The aryl group preferably has 6 to 30 carbon atoms, more preferably has 6 to 20 carbon atoms, and most preferably has 6 to 10 carbon atoms.

Specific examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl and the like.

Specific examples of the substituent of the substituted aryl group
Is, for example, a halogen atom, a nitro group, a sulfo group, a fat
Group, aromatic group, heterocyclic group, -OR₇₁, -SR₇₂,
-CO-R₇₃, -O-CO-R₇₄, -CO-OR₇₅,
-O-CO-OR₇₆, -NR ₇₇R₇₈, -CO-NR₇₉
R₈₀, -NR₈₁-CO-R₈₂, -O-CO-NR
₈₃R₈₄, -SiR₈₅R₈₆R₈₇R₈₈Or -O-SiR₈₉R
₉₀R₉₁R₉₂Etc.

R ₇₁ , R ₇₂ , R ₇₃ , R ₇₄ , R ₇₅ , R ₇₆ , R
₇₇ , R ₇₈ , R ₇₉ , R ₈₀ , R ₈₁ , R ₈₂ , R ₈₃ , R ₈₄ ,
R ₈₅ , R ₈₆ , R ₈₇ , R ₈₈ , R ₈₉ , R ₉₀ , R ₉₁ and R
₉₂ is a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

The aryl part of the substituted aryl group has the same meaning as the above aryl group. Specific examples of the substituted aryl group include p-biphenylyl, 4-phenylethynylphenyl, 2-methoxyphenyl, 3-methoxyphenyl and 4
-Methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 3-propoxyphenyl, 4-propoxyphenyl, 2-butoxyphenyl, 3-butoxyphenyl, 4-butoxyphenyl, 2 -Hexyloxyphenyl, 3-hexyloxyphenyl, 4-hexyloxyphenyl, 2-octyloxyphenyl, 3-octyloxyphenyl, 4-octyloxyphenyl, 2-dodecyloxyphenyl, 3-dodecyloxyphenyl,
4-dodecyloxyphenyl, 2-tetracosyloxyphenyl, 3-tetracosyloxyphenyl, 4-tetracosyloxyphenyl, 3,4-dimethoxyphenyl, 3,4-diethoxyphenyl, 3,4-dihexyl Oxyphenyl, 2,4-dimethoxyphenyl, 2,4
-Diethoxyphenyl, 2,4-dihexyloxyphenyl, 3,5-dimethoxyphenyl, 3,5-dimethoxyphenyl, 3,5-dihexyloxyphenyl, 3,
4,5-trimethoxyphenyl, 3,4,5-triethoxyphenyl, 3,4,5-trihexyloxyphenyl, 2,4,6-trimethoxyphenyl, 2,4,6-
Triethoxyphenyl, 2,4,6-trihexyloxyphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3
-Chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl,
3,4-difluorophenyl, 3,4-dichlorophenyl, 3,4-dibromophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2,4-dibromophenyl, 3,5-difluorophenyl, 3,5 -Dichlorophenyl, 3,5-dibromophenyl, 3,4,5
-Trifluorophenyl, 3,4,5-trichlorophenyl, 3,4,5-tribromophenyl, 2,4,6-
Trifluorophenyl, 2,4,6-trichlorophenyl, 2,4,6-tribromophenyl, pentafluorophenyl, pentachlorophenyl, pentabromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 2 -Formylphenyl, 3-formylphenyl, 4-formylphenyl, 2-benzoylphenyl, 3-benzoylphenyl, 4-benzoylphenyl, 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl, o-tolyl, m- Trilyl, p-tolyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2- (2-methoxyethoxy) phenyl, 3- (2-methoxyethoxy) phenyl, 4- (2-methoxyethoxy) phenyl , 2-ethoxycarbonylphenyl, - ethoxycarbonyl phenyl, 4-ethoxycarbonyl phenyl, 2-benzoyloxy-phenyl, 3-benzoyloxy-phenyl, and 4-benzoyloxy each group phenyl and the like.

In the present invention, the heterocyclic group may have a substituent. The heterocycle in the heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic ring in the heterocyclic group may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. Examples of the hetero atom in the hetero ring include B, N, O, S,
Each atom such as Se or Te can be mentioned.

Specific examples of the heterocycle in the heterocyclic group include, for example, pyrrolidine ring, morpholine ring, 2-bora-1,3.
-Dioxolane ring and 1,3-thiazolidine ring.

Specific examples of the unsaturated heterocyclic ring in the unsaturated heterocyclic group include, for example, imidazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzotriazole ring, benzoselenazole ring, pyridine ring and pyrimidine ring. Alternatively, a quinoline ring and the like can be mentioned.

Specific examples of the substituent of the heterocyclic group are the same as the specific examples of the substituent of the substituted aryl group.

The compound having a triphenylene ring preferably has a molecular weight of 300 to 2,000. The boiling point of the compound is preferably 260 ° C. or higher. The boiling point can be measured using a commercially available measuring device (for example, TG / DTA100, manufactured by Seiko Instruments Inc.). Specific examples of compounds having a triphenylene ring are shown below.

A plurality of Rs shown below mean the same group.

[0103]

[Chemical 4]

(1) Fluoro (2) Chloro (3) Bromo (4) Formyl (5) Benzoyl (6) Carboxyl (7) Butylamino (8) Dibenzylamino (9) Trimethylsilyloxy (10) 1-Pentynyl ( 11) ethoxycarbonyl (12) 2-hydroxyethoxycarbonyl (13) phenoxycarbonyl (14) N-phenylcarbamoyl (15) N, N-diethylcarbamoyl (16) 4-methoxybenzoyloxy (17) N-phenylcarbamoyloxy ( 18) Hexyloxy (19) 4-hexyloxy benzoyloxy (20) ethoxy (21) benzoyloxy (22) m-dodecyloxyphenylthio (23) t-octylthio (24) p-fluorobenzoylthio (25) isobutyrylthio ( 26) p-methyl Nensulfinyl (27) Ethanesulfinyl (28) Benzenesulfonyl (29) Methanesulfonyl (30) 2-Methoxyethoxy (31) Propoxy (32) 2-Hydroxyethoxy (33) 2-Carboxyethoxy (34) 3-Heptenyloxy (35 ) 2-Phenylethoxy (36) trichloromethoxy (37) 2-propynyloxy (38) 2,4-octadiynyloxy (39) perfluoropentyloxy (40) ethoxycarbonylmethoxy (41) p-methoxyphenoxy (42) ) M-Ethoxyphenoxy (43) o-chlorophenoxy (44) m-dodecyloxyphenoxy (45) 4-pyridyloxy (46) pentafluorobenzoyloxy (47) p-hexyloxybenzoyloxy (48) 1-naphthoyl Oxy (49) 2-naphthoyloxy (50) 5-imidazolecarbonyloxy (51) o-phenoxycarbonylbenzoyloxy (52) m- (2-methoxyethoxy) benzoyloxy (53) o-carboxybenzoyloxy (54) p-formylbenzoyloxy (55) m-ethoxycarbonyl benzoyloxy (56) p-pivaloylbenzoyloxy (57) propionyloxy (58) phenylacetoxy (59) cinnamoyloxy (60) hydroxyacetoxy (61) ethoxycarbonyl Acetoxy (62) m-butoxyphenyl propioroyloxy (63) propioloyloxy (64) trimethylsilyl propioroyloxy (65) 4-octenoyloxy (66) 3-hydroxypropionyloxy ( 67) 2-methoxyethoxyacetoxy (68) perfluorobutyryloxy (69) methanesulfonyloxy (70) p-toluenesulfonyloxy (71) triethylsilyl (72) m-butoxyphenoxycarbonylamino (73) hexyl (74) Phenyl (75) 4-pyridyl (76) benzyloxycarbonyloxy (77) m-chlorobenzamide (78) 4-methylanilino

[0105]

[Chemical 5]

(79) Nitro (80) Sulfo (81) Formyl (82) Carboxyl (83) Methoxycarbonyl (84) Benzyloxycarbonyl (85) Phenoxycarbonyl

[0107]

[Chemical 6]

(86) Butoxy (87) Hexyloxy (88) Dodecyloxy (89) Hexanoyloxy (90) Carboxymethoxy

[0109]

[Chemical 7]

[0110]

[Chemical 8]

[0111]

[Chemical 9]

[0112]

[Chemical 10]

[0113]

[Chemical 11]

[0114]

[Chemical 12]

As the discotic compound, a compound having a 1,3,5-triazine ring or a compound having a porphyrin skeleton can be preferably used.

Among the compounds having a 1,3,5-triazine ring, compounds represented by the following general formula (III) are preferable.

[0117]

[Chemical 13]

In the general formula (III), 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, —N
R ₆ —, —O— or —S—; R ¹ , R ² and R ³ are an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; and R ₄ , R ₅ and R ₆ are It is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. The compound represented by formula (I) is particularly preferably a melamine compound.

The melamine compound has the general formula (I)
X¹, X²And X³, -NR_Four-, -NR
_Five-And-NR₆-Or X¹, X²And X
³Is a single bond, and R¹, R²And R³Becomes a nitrogen atom
It is a heterocyclic group having a free valence. -X¹-R¹, -X²
-R²And -X³-R³Are preferably the same substituents
Good R¹, R²And R³May be an aryl group
Particularly preferred. R_Four, R _FiveAnd R₆Is a hydrogen atom
And are particularly preferred.

The alkyl group is preferably a chain alkyl group rather than a cyclic alkyl group. A linear alkyl group is preferable to a branched chain alkyl group.

The alkyl group preferably has 1 to 30 carbon atoms, more preferably has 1 to 20 carbon atoms, further preferably has 1 to 10 carbon atoms, and further preferably has 1 to 8 carbon atoms. , 1 to 6 is most preferable. The alkyl group may have a substituent.

Specific examples of the substituent include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy and epoxyethyloxy) and an acyloxy group (for example, acryloyloxy, methacryloyloxy) and the like. The alkenyl group is preferably a chain alkenyl group rather than a cyclic alkenyl group. A linear alkenyl group is preferable to a branched chain alkenyl group. The alkenyl group preferably has 2 to 30 carbon atoms, more preferably has 2 to 20 carbon atoms, further preferably has 2 to 10 carbon atoms, and further preferably has 2 to 8 carbon atoms. Most preferably, it is 6. The alkenyl group may have a substituent.

Specific examples of the substituent include a halogen atom,
Alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) or acyloxy group (for example,
Each group such as acryloyloxy, methacryloyloxy)
Is mentioned.

The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have a substituent.

Specific examples of the substituent include, for example, halogen atom, hydroxyl, cyano, nitro, carboxyl, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, alkoxycarbonyl group. , An alkenyloxycarbonyl group, an aryloxycarbonyl group, sulfamoyl, an alkyl-substituted sulfamoyl group, an alkenyl-substituted sulfamoyl group, an aryl-substituted sulfamoyl group,
Examples include sulfonamide group, carbamoyl, alkyl-substituted carmoyl group, alkenyl-substituted carbamoyl group, aryl-substituted carbamoyl group, amide group, alkylthio group, alkenylthio group, arylthio group and acyl group. The alkyl group has the same meaning as the alkyl group described above.

Alkyl group of alkoxy group, acyloxy group, alkoxycarbonyl group, alkyl-substituted sulfamoyl group, sulfonamide group, alkyl-substituted carbamoyl group, amide group, alkylthio group and acyl group has the same meaning as the above-mentioned alkyl group.

The above alkenyl group has the same meaning as the above-mentioned alkenyl group. The alkenyl moiety of the alkenyloxy group, acyloxy group, alkenyloxycarbonyl group, alkenyl-substituted sulfamoyl group, sulfonamide group, alkenyl-substituted carbamoyl group, amide group, alkenylthio group and acyl group has the same meaning as the above-mentioned alkenyl group.

Specific examples of the aryl group include phenyl, α-naphthyl, β-naphthyl, 4-methoxyphenyl, 3,4-diethoxyphenyl, 4-octyloxyphenyl and 4-dodecyloxyphenyl. Each group is mentioned.

Aryloxy group, acyloxy group, aryloxycarbonyl group, aryl-substituted sulfamoyl group, sulfonamide group, aryl-substituted carbamoyl group,
Examples of the amide group, the arylthio group and the acyl group have the same meaning as the above aryl group.

When X ¹ , X ² or X ³ is --NR--, --O-- or --S--, the heterocyclic group preferably has aromaticity.

The heterocycle in the aromatic heterocyclic group is generally an unsaturated heterocycle, preferably a heterocycle having the largest number of double bonds. The heterocycle is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring.

The hetero atom in the heterocycle is preferably each atom such as N, S or O, and particularly preferably N atom.

As the heterocyclic ring having aromaticity, a pyridine ring (as the heterocyclic group, for example, 2-pyridyl or 4
Each group such as -pyridyl) is particularly preferable. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the above examples of the substituent of the aryl moiety.

When X ¹ , X ² or X ³ is a single bond, the heterocyclic group is preferably a heterocyclic group having a free valence at the nitrogen atom. The heterocyclic group having a free valence on the nitrogen atom is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring,
A 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is most preferable. The heterocyclic group may have a plurality of nitrogen atoms.

Further, the heteroatom in the heterocyclic group may have a heteroatom other than nitrogen atom (for example, O atom, S atom). The heterocyclic group may have a substituent. Specific examples of the substituent of the heterocyclic group are synonymous with the specific examples of the substituent of the aryl moiety.

Specific examples of the heterocyclic group having a free valence on the nitrogen atom are shown below.

[0137]

[Chemical 14]

[0138]

[Chemical 15]

The molecular weight of the compound having a 1,3,5-triazine ring is preferably 300-2000.
The boiling point of the compound is preferably 260 ° C. or higher. The boiling point is measured by a commercially available measuring device (for example, TG / DTA1
00, manufactured by Seiko Instruments Inc.).

Specific examples of the compounds having a 1,3,5-triazine ring are shown below. In addition, a plurality of Rs shown below
Represent the same group.

[0141]

[Chemical 16]

(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-furil

[0143]

[Chemical 17]

[0144]

[Chemical 18]

(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-diphenyl Phenyl (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-triphenyl Phenyl (69) 3,4,5-triphenylthiophenyl (70) 3,4,5-trichlorophenyl (71) 3,4,5-tribe Nazoylphenyl (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-trihydroxy Phenyl

[0146]

[Chemical 19]

(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-jibuto Cyphenyl (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-triphenylthio Phenyl (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

[0148]

[Chemical 20]

(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

[0150]

[Chemical 21]

(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

[0152]

[Chemical formula 22]

(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

[0154]

[Chemical formula 23]

(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

[0156]

[Chemical formula 24]

(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-phenoxy Phenyl (243) 4-hi Rokishifeniru (244) 3-butyl-phenyl (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-phenoxy Phenyl (264) 3-hi Rokishifeniru (265) 2-butyl-phenyl (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-phenoxy Phenyl (285) 2-hi Roxyphenyl (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-ethoxy) Ethyl) 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-ethoxy) Ethyl) phenyl (316) 2,4-diphenylphenyl (317) 2,4-diethoxycarbonylpheny (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-diethoxycarbonyl Phenyl (332) 2,3-didodecyloxyphenyl (333) 2,3-dimethylphenyl (334) 2,3- Chlorophenyl (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-ethoxy) Ethyl) 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 (3 1) 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 (36 6) 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 (37
9) 2,4,6-trimethoxyphenyl (380) 2,4,6-tri-N-methylaminophenyl (381) 2,4,6-triisobutyrylaminophenyl (382) 2,4,6 -Triphenoxyphenyl (38
3) 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-methylsulf Moil -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-ethylsulfate Famoyl-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-phenylsulfa Moyle-
1-naphthyl (412) methyl (413) ethyl (414) butyl (415) octyl (416) dodecyl (417) 2-butoxy-2-ethoxyethyl (418) benzyl (419) 4-methoxybenzyl

[0158]

[Chemical 25]

(424) Methyl (425) Phenyl (426) Butyl

[0160]

[Chemical formula 26]

(430) Methyl (431) ethyl (432) Butyl (433) Octyl (434) Dodecyl (435) 2-Butoxy 2-ethoxyethyl (436) benzyl (437) 4-methoxybenzyl

[0162]

[Chemical 27]

[0163]

[Chemical 28]

In the present invention, a melamine polymer may be used as the compound having a 1,3,5-triazine ring. The melamine polymer is preferably synthesized by a polymerization reaction of a melamine compound represented by the following general formula (IV) and a carbonyl compound.

[0165]

[Chemical 29]

In the above synthetic reaction scheme, R ¹¹ , R
¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

The above-mentioned alkyl group, alkenyl group, aryl group, heterocyclic group and substituents thereof have the above general formula (I).
Each group and the substituents thereof described in 1 above have the same meanings.

The polymerization reaction of the melamine compound and the carbonyl compound is the same as the usual method for synthesizing a melamine resin (eg, melamine formaldehyde resin). Also,
You may use a commercially available melamine polymer (melamine resin).

The molecular weight of the melamine polymer is 2,000-40.
It is preferable that it is ten thousand. Specific examples of the repeating unit of the melamine polymer are shown below.

[0170]

[Chemical 30]

MP-1: R¹³, R¹⁴, R¹⁵, R¹⁶: CH
₂OH MP-2: R¹³, R¹⁴, R¹⁵, R¹⁶: CH₂OCH₃ MP-3: R¹³, R¹⁴, R¹⁵, R^16:CH₂O-i-C_Four
H₉ MP-4: R¹³, R¹⁴, R¹⁵, R¹⁶: CH₂Onc_Four
H₉ MP-5: R¹³, R¹⁴, R¹⁵, R¹⁶: CH₂NHCOC
H = CH₂ MP-6: R¹³, R¹⁴, R¹⁵, R¹⁶: CH₂NHCO
(CH₂)₇CH = CH (CH₂)₇CH₃ MP-7: R¹³, R¹⁴, R¹⁵: CH₂OH; R¹⁶: CH₂
OCH₃ MP-8: R¹³, R¹⁴, R¹⁶: CH₂OH; R¹⁵: CH₂
OCH₃ MP-9: R¹³, R¹⁴: CH₂OH; R¹⁵, R¹⁶: CH₂
OCH₃ MP-10: R¹³, R¹⁶: CH₂OH; R¹⁴, R¹⁵: C
H₂OCH₃ MP-11: R¹³: CH₂OH; R¹⁴, R¹⁵, R¹⁶: C
H₂OCH₃ MP-12: R¹³, R¹⁴, R¹⁶: CH₂OCH₃; R¹⁵:
CH₂OH MP-13: R¹³, R¹⁶: CH₂OCH₃; R¹⁴, R¹⁵:
CH₂OH MP-14: R¹³, R¹⁴, R¹⁵: CH₂OH; R¹⁶: C
H₂O-i-C_FourH₉ MP-15: R¹³, R¹⁴, R¹⁶: CH₂OH; R¹⁵: C
H₂O-i-C_FourH₉ MP-16: R¹³, R¹⁴: CH₂OH; R¹⁵, R¹⁶: C
H₂O-i-C_FourH₉ MP-17: R¹³, R¹⁶: CH₂OH; R¹⁴, R¹⁵: C
H₂O-i-C_FourH₉ MP-18: R¹³: CH₂OH; R¹⁴, R¹⁵, R¹⁶: C
H₂O-i-C_FourH₉ MP-19: R¹³, R¹⁴, R¹⁶: CH₂O-i-C
_FourH₉; R¹⁵: CH₂OH MP-20: R¹³, R¹⁶: CH₂O-i-C_FourH₉;
R¹⁴, R¹⁵: CH₂OH MP-21: R¹³, R¹⁴, R¹⁵: CH₂OH; R¹⁶: C
H₂Onc_FourH₉ MP-22: R¹³, R¹⁴, R¹⁶: CH₂OH; R¹⁵: C
H₂Onc_FourH₉ MP-23: R¹³, R¹⁴: CH₂OH; R¹⁵, R¹⁶: C
H₂Onc_FourH₉ MP-24: R¹³, R¹⁶: CH₂OH; R¹⁴, R¹⁵: C
H₂Onc_FourH₉ MP-25: R¹³: CH₂OH; R¹⁴, R¹⁵, R¹⁶: C
H_2O-N-C_FourH₉ MP-26: R¹³, R¹⁴, R¹⁶: CH₂Onc
_FourH₉; R¹⁵: CH₂OH MP-27: R¹³, R¹⁶: CH₂Onc_FourH₉;
R¹⁴, R¹⁵: CH₂OH MP-28: R¹³, R¹⁴: CH₂OH; R¹⁵: CH₂OC
H₃; R¹⁶: CH₂Onc_FourH₉ MP-29: R¹³, R¹⁴: CH₂OH; R¹⁵: CH₂O-
n-C_FourH₉; R¹⁶: CH₂OCH₃ MP-30: R¹³, R¹⁶: CH₂OH; R¹⁴: CH₂OC
H₃; R¹⁵: CH₂Onc_FourH₉ MP-31: R¹³: CH₂OH; R¹⁴, R¹⁵: CH₂OC
H₃; R¹⁶: CH₂Onc_FourH₉ MP-32: R¹³: CH₂OH; R¹⁴, R¹⁶: CH₂OC
H₃; R¹⁵: CH₂Onc_FourH₉ MP-33: R¹³: CH₂OH; R¹⁴: CH₂OCH₃;
R¹⁵, R¹⁶: CH₂Onc_FourH₉ MP-34: R¹³: CH₂OH; R¹⁴, R¹⁵: CH₂O-
n-C_FourH₉; R₁₆: CH₂OCH₃ MP-35: R¹³, R¹⁴: CH₂OCH₃; R¹⁵: CH₂
OH; R¹⁶: CH₂Onc_FourH₉ MP-36: R¹³, R¹⁶: CH₂OCH₃; R¹⁴: CH₂
OH; R¹⁵: CH₂Onc_FourH₉ MP-37: R¹³: CH₂OCH₃; R¹⁴, R¹⁵: CH₂
OH; R¹⁶: CH₂Onc_FourH₉ MP-38: R¹³, R¹⁶: CH₂Onc_FourH₉;
R¹⁴: CH₂OCH₃; R¹⁵: CH₂OH MP-39: R¹³: CH₂OH; R¹⁴: CH₂OCH₃;
R¹⁵: CH₂On-C4H9; R¹⁶: CH₂NHCOC
H = CH₂ MP-40: R¹³: CH₂OH; R¹⁴: CH₂OCH₃;
R¹⁵: CH₂NHCOCH = CH₂; R¹⁶: CH₂On
-C_FourH₉ MP-41: R¹³: CH₂OH; R¹⁴: CH₂Onc
_FourH₉; R¹⁵: CH₂NHCOCH = CH₂; R¹⁶: CH₂
OCH₃ MP-42: R¹³: CH₂OCH₃; R¹⁴: CH₂OH;
R¹⁵: CH₂Onc _FourH₉; R^16:CH₂NHCOCH
= CH₂ MP-43: R¹³: CH₂OCH₃; R¹⁴: CH₂OH;
R¹⁵: CH₂NHCOCH = CH₂; R¹⁶: CH₂On
-C_FourH₉ MP-44: R¹³: CH₂Onc_FourH₉; R¹⁴: CH₂
OCH₃; R¹⁵: CH₂OH; R¹⁶: CH₂NHCOCH
= CH₂ MP-45: R¹³: CH₂OH; R¹⁴: CH₂OCH₃;
R¹⁵: CH₂NHCO (CH₂)₇CH = CH (CH₂)₇
CH₃; R¹⁶: CH₂NHCOCH = CH₂ MP-46: R¹³: CH₂OH; R¹⁴: CH₂OCH₃;
R¹⁵: CH₂NHCOCH = CH₂; R¹⁶: CH₂NHC
O (CH₂)₇CH = CH (CH₂)₇CH₃ MP-47: R¹³: CH₂OH; R¹⁴: CH₂NHCO
(CH₂)₇CH = CH (CH₂)₇CH₃; R¹⁵: CH₂N
HCOCH = CH₂; R¹⁶: CH₂OCH₃ MP-48: R¹³: CH₂OCH₃; R¹⁴: CH₂OH;
R¹⁵: CH₂NHCO (CH₂)₇CH = CH (CH₂)₇
CH₃; R¹⁶: CH₂NHCOCH = CH₂ MP-49: R¹³: CH₂OCH₃; R¹⁴: CH₂OH;
R¹⁵: CH₂NHCOCH = CH₂; R¹⁶: CH₂NHC
O (CH₂)₇CH = CH (CH₂)₇CH₃ MP-50: R¹³: CH₂NHCO (CH₂)₇CH = C
H (CH₂)₇CH₃; R ¹⁴: CH₂OCH₃; R¹⁵: CH₂
OH; R¹⁶: CH₂NHCOCH = CH₂

[0172]

[Chemical 31]

MP-51: R¹³, R¹⁴, R¹⁵, R¹⁶: C
H₂OH MP-52: R¹³, R¹⁴, R¹⁵, R¹⁶: CH₂OCH₃ MP-53: R¹³, R¹⁴, R¹⁵, R¹⁶: CH₂O-i-
C_FourH₉ MP-54: R¹³, R¹⁴, R¹⁵, R¹⁶: CH₂On-
C_FourH₉ MP-55: R¹³, R¹⁴, R¹⁵, R¹⁶: CH₂NHCO
CH = CH₂ MP-56: R¹³, R¹⁴, R¹⁵, R¹⁶: CH₂NHCO
(CH₂)₇CH = CH (CH₂)₇CH₃ MP-57: R¹³, R¹⁴, R¹⁵: CH₂OH; R¹⁶: C
H₂OCH₃ MP-58: R¹³, R¹⁴, R¹⁶: CH₂OH; R¹⁵: C
H₂OCH₃ MP-59: R¹³, R¹⁴: CH₂OH; R¹⁵, R¹⁶: C
H₂OCH₃ MP-60: R¹³, R¹⁶: CH₂OH; R¹⁴, R¹⁵: C
H₂OCH₃ MP-61: R¹³: CH₂OH; R¹⁴, R¹⁵, R¹⁶: C
H₂OCH₃ MP-62: R¹³, R¹⁴, R¹⁶: CH₂OCH₃; R¹⁵:
CH₂OH MP-63: R¹³, R¹⁶: CH₂OCH₃; R¹⁴, R¹⁵:
CH₂OH MP-64: R¹³, R¹⁴, R¹⁵: CH₂OH; R¹⁶: C
H₂O-i-C_FourH₉ MP-65: R¹³, R¹⁴, R¹⁶: CH₂OH; R¹⁵: C
H₂O-i-C_FourH₉ MP-66: R¹³, R¹⁴: CH₂OH; R¹⁵, R¹⁶: C
H₂O-i-C_FourH₉ MP-67: R¹³, R¹⁶: CH₂OH; R¹⁴, R¹⁵: C
H₂O-i-C_FourH₉ MP-68: R¹³: CH₂OH; R¹⁴, R¹⁵, R¹⁶: C
H₂O-i-C_FourH₉ MP-69: R¹³, R¹⁴, R¹⁶: CH₂O-i-C
_FourH₉; R¹⁵: CH₂OH MP-70: R¹³, R¹⁶: CH₂O-i-C_FourH₉;
R¹⁴, R¹⁵: CH₂OH MP-71: R¹³, R¹⁴, R¹⁵: CH₂OH; R¹⁶: C
H₂Onc_FourH₉ MP-72: R¹³, R¹⁴, R¹⁶: CH₂OH; R¹⁵: C
H₂Onc_FourH₉ MP-73: R¹³, R¹⁴: CH₂OH; R¹⁵, R¹⁶: C
H₂Onc_FourH₉ MP-74: R¹³, R¹⁶: CH₂OH; R¹⁴, R¹⁵: C
H₂Onc_FourH₉ MP-75: R¹³: CH₂OH; R¹⁴, R¹⁵, R¹⁶: C
H₂Onc_FourH₉ MP-76: R¹³, R¹⁴, R¹⁶: CH₂Onc
_FourH₉; R¹⁵: CH₂OH MP-77: R¹³, R¹⁶: CH₂Onc_FourH₉;
R¹⁴, R¹⁵: CH₂OH MP-78: R¹³, R¹⁴: CH₂OH; R¹⁵: CH₂OC
H₃; R¹⁶: CH₂Onc_FourH₉ MP-79: R¹³, R¹⁴: CH₂OH; R¹⁵: CH₂O-
n-C_FourH₉; R¹⁶: CH₂OCH₃ MP-80: R¹³, R¹⁶: CH₂OH; R¹⁴: CH₂OC
H₃; R¹⁵: CH₂Onc_FourH₉ MP-81: R¹³: CH₂OH; R¹⁴, R¹⁵: CH₂OC
H₃; R¹⁶: CH₂Onc_FourH₉ MP-82: R¹³: CH₂OH; R¹⁴, R¹⁶: CH₂OC
H₃; R¹⁵: CH₂Onc_FourH₉ MP-83: R¹³: CH₂OH; R¹⁴: CH₂OCH₃;
R¹⁵, R¹⁶: CH₂Onc_FourH₉ MP-84: R¹³: CH₂OH; R¹⁴, R¹⁵: CH₂O-
n-C_FourH₉; R¹⁶: CH₂OCH₃ MP-85: R¹³, R¹⁴: CH₂OCH₃; R¹⁵: CH₂
OH; R¹⁶: CH₂Onc_FourH₉ MP-86: R¹³, R¹⁶: CH₂OCH₃; R¹⁴: CH₂
OH; R¹⁵: CH₂Onc_FourH₉ MP-87: R¹³: CH₂OCH₃; R¹⁴, R¹⁵: CH₂
OH; R¹⁶: CH₂Onc_FourH₉ MP-88: R¹³, R¹⁶: CH₂Onc_FourH₉;
R¹⁴: CH₂OCH₃; R¹⁵: CH₂OH MP-89: R¹³: CH₂OH; R¹⁴: CH₂OCH₃;
R¹⁵: CH₂Onc _FourH₉; R¹⁶: CH₂NHCOCH
= CH₂ MP-90: R¹³: CH₂OH; R¹⁴: CH₂OCH₃;
R¹⁵: CH₂NHCOCH = CH₂; R¹⁶: CH₂On
-C_FourH₉ MP-91: R¹³: CH₂OH; R¹⁴: CH₂Onc
_FourH₉; R¹⁵: CH₂NHCOCH = CH₂; R¹⁶: CH₂
OCH₃ MP-92: R¹³: CH₂OCH₃; R¹⁴: CH₂OH;
R¹⁵: CH₂Onc _FourH₉; R¹⁶: CH₂NHCOCH
= CH₂ MP-93: R¹³: CH₂OCH₃; R¹⁴: CH₂OH;
R¹⁵: CH₂NHCOCH = CH₂; R¹⁶: CH₂On
-C_FourH₉ MP-94: R¹³: CH₂Onc_FourH₉; R¹⁴: CH₂
OCH₃; R¹⁵: CH₂OH; R¹⁶: CH₂NHCOCH
= CH₂ MP-95: R¹³: CH₂OH; R¹⁴: CH₂OCH₃;
R¹⁵: CH₂NHCO (CH₂)₇CH = CH (CH₂)₇
CH₃; R¹⁶: CH₂NHCOCH = CH₂ MP-96: R¹³: CH₂OH; R¹⁴: CH₂OCH₃;
R¹⁵: CH₂NHCOCH = CH₂; R¹⁶: CH₂NHC
O (CH₂)₇CH = CH (CH₂)₇CH₃ MP-97: R¹³: CH₂OH; R¹⁴: CH₂NHCO
(CH₂)₇CH = CH (CH₂)₇CH₃; R¹⁵: CH₂N
HCOCH = CH₂; R¹⁶: CH₂OCH₃ MP-98: R¹³: CH₂OCH₃; R¹⁴: CH₂OH;
R¹⁵: CH₂NHCO (CH₂)₇CH = CH (CH₂)₇
CH₃; R¹⁶: CH₂NHCOCH = CH₂ MP-99: R¹³: CH₂OCH₃; R¹⁴: CH₂OH;
R¹⁵: CH₂NHCOCH = CH₂; R¹⁶: CH₂NHC
O (CH₂)₇CH = CH (CH₂)₇CH₃ MP-100: R¹³: CH₂NHCO (CH₂)₇CH =
CH (CH₂)₇CH₃; R¹⁴: CH₂OCH₃; R¹⁵: C
H₂OH; R¹⁶: CH₂NHCOCH = CH₂

[0174]

[Chemical 32]

MP-101: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ :
_{CH 2 OH MP-102: R} 13, R 14, R 15, R 16: CH 2 OCH 3 MP-103: R 13, R 14, R 15, R 16: CH 2 O-i
_{-C 4 H 9 MP-104:} R 13, R 14, R 15, R 16: CH 2 O-n
_{-C 4 H 9 MP-105:} R 13, R 14, R 15, R 16: CH 2 NHC
_{OCH = CH 2 MP-106:} R 13, R 14, R 15, R 16: CH 2 NHC
_{O (CH 2) 7 CH =} CH (CH 2) 7 CH 3 MP-107: R 13, R 14, R 15: CH 2 OH; R 16:
_{CH 2 OCH 3 MP-108:} R 13, R 14, R 16: CH 2 OH; R 15:
_{CH 2 OCH 3 MP-109:} R 13, R 14: CH 2 OH; R 15, R 16:
_{CH 2 OCH 3 MP-110:} R 13, R 16: CH 2 OH; R 14, R 15:
_{CH 2 OCH 3 MP-111:} R 13: CH 2 OH; R 14, R 15, R 16:
_{CH 2 OCH 3 MP-112:} R 13, R 14, R 16: CH 2 OCH 3;
_{^{R 15: CH 2 OH MP-}} 113: R 13, R 16: CH 2 OCH 3; R 14,
_{^{R 15: CH 2 OH MP-}} 114: R 13, R 14, R 15: CH 2 OH; R 16:
_{CH 2 O-i-C 4} H 9 MP-115: R 13, R 14, R 16: CH 2 OH; R 15:
_{CH 2 O-i-C 4} H 9 MP-116: R 13, R 14: CH 2 OH; R 15, R 16:
_{CH 2 O-i-C 4} H 9 MP-117: R 13, R 16: CH 2 OH; R 14, R 15:
_{CH 2 O-i-C 4} H 9 MP-118: R 13: CH 2 OH; R 14, R 15, R 16:
_{CH 2 O-i-C 4} H 9 MP-119: R 13, R 14, R 16: CH 2 O-i-C 4 H
_{^{9; R 15: CH 2 OH}} MP-120: R 13, R 16: CH 2 O-i-C 4 H 9; R
_{^{14, R 15: CH 2 OH}} MP-121: R 13, R 14, R 15: CH 2 OH; R 16:
_{CH 2 O-n-C 4} H 9 MP-122: R 13, R 14, R 16: CH 2 OH; R 15:
_{CH 2 O-n-C 4} H 9 MP-123: R 13, R 14: CH 2 OH; R 15, R 16:
_{CH 2 O-n-C 4} H 9 MP-124: R 13, R 16: CH 2 OH; R 14, R 15:
_{CH 2 O-n-C 4} H 9 MP-125: R 13: CH 2 OH; R 14, R 15, R 16:
_{CH 2 O-n-C 4} H 9 MP-126: R 13, R 14, R 16: CH 2 O-n-C 4 H
_{^{9; R 15: CH 2 OH}} MP-127: R 13, R 16: CH 2 O-n-C 4 H 9; R
¹⁴ , R ¹⁵ : CH ₂ OH MP-128: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ O
_{^{CH 3; R 16: CH 2}} O-n-C 4 H 9 MP-129: R 13, R 14: CH 2 OH; R 15: CH 2 O
_{-N-C 4 H 9; R} 16: CH 2 OCH 3 MP-130: R 13, R 16: CH 2 OH; R 14: CH 2 O
_{^{CH 3; R 15: CH 2}} O-n-C 4 H 9 MP-131: R 13: CH 2 OH; R 14, R 15: CH 2 O
_{^{CH 3; R 16: CH 2}} O-n-C 4 H 9 MP-132: R 13: CH 2 OH; R 14, R 16: CH 2 O
_{^{CH 3; R 15: CH 2}} O-n-C 4 H 9 MP-133: R 13: CH 2 OH; R 14: CH 2 OC
_{^{H 3; R 15, R 16}} : CH 2 O-n-C 4 H 9 MP-134: R 13: CH 2 OH; R 14, R 15: CH 2 O
_{-N-C 4 H 9; R} 16: CH 2 OCH 3 MP-135: R 13, R 14: CH 2 OCH 3; R 15: CH
_{^{2 OH; R 16: CH 2}} O-n-C 4 H 9 MP-136: R 13, R 16: CH 2 OCH 3; R 14: CH
_{^{2 OH; R 15: CH 2}} O-n-C 4 H 9 MP-137: R 13: CH 2 OCH 3; R 14, R 15: CH
_{^{2 OH; R 16: CH 2}} O-n-C 4 H 9 MP-138: R 13, R 16: CH 2 O-n-C 4 H 9; R
_{^{14: CH 2 OCH 3; R}} 1 5: CH 2 OH MP-139: R 13: CH 2 OH; R 14: CH 2 OC
_{^{H 3; R 15: CH 2}} O-n-C 4 H 9; R 16: CH 2 NHC
_{OCH = CH 2 MP-140:} R 13: CH 2 OH; R 14: CH 2 OC
_{^{H 3; R 15: CH 2}} NHCOCH = CH 2; R 16: CH 2 O
_{-N-C 4 H 9 MP-} 141: R 13: CH 2 OH; R 14: CH 2 O-n-
^{_{C 4 H 9; R 15:}} CH 2 NHCOCH = CH 2; R 16: CH
₂ OCH ₃ MP-142: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ O
_{^{H; R 15: CH 2 O}} -n-C 4 H 9; R 16: CH 2 NHCO
_{CH = CH 2 MP-143:} R 13: CH 2 OCH 3; R 14: CH 2 O
H; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ O
_{-N-C 4 H 9 MP-} 144: R 13: CH 2 O-n-C 4 H 9; R 14: C
H ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ NHCOC
_{H = CH 2 MP-145:} R 13: CH 2 OH; R 14: CH 2 OC
_{^{H 3; R 15: CH 2}} NHCO (CH 2) 7 CH = CH (CH
^{_{2) 7 CH 3; R 16}} : CH 2 NHCOCH = CH 2 MP-146: R 13: CH 2 OH; R 14: CH 2 OC
_{^{H 3; R 15: CH 2}} NHCOCH = CH 2; R 16: CH 2 N
_{HCO (CH 2) 7 CH =} CH (CH 2) 7 CH 3 MP-147: R 13: CH 2 OH; R 14: CH 2 NHCO
_{(CH 2) 7 CH = CH} (CH 2) 7 CH 3; R 15: CH 2 N
HCOCH = CH ₂ ; R ¹⁶ : CH ₂ OCH ₃ MP-148: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ O
H; R ¹⁵ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (C
_{H 2) 7 CH 3; R} 16: CH 2 NHCOCH = CH 2 MP-149: R 13: CH 2 OCH 3; R 14: CH 2 O
H; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ N
_{HCO (CH 2) 7 CH =} CH (CH 2) 7 CH 3 MP-150: R 13: CH 2 NHCO (CH 2) 7 CH =
CH (CH ₂ ) ₇ CH ₃ ; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : C
H ₂ OH; R ¹⁶ : CH ₂ NHCOCH = CH ₂

[0176]

[Chemical 33]

MP-151: R ¹³ , R ¹⁴ , R ¹⁵ , R ^16:
_{CH 2 OH MP-152: R} 13, R 14, R 15, R 16: CH 2 OCH 3 MP-153: R 13, R 14, R 15, R 16: CH 2 O-i
_{-C 4 H 9 MP-154:} R 13, R 14, R 15, R 16: CH 2 O-n
_{-C 4 H 9 MP-155:} R 13, R 14, R 15, R 16: CH 2 NHC
_{OCH = CH 2 MP-156:} R 13, R 14, R 15, R 16: CH 2 NHC
_{O (CH 2) 7 CH =} CH (CH 2) 7 CH 3 MP-157: R 13, R 14, R 15: CH 2 OH; R 16:
_{CH 2 OCH 3 MP-158:} R 13, R 14, R 16: CH 2 OH; R 15:
_{CH 2 OCH 3 MP-159:} R 13, R 14: CH 2 OH; R 15, R 16:
_{CH 2 OCH 3 MP-160:} R 13, R 16: CH 2 OH; R 14, R 15:
_{CH 2 OCH 3 MP-161:} R 13: CH 2 OH; R 14, R 15, R 16:
_{CH 2 OCH 3 MP-162:} R 13, R 14, R 16: CH 2 OCH 3;
_{^{R 15: CH 2 OH MP-}} 163: R 13, R 16: CH 2 OCH 3; R 14,
_{^{R 15: CH 2 OH MP-}} 164: R 13, R 14, R 15: CH 2 OH; R 16:
_{CH 2 O-i-C 4} H 9 MP-165: R 13, R 14, R 16: CH 2 OH; R 15:
_{CH 2 O-i-C 4} H 9 MP-166: R 13, R 14: CH 2 OH; R 15, R 16:
_{CH 2 O-i-C 4} H 9 MP-167: R 13, R 16: CH 2 OH; R 14, R 15:
_{CH 2 O-i-C 4} H 9 MP-168: R 13: CH 2 OH; R 14, R 15, R 16:
_{CH 2 O-i-C 4} H 9 MP-169: R 13, R 14, R 16: CH 2 O-i-C 4 H
_{^{9; R 15: CH 2 OH}} MP-170: R 13, R 16: CH 2 O-i-C 4 H 9; R
_{^{14, R 15: CH 2 OH}} MP-171: R 13, R 14, R 15: CH 2 OH; R 16:
_{CH 2 O-n-C 4} H 9 MP-172: R 13, R 14, R 16: CH 2 OH; R 15:
_{CH 2 O-n-C 4} H 9 MP-173: R 13, R 14: CH 2 OH; R 15, R 16:
_{CH 2 O-n-C 4} H 9 MP-174: R 13, R 16: CH 2 OH; R 14, R 15:
_{CH 2 O-n-C 4} H 9 MP-175: R 13: CH 2 OH; R 14, R 15, R 16:
_{CH 2 O-n-C 4} H 9 MP-176: R 13, R 14, R 16: CH 2 O-n-C 4 H
_{^{9; R 15: CH 2 OH}} MP-177: R 13, R 16: CH 2 O-n-C 4 H 9; R
¹⁴ , R ¹⁵ : CH ₂ OH MP-178: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ O
_{^{CH 3; R 16: CH 2}} O-n-C 4 H 9 MP-179: R 13, R 14: CH 2 OH; R 15: CH 2 O
_{-N-C 4 H 9; R} 16: CH 2 OCH 3 MP-180: R 13, R 16: CH 2 OH; R 14: CH 2 O
_{^{CH 3; R 15: CH 2}} O-n-C 4 H 9 MP-181: R 13: CH 2 OH; R 14, R 15: CH 2 O
_{^{CH 3; R 16: CH 2}} O-n-C 4 H 9 MP-182: R 13: CH 2 OH; R 14, R 16: CH 2 O
_{^{CH 3; R 15: CH 2}} O-n-C 4 H 9 MP-183: R 13: CH 2 OH; R 14: CH 2 OC
_{^{H 3; R 15, R 16}} : CH 2 O-n-C 4 H 9 MP-184: R 13: CH 2 OH; R 14, R 15: CH 2 O
_{-N-C 4 H 9; R} 16: CH 2 OCH 3 MP-185: R 13, R 14: CH 2 OCH 3; R 15: CH
_{^{2 OH; R 16: CH 2O}} -n-C 4 H 9 MP-186: R 13, R 16: CH 2 OCH 3; R 14: CH
_{^{2 OH; R 15: CH 2}} O-n-C 4 H 9 MP-187: R 13: CH 2 OCH 3; R 14, R 15: CH
_{^{2 OH; R 16: CH 2}} O-n-C 4 H 9 MP-188: R 13, R 16: CH 2 O-n-C 4 H 9; R
_{^{14: CH 2 OCH 3; R}} 1 5: CH 2 OH MP-189: R 13: CH 2 OH; R 14: CH 2 OC
_{^{H 3; R 15: CH 2}} O-n-C 4 H 9; R 16: CH 2 NHC
_{OCH = CH 2 MP-190:} R 13: CH 2 OH; R 14: CH 2 OC
_{^{H 3; R 15: CH 2}} NHCOCH = CH 2; R 16: CH 2 O
_{-N-C 4 H 9 MP-} 191: R 13: CH 2 OH; R 14: CH 2 O-n-
^{_{C 4 H 9; R 15:}} CH 2 NHCOCH = CH 2; R 16: CH
₂ OCH ₃ MP-192: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ O
_{^{H; R 15: CH 2 O}} -n-C 4 H 9; R 16: CH 2 NHCO
_{CH = CH 2 MP-193:} R 13: CH 2 OCH 3; R 14: CH 2 O
H; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ O
_{-N-C 4 H 9 MP-} 194: R 13: CH 2 O-n-C 4 H 9; R 14: C
H ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ NHCOC
_{H = CH 2 MP-195:} R 13: CH 2 OH; R 14: CH 2 OC
_{^{H 3; R 15: CH 2}} NHCO (CH 2) 7 CH = CH (CH
₂ ) ₇ CH ₃ ; R ¹⁶ : CH ₂ NHCOCH = CH ₂ MP-196: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OC
_{^{H 3; R 15: CH 2}} NHCOCH = CH 2; R 16: CH 2 N
_{HCO (CH 2) 7 CH =} CH (CH 2) 7 CH 3 MP-197: R 13: CH 2 OH; R 14: CH 2 NHCO
_{(CH 2) 7 CH = CH} (CH 2) 7 CH 3; R 15: CH 2 N
^{_{HCOCH = CH 2; R 16:}} CH 2 OCH 3 MP-198: R 13: CH 2 OCH 3; R 14: CH 2 O
H; R ¹⁵ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (C
_{H 2) 7 CH 3; R} 16: CH 2 NHCOCH = CH 2 MP-199: R 13: CH 2 OCH 3; R 14: CH 2 O
H; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ N
_{HCO (CH 2) 7 CH =} CH (CH 2) 7 CH 3 MP-200: R 13: CH 2 NHCO (CH 2) 7 CH =
CH (CH ₂ ) ₇ CH ₃ ; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : C
H ₂ OH; R ¹⁶ : CH ₂ NHCOCH = CH _{2 In the} present invention, a copolymer in which two or more kinds of the above repeating units are combined may be used. You may use together 2 or more types of homopolymers or copolymers.

Further, compounds having two or more kinds of 1,3,5-triazine rings may be used in combination. Two or more kinds of discotic compounds (for example, a compound having a 1,3,5-triazine ring and a compound having a porphyrin skeleton) may be used in combination.

In addition, specific examples of the additives of the present invention other than the above will be given below.

[0180]

[Chemical 34]

[0181]

[Chemical 35]

[0182]

[Chemical 36]

[0183]

[Chemical 37]

[0184]

[Chemical 38]

[0185]

[Chemical Formula 39]

[0186]

[Chemical 40]

In the dope, additives other than the above, antioxidants, dyes, fluorescent whitening agents (for example, Japanese Patent Application No. 2002-123) are used.
821) and the like can also be added.

These compounds may be added together with the cellulose ester or the solvent during the preparation of the cellulose ester solution, or may be added during or after the preparation of the solution.
For liquid crystal display devices, it is preferable to add an antioxidant or the like that imparts heat and humidity resistance.

As the antioxidant, hindered phenol compounds are preferably used, and 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t] are used. -Butyl-4-hydroxyphenyl) propionate], triethylene glycol-
Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate], 2,4-bis-
(N-octylthio) -6- (4-hydroxy-3,5
-Di-t-butylanilino) -1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate, N, N'-
Hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-)
4-hydroxybenzyl) benzene, tris- (3,5
-Di-t-butyl-4-hydroxybenzyl) -isocyanurate and the like. In particular, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred. Further, for example, N, N'-bis [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionyl] hydrazine-based metal deactivators and tris (2,4-di-)
A phosphorus-based processing stabilizer such as t-butylphenyl) phosphite may be used in combination. The addition amount of these compounds is preferably 1 to 1.0 ppm, and more preferably 10 to 1000 ppm in terms of mass ratio with respect to the cellulose ester.

In the stretched film of the present invention, it is preferable from the viewpoint of productivity that the fine particles added as a matting agent be added mainly to the addition liquid.

In the present invention, the fine particles are not particularly limited, but preferably used fine particles are, for example, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc,
Examples thereof include fine particles of inorganic compounds such as clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate.

The content of these fine particles in the cellulose ester film is preferably 0.03 to 1% by mass, more preferably 0.05 to 0.5% by mass, and especially 0.15% by mass. It is preferable that the content is 0.4 mass%.

Specific examples of fine particles of zirconium oxide are commercially available, for example, under the trade names of Aerosil R976 and R811 (all manufactured by Nippon Aerosil Co., Ltd.) and are preferably used in the present invention.

The fine particles are more preferably a compound containing silicon because the turbidity of the stretched film is lowered, and silicon dioxide is particularly preferable. Above all, it is preferable that the surface is surface-treated with an organic compound, since the affinity with the cellulose ester resin containing the additive is excellent.

Specific examples thereof include Aerosil R972, R972V, R974, R812, 20.
0, 200V, 300, R202, OX50, TT60
It is commercially available under the trade name of 0 (all manufactured by Nippon Aerosil Co., Ltd.) and is preferably used in the present invention.

It is more preferable that the silicon dioxide fine particles have a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more.

Specific examples of the silicon dioxide fine particles which satisfy these requirements are, for example, Aerosil 200V (average primary particle diameter 12 nm) and Aerosil R972V (average primary particle diameter 16 nm), which keeps the haze of the stretched film low. However, it is particularly preferable because it has a large effect of reducing the friction coefficient.

Further, examples of the polymer include silicone resin, fluorine resin and acrylic resin. Among them, silicone resin is preferable, and one having a three-dimensional network structure is particularly preferable.

Specifically, for example, Tospearl 103,
105, 108, 120, 145, 3120
And 240 (these are manufactured by Toshiba Silicone Co., Ltd.) and are preferably used in the present invention.

The fine particle dispersion liquid may contain a resin in order to keep the dispersion state of the fine particles stable. The weight average molecular weight of the resin to be added is preferably 3,000 to 9,000, more preferably 5,000 to 50,000, and further preferably 10,000 to 30,000.

The resin is not particularly limited and widely known resins can be used, but the following resins can be more preferably used.

As the resin preferably used in the matting agent dispersion of the present invention, there may be mentioned a homopolymer or a copolymer having an ethylenically unsaturated monomer unit, more preferably polymethyl acrylate or polymethacrylate. Acrylic acid or methacrylic acid such as ethyl acrylate, polypropyl acrylate, poly (cyclohexyl acrylate), alkyl acrylate copolymer, poly (methyl methacrylate), poly (ethyl methacrylate), poly (methacrylic acid cyclohexyl), methacrylic acid alkyl ester copolymer, etc. Is a homopolymer or copolymer of acid ester, further acrylic acid or methacrylic acid ester is excellent in transparency, compatibility, a homopolymer or copolymer having an acrylic acid ester or methacrylic acid ester unit, particularly, Contains acrylic acid or methyl methacrylate units That homopolymer or copolymer is preferred. Among them, polymethylmethacrylate is preferable.

Other resins include, for example, cellulose acetate, cellulose acetate propionate,
Cellulose ester resins having a degree of substitution of acyl groups such as cellulose acetate butyrate of 1.8 to 2.80; degree of substitution of alkyl groups such as cellulose methyl ether, cellulose ethyl ether and cellulose propyl ether of 2.0 to
2.80 Cellulose ether resin; Polyamide resin of polymer of alkylenedicarboxylic acid and diamine; Polymer of alkylenedicarboxylic acid and diol, Polymer of alkylenediol and dicarboxylic acid, Polymer of cyclohexanedicarboxylic acid and diol , Polyester resins such as polymers of cyclohexanediol and dicarboxylic acids, polymers of aromatic dicarboxylic acids and diols; vinyl acetate resins such as polyvinyl acetate and vinyl acetate copolymers; polyvinyl acetals such as polyvinyl acetal and polyvinyl butyral. Resin: Epoxy resin as shown below, ketone resin as shown below, polyurethane resin as shown below such as linear polymer of alkylene diisocyanate and alkylene diol, etc. can be mentioned, and selected from these. at least Preferably contains One.

As the epoxy resin, a compound having two or more epoxy groups in one molecule forms a resin by a ring-opening reaction, and the following epoxy resins can be mentioned. Araldide E as a commercial product
There are PN1179 and Araldide AER260 (manufactured by Asahi Chiba Co., Ltd.).

The weight average molecular weight of Araldite EPN1179 is about 405. n indicates the degree of polymerization.

[0206]

[Chemical 41]

The ketone resin can be obtained by polymerizing vinyl ketones, and the ketone resins shown below can be mentioned. Typical commercially available products are Hirac 110 and Hirac 110H (Hitachi Kasei Co., Ltd.
Made). n indicates the degree of polymerization.

[0208]

[Chemical 42]

In the present invention, the content of the fine particles in the fine particle dispersion is preferably 0.1 to 2.0% by mass based on the mass of the organic solvent, and the resin concentration depends on the molecular weight, but it is usually 5 to 50 mass% is preferable.

The stretched cellulose ester film of the present invention can be produced, for example, by the following method. The fine particles are contained in the stretched cellulose ester film of the present invention, and it is desirable that the fine particles are previously dispersed in a solvent. An additive is added to this fine particle dispersion liquid, and this is mixed with a cellulose ester solution to prepare a cellulose ester solution containing fine particles, which is cast on a support such as a metal belt and peeled off, and then the solvent is removed. It is a method of stretching in the state of containing.

Particularly, the fine particle dispersion preferably contains a plasticizer. It is also preferable that the fine particle dispersion contains a small amount of cellulose ester.

The total additive concentration based on the total solid content of the fine particle dispersion added when preparing the cellulose ester solution is the total additive concentration based on the total solid content of the cellulose ester solution prepared using the fine particle dispersion. It is preferable to increase 1.1 times to 9 times as much as the gap, because the gap between the primary particles forming the secondary particles and the additive concentration in the vicinity of the secondary particles can be increased, and more preferably 1. .2
~ 7 times.

The total additive concentration can be calculated by the following formula. Total additive concentration of fine particle dispersion (%) = content of additives excluding fine particles and cellulose ester in fine particle dispersion (g) / mass of total solid content in fine particle dispersion (g) × 100 of cellulose ester solution Total additive concentration (%) = content of additives excluding fine particles and cellulose ester in cellulose ester solution (g) / mass of total solid content in cellulose ester solution (g) × 100 1.1 × of cellulose ester solution Total additive concentration ≦ total additive concentration of fine particle dispersion ≦ 9 × total additive concentration of cellulose ester solution Also, preferably, the above fine particle dispersion is mixed in-line with the cellulose ester solution and cast. Is.

After adding the fine particle dispersion, it is preferable to cast the mixture within 1 hour, more preferably within 30 minutes, further preferably within 10 minutes, and particularly preferably within 5 minutes.

If the fine particle dispersion is mixed and left for a long time, the additive concentration in the vicinity of the secondary particles becomes uniform, which is not preferable.

That is, by using the stretched cellulose ester film of the present invention, a display device having excellent visibility can be obtained.

In the present invention, the cellulose ester solution is also referred to as a cellulose ester dope or simply dope.

[0218] The cellulose used as the raw material of the cellulose ester used in the present invention is not particularly limited, but cotton linter, wood pulp, kenaf and the like can be mentioned. The cellulose esters obtained from them can be mixed and used in arbitrary proportions.

The cellulose esters obtained from these may be mixed and used in arbitrary proportions. In these cellulose esters, the cellulose raw material has an acylating agent as an acid anhydride (acetic anhydride, propionic anhydride,
Butyric anhydride) can be obtained by a conventional method using an organic acid such as acetic acid or an organic solvent such as methylene chloride and a protic catalyst such as sulfuric acid.

Particularly in the case of mixed acid cellulose ester,
For example, a mixed acid ester can be obtained by reacting by the method described in JP-A-10-45804. The acyl group substitution degree can be measured according to ASTM-D817-96.

Number average molecular weight of cellulose ester (M
The n) is preferably 70,000 to 250,000, which has a high mechanical strength when molded and has an appropriate dope viscosity, and more preferably 80,000 to 150,000.
00.

The cellulose ester film of the present invention is manufactured (film formation) by a method called a solution casting film formation method.

In this method, an endless metal belt (for example, a stainless belt) that moves indefinitely or a rotating metal drum (for example, a drum whose surface is chrome-plated with cast iron) is used.
A dope (a cellulose ester solution) is cast from a pressure die onto a casting metal support (hereinafter, also simply referred to as a metal support), and a web (metal casting) on the metal support is cast. The doped film) from the metal support,
It is manufactured by drying.

In order to produce the cellulose ester film of the present invention having a multi-layer structure, a sequential multi-layer casting method in which two or more layers are formed through different dies, in a die having two or three or more slits. Simultaneous multi-layer casting method in which each dope is merged into a structure of two layers or three layers or more,
Any of the multilayer casting methods in which the sequential multilayer casting and the simultaneous multilayer casting are combined is preferably used. A simultaneous multi-layer casting method in which each dope is merged in a die having two or three or more slits to form a structure of two layers or three or more layers is preferably used, which is also called co-casting.

The method for producing the cellulose ester laminated film of the present invention will be described with reference to the drawings shown in FIGS. FIG. 2 is a process diagram showing an example of the production apparatus for a cellulose ester laminated film of the present invention, and FIG.
Shows a sectional view of the slit die 6 of FIG. The dope liquid tank 1 for preparing the cellulose ester dope liquid contains the dope liquid 1a, and the particle addition liquid tank 2 contains the particle addition liquid 2a. Dope liquid 1a
Is the in-line mixer 5 by the liquid feed pumps 4b and 4c.
a and 5b, and the particulate addition liquid 2a is sent to the in-line mixer 5a by the pump 4a. The dope solution 1a and the fine particle additive solution 2a are sufficiently mixed by the in-line mixer 5a and sent to the slit 13 of the slit die 6. Similarly, the dope liquid 1 a and the ultraviolet absorber additive liquid 3 a put in the ultraviolet absorber additive liquid tank 3 are sufficiently mixed by the in-line mixer 5 b and sent to the slit 12 of the slit die 6. The layers above and below the slit die 6 are composed of a mixed solution of the dope solution 1a and the fine particle additive solution 2a, and the middle layer is a mixture solution of the dope solution 1a and the ultraviolet absorber additive solution 3a. From the drum 7, and is cast on the casting belt 8 that continuously moves from the drum 7. The three-layered cast cellulose ester dope layer is dried and then peeled from the casting belt by the roller 9 as the cellulose ester laminated film 10.

In the production of the optical film of the present invention, it is preferable to maintain higher flatness by casting a dope and then applying a tenter when peeling it from the belt or drum and drying.

The organic solvent used for the preparation of these dopes is preferably one which can dissolve the cellulose ester and has an appropriate boiling point. For example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, acetone,
Tetrahydrofuran, 1,3-dioxolane, 1,4-
Dioxane, cyclohexanone, ethyl formate, 2,2
2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 1,3-difluoro-2
-Propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,
3,3,3-hexafluoro-2-propanol, 2,
2,3,3,3-pentafluoro-1-propanol,
Examples thereof include nitroethane, 1,3-dimethyl-2-imidazolidinone, and methyl acetoacetate. Organic halogen compounds such as methylene chloride, dioxolane derivatives, methyl acetate, ethyl acetate, and acetone are preferable organic solvents (ie, , Good solvent).

The cellulose ester dope of the present invention comprises
In addition to the above organic solvent, it is preferable that 1 to 40% by mass of alcohol having 1 to 4 carbon atoms be contained in the whole organic solvent. After casting the dope onto the casting support, the solvent begins to evaporate and the alcohol content increases, and the web (casting film) gels, making the web strong and easy to separate from the casting support. It also has the function of promoting the dissolution of the cellulose ester of the non-chlorine type organic solvent when it is used as a gelling solvent, or when the proportion thereof is small. The organic solvent may contain water in an amount of 0.01 to 1.5%.

As the alcohol having 1 to 4 carbon atoms,
Methanol, ethanol, n-propanol, iso-
Propanol, n-butanol, sec-butanol,
Mention may be made of tert-butanol. Of these, ethanol is preferred because it has a stable dope, a relatively low boiling point, a good drying property, and no toxicity.

The concentration of cellulose ester in the dope is 1
It is preferable to adjust the dope viscosity in the range of 5 to 40% by mass and the range of 10 to 50 Pa · s in order to obtain good stretched film surface quality. Also, the dope is methyl acetate or 1 to 4 carbon atoms.
It can also be adjusted by heating or by a known cooling dissolution method using a non-chlorine-based solvent containing alcohol or the like.

In the present invention, it is preferable to use a dope containing substantially no chlorine-based solvent.

The term "substantially free of chlorine-based solvent" means that the content of chlorine-based solvent such as methylene chloride is less than 1%, preferably 0%.
In that case, a non-chlorine solvent such as methyl acetate, acetone, dioxolane, methanol, ethanol or butanol is preferably used.

In the present invention, it is particularly preferable to use a dope having secondary particles produced by using such a non-chlorine type solvent, and it is possible to reduce the haze of a stretched cellulose ester film having R ₀ of 30 nm or more. A manufacturing method can be provided.

The peeling tension when peeling the dope film (also referred to as web) after the dope is cast on the support is 250 N.
/ M or less, and the transport tension is 300 N /
m or less, more preferably 250 N
/ M or less, more preferably 100
~ 200 N / m. In the drying step, it is preferable to apply tension in the width direction by a tenter to stretch the film.

The stretching ratio of the cellulose ester film by a tenter is preferably 1.15 to 2.0 times, and the residual solvent amount of the web during stretching is preferably 3 to 30% by mass.

In the stretching, the residual solvent amount of the web is 0 to 3% by mass.
Although it can be carried out by heating at less than 3% by mass, the haze hardly increases when the content is 3% by mass or more, and the dimensional stability of the obtained film is excellent, and the haze hardly increases when the content is 30% by mass or less. The residual solvent is preferably in the above range because the desired optical characteristics (R ₀ , R _t ) can be easily obtained.

In the present invention, the residual solvent amount of the web is determined by the following formula. Amount of residual solvent (%) = [(mass before heat treatment of web-mass after heat treatment of web) / (mass after heat treatment of web)]
× 100 In addition, the heat treatment at the time of measuring the residual solvent amount is 115 ° C.
It is to heat-treat for 1 hour.

The above stretched cellulose ester film is particularly preferably used as a retardation film, and can be laminated with a polarizer or a polarizing plate to form an elliptically polarizing plate. The stretched cellulose ester film of the present invention has little variation in retardation value even during storage in a roll state, and an elliptically polarizing plate produced using this has uniform properties.

When the stretched cellulose ester film of the present invention is used as a polarizing plate protective film, it is preferable that the stretched cellulose ester film is laminated so that the absorption axis of the polarizer and the slow axis of the stretched cellulose ester film are orthogonal to each other.

The term "orthogonal" as used herein means that the angle formed when the absorption axis and the slow axis are projected on the same plane is 80 ° -100.
It means that it is °. The angle is preferably 85 ° to 90 °, particularly preferably 90 ° ± 1 °.

According to the present invention, retardation films such as λ / 2 plate and λ / 4 plate can be preferably produced.

If necessary, an antistatic layer, a conductive layer (ITO, zinc oxide layer, tin oxide), a hard coat layer, an ultraviolet curable resin layer, an antireflection layer (silicon oxide layer, titanium oxide layer, etc.), Alignment film, gas barrier film, optical anisotropic layer in which liquid crystalline compound (rod-shaped liquid crystal, discotic liquid crystal, etc.) is aligned and fixed, coating, sputtering, vapor deposition, atmospheric pressure plasma CVD
And the like.

The stretched cellulose ester film of the present invention is used as a retardation film of TN type, HAN type, OCB
It is useful as an optical compensation film for a liquid crystal display device of a liquid crystal type, a VA type or the like, or a reflection type liquid crystal display device, and it is possible to obtain a display device having a wide viewing angle and excellent visibility.

[0244]

The present invention will be specifically described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 [Preparation of Stretched Cellulose Ester Film] <Preparation of Dope A> (Preparation of Silicon Oxide Fine Particle Dispersion) Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd., average particle size of primary particles 16 nm) 1 kg Ethanol After stirring and mixing 9 kg or more with a dissolver for 40 minutes, dispersion was carried out using a Manton-Gorlin type high-pressure dispersion device to prepare a silicon oxide fine particle dispersion liquid.

(Preparation of Additive Liquid A) (See Table 1) Methylene chloride 140 kg Cellulose acetate (acetyl group substitution degree 2.7) 5 kg Ester of trimethylolpropane and cyclohexanecarboxylic acid (compound A) 2 kg or more in a closed container. It was charged, completely dissolved with heating and stirring, and filtered. To this, 10 kg of the above silicon oxide fine particle dispersion liquid was added with stirring, and the mixture was further stirred for 30 minutes and then filtered to prepare an addition liquid A.

(Preparation of Cellulose Ester Solution A) (Refer to Table 1) Methylene chloride 440 kg Ethanol 35 kg Cellulose acetate (acetyl group substitution degree 2.7) 100 kg Ester of trimethylolpropane and cyclohexanecarboxylic acid (Compound A) 10 kg The solvent was placed in a closed container, the remaining materials were placed in that order with stirring, and the ingredients were completely dissolved and mixed with heating and stirring. The solution was cooled to a temperature at which it was cast, allowed to stand overnight, and subjected to a defoaming operation. Then, the solution was placed in Azumi Filter Paper No. No. manufactured by Azumi Filter Paper Co., Ltd. Filtered using 244.

The additive solution A was fed to the cellulose ester solution A through separate pipes to obtain the cellulose ester solution A100.
In-line mixer (Toray Co., Ltd. static type in-tube mixer Hi-Mixer, S
WJ) and mixed to obtain a dope A. This was immediately sent to a die and cast on a support.

The dope A whose temperature was adjusted to 30 ° C. was introduced into the die, and the dope was uniformly cast on the endless stainless belt (support) through the die slit. The casting portion of the endless stainless belt was heated with warm water of 35 ° C. from the back surface.

After casting, the dope film on the support (hereinafter referred to as a web after casting on a stainless steel belt) is 44 ° C.
Was dried by applying warm air, and after 120 seconds from the casting, the amount of the peeling residual solvent was 80% by mass, peeling was carried out, and the peeling was carried out while being conveyed by a large number of rolls.

The temperature of the endless stainless belt at the peeling section was set to 11 ° C. The peeled web was conveyed in the first drying zone set at 50 ° C for 1 minute, and then at the inlet of the second drying zone, the edge of the web was gripped with a tenter at 80 ° C, and the widthwise direction at 120 ° C. It was stretched 1.4 times. After stretching, after holding for a few seconds while maintaining the width, the width retention was released, and the film was conveyed in the third drying zone set at 115 ° C. for 20 minutes to be dried to obtain a stretched cellulose ester having a film thickness of 80 μm. A film A was obtained.

Cellulose ester solution A shown in Table 1 below
Cellulose ester solution B shown in Table 2 below with addition liquid A
A dope B was prepared by changing the additive liquid B to the dope A, and a cellulose ester film B was obtained in the same manner except that this was used instead of the dope A.

Similarly, the dope C to K was prepared by changing the cellulose ester solution and the additive liquid shown in Tables 3 to 11 below.
Stretched cellulose ester films C to K were produced in the same manner except that this was used instead of the dope A. A stretched cellulose ester film L was obtained in the same manner as the stretched cellulose ester film K except that the stretching with a tenter was 1.1 times. The acyl group substitution degree of the cellulose ester and the number average molecular weight of the cellulose ester in the following table were measured by the following methods.

(Measurement of degree of acyl substitution of cellulose ester) The measurement was carried out according to the method specified in ASTM-D817-96.

(Number Average Molecular Weight of Cellulose Ester) It was measured by high performance liquid chromatography under the following conditions.

Solvent: Acetone Column: MPW × 1 (manufactured by Tosoh Corporation) Sample concentration: 0.2 mass / volume% Flow rate: 1.0 ml / min Sample injection amount: 300 μl Standard sample: polymethylmethacrylate (MW =) 188,2
00) Temperature: 23 ° C. Detector: Differential refractometer.

[0257]

[Table 1]

[0258]

[Table 2]

[0259]

[Table 3]

[0260]

[Table 4]

[0261]

[Table 5]

[0262]

[Table 6]

[0263]

[Table 7]

[0264]

[Table 8]

[0265]

[Table 9]

[0266]

[Table 10]

[0267]

[Table 11]

[0268]

[Chemical 43]

The stretched cellulose ester films A to L were evaluated as follows.

(Haze value) A haze meter (1001DP type, manufactured by Nippon Denshoku Industries Co., Ltd.) according to K-7105.
Was measured using.

(Measurement of Retardation Values R ₀ and R _t ) 23
Automatic birefringence meter KOBRA for each stretched cellulose ester film stored for 24 hours at 55 ° C and 55% RH
The birefringence was measured at a wavelength of 590 nm using -21ADH (manufactured by Oji Scientific Instruments Co., Ltd.) to determine retardation values R ₀ and R _t .

R _O = (Nx−Ny) × d R _t = {(Nx + Ny) / 2−Nz} × d Nx is the refractive index in the in-plane slow axis direction of the stretched cellulose ester film, and Ny is the in-plane. The refractive index in the direction orthogonal to Nx, Nz the refractive index in the film thickness direction, and d the thickness (nm) of the stretched cellulose ester film.

(Change in Retardation Value with Time) Stretched Cellulose Ester Film A to
Regarding L, each sample was wrapped in a polyethylene sheet to prevent dust adhesion, and then stored in a warehouse at 35 ° C. and 80% RH for 1 month, and the retardation value R ₀₁ was measured in the same manner as above. Expressed as a difference.

Change with time of retardation value of film = (R ₀₁ −
R ₀ ) (Evaluation of deterioration of winding shape = Evaluation of storability) With respect to the stretched cellulose ester films A to L produced as described above, each sample was wrapped with a polyethylene sheet to prevent dust from adhering, and then at 35 ° C. and 80 ° C. It was stored in a warehouse of% RH for 1 month, the state of winding after 1 month was visually observed, and the rank was evaluated as follows.

⊚: No changes such as wrinkles and deformation are observed on the roll surface. ○: Slight wrinkles are observed on the roll surface, but no deformation is observed. Δ: Weak wrinkles are observed on the roll surface. Deformation is also recognized in part: strong wrinkles on the surface to the inside of the roll, strong deformation on the surface, and deformation to the inside. The practicality judgment for the above ranks is as follows.

⊚: Can be used without cutting, ◯: Can be used by cutting several meters, Δ: Can be used by cutting several turns (several meters to several tens of meters) from the surface, ×: Deformation of winding Until it disappears (100
It cannot be used unless it is removed up to m or more).

<Average Particle Size of Secondary Particles> Ten tomographic photographs in the thickness direction of each stretched cellulose ester film were taken at random, and 10 μm from the surface of each tomographic photograph was taken.
The particle size of fine particles in a cross-sectional area of 1000 μm ² at a position within m was measured and calculated as the average value of the fine particle sizes at 10 points. As a result, in all cases, the average particle size is 0.2 to 0.3 μ.
It had m secondary particles.

<Additive Concentration Ratio> The total average content (Y) of the additives in the solid content contained in the cellulose ester solution (the average content of the additives in the stretched film) was calculated and included in the additive solution. The total content (Z) of the additives contained in the solid content other than the fine particles (content of the additives near the secondary particles) was calculated, and this ratio was defined as the additive concentration ratio (Z / Y). The results are shown below.

Further, when the stretched film C was compared with the peak intensity of the phosphorus atom in the vicinity of the secondary particles in the film by using an electron microanalyzer, and the peak intensity in the portion away from the particles, The additive concentration is 1.
It was confirmed to be 1 times or more.

[0280]

[Table 12]

Example 2 << Preparation of Elliptical Polarizing Plate and Liquid Crystal Display >> (Preparation of Elliptical Polarizing Plate) (a) Preparation of Polarizing Film A polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretching ratio: 5). Doubled). This was dipped in an aqueous solution containing 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then dipped in an aqueous solution of 68 ° C. containing 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. . This was washed with water and dried to obtain a polarizing film.

Then, in accordance with the following steps 1 to 5, the stretched cellulose ester film of the present invention was used as a polarizing plate protective film, and the above polarizing film and another cellulose ester film B (polarizing plate protective film) as Konikacak ( KC8UX2MW manufactured by Konica Co., Ltd. was attached to produce an elliptically polarizing plate.

(B) Preparation of elliptically polarizing plate A Step 1: The stretched cellulose ester film and another cellulose ester film B are dipped in a 2 mol / L sodium hydroxide solution at 50 ° C. for 90 seconds, washed with water and dried. A saponified cellulose ester film was obtained. Step 2: The polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds. Step 3: Excessive amount of the polarizing film adhered to the polarizing film in step 2. The adhesive was lightly wiped off, placed on the cellulose ester film treated in step 1, and arranged so that the absorption axis of the polarizing film and the slow axis of the stretched cellulose ester film were orthogonal to each other. Step 4: Hand roller In step 3, the cellulose ester film B laminated in step 3, the laminate of the polarizing film and the stretched cellulose ester film A from the end of the excess adhesive agent It was adhered to remove the air bubbles. The pressure of the hand roller is 20-30
N / cm ² , the roller speed was about 2 m / min. Step 5: A sample in which the polarizing film and the polarizing plate protective film laminated in Step 4 were laminated in a dryer at 80 ° C. for 2 minutes, An elliptically polarizing plate A was produced.

As in the preparation of the elliptically polarizing plate A, other B
Elliptic polarizing plates B to L were produced using the stretched cellulose ester films of L to L.

(Manufacturing Method of Liquid Crystal Display Device) Commercially available liquid crystal display device (manufactured by NEC Mitsubishi Electric Visual System Co., Ltd.,
Color LCD monitor RDT151M Model name LXA576
The polarizing plates on both sides of W) are carefully peeled off, and the elliptically polarizing plates A to L prepared above, which are aligned in the polarization direction, are attached so that the stretched cellulose ester film is on the liquid crystal cell side to prepare each liquid crystal display device. did.

(Measurement of Left and Right Viewing Angle) The viewing angle was measured by using the liquid crystal display device obtained above by EZ-manufactured by ELDIM.
The viewing angle in the left-right direction was measured using contrast. As the evaluation of the viewing angle, the contrast ratio at the time of white display and black display of the liquid crystal display device was 10 or more, and the range of the tilt angle from the normal direction to the display surface showing the region where the inversion occurred was expressed.

(Evaluation of Visibility) Each of the liquid crystal display devices obtained above was placed on a desk having a height of 80 cm from the floor, and a daylight straight tube fluorescent lamp ( FLR4
0S ・ D / M-X Matsushita Electric Industrial Co., Ltd.) 40W × 2
Four sets are arranged with one set of books, and under this illumination, the liquid crystal display screen is visually observed from a direction of 80 ° to the normal line of the liquid crystal display screen, and evaluated according to the following criteria. The average of 5 evaluations was shown.

⊚: There is no gradation reversal even when viewed from the horizontal 80 ° direction, and black is seen and the image is extremely clear. ○: No gradation reversal is observed when viewed from the horizontal 80 ° direction, and black Appears to be visible △: There is no gradation reversal when viewed from the horizontal 80 ° direction, but black is not visible and the image cannot be clearly seen ×: The gradation is reversed when viewed from the lateral 80 ° direction And, I can't stand watching it from an angle.

The results of the above evaluations are shown below.

[0290]

[Table 13]

As is clear from the above results, the liquid crystal display device using the elliptically polarizing plate of the present invention has better visibility and viewing angle characteristics than the liquid crystal display device using the comparative elliptically polarizing plate. It can be seen that the characteristics are also excellent.

For each liquid crystal display device,
The contrast was visually evaluated. As a result, it was confirmed that the liquid crystal display device using the elliptically polarizing plate of the present invention maintained a high contrast over a long period of time as compared with the liquid crystal display device using the elliptically polarizing plate of the comparative example.

Example 3 [Preparation of Stretched Cellulose Ester Film] <Preparation of Dope M> (See Table 14) (Preparation of Silicon Oxide Fine Particle Dispersion) Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd., average particle diameter of primary particles) 16 nm) 1 kg Ethanol 9 kg or more was stirred and mixed with a dissolver for 40 minutes, and then dispersed using a Manton-Gaulin type high-pressure disperser to prepare a silicon oxide fine particle dispersion.

(Preparation of Fine Particle Dispersion M) Methyl acetate 90 kg Ethanol 20 kg Cellulose acetate propionate 5 kg (Acetyl group substitution degree 1.9, Propionyl group substitution degree 0.8) Triphenyl phosphate 2 kg Biphenyldiphenyl phosphate 1 kg or more is sealed. It was put into a container, completely dissolved while heating and stirring, and filtered. To this, 10 kg of the above-mentioned silicon oxide fine particle dispersion was added with stirring, stirred for 30 minutes, and then filtered to prepare a fine particle dispersion M.

(Preparation of Cellulose Ester Solution M) (See Table 14) Methyl acetate 300 kg Ethanol 100 kg Cellulose acetate propionate 100 kg (Acetyl group substitution degree 1.9, Propionyl group substitution degree 0.8) Triphenyl phosphate 9 kg Biphenyldiphenyl Phosphate 3 kg Tinuvin 109 0.7 kg Tinuvin 171 0.7 kg The above solvent was charged into a closed container, the remaining materials were sequentially charged with stirring, and the mixture was heated to 70 ° C. and completely dissolved with stirring to mix them. The solution was cooled to a temperature at which it was cast, allowed to stand overnight, and subjected to a defoaming operation. Then, the solution was placed in Azumi Filter Paper No. No. manufactured by Azumi Filter Paper Co., Ltd. Filtered using 244.

The fine particle dispersion M is fed to the cellulose ester solution M through separate pipes to obtain the cellulose ester solution M.
The in-line mixer (Toray Co., Ltd. static in-tube mixer Hi-M) was used at a ratio of 100 kg of the fine particle dispersion M to 3 kg.
mixer, SWJ) and filtered to obtain dope M. This was immediately sent to a die and cast on a support.

The dope M whose temperature was adjusted to 60 ° C. was introduced into the die, and the dope was uniformly cast on the endless stainless belt (support) through the die slit. The casting portion of the endless stainless belt was heated from the back surface with hot water at 60 ° C.

After casting, the dope film on the support (hereinafter referred to as a web after casting on a stainless steel belt) has a temperature of 80 ° C.
Hot air to dry and remove residual solvent amount 80% by mass
Was peeled off and dried while being conveyed by a large number of rolls.

The temperature of the endless stainless belt at the peeling section was set to 11 ° C. The peeled web is conveyed through the first drying zone set at 70 ° C for 1 minute, then at the inlet of the second drying zone, the temperature is set to 90 ° C and the end of the web is gripped by a tenter, and the width direction is kept at a predetermined temperature. Was stretched to a predetermined draw ratio. After stretching, hold the width for a few seconds, release the width hold, and then carry it for 30 minutes in the third drying zone set at 125 ° C to dry it, and to lift it at both ends of the width. 80μ film thickness with knurling of 12μm
m stretched cellulose ester film 3-1 was obtained. Stretched cellulose ester film 3-2 to 3 in the same manner except that the stretching temperature and the stretching ratio are changed as shown in Table 19.
Got 5.

Comparative stretched cellulose ester films 3-12 and 3-13 were obtained in the same manner except that the following dope Q was used in place of the dope M.

The dope Q was prepared by mixing 100 kg of the cellulose ester solution Q shown in Table 18 below and 3 kg of the fine particle dispersion Q in an in-line mixer (Toray Co., Ltd. static in-tube mixer Hi-Mixer, SWJ) and filtering. I got it. This was immediately sent to a die and cast on a support.

Using doped N, doped O, and doped P,
A laminated cellulose ester film was obtained by a co-casting method using the apparatus shown in FIG. The dry film thickness of the surface layer (skin layer) formed of dope O or dope P was 8 μm.

Dope N and dope O, the temperature of which was adjusted to 60 ° C., were introduced into the die, and the dope was uniformly cast on the endless stainless belt (support) through the die slit. The ratio of each dope is as follows: skin layer (using dope O, 8μ after drying)
m) / core layer (using dope N, 64 μm after drying) / skin layer (using dope O, 8 μm after drying) and cast. The casting portion of the endless stainless belt was heated from the back surface with hot water at 60 ° C.

After casting, the dope film on the support (hereinafter referred to as a web after casting on a stainless steel belt) has a temperature of 80 ° C.
Hot air to dry and remove residual solvent amount 80% by mass
Was peeled off and dried while being conveyed by a large number of rolls.

The temperature of the endless stainless belt at the peeling portion was 11 ° C. The peeled web is conveyed through the first drying zone set at 70 ° C for 1 minute, then at the inlet of the second drying zone, the temperature is set to 90 ° C and the end of the web is gripped by a tenter, and the width direction is kept at a predetermined temperature. Was stretched to a predetermined draw ratio. After stretching, hold the width for a few seconds while maintaining the width, then release the width hold and carry it in the third drying zone set at 125 ° C for 30 minutes to dry it, and to lift it at both ends of the width. 80μ film thickness with knurling of 12μm
m stretched cellulose ester film 3-6 was obtained. Stretched cellulose ester films 3-7 to 3-3 in the same manner except that the stretching temperature and the stretching ratio were changed as shown in Table 19.
Got 9. A stretched cellulose ester film 3-10 was obtained in the same manner except that the dope O was changed to the dope P. Stretching was performed in the same manner except that the skin layer (using dope O, 8 μm after drying) / core layer (using dope N, 64 μm after drying) / skin layer (using dope N, 8 μm after drying) was prepared and cast. The cellulose ester film 3-11 was obtained. Obtained stretched cellulose ester film 3-1
As a result of confirming the particle diameters of the secondary particles in the same manner as in Example 1, the average particle diameters of 0.2 to 0.3
It had secondary particles of μm.

[0306]

[Table 14]

[0307]

[Table 15]

[0308]

[Table 16]

[0309]

[Table 17]

[0310]

[Table 18]

[0311]

[Table 19]

The stretched cellulose ester film is 3-6.
3-11 were produced by the co-casting method. Y and Z were determined for the cellulose ester layer on the surface formed of dope O or dope P to which fine particles were added.

Evaluations were made in the same manner as in Example 1, and the results shown in Table 20 below were obtained.

[0314]

[Table 20]

As can be seen from Table 20, the stretched cellulose ester film of the present invention has extremely low haze, little variation in retardation with time, and little deterioration in winding shape.

The haze was remarkably reduced by using a non-chlorine solvent. Further, using this stretched cellulose ester film, a polarizing plate was prepared in the same manner as in Example 2. The polarizing plate of a commercially available liquid crystal display device was peeled off, and polarizing plates with their polarization axes aligned were attached to each other, and the visibility was evaluated. The evaluation criteria were in accordance with the visibility evaluation of Example 2. As a result, it was confirmed that the visibility of the liquid crystal display device was remarkably improved by using the polarizing plate using the stretched cellulose ester film of the present invention.

[0317]

As demonstrated in the examples, according to the present invention,
Stretched cellulose ester film and its manufacturing method, elliptically polarizing plate and display device using the stretched cellulose ester film improved visibility and viewing angle even when the cellulose ester film is stretched at a high magnification, haze is small, and, Further, the cost of the polarizing plate protective film can be reduced, and the film has an excellent effect.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of the vicinity of secondary particles of the present invention.

FIG. 2 is a process drawing showing an example of an apparatus for producing a cellulose ester laminated film of the present invention.

FIG. 3 shows a sectional view of a slit die.

[Explanation of symbols]

1 Dope liquid tank 1a Dope solution 2 Fine particle additive liquid tank 3 UV absorber additive liquid tank 4b, 4c Liquid feed pump 5a, 5b In-line mixer 6 slit die 7 drums 8 casting belt 9 Laura 10 Cellulose ester laminated film 11 casting mouth 12, 13 slits

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // B29K 1:00 B29K 1:00 B29L 7:00 B29L 7:00 F term (reference) 2H091 FA08X FA08Z FB02 FC07 GA16 LA12 LA16 4F071 AA09 AB26 AD02 AE17 AF30 AF35 AH12 BA02 BB02 BB07 BB08 BC02 4F210 AA01 AB07 AB24 AG01 AH73 QA02 QC03 QD01 QG01 QG18 QW17 4J002 AB021 DJ016 FD016 GP00

Claims (16)

[Claims] 1. A stretched cellulose ester film having secondary particles having an average particle size of 0.1 to 5 μm containing primary fine particles having an average particle size of 0.001 or more and less than 0.1 μm,
A stretched cellulose ester film, wherein the content of the additive in the vicinity of the secondary particles is higher than the average content of the additive in the stretched cellulose ester film. 2. The stretched cellulose ester film according to claim 1, wherein the average content of the additive in the stretched cellulose ester film is 3 to 30%. 3. The stretched cellulose ester film according to claim 1, wherein at least one of the additives is an additive having three or more aromatic rings or cycloalkyl rings in the molecule. 4. The stretched cellulose ester film according to claim 1, which is stretched by 1.15 to 2 times in at least one direction. 5. The in-plane retardation R ₀ is 30 to 20.
The retardation R _t in the film thickness direction is 80 to 30 at 0 nm.
It is 0 nm, Any one of Claims 1-4 characterized by the above-mentioned.
The stretched cellulose ester film according to the item. 6. The content of the additive in the vicinity of the secondary particles is 1. The average content of the additive in the stretched cellulose ester film is 1.
The stretched cellulose ester film according to claim 1, wherein the stretched cellulose ester film is at least 1 time. 7. A dope solution prepared by mixing a cellulose ester solution obtained by dissolving cellulose ester in an organic solvent with a fine particle dispersion containing an additive is cast on a support, peeled, and then containing a solvent. Web to 1.15-2
A method for producing a stretched cellulose ester film, which comprises double stretching. 8. The method for producing a stretched cellulose ester film according to claim 7, wherein the content of the additive contained in the fine particle dispersion is higher than the content of the additive contained in the cellulose ester solution. 9. The stretched cellulose ester film according to claim 7, wherein the fine particle dispersion is mixed inline with a cellulose ester solution, and the obtained dope solution is cast on a support. Production method. 10. A stretched cellulose ester film produced by the method for producing a stretched cellulose ester film according to any one of claims 7 to 9. 11. An elliptically polarizing plate comprising the stretched cellulose ester film according to any one of claims 1 to 6. 12. A display device comprising the stretched cellulose ester film according to any one of claims 1 to 6. 13. The average particle size is 0.001 or more and 0.1 μm.
In the method for producing a stretched cellulose ester film having a cellulose ester layer having secondary particles having an average particle size of 0.1 to 5 μm containing primary fine particles of less than 1%, the average content of the additive of the cellulose ester layer is more than A method for producing a stretched cellulose ester film, which comprises stretching a web in a state where a content of an additive near a secondary particle is large. 14. The method for producing a stretched cellulose ester film according to claim 13, wherein at least one of the additives is a plasticizer. 15. The method for producing a stretched cellulose ester film according to claim 13, wherein the web having the cellulose ester layer formed by co-casting is stretched. 16. The method for producing a stretched cellulose ester film according to claim 13, wherein the cellulose ester layer is formed of a dope containing substantially no chlorine-based solvent.