KR102085413B1 - Long optical film, its manufacturing method, polarizing plate and display device - Google Patents

Abstract

(1)
(식 중, X는 헤테로 원자 또는 탄소 원자를 나타낸다. Q는 질소 원자 및 X와 함께 방향족 헤테로환을 형성하는 데 필요한 원자군을 나타낸다. R₁ 내지 R₄는, 각각 수소 원자 또는 치환기를 나타낸다.)An object of the present invention is a long optical film containing a cycloolefin resin and a retardation increasing agent and elongated to have a slow axis inclined with respect to the longitudinal direction, to reduce retardation unevenness in the width direction and to improve appearance (wrinkling and sagging). It is to provide a good long optical film. The long optical film of this invention is a long optical film containing a cycloolefin resin and a retardation increasing agent, and the slow axis of an in-plane direction inclined in the range of 45 +/- 10 degrees with respect to a longitudinal direction, The following general formula ( It is characterized by containing the compound which has a structure represented by 1).

(One)
(Wherein X represents a hetero atom or a carbon atom. Q represents a group of atoms necessary to form an aromatic heterocycle together with a nitrogen atom and X. R ₁ to R ₄ each represent a hydrogen atom or a substituent). )

Description

Long optical film, its manufacturing method, polarizing plate and display device

This invention relates to a long optical film, its manufacturing method, a polarizing plate, and a display apparatus. More specifically, this invention is an elongate optical film extended | stretched so that it might have the slow axis inclined with respect to the longitudinal direction, and it is related with the elongate optical film which reduces the phase difference nonuniformity of the width direction, and is favorable in appearance (wrinkle, sagging).

The manufacturing method of extending | stretching the film containing cycloolefin resin in diagonal direction so that it may have a slow axis inclined with respect to the longitudinal direction is disclosed (for example, refer patent document 1).

On the other hand, in recent years, although the film used for the liquid crystal display device is required to be thinned, compared to the melt casting film forming method, the solution casting film forming method can give a function especially by adding an additive as a film forming method of a film, Especially Suitable for thinning

However, when adding a retardation increasing agent to a cycloolefin resin and manufacturing a thin film which has a slow axis in diagonal direction, it formed into a film by the said solution casting film forming method, and extended | stretched in the diagonal direction, As a result, the phase difference nonuniformity of the width direction It was found that appearance defects such as wrinkles and sagging of the film occurred.

Japanese Patent Publication No. 2014-38357

This invention is made | formed in view of the said problem and the situation, The solving subject is the elongate optical film which contains a cycloolefin resin and a retardation increasing agent, and extended | stretched so that it might have a slow axis inclined with respect to the longitudinal direction, and the phase difference of the width direction It is to provide a long optical film, a method of manufacturing the same, a polarizing plate, and a display device having good unevenness and good appearance (wrinkling and sagging).

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, this inventor contains a cycloolefin resin and a retardation synergist in the process of examining the cause of the said problem, and the slow axis of in-plane direction is 45 +/- 10 degree with respect to a longitudinal direction. When the elongate optical film inclined inside contains the compound which has a specific structure, it discovered that the retardation unevenness of the width direction was reduced, and the long optical film with favorable external appearance (wrinkle, sagging) was obtained.

That is, the said subject which concerns on this invention is solved by the following means.

1. A long optical film containing a cycloolefin resin and a retardation increasing agent and having a slow axis in the in-plane direction inclined within a range of 45 ± 10 ° with respect to the longitudinal direction, represented by the following general formula (1) A long optical film containing a compound having a compound.

(Wherein X represents a hetero atom or a carbon atom. Q represents a group of atoms necessary to form an aromatic heterocycle together with a nitrogen atom and X. R ₁ to R ₄ each represent a hydrogen atom or a substituent). )

2. The long optical film according to item 1, wherein the film thickness is 25 µm or less.

3. A dope containing a cycloolefin resin, a retardation increasing agent, and a compound having a structure represented by the following general formula (1) is produced, and formed into a film by the solution casting film forming method using the dope. It diagonally stretches in the direction within the range of 45 +/- 10 degrees, and adjusts the difference of the maximum value and minimum value of the variation of the retardation value Ro of the width direction in the range of 0-4 nm, The manufacturing method of the long optical film characterized by the above-mentioned.

(Wherein X represents a hetero atom or a carbon atom. Q represents a group of atoms necessary to form an aromatic heterocycle together with a nitrogen atom and X. R ₁ to R ₄ each represent a hydrogen atom or a substituent). )

4. The optical film obtained from the elongate optical film of Claim 1 or 2 is provided. The polarizing plate characterized by the above-mentioned.

5. Display apparatus characterized by including optical film obtained from elongate optical film of claim 1 or 2.

By the said means of this invention, it is a long optical film containing a cycloolefin resin and a retardation raise agent, and extended | stretched so that it might have a slow axis inclined with respect to the longitudinal direction, and reduces the phase difference nonuniformity of the width direction, and looks (wrinkles, sags). ) Can provide a good long optical film.

Although it is not clear about the expression mechanism or action mechanism of the effect of this invention, it estimates as follows.

In the diagonal stretch process, fluctuations tend to occur in the temperature applied to the right end and left end of the film. Therefore, a difference also arises in the film temperature at the time of conveyance, and since the orientation degree of resin in the film at the time of extending | stretching differs in the width direction, it is estimated that phase difference nonuniformity tends to occur.

In particular, since the cycloolefin resin has little interaction between resins represented by hydrogen bonds due to its molecular structure, energy applied by heat tends to be used for the movement of the resin.

Therefore, in the expression of the phase difference which is considered to be due to the ease of movement of resin, it has the characteristic that the sensitivity with respect to temperature is high, and it is thought that phase difference nonuniformity tends to arise by the temperature fluctuation at the time of diagonal stretch.

Since the retardation increasing agent increases the in-plane retardation Ro in the unstretched state, it is possible to increase Ro after stretching the film, but it does not change the sensitivity to the temperature of the resin.

On the other hand, since the compound which has a structure represented by the said General formula (1) which has a hydroxyl group in the vicinity of a nitrogen atom forms interaction with cycloolefin resin by the oxygen atom of the said hydroxyl group, or it is easy to penetrate between resins, Energy by heat is used to solve the interaction formed between the resin or between the resin and the compound having the structure represented by the general formula (1), or the molecular motion of the compound having the structure represented by the general formula (1). By the buffering effect of the said compound, it is estimated that there exists an effect which reduces the temperature sensitivity at the time of phase difference expression of resin.

For this reason, fluctuation | variation in retardation expression is suppressed, and it is estimated that phase difference nonuniformity at the time of finishing after diagonal stretch becomes small.

Moreover, in diagonal stretch, shrinkage force is added to the longitudinal direction of a film by conveying on the thing with a speed difference in the left and right of a film, or conveying on the curved rail. At that time, when the shrinkage amount of the film is smaller than the shrinkage amount applied thereto, wrinkles and sagging occur on the film, which results in poor appearance. By containing the compound which has a structure represented by the said General formula (1) this time, since shrinkage amount of a film became large, it is estimated that generation | occurrence | production of wrinkles and sagging was able to be suppressed.

1 is a schematic view showing an example of a rail pattern of an inclined stretching machine applicable to the method for producing an optical film of the present invention.
It is a schematic diagram which shows an example (example which diagonally stretches after drawing out from a long film original fabric roll) of the manufacturing method which concerns on embodiment of this invention.
It is a schematic diagram which shows an example (example which diagonally stretches after feeding out from a long film original fabric roll) of the manufacturing method which concerns on embodiment of this invention.
It is a schematic diagram which shows an example (example which diagonally stretches after feeding out from a long film original fabric roll) of the manufacturing method which concerns on embodiment of this invention.
It is a schematic diagram which shows an example (example which diagonally stretches continuously, without winding a long film original fabric) of the manufacturing method which concerns on embodiment of this invention.
It is a schematic diagram which shows an example (example which diagonally stretches continuously, without winding a long film original fabric) of the manufacturing method which concerns on embodiment of this invention.
4 is a schematic cross-sectional view showing an example of the configuration of the display device of the present invention.

The long optical film of the present invention is a long optical film containing a cycloolefin resin and a retardation increasing agent, wherein the slow axis in the in-plane direction is inclined within a range of 45 ± 10 ° with respect to the longitudinal direction. It is characterized by containing the compound which has a structure represented by 1). This feature is a technical feature common to the invention of each claim.

As embodiment of this invention, in the thin film film whose film thickness of the said long optical film is 25 micrometers or less from a viewpoint of the effect expression of this invention, the expression of the effect is high and it is preferable.

The manufacturing method of the elongate optical film of this invention produces the dope containing a cycloolefin resin, a retardation increasing agent, and the said specific compound, and after forming into a film by the solution casting film forming method using the said dope, about the longitudinal direction It is preferable to diagonally stretch in the direction of 45 +/- 10 degrees, and to adjust the difference of the maximum value and minimum value of the variation of the retardation value Ro of the width direction in the range of 0-4 nm.

The optical film obtained from the elongate optical film of this invention is comprised suitably for display apparatuses, such as a polarizing plate, a liquid crystal display device, and an organic electroluminescent display device.

EMBODIMENT OF THE INVENTION Hereinafter, the form and aspect for implementing this invention, its component, and this invention are demonstrated in detail. In addition, in this application, "-" uses the numerical value described before and after that by the meaning included as a lower limit and an upper limit.

≪Summary of the long optical film of this invention≫

The long optical film of this invention contains a cycloolefin resin and a retardation increasing agent, and is a long optical film in which the slow axis of an in-plane direction inclines within the range of 45 +/- 10 degrees with respect to a longitudinal direction, Comprising: It is characterized by containing the compound which has a structure represented by 1).

Moreover, the manufacturing method of the elongate optical film of this invention produces the dope containing a cycloolefin resin, a retardation increasing agent, and the compound which has a structure represented by the said General formula (1), and uses the said dope to cast solution After film formation by the film forming method, the film is diagonally stretched in the direction of 45 ± 10 ° with respect to the longitudinal direction, and the difference between the maximum value and the minimum value of the variation of the retardation value Ro in the width direction is adjusted within the range of 0 to 4 nm. It features. The long optical film manufactured in this way can produce a long circularly polarizing plate by bonding so that a long polarizer may be made to match a longitudinal direction, and the said circularly polarizing plate is antireflection, for example as a polarizing plate of an organic electroluminescent display device. It is useful as a circularly polarizing plate with reduced sex and color unevenness.

The "long optical film" used in the present invention refers to a film having a wound length of 100 m or more, preferably 500 m or more, more preferably 1000 m or more, still more preferably 3000 m or more, and particularly preferably 5000 m or more.

Hereinafter, the component of this invention is demonstrated in detail.

[1] a compound having a structure represented by General Formula (1)

In the long optical film (henceforth an "optical film") of this invention, it is an elongate optical film extended | stretched so as to have the slow axis inclined with respect to the longitudinal direction, and reduces the phase difference nonuniformity of the width direction, and looks (wrinkles, sags). In order to provide this favorable long optical film, the compound which has a structure represented by following General formula (1) is contained.

(Wherein X represents a hetero atom or a carbon atom. Q represents a group of atoms necessary to form an aromatic heterocycle together with a nitrogen atom and X. R ₁ to R ₄ each represent a hydrogen atom or a substituent). )

X represents a hetero atom or a carbon atom, Q represents the atom group required to form an aromatic hetero ring with a nitrogen atom and X, and the said aromatic hetero ring may have a substituent.

An aromatic heterocyclic ring is generally an unsaturated heterocyclic ring, Preferably it is a heterocyclic ring which has the largest double bond. It is preferable that a hetero ring is a 5-membered ring, a 6-membered ring, or a 7-membered ring, and it is more preferable that it is a 5- or 6-membered ring. It is preferable that the hetero atom of a hetero ring is N, S, or O, and it is especially preferable that it is N. As a hetero ring which has aromaticity, it is preferable that they are a pyrrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring, and a 1,3,5-triazine ring. Especially, it is preferable that they are a 1,2,3-triazole ring, a 1,2,4-triazole ring, and a 1,3,5-triazine ring.

The heterocyclic group may have a substituent, and when two or more exist, may be same or different, and may form a ring. The following can be applied as an example of the substituent of R <_1> -R <_4> and the substituent of the said heterocyclic group.

Halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, e.g. methyl group, ethyl group, n-propyl group, isopropyl group, tert- Butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group (preferably a C3-C30 substituted or unsubstituted cycloalkyl group, for example, cyclohexyl group, cyclopentyl group, 4-n- Dodecylcyclohexyl group) and a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms). For example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octan-3-yl), alkenyl group (preferably substituted or unsubstituted with 2 to 30 carbon atoms) Ring alkenyl groups such as vinyl and aryl groups, cycloalkenyl groups (preferably, having from 3 to 30 carbon atoms) Or an unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl and 2-cyclohexen-1-yl group. ), A bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a hydrogen atom of bicycloalkene having one double bond) A monovalent group which has been removed, for example, a bicyclo [2,2,1] hept-2-en-1-yl group, a bicyclo [2,2,2] oct-2-en-4-yl group), An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, an ethynyl group, a propargyl group), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, For example, a phenyl group, p-tolyl group, naphthyl group), heterocyclic group (preferably a 5 or 6 membered substituted or unsubstituted, aromatic or non-aromatic) It is a monovalent group which removed one hydrogen atom from the heterocyclic compound of, More preferably, it is a 5- or 6-membered aromatic heterocyclic group of C3-C30. For example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group (preferably, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy group, Ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group), aryloxy group (preferably substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, For example, phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylamino phenoxy group, silyloxy group (preferably, C3-C20 silyl) Oxy group, for example trimethylsilyloxy group, tert-butyldimethylsilyloxy group), heterocycle Oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 1 to 30 carbon atoms, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyl jade) A time period, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, a formyloxy group, an acetyloxy group, a pivaloyloxy group, Stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example N, N -Dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group), alkoxy Carbonyloxy group (preferably substituted or unsubstituted with 2 to 30 carbon atoms Cooxycarbonyloxy group, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n-octylcarbonyloxy group, aryloxycarbonyloxy group (preferably Is a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, a phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group), Amino group (preferably, amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alino group having 6 to 30 carbon atoms, for example, amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms) Carr Nylamino group, for example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group), aminocarbonylamino group (preferably, substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms) For example, carbamoylamino group, N, N- dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group, alkoxycarbonylamino group (preferably C2-C30) Substituted or unsubstituted alkoxycarbonylamino group, for example, methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbon Carbonylamino group), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxy) A carbonylamino group, a p-chlorophenoxycarbonylamino group, a mn-octyloxyphenoxycarbonylamino group), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example sulfa A monoamino group, N, N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group), alkyl and arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, 6 to 6 carbon atoms) A substituted or unsubstituted arylsulfonylamino group of 30, for example, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group) , Mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example methylthio group, ethylthio group, n-hexadecylthio group), arylthio group (preferably Crab is substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group, heterocyclic thio group (preferably 2 to 30 carbon atoms) Substituted or unsubstituted heterocyclic thio group, for example, 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group, sulfamoyl group (preferably substituted or unsubstituted from 0 to 30 carbon atoms) Sulfamoyl groups, for example N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group , N- (N'phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 30) Substituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and aryl Sulfonyl groups (preferably, substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30, such as methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p -Methylphenylsulfonyl group), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, for example, acetyl group, pivaloyl) Benzoyl group), aryloxycarbonyl group (preferably substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, p-tert -Butylphenoxycarbonyl group), alkoxycarbonyl group (preferably substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxide) Carbonyl group, n-octadecyloxycarbonyl group, carbamoyl group (preferably, substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example carbamoyl group, N-methylcarbamoyl group, N, N- Dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group), aryl and heterocyclic azo groups (preferably substituted or unsubstituted aryl having 6 to 30 carbon atoms) Azo groups, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), and A rare group (preferably, N-succinimide group, N-phthalimide group), phosphino group (preferably, a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino group) , Diphenylphosphino group, methylphenoxyphosphino group, phosphinyl group (preferably substituted with 2 to 30 carbon atoms, Unsubstituted phosphinyl groups, for example phosphinyl groups, dioctyloxyphosphinyl groups, diethoxy phosphinyl groups, phosphinyloxy groups (preferably substituted or unsubstituted phosphinyl jade having 2 to 30 carbon atoms) Period, for example, diphenoxyphosphinyloxy group, dioxyphosphinyloxy group, phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino group) , Dimethylaminophosphinylamino group), silyl group (preferably, a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example trimethylsilyl group, tert-butyldimethylsilyl group, phenyldimethylsilyl group) have.

It is preferable that the said heterocyclic ring is a 1,2,3-triazole ring, and, as for the compound which has a structure represented by General formula (1), it is preferable that it is a benzotriazole type compound represented by the following general formula (2).

In the formula, G ₁ represents a hydrogen atom. G ₂ represents a hydrogen atom, a cyano group, a chlorine atom, a fluorine atom, a -CF ₃ group, a -CO-G ₃ group, an E ₃ SO- group, or an E ₃ SO ₂ -group.

G ₃ is a straight or branched chain alkyl group having 1 to 24 carbon atoms, a straight or branched chain alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and a 7 to 15 carbon atoms The phenyl group or the phenylalkyl group in which the phenyl ring is substituted by 1 to 4 carbon atoms in the phenylalkyl group, the phenyl group or the alkyl group having 1 to 4 carbon atoms.

E ₁ represents the phenyl group or the phenylalkyl group in which a phenyl ring is substituted by 1 to 4 carbon atoms having 7 to 15 carbon atoms, a phenyl group or an alkyl group having 1 to 4 carbon atoms.

E ₂ is a straight or branched chain alkyl group having 1 to 24 carbon atoms, a straight or branched chain alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and a 7 to 15 carbon atoms The phenyl group or the phenylalkyl group in which the phenyl ring is substituted by 1 to 3 carbon atoms in the phenylalkyl group, the phenyl group or the alkyl group having 1 to 4 carbon atoms.

Or E ₂ is one or more -OH groups, -OCOE ₁₁ groups, -OE ₄ groups, -NCO groups, -NH ₂ groups, -NHCOE ₁₁ groups, -NHE ₄ groups or -N (E ₄ ) ₂ groups Or an alkyl group having 1 to 24 carbon atoms or 2 to 18 carbon atoms substituted by a mixture thereof (wherein, E ₄ represents a linear or branched alkyl group having 1 to 24 carbon atoms). The alkenyl group; Or interrupted by one or more -O- groups, -NH- groups or -NE ₄ -groups, or mixtures thereof, and unsubstituted or one or more -OH groups, -OE ₄ groups or- The alkyl group or the alkenyl group which may be substituted by an NH ₂ group, or a mixture thereof.

E ₁₁ is a hydrogen atom, a linear or branched alkylene group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a straight or branched alkenyl group having 2 to 18 carbon atoms, or a carbon atom An aryl group having 6 to 14 or an aralkyl group having 7 to 15 carbon atoms.

E ₃ is an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and having 7 to 15 carbon atoms. The aryl group substituted by one or two phenylalkyl groups, aryl groups having 6 to 10 carbon atoms, or alkyl groups having 1 to 4 carbon atoms, or 1,1,2,2-tetrahydroperfluoroalkyl groups (The perfluoroalkyl moiety of this group contains 6 to 16 carbon atoms), or general formula (2), wherein G ₁ represents a hydrogen atom, and G ₂ Represents a chlorine atom, a fluorine atom, a -CF ₃ group, an E ₃ SO- group or an E ₃ SO ₂ -group, E ₁ represents a hydrogen atom or a linear or branched alkyl group having 1 to 24 carbon atoms, E ₂ have the same meanings as defined in the above, and E ₃ is a carbon atom in 1 A compound represented by a straight or branched chain alkyl group of 7.

Hereinafter, although the specific example of the preferable benzotriazole type compound of this invention is shown to the following exemplary compounds 1-6, it is not limited to this.

Moreover, it is preferable that the said heterocyclic ring is a compound which has a structure represented by General formula (1) which concerns on this invention, and a preferable compound is the following General formula (3) It is a compound represented by.

In the formula, R ¹ is a straight or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, and carbon Or an alkylaryl group having 7 to 18 atoms or an arylalkyl group having 7 to 18 carbon atoms. However, these alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkylaryl groups or arylalkyl groups may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, It may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group. In addition, said substitution and interruption may be combined. R ² represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 3 to 8 carbon atoms, R ³ represents at least one hydroxy group and a hydrogen atom when not a hydroxy group, and R ⁴ represents hydrogen An atom or -OR ¹ ;

Examples of the linear or branched alkyl group having 1 to 12 carbon atoms represented by R ¹ of the general formula (3) according to the present invention include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, Straight or branched chains such as tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl And an alkyl group.

Examples of the cycloalkyl group having 3 to 8 carbon atoms represented by R ¹ in General Formula (3) include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and the like.

Examples of the aryl group having 6 to 18 carbon atoms or the alkylaryl group having 7 to 18 carbon atoms represented by R ¹ in General Formula (3) include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tertbutylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-dizetertbutylphenyl, 2,5-dizetertbutylphenyl, 2,6-di-tertbutylphenyl, 2,4-diesetpentylphenyl, 2,5-digeze And triamyl phenyl, 2,5-dithioctylphenyl, biphenyl, 2,4,5-trimethylphenyl, and the like. Examples of the arylalkyl group having 7 to 18 carbon atoms include benzyl, phenethyl, and 2-phenyl. Propan-2-yl, diphenylmethyl, etc. are mentioned.

In the general formula (3), examples of the alkenyl group having 3 to 8 carbon atoms represented by R ¹ and R ² include, for example, linear and branched propenyl, butenyl, pentenyl, hexenyl, heptenyl, Octenyl is exemplified regardless of the position of the unsaturated bond.

In the general formula (3), examples of the alkyl group having 1 to 8 carbon atoms represented by R ² include methyl, ethyl, propyl, isopropyl, butyl, second butyl, third butyl, isobutyl and amyl. And tertiary amyl, octyl, tertiary octyl, and the like, and among them, the methyl group is preferable because of its excellent ultraviolet absorption ability.

Although the following exemplary compounds 7-17 are shown as a specific example of the triazine type compound represented by the said General formula (3), it is not limited to this.

In this invention, the compound which has a structure represented by General formula (1) can be used individually by 1 type or in combination of 2 or more types.

When the dry film thickness of the optical film of this invention is 5-50 micrometers from the viewpoint of the compatibility of the compound with a solvent or cycloolefin resin, the molecular weight of the compound which has a structure represented by General formula (1) is 100, It is preferable to exist in the range of -3000, More preferably, it exists in the range of 100-800. If it is in the range of 100-800, precipitation of a compound itself and generation | occurrence | production of a bleed out can be suppressed, and a compound can be disperse | distributed uniformly in dope.

The addition method of the compound which has a structure represented by General formula (1) mentioned above is alcohol, such as methanol, ethanol, butanol, organic solvent, such as methylene chloride, methyl acetate, acetone, dioxolane, or a mixed solvent thereof, for example. You may add to dope after melt | dissolving in, or may add in dope composition directly. In addition, an organic solvent may be used individually by 1 type, and may mix and use two or more types of organic solvent in arbitrary ratios.

Although the usage-amount of the compound which has a structure represented by General formula (1) is not specifically limited in the range which exhibits the effect of this invention, From a viewpoint of prevention of bleeding out and precipitation, 2-20 mass% with respect to a cycloolefin resin. The inside of the range of is preferable, and the range of 3-10 mass% is more preferable.

[2] cycloolefin resins

As a cycloolefin resin which concerns on this invention, the following (co) polymer is mentioned.

[Wherein, R ¹ to R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a halogen atom, a hydroxy group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, a silyl group, or a polar group (that is, a halogen group). Atom, hydroxy group, ester group, alkoxy group, cyano group, amide group, imide group or silyl group). However, two or more R ¹ to R ⁴ may be bonded to each other to form an unsaturated bond, a monocyclic ring or a polycyclic ring, and the monocyclic or polycyclic ring may have a double bond or may form an aromatic ring. An alkylidene group may be formed with R ¹ and R ² or with R ³ and R ⁴ . p and m are integers greater than or equal to 0.]

In said general formula (4), R <^1> and R <^3> is a hydrogen atom or a C1-C10, More preferably, it is 1-4, Especially preferably, it is a hydrocarbon group of ^1-2 , R <^2> and R <^4> is a hydrogen atom Or a monovalent organic group, at least one of R ² and R ⁴ represents a polar group having a polarity other than a hydrogen atom and a hydrocarbon group, m is an integer of 0 to 3, and p is an integer of 0 to 3, more preferably Is m + p = 0 to 4, more preferably 0 to 2, particularly preferably m = 1 and p = 0. The specific monomer whose m = 1 and p = 0 is preferable at the point where the glass transition temperature of cycloolefin resin obtained is high, and its mechanical strength is also excellent.

As a polar group of the said specific monomer, a carboxy group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amide group, a cyano group, etc. are mentioned, These polar groups may be couple | bonded through coupling groups, such as a methylene group. Moreover, the hydrocarbon group etc. which the bivalent organic group which has polarity, such as a carbonyl group, an ether group, a silyl ether group, a thioether group, and an imino group, are couple | bonded and couple | bonded are mentioned as a polar group. In these, a carboxy group, a hydroxyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group is preferable, and an alkoxycarbonyl group or an aryloxycarbonyl group is especially preferable.

In addition, R ^2, and R is at least one type of the ⁴ - (CH ₂₎ a polar group of monomers represented by nCOOR, the resulting cycloolefin resin has a high glass transition temperature and low moisture absorption, in that has excellent adhesion to various materials desirable. In the formula relating to the specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2 carbon atoms, preferably an alkyl group.

Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene and dicyclopentadiene.

As carbon number of a cycloolefin, 4-20 are preferable and 5-12 are more preferable.

In this invention, cycloolefin resin can be used individually by 1 type or in combination of 2 or more types.

The preferred molecular weight of the cycloolefin resin according to the present invention is 0.2 to 5 cm ³ / g, more preferably 0.3 to 3 cm ³ / g, particularly preferably 0.4 to 1.5 cm ³ / g in intrinsic viscosity [η] inh, The number average molecular weight (Mn) of polystyrene conversion measured by gel permeation chromatography (GPC) is 8000 to 100000, more preferably 10000 to 80000, particularly preferably 12000 to 50000, and the weight average molecular weight (Mw) is 20000 to Suitable ranges are 300000, more preferably 30000 to 250000, particularly preferably 40000 to 200000.

When the intrinsic viscosity [η] inh, the number average molecular weight and the weight average molecular weight are in the above ranges, the heat resistance, water resistance, chemical resistance, mechanical properties of the cycloolefin resin and molding processability as the optical film of the present invention are improved.

As glass transition temperature (Tg) of the cycloolefin resin which concerns on this invention, it is 110 degreeC or more normally, Preferably it is 110-350 degreeC, More preferably, it is 120-250 degreeC, Especially preferably, it is 120-220 degreeC. When Tg is less than 110 degreeC, since it deforms by use under high temperature conditions or secondary processing, such as coating and printing, it is unpreferable. On the other hand, when Tg exceeds 350 degreeC, shaping | molding process becomes difficult and the possibility of resin deterioration by the heat at the time of shaping | molding process becomes high.

In the cycloolefin resin, specific hydrocarbon-based resins or known materials, for example, described in Japanese Patent Application Laid-Open No. 9-221577 and Japanese Patent Application Laid-Open No. 10-287732 within the range of not impairing the effects of the present invention. The thermoplastic resin, the thermoplastic elastomer, the rubbery polymer, the organic fine particles, the inorganic fine particles and the like may be blended, and additives such as specific wavelength dispersants, sugar ester compounds, rubber particles, and plasticizers may be included.

The cycloolefin resin demonstrated above can use a commercial item suitably, As an example of a commercial item, it is marketed by JSR Co., Ltd. under brand names, such as ATON G, ATON F, ATON R, and ATON RX, and also Nippon Xeon (Note) ) Are marketed under the trade names Zeonor ZF14, ZF16, Zeonex 250 or Zeonex 280, and these may be used.

[3] retardation synergists

The addition of the retardation increasing agent to the optical film of the present invention compensates for the phase difference insufficient when the film is thinned, and also avoids excessive stretching operation, and fine cracks in the film generated during stretching to adjust the phase difference. G)) and the decrease in contrast caused by the arrangement of foreign matters.

It is preferable to contain a retardation increasing agent in the ratio of 0.5-10 mass%, for example, and also to contain it in the ratio of 2-6 mass%. By employing a retardation synergist, high Ro expressionability is obtained at a low draw ratio. Although it does not specifically determine as a kind of retardation increasing agent, The thing containing a disk shaped or rod-shaped compound is mentioned. As said disk-shaped or rod-shaped compound, the compound which has at least 2 aromatic ring can be used suitably as a retardation increasing agent.

It is preferable to use the said disk shaped retardation increasing agent in 0.5-10 mass parts with respect to 100 mass parts of said cycloolefin resins, It is more preferable to use in the range of 1-8 mass parts, It is 2-6 It is more preferable to use in the range of a mass part.

It is preferable that it is 0.5-10 mass parts with respect to 100 mass parts of cycloolefin resin, and, as for the addition amount of the retardation increasing agent containing the said rod-shaped compound, it is more preferable that it is 2-6 mass parts.

You may use together 2 or more types of retardation increasing agents.

It is preferable that the retardation increasing agent has a maximum absorption in the wavelength region of 250 to 400 nm, and preferably does not have substantially the absorption in the visible region.

A disk shaped compound is demonstrated. As a disk shaped compound, the compound which has at least 2 aromatic ring can be used.

In the present specification, the "aromatic ring" includes an aromatic hetero ring in addition to an aromatic hydrocarbon ring.

It is especially preferable that an aromatic hydrocarbon ring is a 6-membered ring (that is, a benzene ring).

Aromatic heterocycles are generally unsaturated heterocycles. It is preferable that an aromatic hetero ring is a 5-membered ring, a 6-membered ring, or a 7-membered ring, and it is more preferable that it is a 5-membered ring or a 6-membered ring. An aromatic heterocycle generally has the largest number of double bonds. As a hetero atom, a nitrogen atom, an oxygen atom, and a sulfur atom are preferable, and a nitrogen atom is especially preferable. Examples of aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring, Pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring.

As an aromatic ring, a benzene ring, a condensed benzene ring, and biphenyls are preferable. In particular, a 1,3,5-triazine ring is used preferably. Specifically, for example, the compound disclosed in Japanese Patent Laid-Open No. 2001-166144 is preferably used.

It is preferable that carbon number of the aromatic ring which a phase difference (retardation) expression agent has is 2-20, It is more preferable that it is 2-12, It is further more preferable that it is 2-8, It is most preferable that it is 2-6.

The bonding relationship between two aromatic rings can be classified into (a) forming a condensed ring, (b) being directly linked to a single bond, and (c) bonding through a linking group. Cannot form). The coupling relationship may be any of (a) to (c).

Examples of the condensed ring (condensed ring of two or more aromatic rings) in (a) include indene ring, naphthalene ring, azulene ring, fluorene ring, phenanthrene ring, anthracene ring, acenaphthylene ring, biphenylene ring, naphthacene ring , Pyrene ring, indole ring, isoindole ring, benzofuran ring, benzothiophene ring, indoliazine ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring, purine ring, indazole ring, chromen ring, Quinoline ring, isoquinoline ring, quinoline ring, quinazoline ring, cinnoline ring, quinoxaline ring, phthalazine ring, putridine ring, carbazole ring, acridine ring, phenanthridine ring, xanthene ring, phenazine ring, pheno Thiazine ring, phenoxatin ring, phenoxazine ring, and thianthrene ring. Naphthalene ring, azulene ring, indole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring and quinoline ring are preferable.

It is preferable that the single bond of (b) is a bond between the carbon atoms of two aromatic rings. Two aromatic rings may be bonded by two or more single bonds to form an aliphatic ring or a non-aromatic heterocycle between the two aromatic rings.

It is preferable that the linking group of (c) couple | bonds with the carbon atom of two aromatic rings. It is preferable that a coupling group is an alkylene group, an alkenylene group, an alkynylene group, -CO-, -O-, -NH-, -S-, or a combination thereof. An example of the coupling group which consists of a combination is shown below. In addition, the left-right relationship of the example of the following coupler may be reversed. c1: -CO-O-, c2: -CO-NH-, c3: -alkylene-O-, c4: -NH-CO-NH-, c5: -NH-CO-O-, c6: -O- CO-O-, c7: -O-alkylene-O-, c8: -CO-alkenylene-, c9: -CO-alkenylene-NH-, c10: -CO-alkenylene-O-, c11:- Alkylene-CO-O-alkylene-O-CO-alkylene-, c12: -O-alkylene-CO-O-alkylene-O-CO-alkylene-O-, c13: -O-CO- Alkylene-CO-O-, c14: -NH-CO-alkenylene-, c15: -O-CO-alkenylene-

The aromatic ring and the linking group may have a substituent.

Examples of the substituent include halogen atom (F, Cl, Br, I), hydroxy group, carboxyl group, cyano group, amino group, nitro group, sulfo group, carbamoyl group, sulfamoyl group, ureido group, alkyl group, alkenyl group, alkynyl group , Aliphatic acyl group, aliphatic acyloxy group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, aliphatic amide group, aliphatic sulfonamide group, aliphatic substituted amino group, aliphatic substituted carbamoyl group, aliphatic substitution Sulfamoyl groups, aliphatic substituted ureido groups and non-aromatic heterocyclic groups are included.

It is preferable that carbon number of an alkyl group is 1-8. A chain alkyl group is more preferable than a cyclic alkyl group, and a linear alkyl group is especially preferable. The alkyl group may further have a substituent (for example, a hydroxyl group, a carboxy group, an alkoxy group, an alkyl substituted amino group). Examples of the alkyl group (including a substituted alkyl group) include methyl group, ethyl group, n-butyl group, n-hexyl group, 2-hydroxyethyl group, 4-carboxybutyl group, 2-methoxyethyl group and 2-diethylaminoethyl group Each group of is included.

It is preferable that carbon number of an alkenyl group is 2-8. The linear alkenyl group is more preferable than the cyclic alkenyl group, and the linear alkenyl group is particularly preferable. The alkenyl group may further have a substituent. Examples of the alkenyl group include vinyl group, allyl group and 1-hexenyl group.

It is preferable that carbon number of an alkynyl group is 2-8. The linear alkynyl group is more preferable than the cyclic alkynyl group, and the linear alkynyl group is particularly preferable. The alkynyl group may further have a substituent. Examples of the alkynyl group include an ethynyl group, a 1-butynyl group and a 1-hexynyl group.

It is preferable that carbon number of an aliphatic acyl group is 1-10. Examples of aliphatic acyl groups include acetyl groups, propanoyl groups and butanoyl groups.

It is preferable that carbon number of an aliphatic acyloxy group is 1-10. Examples of aliphatic acyloxy groups include acetoxy groups.

It is preferable that carbon number of an alkoxy group is 1-8. The alkoxy group may further have a substituent (for example, an alkoxy group). Examples of the alkoxy group (including a substituted alkoxy group) include methoxy group, ethoxy group, butoxy group and methoxyethoxy group.

It is preferable that carbon number of an alkoxycarbonyl group is 2-10. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

It is preferable that carbon number of an alkoxycarbonylamino group is 2-10. Examples of the alkoxycarbonylamino group include a methoxycarbonylamino group and an ethoxycarbonylamino group.

It is preferable that carbon number of an alkylthio group is 1-12. Examples of the alkylthio group include methylthio group, ethylthio group and octylthio group.

It is preferable that carbon number of an alkylsulfonyl group is 1-8. Examples of the alkylsulfonyl group include a methanesulfonyl group and an ethanesulfonyl group.

It is preferable that carbon number of an aliphatic amide group is 1-10. Examples of aliphatic amide groups include acetamide.

It is preferable that carbon number of an aliphatic sulfonamide group is 1-8. Examples of aliphatic sulfonamide groups include methanesulfonamide groups, butanesulfonamide groups and n-octanesulfonamide groups.

It is preferable that carbon number of an aliphatic substituted amino group is 1-10. Examples of the aliphatic substituted amino group include a dimethylamino group, diethylamino group and 2-carboxyethylamino group.

It is preferable that carbon number of an aliphatic substituted carbamoyl group is 2-10. Examples of aliphatic substituted carbamoyl groups include methylcarbamoyl groups and diethylcarbamoyl groups.

It is preferable that carbon number of an aliphatic substituted sulfamoyl group is 1-8. Examples of the aliphatic substituted sulfamoyl group include a methyl sulfamoyl group and a diethyl sulfamoyl group.

It is preferable that carbon number of an aliphatic substituted ureido group is 2-10. Examples of aliphatic substituted ureido groups include methylureido groups.

Examples of the nonaromatic heterocyclic group include a piperidino group and a morpholino group.

It is preferable that the molecular weight of a phase difference (retardation) expression agent is 300-800.

It is preferable to use the triazine compound which has a structure represented by following General formula (I) as a disk shaped compound.

In said general formula (I), R <^1> respectively independently represents the aromatic ring or heterocyclic ring which has a substituent at least in an ortho position, a meta position, and a para position.

Each X independently represents a single bond or NR ^2- . Here, each R ² independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

It is preferable that the aromatic ring which R <^1> represents is a phenyl group or a naphthyl group, and it is especially preferable that it is a phenyl group. The aromatic ring represented by R ¹ may have at least one substituent at any substitution position. Examples of the substituent include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyl group, an alkenyloxycarbonyl group, Aryloxycarbonyl group, sulfamoyl group, alkyl substituted sulfamoyl group, alkenyl substituted sulfamoyl group, aryl substituted sulfamoyl group, sulfonamide group, carbamoyl, alkyl substituted carbamoyl group, alkenyl substituted carbamoyl group, aryl substituted Carbamoyl groups, amide groups, alkylthio groups, alkenylthio groups, arylthio groups and acyl groups are included.

It is preferable that the heterocyclic group which R <^1> represents has aromaticity. The heterocycle which has aromaticity is generally an unsaturated heterocycle, Preferably it is a heterocycle which has the largest double bond. It is preferable that a heterocyclic ring is a 5-membered ring, a 6-membered ring, or a 7-membered ring, It is more preferable that it is a 5-membered ring or a 6-membered ring, It is most preferable that it is a 6-membered ring. It is preferable that the hetero atom of a heterocycle is a nitrogen atom, a sulfur atom, or an oxygen atom, and it is especially preferable that it is a nitrogen atom. As a heterocyclic ring which has aromaticity, a pyridine ring (as a heterocyclic group, 2-pyridyl or 4-pyridyl) is especially preferable. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as those of the substituent of the aryl moiety.

It is preferable that the heterocyclic group when X is a single bond is a heterocyclic group which has a free valency in a nitrogen atom. It is preferable that the heterocyclic group which has a free valency in a nitrogen atom is a 5-membered ring, a 6-membered ring, or a 7-membered ring, It is more preferable that it is a 5- or 6-membered ring, It is most preferable that it is a 5-membered ring. The heterocyclic group may have a plurality of nitrogen atoms. In addition, the heterocyclic group may have hetero atoms (for example, O and S) other than a nitrogen atom. Below, the example of the heterocyclic group which has a free valency in a nitrogen atom is shown.

Although the cyclic alkyl group or a chain alkyl group may be sufficient as the alkyl group which R <^2> represents, a linear alkyl group is preferable and a linear alkyl group is more preferable than the linear alkyl group which has a branch.

The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 10, still more preferably 1 to 8, and most preferably 1 to 6. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (e.g., methoxy group, ethoxy group) and an acyloxy group (e.g., acryloyloxy group, methacryloyloxy group).

Although the alkenyl group which R <^2> represents may be a cyclic alkenyl group or a linear alkenyl group, it is preferable to represent a linear alkenyl group, and it is more preferable to represent a linear alkenyl group rather than the branched alkenyl group which has a branch. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 10, still more preferably 2 to 8, and most preferably 2 to 6 . The alkenyl group may have a substituent. Examples of the substituent are the same as the substituent of the alkyl group described above.

The aromatic ring group and heterocyclic group which R <^2> represents are the same as the aromatic ring and heterocycle which R <^1> represents, and the preferable range is also the same. The aromatic ring group and the heterocyclic group may further have a substituent, and examples of the substituent are the same as those of the aromatic ring and the heterocycle of R ¹ .

Although the specific example of a compound represented by general formula (I) below is given, it is not limited to these.

As a disk shaped compound, the triphenylene compound represented with the following general formula (II) can also be used preferably.

In said general formula (II), R <^1> , R <^2> , R <^3> , R <^4> , R <^5> and R <^6> respectively independently represent a hydrogen atom or a substituent.

As a substituent which R <^1> , R <^2> , R <^3> , R <^4> , R <^5> and R <^6> respectively represent, it is an alkyl group (preferably C1-C40, More preferably, it is C1-C30, Especially preferably, it is C1-C20 It is an alkyl group of, for example, methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc. are mentioned, for example. Alkenyl group (preferably an alkenyl group having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and particularly preferably 2 to 20 carbon atoms, for example, a vinyl group, an allyl group, and 2-bute) And an alkynyl group (preferably, an alkynyl group having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and particularly preferably 2 to 20 carbon atoms), for example. Propargyl, 3-pentynyl, etc.), aryl (preferably burnt) 6 to 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, a phenyl group, p-methylphenyl group, naphthyl group, etc.), substituted or unsubstituted. The amino group (preferably an amino group having 0 to 40 carbon atoms, more preferably 0 to 30 carbon atoms, particularly preferably 0 to 20 carbon atoms, for example, an unsubstituted amino group, methylamino group, dimethylamino group, diethylamino group, A lino group, etc.), an alkoxy group (preferably an alkoxy group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms, for example, a methoxy group, an ethoxy group) , Butoxy group, etc.), an aryloxy group (preferably a C6-C40, More preferably, it is a C6-C30, Especially preferably, it is a C6-C20 aryloxy group, For example, a phenyloxy group, 2-naphthyloxy group, etc. are mentioned, Acyl group (preferably C1-C40, More preferably, it is C1-C20, Especially preferably, it is an acyl group of C1-C20) For example, an acetyl group, benzoyl group, formyl group, pivaloyl group, etc. can be mentioned, The alkoxycarbonyl group (preferably C2-C40, More preferably, C2-C30, Especially preferably, C2-C) It is an alkoxycarbonyl group of 20, For example, a methoxycarbonyl group, an ethoxycarbonyl group, etc. are mentioned, The aryloxycarbonyl group (preferably C7-C40, More preferably, it is C7-C30, Especially preferably, C7 is C7). It is an aryloxycarbonyl group of 20 to 20, for example, a phenyloxy carbonyl group, etc.), an acyloxy group (preferably C2-C40, More preferably, it is C2-C2). 30, particularly preferably an acyloxy group having 2 to 20 carbon atoms, and examples thereof include an acetoxy group, a benzoyloxy group, and the like, and an acylamino group (preferably 2 to 40 carbon atoms, more preferably 2 carbon atoms). 30 to 30, particularly preferably an acylamino group having 2 to 20 carbon atoms, for example, an acetylamino group, a benzoylamino group, etc., an alkoxycarbonylamino group (preferably 2 to 40 carbon atoms, more preferably 2 carbon atoms) 30 to 30, particularly preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms, for example, a methoxycarbonylamino group and the like, a aryloxycarbonylamino group (preferably 7 to 40 carbon atoms), more preferably Is an aryloxycarbonylamino group having 7 to 30 carbon atoms, particularly preferably 7 to 20 carbon atoms, and examples thereof include a phenyloxycarbonylamino group and the like. And sulfonylamino group (preferably a sulfonylamino group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms, for example, a methanesulfonylamino group and a benzenesulfonylamino group). And sulfamoyl groups (preferably sulfamoyl groups having 0 to 40 carbon atoms, more preferably 0 to 30 carbon atoms, and particularly preferably 0 to 20 carbon atoms, for example, sulfamoyl group and methyl). Sulfamoyl group, dimethyl sulfamoyl group, phenyl sulfamoyl group, and the like), carbamoyl group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms). Carbamoyl group, for example, an unsubstituted carbamoyl group, methyl carbamoyl group, diethyl carbamoyl group, phenylcarbamoyl group, etc.), alkylthio group (preferably 1 to 4 carbon atoms) 0, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms, for example, methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthi Group, an octylthio group, etc.), an arylthio group (preferably C6-C40, More preferably, C6-C30, Especially preferably, C1-C20, For example, a phenylthio group etc. The sulfonyl group (preferably a C1-C40, More preferably, it is a C1-C30 sulfonyl group, Especially preferably, it is a C1-C20 sulfonyl group, For example, a mesyl group, a tosyl group, etc. are mentioned). Sulfinyl group (preferably a sulfinyl group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms, for example, methanesulfonyl group, benzenesulfinyl group, etc.) Ureido (bar) It is preferably a ureido group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms. Examples thereof include an unsubstituted ureido group, a methyl ureido group, a phenyl ureido group, and the like. Phosphate amide group (preferably a phosphate amide group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms, for example, diethyl phosphate amide group and phenyl phosphate amide group). And the like), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino A group, a hydrazino group, an imino group, a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, for example, a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom) Heterocyclic group having a group, for example, imidazolyl group, pyridyl group, quinolyl group, furyl group, piperidyl group, morpholino group, benzooxazolyl group, benzimidazolyl group, benzthiazolyl group, 1, 3,5-triazyl group, etc.), a silyl group (preferably, C3-C40, More preferably, it is C3-C30, Especially preferably, it is a C3-C24 silyl group, For example, Trimethylsilyl group, triphenylsilyl group, and the like). These substituents may further be substituted by these substituents. In addition, when it has two or more substituents, it may be same or different. In addition, when possible, they may combine with each other and form the ring.

As a substituent which R <^1> , R <^2> , R <^3> , R <^4> , R <^5> and R <^6> represent, respectively, Preferably they are an alkyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an alkylthio group, or a halogen atom.

Although the specific example of a compound represented by general formula (II) below is given, it is not limited to these.

As for the compound represented by general formula (I), the method described in Unexamined-Japanese-Patent No. 2003-344655, and the compound represented by general formula (II) are, for example, Unexamined-Japanese-Patent No. 2005-134884. It can synthesize | combine by a well-known method, such as the method of description.

In this invention, the rod-shaped compound which has a linear molecular structure can also be used preferably. The linear molecular structure means that the molecular structure of the rod-shaped compound is linear in the thermodynamic most stable structure. The thermodynamic most stable structure can be obtained by crystal structure analysis or molecular orbital calculation. For example, molecular orbital calculations are performed using molecular orbital calculation software (for example, WinMOPAC2000, manufactured by Fujitsu Co., Ltd.) to obtain the structure of the molecule in which the heat of production of the compound is the smallest. The linear structure means that in the thermodynamic most stable structure calculated and calculated as described above, the angle formed by the main chain in the molecular structure is 140 degrees or more.

As a rod-shaped compound which has at least two aromatic rings, the compound represented by the following general formula (III) is preferable.

General formula (III): Ar ₁ -L ₁ -Ar ₂

In General Formula (III), Ar ₁ and Ar ₂ each independently represent an aromatic group.

In the present specification, the aromatic group includes an aryl group (aromatic hydrocarbon group), a substituted aryl group, an aromatic heterocyclic group, and a substituted aromatic heterocyclic group.

An aryl group and a substituted aryl group are more preferable than an aromatic heterocyclic group and a substituted aromatic heterocyclic group. The heterocycle of an aromatic heterocyclic group is generally unsaturated. It is preferable that an aromatic hetero ring is a 5-membered ring, a 6-membered ring, or a 7-membered ring, and it is more preferable that it is a 5-membered ring or a 6-membered ring. Aromatic heterocycles generally have the largest number of double bonds. As a hetero atom, a nitrogen atom, an oxygen atom, or a sulfur atom is preferable, and a nitrogen atom or a sulfur atom is more preferable.

As an aromatic ring of an aromatic group, a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, and a pyrazine ring are preferable, and a benzene ring is especially preferable. .

Examples of the substituent of the substituted aryl group and the substituted aromatic heterocyclic group include halogen atom (F, Cl, Br, I), hydroxy group, carboxyl group, cyano group, amino group, alkylamino group (for example, methylamino group, ethylamino group, butyl) Each group of amino group, dimethylamino group), nitro group, sulfo group, carbamoyl group, alkylcarbamoyl group (for example, N-methylcarbamoyl group, N-ethylcarbamoyl group, N, N-dimethylcarbamoyl group) Each group), sulfamoyl group, alkyl sulfamoyl group (for example, N-methyl sulfamoyl group, N-ethyl sulfamoyl group, N, N-dimethyl sulfamoyl group), ureido group, alkyl urea Pottery (for example, N-methylureido group, N, N-dimethylureido group, each group of N, N, N'-trimethylureido group), alkyl group (for example, methyl group, ethyl group, propyl group, butyl group) , Pentyl, heptyl, octyl, isopropyl, s-butyl, tert-amyl, cyclohexyl, cyclopentyl groups) , Alkenyl groups (eg, vinyl, allyl, hexenyl groups), alkynyl groups (eg, ethynyl groups, butynyl groups), acyl groups (eg, formyl groups, acetyl groups, buty Aryl group, hexanoyl group, each group of lauryl group), acyloxy group (for example, acetoxy group, butyryloxy group, hexanoyloxy group, each group of lauryloxy group), an alkoxy group (for example, methoxyl Period, ethoxy group, propoxy group, butoxy group, pentyloxy group, heptyloxy group, each group of octyloxy group, aryloxy group (for example, phenoxy group), alkoxycarbonyl group (for example, methoxycarbonyl group , Ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, heptyloxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkoxycarbonylamino group (for example, butoxycarbon Bonylamino group, hexyloxycarbonylamino group), alkylthio group (for example Eh, methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, heptylthio group, octylthio group), arylthio group (for example, phenylthio group), alkylsulfonyl group (For example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, heptylsulfonyl group, octylsulfonyl group), amide group (for example, acetamide group, butylamide Group, hexylamide group, each group of laurylamide group) and non-aromatic heterocyclic group (for example, morpholinyl group, pyradinyl group) are included.

Especially, as a preferable substituent, a halogen atom, a cyano group, a carboxy group, a hydroxyl group, an amino group, an alkylamino group, an acyl group, an acyloxy group, an amide group, an alkoxycarbonyl group, an alkoxy group, an alkylthio group, and an alkyl group are mentioned.

The alkyl portion and alkyl group of the alkylamino group, the alkoxycarbonyl group, the alkoxy group and the alkylthio group may further have a substituent. Examples of the alkyl moiety and the substituent of the alkyl group include a halogen atom, a hydroxy group, a carboxy group, a cyano group, an amino group, an alkylamino group, a nitro group, a sulfo group, a carbamoyl group, an alkylcarbamoyl group, a sulfamoyl group, an alkylsulfamoyl group, and a urea. Earthenware, alkylureido group, alkenyl group, alkynyl group, acyl group, acyloxy group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonylamino group, alkylthio group, arylthio group, alkylsulfonyl group, Amide groups and nonaromatic heterocyclic groups are included. As a substituent of an alkyl part and an alkyl group, a halogen atom, a hydroxyl group, an amino group, an alkylamino group, an acyl group, an acyloxy group, an acylamino group, an alkoxycarbonyl group, and an alkoxy group are preferable.

In General Formula (III), L ₁ is a divalent linking group selected from a group consisting of an alkylene group, an alkenylene group, an alkynylene group, -O-, -CO-, and a combination thereof. The alkylene group may have a cyclic structure. As a cyclic alkylene group, cyclohexylene is preferable and 1, 4- cyclohexylene is especially preferable. As a linear alkylene group, a linear alkylene group is more preferable than the alkylene group which has a branch.

It is preferable that carbon number of an alkylene group is 1-20, More preferably, it is 1-15, More preferably, it is 1-10, More preferably, it is 1-8, Most preferably, it is 1-6. .

It is preferable that an alkenylene group and an alkynylene group have a linear structure rather than a cyclic structure, and it is more preferable to have a linear structure rather than the linear structure which has a branch.

The number of carbon atoms of the alkenylene group and the alkynylene group is preferably 2 to 10, more preferably 2 to 8, still more preferably 2 to 6, still more preferably 2 to 4, and most preferably Preferably 2 (vinylene group or ethynylene group).

It is preferable that carbon number of an arylene group is 6-20, More preferably, it is 6-16, More preferably, it is 6-12.

In the molecular structure of General formula (III), it is preferable that the angle which Ar <_1> and Ar <_2> form by sandwiching L <_1> is 140 degree or more.

As a rod-shaped compound, the compound represented by the following general formula (IV) is more preferable.

Formula (IV): Ar ₁ -L ₂ -XL ₃ -Ar ₂

In General Formula (IV), Ar ₁ and Ar ₂ each independently represent an aromatic group. The definition and the example of an aromatic group are the same as Ar <_1> and Ar <_2> of General formula (III).

In General Formula (IV), L ₂ and L ₃ are each independently a divalent linking group selected from a group consisting of an alkylene group, —O—, —CO— and a combination thereof.

It is preferable that an alkylene group has a linear structure rather than a cyclic structure, and it is more preferable to have a linear structure rather than the linear structure which has a branch.

It is preferable that carbon number of an alkylene group is 1-10, More preferably, it is 1-8, More preferably, it is 1-6, More preferably, it is 1-4, 1 or 2 (methylene group or ethylene Group).

L ₂ and L ₃ are particularly preferably -O-CO- or CO-O-.

In general formula (IV), X is a 1, 4- cyclohexylene group, a vinylene group, or an ethynylene group.

As a specific example of a compound represented by general formula (III) or (IV), the compound of Unexamined-Japanese-Patent No. 2004-109657 can be mentioned.

In the ultraviolet absorption spectrum of a solution, you may use together two or more types of rod-shaped compounds whose maximum absorption wavelength ((lambda) max) is longer than 250 nm.

The rod-shaped compound can be synthesized with reference to the method described in the literature. As literature, Mol. Cryst. Liq. Cryst., Vol. 53, p. 229 (1979), p. 89, p. 93 (1982), p. 145, p. 111 (1987), p. 170, p. 43 (1989), J. Am. Chem. Soc., Vol. 113, p. 1349 (1991), p. 118, p. 5346 (1996), p. 92, p. 1582 (1970), J. 0rg. Chem., 40, 420 pages (1975), Tetrahedron, 48, 16, 3437 pages (1992).

Moreover, you may use the rod-shaped aromatic compound of pages 11-14 of Unexamined-Japanese-Patent No. 2004-50516 as said retardation increasing agent.

When producing the optical film of this invention by the solvent casting method, you may add the said retardation increasing agent in dope. Addition may be performed at any timing, for example, after dissolving the retardation synergist in an organic solvent such as alcohol, methylene chloride, dioxolane, or the like may be added to a cycloolefin solution (dope) or added directly in the dope composition. You may also

In addition, the specific example of the preferable compound of rod-shaped compound other than what is described in each said publication is shown below.

The said specific examples (1)-(34), (41), (42) have two asymmetric carbon atoms in the 1-position and 4-position of a cyclohexane ring. However, since specific examples (1), (4) to (34), (41), and (42) have a symmetric meso-type molecular structure, there is no optical isomer (optical activity), and geometric isomers (trans and cis) Only). The trans form (1-trans) and cis form (1-cis) of specific example (1) are shown below.

As mentioned above, the rod-shaped compound preferably has a linear molecular structure. Therefore, the trans type is more preferable than the sheath type.

Specific examples (2) and (3) have optical isomers (four kinds of isomers in total) in addition to geometric isomers. As for the geometric isomers, the trans type is more preferable than the cis type. About an optical isomer, there is no inferior well in particular, Any of D, L, or a racemate may be sufficient.

In the specific examples (43)-(45), a trans type and a cis type exist in the center vinylene bond. For the same reason as described above, the trans type is more preferable than the cis type.

[4] additives

The optical film of this invention may contain a plasticizer, antioxidant, a mat agent, an optical stabilizer, an antistatic agent, a peeling agent, etc. other than the said additive. The main additives are described in detail below.

[Plasticizer]

Examples of plasticizers include polyester compounds, polyhydric alcohol ester compounds, polyhydric carboxylic acid ester compounds (including phthalic acid ester compounds), glycolate compounds and ester compounds (fatty acid ester compounds and phosphate ester compounds, etc.). ) Is included. These may be used independently or may be used in combination of 2 or more types.

The plasticizer suitable for the optical film of this invention is a polyester compound containing the repeating unit obtained by making dicarboxylic acid and diol react.

Dicarboxylic acid which comprises a polyester compound is aromatic dicarboxylic acid, aliphatic dicarboxylic acid, or alicyclic dicarboxylic acid, Preferably it is aromatic dicarboxylic acid. One type or two or more types of dicarboxylic acids may be used.

The diol constituting the polyester compound is an aromatic diol, an aliphatic diol or an alicyclic diol, preferably an aliphatic diol, and more preferably a diol having 1 to 4 carbon atoms. The diol may be one kind or a mixture of two or more kinds.

Especially, it is preferable that a polyester compound contains the repeating unit obtained by making dicarboxylic acid containing at least aromatic dicarboxylic acid, and diol of 1 to 4 carbon atoms react, and aromatic dicarboxylic acid and aliphatic dicarboxylic acid. It is more preferable to include the repeating unit obtained by making dicarboxylic acid containing an acid react with C1-C4 diol.

Although both ends of a polyester compound molecule do not need to be sealed even if it is sealed, it is preferable that it is sealed from a viewpoint of reducing the moisture permeability of a film.

The polyhydric alcohol ester compound is an ester compound (alcohol ester) of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably a 2 to 20 valent aliphatic polyhydric alcohol ester. It is preferable that a polyhydric alcohol ester compound has an aromatic ring or a cycloalkyl ring in a molecule | numerator.

Preferred examples of the aliphatic polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol , 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, trimethylolpropane, Pentaerythritol, trimethylolethane, xylitol and the like. Especially, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylol propane, xylitol, etc. are preferable.

The monocarboxylic acid is not particularly limited and may be aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, or the like. In order to improve the moisture permeability of a film and to make it hard to volatilize, an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferable. 1 type may be sufficient as a monocarboxylic acid, and 2 or more types of mixtures may be sufficient as it. In addition, all of the hydroxyl groups contained in aliphatic polyhydric alcohol may be esterified, and a part of hydroxyl groups may be left as it is.

The aliphatic monocarboxylic acid is preferably a fatty acid having a straight or branched chain having 1 to 32 carbon atoms. Carbon number of aliphatic monocarboxylic acid becomes like this. More preferably, it is 1-20, More preferably, it is 1-10. Examples of aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelagonic acid, capric acid, 2-ethyl-hexanoic acid, undecyl acid, lauric acid, Tridecyl acid, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachnic acid, behenic acid, lignoseric acid, sertric acid, heptacoic acid, montanic acid, meli Saturated fatty acids such as acetic acid and lacseric acid; Unsaturated fatty acids such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, and the like. Especially, in order to improve the compatibility with cellulose acetate, acetic acid or a mixture of acetic acid and other monocarboxylic acids is preferable.

Examples of the alicyclic monocarboxylic acid include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and the like.

Examples of the aromatic monocarboxylic acid include benzoic acid; One to three alkyl groups or alkoxy groups (for example, methoxy or ethoxy groups) are introduced into the benzene ring of benzoic acid (for example, toluic acid); Aromatic monocarboxylic acids (for example, biphenyl carboxylic acid, naphthalene carboxylic acid, tetralin carboxylic acid etc.) which have two or more benzene rings are contained, Preferably it is benzoic acid.

As a specific example of a polyhydric alcohol ester compound, the compound of Unexamined-Japanese-Patent No. 2006-113239 can be mentioned.

The polyhydric carboxylic acid ester compound is an ester compound of a bivalent or more, preferably 2-20 valent polyhydric carboxylic acid and an alcohol compound. It is preferable that polyhydric carboxylic acid is 2-20 valent aliphatic polyhydric carboxylic acid, 3-20 valent aromatic polyhydric carboxylic acid, or 3-20 valent alicyclic polyhydric carboxylic acid.

Examples of the polyhydric carboxylic acid ester compound include triethyl citrate, tributyl citrate, acetyl triethyl citrate (ATEC), acetyl tributyl citrate (ATBC), benzoyltributyl citrate, acetyl triphenyl citrate, Acetyltribenzyl citrate, dibutyl tartarate, diacetyl dibutyl tartarate, tributyl trimellitic acid, tetrabutyl pyromellitic acid and the like.

Examples of the glycolate compound include alkylphthalyl alkyl glycolates. Examples of the alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, and methyl phthalyl ethyl. Glycolate, Ethylphthalylmethylglycolate, Ethylphthalylpropylglycolate, Methylphthalylbutylglycolate, Ethylphthalylbutylglycolate, Butylphthalylmethylglycolate, Butylphthalylethylglycolate, Propylphthalylbutylglycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl methyl glycolate, octyl phthalyl ethyl glycolate, and the like, preferably ethyl phthalyl ethyl glycolate. to be.

The ester compound includes a fatty acid ester compound, a citric acid ester compound, a phosphate ester compound and the like.

Examples of the fatty acid ester compounds include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate and the like. Examples of the citrate ester compound include acetyl trimethyl citrate, acetyl triethyl citrate, acetyl tributyl citrate and the like. Examples of the phosphate ester compound include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, biphenyl diphenyl phosphate, trioctyl phosphate and tributyl phosphate, and preferably triphenyl phosphate. to be.

Especially, a polyester compound, a glycolate compound, and a phosphate ester compound are preferable, and a polyester compound is especially preferable.

Content of a plasticizer becomes like this. Preferably it is the range of 1-20 mass% with respect to a cellulose acetate, More preferably, it is the range of 1.5-15 mass%. If content of a plasticizer exists in the said range, a plasticity provision effect can be expressed and the exudation resistance of the plasticizer from an optical film is also excellent.

[Antioxidant]

The said cycloolefin resin can contain the phenol type compound which functions as an antioxidant from a viewpoint of improving storage stability. Antioxidants may be used alone or in combination with phenolic compounds, while other common antioxidants such as hindered amine compounds, phosphorus compounds, sulfur compounds, acrylate compounds, benzofuranone compounds, and the like may not impair the effects of the present invention. It can also be used in combination.

Although the addition amount of the said phenolic compound with respect to 100 mass parts of cycloolefin resin can be designed suitably, it is preferable that it is the range of 0.001-10 mass parts, and it is more preferable that it is the range which is 0.05-5 mass parts.

Phenolic compounds are known compounds and are described, for example, in columns 12 to 14 of US Pat. No. 4,840,405, including 2,6-dialkylphenol derivative compounds. As a preferable compound among these compounds, the compound represented with the following general formula (A) is preferable.

In the formula, R ₅₁ to R ₅₆ each represent a hydrogen atom or a substituent. As a substituent, a halogen atom (for example, a fluorine atom, a chlorine atom, etc.), an alkyl group (for example, a methyl group, an ethyl group, isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trifluoromethyl group, t-butyl group etc.), Cycloalkyl groups (e.g., cyclopentyl groups, cyclohexyl groups, etc.), aralkyl groups (e.g. benzyl groups, 2-phenethyl groups, etc.), aryl groups (e.g. phenyl groups, naphthyl groups, p-tolyl groups, p- Chlorophenyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (for example, phenoxy group, etc.), cyano group, acylamino group (for example, acetylamino group) , Propionylamino group, etc.), alkylthio group (for example, methylthio group, ethylthio group, butylthio group, etc.), arylthio group (for example, phenylthio group, etc.), sulfonylamino group (for example, methane sulfide) Phenylamino group, benzenesulfonylamino group, etc.), ureido group (for example, 3-methyl-woo Ido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethyl sulfamoylamino group, etc.), carbamoyl group (for example, methyl carbamoyl group, ethyl carbamoyl group, dimethyl) Carbamoyl group, etc.), sulfamoyl group (for example, ethyl sulfamoyl group, dimethyl sulfamoyl group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenoxy) Carbonyl group, etc.), sulfonyl group (for example, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (for example, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group , Dimethylamino group, etc.), cyano group, hydroxyl group, nitro group, nitroso group, amine oxide group (for example, pyridine-oxide group), imide group (for example, phthalimide group, etc.), disulfide group (for example, Benzene disulfide group, benzo Azolyl-2-disulfide group, etc.), carboxyl group, sulfo group, heterocyclic group (for example, pyrrole group, pyrrolidyl group, pyrazolyl group, imidazolyl group, pyridyl group, benzimidazolyl group, benzthia Jolyl group, benzoxazolyl group, etc.) etc. are mentioned. These substituents may further be substituted.

Moreover, the phenol type compound in which R <_51> is a hydrogen atom and R <_52> , R <_56> is a t-butyl group, respectively is preferable.

As a phenolic antioxidant, it is preferable that it is a hindered phenol type compound, As a specific example of this compound, n-octadecyl 3- (3, 5-di-t- butyl- 4-hydroxyphenyl) propionate, n-octadecyl3- (3,5-di-t-butyl-4-hydroxyphenyl) -acetate, n-octadecyl3,5-di-t-butyl-4-hydroxybenzoate, n-hexyl 3,5-di-t-butyl-4-hydroxyphenylbenzoate, n-dodecyl 3,5-di-t-butyl-4-hydroxyphenylbenzoate, neo-dodecyl3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate, dodecylβ (3,5-di-t-butyl-4-hydroxyphenyl) propionate, ethylα- (4-hydroxy- 3,5-di-t-butylphenyl) isobutyrate, octadecylα- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecylα- (4-hydroxy-3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 2- (n-octylthio) ethyl3,5-di-t-butyl-4-hydroxy-benzoate, 2- (n- Octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-phen Nyl acetate, 2- (n-octadecylthio) ethyl 3,5-di-t-butyl-4-hydroxyphenylacetate, 2- (n-octadecylthio) ethyl 3,5-di-t-butyl- 4-hydroxy-benzoate, 2- (2-hydroxyethylthio) ethyl 3,5-di-t-butyl-4-hydroxybenzoate, diethyl glycol bis- (3,5-di-t- Butyl-4-hydroxy-phenyl) propionate, 2- (n-octadecylthio) ethyl3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, stearamido N , N-bis- [ethylene3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], n-butylimino N, N-bis- [ethylene3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], 2- (2-stearoyloxyethylthio) ethyl 3,5-di-t-butyl-4-hydroxybenzoate, 2- (2-Stearoyloxyethylthio) ethyl 7- (3-methyl-5-t-butyl-4-hydroxyphenyl) heptanoate, 1,2-propylene glycol bis- [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate], ethylene glycol bis- [3- (3,5-di-t- Methyl-4-hydroxyphenyl) propionate], neopentylglycolbis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], ethylene glycol bis- (3, 5-di-t-butyl-4-hydroxyphenylacetate), glycerin-ln-octadecanoate-2,3-bis- (3,5-di-t-butyl-4-hydroxyphenylacetate), Pentaerythritol-tetrakis- [3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate], 1,1,1-trimethylolethane-tris- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], sorbitol hexa- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2-hydroxyethyl7- (3-methyl-5-tbutyl-4-hydroxyphenyl) propionate, 2-stearoyloxyethyl 7- (3-methyl-5-t-butyl-4-hydroxy Hydroxyphenyl) heptanoate, 1,6-n-hexanediol-bis [(3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis (3 , 5-di-t-butyl-4-hydroxyhydrocinnamate) The can.

Especially, although the following exemplary compound is shown as a specific example of a useful hindered phenolic antioxidant, it is not limited to this.

In addition, the phenol compound of the said type is marketed under the brand names "Irganox1035", "Irganox1076", and "Irganox1010", for example from BASF Japan.

[Mat]

It is preferable to add microparticles | fine-particles to a optical film of this invention as a mat agent, in order to prevent a flaw or deterioration of conveyability when the produced film is handled.

As microparticles | fine-particles, the microparticles | fine-particles of an inorganic compound and the microparticles | fine-particles of resin are mentioned. Examples of the fine particles of the inorganic compound include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and the like. Can be mentioned. It is preferable that microparticles | fine-particles contain silicon from the point which becomes turbidity low, and especially silicon dioxide is preferable.

The average particle diameter of the primary particles of the fine particles is preferably in the range of 5 to 400 nm, more preferably in the range of 10 to 300 nm. These may be contained mainly as a secondary aggregate within the range of particle size 0.05-0.3 micrometer, and if it is a particle | grain in the range of average particle diameter 80-400 nm, it is also preferable that it is contained as a primary particle, without aggregation.

It is preferable that it is in the range of 0.01-1 mass%, and, as for content of these microparticles | fine-particles in a film, it is especially preferable to exist in the range which is 0.05-0.5 mass%.

In the case of the optical film of the multilayer constitution by a covalent smoke method, it is preferable to contain this addition amount microparticles on the surface.

The fine particles of silicon dioxide are commercially available under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, and TT600 (above Nippon Aerosil Co., Ltd.). .

The fine particles of zirconium oxide are commercially available under the trade names of Aerosil R976 and R811 (above Nippon Aerosil Co., Ltd.), for example, and can be used.

Examples of the fine particles of the resin include silicone resins, fluororesins, and acrylic resins. A silicone resin is preferable, and it is especially preferable to have a three-dimensional network structure, for example, of Tospearl 103, 105, 108, 120, 145, 3120 and 240 (above manufactured by Toshiba Silicone Co., Ltd.) It is marketed under a brand name, and can be used.

Among them, aerosil 200V and aerosil R972V are particularly preferably used because the effect of lowering the coefficient of friction is great while keeping the haze of the base film low.

In the base film which concerns on this invention, it is preferable that the kinetic friction coefficient of at least one surface exists in the range of 0.2-1.0.

[5] methods of manufacturing optical films

As for the manufacturing method of the optical film of this invention, it is preferable to employ | adopt the solution casting film forming method (henceforth a solution casting method) from a viewpoint of thinning of a film as mentioned above, and a well-known method can be employ | adopted suitably. .

The characteristic of the manufacturing method of the optical film of this invention manufactures the dope containing a cycloolefin resin, a retardation increasing agent, and the compound which has a structure represented by the said General formula (1), and uses the said dope to produce a solution casting film After film forming by the method, the film is obliquely stretched in the direction of 45 ± 10 ° with respect to the longitudinal direction, and the difference between the maximum value and the minimum value of the variation of the retardation value Ro in the width direction is adjusted within the range of 0 to 4 nm. It is done.

In order to adjust the difference of the maximum value and the minimum value of the fluctuation | variation of the retardation value Ro of the said width direction in the range of 0-4 nm, it is achieved by containing the compound which has a structure represented by the said General formula (1), In addition to the adjustment of the related types, the addition amount, etc., it is possible to control the retardation value before stretching, the amount of residual solvent at the time of stretching, the stretching temperature, the stretching ratio, the stretching speed such as the stretching speed, the tension at the stretching, and the shape of the stretching apparatus. Can be.

As a solvent used for the solution casting method, For example, Chlorine solvents, such as chloroform and dichloromethane; Aromatic solvents such as toluene, xylene, benzene, and mixed solvents thereof; Alcohol solvents such as methanol, ethanol, isopropanol, n-butanol and 2-butanol; Methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethyl sulfoxide, dioxane, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone (MEK), ethyl acetate, diethyl ether; Etc. can be mentioned. 1 type of these solvents may be used and may use 2 or more types together.

The solvent used in the present invention is preferably a mixed solvent of a good solvent and a poor solvent, and the good solvent is, for example, dichloromethane or a non-chlorine-based organic solvent as methyl chloride, ethyl acetate, amyl acetate as a chlorine organic solvent. , Acetone, methyl ethyl ketone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3 -Hexafluoro-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, nitroethane, methanol, ethanol, n-propanol, iso-propanol, n- Butanol, sec-butanol, tert-butanol, etc. are mentioned, Especially, it is preferable that it is dichloromethane.

It is preferable that the poor solvent is an alcohol solvent, and it is preferable that the alcohol solvent is selected from methanol, ethanol and butanol from the viewpoint of improving the peelability and enabling high speed and flexibility.

In this invention, if it is a mixed solvent, it is preferable to use 55 mass% or more of the said good solvent with respect to solvent whole quantity, More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more.

When forming an optical film by the solution casting method, the dope containing the compound and solvent which have the structure represented by the said cycloolefin resin, a retardation increasing agent, and General formula (1) is manufactured, and the said dope is made to support on a support body. Flexible

That is, the process which melt | dissolves the compound which has at least a cycloolefin resin, a retardation increasing agent, and the structure represented by General formula (1) to manufacture a dope, the process which casts a dope on the belt-shaped or drum-shaped metal support body, and is flexible It is preferable to have the process of drying the dope made as a web, the process of peeling from a metal support body, the process of extending | stretching or holding a width, the process of further drying, and the process of winding up the finished film.

In the solution casting method, the concentration of the cycloolefin resin in the dope is preferable because the higher concentration can reduce the drying load after casting the metal support, but if the concentration of the cycloolefin resin is too high, the load during filtration increases. Filtration accuracy worsens. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%. It is preferable that the surface of the metal support body in the casting process is mirror-finished, and as a metal support body, the drum which plated the surface with the stainless steel belt or the casting is used preferably.

The width of the cast can be 1 to 4 m. The surface temperature of the metal support of a casting process is set to below the temperature which -50 degreeC-boils and does not foam. The higher the temperature, the faster the drying speed of the web. However, if the temperature is too high, the web may foam or the planarity may deteriorate.

As preferable support body temperature, it determines suitably at 0-100 degreeC, and 5-30 degreeC is more preferable. Or it is also a preferable method to gelatinize a web by cooling and peeling from a drum in the state containing many residual solvents. Although the method of controlling the temperature of a metal support body is not specifically limited, There exists a method of spraying warm air or cold wind, or the method of making hot water contact the back side of a metal support body. Since the use of warm water makes heat transfer more efficient, the time until the temperature of the metal support becomes constant is preferable.

In the case of using the warm air, in consideration of the temperature drop of the web due to latent heat of evaporation of the solvent, the wind having a temperature higher than the target temperature may be used while the foaming is also prevented while the warm air is used above the boiling point of the solvent.

It is preferable to change the temperature of a support body and the temperature of a drying wind until it peels from casting | flow_spread especially, and to dry efficiently.

In order that an optical film may show favorable planarity, 10-150 mass% is preferable, and, as for the residual solvent amount at the time of peeling a web from a metal support body, More preferably, it is 20-40 mass% or 60-130 mass%, Especially Preferably it is 20-30 mass% or 70-120 mass%.

The residual solvent amount is defined by the following formula.

Residual solvent amount (mass%) = {(M-N) / N} × 100

In addition, M is the mass of the sample extract | collected at the arbitrary time in the manufacture or after manufacture of a web or a film, and N is the mass after heating M at 115 degreeC for 1 hour.

Moreover, in the drying process of an optical film, it is preferable to peel a web from a metal support body and to dry it, and to make residual solvent amount 1 mass% or less, More preferably, it is 0.1 mass% or less, Especially preferably, It is 0-0.01 mass% or less.

In the film drying process, generally, the method of drying while conveying a web is employ | adopted by the roller drying method (the method of passing a web through several rollers arrange | positioned up and down alternately), and a tenter system.

The optical film of this invention is characterized by diagonally extending | stretching the said web in the direction of 45 +/- 10 degree with respect to a longitudinal direction, after forming into a film by the solution casting film forming method using the said dope. The stretching is also preferable from the viewpoint of adjusting the smoothness of the film.

In the manufacturing method of the optical film of this invention, although extending | stretching in the diagonal direction is necessary, you may extend | stretch in diagonal direction after extending | stretching in a longitudinal direction and / or the width direction. In this case, you may carry out continuously, It is also preferable to wind up and diagonally stretch, after winding an optical film once.

First, the method of extending | stretching in a longitudinal direction and / or a width direction is demonstrated.

The stretching operation may be divided into multiple stages. In addition, when performing biaxial stretching (stretching to a length direction and a width direction), you may perform simultaneous biaxial stretching or it may carry out in steps. In this case, being stepwise, for example, it is also possible to sequentially perform stretching in which the stretching directions are different, divide the stretching in the same direction into multiple stages, and add stretching in different directions to any of the stages.

In other words, for example, the following stretching steps are possible:

ㆍ stretch in the length direction → stretch in the width direction → stretch in the length direction → stretch in the length direction

ㆍ stretch in the width direction → stretch in the width direction → stretch in the length direction → stretch in the length direction

In addition, simultaneous biaxial stretching also includes extending | stretching in one direction and reducing the tension and shrinking the other one.

It is preferable that the amount of residual solvent at the time of extending | stretching start exists in the range of 2-50 mass%.

When the amount of the residual solvent is 2% by mass or more, the film thickness variation is small, and is preferable from the viewpoint of planarity. When the amount of the residual solvent is within 50% by mass, the unevenness of the surface decreases, and the planarity is improved.

In the manufacturing method of the optical film of this invention, you may extend | stretch to a width direction preferably in a longitudinal direction and / or a width direction so that the film thickness after extending | stretching may become a desired range. Although different depending on the type of resin, when the lowest Tg among the glass transition points (Tg) of the film is TgL and the highest Tg is TgH, the film is drawn in a temperature range of (TgL-200) to (TgH + 50) ° C. It is preferable. When extending | stretching in the said temperature range, since extending | stretching stress can be reduced, haze becomes low. Moreover, the optical film containing the cycloolefin resin which suppresses generation | occurrence | occurrence | production of a fracture, and is excellent in planarity and the coloring property of the film itself is obtained. As for extending | stretching temperature, it is more preferable to carry out in the range of (TgL-150)-(TgH + 40) degreeC.

In the manufacturing method of the optical film of this invention, the film which has the self-supportability peeled from the support body can be extended | stretched in a longitudinal direction by restrict | limiting a traveling speed with an extending | stretching roller. As for the draw ratio of a longitudinal direction, 1.03-2.00 times are preferable in the temperature range of 30-250 degreeC, More preferably, it is 1.10-1.80 times, More preferably, it is 1.20-1.60 times.

In the stretching in the width direction, for example, a method of drying the entire drying process or a part of the processes disclosed in Japanese Patent Application Laid-Open No. 62-46625 while maintaining the width of both ends of the film with a clip or pin in the width direction ( It is called a tenter system), and the tenter system using a clip is especially used preferably.

It is preferable that the film extended | stretched in the longitudinal direction or the unstretched film is extended in the width direction, introduce | transduced into a tenter in the state in which the width direction both ends were gripped by the clip, and traveling with a tenter clip. Although the draw ratio of the width direction is not specifically limited, 1.03-2.00 times are preferable in the temperature range of 30-300 degreeC, More preferably, they are 1.10-1.80 times, More preferably, they are 1.20-1.60 times.

At the time of extending | stretching to the width direction, extending | stretching at the extending | stretching speed of 50-1000% / min in a film width direction is preferable from a viewpoint of improving the planarity of a film.

If the stretching speed is 50% / min or more, the planarity is improved and the film can be processed at high speed. Therefore, the stretching speed is preferable from the viewpoint of production aptitude, and if it is within 1000% / min, the film can be processed without breaking. , desirable.

More preferably, the stretching speed is in the range of 100 to 500% / min. The drawing speed is defined by the following formula.

Stretching speed (% / min) = [(d ₁ / d ₂ ) -1] × 100 (%) / t

(In the above formula, d ₁ is the width dimension of the stretching direction of the resin film after stretching, d ₂ is the width dimension of the stretching direction of the resin film before stretching, and t is the time (min) required for stretching. )

In an extending process, after extending | stretching normally, maintenance and relaxation are performed. That is, it is preferable that this process performs the extending | stretching step which extends a film, the holding | maintenance step which keeps a film in an extended state, and the relaxation step which relaxes a film in the extending direction. In the holding step, the stretching at the stretching ratio achieved in the stretching step is maintained at the stretching temperature in the stretching step. In the relaxation step, the stretching in the stretching step is maintained in the holding step, followed by releasing the tension for stretching to relax the stretching. The relaxation step may be performed at or below the stretching temperature in the stretching step.

Subsequently, the film after extending | stretching is heated and dried. When the film is heated by hot air or the like, a means for discharging the used hot air (air containing solvent or air containing moisture) is provided, and means for preventing mixing of the used hot air is also preferably used. The hot air temperature is more preferably in the range of 40 to 350 ° C. Moreover, about 5 second-30 minutes are preferable, and, as for drying time, 10 second-15 minutes are more preferable.

In addition, the heat-drying means is not limited to hot air, and infrared rays, a heating roller, a microwave, etc. can be used, for example. From a viewpoint of simplicity, it is preferable to dry by hot air, etc., conveying a film by the roller arrange | positioned in a zigzag shape. The drying temperature is more preferably in the range of 40 to 350 ° C. in consideration of the residual solvent amount, the stretching ratio in conveyance, and the like.

In a drying process, it is preferable to dry a film until the amount of residual solvents becomes 0.5 mass% or less.

A winding process is a process of winding up the obtained film and cooling to room temperature. What is necessary is just to be used generally, and the winding machine can be wound up by the winding methods, such as the static tension method, the static torque method, the taper tension method, and the program tension control method with constant internal stress.

[Inclination extension]

As described above, the optical film (retardation film) of the present invention is subjected to the film formation by the solution casting film forming method using the above dope, and then the web is diagonally stretched in the direction within the range of 45 ± 10 ° with respect to the longitudinal direction, It is preferable to adjust the difference of the maximum value and the minimum value of the fluctuation | variation of the retardation value Ro of the width direction in the range of 0-4 nm. For extending | stretching to a diagonal direction, Unexamined-Japanese-Patent No. 2005-321543 and Unexamined-Japanese-Patent No. 2013-120208 can be referred.

(Stretching by an inclined drawing device)

The diagonal stretch method extended | stretched in the direction of 45 +/- 10 degrees is demonstrated below.

In the manufacturing method of the optical film of this invention, it is preferable to use a diagonal stretch apparatus as a method of providing the optical film with the diagonal direction (the ground axis is inclined).

As the oblique stretching apparatus applicable to the present invention, by varying the rail pattern, the orientation angle of the film can be set freely, the orientation axis of the film can be oriented with high precision and left and right equally over the film width direction, and It is preferable that it is a film extending | stretching apparatus which can control film thickness and retardation with high precision.

1 is a schematic view showing an example of a rail pattern of an inclined stretching apparatus applicable to the production of an optical film of the present invention. 1 is an example and the extending | stretching apparatus applicable by this invention is not limited to this.

Generally, in the diagonal stretch apparatus, as shown in FIG. 1, the feeding direction D1 of a long film original fabric differs from the winding direction D2 of the stretched film after extending | stretching, and has comprised feeding angle (theta) i. Feeding angle (theta) i can be arbitrarily set to a desired angle in the range exceeding 0 degrees and less than 90 degrees, and is adjusted in the range of 45 +/- 10 degrees in the case of this invention. θ i is preferably in the range of 45 ± 5 °, more preferably in the range of 45 ± 2 °. By adjusting in the said range, it becomes possible to produce the circularly-polarizing plate mentioned later with a roll-to-roll system with a long polarizer.

The long film original fabric is gripped by left and right grippers (tenters) at an inclined stretching device inlet (position A in the drawing), and travels along with travel of the grippers. The left and right grippers are asymmetrical left and right grippers Ci and Co facing in a direction substantially perpendicular to the advancing direction (feeding direction D1) of the film at the inlet of the inclined stretching device (position A in the figure). The film is held on the in-rail Ri and Ro, and the film held by the tenter is opened at the position at the end of the stretching (the position B in the drawing).

At this time, the left and right grippers, which faced each other at the inlet of the inclined stretching device (position A in the drawing), travel along the rails Ri and Ro which are asymmetrical, so that the grippers Ci that travel on the Ri side are And the positional relationship which advances with respect to the holding | gripping tool Co which travels Ro side.

That is, at the inclination stretching apparatus inlet (gripping start position by the gripping opening of the film) A, the gripping openings Ci and Co facing each other in a direction substantially perpendicular to the feeding direction D1 of the film are obtained when the stretching of the film is completed. In the state in position B, the straight line which connected the holding | gripping tool Ci and Co inclines by the angle (theta) L with respect to the direction substantially perpendicular to the winding direction D2 of a film.

According to the above method, a film original fabric is diagonally stretched. Almost vertical here means the thing of the range of 90 +/- 1 degree.

When it demonstrates in more detail, in the method of manufacturing the optical film of this invention, it is preferable to perform diagonal stretch using the tenter which can be diagonally stretched mentioned above.

This stretching apparatus is an apparatus which heats a film original fabric to arbitrary temperatures which can be extended | stretched, and diagonally stretches.

This stretching apparatus is equipped with a pair of rail and many holding | gripping tools which drive | work this rail top from the left and right which a heating zone and the holding | gripping tool for conveying a film drive | work.

Both ends of the film sequentially supplied to the inlet of the stretching apparatus are gripped by the gripper, the film is guided into the heating zone, and the film is opened from the gripper at the outlet of the stretching apparatus. The film opened from the gripper is wound around the winding core. The pair of rails each have an endless continuous trajectory, and the gripping openings in which the gripping of the film is opened at the exit of the stretching apparatus travel outside and return to the inlet sequentially.

Moreover, the rail pattern of a extending | stretching apparatus becomes asymmetrical from left to right, and the rail pattern can be adjusted manually or automatically according to the orientation angle, draw ratio, etc. which are given to the elongate stretched film which should be manufactured.

In the diagonal stretch apparatus used by this invention, it is preferable that the position of each rail part and rail connection part can be set freely, and a rail pattern can be changed arbitrarily ((circle part in FIG. 1 shows an example of a connection part).).

In this invention, the holding | gripping tool of an extending | stretching apparatus maintains a fixed space | interval with the holding | gripping tool of back and front, and runs at a fixed speed. Although the traveling speed of a holding | gripping tool can be selected suitably, it is usually in the range of 1-100 m / min.

The traveling speed difference between the pair of left and right grippers is usually 1% or less, preferably 0.5% or less, and more preferably 0.1% or less of the travel speed. This is because if there is a difference in advancing speed at the right and left sides of the film at the exit of the stretching step, wrinkles and slippage occur at the exit of the stretching step, and therefore, the speed difference between the left and right grip ports is required to be substantially the same speed.

In general stretching apparatuses, there are speed irregularities that occur in orders of seconds or less, depending on the period of the teeth of the sprocket driving the chain, the frequency of the driving motor, and the like, and often produce several percent of the nonuniformity. This does not apply to speed differences.

In the stretching apparatus applicable to this invention, especially the location where the conveyance of a film obliquely requires a large bending rate in the rail which regulates the trajectory of a holding | gripping tool. For the purpose of avoiding interference between grippers due to sudden bending or localized stress concentration, it is preferable that the trajectory of the gripper is curved at the bent portion.

In the present invention, the long film original fabric is held at both ends of the inclined stretching device (position A in the drawing) by the gripping openings on the left and right, and travels along the running of the gripping opening. At the inlet of the inclined stretching device (the position of A in the drawing), the left and right grippers opposed to each other in a direction substantially perpendicular to the film advancing direction (feeding direction D1) travel on a left and right asymmetric rail, and the preheating zone and the stretching are performed. The zone passes through a heating zone having a thermal fixation zone.

The preheating zone refers to a section in which the interval between the gripper gripping both ends is maintained at a constant interval at the heating zone inlet.

The stretching zone refers to a section from which the interval between the grippers holding the both ends begins to reach a predetermined interval. In the stretching zone, oblique stretching as described above is performed, but may be stretched in the longitudinal direction or the transverse direction before and after oblique stretching as necessary. In the case of the oblique stretching, it is accompanied by shrinkage in the MD direction (the fast axis direction) which is a direction perpendicular to the slow axis during bending.

The heat fixation zone refers to a section in which the grippers at both ends travel in parallel with each other in a period in which the interval between the grippers behind the stretching zone is constant again. After passing through the heat setting zone, you may pass the section (cooling zone) in which the temperature in a zone is set to the glass transition temperature Tg or less of the thermoplastic resin which comprises a film. At this time, in consideration of shrinkage of the film due to cooling, it may be a rail pattern that narrows the gap between the gripping holes that face each other in advance.

The temperature of each zone is with respect to the glass transition temperature Tg of cycloolefin resin, the temperature of a preheating zone is in the range of Tg- (Tg + 30 degreeC), and the temperature of an extending zone is in the range of Tg- (Tg + 30 degreeC). It is preferable to set the temperature of a cooling zone in the range of (Tg-30 degreeC)-Tg.

Moreover, in order to control the thickness nonuniformity of the width direction, you may provide a temperature difference in the width direction in an extending zone. In order to put a temperature difference in a width direction in an extending zone, the method of adjusting the opening degree of the nozzle which blows warm air into a constant temperature chamber so as to put a difference in the width direction, or heat-controlling by arrange | positioning a heater in the width direction is well-known. Method can be used.

The lengths of the preheating zone, the stretching zone, the shrinking zone, and the cooling zone can be appropriately selected. The length of the preheating zone is usually in the range of 100 to 150% with respect to the length of the stretching zone, and the length of the fixed zone is usually 50 to 100. It is in the range of%.

The draw ratio (W / Wo) in an extending process becomes like this. Preferably it exists in the range of 1.3-3.0, More preferably, it exists in the range of 1.5-2.8. If the draw ratio is in this range, the thickness nonuniformity of the width direction can be made small.

In the stretching zone of the diagonal stretching apparatus, it is possible to further improve the thickness nonuniformity in the width direction when a difference is made in the stretching temperature in the width direction. In addition, Wo represents the film width before extending | stretching, and W represents the film width after extending | stretching.

As a diagonal stretch method applicable in this invention, the extending | stretching method shown to FIG. 2A-FIG. 2C, FIG. 3A, and FIG. 3B is mentioned besides the method shown in the said FIG.

Fig. 2 is a schematic view showing an example of an example of a manufacturing method applicable to the present invention (an example of diagonal drawing after feeding from a long film raw material roller), and shows a pattern for feeding out and diagonally stretching a long film raw material once wound in a roll shape. .

Fig. 3 is a schematic view showing an example of another manufacturing method applicable to the present invention (example of continuous diagonal stretching without winding a long film original fabric), and showing a pattern for continuously performing diagonal stretching without winding a long film original fabric. Indicates.

In FIG.2 and FIG.3, the code | symbol 15 has shown the diagonal stretch apparatus, the code | symbol 16, the film feeding apparatus, the code | symbol 17, the conveyance direction change device, the code | symbol 18, the winding device, and the code | membrane apparatus 19. In each figure, the code | symbol which shows the same thing may be abbreviate | omitted.

The film feeding device 16 is slidable and swivelable or is slidable so that the film is fed at a predetermined angle with respect to the inclined stretching device inlet, and is slidable to the inclined stretching device inlet by the conveying direction changing device 17. It is preferable that the film can be sent out.

2A-2C have shown the pattern which changed the arrangement | positioning of the film feeding apparatus 16 and the conveyance direction changing apparatus 17, respectively.

3A and 3B show a pattern in which the film formed by the film forming apparatus 19 is directly fed to the oblique stretching apparatus 15.

By setting the film feeding device 16 and the conveying direction changing device 17 in such a configuration, it becomes possible not only to narrow the width of the entire manufacturing apparatus, but also to finely control the feeding position and angle of the film. It becomes possible to obtain the elongate stretched film with small fluctuation | variation of a film thickness and an optical value. In addition, by making the film feeding device 16 and the conveying direction change device 17 movable, the bite defect to the film of a left-right clip can be prevented effectively.

The winding device 18 is capable of finely controlling the take-up position and angle of the film by arranging the film to be taken at a predetermined angle with respect to the inclined stretching device outlet, whereby the variation in film thickness and optical value is small. It becomes possible to obtain a long stretched film. Therefore, while the wrinkle generation of a film can be effectively prevented, since the winding property of a film improves, it becomes possible to wind a film long.

In this invention, the take-out tension T (N / m) of the film after extending | stretching is 100N / m <T <300N / m, Preferably it adjusts within the range of 150N / m <T <250N / m.

[6] properties of optical films

Although the thickness of the optical film of this invention differs according to a use purpose, it is the range of 5-200 micrometers normally, the range of 5-100 micrometers is preferable, It is preferable that it is 5-50 micrometers for liquid crystal display devices, In consideration of recent thinning, the thickness is more preferably 25 µm or less, and particularly preferably 20 µm or less.

In thinning an optical film to 25 micrometers or less, generally, in order to maintain the performance of a transparent resin film, it is necessary to increase content of an additive, and the bleed out of an additive becomes a problem, but it is general according to this invention. Since the compound which has a structure represented by Formula (1) is excellent in bleed-out resistance, thin film formation is possible.

In the production of the film thickness, the solid content concentration contained in the dope, the slit gap of the die mold, the extrusion pressure from the die, the metal support speed and the like may be adjusted so as to have a desired thickness. The range of 0.5-4 m is preferable, as for the width | variety of the optical film obtained as mentioned above, More preferably, it is the range of 0.6-3 m, More preferably, it is 0.8-2.5 m. It is preferable to wind up the length in the range of 100-10000m per roll, More preferably, it is the range of 500-9000m, More preferably, it is the range of 1000-8000m.

The optical film of this invention can implement | achieve a desired optical characteristic by suitably adjusting process conditions, such as the polymer structure to be used, the kind and addition amount of an additive, extending | stretching temperature, a draw ratio, and residual volatile matter at the time of peeling.

In the present specification, Ro and Rt each represent an in-plane retardation value and a retardation value in the thickness direction at an optical wavelength of 550 nm in an environment of 23 ° C.55% RH.

Ro is measured by injecting light having a wavelength of 550 nm in the film normal direction in KOBRA 21ADH (manufactured by Oji Scientific Instruments Co., Ltd.). Rt is a retardation value measured by injecting light having a wavelength of 550 nm from a direction inclined + 40 ° with respect to the film normal direction using the Ro, the in-plane slow axis (determined by KOBRA 21ADH) as the inclination axis (rotation axis). Based on the retardation values measured in a total of three directions of retardation values measured by injecting light having a wavelength of λnm from a direction inclined at -40 ° with respect to the film normal direction using the in-plane slow axis as the inclination axis (rotation axis). KOBRA 21ADH is calculated. Here, the hypothetical value of the average refractive index may be a polymer handbook (JOHN WILEY & SONS, INC) and catalog values of various optical films. The thing with which the value of an average refractive index is unknown can be measured with an Abbe refractometer. By inputting the assumption values and film thicknesses of these average refractive indices, KOBRA 21ADH calculates n _x , n _y , n _z, and calculates the retardation value based on the following formulas (i) and (ii).

Formula (i): Ro = (n _x -n _y ) x d (nm)

Formula (ii): Rt = {(n _x + n _y ) / 2-n _z } × d (nm)

(In formula, Ro represents the in-plane retardation value in a film, Rt represents the retardation value of the thickness direction in a film. Moreover, d represents the thickness (nm) of an optical film. N _x is a film of In-plane maximum refractive index is shown and it is also called the refractive index of a slow axis direction n _y represents the refractive index of the direction orthogonal to a slow axis in a film plane, n _z represents the refractive index of the film in a thickness direction.)

The slow axis in the in-plane direction of the optical film of the present invention is inclined within the range of 45 ± 10 ° with respect to the longitudinal direction.

Although the retardation value of the optical film of this invention is not specifically limited, In order to function as a (lambda) / 4 plate in a visible light region, when a range of Ro is 100-180 nm and Rt is a range of 50-200 nm, a circularly-polarizing plate is provided. It can be used suitably for one display apparatus.

It is preferable that the optical film of this invention is high transparency from a viewpoint of contrast improvement or brightness improvement. The total light transmittance measured after humidity in the environment of 23 ° C.55% RH is 80% or more, preferably 85% or more, more preferably 90% or more, particularly preferably 95% or more. The total light transmittance can be measured according to JIS7573 "Method of Obtaining Plastic-Total Light Transmittance and Total Light Reflectance".

It is preferable that it is 3% or less in equilibrium moisture content in 25 degreeC 60% RH from a viewpoint of retardation variation and bending, and, as for the optical film of this invention, it is more preferable that it is 1% or less. By setting the equilibrium moisture content to 3% or less, it is easy to cope with the change in humidity, and the optical properties and dimensions are less likely to change more preferably.

The equilibrium moisture content is left for 4 hours or more in a humidified room at 23 ° C. and 20% RH, followed by 24 hours in a humidified room at 23 ° C. and 80% RH, and the sample is placed in a trace moisture meter (eg, Mitsubishi. After drying and vaporizing moisture at the temperature of 150 degreeC using Kagaku Analytec Co., Ltd. product, CA-20 type | mold, it quantitates by the Karl Fisher method.

[7] optical film applications

It is preferable that the optical film (henceforth the optical film of this invention) obtained from the elongate optical film of this invention is a functional film used for various display apparatuses, such as a liquid crystal display, a plasma display, an organic electroluminescent display, and a touch panel. Specifically, the optical film of the present invention may be an optical compensation film such as a polarizing plate protective film for liquid crystal display devices, a retardation film, an antireflection film, a brightness enhancement film, a hard coating film, an antiglare film, an antistatic film, and an enlarged viewing angle. have. Typically, the optical film of this invention is a polarizing plate protective film.

[7.1] circular polarizers

A circularly polarizing plate can be manufactured using the optical film of this invention. It is preferable that a circularly polarizing plate is produced by cutting out the long roll which has a long protective film, a long polarizer, and a long this invention optical film (optical film provided with (lambda) / 4 phase difference) in this order.

The circular polarizing plate is produced using the optical film of the present invention, and in particular, it is preferable that the circular polarizing plate is produced using a film having a λ / 4 retardation. Therefore, the organic electroluminescent display device (also referred to as an organic EL display device) described later And the like, the effect of shielding the specular reflection of the metal electrode of the organic EL element can be exhibited at all wavelengths of visible light. As a result, black projection can be improved while the projection at the time of observation can be prevented.

Moreover, it is preferable that the said circularly polarizing plate is equipped with the ultraviolet absorption function.

It is preferable from a viewpoint that both the polarizer and the organic electroluminescent element can express the protective effect with respect to an ultraviolet-ray if the protective film of the visual recognition side is equipped with the ultraviolet absorbing function.

Moreover, when the phase difference film on the light-emitting side also has an ultraviolet absorbing function, when it is used for the display apparatus provided with an organic EL element, deterioration of an organic EL element can be suppressed more.

Moreover, the said circularly polarizing plate has a polarizer which has an absorption axis in a longitudinal direction by using the optical film of this invention which adjusted the angle of slow axis (that is, orientation angle (theta)) to be in the range of 45 +/- 10 degrees with respect to a longitudinal direction as a retardation film. In a roll-to-roll system, the formation of the adhesive layer and the bonding of the polarizer and the retardation film are enabled by a consistent production line.

Specifically, after finishing the process of extending | stretching a polarizing film in the longitudinal direction and manufacturing the polarizer which has an absorption axis in a longitudinal direction, the process of bonding a polarizer and retardation film in the following drying process or after a drying process can be incorporated. have. Each can be fed continuously, and also wound up in a rolled state after joining, thereby connecting to a production line consistent with the next process.

In addition, when bonding a polarizer and retardation film, a protective film can also be supplied in a roll state at the same time, and can also be bonded continuously. It is more preferable to bond retardation film and a protective film simultaneously to a polarizer from a viewpoint of a performance and a production efficiency. That is, after finishing the process of extending | stretching a polarizing film and manufacturing a polarizer, after a drying process performed or after a drying process, a protective film and retardation film are respectively bonded by the adhesive agent on both surfaces, and the circular polarizing plate of a roll state is It is also possible to obtain.

Although the said circularly-polarizing plate can be provided in a liquid crystal display device or an organic electroluminescence display, when it applies to an organic electroluminescence display, it exhibits the effect which shields the mirror surface reflection of the metal electrode of an organic electroluminescent illuminator.

(Protective film)

It is preferable that the said circularly-polarizing plate clamps a polarizer by the optical film and protective film of this invention.

As such a protective film, another cellulose ester containing film is used suitably, For example, a commercially available cellulose ester film (for example, Konica Minolta Tak KC8UX, KC5UX, KC4UX, KC8UCR3, KC4SR, KC4BR, KC4CR, KC4DR, KC4FR, KC4KR) , KC8UY, KC6UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC2UA, KC4UA, KC6UAKC, 2UAH, KC4UAH, KC6UAH, Fuji Kota Minolta Co., Ltd., Fuji Tak T40UZ, Fuji Taku T60UZ Fuji Tak TD60UL, Fuji Tak TD40UL, Fuji Tak R02, Fuji Tak R06, and above Fuji Film Co., Ltd. are preferably used.

Although the thickness in particular of a protective film is not restrict | limited, It can be about 10-200 micrometers, Preferably it exists in the range of 10-100 micrometers, More preferably, it exists in the range of 10-70 micrometers.

(Polarizer)

A polarizer is an element which only passes the light of a polarization plane of a fixed direction, and the polyvinyl alcohol-type polarizing film is contained as an example.

In the polyvinyl alcohol polarizing film, there are those obtained by dyeing iodine on a polyvinyl alcohol-based film and dyeing a dichroic dye.

A polarizer is uniaxially stretched after uniaxially stretching a polyvinyl alcohol film, or uniaxially stretched after dyeing a polyvinyl alcohol film, and preferably obtained by further performing a durability treatment with a boron compound.

It is preferable that it is in the range of 5-30 micrometers, and, as for the film thickness of a polarizer, it is more preferable to exist in the range which is 5-15 micrometers.

As a polyvinyl alcohol film, content of 1-4 mol%, polymerization degree 2000-4000, saponification degree 99.0-99.99 mol% of ethylene unit as described in Unexamined-Japanese-Patent No. 2003-248123, 2003-342322, etc. are mentioned. Ethylene-modified polyvinyl alcohol is preferably used. Moreover, it is preferable to produce a polarizer by bonding with the optical film of this invention by the method of Unexamined-Japanese-Patent No. 2011-100161, Unexamined-Japanese-Patent No. 4471205, and 4804589.

(glue)

Although bonding of the optical film and polarizer of this invention is not specifically limited, After saponifying the said optical film, it can carry out using a fully saponified polyvinyl alcohol-type adhesive agent.

Moreover, although it can also bond using an active-ray curable adhesive etc., it is preferable that it is joining using a photocurable adhesive agent from the point which the elasticity modulus of the adhesive bond layer obtained is high, and it is easy to suppress deformation of a polarizing plate.

As a preferable example of a photocurable adhesive agent, (alpha) cationically polymerizable compound, ((beta)) photocationic polymerization initiator, ((gamma)) which is disclosed by Unexamined-Japanese-Patent No. 2011-028234, it is maximum to the light of wavelength longer than 380 nm. The photocurable adhesive composition containing each component of the photosensitizer which shows absorption, and ((delta)) naphthalene type photosensitization adjuvant is mentioned. However, other photocurable adhesive agents may be used.

[Method for Manufacturing Polarizing Plate]

Hereinafter, an example of the manufacturing method of the polarizing plate using a photocurable adhesive agent is demonstrated.

The polarizing plate is (1) an adhesive treatment step of applying the following photocurable adhesive to at least one of a pretreatment step for facilitating adhesion treatment of the surface to which the polarizer of the optical film is adhered, (2) the adhesive face of the polarizer and the optical film, ( 3) a bonding process for bonding the polarizer and the optical film through the obtained adhesive layer, and (4) a curing process for curing the adhesive layer in a state where the polarizer and the optical film are bonded through the adhesive layer. Can be. What is necessary is just to implement the pretreatment process of (1) as needed.

<Pretreatment Process>

In a pretreatment process, an adhesion facilitation process is performed to the adhesive surface of an optical film with a polarizer.

In the case of adhering the optical film to both surfaces of the polarizer, the adhesion facilitating treatment is performed on the adhesive surface of each optical film with the polarizer. Examples of the adhesion facilitating treatment include corona treatment and plasma treatment.

<Adhesive Coating Process>

In an adhesive agent application process, the said photocurable adhesive agent is apply | coated to at least one of the adhesive surfaces of a polarizer and an optical film.

When apply | coating a photocurable adhesive agent directly to the surface of a polarizer or an optical film, there is no special limitation in the coating method. For example, various coating methods, such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater, can be used.

Moreover, the method which softens a photocurable adhesive agent between a polarizer and an optical film, pressurizes with a roller, etc. and presses it uniformly can also be used.

<Joining process>

In this way, after apply | coating a photocurable adhesive agent, it is provided to a joining process.

In this bonding process, when a photocurable adhesive agent is apply | coated to the surface of a polarizer in the previous application | coating process, an optical film overlaps there, for example. When a photocurable adhesive agent is apply | coated to the surface of an optical film in the previous application | coating process, a polarizer overlaps there.

In addition, when a photocurable adhesive agent is cast between a polarizer and an optical film, a polarizer and an optical film overlap in that state. As a case where an optical film is adhere | attached on both surfaces of a polarizer, when a photocurable adhesive agent is used for both surfaces, an optical film superimposes on both surfaces of a polarizer via a photocurable adhesive agent, respectively. And usually, in this state, from both surfaces (when superimposing an optical film on the single side | surface of a polarizer, a polarizer side and an optical film side, and an optical film side of both surfaces when an optical film is superimposed on both surfaces of a polarizer), It is pressed by a roll or the like.

The material of a roll can use a metal, rubber | gum, etc. The rollers arranged on both surfaces may be the same material or different materials.

<Hardening process>

In a hardening process, an active energy ray is irradiated to an uncured photocurable adhesive agent, and the adhesive bond layer containing an epoxy compound or an oxetane compound is hardened. Thereby, the polarizer and optical film which were superimposed through the photocurable adhesive agent are adhere | attached.

When bonding an optical film to the single side | surface of a polarizer, you may irradiate an active energy ray from anywhere on the polarizer side or the optical film side.

In addition, when bonding an optical film to both surfaces of a polarizer, in the state which superimposed the optical film on both surfaces of a polarizer through a photocurable adhesive agent, the active energy ray is irradiated from either optical film side, and both sides photocurable adhesive agent It is advantageous to cure simultaneously.

As active energy rays, visible rays, ultraviolet rays, X-rays, electron beams and the like can be used, and in general, electron beams or ultraviolet rays are preferably used since they are easy to handle and have a sufficient curing rate.

Arbitrary suitable conditions can be employ | adopted as long as the irradiation conditions of an electron beam can be hardening the said adhesive agent. For example, as for electron beam irradiation, acceleration voltage becomes like this. Preferably it exists in the range of 5-300 kV, More preferably, it exists in the range of 10-250 kV. If the accelerating voltage is within the above range, the electron beam reaches the adhesive agent and can be hardened reliably, and the penetration force passing through the sample is too strong so that the electron beam may spring up and there is no fear of damaging the transparent optical film or polarizer.

As irradiation dose, it exists in the range of 5-100 kGy, More preferably, it exists in the range of 10-75 kGy. When the irradiation dose is within the above range, the adhesive is sufficiently cured and the reduction in mechanical strength and yellowing can be prevented without damaging the transparent optical film or the polarizer, and the predetermined optical properties can be obtained.

Irradiation conditions of an ultraviolet-ray can adopt arbitrary appropriate conditions as long as it is a condition which can harden the said adhesive agent. Dose of ultraviolet radiation at a cumulative light intensity and in a range of 50 to 1500mJ / cm ² preferably, and more preferably in a range of 100 to 500mJ / cm ^2.

In the polarizing plate obtained as mentioned above, although the thickness of an adhesive bond layer is not specifically limited, Usually, it exists in the range of 0.01-10 micrometers, Preferably it exists in the range of 0.5-5 micrometers.

[7.2] display devices

The display apparatus of this invention is equipped with the optical film obtained from the elongate optical film of this invention, and is produced.

Moreover, it is preferable that the display apparatus of this invention is equipped with the circularly-polarizing plate using the optical film of this invention, and organic electroluminescent element. By using the optical film of this invention, the projection at the time of observation can be prevented and the organic electroluminescence display which black expression improved was obtained.

The screen size of the display device is not particularly limited and can be 20 inches or more.

4 is a schematic explanatory diagram of a configuration in the case where the display device of the present invention includes an organic EL element. The display device configuration of the present invention is not limited to that shown in FIG. 4.

As shown in FIG. 4, the metal electrode 102, the TFT 103, the organic light emitting layer 104, the transparent electrode (ITO, etc.) 105 are sequentially disposed on the transparent substrate 101 using glass, polyimide, or the like. On the organic EL element b having the insulating layer 106, the sealing layer 107, and the functional film 108 (can be omitted), the polarizer 110 is the λ / 4 retardation film 109 which is the optical film of the present invention. And the long circular polarizing plate c sandwiched by the protective film 111 are provided to constitute the display device a.

It is preferable that the hardened layer 112 is laminated | stacked on the protective film 111. FIG.

The cured layer 112 not only prevents scratches on the surface of the display device but also has an effect of preventing warping due to an elongated circular polarizing plate.

Furthermore, you may have the antireflection layer 113 on a hardened layer.

The thickness of the said organic electroluminescent element itself is about 1 micrometer.

Generally, the display apparatus provided with organic electroluminescent element laminates | stacks a metal electrode, an organic light emitting layer, and a transparent electrode in order on the transparent substrate, and forms the element (organic EL element) which is a light-emitting body.

Here, an organic light emitting layer is a laminated body of various organic thin films, For example, the laminated body of the hole injection layer containing a triphenylamine derivative etc., and the light emitting layer containing fluorescent organic solids, such as anthracene, and such a light emitting layer and perylene The structure which has various combinations, such as the laminated body of the electron injection layer containing a derivative | guide_body, etc., these laminated bodies of a hole injection layer, a light emitting layer, and an electron injection layer, is known.

In the display device, by applying a voltage to the transparent electrode and the metal electrode, holes and electrons are injected into the organic emission layer, and energy generated by recombination of these holes and electrons excites the fluorescent material, and the excited fluorescent material is in a ground state. It emits light on the principle of emitting light when it returns to. The mechanism of intermediate recombination is the same as that of a general diode, and as can be expected from this, the current and the emission intensity exhibit strong nonlinearity accompanied by rectification with respect to the applied voltage.

In the display device, in order to take out light emission from the organic light emitting layer, at least one electrode is required to be transparent, and it is usually preferable to use a transparent electrode formed of a transparent conductor such as indium tin oxide (ITO) as the anode. Do.

On the other hand, in order to facilitate electron injection and increase luminous efficiency, it is important to use a material having a small work function for the cathode, and metal electrodes such as Mg-Ag and Al-Li are usually used.

The circularly polarizing plate having the above retardation film can be applied to a display device including a large screen having a screen size of 20 inches or more, that is, a diagonal distance of 50.8 cm or more.

Example

Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, a "mass part" or the "mass%" is represented.

Example 1

[Cycloolefin resin]

As the cycloolefin resin used in the examples, the following cycloolefin resins A and B were used.

Cycloolefin resin A: ARTON G7810 (product made by JSR Corporation)

Cycloolefin resin B: ARTON R5000 (product made by JSR Corporation)

[Retardation synergist]

Retardation synergist 1: Triazine compound I- (3) represented by general formula (I)

Retardation synergist 2: Rod-shaped compound (4) which has two aromatic rings represented by general formula (III)

Retardation synergist 3: Triphenylene compound V-1 represented by general formula (II)

In the table, the retardation synergist is denoted by R 1, R 2, and R 3 in order.

[Compound having a structure represented by General Formula (1)]

As a compound which has a structure represented by General formula (1), the following exemplary compound 1, 2, and 7 were used.

Example compound 1: Tinuvin 928 (manufactured by BASF Japan Co., Ltd.)

Exemplary compound 2: Tinuvin 109 (manufactured by BASF Japan Co., Ltd.)

Example compound 7: LA-F70 (made by ADEKA Co., Ltd.)

Comparative Compound

The following comparative compound 1 was used as a comparative example.

[Production of Optical Film 101]

Preparation of Particulate Dispersion

11.3 mass parts of fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.) and 84 mass parts of ethanol were stirred and mixed with a dissolver for 50 minutes, and then dispersed in Manton-Gaulin.

5 mass parts of fine particle dispersion was added slowly to 100 mass parts of fully stirred dichloromethane in a dissolution tank. In addition, the particle size of the secondary particles was dispersed with an attritor so as to have a predetermined size. This was filtered by FineMet NF manufactured by Nippon Seishen Co., Ltd., to prepare a fine particle addition liquid.

<Production of main dope>

The main dope of the following composition was manufactured. First dichloromethane was added to the pressure dissolution tank. It injected | threw-in stirring the cycloolefin resin and fine particle addition liquid to the pressure dissolution tank containing dichloromethane. It was dissolved completely while heating and stirring. This was filtered using Azumi Rossi No. 244 manufactured by Azumi Rossi Co., Ltd. to prepare a main dope.

100 mass parts of cycloolefin resin A

200 parts by mass of dichloromethane

10 parts by mass of ethanol

3 parts by mass of fine particle addition liquid

Subsequently, the main dope was uniformly cast on the stainless steel belt support body at the temperature of 31 degreeC, and 1800 mm width using an endless belt casting apparatus. The temperature of the stainless steel belt was controlled at 28 degreeC.

On the stainless steel belt support, the solvent was evaporated until the amount of residual solvent in the cast film became 30%. Then, it peeled from the stainless steel belt support body by peeling tension of 128 N / m. The peeled film was diagonally stretched 2.0 times in the direction which the said (theta) i becomes 45 degrees with respect to the longitudinal direction using the apparatus of FIG. 3A under the conditions of 160 degreeC. The residual solvent at the time of extending | stretching start was 5 mass%. Then, drying was complete | finished, conveying a dry zone with many rollers, the edge part which inserted with the tenter clip was slit by the laser cutter, and it wound up after that, and obtained the optical film 101 with a film thickness of 20 micrometers.

[Production of Optical Film 102]

In the preparation of the optical film 101, an optical film 102 was produced in the same manner except that the following main dope was used.

<Production of main dope>

The main dope of the following composition was manufactured. First, dichloromethane and ethanol were added to the pressure dissolution tank. Cycloolefin resin A, the retardation increasing agent 1, and the fine particle addition liquid were thrown into the pressure dissolution tank containing dichloromethane and ethanol, stirring. It was dissolved completely while heating and stirring. This was filtered using Azumi Rossi No. 244 manufactured by Azumi Rossi Co., Ltd. to prepare a main dope.

100 mass parts of cycloolefin resin A

200 parts by mass of dichloromethane

10 parts by mass of ethanol

3 parts by mass of retardation synergist

3 parts by mass of fine particle addition liquid

[Production of Optical Film 103]

In the preparation of the optical film 102, an optical film 103 was produced in the same manner except that the retardation increasing agent 2 was used instead of the retardation increasing agent 1.

[Production of Optical Film 104]

In the preparation of the optical film 102, an optical film 104 was produced in the same manner except that the retardation increasing agent 3 was used instead of the retardation increasing agent 1.

[Production of Optical Film 105]

In the preparation of the optical film 102, the following main dope was used, and the optical film 105 was produced similarly except having made the direction of extending | stretching into the direction which the said (theta) i becomes 30 degrees with respect to a longitudinal direction.

<Production of main dope>

The main dope of the following composition was manufactured. First, dichloromethane and ethanol were added to the pressure dissolution tank. The cycloolefin resin A, the retardation increasing agent 1, and the fine particle addition liquid were thrown into the pressure dissolution tank containing dichloromethane and ethanol, stirring. It was dissolved completely while heating and stirring. This was filtered using Azumi Rossi No. 244 manufactured by Azumi Rossi Co., Ltd. to prepare a main dope.

100 mass parts of cycloolefin resin A

200 parts by mass of dichloromethane

10 parts by mass of ethanol

3 parts by mass of retardation synergist

Compound having a structure represented by General Formula (1): 3 parts by mass of Exemplary Compound 1

3 parts by mass of fine particle addition liquid

[Production of Optical Films 106 to 109]

In the production of the optical film 104, the optical films 106 to 109 were produced in the same manner except that the stretching direction was changed to the directions in which the above? I became 60 °, 35 °, 55 ° and 45 ° with respect to the longitudinal direction. It was.

[Production of Optical Films 110 to 129]

In preparation of the optical film 109, except having changed the kind of cycloolefin resin, the kind and addition amount of a retardation increasing agent, and the kind and addition amount of the exemplary compound which have a structure represented by General formula (1), respectively, and the film thickness, respectively. In the same manner, optical films 110 to 129 were produced.

≪Evaluation≫

About the produced optical films 101-129, it evaluated by the following method.

(1) phase difference unevenness

Ten points were sampled at 50 mm intervals in the width direction of each optical film, and the retardation value Ro (light wavelength 550 nm) was measured in the following procedure.

The difference between the maximum value and the minimum value of all the measured values was evaluated according to the following criteria as phase difference unevenness.

A: phase difference unevenness is less than 1 nm

B: phase difference unevenness is 1 nm or more but less than 2 nm

C: phase difference unevenness is 2 nm or more but less than 4 nm

D: phase difference nonuniformity is 4 nm or more and less than 6 nm

E: 6 nm or more in phase difference nonuniformity

Here, if it is C level or more, there is no problem practically, it is preferable that it is B level, and it is more preferable that it is A level.

(Measurement of phase difference value Ro)

Ro represents the in-plane retardation value at an optical wavelength of 550 nm in an environment of 23 ° C.55% RH.

Ro was measured by injecting light having a wavelength of 550 nm in the film normal line direction in KOBRA 21ADH (manufactured by Oji Scientific Instruments Co., Ltd.). The average refractive index value was measured with an Abbe refractometer. By inputting the assumption values and the film thicknesses of these average refractive indices, KOBRA 21ADH calculates n _x , n _y , n _z and calculates the phase difference value Ro based on the following formula (i).

Formula (i): Ro = (n _x -n _y ) x d (nm)

(In formula, d represents the thickness (nm) of an optical film. N _x represents the largest refractive index (ground axis) in the plane of a film, and n _y represents the refractive index of the direction orthogonal to a slow axis in a film plane. Indicates.)

(2) Poor appearance (wrinkling, sagging)

In the production process, the appearance of the film after 10 lots of diagonal stretching was visually observed, and the degree of occurrence of wrinkles and sagging was evaluated based on the following criteria.

◎: There are no wrinkles or sags in all 10 lots

(Circle): There are no wrinkles and sagging with respect to 9 lots, and generation | occurrence | production of the other 1 lot wrinkles and sagging is also slight

(Triangle | delta): No wrinkles and sagging generate | occur | produced with respect to 6 lots, and the practically impossible level was mixed among the other 4 lots of wrinkles and sagging.

X: There are no wrinkles and sagging with respect to 4 lots, and wrinkles and sagging of the remaining 6 lots are practically impossible levels.

Table 1 shows the above evaluation results.

From Table 1, it turns out that the structural optical film of this invention is excellent in retardation nonuniformity and also produces the appearance defect (wrinkle, sagging).

Example 2

In the preparation of the optical film 109 of Example 1, the optical film of the present invention was similarly prepared except for changing to the exemplary compounds 3, 8, and 9 of the compound having a structure represented by the following General Formula (1) instead of the exemplary compound 1. Was prepared, and the retardation nonuniformity evaluated in Example 1 was evaluated, the result of the optical film 109 was reproduced, and the result which was excellent in retardation nonuniformity was obtained.

Exemplary compound 3: Tinuvin 171 (manufactured by BASF Japan Co., Ltd.)

Example compound 8: Tinuvin 479 (manufactured by BASF Japan Co., Ltd.)

Example compound 9: Tinuvin 460 (manufactured by BASF Japan Co., Ltd.)

Example 3

(Production of circularly polarizing plate)

Using the produced optical films 101-129, circularly polarizing plates 101-129 were produced by the following procedures.

A roll-shaped polyvinyl alcohol film having a thickness of 80 µm was continuously stretched five times in an aqueous solution of iodine and dried to obtain a polarizer having a thickness of 20 µm. Using an acrylic adhesive as an adhesive, bonding is performed using an adhesive such that the slow axis of each optical film produced in Example 1 and the absorption axis of the polarizer are 45 °, and a protective film (Konica Minolta Tag KC4UY, 40 micrometers in thickness and Konica Minolta Co., Ltd. were bonded together by the water pool, and the circularly-polarizing plate was produced.

(Production of organic EL cell)

According to the method described in the Example of Unexamined-Japanese-Patent No. 2010-20925 using the alkali free glass for 50 inches (127 cm) of thickness 3mm, it is shown in FIG. 8 of Unexamined-Japanese-Patent No. 2010-20925. An organic EL cell containing the described configuration was produced.

(Production of display device)

After apply | coating an adhesive agent to the surface of the optical film ((lambda) / 4 phase difference film) of each circularly polarizing plate produced above, the display apparatus was produced by bonding to the visual recognition side of organic electroluminescent cell.

≪Evaluation of display device≫

About each produced display device, the basic display characteristics, such as black color characteristic and reflectivity (visibility), were evaluated in accordance with a conventional method.

(1) color irregularity

The display was made black display in the environment of 23 degreeC * 55% RH, and it observed from the angle of the front and the inclination 45 degrees, and evaluated the color nonuniformity resulting from the retardation nonuniformity of an optical film based on the following reference | standard.

A: No color irregularity was observed

B: Weak color nonuniformity was observed in the area of 1/8 or less of the display surface.

C: A weak color unevenness was observed in an area exceeding 1/8 of the display surface and less than 1/4

D: A weak color nonuniformity was observed in the area over 1/4 of the display surface.

E: A strong color unevenness was observed in an area exceeding 1/4 of the display surface.

Although there is no problem practically if it is C level or more, it is preferable that it is B level or more, and it is especially preferable that it is A level or more.

(2) visibility

The display device was visually viewed from the front to evaluate the reflectivity (visibility).

(Double-circle): The reflectivity of a circularly polarizing plate is good, black expression is excellent, and visibility is favorable.

(Circle): The reflectivity of a circularly polarizing plate is favorable, but the contrast of a little black expression seems low.

(Triangle | delta): The reflectivity of a circularly polarizing plate is slightly inferior, and the contrast of black expression is seen low

X: The reflectivity of the circularly polarizing plate is poor, and the contrast of the black expression is obviously low.

Here, if it is more than (circle) level, there is no problem practically, and it is especially preferable that it is more than a level.

From the result of Table 2, it turns out that the display apparatus provided with the circularly-polarizing plate produced using the optical film of this invention is excellent in both color nonuniformity and visibility.

The long optical film of this invention is a long optical film containing a cycloolefin resin and a retardation raise agent, and extended | stretched so that it might have the slow axis inclined with respect to the longitudinal direction, and reduces the phase difference nonuniformity of the width direction, and looks (wrinkles, sags). ), It is suitable for display devices such as circular polarizing plates and organic electroluminescent elements.

F optical film
θi bending angle (feed angle)
Ci, Co grip
Ri, Ro rail
Film Width Before Wo Stretching
Film width after stretching
16 film feeding device
17 Return direction change device
18 winding device
19 production equipment
a display device
b organic EL element
c circular polarizer
101 transparent substrate
102 metal electrode
103 TFT
104 organic light emitting layer
105 transparent electrode
106 insulation layer
107 sealing layer
108 functional film
109 λ / 4 retardation film
110 polarizer
111 protective film
112 hardened layer
113 antireflective layer

Claims (5)

A long optical film containing a cycloolefin resin and a retardation increasing agent and having a slow axis in the in-plane direction inclined within a range of 45 ± 10 ° with respect to the longitudinal direction, having a structure represented by the following general formula (3). A long optical film containing a compound.

(Wherein R ¹ represents a straight or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an alkenyl group having 3 to 8 carbon atoms, provided that these alkyl groups, cycloalkyl groups or The alkenyl group may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and may be substituted with an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group. In addition, the substitution and interruption may be combined, R ² represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 3 to 8 carbon atoms, and R ³ is at least one hydroxy group And a hydrogen atom when not a hydroxy group, and R ⁴ represents a hydrogen atom or -OR ¹ . The long optical film according to claim 1, wherein the film thickness is 25 µm or less. After preparing dope containing cycloolefin resin, the retardation increasing agent, and the compound which has a structure represented by following General formula (3), and forming into a film by the solution casting film forming method using this dope, it is 45 with respect to the longitudinal direction. It diagonally stretches in the direction of the range of +/- 10 degrees, and adjusts the difference of the maximum value and minimum value of the fluctuation | variation of the retardation value Ro of the width direction in the range of 0-4 nm, The manufacturing method of the long optical film characterized by the above-mentioned.

(Wherein R ¹ represents a straight or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an alkenyl group having 3 to 8 carbon atoms, provided that these alkyl groups, cycloalkyl groups or The alkenyl group may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and may be substituted with an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group. In addition, the substitution and interruption may be combined, R ² represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 3 to 8 carbon atoms, and R ³ is at least one hydroxy group And a hydrogen atom when not a hydroxy group, and R ⁴ represents a hydrogen atom or -OR ¹ . The optical film obtained from the elongate optical film of Claim 1 or 2 is provided. The polarizing plate characterized by the above-mentioned. The optical film obtained from the elongate optical film of Claim 1 or 2 is provided, The display apparatus characterized by the above-mentioned.

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