JP2008225166A - Optical film and method for manufacturing the same, polarizing plate and method for manufacturing the same, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical film without causing deformation failure of an optical film raw fabric such as a horseback failure, a protrusion failure even when being stored for a long period of time period, and to provide a polarizing plate using the optical film and a liquid crystal display device using the polarizing plate. <P>SOLUTION: In the optical film having a cellulose ester, the optical film characteristically contains a compound represented by a general formula (1). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an optical film, a manufacturing method thereof, a polarizing plate, a manufacturing method thereof, and a liquid crystal display device.

  In recent years, notebook computers have been developed to be thinner and lighter, larger screens, and higher definition. Along with this, there has been an increasing demand for thinner, wider and higher quality optical films for liquid crystal display devices.

  By the way, in general, an optical film using cellulose ester is widely used as a polarizing plate protective film as an optical film for a liquid crystal display device.

  These optical films are usually wound around a core to form an optical film, which is stored and transported.

  Until now, these optical films have been produced exclusively by the solution casting method. The solution casting method is a film forming method in which a solution in which cellulose ester is dissolved in a solvent is cast to obtain an optical film shape, and then the solvent is evaporated and dried to obtain an optical film. Since an optical film formed by the solution casting method has high flatness, a high-quality liquid crystal display without unevenness can be obtained using this optical film.

  However, the solution casting method requires a large amount of an organic solvent and has a problem of a large environmental load. Because optical films are formed using halogen-based solvents with high environmental impact due to their dissolution characteristics, reduction of solvent usage is particularly required, and production of optical films should be increased by solution casting film formation. Has become difficult.

  In addition, since the solvent remaining inside the optical film must be removed, the capital investment and production cost for the production line such as the drying line, the drying energy, and the recovery and regeneration device for the evaporated solvent are enormous, Reducing these has become an important issue.

  On the other hand, a technique for improving spectral characteristics and mechanical characteristics by adding a hindered phenol antioxidant, a hindered amine light stabilizer, and an acid scavenger to the cellulose ester at a certain addition amount ratio is disclosed ( For example, see Patent Document 1). A technique using a polyhydric alcohol ester plasticizer as a plasticizer (for example, see Patent Document 2) and a technique for limiting the polyhydric alcohol ester plasticizer to a specific structure (for example, see Patent Document 3) are also disclosed. Yes. Further, as a technique for preventing the deterioration of organic materials, a stabilizer composition containing various stabilizers and phosphites is known (for example, see Patent Document 4).

  However, in any case, an optical film for optical use has a production load and equipment load associated with the use of a solvent in the production process, and the optical properties and mechanical properties are insufficient.

  In recent years, attempts have been made to melt-form cellulose ester for silver salt photography or polarizer protective film. Cellulose ester is a polymer having a very high viscosity when melted, and has a glass transition temperature. Therefore, even if the cellulose ester is melted and extruded from a die and cast on a cooling drum or cooling belt, it is difficult to level, and the optical properties and mechanical properties are lower than those of a solution cast optical film. (See, for example, Patent Document 5 and Patent Document 6).

  For this reason, if the melted optical film is stored for a long time in the state of the original optical film wound on the core, the horse's spine failure or the core portion of the optical film original starts a failure called core transfer and winding. It has been found that there is a problem that the optical film is likely to be wrinkled.

  A horse's back failure is a failure in which the original optical film is deformed into a U shape like a horse's back, and a belt-like convex part is formed at a pitch of about 2 to 3 cm in the vicinity of the center, and the optical film remains deformed. For this reason, when processed into a polarizing plate, the surface appears to be distorted. Until now, horse back failure has been reduced by reducing the coefficient of dynamic friction between the bases and adjusting the height of the knurling (embossing) on both sides.

Moreover, the core transfer is an optical film deformation failure caused by the irregularities of the core and the optical film.
Such deformation of the optical film is a problem because the surface appears distorted when processed into a polarizing plate.

  The optical film installed on the outermost surface of the liquid crystal display is subjected to clear hard processing, anti-glare processing, and anti-recursion processing. When these processes are performed, if the surface of the optical film is deformed, coating unevenness or vapor deposition unevenness is caused, which causes the product yield to be greatly deteriorated.

  These failures did not become a big problem in the optical film produced by the conventional solution casting, but it turned out that the optical film produced by the melt film formation becomes a big problem because the flatness of the optical film is low. .

  In particular, in recent years, with the increase in size of screens, it is desired that the width of the original optical film is wide and the winding length is long.

Therefore, the optical film original fabric becomes wide, and the optical film original fabric load tends to increase. Since these failures are more likely to occur, improvement is desired.
JP 2003-192920 A JP 2003-12823 A JP 2003-96236 A Japanese Patent Laid-Open No. 11-222493 Japanese National Patent Publication No. 6-501040 JP 2000-352620 A

  The present invention has been made in view of the above problems, and an object of the present invention is an optical film that does not cause deformation failure of the original optical film, such as a horse back failure or a convex failure, even if stored for a long time, and a method for producing the same It is providing the polarizing plate, its manufacturing method, and a liquid crystal display device.

  The above object of the present invention is achieved by the following configurations.

  1. An optical film having a cellulose ester, wherein the optical film contains a compound represented by the following general formula (I).

(Wherein R ₁ represents a substituent; R ₂ represents a hydrogen atom or a substituent; R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ₄ represents a hydrogen atom or 1 carbon atom) Represents an alkyl group of ˜8, R ₅ represents a hydrogen atom or a substituent, R ₆ represents a hydrogen atom or a substituent, R ₇ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₈ Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, n represents an integer of 1 to 4, and A represents a 1 to 4 valent group.)
2. The optical film according to the item 1, wherein the optical film is produced by a melt casting method using a melt containing at least one selected from a cellulose ester and a compound represented by the following general formula (I): A method for producing a film.

(Wherein R ₁ represents a substituent; R ₂ represents a hydrogen atom or a substituent; R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ₄ represents a hydrogen atom or 1 carbon atom) Represents an alkyl group of ˜8, R ₅ represents a hydrogen atom or a substituent, R ₆ represents a hydrogen atom or a substituent, R ₇ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₈ Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, n represents an integer of 1 to 4, and A represents a 1 to 4 valent group.)
3. A polarizing plate having the optical film according to 1 or the optical film obtained by the method for producing an optical film according to 2 above on at least one surface of a polarizer.

  4). A method for producing a polarizing plate, comprising: winding the polarizing plate according to 3 above into a roll-like long shape, then drawing out the wound state and attaching the polarizing plate to a polarizer.

  5. 4. A liquid crystal display device using the polarizing plate according to 3 above on at least one surface of a liquid crystal cell.

  6). 5. A liquid crystal display device comprising a polarizing plate obtained by the method for producing a polarizing plate as described in 4 above, on at least one surface of a liquid crystal cell.

  The optical film of the present invention, its manufacturing method, polarizing plate, its manufacturing method, and liquid crystal display device are excellent in that there is no deformation failure of the original optical film, such as horse back failure or convex failure, even if stored for a long period of time. Have

  Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto.

<< Compound Represented by Formula (1) >>
The present invention is characterized in that in the optical film having a cellulose ester, the optical film contains the compound represented by the general formula (1).

  Next, the compound of the general formula (1) of the present invention will be described in detail.

In the general formula (1), R ₁ represents a substituent. R _{1 s} may be the same or different, and examples of the substituent include an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. C5-C12 cycloalkyl group substituted with alkyl group, C5-C12 cycloalkenyl group, C5-C12 cycloalkenyl group substituted with C1-C4 alkyl group, phenyl group , A phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, or a group: —CH ₂ —S—X ₁ .

X ₁ is an alkyl group having 1 to 25 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group, or 1 carbon atom. Represents a phenyl group substituted with an alkyl group of ˜4, a phenylalkyl group of 7 to 9 carbon atoms, or — (CH ₂ ) _r COO—Y ₁ .

Y ₁ is an alkyl group having 1 to 25 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group, or 1 carbon atom. Represents a phenyl group substituted with an alkyl group of ˜4 or a phenylalkyl group of 7 to 9 carbon atoms.

In the general formula (1), R ₂ represents a hydrogen atom or a substituent.

R ₂ may be the same as or different from each other, and examples of the substituent include an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, C5-C12 cycloalkyl group substituted with alkyl group, C5-C12 cycloalkenyl group, C5-C12 cycloalkenyl group substituted with C1-C4 alkyl group, phenyl group , A phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, or a group: —CH ₂ —S—X ₁ , — (CH ₂ ) _p COO—X ₂ or — _{(CH 2) q O-X} 3 can be mentioned.

X ₁ is identical to X ₁ in R _1.

X ₂ is an alkyl group having 1 to 25 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group, or 1 carbon atom. Represents a phenyl group substituted with an alkyl group of ˜4 or a phenylalkyl group of 7 to 9 carbon atoms.

X ₃ is an alkyl group having 1 to 25 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group, or 1 carbon atom. A phenyl group substituted with -4 alkyl groups, a phenylalkyl group with 7-9 carbon atoms, an alkanoyl group with 1-25 carbon atoms, an alkenoyl group with 3-25 carbon atoms; an oxygen atom, a sulfur atom or> NY Represents an alkanoyl group having 3 to 25 carbon atoms, a cycloalkylcarbonyl group having 6 to 9 carbon atoms, a benzoyl group, a benzoyl group substituted with an alkyl group having 1 to 4 carbon atoms, a tenoyl group or a furoyl group interrupted by ₂ .

Y ₂ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

  p represents 0, 1 or 2, and q represents an integer of 0 to 8.

In the general formula (1), R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R may be the same or different and is preferably a hydrogen atom.

In the general formula (1), R ₄ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ₄ is preferably an alkyl group having 1 to 4 carbon atoms.

In the general formula (1), R ₅ represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, a phenyl group, —CH ₂ —COO—X ₄ or —CN.

X ₄ is an alkyl group having 1 to 25 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, or a phenyl group And a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms.

In the general formula (1), R ₆ represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a phenyl group, —COO—X ₅ , —CN, or —CON (X ₆ ) (X ₇ ).

X ₅ is an alkyl group having 1 to 25 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, or a phenyl group And a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms.

X ₆ and X ₇ are each a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. A cycloalkyl group having 5 to 12 carbon atoms, a cycloalkenyl group having 5 to 12 carbon atoms, a cycloalkenyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, A phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, or a phenylalkyl group having 7 to 9 carbon atoms is represented.

In the general formula (1), R ₇ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

In the general formula (1), R ₈ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

  In the general formula (1), n represents an integer of 1 to 4.

  In the general formula (1), A represents a 1 to 4 valent group.

When n is 1, A is a group: —O—Z ₁ , —N (Z ₂ ) (Z ₃ ), —NH (OZ ₄ ), —O—N═C (Z ₅ ) (Z ₆ ), — S (O) _m Z ₇ , —NH—Z ₈ or —S—Z ₈ , or A is also substituted with an unsubstituted or unsubstituted alkyl group having 1 to 4 carbon atoms at the nitrogen atom. Represents a substituted heterocyclic group.
m represents 1 or 2.

Z ₁ is a hydrogen atom, an alkyl group having 1 to 25 carbon atoms; an oxygen atom, a sulfur atom, or an alkyl group having 3 to 25 carbon atoms and an alkenyl group having 3 to 24 carbon atoms interrupted by> N—Y ₂ Monocyclic saturated hydrocarbon groups containing 5 to 20 carbon atoms, bicyclic saturated hydrocarbon groups containing 7 to 20 carbon atoms, and tricyclic saturated hydrocarbons containing 10 to 20 carbon atoms A cycloalkenyl group having 5 to 12 carbon atoms, a cycloalkenyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, a phenyl ring A phenylalkyl group having 7 to 9 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a tetrahydrofurfuryl group, a tetrahydroabiethyl group, Alkanoyl group having 1 to 25 atoms, alkenoyl group having 3 to 25 carbon atoms; oxygen atom, sulfur atom or alkanoyl group having 3 to 25 carbon atoms interrupted by> N—Y ₂ , 6 to 9 carbon atoms A cycloalkylcarbonyl group, a benzoyl group, a benzoyl group substituted with an alkyl group having 1 to 4 carbon atoms, a thenoyl group, a furoyl group, or the following formula IIa or formula IIb.

Wherein T ₁ and T ₂ are each independently of each other a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, A carbon atom substituted with an alkyl group having 5 to 12 carbon atoms, a cycloalkenyl group having 5 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms A cycloalkenyl group having 5 to 12 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, or a —CH ₂ —S—X ₁ group; Representation;
T ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; T ₄ represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, or 5 to 12 carbon atoms. A cycloalkyl group having 5 to 12 carbon atoms, a cycloalkenyl group having 5 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms. A substituted cycloalkenyl group having 5 to 12 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, —CH ₂ —S— X _{1 represents} — (CH ₂ ) _p COO—X ₂ or — (CH ₂ ) _q O—X ₃ ;
T ₅ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 2 to 4 carbon atoms substituted with an OH group, O., —OH, —NO, —CH ₂ CN, 1 carbon atom. An alkoxy group having 1 to 18 carbon atoms, a cycloalkoxy group having 5 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, and an alkyl group having 1 to 4 carbon atoms on the phenyl ring. And a phenylalkyl group having 7 to 9 carbon atoms substituted with an alkanoyl group having 1 to 8 carbon atoms, an alkenoyl group having 3 to 8 carbon atoms, or a benzoyl group. w represents 0 or 1;

Z ₂ is a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an alkyl group having 2 to 25 carbon atoms substituted with an OH group, an alkenyl group having 3 to 24 carbon atoms, or a cyclohexane having 5 to 12 carbon atoms. An alkyl group, a cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, or 7 carbon atoms. A phenylalkyl group having 9 to 9 carbon atoms, an alkanoyl group having 1 to 25 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms; an alkanoyl group having 3 to 25 carbon atoms interrupted by an oxygen atom, a sulfur atom or> N—Y ₂ Benzoyl substituted with a cycloalkyl group having 6 to 9 carbon atoms, a benzoyl group, or an alkyl group having 1 to 4 carbon atoms Group, thenoyl group, furoyl group, group: — (CH ₂ ) _p COO—X ₂ or a group represented by formula IIb.

Z ₃ is a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an alkyl group having 2 to 25 carbon atoms substituted with an OH group, an alkenyl group having 3 to 24 carbon atoms, or a cyclohexane having 5 to 12 carbon atoms. An alkyl group, a cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, or 7 carbon atoms. Or a phenylalkyl group of 9 or a group represented by Formula IIb.

T ₆ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group And a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms.

T ₆ is preferably T ₆ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a cyclohexane having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms. An alkyl group, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, or a phenylalkyl group having 7 to 9 carbon atoms.

Or Z ₂ and Z ₃ together represent an alkylene group having 3 to 6 carbon atoms, an oxoalkylene group having 3 to 6 carbon atoms, or an oxygen atom, a sulfur atom or a carbon atom interrupted by> NT _6. It is represented by 3 to 6 alkylene groups.

Z ₄ is an alkyl group having 1 to 25 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group And a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms.

Z ₅ and Z ₆ are each independently a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or 1 carbon atom. A cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 4 to 4 carbon atoms, a cycloalkenyl group having 5 to 12 carbon atoms, and a carbon atom having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms. A cycloalkenyl group, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, or a phenylalkyl group having 7 to 9 carbon atoms.

Z ₇ is an alkyl group having 1 to 25 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group And a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms or a group: — (CH ₂ ) _r COO—Y ₁ .

Z ₈ is an unsubstituted or substituted 2-benzoxazolyl group substituted with an alkyl group having 1 to 4 carbon atoms or an unsubstituted or substituted 2-benzothiazolyl group substituted with an alkyl group having 1 to 4 carbon atoms. expressed.

  When n is 2, A represents the following formula IIIa, formula IIIb, formula IIIc, formula IIId, formula IIIe or formula IIIf.

[Wherein, G ₁ and G ₃ are each independently a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 3 to 24 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, A cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a 7 to 9 carbon atom represents _{(CH 2) p COO-X} 2 group or a group represented by the formula IIb - phenylalkyl group;
G ₂ is an alkylene group having 2 to 12 carbon atoms; oxygen atom, sulfur atom, or> N—Y ₂ interrupted alkylene group having 4 to 20 carbon atoms, alkenylene group having 4 to 20 carbon atoms, carbon atom number An alkynylene group having 4 to 20 carbon atoms, (alkylene having 1 to 4 carbon atoms) -phenylene- (alkylene having 1 to 4 carbon atoms), a group having two free electrons and containing 5 to 12 carbon atoms Cyclic saturated hydrocarbon group, bicyclic saturated hydrocarbon group having two free electron valences and containing 7 to 30 carbon atoms, phenylene group, phenylene group substituted by alkyl group having 1 to 4 carbon atoms A naphthylene group, an alkanedioyl group having 2 to 20 carbon atoms, an alkenedioyl group having 4 to 20 carbon atoms, or a carboxybenzoyl group;
G ₄ and G ₆ are each independently a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 3 to 24 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or 1 carbon atom. A cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 4 to 4 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, or Represents a group of formula IIb;
G ₅ is an alkylene group having 2 to 12 carbon atoms; an oxygen atom, a sulfur atom or an alkylene group having 4 to 20 carbon atoms interrupted by> N—Y ₂ , an alkenylene group having 4 to 20 carbon atoms, a carbon atom An alkynylene group having 4 to 20 carbon atoms, an (alkylene having 1 to 4 carbon atoms) -phenylene- (alkylene having 1 to 4 carbon atoms) group, having two free electron valences and containing 5 to 12 carbon atoms Monocyclic saturated hydrocarbon group, bicyclic saturated hydrocarbon group having two free electron valences and containing 7 to 30 carbon atoms, phenylene group, phenylene substituted with alkyl group having 1 to 4 carbon atoms Represents a group or a naphthylene group;
G ₇ is an alkylene group having 2 to 20 carbon atoms; an oxygen atom, a sulfur atom or an alkylene group having 4 to 20 carbon atoms interrupted by> N—Y ₂ , an alkenylene group having 4 to 20 carbon atoms, a carbon atom An alkynylene group having 4 to 20 carbon atoms, (alkylene having 1 to 4 carbon atoms) -phenylene- (alkylene having 1 to 4 carbon atoms), two free electron valences, and 5 to 12 carbon atoms Substituted with a monocyclic saturated hydrocarbon group containing 2, a bicyclic saturated hydrocarbon group having two free electron valences and containing 7 to 30 carbon atoms, a phenylene group, and an alkyl group having 1 to 4 carbon atoms A phenylene group or a naphthylene group, an alkanedioyl group having 2 to 20 carbon atoms, an alkenedioyl group having 4 to 20 carbon atoms, a carboxybenzoyl group, or It is a group represented by formula IVa, formula IVb or IVc.

(In the formula, each D ₁ is independently substituted with a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents a cycloalkyl group having 5 to 12 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms;
The substituents D ₂ are each independently a carbon atom substituted with a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents a cycloalkyl group having 5 to 12 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, or a phenylalkyl group having 7 to 9 carbon atoms;
D ₃ and D ₄ each independently represent a hydrogen atom, CF ₃ , an alkyl group having 1 to 12 carbon atoms or a phenyl group, or D ₃ and D ₄ together with the bonded carbon atom Thus, a cycloalkylidene ring having 5 to 12 carbon atoms which is unsubstituted or substituted by alkyl having 1 to 4 carbon atoms can be formed. v represents 0 or 1. )
G ₈ and G ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 3 to 24 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or 1 carbon atom. A cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 4 to 4 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, or Represents a group of formula IIb;
G ₉ and G ₁₁ are alkylene groups having 2 to 12 carbon atoms; oxygen atoms, sulfur atoms or alkylene groups having 4 to 20 carbon atoms interrupted by> N—Y ₂ , alkenylene having 4 to 20 carbon atoms Groups, alkynylene groups having 4 to 20 carbon atoms, (alkylenes having 1 to 4 carbon atoms) -phenylene- (alkylenes having 1 to 4 carbon atoms) groups, two free electron valences and 5 to 12 carbon atoms A monocyclic saturated hydrocarbon group containing carbon atoms, a bicyclic saturated hydrocarbon group having two free electron valences and 7 to 30 carbon atoms, a phenylene group, an alkyl group having 1 to 4 carbon atoms Represents a substituted phenylene group or naphthylene group;
G ₁₂ is substituted with a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 3 to 24 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. A cycloalkyl group having 5 to 12 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, or a group represented by Formula IIb ;
Substituents D ₁ are each independently of _one another substituted with a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents a cycloalkyl group having 5 to 12 atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, or a phenylalkyl group having 7 to 9 carbon atoms;
The substituents D ₂ are each independently a carbon atom substituted with a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents a cycloalkyl group having 5 to 12 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, or a phenylalkyl group having 7 to 9 carbon atoms;
D ₃ and D ₄ each independently represent a hydrogen atom, CF ₃ , an alkyl group having 1 to 12 carbon atoms or a phenyl group, or D ₃ and D ₄ together with the bonded carbon atom To form a cycloalkylidene ring having 5 to 12 carbon atoms which is unsubstituted or substituted with an alkyl having 1 to 4 carbon atoms; t represents 1 or 2; ]
When n is 3, A represents the following formula Va, formula Vb or formula Vc.

(In the formula, E ₁ represents an alkanetriyl group having 3 to 7 carbon atoms; E ₂ and E ₃ represent an alkylene group having 2 to 8 carbon atoms.)
When n is 4, A represents the following formula VI group.

(In the formula, E ₄ represents an alkanetetrayl group having 4 to 10 carbon atoms or an alkanetetrayl group having 4 to 10 carbon atoms interrupted by an oxygen atom.)
Below, the compound of General formula (1) is demonstrated in detail.

  An alkyl group of up to 25, preferably up to 18, most preferably up to 10 carbon atoms is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, Isobutyl group, tertiary butyl group, 2-ethylbutyl group, n-pentyl group, tertiary pentyl group, isopentyl group, 1-methylpentyl group, 1,3-dimethylbutyl group, n-hexyl group, 1-methylhexyl group N-heptyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, n-octyl group, 2-ethylhexyl group, 1,1,3- Trimethylhexyl group, 1,1,3,3-tetramethylpentyl group, nonyl group, decyl group, undecyl group, 1-methylundecyl group, dodecyl group, 1,1,3,3 , 5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl.

_One of the preferred meanings of R ₁ and R ₂ is a branched alkyl group having 1 to 10 carbon atoms, more particularly an alkyl group having 1 to 5 carbon atoms, typically a methyl group or a tertiary butyl group. And a tertiary pentyl group.

One of the preferred meanings of R ₄ is preferably an alkyl group having 1 to 4 carbon atoms, particularly a methyl group.

One of the preferred meanings of Y ₂ is an alkyl group having 1 to 4 carbon atoms, particularly a methyl group. One of the preferred meanings of Z ₁ and Z ₂ is an alkyl group having 1 to 18 carbon atoms.

Z ₇ is preferably an alkyl group having 1 to 18 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms.

Preferred groups for T ₁ , T ₂ and T ₄ are alkyl groups having 1 to 4 carbon atoms, particularly preferably a methyl group and a tertiary butyl group.

One of the preferred meanings of T ₅ is preferably an alkyl group having 1 to 4 carbon atoms, particularly a methyl group.

A preferred group for T ₆ is an alkyl group having 1 to 4 carbon atoms.

Examples of the alkylene group having 2 to 25 carbon atoms interrupted by an oxygen atom, a sulfur atom or> N—Y ₂ include CH ₃ —O—CH ₂ CH ₂ —, CH ₃ —CH ₂ —O—CH ₂ —CH. _{2 -CH 2 -O -, (CH} 3) 2 CH-O-CH 2 -CH 2 -, CH 3 -S-CH 2 CH 2 -, CH 3 -NH-CH 2 CH 2 -, CH 3 -N (CH ₃ ) —CH ₂ CH ₂ —, CH ₃ —O—CH ₂ CH ₂ —O—CH ₂ CH ₂ —, CH ₃ — (O—CH ₂ CH ₂ —) ₂ O—CH ₂ CH ₂ —, CH ₃ — (O—CH ₂ CH ₂ —) ₃ O—CH ₂ CH ₂ — or CH ₃ — (O—CH ₂ CH ₂ —) ₄ O—CH ₂ CH ₂ —.

An oxygen atom or an alkyl group having 3 to 25 carbon atoms interrupted by> N—Y ₂ is preferable, and an alkyl group having 3 to 10 carbon atoms interrupted by an oxygen atom is more preferable.

Further, alkyl- (OCH ₂ CH ₂ ) _1-10 having 1 to 5 carbon atoms and alkyl- (OCH ₂ CH ₂ ) _1-2- having 1 to 5 carbon atoms are particularly preferable.

  An alkyl group having 2 to 25 carbon atoms substituted with —OH group, particularly an alkyl group having 2 to 4 carbon atoms substituted with —OH group is typically 2-hydroxyethyl group or 2-hydroxypropyl group. , 2-hydroxybutyl group or 4-hydroxybutyl group.

  The alkoxy group having 1 to 18 carbon atoms is typically a methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, pentoxy group, isopentoxy group, hexoxy group, heptoxy group, octoxy group. Decyloxy group, dodecyloxy group, tetradecyloxy group, hexadecyloxy group or octadecyloxy group. The alkoxy group having 6 to 12 carbon atoms is particularly preferably a heptyloxy group or an octyloxy group.

  The alkenyl group having up to 24, preferably up to 18 carbon atoms is typically vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, 3-methyl-2-butenyl, n-2-octenyl group, n-2-dodecenyl group, isododecenyl group, n-2-octadecenyl group or n-4-octadecenyl group.

  An alkenyl group in which the carbon atom at the 1-position is saturated is preferable. Particularly preferred are alkenyl groups having 3 to 18 carbon atoms.

  A cycloalkyl group having 5 to 12 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, typically a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecyl group, 2- or 4-methylcyclohexyl group, dimethylcyclohexyl group, trimethylcyclohexyl group or tert-butylcyclohexyl group. Preference is given to a cycloalkyl group having 5 to 8 carbon atoms which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms, more particularly a cyclohexyl group.

A preferred group for R ₁ is a cyclohexyl group.

  Examples of the cycloalkoxy group having 5 to 12 carbon atoms include a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, a cyclodecyloxy group, and a cyclododecyloxy group. A cyclopentyloxy group and a cyclohexyloxy group are particularly preferred.

  A monocyclic saturated hydrocarbon group containing 5 to 20 carbon atoms is typically unsubstituted or substituted with a cycloalkyl group having 5 to 12 carbon atoms or a cycloalkyl group substituted with an alkyl group having 1 to 4 carbon atoms. An alkyl group moiety substituted with an alkyl group having 1 to 4 carbon atoms (cycloalkyl having 5 to 12 carbon atoms)-(alkyl having 1 to 4 carbon atoms), typically a cyclohexylmethyl group, A methylcyclohexylmethyl group or a dimethylcyclohexylmethyl group;

  The bicyclic saturated hydrocarbon group containing 7 to 20 carbon atoms is typically the following ex-1 to ex-6.

  Typical examples of the tricyclic saturated hydrocarbon group containing 10 to 20 carbon atoms are the following ex-7 and ex-8.

  Examples of the cycloalkenyl group having 5 to 12 carbon atoms which are unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms include, for example, a cyclohex-2-enyl group, a cyclohept-3-enyl group, a 4-tert-butylcyclohexene- 2-enyl. Of these, a cyclohexenyl group is preferable.

  The phenyl group substituted with an alkyl group having 1 to 4 carbon atoms is typically a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a diethylphenyl group, an isopropylphenyl group, or a tertiary butylphenyl group. Di-tert-butylphenyl group or methyl-di-tert-butylphenyl group.

  Typical examples of the cycloalkylidene ring having 5 to 12 carbon atoms which are unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms include the following ex-9 and ex-10.

  A cycloalkylidene ring having 5 to 8 carbon atoms is preferred.

  Moreover, in the unsubstituted or phenyl group, the phenylalkyl group having 7 to 9 carbon atoms substituted by the alkyl group having 1 to 4 carbon atoms is, for example, benzyl group, phenethyl group, 3-phenylpropyl group, α-methyl A benzyl group, an α, α-dimethylbenzyl group, a methylbenzyl group, a dimethylbenzyl group, a trimethylbenzyl group and a tert-butylbenzyl group;

  Alkanoyl groups containing up to 25 carbon atoms are methanoyl, ethanoyl, propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, It may be a tetradecanoyl group, a pentadecanoyl group, a hexadecanoyl group, an octadecanoyl group, a nonadecanoyl group or an eicosanoyl group. An alkanoyl group having 1 to 18 carbon atoms is a preferred meaning.

An alkanoyl group having 3 to 25 carbon atoms having an oxygen atom, sulfur atom or group:> N—Y ₂ is typically represented by —CO—CH ₂ CH ₂ —S— (alkyl having 1 to 10 carbon atoms). ) Group, —CO—CH ₂ CH ₂ —O— (C 1 -C 10 alkyl) group and —CO—CH ₂ CH ₂ —N (Y ₂ ) — (C 1 -C 10 alkyl) group. It is.

An oxygen atom or an alkanoyl group having 3 to 25 carbon atoms having> N—Y ₂ is preferred.

  Alkenoyl groups of 3 to 25 carbon atoms are typically acryloyl, methacryloyl, crotonoyl, isocrotonoyl and oleoyl groups. Alkenoyl groups having 3 to 18 carbon atoms are preferred.

  The cycloalkylcarbonyl group having 6 to 9 carbon atoms is, for example, a cyclopentylcarbonyl group, a cyclohexylcarbonyl group, a cycloheptylcarbonyl group, or a cyclooctylcarbonyl group.

  The benzoyl group substituted with an alkyl group having 1 to 4 carbon atoms is typically a methylbenzoyl group or a tert-butylbenzoyl group.

  Examples of the unsubstituted or substituted heterocyclic group having a free valence at the nitrogen atom and substituted with an alkyl group having 1 to 4 carbon atoms are the heterocyclic groups represented by ex-11 to ex-26 below.

  5- to 7-membered heteromonocyclic groups and 9- to 10-membered heterobicyclic groups are preferred.

  A particularly preferred heteroatom is a nitrogen atom.

  Preferable groups include an unsubstituted 1-pyrrolyl group substituted with an alkyl group having 1 to 4 carbon atoms, an unsubstituted 1-pyrazolyl group substituted with an alkyl group having 1 to 4 carbon atoms, an unsubstituted group. 1-imidazolyl group, 1-triazolyl group, substituted or substituted with an alkyl group having 1 to 4 carbon atoms, substituted or 1-benzimidazolyl group substituted with an alkyl group having 1 to 4 carbon atoms, or 1 -A benzotriazolyl group.

Z ₈ is typically a group represented by the following ex-27 to ex-30.

  The alkylene groups containing up to 20, preferably up to 12 or up to 6 carbon atoms are typically ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyl. A trimethylene group, a hexamethylene group, a heptamethylene group, a trimethylhexamethylene group, an octamethylene group, a decamethylene group, an undecamethylene group or a dodecamethylene group.

One of the preferred meanings of G ₂ , G ₅ , G ₇ , G ₉ and G ₁₁ is an alkylene group having 2 to 8 carbon atoms.

The alkylene group having 4 to 20 carbon atoms interrupted by an oxygen atom, sulfur atom or> N—Y ₂ is typically —CH ₂ CH ₂ —O—CH ₂ CH ₂ —, —CH ₂ CH ₂ —. _{S-CH 2 CH 2 -,} - CH 2 CH 2 -NH-CH 2 CH 2 -, - CH 2 CH 2 CH 2 -NH-CH 2 CH 2 CH 2 -, - CH 2 -CH 2 -CH 2 - _{NH-CH 2 -CH 2 -,} - CH 2 -CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -CH 2 -, - (CH 2) 6 -NH- (CH 2) 6 -, _{-CH 2 CH 2 -N (CH 3} ) -CH 2 CH 2 -, - CH 2 CH 2 CH 2 -N (CH 3) -CH 2 CH 2 CH 2 -, - CH 2 CH 2 - (O-CH _{2 CH 2 -) 2 O-} CH 2 CH 2 -, - CH 2 CH 2 - (O-CH 2 CH 2 -) 3 O-CH 2 CH 2 -, - CH 2 CH 2 - (O-CH 2 C _{2 -) 4 O-CH 2} CH 2 -, - CH 2 CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 _{-NH-CH 2 CH 2 -NH-} CH 2 CH 2 -, - CH 2 CH 2 CH 2 -NH-CH 2 CH 2 -NH-CH 2 CH 2 CH 2 - or -CH ₂ CH ₂ CH ₂ -NH _{-CH 2 CH 2 CH 2 CH 2} -NH-CH 2 CH 2 CH 2 - is. An oxygen atom or an alkylene group having 4 to 20 carbon atoms interrupted by> N—Y ₂ is preferred, and —CH ₂ CH ₂ —O—CH ₂ CH ₂ — and —CH ₂ CH ₂ CH ₂ CH ₂ —O— are preferred. CH ₂ CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ CH ₂ CH ₂ — is particularly preferred.

A preferred group of —N (Z ₂ ) (Z ₃ ) is a morpholino group.

An alkylene group having 3 to 6 carbon atoms interrupted by> N—T ₆ is typically —CH ₂ CH ₂ —N (CH ₃ ) —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —. N (CH ₃ ) —CH ₂ CH ₂ CH ₂ —.

The oxoalkylene group having 3 to 6 carbon atoms is typically —CO—CH ₂ CH ₂ CH ₂ CH ₂ —.

  The alkenylene group having 4 to 20 carbon atoms is typically a 2-but-1,4-enylene group, a 3-pent-1,5-enylene group or a 2-hex-1,6-enylene group.

The alkynylene group 20 C 4 -C Typically, 2-butynylene _{(-CH 2 -C = C-CH} 2 -), 2- pentynylene group, 2-hexynylene group, 3-hexynylene group, 3- A heptynylene group, a 2-decynylene group, a 4-decynylene group or an 8-octadecylene group.

  Typical examples of the (C1-C4 alkylene) phenylene- (C1-C4 alkylene) group include the following groups.

  Typical examples of the monocyclic saturated hydrocarbon group having two free electron valences and containing 5 to 12 carbon atoms include the following groups.

And a cycloalkylene group having 5 to 12 carbon atoms such as a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, or a cyclooctylene group.

  Typical examples of the bicyclic saturated hydrocarbon group having two free electron valences and containing 7 to 30 carbon atoms include the following groups.

  The phenylene group substituted with an alkyl group having 1 to 4 carbon atoms is typically a methylphenylene group or a tert-butylphenylene group.

  The alkanedioyl group having 2 to 20 carbon atoms is typically an ethanediol oil group, a propanediol oil group, a butanediol oil group, a pentanediol oil group, a hexanediol oil group, a heptanediol oil group, an octanediol oil group, or a nonanediol group. Or a decandioyl group.

  Alkanedioyl groups having 2 to 10 carbon atoms are preferred.

  The alkenedioyl group having 4 to 20 carbon atoms is typically a maleoyl group, a fumaroyl group, a citraconoyl group or a mesaconoyl group.

  Typical examples of the alkanetriyl group having 3 to 7 carbon atoms include the following groups.

  Typical examples of the alkanetetrayl group having 4 to 10 carbon atoms or the alkanetetrayl group having 4 to 10 carbon atoms having an oxygen atom include the following groups.

In the general formula (1), R ₅ , R ₆ , R ₇ and R ₈ are preferably hydrogen atoms.

  The variable n is preferably 1 or 2.

Preferred compounds of the formula I are those in which the substituents R ₁ are each independently of each other an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or 5 to 8 carbon atoms. A cycloalkyl group having 5 to 8 carbon atoms, a cycloalkenyl group having 5 to 8 carbon atoms, or an alkyl group having 1 to 4 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms A substituted cycloalkenyl group having 5 to 8 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, or —CH ₂ —S It represents the -X ₁ group.

The substituents R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 1 to 1 carbon atoms. A cycloalkyl group having 5 to 8 carbon atoms substituted with 4 alkyl groups, a cycloalkenyl group having 5 to 8 carbon atoms, and 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms A cycloalkenyl group, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, or a group: —CH ₂ —S—X ₁ , — (CH ₂ ) _p COO-X ₂ or - represents a _{(CH 2) q O-X} 3.

The substituents R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
R ₄ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
R ₅ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group;
R ₆ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group;
R ₇ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
R ₈ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group;
X ₁ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, or a phenyl group Represents a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, or — (CH ₂ ) _r COO—Y ₁ ;
X ₂ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, or a phenyl group Represents a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms;
X ₃ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, or a phenyl group And a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, an alkanoyl group having 1 to 18 carbon atoms, and an alkenoyl group having 3 to 18 carbon atoms.

Substituted with an oxygen atom or an alkanoyl group having 3 to 18 carbon atoms interrupted by> N—Y ₂ , a cycloalkylcarbonyl group having 6 to 9 carbon atoms, a benzoyl group, or an alkyl group having 1 to 4 carbon atoms A benzoyl group, a tenoyl group or a furoyl group is represented.

Y ₁ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, or a phenyl group Represents a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms.

Y ₂ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

  p represents 0, 1 or 2, and q represents an integer of 0 to 8.

  r represents 1 or 2;

n represents an integer of 1 to 4, and when n represents 1, A represents a group: —O—Z ₁ , —N (Z ₂ ) (Z ₃ ), —NH (OZ ₄ ), —O—N ═C (Z ₅ ) (Z ₆ ), —S (O) _m Z ₇ , —NH—Z ₈ or —S—Z ₈ , or A is also unsubstituted with a free valence at the nitrogen atom Or a heterocyclic group substituted with an alkyl group having 1 to 4 carbon atoms;
Z ₁ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms; an oxygen atom or an alkyl group having 3 to 18 carbon atoms interrupted by> N—Y ₂ , an alkenyl group having 3 to 18 carbon atoms, a carbon atom A cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a cycloalkenyl group having 5 to 8 carbon atoms, or 1 to 4 carbon atoms A cycloalkenyl group having 5 to 8 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, or a 7 to 9 carbon atom substituted with an alkyl group having 1 to 4 carbon atoms in the phenyl ring. 9 phenylalkyl groups, tetrahydrofurfuryl groups, tetrahydroabiethyl groups, alkanoyl groups having 1 to 18 carbon atoms, 3 carbon atoms 18 alkenoyl groups; oxygen atoms or alkanoyl groups having 3 to 18 carbon atoms interrupted by> N—Y ₂ , cycloalkylcarbonyl groups having 6 to 9 carbon atoms, benzoyl groups, 1 to 4 carbon atoms Represents a benzoyl group, a tenoyl group, a furoyl group or a group represented by the formula IIa or IIb substituted with an alkyl group; Z ₂ is substituted with a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an OH group 5 to 8 carbon atoms substituted by an alkyl group having 2 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkyl group having 1 to 4 carbon atoms A cycloalkyl group, a phenyl group, a phenyl group substituted by an alkyl group having 1 to 4 carbon atoms, a phenylalkyl having 7 to 9 carbon atoms An alkanoyl group of 1 to 18 carbon atoms, alkenoyl of 3 to 18 carbon atoms; an oxygen atom or> N-Y ₂ in interrupted alkanoyl group having a carbon number of 3 to 18, 9 6 -C A cycloalkylcarbonyl group, a benzoyl group, a benzoyl group substituted with an alkyl group having 1 to 4 carbon atoms, a tenoyl group, a furoyl group, a group: — (CH ₂ ) _p COO-X ₂ or a group represented by Formula IIb Represents.

Z ₃ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyl group having 2 to 18 carbon atoms substituted with an OH group, an alkenyl group having 3 to 18 carbon atoms, or a cyclohexane having 5 to 8 carbon atoms. An alkyl group, a cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, or 7 carbon atoms Or a phenylalkyl group of 9 or a group represented by formula IIb.

Or Z ₂ and Z ₃ is an alkylene group of 6 C 3 -C together, C 3 -C interrupted by oxo alkylene group or an oxygen atom or> N-T ₆ 6 3 -C 6 Represents an alkylene group.

Z ₄ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group Represents a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms.

Z ₅ and Z ₆ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 1 carbon atom. A cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 4 to 4 carbon atoms, a cycloalkenyl group having 5 to 8 carbon atoms, or a carbon atom having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms A cycloalkenyl group, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, or a phenylalkyl group having 7 to 9 carbon atoms.

Or Z ₅ and Z ₆ together with the carbon atoms to which they are attached form a cycloalkylidene ring having 5 to 8 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms; ₇ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group, It represents a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms or a — (CH ₂ ) _r COO—Y ₁ group.

Z ₈ represents an unsubstituted or substituted 2-benzoxazolyl group substituted with an alkyl group having 1 to 4 carbon atoms or an unsubstituted or substituted 2-benzothiazolyl group substituted with an alkyl group having 1 to 4 carbon atoms. To express.

T ₁ and T ₂ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 1 carbon atom. A cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 4 to 4 carbon atoms, a cycloalkenyl group having 5 to 8 carbon atoms, or a carbon atom having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms A cycloalkenyl group, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, or a group: —CH ₂ —S—X ₁ .

T ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, T ₄ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or 5 to 8 carbon atoms. A cycloalkyl group having 5 to 8 carbon atoms, a cycloalkenyl group having 5 to 8 carbon atoms, or an alkyl group having 1 to 4 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms A substituted cycloalkenyl group having 5 to 8 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, —CH ₂ —S— X _{1 represents} a — (CH ₂ ) _p COO—X ₂ or — (CH ₂ ) _q O—X ₃ group.

T ₅ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, —OH, an alkoxy group having 6 to 12 carbon atoms, a cycloalkoxy group having 5 to 8 carbon atoms, an allyl group, a benzyl group, or an acetyl group. .

T ₆ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group Represents a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms.

  m represents 1 or 2, w represents 0 or 1, and n represents 2; A represents a group represented by the formula IIIa, IIIb, IIIc, IIId, IIIe or IIIf.

G ₁ and G ₃ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 1 carbon atom. A cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 4 to 4 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, represents a group represented by the group _{:-( CH 2) p COO-X} 2 or formula IIb. G ₂ is an alkylene group having 2 to 12 carbon atoms; an oxygen atom or an alkylene group having 4 to 12 carbon atoms interrupted by> N—Y ₂ , an alkenylene group having 4 to 12 carbon atoms, or 4 to 4 carbon atoms 12 alkynylene groups, (C1-C4 alkylene) -phenylene- (C1-C4 alkylene) groups, two free-electron valences and monocyclics containing 5-12 carbon atoms A saturated hydrocarbon group, a phenylene group, a phenylene group or a naphthylene group substituted with an alkyl group having 1 to 4 carbon atoms, an alkanedioyl group having 2 to 18 carbon atoms, and an alkenedioyl group having 4 to 18 carbon atoms or carboxy represents a benzoyl group; G ₄ and G ₆ are independently each other, hydrogen atom, an alkyl group of 1 to 18 carbon atoms, An alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group, a carbon atom A phenyl group substituted by an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms or a group represented by formula IIb; G ₅ is an alkylene group having 2 to 12 carbon atoms; an oxygen atom Or an alkylene group having 4 to 12 carbon atoms interrupted by> N—Y ₂ , an alkenylene group having 4 to 12 carbon atoms, an alkynylene group having 4 to 12 carbon atoms, (an alkylene having 1 to 4 carbon atoms) -Phenylene- (C1-C4 alkylene) group, monocyclic saturated hydrocarbon group having 2 free electron valences and containing 5 to 12 carbon atoms Represents a phenylene group, a phenylene group substituted with an alkyl group having 1 to 4 carbon atoms, or a naphthylene group.

G ₇ is an alkylene group having 2 to 12 carbon atoms; an oxygen atom or an alkylene group having 4 to 12 carbon atoms interrupted by> N—Y ₂ , an alkenylene group having 4 to 12 carbon atoms, or 4 to 4 carbon atoms 12 alkynylene groups, (C1-C4 alkylene) -phenylene- (C1-C4 alkylene) groups, two free-electron valences and monocyclics containing 5-12 carbon atoms A saturated hydrocarbon group, a phenylene group, a phenylene group or a naphthylene group substituted with an alkyl group having 1 to 4 carbon atoms, an alkanedioyl group having 2 to 18 carbon atoms, and an alkenedioyl group having 4 to 18 carbon atoms Represents a carboxybenzoyl group.

G ₈ and G ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 1 carbon atom. A cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 4 to 4 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, or Represents a group represented by Formula IIb.

G ₉ and G ₁₁ are each an alkylene group having 2 to 12 carbon atoms; an oxygen atom or an alkylene group having 4 to 12 carbon atoms interrupted by> N—Y ₂ , an alkenylene group having 4 to 12 carbon atoms, carbon An alkynylene group having 4 to 12 atoms, an (alkylene having 1 to 4 carbon atoms) -phenylene- (alkylene having 1 to 4 carbon atoms) group, two free electron valences and 5 to 12 carbon atoms; A monocyclic saturated hydrocarbon group, a phenylene group, a phenylene group or a naphthylene group substituted with an alkyl group having 1 to 4 carbon atoms; G ₁₂ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon An alkenyl group having 3 to 18 atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms. 8 cycloalkyl group and a phenyl group, a phenylalkyl group or a group of the formula IIb phenyl group substituted with an alkyl group of 1 to 4 carbon atoms, C 7 -C 9.

  And t is a compound representing 1 or 2.

Preference is likewise given to those in which the substituents R ₁ are, independently of _one another, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms. Represents a cycloalkenyl group having 5 to 8 carbon atoms, a phenyl group, a phenylalkyl group having 7 to 9 carbon atoms, or a group: —CH ₂ —S—X ₁ , wherein the substituents R ₂ are each independently of each other. Hydrogen atom, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 18 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, cycloalkenyl group having 5 to 8 carbon atoms, phenyl group, carbon A phenylalkyl group having 7 to 9 atoms or a group: —CH ₂ —S—X ₁ , — (CH ₂ ) _p COO—X ₂ or — (CH ₂ ) _q O—X ₃ ; substituent R ₃ Is water It represents an atom; R ₄ represents an alkyl of 1 to 4 hydrogen or carbon atoms; R ₅ represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms; R ₆ is a hydrogen atom, a carbon R ₇ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ₈ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group; Represents.

X ₁ represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a phenyl group, a phenylalkyl group having 7 to 9 carbon atoms, or — (CH ₂ ) _r COO—Y ₁ . X ₂ represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a phenyl group, or a phenylalkyl group having 7 to 9 carbon atoms; X ₃ represents 1 to 10 carbon atoms; Alkyl group, cycloalkyl group having 5 to 8 carbon atoms, phenyl group, phenylalkyl group having 7 to 9 carbon atoms, alkanoyl group having 1 to 10 carbon atoms, alkenoyl group having 3 to 18 carbon atoms, oxygen An alkanoyl group having 3 to 18 carbon atoms interrupted by atoms; or a benzoyl group, wherein Y ₁ is an alkyl group having 1 to 10 carbon atoms, a carbon atom A cycloalkyl group having 5 to 8 children, a phenyl group or a phenylalkyl group having 7 to 9 carbon atoms; p represents 0, 1 or 2; q represents an integer of 0 to 8; N represents an integer of 1 to 4, and when n represents 1, A represents a group: —O—Z ₁ , —N (Z ₂ ) (Z ₃ ), —NH (OZ ₄ ), _{-O-N = C (Z 5} ) (Z 6), - S (O) m Z 7, or represents -NH-Z _8, or -S-Z _8, or a a free valence in the nitrogen atom And an unsubstituted or substituted heterocyclic group substituted with an alkyl group having 1 to 4 carbon atoms.

Z ₁ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyl group having 3 to 18 carbon atoms interrupted by an oxygen atom, an alkenyl group having 3 to 18 carbon atoms, or a cyclohexane having 5 to 8 carbon atoms. An alkyl group, a cycloalkenyl group having 5 to 8 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, a tetrahydrofurfuryl group, an alkanoyl group having 1 to 10 carbon atoms, an alkenoyl group having 3 to 18 carbon atoms, An alkanoyl group having 3 to 18 carbon atoms interrupted by an oxygen atom; a benzoyl group or a group represented by formula IIa or formula IIb;

Z ₂ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyl group having 2 to 10 carbon atoms substituted with an OH group, an alkenyl group having 3 to 18 carbon atoms, or a cyclohexane having 5 to 8 carbon atoms. Alkyl group, phenyl group, phenylalkyl group having 7 to 9 carbon atoms, alkanoyl group having 1 to 10 carbon atoms, alkenoyl group having 3 to 18 carbon atoms, alkenoyl group, 3 to 3 carbon atoms interrupted by oxygen atom 18 alkanoyl groups;
A benzoyl group, a group: — (CH ₂ ) _p COO—X ₂ or a group represented by Formula IIb;
Z ₃ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyl group having 2 to 10 carbon atoms substituted with an OH group, an alkenyl group having 3 to 18 carbon atoms, or a cyclohexane having 5 to 8 carbon atoms. Represents an alkyl group, a phenyl group, a phenylalkyl group having 7 to 9 carbon atoms or a group represented by formula IIb, or Z ₂ and Z ₃ together represent an alkylene group having 3 to 6 carbon atoms, carbon Represents an oxoalkylene group having 3 to 6 atoms or an alkylene group having 3 to 6 carbon atoms interrupted by an oxygen atom;
Z ₄ represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a phenyl group, or a phenylalkyl group having 7 to 9 carbon atoms;
Z ₅ and Z ₆ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 5 carbon atoms. Represents a cycloalkenyl group having 8 to 8 carbon atoms, a phenyl group, or a phenylalkyl group having 7 to 9 carbon atoms, or Z ₅ and Z ₆ together with the carbon atoms to which they are bonded, is a cyclohexane having 5 to 8 carbon atoms. Forms an alkylidene ring.

Z ₇ represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a phenyl group, a phenylalkyl group having 7 to 9 carbon atoms, or a — (CH ₂ ) —COO—Y ₁ group. To express.

Z ₈ represents an unsubstituted or substituted 2-benzoxazolyl group substituted with an alkyl group having 1 to 4 carbon atoms or an unsubstituted or substituted 2-benzothiazolyl group substituted with an alkyl group having 1 to 4 carbon atoms. Representation;
T ₁ and T ₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 5 carbon atoms. Represents a cycloalkenyl group having 8 to 8 carbon atoms, a phenyl group, a phenylalkyl group having 7 to 9 carbon atoms, or a —CH ₂ —S—X ₁ group.

T ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

T ₄ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkenyl group having 5 to 8 carbon atoms, or a phenyl group. Represents a phenylalkyl group having 7 to 9 carbon atoms, —CH ₂ —S—X ₁ , — (CH ₂ ) _p COO—X ₂ or — (CH ₂ ) _q O—X ₃ .

T ₅ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, —OH, an alkoxy group having 6 to 12 carbon atoms, a cycloalkoxy group having 5 to 8 carbon atoms, an allyl group, a benzyl group, or an acetyl group. M represents 1 or 2; w represents 0 or 1; when n represents 2; A represents a group represented by Formula IIIa, Formula IIIb, Formula IIIc, Formula IIId, Formula IIIe, or Formula IIIf; .

G ₁ and G ₃ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a phenyl group, carbon Represents a phenylalkyl group having 7 to 9 atoms, — (CH ₂ ) _p COO—X ₂ group or a group represented by the formula IIb, and G ₂ is interrupted by an alkylene group having 2 to 10 carbon atoms and an oxygen atom. An alkylene group having 4 to 12 carbon atoms, an alkenylene group having 4 to 10 carbon atoms, an alkynylene group having 4 to 10 carbon atoms, (alkylene having 1 to 4 carbon atoms) -phenylene- (1 to 1 carbon atom) 4 alkylene) group, a monocyclic saturated hydrocarbon group having 2 free electron valences and 5 to 10 carbon atoms, a phenylene group, an aryl having 2 to 10 carbon atoms. A lucandioyl group, an alkenedioyl group having 4 to 10 carbon atoms or a carboxybenzoyl group; G ₄ and G ₆ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a carbon atom; It represents an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a phenyl group, a phenylalkyl group having 7 to 9 carbon atoms, or a group represented by the formula IIb.

G ₅ is an alkylene group having 2 to 10 carbon atoms, an alkylene group having 4 to 12 carbon atoms interrupted by an oxygen atom, an alkenylene group having 4 to 10 carbon atoms, an alkynylene group having 4 to 10 carbon atoms, ( C1-C4 alkylene) -phenylene- (C1-C4 alkylene) group, monocyclic saturated hydrocarbon group or phenylene having two free electron valences and containing 5 to 10 carbon atoms G ₇ represents an alkylene group having 2 to 10 carbon atoms, an alkylene group having 4 to 12 carbon atoms interrupted by an oxygen atom, an alkenylene group having 4 to 10 carbon atoms, or 4 to 10 carbon atoms. An alkynylene group (an alkylene having 1 to 4 carbon atoms) -phenylene- (an alkylene having 1 to 4 carbon atoms), and two free electron valences. And a monocyclic saturated hydrocarbon group containing 5 to 10 carbon atoms, a phenylene group, an alkanedioyl group having 2 to 10 carbon atoms, an alkenedioyl group having 4 to 10 carbon atoms, or a carboxybenzoyl group. To express.

G ₈ and G ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a phenyl group, carbon It represents a phenylalkyl group having 7 to 9 atoms or a group represented by the formula IIb.

G ₉ and G ₁₁ are each an alkylene group having 2 to 10 carbon atoms, an alkylene group having 4 to 12 carbon atoms interrupted by an oxygen atom, an alkenylene group having 4 to 10 carbon atoms, or an alkyl group having 4 to 10 carbon atoms. Alkynylene group, (C 1 -C 4 alkylene) -phenylene- (C 1 -C 4 alkylene) group, monocyclic saturated carbonization with two free electrons and 5 to 10 carbon atoms G ₁₂ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a phenyl group, or a carbon atom; A phenylalkyl group of formulas 7 to 9 or a group of formula IIb; and t is a compound of formula I, which represents 1 or 2.
In the formula, n is 1; A represents a group represented by the formula: —N (Z ₂ ) (Z ₃ );
Z ₂ represents a hydrogen atom, and Z ₃ represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an alkyl group having 2 to 25 carbon atoms substituted with an OH group, and an alkenyl group having 3 to 24 carbon atoms. Substituted with a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group, or an alkyl group having 1 to 4 carbon atoms Preference is also given to compounds of the formula I which represent a substituted phenyl group, a phenylalkyl group of 7 to 9 carbon atoms or a group of the formula IIb.

Other preferred compounds of formula I are those wherein n is 1 and A represents a group represented by -O-Z ₁ .

A compound in which Z ₁ represents an alkyl group having 1 to 25 carbon atoms interrupted by an oxygen atom or a group represented by formula IIa; and w represents 1.

Further preferred examples of the present invention are those wherein the substituent R ₁ is the same and represents an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and the substituent R ₂ is the same. And an alkyl group having 1 to 5 carbon atoms; a substituent R ₃ represents a hydrogen atom and R ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Particularly preferred compounds of the formula I are those in which the substituents R ₁ are the same and represent an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and the substituents R ₂ are the same Yes and represents an alkyl group having 1 to 5 carbon atoms; the substituent R ₃ represents a hydrogen atom and R ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ₅ , R ₆ , R ₇ And R ₈ represents a hydrogen atom; when n represents 1 or 2, and n represents 1, A represents a group: —O—Z ₁ , —N (Z ₂ ) (Z ₃ ), —NH (OZ _{4), - O-N =} C (Z 5) (Z 6), - S (O) m Z 7, or represents -NH-Z _8, or -S-Z _8, or a is also at liberty nitrogen atom It represents an unsubstituted or unsubstituted heterocyclic group substituted with an alkyl group having 1 to 4 carbon atoms.

Z ₁ is an alkyl group having 1 to 18 carbon atoms, an alkyl group having 3 to 10 carbon atoms interrupted by an oxygen atom, a cycloalkyl group having 5 to 8 carbon atoms, a tetrahydrofurfuryl group, a formula IIa or a formula IIb. Represents a group represented by

Z ₂ is an alkyl group having 1 to 18 carbon atoms, an alkyl group having 2 to 4 carbon atoms substituted with an —OH group, a phenylalkyl group having 7 to 9 carbon atoms, — (CH ₂ ) —COO—X ₂ groups or groups represented by formula IIb are represented.

Z ₃ is represented by a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyl group having 2 to 4 carbon atoms substituted with an —OH group, a phenylalkyl group having 7 to 9 carbon atoms, or Formula IIb Represents a group;
Or Z ₂ and Z ₃ together represent an oxoalkylene group having 3 to 6 carbon atoms or an alkylene group having 3 to 6 carbon atoms interrupted by an oxygen atom; Z ₄ is a group having 7 to 9 carbon atoms; Represents a phenylalkyl group;
Z ₅ and Z ₆ together with the carbon atoms to which they are attached C 5 -C form a cycloalkylidene ring 8; Z ₇ represents an alkyl group having 1 to 10 carbon atoms; Z ₈ is Represents a 2-benzoxazolyl group which is unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms or a 2-benzothiazolyl group which is unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms;
T ₁ , T ₂ , T ₃ and T ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
T ₅ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

X ₂ represents an alkyl group having 1 to 10 carbon atoms; m represents 1 or 2; p represents 1; w represents 0 or 1; and n represents 2;
A represents formula IIIa, formula IIIb, formula IIIc or formula IIIf; G ₁ and G ₃ each independently represent a hydrogen atom, a phenylalkyl group having 7 to 9 carbon atoms or a group represented by formula IIb. Representation;
G ₂ represents an alkylene group having 2 to 8 carbon atoms, a monocyclic saturated hydrocarbon group having 2 free electron valences and containing 10 carbon atoms;
G ₇ represents an alkylene group having 2 to 8 carbon atoms or an alkylene group having 4 to 12 carbon atoms interrupted by an oxygen atom;
G ₁₂ represents a phenylalkyl group having 7 to 9 carbon atoms or a group represented by the formula IIb.

  Although the compound represented with General formula (1) below is shown concretely below, this invention is not limited to these.

  The compound represented by the general formula (1) is preferably added in an amount of 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and more preferably 0.5 to It is preferable to add 2% by mass.

《Cellulose ester》
Next, the cellulose ester used in the present invention will be described in detail.

  The optical film of the present invention is produced by a solution casting method or a melt casting method.

  In the solution casting method, a solution (dope) in which a cellulose ester is dissolved in a solvent is cast on a support, and the solvent is evaporated to form an optical film.

  In the melt casting method for an optical film according to claim 2 of the present invention, an optical film is formed by casting a melted cellulose ester (melt) on a support.

  Since the melt casting method can significantly reduce the amount of organic solvent used in the production of optical films, environmental suitability has been greatly improved compared to conventional solution casting methods that use large amounts of organic solvents. Since a film is obtained, it is preferable to produce an optical film by a melt casting method.

  The melt casting in the present invention is a method in which a cellulose ester is heated and melted to a temperature showing fluidity without substantially using a solvent, and a film is formed using this, for example, extruding a fluid cellulose ester from a die. This is a method for forming a film.

  In addition, although a solvent may be used in a part of the process of preparing the molten cellulose ester, in the melt film forming process in which the film is formed into a film, the forming process is substantially performed without using the solvent.

  The cellulose ester constituting the optical film is not particularly limited as long as it is a meltable film-forming cellulose ester. For example, an aromatic carboxylic acid ester or the like is also used, but in consideration of the characteristics of the obtained optical film such as optical characteristics. And lower fatty acid esters of cellulose are preferably used.

  In the present invention, the lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 5 or less carbon atoms. For example, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose pivalate and the like are preferable lower cellulose esters of cellulose. It is mentioned as a thing.

  This is because the cellulose ester substituted with a fatty acid having 6 or more carbon atoms has good melt film-forming properties, but the resulting optical film has low mechanical properties and is substantially difficult to use as an optical film.

  In order to achieve both mechanical properties and melt film-forming properties, mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate may be used.

  In the present invention, the cellulose ester constituting the optical film is a cellulose ester having an aliphatic acyl group having 2 or more carbon atoms, and the cellulose ester has a total acyl group carbon number of 6.2 to 7.5. Ester.

  The total number of acyl groups in the cellulose ester is preferably 6.5 to 7.2, and more preferably 6.7 to 7.1.

  However, the total number of carbon atoms in the acyl group is the sum of the products of the substitution degree of each acyl group in the cellulose ester and the number of carbon atoms. Furthermore, the number of carbon atoms of the aliphatic acyl group is preferably 2 to 6 from the viewpoint of cellulose synthesis productivity and cost.

  The portion not substituted with an acyl group usually exists as a hydroxyl group. These can be synthesized by known methods.

  Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a pentanate group, and a hexanate group. Examples of the cellulose ester include cellulose propionate, cellulose butyrate, and cellulose pentanate.

  Further, mixed fatty acid esters such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate pentanate may be used as long as the above-mentioned side chain carbon number is satisfied.

  Among these, cellulose acetate propionate and cellulose acetate butyrate are particularly preferable.

  Note that triacetyl cellulose and diacetyl cellulose, which are cellulose esters generally used in solution casting film formation, do not satisfy the condition of the number of side chain carbon atoms, and thus are not included in the present invention.

  In general, the mechanical properties and saponification properties of a cellulose ester film and the melt film-forming property of a cellulose ester are in a trade-off relationship with respect to the total substitution degree of acyl groups of the cellulose ester.

  For example, in cellulose acetate propionate, when the total substitution degree of acyl groups is increased, mechanical properties are lowered and melt film-forming properties are improved. In this invention, it discovered that the optical film mechanical property, saponification property, and melt film-forming property can be made compatible by making the acyl group total carbon number of a cellulose ester into 6.2-7.2. The details of this mechanism are unknown, but it is assumed that the influence on the optical film mechanical properties, saponification properties, and melt film-forming properties varies depending on the carbon number of the acyl group.

  That is, in the case of the same substitution degree, a long-chain acyl group such as a propionyl group or a butyryl group becomes more hydrophobic than an acetyl group, thereby improving melt film-forming properties.

  Therefore, when achieving the same melt film-forming property, the substitution degree of propionyl group and butyryl group may be lower than that of acetyl group, so that it is presumed that the deterioration of mechanical properties and saponification properties can be suppressed.

  The cellulose ester used in the present invention has a weight average molecular weight Mw / number average molecular weight Mn ratio of 1.0 to 5.5, particularly preferably 1.4 to 5.0, and more preferably 2 0.0-3.0. Mw is preferably 100,000 to 500,000, and more preferably 150,000 to 300,000.

  The average molecular weight and molecular weight distribution of the cellulose ester can be measured by a known method using high performance liquid chromatography. Using this, the number average molecular weight and the weight average molecular weight are calculated. The measurement conditions are as follows.

Solvent: Tetohydrofuran Device: HLC-8220 (manufactured by Tosoh Corporation)
Column: TSKgel SuperHM-M (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample temperature: 0.1% by mass
Injection volume: 10 μl
Flow rate: 0.6ml / min
Calibration curve:
Standard polystyrene: A calibration curve with 9 samples from PS-1 (Polymer Laboratories) Mw = 2,560,000 to 580 was used.

  The cellulose ester raw material cellulose used in the present invention may be wood pulp or cotton linter, and the wood pulp may be softwood or hardwood, but softwood is more preferred.

  Cotton linter is preferably used from the viewpoint of releasability during film formation.

  The cellulose ester made from these can be mixed suitably or can be used independently.

  For example, the ratio of cellulose ester derived from cellulose linter: cellulose ester derived from wood pulp (coniferous): cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50:50: 0, 20: 80: 0, 10: 90: 0, 0: 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, 40:30:30.

  The cellulose ester can be obtained, for example, by substituting the hydroxyl group of the raw material cellulose with acetic anhydride, propionic anhydride and / or butyric anhydride in the usual manner using an acetyl group, propionyl group and / or butyl group within the above range. .

  The method for synthesizing such a cellulose ester is not particularly limited, and for example, it can be synthesized with reference to the method described in JP-A-10-45804 or JP-A-6-501040.

  The degree of substitution of acyl groups such as acetyl, propionyl and butyl groups can be measured according to ASTM-D817-96.

  In addition, industrially, cellulose esters are synthesized using sulfuric acid as a catalyst, but this sulfuric acid is not completely removed, and the remaining sulfuric acid causes various decomposition reactions during melt film formation, resulting in an optical film. In view of the effects of the present invention, the residual sulfuric acid content in the cellulose ester used in the present invention is preferably in the range of 0.1 to 40 ppm in terms of elemental sulfur.

  These are considered to be contained in the form of salts.

  This is not well understood, although an increase in the number of washings may affect the resin.

  Furthermore, the range of 0.1-30 ppm is preferable. The residual sulfuric acid content can be similarly measured by ASTM-D817-96.

The total residual acid amount including other residual acids (such as acetic acid) is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 100 ppm or less.

  Compared to the case where the synthesized cellulose ester is washed in a solution casting method, the residual acid content can be made within the above range by manufacturing the optical film by the melt casting method. In this case, an optical film with reduced adhesion to the lip portion and excellent flatness can be obtained, and an optical film with good dimensional change, mechanical strength, transparency, moisture resistance, Rt value and Ro value described later can be obtained. be able to.

  In addition to washing with water, the cellulose ester can be washed with a poor solvent such as methanol or ethanol, or as a result, a mixed solvent of a poor solvent and a good solvent can be used. Organic impurities in the molecule can be removed.

  Furthermore, washing of the cellulose ester is preferably performed in the presence of an antioxidant such as a hindered amine or a phosphite, which improves the heat resistance and film formation stability of the cellulose ester.

  In order to improve the heat resistance, mechanical properties, optical properties, etc. of cellulose ester, it can be dissolved in a good solvent of cellulose ester and then reprecipitated in a poor solvent to remove low molecular weight components and other impurities of cellulose ester. it can. At this time, it is preferable to carry out in the presence of an antioxidant as in the case of washing the cellulose ester.

  Furthermore, another polymer or a low molecular weight compound may be added after the cellulose ester reprecipitation treatment.

  In addition, the cellulose ester preferably used in the present invention is preferable because it has few bright spot foreign matters when it is formed into an optical film.

  Bright spot foreign matter is two polarizing plates placed at right angles (crossed Nicols), an optical film is placed between them, light from the light source is applied from one side, and the optical film is observed from the other side. This is the point where the light from the light source appears to leak.

  At this time, the polarizing plate used for the evaluation is desirably composed of a protective film having no bright spot foreign matter, and a polarizing plate using a glass plate for protecting the polarizer is preferably used.

  One of the causes of bright spot foreign matter is the unacetylated or low acetylated cellulose contained in the cellulose ester. Use a cellulose ester with less bright spot foreign matter (use a cellulose ester with a small dispersion degree of substitution). And filtering the melted cellulose ester, or removing the bright spot foreign matters through the filtration process in the same way once in the solution state in at least one of the process of synthesizing the cellulose ester and the process of obtaining the precipitate You can also.

  Since the molten resin has a high viscosity, the latter method is more efficient.

As the optical film thickness decreases, the number of bright spot foreign matter per unit area decreases, and as the cellulose ester content in the optical film decreases, the bright spot foreign matter tends to decrease. The diameter of 0.01 mm or more is preferably 200 pieces / cm ² or less, more preferably 100 pieces / cm ² or less, further preferably 50 pieces / cm ² or less, and 30 pieces / cm ^2. More preferably, it is more preferably 10 or less / cm ² , but most preferably none.

Moreover, it is preferable that it is 200 pieces / cm < ² > or less also about the bright spot of 0.005-0.01 mm or less, It is more preferable that it is 100 pieces / cm < ² > or less, It is 50 pieces / cm < ² > or less. More preferably, it is more preferably 30 pieces / cm ² or less, still more preferably 10 pieces / cm ² or less, and most preferably none.

  When removing bright spot foreign matter by melt filtration, filtering the cellulose ester composition to which a plasticizer, a deterioration inhibitor, an antioxidant, etc. are added and mixed is more effective than filtering the melted cellulose ester alone. It is preferable because the removal efficiency of point foreign matters is high.

  Of course, the cellulose ester may be dissolved in a solvent during the synthesis and reduced by filtration. What mixed the ultraviolet absorber and other additives suitably can be filtered.

  Filtration is preferably performed with a viscosity of the melt containing cellulose ester of 10,000 P or less, more preferably 5000 P or less, even more preferably 1000 P or less, and even more preferably 500 P or less.

  As the filter medium, conventionally known materials such as glass fibers, cellulose fibers, filter paper, fluorine resins such as tetrafluoroethylene resin are preferably used, and ceramics, metals and the like are particularly preferably used. The absolute filtration accuracy is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 10 μm or less, and even more preferably 5 μm or less.

  These can be used in combination as appropriate. The filter medium can be either a surface type or a depth type, but the depth type is preferably used because it is relatively less clogged.

  In another embodiment, a cellulose ester obtained by dissolving the raw material cellulose ester at least once in a solvent and then drying the solvent may be used. In that case, a cellulose ester which is dissolved in a solvent together with at least one of a plasticizer, an ultraviolet absorber, a deterioration inhibitor, an antioxidant and a matting agent and then dried is used.

  As the solvent, a good solvent used in a solution casting method such as methylene chloride, methyl acetate or dioxolane can be used, and a poor solvent such as methanol, ethanol or butanol may be used at the same time. You may cool to -20 degrees C or less in the process of dissolution, or you may heat to 80 degrees C or more. When such a cellulose ester is used, each additive in a molten state can be easily made uniform, and optical characteristics can be made uniform.

  The polarizing plate protective film of the present invention may be appropriately mixed with polymer components other than cellulose ester. The polymer component to be mixed is preferably one having excellent compatibility with the cellulose ester, and the transmittance when formed into an optical film is preferably 80% or more, more preferably 90% or more, and further preferably 92% or more.

"Additive"
In the optical film of the present invention, various additives other than the compound of the general formula (1) can be added to the cellulose ester.

"Antioxidant"
Since cellulose ester is decomposed not only by heat but also by oxygen at a high temperature, the optical film of the present invention preferably contains an antioxidant as a deterioration preventing agent.

  The antioxidant useful in the present invention can be used without limitation as long as it is a compound that suppresses deterioration of the melt molding material due to oxygen, but among the useful antioxidants, phenolic compounds, hindered amine compounds, Phosphorus compounds, sulfur compounds, heat-resistant processing stabilizers, oxygen scavengers, etc. are mentioned, among these, phenol compounds, hindered amine compounds, phosphorus compounds, lactone compounds, compounds having acrylate groups and phenolic hydroxyl groups, among others Is preferred.

  By blending these antioxidants, it is possible to prevent coloring and strength reduction of the molded product due to heat during heat molding or deterioration due to thermal oxidation without lowering transparency, heat resistance and the like. These antioxidants can be used alone or in combination of two or more.

  By blending these antioxidants, it is possible to prevent coloring and strength reduction of the molded product due to heat during heat molding or deterioration due to thermal oxidation without lowering transparency, heat resistance and the like.

  These antioxidants can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected within the range not impairing the object of the present invention. 0.01 mass% or more and 10 mass% or less is preferable with respect to mass, More preferably, it is 0.1 mass% or more and 5.0 mass% or less, More preferably, it is 0.2 mass% or more and 2.0 mass%. It is as follows.

(Phenolic antioxidant)
Phenol-based antioxidants are known compounds. In addition to alkyl group-substituted phenols such as para-t-butylphenol and para- (1,1,3,3-tetramethylbutyl) phenol, for example, US Pat. Examples include 2,6-dialkylphenol derivative compounds, so-called hindered phenol compounds, described in columns 12 to 14 of No. 839,405, and among these, hindered phenol compounds are preferable.

  Specific examples of the hindered phenol phenol compound include n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, n-octadecyl 3- (3,5-di-t- Butyl-4-hydroxyphenyl) -acetate, n-octadecyl 3,5-di-t-butyl-4-hydroxybenzoate, n-hexyl 3,5-di-t-butyl-4-hydroxyphenylbenzoate, n-dodecyl 3,5-di-t-butyl-4-hydroxyphenylbenzoate, neo-dodecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, dodecyl β (3,5-di-t- Butyl-4-hydroxyphenyl) propionate, ethyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobuty Rate, octadecyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl α- (4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2- (N-octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2- (n-octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-phenyl acetate, 2- ( n-octadecylthio) ethyl 3,5-di-t-butyl-4-hydroxyphenyl acetate, 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) ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, stearamide N, N-bis- [ Ethylene 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], n-butylimino N, N-bis- [ethylene 3- (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- -Hydroxyphenyl) propionate], ethylene glycol bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], neopentylglycol bis- [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate], ethylene glycol bis- (3,5-di-t-butyl-4-hydroxyphenyl acetate), glycerin-1-n-octadecanoate-2,3-bis- ( 3,5-di-t-butyl-4-hydroxyphenyl acetate), 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-hydroxyethyl 7- (3-methyl-5-tbutyl-4-hydroxyphenyl) propionate, 2-stearoyloxyethyl 7- (3-methyl-5-t-butyl-4-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 above type of phenolic compounds are commercially available from Ciba Specialty Chemicals under the trade names “IRGANOX1076” and “IRGANOX1010”, for example.

  Other hindered amine compounds (HALS) are described, for example, in columns 5 to 11 of US Pat. No. 4,619,956 and columns 3 to 5 of US Pat. No. 4,839,405. As shown, 2,2,6,6-tetraalkylpiperidine compounds, or their acid addition salts or complexes of them with metal compounds are preferred.

  As a commercial item, LA52 (Asahi Denka Co., Ltd. product) can also be mentioned.

(Phosphorus antioxidant)
Examples of phosphorus antioxidants useful in the present invention include phosphite compounds and phosphonite compounds. Specific examples of the phosphite compound include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di -T-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10- Mono, such as tetra-t-butyldibenz [d, f] [1.3.2] dioxaphosphine, tridecyl phosphite Sphite compounds; 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis (phenyl-di-alkyl (C12- And diphosphite compounds such as C15) phosphite). The above-mentioned types of phosphite compounds are, for example, from Sumitomo Chemical Co., Ltd., "Sumizer GP", from Asahi Denka Kogyo Co., Ltd. It is commercially available under the trade names of “ADK STAB HP-10” and “ADK STAB 2112”.

  Specific examples of the phosphonite compound include dimethyl-phenylphosphonite, di-t-butyl-phenylphosphonite, diphenyl-phenylphosphonite, di- (4-pentyl-phenyl) -phenylphosphonite, di- (2- t-butyl-phenyl) -phenylphosphonite, di- (2-methyl-3-pentyl-phenyl) -phenylphosphonite, di- (2-methyl-4-octyl-phenyl) -phenylphosphonite, di- ( 3-butyl-4-methyl-phenyl) -phenylphosphonite, di- (3-hexyl-4-ethyl-phenyl) -phenylphosphonite, di- (2,4,6-trimethylphenyl) -phenylphosphonite, Di- (2,3-dimethyl-4-ethyl-phenyl) -phenylphosphonite, di- (2,6-diethi -3-butylphenyl) -phenylphosphonite, di- (2,3-dipropyl-5-butylphenyl) -phenylphosphonite, di- (2,4,6-tri-t-butylphenyl) -phenylphosphonite Bis (2,4-di-t-butyl-5-methylphenyl) biphenyl-4-yl-phosphonite, bis (2,4-di-t-butyl-5-methylphenyl) -4 '-(bis ( 2,4-di-tert-butyl-5-methylphenoxy) phosphino) biphenyl-4-yl-phosphonite, tetrakis (2,4-di-tert-butyl-phenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,5-di-t-butyl-phenyl) -4,4'-biphenylenediphosphonite, tetrakis (3,5-di-t-butyl-phenyl) -4,4'-bif Nylene diphosphonite, tetrakis (2,3,4-trimethylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,3-dimethyl-5-ethyl-phenyl) -4,4'-biphenylene diphospho Knight, tetrakis (2,3-dimethyl-4-propylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,3-dimethyl-5-t-butylphenyl) -4,4'-biphenylene diphospho Knight, tetrakis (2,5-dimethyl-4-t-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,3-diethyl-5-methylphenyl) -4,4'-biphenylene diphospho Knight, tetrakis (2,6-diethyl-4-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4,5-triethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-diethyl-4-propylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2, 5-diethyl-6-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3-diethyl-5-t-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2, 5-diethyl-6-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3-dipropyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2, 6-dipropyl-4-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-dipropyl-5- Tilphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3-dipropyl-6-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-dipropyl-5-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3-dibutyl-4-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,5-dibutyl-3-methylphenyl) -4 , 4'-biphenylenediphosphonite, tetrakis (2,6-dibutyl-4-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl-3-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4 4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl-6-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,5-di-t-butyl-3- Methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,5-di-t-butyl-4-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,5-di-) t-butyl-6-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-t-butyl-3-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis ( 2,6-di-t-butyl-4-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3-dibutyl-4-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-dibutyl-3-ethylphenyl) -4 , 4'-biphenylenediphosphonite, tetrakis (2,5-dibutyl-4-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl-3-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl-5-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl) -6-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,5-di-t-butyl-3-ethylphenyl) -4,4'- Phenylenediphosphonite, tetrakis (2,5-di-t-butyl-4-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,5-di-t-butyl-6-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-t-butyl-3-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-t-butyl) -4-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-t-butyl-5-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3 , 4-tributylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4,6-tri-t-butylphenyl) -4,4'-biphenylene Phosphonite, and the like. The phosphorus compound of the above type is commercially available from Ciba Specialty Chemicals, Inc. under the trade name “IRGAFOS P-EPQ” and from Sakai Chemical Industry Co., Ltd., as “GSY-P101”.

  As the phosphorus antioxidant useful in the present invention, a phosphonite compound is preferable, and among them, 4,4 ′ such as tetrakis (2,4-di-t-butyl-phenyl) -4,4′-biphenylenediphosphonite. -Biphenylene diphosphonite compounds are preferred, and tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene diphosphonite is particularly preferred.

(Lactone compound)
As one of the antioxidants useful in the present invention, a lactone compound is preferable.
As the lactone compound, compounds described in JP-A-7-233160 and JP-A-7-247278 are preferable, and a lactone compound represented by the following general formula (2) is particularly preferable.

In the general formula (2), R _{22 to} R ₂₆ each independently represent a hydrogen atom or a substituent, and the substituent represented by R _{22 to} R ₂₆ is, for example, an alkyl group (for example, a methyl group, Ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, trifluoromethyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group etc.), aryl group ( For example, phenyl group, naphthyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.) Alkenyl group (for example, vinyl group, 2-propenyl group, 3-butenyl group, 1-methyl-3-pro Nyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group, cyclohexenyl group, etc.), halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom etc.), alkynyl group ( For example, propargyl group etc.), heterocyclic group (eg pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group etc.), alkylsulfonyl group (eg methylsulfonyl group, ethylsulfonyl group etc.), arylsulfonyl group (eg phenyl) Sulfonyl group, naphthylsulfonyl group, etc.), alkylsulfinyl group (eg, methylsulfinyl group, etc.), arylsulfinyl group (eg, phenylsulfinyl group, etc.), phosphono group, acyl group (eg, acetyl group, pivaloyl group, benzoyl group, etc.) ), Carbamoyl groups (eg aminocarbo Nyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, butylaminocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, Dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group), sulfonamide Groups (eg, methanesulfonamide groups, benzenesulfonamide groups, etc.), cyano groups, alkoxy groups (eg, methoxy groups, ethoxy groups, Group), aryloxy group (for example, phenoxy group, naphthyloxy group, etc.), heterocyclic oxy group, siloxy group, acyloxy group (for example, acetyloxy group, benzoyloxy group, etc.), sulfonic acid group, sulfonic acid salt Aminocarbonyloxy group, amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, etc.), anilino group (for example, phenylamino group) Chlorophenylamino group, toluidino group, anisidino group, naphthylamino group, 2-pyridylamino group, etc., imide group, ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, Dodecylureido group, Feni Ureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), alkoxycarbonylamino group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl) Etc.), aryloxycarbonyl groups (for example, phenoxycarbonyl groups, etc.), heterocyclic thio groups, thioureido groups, carboxyl groups, carboxylic acid salts, hydroxyl groups, mercapto groups, nitro groups and the like. These substituents may be further substituted with the same substituent.

  In the general formula (2), n represents 1 or 2.

In the general formula (2), when n is 1, R ₂₁ represents a substituent, and when n is 2, R ₂₁ represents a divalent linking group.

When R ₂₁ represents a substituent, examples of the substituent include the same groups as the substituents represented by R _{22 to} R _{26 in} the general formula (2). When R ₆₁ represents a divalent linking group, examples of the divalent linking group include an alkylene group that may have a substituent, an arylene group that may have a substituent, an oxygen atom, a nitrogen atom, and a sulfur atom. Or a combination of these linking groups.

  In the general formula (2), n is preferably 1.

  Next, although the specific example of a compound represented by the said General formula (2) in this invention is shown, this invention is not limited by the following specific examples.

(Other additives)
In addition to cellulose ester and the compound of the present invention and antioxidant, the optical film of the present invention includes a plasticizer, a stabilizer, a slip agent, a matting agent, a filler, an inorganic polymer, an organic polymer, a dye, a pigment, Phosphor, ultraviolet absorber, infrared absorber, dichroic dye, refractive index adjuster, retardation control agent, gas permeation inhibitor, antibacterial agent, conductivity imparting agent, biodegradability imparting agent, anti-gelling agent, Additives having various functions such as a viscosity modifier may be added as desired.

  Since the cellulose ester of the present invention is melted and formed at a high temperature of 200 to 250 ° C., the cellulose ester is a process in which decomposition and deterioration of the cellulose ester are likely to occur as compared with conventional solution casting film formation. Among the agents, a stabilizer is preferably added to the optical film forming material.

  Examples of the stabilizer include, but are not limited to, an acid scavenger, a hindered amine light stabilizer, an ultraviolet absorber, a peroxide decomposer, a radical scavenger, and a metal deactivator.

  These are described in JP-A-3-199201, JP-A-5-1907073, JP-A-5-194789, JP-A-5-271471, JP-A-6-107854, and the like. It is preferable that at least one selected from these is included in the optical film forming material.

  Further, when the optical film of the present invention is used as a polarizer protective film, a retardation film, etc., since the polarizer is weak against ultraviolet rays, at least the optical film on the light incident side with respect to the polarizer has an ultraviolet absorber. It is preferable to contain.

  Moreover, when using the optical film of this invention as a phase difference film, the additive for adjusting retardation can be contained. As the compound to be added for adjusting the retardation, a retardation controlling agent as described in European Patent No. 911,656A2 can also be used.

  In addition, an organic polymer or an inorganic polymer can be added to the optical film in order to control the viscosity at the time of heating and melting and adjust the physical properties of the optical film after processing the optical film.

  When these additives are added to the cellulose ester resin, the total amount including them is preferably 1 to 30% by mass with respect to the mass of the cellulose resin. If it is 1% by mass or less, the melt film-forming property is lowered, and if it is 30% by mass or more, the mechanical properties and storage stability of the obtained optical film may not be ensured.

<Acid scavenger>
Cellulose ester is preferably decomposed by an acid in a high temperature environment where melt film formation is performed. Therefore, the optical film of the present invention preferably contains an acid scavenger as a stabilizer.

  Any acid scavenger useful in the present invention can be used without limitation as long as it is a compound that reacts with an acid to inactivate the acid, and is described in U.S. Pat. No. 4,137,201. A compound having an epoxy group is preferred.

  Epoxy compounds as such acid scavengers are known in the art and are derived by condensation of various polyglycol diglycidyl ethers, particularly about 8 to 40 moles of ethylene oxide per mole of polyglycol. Glycol, diglycidyl ether of glycerol, etc., metal epoxy compounds (such as those conventionally used in and with vinyl chloride polymer compositions), epoxidized ether condensation products, diphenols of bisphenol A Glycidyl ether (ie, 4,4'-dihydroxydiphenyldimethylmethane), epoxidized unsaturated fatty acid ester (especially an ester of an alkyl of about 4 to 2 carbon atoms of a fatty acid of 2 to 22 carbon atoms (for example, Butyl epoxy stearate) And epoxidized vegetable oils and other unsaturated natural oils (sometimes epoxies) that may be represented and exemplified by compositions of various epoxidized long chain fatty acid triglycerides and the like (eg, epoxidized soybean oil, epoxidized linseed oil, etc.) Natural fatty glycerides or unsaturated fatty acids, which generally contain 12 to 22 carbon atoms). Further, as a commercially available epoxy group-containing epoxide resin compound, EPON 815C and other epoxidized ether oligomer condensation products of the following general formula (3) can also be preferably used.

  In General formula (3), n is an integer of 0-12.

  Other acid scavengers that can be used include those described in paragraphs 87 to 105 of JP-A-5-194788.

  The acid scavenger is preferably added in an amount of 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and further preferably 0.5 to 2% by mass with respect to the cellulose ester. Two or more of these may be used in combination.

  In addition, although an acid scavenger may be called an acid scavenger, an acid capture agent, an acid catcher, etc., in this invention, it can use without a difference by these names.

<Ultraviolet absorber>
The ultraviolet absorber is excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less from the viewpoint of preventing deterioration of the polarizer and the display device with respect to ultraviolet rays, and has little absorption of visible light having a wavelength of 400 nm or more from the viewpoint of liquid crystal display properties. Those are preferred. Examples of the ultraviolet absorber used in the present invention include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like. However, benzophenone compounds, less colored benzotriazole compounds, and triazine compounds are preferable.

  Further, ultraviolet absorbers described in JP-A Nos. 10-182621 and 8-337574, and polymer ultraviolet absorbers described in JP-A Nos. 6-148430 and 2003-113317 may be used.

  Specific examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzo Triazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 Chlorobenzotriazole, 2- (2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy- '-Tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-(2-octyloxycarbonylethyl) -phenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-3 '-(1-methyl-1-phenylethyl) -5'-(1,1,3,3, -tetramethylbutyl) -phenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H) -Benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro- H- benzotriazol-2-yl) can be mentioned mixtures of phenyl] propionate, and the like.

  As commercially available products, TINUVIN 171, TINUVIN 900, TINUVIN 928, TINUVIN 360 (all manufactured by Ciba Specialty Chemicals), LA31 (manufactured by Asahi Denka), RUVA-100 (Made by Otsuka Chemical).

  Specific examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy- 5-benzoylphenylmethane) and the like, but are not limited thereto.

  In the present invention, the ultraviolet absorber is preferably added in an amount of 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and further preferably 0.5 to 2% by mass. Two or more of these may be used in combination.

  These benzotriazole structures and triazine structures may be part of the polymer or regularly pendant to the polymer, and the molecular structure of other additives such as plasticizers, antioxidants, and acid scavengers. Some may be introduced.

  Although it does not specifically limit as a conventionally well-known ultraviolet absorptive polymer, For example, the polymer which homopolymerized RUVA-93 (made by Otsuka Chemical), the polymer which copolymerized RUVA-93, and another monomer, etc. are mentioned. . Specific examples include PUVA-30M obtained by copolymerization of RUVA-93 and methyl methacrylate at a ratio (mass ratio) of 3: 7, and PUVA-50M obtained by copolymerization at a ratio of 5: 5 (mass ratio). It is done. Furthermore, the polymer etc. which are described in Unexamined-Japanese-Patent No. 2003-113317 are mentioned.

《Plasticizer》
In the production of an optical film comprising the cellulose ester according to the present invention, it is preferable to add at least one plasticizer in the optical film molding material.

  Generally, a plasticizer is an additive having an effect of improving brittleness or imparting flexibility by being added to a polymer, but in the present invention, a cellulose ester alone is used. A plasticizer is added to lower the melting temperature than the melting temperature, and to lower the melt viscosity of the optical film constituting material containing the plasticizer than the cellulose resin alone at the same heating temperature. Moreover, since it adds also in order to improve the hydrophilic property of a cellulose ester and to improve the water vapor transmission rate of an optical film, it has a function as a moisture permeation preventive agent.

  Here, the melting temperature of the optical film constituting material means a temperature at which the material is heated to exhibit fluidity. In order to melt and flow the cellulose ester, it is necessary to heat at least a temperature higher than the glass transition temperature.

  Above the glass transition temperature, the elastic modulus or viscosity decreases due to heat absorption, and fluidity is exhibited.

  However, since the molecular weight of cellulose ester may decrease due to thermal decomposition at the same time as melting at high temperatures, it may adversely affect the mechanical properties of the resulting optical film, so it is necessary to melt the cellulose ester at as low a temperature as possible. There is.

  In order to lower the melting temperature of the optical film constituting material, it can be achieved by adding a plasticizer having a melting point or glass transition temperature lower than the glass transition temperature of the cellulose ester.

  The optical film of the present invention is preferably an optical film containing 1 to 25% by mass of a plasticizer.

  When the content is less than 1% by mass, the effect of improving the flatness is not recognized, and when the content is more than 25% by mass, bleeding out easily occurs and the temporal stability of the optical film is lowered, which is not preferable. More preferred is an optical film containing 3 to 20% by mass of a plasticizer, and further preferred is an optical film containing 5 to 15% by mass.

  In the present invention, an ester plasticizer composed of a polyhydric alcohol and a monovalent carboxylic acid, and an ester plasticizer composed of a polyvalent carboxylic acid and a monovalent alcohol have a high affinity with the cellulose ester and are preferred.

  Examples of the polyhydric alcohol that is a raw material of the ester plasticizer preferably used in the present invention include the following, but the present invention is not limited thereto.

  Adonitol, arabitol, ethylene glycol, glycerin, diglycerin, 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, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, ditrimethylolpropane, trimethylolethane, pentaethysitol, dipentaerythritol, xylene Mention may be made of the toll and the like. In particular, ethylene glycol, glycerin, and trimethylolpropane are preferable.

  Specific examples of ethylene glycol ester plasticizers that are one of the polyhydric alcohol esters include ethylene glycol alkyl ester plasticizers such as ethylene glycol diacetate and ethylene glycol dibutyrate, and ethylene glycol dicyclopropyl. Examples thereof include ethylene glycol cycloalkyl ester plasticizers such as carboxylate and ethylene glycol dicyclohexylcarboxylate, and ethylene glycol aryl ester plasticizers such as ethylene glycol dibenzoate and ethylene glycol di4-methylbenzoate. These alkylate groups, cycloalkylate groups, and arylate groups may be the same or different, and may be further substituted.

  Further, it may be a mix of alkylate group, cycloalkylate group and arylate group, and these substituents may be covalently bonded.

  Further, the ethylene glycol part may be substituted, the ethylene glycol ester partial structure may be part of the polymer or regularly pendant, and may be an antioxidant, an acid scavenger, an ultraviolet absorber, etc. It may be introduced into a part of the molecular structure of the additive.

  Specific examples of glycerin ester plasticizers that are one of the polyhydric alcohol esters include glycerol alkyl esters such as triacetin, tributyrin, glycerol diacetate caprylate, glycerol oleate propionate, and glycerol tricyclopropylcarboxylate. Glycerol glycerol esters such as glycerol tricyclohexyl carboxylate, glycerol aryl esters such as glycerol tribenzoate and glycerol 4-methylbenzoate, diglycerol tetraacetylate, diglycerol tetrapropionate, diglycerol acetate tricaprylate, diglycerol Tetralaurate, diglycerin alkyl ester, diglycerin tetracyclobutylcarboxylate, diglycerin tet Diglycerol cycloalkyl esters such as cyclopentyl carboxylate, diglycerin tetrabenzoate, diglycerin aryl ester such as diglycerin 3-methylbenzoate or the like. These alkylate groups, cycloalkylcarboxylate groups, and arylate groups may be the same or different, and may be further substituted.

  Further, it may be a mixture of alkylate group, cycloalkylcarboxylate group, and arylate group, and these substituents may be bonded by a covalent bond.

  Furthermore, the glycerin and diglycerin part may be substituted, the partial structure of the glycerin ester and the diglycerin ester may be part of the polymer or regularly pendant, and the antioxidant, acid scavenger, You may introduce | transduce into a part of molecular structure of additives, such as a ultraviolet absorber.

  Specific examples of other polyhydric alcohol ester plasticizers include polyhydric alcohol ester plasticizers described in paragraphs 30 to 33 of JP-A No. 2003-12823.

  These alkylate groups, cycloalkylcarboxylate groups, and arylate groups may be the same or different, and may be further substituted. Further, it may be a mixture of alkylate group, cycloalkylcarboxylate group, and arylate group, and these substituents may be bonded by a covalent bond.

  Furthermore, the polyhydric alcohol part may be substituted, and the partial structure of the polyhydric alcohol may be part of the polymer or regularly pendant, and may be an antioxidant, an acid scavenger, an ultraviolet absorber. May be introduced into a part of the molecular structure of the additive.

  Among the ester plasticizers composed of the polyhydric alcohol and the monovalent carboxylic acid, alkyl polyhydric alcohol aryl esters are preferred. Specifically, the above-mentioned ethylene glycol dibenzoate, glycerin tribenzoate, diglycerin tetrabenzoate, Exemplified compound 16 described in paragraph 31 of JP2003-12823A can be mentioned.

  Specific examples of the dicarboxylic acid ester plasticizer that is one of polyvalent carboxylic acid esters include alkyl dicarboxylic acids such as didodecyl malonate (C1), dioctyl adipate (C4), and dibutyl sebacate (C8). Alkyl ester plasticizers, alkyl dicarboxylic acid cycloalkyl ester plasticizers such as dicyclopentyl succinate and dicyclohexyl adipate, and alkyl dicarboxylic acid aryl ester plastics such as diphenyl succinate and di-4-methylphenyl glutarate , Dicyclohexyl-1,4-cyclohexanedicarboxylate, didecylbicyclo [2.2.1] heptane-2,3-dicarboxylate and other cycloalkyldicarboxylic acid alkyl ester plasticizers, dicyclohexyl-1,2 -Cyclobutane Cycloalkyldicarboxylic acid cycloalkyl ester type plasticizers such as carboxylate and dicyclopropyl-1,2-cyclohexyldicarboxylate, diphenyl-1,1-cyclopropyldicarboxylate, di2-naphthyl-1,4- Cycloalkyldicarboxylic acid aryl ester plasticizers such as cyclohexane dicarboxylate, aryl dicarboxylic acid alkyl ester plasticizers such as diethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, and di-2-ethylhexyl phthalate, dicyclopropyl Aryl dicarboxylic acid cycloalkyl ester plasticizers such as phthalate and dicyclohexyl phthalate, and aryl dicarboxylic acid esters such as diphenyl phthalate and di4-methylphenyl phthalate Ruesuteru based plasticizers.

  These alkoxy groups and cycloalkoxy groups may be the same or different, may be mono-substituted, and these substituents may be further substituted. The alkyl group and cycloalkyl group may be mixed, and these substituents may be bonded together by a covalent bond. Furthermore, the aromatic ring of phthalic acid may be substituted, and a multimer such as a dimer, trimer or tetramer may be used. In addition, the partial structure of phthalate ester may be part of the polymer or regularly pendant to the polymer, and may be part of the molecular structure of additives such as antioxidants, acid scavengers, and UV absorbers. It may be introduced.

  Examples of other polycarboxylic acid ester plasticizers include alkyl polycarboxylic acid alkyl esters such as tridodecyl tricarbarate and tributyl-meso-butane-1,2,3,4-tetracarboxylate. Plasticizers, alkylpolycarboxylic acid cycloalkyl ester plasticizers such as tricyclohexyltricarbarate, tricyclopropyl-2-hydroxy-1,2,3-propanetricarboxylate, triphenyl 2-hydroxy- Alkyl polyvalent carboxylic acid aryl ester plasticizers such as 1,2,3-propanetricarboxylate, tetra-3-methylphenyltetrahydrofuran-2,3,4,5-tetracarboxylate, tetrahexyl-1,2, 3,4-cyclobutanetetracarboxylate, tetrabu Cycloalkyl polycarboxylic acid alkyl ester plasticizers such as ru-1,2,3,4-cyclopentanetetracarboxylate, tetracyclopropyl-1,2,3,4-cyclobutanetetracarboxylate, tricyclohexyl- Cycloalkyl polycarboxylic acid cycloalkyl ester plasticizers such as 1,3,5-cyclohexyl tricarboxylate, triphenyl-1,3,5-cyclohexyl tricarboxylate, hexa-4-methylphenyl-1,2, Cycloalkyl polycarboxylic acid aryl ester plasticizers such as 3,4,5,6-cyclohexylhexacarboxylate, tridodecylbenzene-1,2,4-tricarboxylate, tetraoctylbenzene-1,2,4 , 5-tetracarboxylate and other aryl polyvalent Rubinoic acid alkyl ester plasticizers, tricyclopentylbenzene-1,3,5-tricarboxylate, tetracyclohexylbenzene-1,2,3,5-tetracarboxylate and other aryl polyvalent carboxylic acid cycloalkyl esters Plasticizers of aryl polyvalent carboxylic acid aryl esters such as plasticizers triphenylbenzene-1,3,5-tetracarboxylate, hexa-4-methylphenylbenzene-1,2,3,4,5,6-hexacarboxylate Agents.

  These alkoxy groups and cycloalkoxy groups may be the same or different, and may be monosubstituted, and these substituents may be further substituted.

  The alkyl group and cycloalkyl group may be mixed, and these substituents may be bonded together by a covalent bond. Furthermore, the aromatic ring of phthalic acid may be substituted, and a multimer such as a dimer, trimer or tetramer may be used.

  In addition, the partial structure of phthalate ester may be part of the polymer or may be regularly pendant to the polymer, and introduced into part of the molecular structure of additives such as antioxidants, acid scavengers, UV absorbers, etc. May be.

  Among the ester plasticizers composed of the polyvalent carboxylic acid and the monohydric alcohol, alkyl dicarboxylic acid alkyl esters are preferable, and specific examples include the dioctyl adipate.

  Examples of other plasticizers used in the present invention include phosphate ester plasticizers, carbohydrate ester plasticizers, and polymer plasticizers.

  Specific examples of the phosphoric acid ester plasticizer include phosphoric acid alkyl esters such as triacetyl phosphate and tributyl phosphate, phosphoric acid cycloalkyl esters such as tricyclobenthyl phosphate and cyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, Examples thereof include phosphoric acid aryl esters such as cresylphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, trinaphthyl phosphate, trixylyl phosphate, tris ortho-biphenyl phosphate.

  These substituents may be the same or different, and may be further substituted. Moreover, the mix of an alkyl group, a cycloalkyl group, and an aryl group may be sufficient, and substituents may couple | bond together by the covalent bond.

  Also, alkylene bis (dialkyl phosphate) such as ethylene bis (dimethyl phosphate), butylene bis (diethyl phosphate), alkylene bis (diaryl phosphate) such as ethylene bis (diphenyl phosphate), propylene bis (dinaphthyl phosphate), phenylene bis (dibutyl) Phosphate), arylene bis (dialkyl phosphate) such as biphenylene bis (dioctyl phosphate), phosphate esters such as arylene bis (diaryl phosphate) such as phenylene bis (diphenyl phosphate) and naphthylene bis (ditoluyl phosphate).

  These substituents may be the same or different, and may be further substituted. Moreover, the mix of an alkyl group, a cycloalkyl group, and an aryl group may be sufficient, and substituents may couple | bond together by the covalent bond.

  Furthermore, the partial structure of the phosphate ester may be part of the polymer or may be regularly pendant, and may be introduced into part of the molecular structure of additives such as antioxidants, acid scavengers, and UV absorbers. It may be. Among the above-mentioned compounds, phosphoric acid aryl ester and arylene bis (diaryl phosphate) are preferable, and specifically, triphenyl phosphate and phenylene bis (diphenyl phosphate) are preferable.

  Next, the carbohydrate ester plasticizer will be described. The carbohydrate means a monosaccharide, disaccharide or trisaccharide in which the saccharide is present in the form of pyranose or furanose (6-membered ring or 5-membered ring). Non-limiting examples of carbohydrates include glucose, saccharose, lactose, cellobiose, mannose, xylose, ribose, galactose, arabinose, fructose, sorbose, cellotriose and raffinose. The carbohydrate ester refers to an ester compound formed by dehydration condensation of a hydroxyl group of a carbohydrate and a carboxylic acid. Specifically, it means an aliphatic carboxylic acid ester or an aromatic carboxylic acid ester of a carbohydrate.

  Examples of the aliphatic carboxylic acid include acetic acid and propionic acid, and examples of the aromatic carboxylic acid include benzoic acid, toluic acid, and anisic acid. Carbohydrates have a number of hydroxyl groups depending on the type, but even if a part of the hydroxyl group reacts with the carboxylic acid to form an ester compound, the whole hydroxyl group reacts with the carboxylic acid to form an ester compound. Also good.

  In the present invention, it is preferable that all of the hydroxyl groups react with the carboxylic acid to form an ester compound.

  Specific examples of the carbohydrate ester plasticizer include glucose pentaacetate, glucose pentapropionate, glucose pentabtylate, saccharose octaacetate, saccharose octabenzoate, and of these, saccharose octaacetate is more preferred. preferable.

  Specific examples of the polymer plasticizer include aliphatic hydrocarbon polymers, alicyclic hydrocarbon polymers, polyethyl acrylate, polymethyl methacrylate, methyl methacrylate and 2-hydroxyethyl methacrylate. Acrylic polymers such as polymers (for example, any ratio between 1:99 and 99: 1), vinyl polymers such as polyvinyl isobutyl ether and poly N-vinyl pyrrolidone, polystyrene, poly 4-hydroxystyrene Styrene polymers such as polybutylene succinate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyethers such as polyethylene oxide and polypropylene oxide, polyamides, polyurethanes and polyureas.

  The number average molecular weight is preferably about 1,000 to 500,000, particularly preferably 5,000 to 200,000. If it is 1,000 or less, a problem occurs in volatility, and if it exceeds 500,000, the plasticizing ability is lowered, and the mechanical properties of the optical film are adversely affected. These polymer plasticizers may be a homopolymer composed of one type of repeating unit or a copolymer having a plurality of repeating structures. Two or more of the above polymers may be used in combination.

  The amount of the other plasticizer added is usually 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass, and more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the cellulose ester.

  The optical film of the present invention preferably contains 1 to 25% by mass of an ester plasticizer comprising a polyhydric alcohol and a monovalent carboxylic acid, and an ester plasticizer comprising a polyvalent carboxylic acid and a monohydric alcohol. , And may be used in combination with other plasticizers.

  In the optical film of the present invention, an ester plasticizer comprising a polyhydric alcohol and a monovalent carboxylic acid is more preferred, and an ester plasticizer comprising a trivalent or higher alcohol and a monovalent carboxylic acid is compatible with the cellulose ester. Because it is high and can be added at a high addition rate, bleed-out does not occur even when other plasticizers and additives are used in combination, and other types of plasticizers and additives can be added as necessary. It is most preferable because it can be easily used together.

  It is preferable to contain at least one of the above compounds, and the content is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass with respect to the mass of the cellulose ester resin. Preferably it is 0.2-2 mass%.

  When the content of the compound is less than the above range, the cellulose ester resin is likely to be thermally decomposed, and when the content is more than the range of the addition amount, transparency as a polarizing plate protective film from the viewpoint of compatibility with the resin. This is not preferable because it causes a decrease and the optical film becomes brittle.

(Viscosity reducing agent)
In the present invention, a hydrogen bonding solvent can be added for the purpose of reducing the melt viscosity.

  The hydrogen bonding solvent is J.I. N. As described in Israel Ativili, “Intermolecular Forces and Surface Forces” (Takeshi Kondo, Hiroyuki Oshima, Maglow Hill Publishing, 1991) and electrically negative atoms (oxygen, nitrogen, fluorine, chlorine) An organic solvent capable of producing a hydrogen atom-mediated “bond” between a hydrogen atom covalently bonded to an electronegative atom, ie, a bond having a large bond moment and containing hydrogen, such as O—H (Oxygen hydrogen bond), N—H (nitrogen hydrogen bond), and organic solvent that can arrange adjacent molecules by including F—H (fluorine hydrogen bond).

  These have the ability to form stronger hydrogen bonds with cellulose than intermolecular hydrogen bonds of cellulose resin. In the melt casting method performed in the present invention, the glass transition temperature of the cellulose resin used alone is higher than that. The melting temperature of the cellulose resin composition can be lowered by the addition of a hydrogen bonding solvent, or the melt viscosity of the cellulose resin composition containing a hydrogen bonding solvent can be lowered at the same melting temperature as the cellulose resin. .

  Examples of the hydrogen bonding solvent include alcohols: for example, methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, t-butanol, 2-ethylhexanol, heptanol, octanol, nonanol, dodecanol, ethylene glycol, Propylene glycol, hexylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, hexyl cellosolve, glycerin, etc., ketones: acetone, methyl ethyl ketone, etc., carboxylic acids: for example formic acid, acetic acid, propionic acid, Butyric acid, etc., ethers: eg, diethyl ether, tetrahydrofuran, dioxane, etc., Pyrrolidones: eg, N-methyl Pyrrolidone, etc., amines: for example, can be exemplified trimethylamine, pyridine, etc., and the like.

  These hydrogen bonding solvents can be used alone or in admixture of two or more.

  Among these, alcohol, ketone, and ether are preferable, and methanol, ethanol, propanol, isopropanol, octanol, dodecanol, ethylene glycol, glycerin, acetone, and tetrahydrofuran are particularly preferable.

  Furthermore, water-soluble solvents such as methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerin, acetone, and tetrahydrofuran are particularly preferable. Here, water-soluble means that the solubility in 100 g of water is 10 g or more.

(Retardation control agent)
In the optical use film using the optical film of the present invention, an alignment film may be formed to provide a liquid crystal layer, and polarizing plate processing may be performed by combining the optical film and the retardation derived from the liquid crystal layer to provide optical compensation ability. .

  The compound to be added to control the retardation is an aromatic compound having two or more aromatic rings as described in EP 911,656A2, which is used as a retardation control agent. You can also.

  Two or more aromatic compounds may be used in combination. The aromatic ring of the aromatic compound includes an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring.

  An aromatic heterocyclic ring is particularly preferred, and the aromatic heterocyclic ring is generally an unsaturated heterocyclic ring. Of these, compounds having a 1,3,5-triazine ring are particularly preferred.

(Matting agent)
In the optical film of the present invention, a matting agent can be added in order to impart slipperiness, optical and mechanical functions. Examples of the matting agent include inorganic compound fine particles and organic compound fine particles.

  The shape of the matting agent is preferably a spherical shape, a rod shape, a needle shape, a layer shape, a flat shape or the like. Examples of the matting agent include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate. Examples thereof include inorganic fine particles such as oxides, phosphates, silicates, and carbonates, and crosslinked polymer fine particles.

  Among these, silicon dioxide is preferable because it can reduce the haze of the optical film. These fine particles are preferably surface-treated with an organic substance because the haze of the optical film can be reduced.

  The surface treatment is preferably performed with halosilanes, alkoxysilanes, silazane, siloxane, or the like. The larger the average particle size of the fine particles, the greater the sliding effect, and the smaller the average particle size, the better the transparency. The average primary particle size of the fine particles is in the range of 0.01 to 1.0 μm. The average particle diameter of primary particles of preferable fine particles is preferably 5 to 50 nm, and more preferably 7 to 14 nm. These fine particles are preferably used for generating irregularities of 0.01 to 1.0 μm on the optical film surface.

  Examples of the silicon dioxide fine particles include Aerosil 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600, etc. manufactured by Nippon Aerosil Co., Ltd., preferably Aerosil 200V, R972. , R972V, R974, R202, R812. Two or more kinds of these fine particles may be used in combination.

  When using 2 or more types together, it can mix and use in arbitrary ratios. Fine particles having different average particle sizes and materials, for example, Aerosil 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1.

  These matting agents are preferably added by kneading. Further, as another form, after mixing and dispersing a matting agent previously dispersed in a solvent and a cellulose ester and / or a plasticizer and / or an ultraviolet absorber, a solid material obtained by volatilizing or precipitating the solvent is obtained. It is preferable to use it in the production process of the ester melt from the viewpoint that the matting agent can be uniformly dispersed in the cellulose resin.

  The matting agent can also be added to improve the mechanical, electrical and optical properties of the optical film.

  In addition, although the slipperiness of the optical film obtained improves, so that these microparticles | fine-particles are added, since haze raises, so that it adds, Preferably content is 0.001-5 mass%, More preferably, it is 0.00. It is 005-1 mass%, More preferably, it is 0.01-0.5 mass%.

  The optical film of the present invention preferably has an haze value of less than 1.0%, more preferably less than 0.5% because an optical material is affected when the haze value exceeds 1.0%. The haze value can be measured based on JIS-K7136.

(Polymer material)
In the optical film of the present invention, polymer materials and oligomers other than cellulose ester may be appropriately selected and mixed.

  The above-described polymer materials and oligomers are preferably those having excellent compatibility with the cellulose ester, and the transmittance when formed into an optical film is 80% or more, more preferably 90% or more, more preferably 92% or more. .

  The purpose of mixing at least one of polymer materials and oligomers other than cellulose ester includes meaning to improve viscosity control at the time of heating and melting and optical film physical properties after optical film processing. In this case, it can contain as an above-mentioned other additive.

  The optical film constituent material is required to have little or no volatile component in the melting and film forming process.

  This is for foaming during heating and melting to reduce or avoid defects inside the optical film and flatness deterioration of the optical film surface.

  The content of the volatile component when the optical film constituting material is melted is 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and still more preferably 0.1% by mass. It is desirable that

  In the present invention, a heat loss from 30 ° C. to 250 ° C. is determined using a differential thermogravimetric measuring device (TG / DTA200 manufactured by Seiko Denshi Kogyo Co., Ltd.), and the amount is defined as the content of volatile components.

  It is preferable that the optical film constituent material used removes volatile components typified by the moisture and the solvent before film formation or during heating.

  A known drying method can be applied to the removal method, and it can be performed by a method such as a heating method, a reduced pressure method, a heated reduced pressure method, or the like, and may be performed in air or in an atmosphere where nitrogen is selected as an inert gas.

  When performing these well-known drying methods, it is preferable on the quality of an optical film to carry out in the temperature range which an optical film constituent material does not decompose.

  By drying before film formation, the generation of volatile components can be reduced and divided into resin alone or at least one mixture or compatible material other than resin among resin and optical film constituent materials. It can also be dried. The drying temperature is preferably 70 ° C. or higher.

  When a material having a glass transition temperature is present in the material to be dried, heating to a drying temperature higher than the glass transition temperature may cause the material to melt and become difficult to handle. It is preferable that it is below the temperature.

  When a plurality of substances have a glass transition temperature, the glass transition temperature with the lower glass transition temperature is used as a reference. More preferably, they are 70 degreeC or more and (glass transition temperature-5) degreeC or less, More preferably, they are 110 degreeC or more and (glass transition temperature-20) degreeC or less.

  The drying time is preferably 0.5 to 24 hours, more preferably 1 to 18 hours, and further preferably 1.5 to 12 hours. If the drying temperature is too low, the removal rate of volatile components will be low, and it will take too much time to dry.

  Further, the drying process may be divided into two or more stages. For example, the drying process includes a preliminary drying process for storage of materials and a just-before drying process performed immediately before film formation to one week before film formation. Also good.

<Melt casting method>
The method for producing an optical film according to claim 2 of the present invention is characterized by being formed by melt casting.

  The molding method by melt casting that heats and melts without using the solvent (for example, methylene chloride, etc.) used in the solution casting method, more specifically, melt extrusion molding method, press molding method, inflation method, injection molding method And can be classified into blow molding, stretch molding and the like.

  Among these, in order to obtain a polarizing plate protective film having excellent mechanical strength and surface accuracy, the melt extrusion method is excellent.

  The method for producing an optical film according to claim 2 of the present invention will be described below by taking the melt extrusion method as an example.

  FIG. 1 is a schematic flow sheet showing the overall configuration of an apparatus for carrying out the method for producing an optical film according to the present invention, and FIG. 2 is an enlarged view of a cooling roll portion from a casting die.

  1 and 2, the optical film manufacturing method includes mixing an optical film material such as cellulose resin, and then using the extruder 1 to melt and extrude from the casting die 4 onto the first cooling roll 5. While circumscribing the cooling roll 5, it is further circumscribed by a total of three cooling rolls, ie, the second cooling roll 7 and the third cooling roll 8, in order to cool and solidify the optical film 10.

  Next, the optical film 10 peeled off by the peeling roll 9 is then stretched in the width direction by holding both ends of the optical film by the stretching device 12, and then wound by the winding device 16. In addition, a touch roll 6 is provided that clamps the molten film on the surface of the first cooling roll 5 in order to correct the flatness.

  The touch roll 6 has an elastic surface and forms a nip with the first cooling roll 5. Details of the touch roll 6 will be described later.

  In the method for producing an optical film, the conditions for melt extrusion can be performed in the same manner as the conditions used for other thermoplastic resins such as polyester.

  The material is preferably dried beforehand. It is desirable to dry the moisture to 1000 ppm or less, preferably 200 ppm or less by using a vacuum or reduced pressure drier or a dehumidifying hot air drier.

  For example, the cellulose ester-based resin dried under hot air, vacuum or reduced pressure is used in the extruder 1 and melted at an extrusion temperature of about 200 to 300 ° C. and filtered through a leaf disk type filter 2 or the like to remove foreign matters.

  When introducing into the extruder 1 from a supply hopper (not shown), it is preferable to prevent oxidative decomposition or the like under vacuum, reduced pressure, or inert gas atmosphere.

  When additives such as a plasticizer are not mixed in advance, they may be kneaded in the middle of the extruder. In order to add uniformly, it is preferable to use a mixing apparatus such as a static mixer 3.

  In the present invention, it is preferable that the cellulose resin and other additives such as a stabilizer added as necessary are mixed before melting. More preferably, the cellulose resin and the stabilizer are mixed first.

  Mixing may be performed by a mixer or the like, or may be mixed in the cellulose resin preparation process as described above. When a mixer is used, a general mixer such as a V-type mixer, a conical screw type mixer, a horizontal cylindrical type mixer, a Henschel mixer, a ribbon mixer, or the like can be used.

  After mixing the optical film constituting material as described above, the mixture may be directly melted and formed into a film using the extruder 1, but once the optical film constituting material is pelletized, the pellet May be melted by the extruder 1 to form a film.

  Further, when the optical film constituting material includes a plurality of materials having different melting points, a so-called braided semi-melt is once produced at a temperature at which only a material having a low melting point is melted, and the semi-melt is extruded into the extruder 1. It is also possible to form a film by putting it into the film.

  If the optical film material contains materials that are easily pyrolyzed, in order to reduce the number of melting times, a method of directly forming a film without producing pellets, or making a braided semi-melt as described above A method of forming a film from is preferred.

  As the extruder 1, various commercially available extruders can be used, but a melt-kneading extruder is preferable, and a single-screw extruder or a twin-screw extruder may be used.

  When forming a film directly without forming pellets from optical film constituent materials, it is preferable to use a twin-screw extruder because an appropriate degree of kneading is required. However, even with a single-screw extruder, the screw shape can be changed to Maddock. By changing to a kneading type screw such as a mold, unimelt, dalmage, etc., moderate kneading can be obtained, which can be used.

  When a pellet or braided semi-melt is used as the optical film constituent material, it can be used with either a single screw extruder or a twin screw extruder.

  In the extruder 1 and the cooling step after extrusion, it is preferable to reduce the oxygen concentration by replacing with an inert gas such as nitrogen gas or reducing the pressure.

  The melting temperature of the optical film constituent material in the extruder 1 varies depending on the viscosity and discharge amount of the optical film constituent material, the thickness of the sheet to be manufactured, etc., but generally the glass transition temperature Tg of the optical film. On the other hand, it is Tg or more and Tg + 130 ° C. or less, preferably Tg + 10 ° C. or more and Tg + 120 ° C. or less. The melt viscosity at the time of extrusion is 10 to 100,000 poise, preferably 100 to 10,000 poise.

  Further, the residence time of the optical film constituting material in the extruder 1 is preferably shorter, and is within 5 minutes, preferably within 3 minutes, and more preferably within 2 minutes. Although the residence time depends on the type of the extruder 1 and the extrusion conditions, it can be shortened by adjusting the material supply amount, L / D, screw rotation speed, screw groove depth, etc. It is.

  The shape, rotation speed, etc. of the screw of the extruder 1 are appropriately selected depending on the viscosity, discharge amount, etc. of the optical film constituting material. In the present invention, the shear rate in the extruder 1 is 1 / second to 10000 / second, preferably 5 / second to 1000 / second, more preferably 10 / second to 100 / second.

  The extruder 1 that can be used in the present invention is generally available as a plastic molding machine.

  The optical film constituting material extruded from the extruder 1 is sent to the casting die 4 and extruded from the slit of the casting die 4 into an optical film shape. The casting die 4 is not particularly limited as long as it is used for producing a sheet or an optical film.

  The material of the casting die 4 is sprayed or plated with hard chromium, chromium carbide, chromium nitride, titanium carbide, titanium carbonitride, titanium nitride, super steel, ceramic (tungsten carbide, aluminum oxide, chromium oxide), etc. Processing such as buffing, lapping using a # 1000 or higher grinding wheel, plane cutting using a # 1000 or higher diamond grinding wheel (the cutting direction is perpendicular to the resin flow direction), electrolytic polishing, electrolytic composite polishing, etc. And the like.

  A preferred material for the lip portion of the casting die 4 is the same as that of the casting die 4. The surface accuracy of the lip is preferably 0.5S or less, and more preferably 0.2S or less.

  The slit of the casting die 4 is configured so that the gap can be adjusted.

  This is shown in FIG. Of the pair of lips forming the slit 32 of the casting die 4, one is a flexible lip 33 having low rigidity and easily deformed, and the other is a fixed lip 34. A large number of heat bolts 35 are arranged at a constant pitch in the width direction of the casting die 4, that is, in the length direction of the slits 32.

  Each heat bolt 5 is provided with a block 36 having an embedded electric heater 37 and a cooling medium passage, and each heat bolt 35 penetrates each block 36 vertically. The base of the heat bolt 35 is fixed to the die body 31, and the tip is in contact with the outer surface of the flexible lip 33.

  While the block 36 is always air-cooled, the input of the embedded electric heater 37 is increased or decreased to raise or lower the temperature of the block 36, thereby causing the heat bolt 35 to thermally expand and contract, thereby displacing the flexible lip 33 to change the thickness of the optical film. Adjust.

  Thickness gauges are installed at the required locations in the wake of the die, and the web thickness information detected thereby is fed back to the control device. The thickness information is compared with the set thickness information by the control device, and correction control comes from the same device. It is also possible to control the power or the ON rate of the heat bolt heating element by the amount signal. The heat bolt preferably has a length of 20 to 40 cm and a diameter of 7 to 14 mm, and a plurality of, for example, several tens of heat bolts are preferably arranged at a pitch of 20 to 40 mm.

  Instead of the heat bolt, a gap adjusting member mainly composed of a bolt for adjusting the slit gap by manually moving back and forth in the axial direction may be provided. The slit gap adjusted by the gap adjusting member is usually 200 to 1000 μm, preferably 300 to 800 μm, more preferably 400 to 600 μm.

  The first to third cooling rolls are made of seamless steel pipe having a wall thickness of about 20 to 30 mm, and the surface is finished to a mirror surface. A pipe for flowing a cooling liquid is arranged inside the pipe, and the cooling liquid flowing through the pipe can absorb heat from the optical film on the roll.

  Of the first to third cooling rolls, the first cooling roll 5 corresponds to the rotary support of the present invention.

  On the other hand, the touch roll 6 in contact with the first cooling roll 5 has an elastic surface and is deformed along the surface of the first cooling roll 5 by the pressing force to the first cooling roll 5. A nip is formed between the two. That is, the touch roll 6 corresponds to the pinching rotary body of the present invention.

  In FIG. 4, the schematic cross section of one Embodiment (henceforth, touch roll A) of the touch roll 6 is shown. As shown in the drawing, the touch roll A has an elastic roller 42 disposed inside a flexible metal sleeve 41.

  The metal sleeve 41 is made of stainless steel having a thickness of 0.3 mm and has flexibility. If the metal sleeve 41 is too thin, the strength is insufficient, whereas if it is too thick, the elasticity is insufficient. For these reasons, the thickness of the metal sleeve 41 is preferably 0.1 to 1.5 mm.

  The elastic roller 42 is formed in a roll shape by providing a rubber 44 on the surface of a metal inner cylinder 43 that is rotatable via a bearing.

  When the touch roll A is pressed toward the first cooling roll 5, the elastic roller 42 presses the metal sleeve 41 against the first cooling roll 5, and the metal sleep 41 and the elastic roller 42 have the shape of the first cooling roll 5. It deforms corresponding to the familiar shape, and forms a nip with the first cooling roll. Cooling water 45 flows in a space formed between the metal sleeve 41 and the elastic roller 42.

  5 and 6 show a touch roll B which is another embodiment of the pinching rotator. The touch roll B includes a flexible, seamless stainless steel pipe (thickness 4 mm) outer cylinder 51, and a highly rigid metal inner cylinder 52 arranged on the same axis as the inner side of the outer cylinder 51. It is roughly composed. A coolant 54 flows in the space 53 between the outer cylinder 51 and the inner cylinder 52.

  Specifically, in the touch roll B, outer cylinder support flanges 56a and 56b are attached to the rotation shafts 55a and 55b at both ends, and a thin metal outer cylinder 51 is attached between the outer peripheral portions of the both outer cylinder support flanges 56a and 56b. Yes.

  A fluid supply pipe 59 is disposed in the same axial center in a fluid discharge hole 58 formed in the axial center portion of one rotary shaft 55a and forming a fluid return passage 57. The fluid supply pipe 59 is thin-walled. It is connected and fixed to a fluid shaft cylinder 60 arranged at the axial center in the metal outer cylinder 51.

  Inner cylinder support flanges 61a and 61b are attached to both ends of the fluid shaft cylinder 60, respectively, and a thickness of about 15 to 20 mm between the outer periphery of the inner cylinder support flanges 61a and 61b and the other end side outer cylinder support flange 56b. A metal inner cylinder 52 having a thickness is attached.

  A cooling liquid flow space 53 of, for example, about 10 mm is formed between the metal inner cylinder 52 and the thin metal outer cylinder 51, and the metal inner cylinder 52 has a flow space 53 and an inner space near both ends. An outlet 52a and an inlet 52b are formed to communicate with the intermediate passages 62a and 62b outside the cylinder support flanges 61a and 61b, respectively.

  Further, the outer cylinder 51 is thinned within a range in which the thin cylinder theory of elastic mechanics can be applied in order to have flexibility, flexibility, and resilience close to rubber elasticity. The flexibility evaluated by the thin-walled cylinder theory is expressed by the thickness t / roll radius r, and the flexibility increases as t / r decreases.

  In this touch roll B, the flexibility is the optimum condition when t / r ≦ 0.03. Usually, the touch roll generally used has a roll diameter R = 200 to 500 mm (roll radius r = R / 2), a roll effective width L = 500 to 1600 mm, and a horizontally long shape with r / L <1. is there.

  As shown in FIG. 6, for example, when the roll diameter R = 300 mm and the roll effective width L = 1200 mm, the appropriate range of the wall thickness t is 150 × 0.03 = 4.5 mm or less, but the molten sheet width is 1300 mm. On the other hand, when the average linear pressure is clamped at 98 N / cm, the equivalent spring constant is equal by setting the wall thickness of the outer cylinder 51 to 3 mm compared to the rubber roll of the same shape. The nip width k in the roll rotation direction of the nip is also about 9 mm, which is almost the same as the nip width of this rubber roll of about 12 mm.

  The deflection amount at the nip width k is about 0.05 to 0.1 mm.

  Here, t / r ≦ 0.03, but in the case of a general roll diameter R = 200 to 500 mm, flexibility is sufficiently obtained especially when the range of 2 mm ≦ t ≦ 5 mm is obtained. Thinning in processing can be easily performed, and is in a very practical range. If the wall thickness is 2 mm or less, high-precision processing cannot be performed due to elastic deformation during processing.

  The converted value of 2 mm ≦ t ≦ 5 mm is 0.008 ≦ t / r ≦ 0.05 with respect to a general roll diameter, but in practical use, the roll diameter under the condition of t / r≈0.03. The wall thickness should be increased in proportion to For example, when roll diameter: R = 200, t = 2 to 3 mm, and when roll diameter: R = 500, t = 4 to 5 mm.

  The touch rolls A and B are urged toward the first cooling roll by urging means (not shown).

  The urging force of the urging means is F, and the value F / W (linear pressure) obtained by dividing the width W of the optical film in the nip along the rotation axis of the first cooling roll 5 is 9.8 to 147 N / Set to cm.

  According to the present embodiment, a nip is formed between the touch rolls A and B and the first cooling roll 5, and the flatness may be corrected while the optical film passes through the nip.

  Accordingly, the optical film is sandwiched over a long time with a small linear pressure compared to the case where the touch roll is formed of a rigid body and a nip is not formed between the first cooling roll and the flatness is more reliably corrected. be able to. That is, when the linear pressure is smaller than 9.8 N / cm, the die line cannot be sufficiently eliminated.

  On the other hand, if the linear pressure is greater than 147 N / cm, the optical film is difficult to pass through the nip, resulting in unevenness in place of the thickness of the optical film.

  In addition, since the surfaces of the touch rolls A and B are made of metal, the surfaces of the touch rolls A and B can be made smoother than when the surface of the touch roll is rubber. Can be obtained.

  In addition, as a material of the elastic body 44 of the elastic roller 42, ethylene propylene rubber, neoprene rubber, silicon rubber, or the like can be used.

  Now, in order to eliminate the die line satisfactorily by the touch roll 6, it is important that the viscosity of the optical film when the touch roll 6 sandwiches the optical film is in an appropriate range.

  Cellulose esters are known to have a relatively large change in viscosity with temperature.

  Therefore, in order to set the viscosity when the touch roll 6 clamps the optical film to an appropriate range, it is important to set the temperature of the film when the touch roll 6 clamps the optical film to an appropriate range. Become.

  And when the glass transition temperature of an optical film is set to Tg, it is preferable to set temperature T of the optical film just before an optical film is clamped by the touch roll 6 so that Tg <T <Tg + 110 degreeC may be satisfy | filled.

  If the optical film temperature T is lower than Tg, the viscosity of the optical film is too high and the die line cannot be corrected.

  On the contrary, if the temperature T of the optical film is higher than Tg + 110 ° C., the surface of the optical film and the roll do not adhere uniformly, and the die line cannot be corrected. Tg + 10 ° C. <T <Tg + 90 ° C., more preferably Tg + 20 ° C. <T <Tg + 70 ° C.

  In order to set the temperature of the optical film when the touch roll 6 clamps the optical film to an appropriate range, the first cooling is performed from the position P1 at which the melt extruded from the casting die 4 contacts the first cooling roll 5. The length L of the nip between the roll 5 and the touch roll 6 along the rotation direction of the first cooling roll 5 may be adjusted.

  In the present invention, preferred materials for the first roll 5 and the second roll 6 include carbon steel, stainless steel, resin, and the like. The surface accuracy is preferably increased, and the surface roughness is set to 0.3 S or less, more preferably 0.01 S or less.

  In the present invention, it was discovered that the die line correction effect is more greatly manifested by reducing the pressure from the opening (lip) of the casting die 4 to the first roll 5 to 70 kPa or less. Preferably, the reduced pressure is 50 to 70 kPa.

  Although there is no restriction | limiting in particular as a method of keeping the pressure of the part from the opening part (lip | rip) of the casting die 4 to the 1st roll 5 below 70 kPa, Cover the roll periphery from the casting die 4 with a pressure | voltage resistant member, and reduce pressure. There are methods.

  At this time, the suction device is preferably subjected to a treatment such as heating with a heater so that the device itself does not become a place where the sublimate is attached. In the present invention, if the suction pressure is too small, the sublimate cannot be sucked effectively, so it is necessary to set the suction pressure to an appropriate value.

  In the present invention, a film-like cellulose ester resin in a molten state is transferred from the T die 4 to the first roll (first cooling roll) 5, the second cooling roll 7, and the third cooling roll 8 in order and conveyed. While being cooled and solidified, an unstretched optical film 10 is obtained.

  In the embodiment of the present invention shown in FIG. 1, the cooled and solidified unstretched optical film 10 peeled from the third cooling roll 8 by the peeling roll 9 passes through a dancer roll (film tension adjusting roll) 11 to a stretching machine 12. Then, the optical film 10 is stretched in the lateral direction (width direction).

  By this stretching, the molecules in the optical film are oriented.

  As a method for stretching the optical film in the width direction, a known tenter or the like can be preferably used.

  In particular, it is preferable to set the stretching direction to the width direction because lamination with a polarizing film can be performed in a roll form. By stretching in the width direction, the slow axis of the optical film made of the cellulose ester resin becomes the width direction.

  On the other hand, the transmission axis of the polarizing film is also usually in the width direction. By incorporating a polarizing plate in which the transmission axis of the polarizing film and the slow axis of the optical film are parallel to each other into the liquid crystal display device, the display contrast of the liquid crystal display device can be increased and a good viewing angle can be obtained. Is obtained.

  The glass transition temperature Tg of the optical film constituting material can be controlled by making the material type constituting the optical film and the ratio of the constituting material different. When producing a retardation optical film as the optical film, Tg is preferably 120 ° C. or higher, and more preferably 135 ° C. or higher.

  In the liquid crystal display device, in the image display state, the temperature environment of the optical film changes due to the temperature rise of the device itself, for example, the temperature rise derived from the light source.

  At this time, if the Tg of the optical film is lower than the use environment temperature of the optical film, the retardation value derived from the orientation state of the molecules fixed inside the optical film by stretching and the dimensional shape as the optical film are greatly changed. Become.

  If the Tg of the optical film is too high, when the optical film constituent material is made into an optical film, the temperature becomes high, so that the energy consumption for heating becomes high, and the material itself is decomposed when it is made into an optical film, resulting in coloring. Therefore, Tg is preferably 250 ° C. or lower.

  The stretching step may be performed by known heat setting conditions, cooling, and relaxation treatment, and may be appropriately adjusted so as to have the characteristics required for the target optical optical film.

  In order to provide the physical properties of the phase film and the function of the phase film for expanding the viewing angle of the liquid crystal display device, the stretching step and the heat setting treatment are appropriately selected and performed. When such a stretching step and heat setting treatment are included, the heating and pressurizing step is performed before the stretching step and heat setting treatment.

  When producing a retardation film as an optical film and further combining the functions of a polarizing plate protective film, it is necessary to control the refractive index. However, the refractive index can be controlled by a stretching operation. Is a preferred method. Hereinafter, the stretching method will be described.

  In the retardation film stretching process, it is required by stretching 1.0 to 2.0 times in one direction of the cellulose resin and 1.01 to 2.5 times in the direction perpendicular to the optical film plane. Retardation Ro and Rt can be controlled.

  Here, Ro indicates in-plane retardation, the difference between the refractive index in the longitudinal direction MD in the plane and the refractive index in the width direction TD is multiplied by the thickness, and Rt indicates the thickness direction retardation. The difference between the refractive index (average of the longitudinal direction MD and the width direction TD) and the refractive index in the thickness direction is multiplied by the thickness.

  Stretching can be performed, for example, sequentially or simultaneously in the longitudinal direction of the optical film and the direction orthogonal to the longitudinal direction of the optical film, that is, the width direction. At this time, if the stretching ratio in at least one direction is too small, a sufficient phase difference cannot be obtained, and if it is too large, stretching becomes difficult and film breakage may occur.

  Stretching in biaxial directions perpendicular to each other is an effective method for putting the refractive indexes nx, ny, and nz of the optical film within a predetermined range. Here, nx is the refractive index in the longitudinal MD direction, ny is the refractive index in the width TD direction, and nz is the refractive index in the thickness direction.

  For example, when stretching in the melt casting direction, if the shrinkage in the width direction is too large, the value of nz becomes too large. In this case, it can be improved by suppressing the width shrinkage of the optical film or stretching in the width direction. When stretching in the width direction, the refractive index may be distributed in the width direction.

  This distribution may appear when the tenter method is used. By stretching the optical film in the width direction, a contraction force is generated at the center of the optical film, and the phenomenon is caused by the end being fixed. The so-called Boeing phenomenon is considered. Even in this case, by stretching in the casting direction, the bowing phenomenon can be suppressed and the distribution of the phase difference in the width direction can be reduced.

  By stretching in the biaxial directions perpendicular to each other, the film thickness variation of the obtained optical film can be reduced.

  When the film thickness variation of the retardation film is too large, the retardation becomes uneven, and unevenness such as coloring may be a problem when used in a liquid crystal display.

  The film thickness variation of the optical film is preferably in the range of ± 3%, and more preferably ± 1%.

  For the purposes as described above, the method of stretching in the biaxial directions perpendicular to each other is effective, and the stretching ratio in the biaxial directions perpendicular to each other is finally 1.0 to 2.0 times in the casting direction. The width direction is preferably 1.01 to 2.5 times, the casting direction is 1.01 to 1.5 times, and the width direction is 1.05 to 2.0 times. It is more preferable to obtain the required retardation value.

  When the absorption axis of the polarizer exists in the longitudinal direction, the transmission axis of the polarizer coincides with the width direction. In order to obtain a long polarizing plate, the retardation film is preferably stretched so as to obtain a slow axis in the width direction.

  When cellulose ester that obtains positive birefringence with respect to stress is used, the slow axis of the retardation film can be provided in the width direction by stretching in the width direction from the above configuration.

In this case, in order to improve the display quality, the slow axis of the retardation film is preferably in the width direction, and in order to obtain the desired retardation value,
Formula (stretch ratio in the width direction)> (stretch ratio in the casting direction)
It is necessary to satisfy the following conditions.

  After stretching, the end of the optical film is slit to a product width by the slitter 13 and cut off, and then the knurling (embossing) is performed on the both ends of the optical film by the knurling device including the embossing ring 14 and the back roll 15. Application and winding by the winder 16 prevents sticking in the optical film (original winding) F and generation of scratches.

  The knurling method can process a metal ring having an uneven pattern on its side surface by heating or pressing. In addition, since the grip part of the clip of the optical film both ends is deform | transforming normally and cannot be used as an optical film product, it is cut out and reused as a raw material.

  Next, the winding process of the optical film is performed by keeping the shortest distance between the outer peripheral surface of the cylindrically wound optical film and the outer peripheral surface of the mobile transport roll immediately before the optical film as a winding roll. It is to be wound up. In addition, a means such as a static elimination blower for removing or reducing the surface potential of the optical film is provided in front of the winding roll.

  The winder related to the production of the optical film of the present invention may be generally used, and it may be a winding method such as a constant tension method, a constant torque method, a taper tension method, or a program tension control method with a constant internal stress. Can be wound up. In addition, it is preferable that the initial winding tension at the time of winding of a polarizing plate protective film is 90.2-300.8 N / m.

  In the winding process of the optical film in the method of the present invention, it is preferable that the optical film is wound under the environmental conditions of a temperature of 20 to 30 ° C. and a humidity of 20 to 60% RH in terms of achieving the effect of the present invention.

  Thus, the tolerance of the humidity change of the thickness direction retardation (Rt) improves by prescribing | regulating the temperature and humidity in the winding process of an optical film.

  If the temperature in the winding process of the optical film is within the above temperature range, wrinkles are not generated in the winding process, which is preferable in terms of improving the quality of the optical film.

  Moreover, if the humidity in the winding process of the optical film is in the above range, it is difficult to be charged, and it is preferable because it is possible to improve the winding quality, sticking failure, and transportable winding quality of the optical film.

  When winding the polarizing plate protective film in a roll shape, the winding core may be any material as long as it is a cylindrical core, but is preferably a hollow plastic core, as a plastic material May be any heat-resistant plastic that can withstand the heat treatment temperature, and examples thereof include phenol resins, xylene resins, melamine resins, polyester resins, and epoxy resins.

  A thermosetting resin reinforced with a filler such as glass fiber is preferred. For example, a hollow plastic core: a wound core made of FRP and having an outer diameter of 6 inches (hereinafter, inch represents 2.54 cm) and an inner diameter of 5 inches is used.

  The number of turns to these winding cores is preferably 100 turns or more, more preferably 500 turns or more, the winding thickness is preferably 5 cm or more, and the width of the optical film substrate is 80 cm or more. It is preferable that it is 1 m or more.

<Optical film>
In the present invention, the optical film is a functional film used for various display devices such as liquid crystal displays, plasma displays, and organic EL displays. Films, brightness enhancement films, hard coat films, antiglare films, antistatic films, optical compensation films such as viewing angle expansion, and the like are included.

  Although the thickness of the film of the optical film of the present invention varies depending on the purpose of use, the finished optical film is preferably 10 to 500 μm. In particular, the lower limit is 20 μm or more, preferably 35 μm or more. The upper limit is 150 μm or less, preferably 120 μm or less. A particularly preferable range is 25 to 90 μm.

  When the retardation film is thick, the polarizing plate after polarizing plate processing becomes too thick, and is not suitable for the purpose of thin and light in liquid crystal displays used for notebook personal computers and mobile electronic devices. On the other hand, if the retardation film is thin, it is difficult to develop retardation as a retardation film, and in addition, the moisture permeability of the optical film is increased, and the ability to protect the polarizer from humidity is reduced.

  When the slow axis or the fast axis of the retardation film exists in the optical film plane and the angle formed with the film forming direction is θ1, θ1 is −1 to + 1 °, preferably −0.5 to +0.5. To be °.

  This θ1 can be defined as an orientation angle, and the measurement of θ1 can be performed using an automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments).

  When each θ1 satisfies the above relationship, it contributes to obtaining high luminance in a display image, suppressing or preventing light leakage, and contributing to faithful color reproduction in a color liquid crystal display device.

  When the retardation film is used for the multi-domain VA mode, the retardation film is arranged in the above region with the fast axis of the retardation film being θ1, which contributes to the improvement of display image quality. When the plate and the liquid crystal display device are in the MVA mode, for example, the configuration shown in FIG. 7 can be adopted.

  In FIG. 7, 21a and 21b are protective films, 22a and 22b are retardation films, 25a and 25b are polarizers, 23a and 23b are slow axis directions of the film, 24a and 24b are transmission axis directions of the polarizer, 26a, Reference numeral 26b denotes a polarizing plate, 27 denotes a liquid crystal cell, and 29 denotes a liquid crystal display device.

  The retardation Ro distribution in the in-plane direction of the optical film is preferably adjusted to 5% or less, more preferably 2% or less, and particularly preferably 1.5% or less.

  The retardation Rt distribution in the thickness direction of the optical film is preferably adjusted to 10% or less, more preferably 2% or less, and particularly preferably 1.5% or less.

  In the retardation film, it is preferable that the retardation value distribution fluctuation is small. When a polarizing plate including a retardation film is used in a liquid crystal display device, the retardation distribution fluctuation is preferably small from the viewpoint of preventing color unevenness and the like.

  The retardation film is adjusted so as to have a retardation value suitable for improving the display quality of the liquid crystal cell of VA mode or TN mode, and is preferably used in the MVA mode by dividing the retardation film into the above multi-domain as the VA mode. For this purpose, it is required to adjust the in-plane retardation Ro to a value greater than 30 nm and 95 nm or less, and the thickness direction retardation Rt to a value greater than 70 nm and 400 nm or less.

  The in-plane retardation Ro is observed from the normal direction of the display surface when the two polarizing plates are arranged in crossed Nicols and the liquid crystal cell is arranged between the polarizing plates, for example, in the configuration shown in FIG. When in a crossed Nicol state with respect to time, when observed obliquely from the normal line of the display surface, the polarizing plate deviates from the crossed Nicol state, and light leakage caused by this is mainly compensated.

  The retardation in the thickness direction mainly compensates for the birefringence of the liquid crystal cell similarly observed when viewed from an oblique direction when the liquid crystal cell is in the black display state in the TN mode or VA mode, particularly in the MVA mode. Contribute to.

  As shown in FIG. 7, in the liquid crystal display device, when two polarizing plates are arranged above and below the liquid crystal cell, 22a and 22b in the figure can select the distribution of the thickness direction retardation Rt. The total value of both of the above-mentioned ranges and the thickness direction retardation Rt is preferably larger than 140 nm and 500 nm or less.

  In this case, in-plane retardation Ro and thickness direction retardation Rt of 22a and 22b are preferably the same for improving productivity of an industrial polarizing plate. Particularly preferably, the in-plane retardation Ro is larger than 35 nm and not larger than 65 nm, and the thickness direction retardation Rt is larger than 90 nm and not larger than 180 nm, and is applied to the MVA mode liquid crystal cell in the configuration of FIG.

  In the liquid crystal display device, a TAC film having an in-plane retardation Ro = 0 to 4 nm and a thickness direction retardation Rt = 20 to 50 nm and a thickness of 35 to 85 μm as, for example, a commercially available polarizing plate protective film on one polarizing plate, for example, FIG. When used at the position 22b, the polarizing film disposed on the other polarizing plate, for example, the retardation film disposed on 22a in FIG. 7, has an in-plane retardation Ro of more than 30 nm and not more than 95 nm, and The thickness direction retardation Rt is larger than 140 nm and 400 nm or less. The display quality is improved and it is preferable from the viewpoint of production of optical films.

<Liquid crystal display device>
A polarizing plate including the polarizing plate protective film (also serving as a retardation film) of the present invention can exhibit high display quality as compared with a normal polarizing plate, and more preferably a multi-domain liquid crystal display device, more preferably The birefringence mode is suitable for use in a multi-domain liquid crystal display device.

  The polarizing plate of the present invention can be used for MVA (Multi-domain Vertical Alignment) mode, PVA (Patterned Vertical Alignment) mode, CPA (Continuous Pinweal Alignment) mode, OCB (Optical Compensation specific mode, etc.). It is not limited to the mode and the arrangement of the polarizing plates.

  Liquid crystal display devices are being applied as devices for colorization and moving image display, and the display quality is improved by the present invention, and the improvement of contrast and the resistance of polarizing plates improve the display of moving images that are less fatigued and faithful. It becomes possible.

  In a liquid crystal display device including at least a polarizing plate including a retardation film, one polarizing plate including the polarizing plate protective film of the present invention is disposed on the liquid crystal cell, or two are disposed on both sides of the liquid crystal cell. To do.

  At this time, it can contribute to the improvement of display quality by using the polarizing plate protective film side of the present invention contained in the polarizing plate so as to face the liquid crystal cell of the liquid crystal display device. In FIG. 7, the films 22a and 22b face the liquid crystal cell of the liquid crystal display device.

  In such a configuration, the polarizing plate protective film of the present invention can optically compensate the liquid crystal cell. When the polarizing plate of the present invention is used in a liquid crystal display device, at least one polarizing plate in the liquid crystal display device may be the polarizing plate of the present invention. By using the polarizing plate of the present invention, a liquid crystal display device with improved display quality and excellent viewing angle characteristics can be provided.

  In the polarizing plate of the present invention, a polarizing plate protective film of a cellulose derivative is used on the surface opposite to the polarizing plate protective film of the present invention as viewed from the polarizer, and a general-purpose TAC optical film or the like can be used.

  The polarizing plate protective film located on the side far from the liquid crystal cell can be provided with another functional layer in order to improve the quality of the display device.

  For example, an anti-glare, anti-glare, scratch resistance, dust adhesion prevention, and an optical film containing a known functional layer as a display as a constituent for improving brightness, or may be attached to the polarizing plate surface of the present invention. It is not limited to these.

  In general, a retardation film is required to obtain stable optical characteristics that the fluctuation of Ro or Rt is small as the retardation value. In particular, in a liquid crystal display device in a birefringence mode, these fluctuations may cause image unevenness.

  In the present invention, a polarizing plate protective film having an optical film is wound into a roll-like long shape and fed out from a wound state means that an optical film formed by a solution casting method or a melt casting method is wound around a core An optical film wound around the outer periphery of the wound core with a (cylindrical core) as an axis is rolled into a length of 10 m or longer to form a roll-shaped roll, and then fed out from the wound state for polarizing plate processing. It refers to a polarizing plate protective film having

  When an optical film wound up in a roll-like long shape and fed out from a wound state is used, the effect obtained by the present invention is great.

  Since the polarizing plate protective film produced in the present invention is mainly composed of cellulose ester, the alkali treatment step can be utilized by utilizing saponification inherent to cellulose ester. When the resin which comprises a polarizer is polyvinyl alcohol, this can be bonded with a polarizing plate protective film using the completely saponified polyvinyl alcohol aqueous solution similarly to the conventional polarizing plate protective film.

  For this reason, this invention is excellent in the point which can apply the conventional polarizing plate processing method, and is excellent especially in the point from which the roll polarizing plate which is elongate is obtained.

  The production effect obtained by the present invention becomes more remarkable particularly in a long roll of 100 m or more, and the longer the length is 1500 m, 2500 m, or 5000 m, the more the production effect of polarizing plate production is obtained.

  For example, in the production of a polarizing plate protective film, the roll length is 10 to 5000 m, preferably 50 to 4500 m in consideration of productivity and transportability. The width of the optical film at this time is the width of the polarizer or the production. A width suitable for the line can be selected.

  An optical film having a width of 0.5 to 4.0 m, preferably 0.6 to 3.0 m, may be wound into a roll and used for polarizing plate processing. After the film is manufactured and wound on a roll, the film may be cut to obtain a roll having a desired width, and such a roll may be used for polarizing plate processing.

  In the production of the polarizing plate protective film, functional layers such as an antistatic layer, a hard coat layer, a slippery layer, an adhesive layer, an antiglare layer, and a barrier layer may be coated before and / or after stretching. At this time, various surface treatments such as corona discharge treatment, plasma treatment, and chemical treatment can be performed as necessary.

  In the film forming process, the clip gripping portions at both ends of the cut optical film are pulverized or granulated as necessary, and then used as raw materials for the same type of optical film or different types of optical film. It may be reused as a raw material.

  An optical film having a laminated structure can be prepared by co-extrusion of a composition containing cellulose esters having different additive concentrations such as the plasticizer, the ultraviolet absorber, and the matting agent.

  For example, an optical film having a structure of skin layer / core layer / skin layer can be produced. For example, the matting agent can be contained in the skin layer in a large amount or only in the skin layer. The plasticizer and the ultraviolet absorber can be contained in the core layer more than the skin layer, and may be contained only in the core layer.

  In addition, the type of plasticizer and ultraviolet absorber can be changed between the core layer and the skin layer. For example, the skin layer contains a low-volatile plasticizer and / or an ultraviolet absorber, and the core layer has excellent plasticity. It is also possible to add a plasticizer or an ultraviolet absorber excellent in ultraviolet absorption.

  The glass transition temperature of the skin layer and the core layer may be different, and the glass transition temperature of the core layer is preferably lower than the glass transition temperature of the skin layer. At this time, the glass transition temperatures of both the skin and the core can be measured, and an average value calculated from these volume fractions can be defined as the glass transition temperature Tg and similarly handled. Also, the viscosity of the melt containing the cellulose ester during melt casting may be different between the skin layer and the core layer, and the viscosity of the skin layer> the viscosity of the core layer or the viscosity of the core layer ≧ the viscosity of the skin layer may be used.

  The dimensional stability of the optical film of the present invention is less than ± 2.0% when the dimensional stability at 80 ° C. and 90% RH is based on the dimensions of the optical film left at 23 ° C. and 55% RH for 24 hours. Preferably, it is less than 1.0%, More preferably, it is less than 0.5%.

  When using the optical film of the present invention as a retardation film for a polarizing plate protective film, if the retardation film itself has a variation beyond the above range, the retardation absolute value and the orientation angle as the polarizing plate are initially set. The shift may cause a decrease in display quality improvement capability or a deterioration in display quality.

  When using the optical film of this invention as a polarizing plate protective film, the preparation methods of a polarizing plate are not specifically limited, It can manufacture by a general method. The obtained cellulose ester film was treated with an alkali, and a polyvinyl alcohol film was immersed and drawn in an iodine solution. A polarizer film was attached to both sides of the polarizer using a completely saponified polyvinyl alcohol aqueous solution on both sides of the polarizer. The polarizing plate protective film of the present invention is directly bonded to the polarizer on at least one side.

  Instead of the alkali treatment, a polarizing plate may be processed by applying an easy adhesion process as described in JP-A-6-94915 and JP-A-6-118232.

  The polarizing plate is composed of a polarizer and a protective film for protecting both surfaces of the polarizer, and can further be constructed by laminating a protective film on one surface of the polarizing plate and a separate film on the opposite surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection.

  In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the contact bonding layer bonded to a liquid crystal board, and is used for the surface side which bonds a polarizing plate to a liquid crystal cell.

  The polarizer, which is the main component of the polarizing plate, is an element that passes only light having a plane of polarization in a certain direction, and a typical polarizer currently known is a polyvinyl alcohol polarizing film, There are a polyvinyl alcohol film dyed with iodine and a dichroic dye dyed.

  For the polarizer, a polyvinyl alcohol aqueous solution is formed into a film and dyed by uniaxial stretching or dyed or uniaxially stretched and then preferably subjected to a durability treatment with a boron compound. One side of the polarizing plate protective film of the present invention is bonded to the surface of the polarizer to form a polarizing plate.

  It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like. The film thickness of the polarizer is preferably 10 to 30 μm.

  Hereinafter, the embodiments of the present invention will be described specifically by way of examples, but the present invention is not limited thereto.

<Synthesis example>
Synthesis Example 1: Production of Compound 101 (Production Method A)
Dissolve 7.2 g (18 mmol) of 2,2′-methylenebis [6-tert-butyl-4-methylphenol] monoacrylate in 70 ml of dichloromethane. Then 2.17 ml (20 mmol) of benzylamine are slowly added dropwise to this solution at room temperature. The mixture is then further stirred at room temperature for 3 hours. The solvent is removed and the residue is chromatographed on silica gel (eluent: hexane) to give 6.63 g (66%) of compound 101 as a white powder. The melting point is 124-126 ° C.

  Compounds 102, 103, 104 are prepared according to the method described in this synthesis example.

Synthesis Example 2: Production of Compound 105 (Production Method A)
Round bottom with a magnetic stirrer and condenser, 16.57 g (42 mmol) of 2,2′-methylenebis [6-tert-butyl-4-methylphenol] monoacrylate and 2.17 ml (20 mmol) of benzylamine in 150 ml of dichloromethane The flask is charged under argon. The reaction mixture is refluxed overnight and then concentrated on a vacuum rotary evaporator.

  Chromatography on the residue silica gel (eluent: hexane → hexane / ethyl acetate 80: 1) gives 12.44 g (69%) of compound 105 as a white powder. The melting point is 70-76 ° C. Compounds 106-110 are prepared according to the method described in this synthesis example.

Synthesis Example 3: Production of Compound 111 (Production Method A)
4.6 g (8.3 mmol) of 2,2′-ethylidenebis [4,6-di-tert-amylphenol] monoacrylate and 1 g (4.16 mmol) of N, N′-dibenzylethylenediamine were added at 140 ° C. for 4 hours. Stir. The reaction mixture is cooled to room temperature and the crude product is chromatographed on silica gel (eluent: hexane) to give 5.15 g (93%) of compound 111 as an amorphous powder. The melting point is 129-134 ° C.

Synthesis Example 4: Production of Compound 112 (Production Method C)
a) Preparation of 2,4-di-tert-butyl-6- [1- (3,5-di-tert-butyl-2-hydroxyphenyl) ethyl] phenyl 3-chloropropionate 100 ml of xylene 2,2 21.9 g (50 mmol) of '-ethylidenebis [4,6-di-tert-butylphenol] and 48 ml (500 mmol) of 3-chloropropyl chloride are charged into a round bottom flask equipped with a magnetic stirrer, condenser and bubble counter.

  The mixture is refluxed for 15 hours (HCl evolution). Excess acid chloride and toluene are removed by distillation. Crystallization of the residue in acetonitrile yields 15.8 g (60%) of the desired monoester 112a. The melting point is 118 ° C to 121 ° C.

Elemental analysis: C% H% Cl%
Calculated values: 74.90, 9.33, 6.70
Actual value: 75.10, 9.29, 6.13
b) 1.63 g (18.7 mmol) of morpholine are added dropwise to a stirred solution of compound 112a4.5 g (8.5 mmol) in 30 ml of toluene at room temperature and under nitrogen. The reaction mixture is stirred at 70 ° C. for 1 hour, cooled to room temperature, filtered using Hyflo and concentrated by evaporation. Crystallization of the residue in hexane yields 3.9 g (80%) of compound 112 as a white powder. The melting point is 150-152 ° C.

Synthesis Example 5: Production of Compound 113 (Production Method A)
19.7 g (0.04 mol) of 2,2′-ethylidenebis [4,6-di-tert-butylphenol] monoacrylate (prepared sample described in EP-A-500323) and 6.72 g of octylamine (0. 052 mol) is heated to 115 ° C. The colorless solution thus obtained is stirred for 30 minutes at this temperature and then 50 ml of ethanol are added. When the batch is cooled to room temperature, the product crystallizes out. The crystallized product is isolated by filtration and dried under vacuum to give 21.9 g (88%) of compound 113 as a white powder. The melting point is 102-104 ° C. Compounds 114, 115 and 116 are prepared according to the methods described in this general synthesis example.

Synthesis Example 6 Production of Compound 117 (Production Method A)
6.41 g (13 mmol) of 2,2′-ethylidenebis [4,6-di-tert-butylphenol] monoacrylate, 2 g (14.3 mmol) of glycine ethyl ester and 50 ml of ethylene chloride were added to a thermometer, a stirrer, a reflux condenser. And a 200 ml sulfonation flask equipped with a dropping funnel under nitrogen. Then 2 ml of triethylamine (1.45 g, 14.3 mmol) are added dropwise.

  When the addition is complete, the mixture is heated to 50 ° C. and stirred at this temperature for 5 hours.

  The resulting suspension is diluted with 25 ml of hexane and the salts are removed by filtration.

  The solvent is removed on a vacuum rotary evaporator and the crude product is crystallized from hexane to give 3.7 g (48%) of compound 117 as a white powder. The melting point is 121-122 ° C.

Synthesis Example 7: Production of Compound 118 (Production Method A)
6.92 g (14 mmol) of 2,2′-ethylidenebis [4,6-di-tert-butylphenol] monoacrylate and 0.89 g (7.7 mmol) of 1,6-diaminohexane in 40 ml of ethyl acetate are refluxed for 30 minutes. To do. The solvent is then removed by evaporation. Crystallization of the residue from acetonitrile yields 5 g (65%) of compound 118 as a white powder. The melting point is 148 ° C.

Synthesis Example 8 Production of Compound 121 (Production Method B)
3- [2-Oxo-piperidino] propionic acid in 60 ml of dichloromethane (see Davo, GP; Gellman, SH; J. Am. Chem. Soc., 116 (3), 1054-62, 1994) A mixture of 2.05 g (12 mmol) of 2,2′-ethylidenebis [4,6-di-tert-butylphenol] 4.4 g (10 mmol) and 2.06 g (10 mmol) of dicyclohexylcarbodiimide and 50 mg of dimethylaminopyridine. Reflux for hours. Precipitated urea is removed by filtration and the solvent is removed.

  Crystallization of the residue from a 1: 1 mixture of hexane / ethyl acetate gives 2.6 g (44%) of compound 121 as a white powder. The melting point is 217-223 ° C.

Synthesis Example 9 Production of Compound 122 (Production Method A)
6.6 g (13 mmol) of 2,2′-ethylidenebis [4,6-di-tert-butylphenol] monoacrylate, 4 g (23.5 mmol) of O-benzylhydroxylamine hydrochloride and 38 ml (27 mmol) of triethylamine in 70 ml of dichloroethane. Reflux at 65 ° C. for 8 hours. The reaction mixture is diluted with about 10 ml of hexane, the salts are removed by filtration and the solvent is distilled off on a vacuum rotary evaporator. Crystallization of the residue from methanol gives 4.6 g (55%) of compound 122 as a white powder. The melting point is 123 ° C.

Synthesis Example 10: Production of Compound 201 (Production Method A)
4.65 g (33 mmol) of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine in 85 ml of tetrahydrofuran is charged to a 250 ml round bottom flask blanketed with nitrogen. The solution is cooled to 0 ° C. and 5.6 ml (9 mmol) of a 1.6 mol / L solution of butyllithium in hexane is slowly added dropwise.

  The resulting white suspension was stirred for 30 minutes and then a solution of 11.84 g (30 mmol) of 2,2′-ethylidenebis [4,6-di-tert-butylphenol] monoacrylate in 85 ml of tetrahydrofuran was slowly added. Add dropwise.

  The yellow solution is stirred for 3 hours at room temperature.

  The reaction mixture is then concentrated by evaporation and the residue is poured into an aqueous saturated solution of ammonium chloride. After repeated extraction with ethyl acetate, the organic phases are combined, dried using potassium carbonate and concentrated on a vacuum rotary evaporator.

Chromatography of the residue (SiO ₂ : hexane / ethyl acetate 9: 1 → 1: 1) gives 11.06 g (65%) of compound 201 as a white powder.

  The melting point is 104-105 ° C. Compounds 202 and 203 are prepared according to the general procedure described in this synthesis example.

Synthesis Example 11 Production of Compound 204 (Production Method B)
a) Preparation of 3-octyloxypropionic acid 21.7 ml (0.33 mmol) of acrylonitrile in a colorless solution of 39.1 g (0.3 mol) of octanol and benzyltrimethylammonium hydroxide (40% solution in water) at room temperature for 25 minutes And added dropwise over N ₂ (exothermic reaction: Ti 40 ° C.). When this addition is complete, the reaction mixture is stirred at room temperature for an additional 25 minutes.

  Excess acrylonitrile is removed by distillation (vacuum rotary evaporator).

  The resulting crude 3-octyloxypropionitrile (light yellow liquid: GC 97%) is dissolved in 150 ml concentrated hydrochloric acid and 150 ml acetic acid and the solution is heated at 85 ° C. for 3 hours.

The mixture is cooled and poured into 100 ml of water. After extraction with ethyl acetate, the organic phase is separated off, washed with an aqueous saturated solution of NaCl, dried over Na ₂ SO ₄ and concentrated on a vacuum rotary evaporator to give 60 g of 3-octyloxypropionic acid as a colorless liquid. (GC 85% → 85% yield).

Elemental analysis: C% H%
Calculated value: 65.31 10.96
Actual value: 64.94 11.09
b) 7.08 g (35 mmol) of 3-octyloxypropionic acid (see Synthesis Example 11a) in 50 ml of toluene is charged under argon to a 100 ml round bottom flask equipped with a magnetic stirrer and condenser.

To this solution is added 7.6 ml (18.5 g, 105 mmol) thionyl chloride. The mixture is slowly heated to 90 ° C. (generation of HCl and SO ₂ ) and stirred at this temperature for 2 hours. Stirring is continued for an additional 30 minutes while introducing a stream of argon.

  Excess thionyl chloride and toluene are removed by distillation under reduced pressure (20 mbar). The residue (7 g of 3-octyloxypropionyl chloride) is dissolved in 50 ml of toluene and 10.97 g (25 mmol) of 2,2'-ethylidenebis [4,6-di-tert-butylphenol] are added.

  Then 4.9 ml (35 mmol) of triethylamine are added dropwise at 10 ° C. to this solution. The reaction mixture is filtered through celite and the filtrate is concentrated on a vacuum rotary evaporator. When the residue is dissolved in about 30 ml of acrylonitrile, compound 204 crystallizes out. The product is collected by suction filtration and dried to give 14.05 g (90%) of compound 204 as a white powder. The melting point is 114 ° C. Compounds 205-214 are prepared according to the general procedure described in this synthesis example.

Synthesis Example 12 Production of Compound 204 (Production Method B)
6.6 g (15 mmol) of 2,2′-ethylidenebis [4,6-di-tert-butylphenol], 3.8 g (15 mmol) of 3-octyloxypropionic acid and 6 ml of heptane under N ₂ , thermometer, stirrer Load into a 100 ml sulfonated flask equipped with a reflux condenser and dropping funnel.

Next, 4.4 ml (31.5 mmol) of triethylamine is added dropwise to this suspension (the suspension enters the solution) and 0.96 ml (10.5 mmol) of phosphorus oxychloride is added dropwise (exothermic reaction). : Ti 60 ° C.) The suspension thus obtained is heated at 80 ° C. for 1 hour. After cooling to room temperature, 10 ml of water is added (salts dissolve). The organic phase is separated, washed with water, dried with Na ₂ SO ₄ and concentrated on a vacuum rotary evaporator. Crystallization of the residue (about 10 g) in 20 ml of acrylonitrile gives 6.8 g (73%) of compound 204 as a white powder. The melting point is 114-115 ° C.

Synthesis Example 13 Production of Compound 204 (Production Method B)
3-octyloxypropionic acid (GC83%) 12.18 g (0.05 mol), thionyl chloride 4.7 ml (0.065 mol) and benzyltriethylammonium chloride 0.11 g (0.5 mmol) were equipped with a magnetic stirrer and condenser. Into a 50 ml round bottom flask.

The colorless solution is stirred for 10 minutes at room temperature (generation of HCl + SO ₂ ; exothermic reaction: Ti 12 ° C.). The reaction mixture is then heated to 65 ° C. under a gentle stream of N ₂ and stirred at this temperature for 45 minutes. Excess thionyl chloride is removed by distillation (70-80 ° C./40 mbar; 30 minutes).

  The resulting colorless liquid (crude acid chloride) is added to 18 g (0.041 mol) of 2,2'-ethylidenebis [4,6-di-tert-butylphenol].

The mixture is heated to 140 ° C. (generation of HCl) and stirred at this temperature for 30 minutes. The stirring in a weak stream of N ₂ continued for 1 hour.

  The resulting brown liquid is cooled to about 100 ° C. and 70 ml of ethanol are added. The product crystallizes out when the batch is cooled in an ice bath. The crystallized product is isolated by filtration and dried under high vacuum to give 20 g (78%) of compound 204 as a white powder. The melting point is 115 ° C.

Synthesis Example 14 Production of Compound 215 (Production Method B)
a) Preparation of 3- (2-butoxyethoxy) propionic acid 2 ml (3.2 mmol, 10 mol%) of a 1.6N solution of butyllithium was added to 3.8 g (32 mmol) of 2-butoxyethanol in 2 ml of tetrahydrofuran under N ₂ . Add at 10 ° C. The solution is stirred at 10 ° C. for 5 minutes. Next, 2.5 ml (38 mmol) of acrylonitrile is added.

  The reaction mixture is heated to 55 ° C. and stirred at this temperature for 2.5 hours.

  Then a further 0.25 ml (3.8 mmol) of acrylonitrile is added and the mixture is stirred for another hour. The reaction mixture is cooled to room temperature and then poured into water.

  After acidification with 2 mol / L HCl (2 ml) and extraction with toluene, the organic phase is washed with an aqueous saturated solution of NaCl, dried over magnesium sulphate and concentrated on a vacuum rotary evaporator.

Crude 3- (2-butoxyethoxy) propionitrile (4.4 g) is dissolved in 15 ml of concentrated hydrochloric acid and the solution is heated to 80 ° C. for 2.5 hours. The resulting brown solution is cooled at room temperature, diluted with water and extracted once more with ethyl acetate. The organic phases are combined, washed with an aqueous saturated solution of NaCl, dried over MgSO ₄ , concentrated on a vacuum rotary evaporator and dried under high vacuum to give 3- (2-butoxyethoxy) propion as a light brown liquid. 3.2 g (53%) of acid are obtained.

1H-NMR (300 MHz; CDCl ₃ : δ (ppm) 0.91 (t, J = 7.3 Hz, 3H); 1.36 (sexualt, J = 7.6 Hz, 2H); 1.57 (quintet, J = 7.8 Hz, 2H); 2.65 (t, J = 6.3 Hz, 2H); 3.47 (t, J = 6.6 Hz, 2H); 3.56-3.65 (dxm, 4H) 3.77 (t, J = 6.3 Hz, 2H); 9.6 (s, wide, 1H)
b) A solution of 3.1 g (15 mmol) of dicyclohexylcarbodiimide in 10 ml of ethylene chloride was dissolved in 6.6 g (15 mmol) of 2,2′-ethylidenebis [4,6-di-tert-butylphenol], 3- (2 -Butoxyethoxy) -propionic acid is added to a solution of 3.76 g (18 mmol) and dimethylaminopyridine 0.1 g (0.8 mmol, 5 mol%) at room temperature under nitrogen.

  The reaction mixture is stirred at room temperature for 15 hours. Precipitated urea is removed by filtration and the solvent is removed by evaporation. Crystallization of the residue from acetonitrile gives 5 g (54%) of compound 215 as a white powder. The melting point is 88-91 ° C.

Synthesis Example 15: Production of Compound 216 (Production Method B)
a) 3- [3- (2-Carboxyethoxy) propoxy] propanoic acid in 100 ml of toluene (see RV Christian and RM Hixon JACS 70, 1333 (1948)) 10 .02 g (55 mmol) is charged to a 250 ml round bottom flask under nitrogen. To this suspension is added 13.2 mol (180 mmol) thionyl chloride, and the mixture is heated slowly (over 40 minutes) to 90 ° C. (generation of HCl + SO ₂ ) and stirred at this temperature for 1 hour.

  Stirring is continued for an additional 45 minutes at 90 ° C. while introducing a stream of argon. Distillation of excess thionyl chloride and toluene gives the crude bis-acid chloride that is used further directly.

  b) The bis-acid chloride described in Synthesis Example 15a (55 mmol) and 43.87 g (0.1 mol) of 2,2′-ethylidenebis [4,6-di-tert-butylphenol] in 100 ml of toluene under argon Add to a 350 ml sulfonation flask.

  The solution is cooled to 10 ° C. and 16.7 ml (120 mmol) of triethylamine are slowly added dropwise.

  When the addition is complete (after about 50 minutes), the mixture is heated to 70 ° C. and stirred further at this temperature overnight. The precipitated triethylamine hydrochloride is removed by filtration and the filtrate is concentrated by evaporation.

  Chromatography of the residue using silica gel (eluent: Hex / EE 40: 1) gives 21 g (40%) of compound 216 as an amorphous powder. The melting point is 94 ° C. Compounds 217 and 218 are prepared according to the general procedure described in this synthesis example.

Synthesis Example 16 Production of Compound 219 (Production Method B)
a) Preparation of 3- (2,4-di-tert-butylphenoxy) propionic acid 6.2 ml (94 mmol) of acrylonitrile, 9.7 g (47 mmol) of 2,4-di-tert-butylphenol and benzyltrimethylammonium hydroxide ( (40% solution in water) Add to 0.6 ml (1.5 mmol) solution at room temperature under nitrogen for 20 minutes.

  When the addition is complete, the reaction mixture is heated to 65 ° C. and stirred at this temperature for 2.5 hours. Subsequently, excess acrylonitrile is removed by distillation (vacuum rotary evaporator).

  Crude 3- (2,4-di-tert-butylphenoxy) propionitrile is dissolved in 40 ml concentrated hydrochloric acid and 40 ml acetic acid and the solution is heated to 100 ° C. for 10 hours. The mixture is cooled, poured into 60 ml of water and extracted with a 1: 1 mixture of hexane / ethyl acetate.

  The organic phase is separated, washed with an aqueous saturated solution of NaCl, dried using magnesium sulfate and concentrated on a vacuum rotary evaporator. Distillation of the residue (60 ° C./0.1 mbar) gives 10 g (77%) of the desired acid as a whitish beige powder. The melting point is 105-106 ° C.

1H-NMR (300 MHz; CDCl ₃ : δ = 0.89 (t, J = 6.2 Hz, 20H; —CH ₂ —COOH—), 4.27 (t, J = 6.2 Hz, 2H, A—O) —CH ₂ —)
b) 3- (2,4-di-tert-butylphenoxy) propionic acid 10 g (36 mmol), 2,2′-ethylidenebis [4,6-di-tert-butylphenol] 13.1 g (30 mmol), dimethylamino Charge 0.2 g (1.6 mmol, 5 mol%) pyridine and 180 ml dichloromethane to a round bottom flask equipped with a magnetic stirrer and condenser.

Then dicyclohexylcarbodiimide 6.2 g (30 mmol) solution at room temperature and under N ₂ in dichloroethane 20 ml, is added dropwise.

  The mixture is stirred at room temperature for 15 hours. The precipitated urea is removed by filtration and the solvent is removed by evaporation. Crystallization of the residue from hexane gives 10 g (48%) of compound 219 as a white powder. The melting point is 185 ° C.

  Compound 220 is prepared in the same manner as described in Synthesis Example 16b from commercially available 3-phenoxypropionic acid and 2,2'-ethylidenebis [4,6-di-tert-butylphenol].

Synthesis Example 17 Production of Compound 221 (Production Method B)
a) Preparation of 3-cyclohexylideneaminoxypropionic acid 32.8 g (0.29 mol) of cyclohexanone oxime, 26 g (0.26 mmol) of ethyl acrylate, 26 ml (0.052 mol) of 2 mol / L solution of KOH in ethanol and 150 ml of ethanol The mixture is stirred at 60 ° C. for 96 hours and then concentrated on a vacuum rotary evaporator. The residue (orange oil) is dissolved in 175 g (0.31 mol) of a 10% solution of KOH in ethanol and the solution is heated at 60 ° C. for 1 hour.

The solvent is distilled off and the solid residue is taken up in water. After acidifying with about 15 ml of concentrated hydrochloric acid and extraction with ethyl acetate, the organic phase is washed with water, dried over Na ₂ SO ₄ and concentrated on a vacuum rotary evaporator.

  Distillation of the residue gives 11.8 g (25%) of the desired acid as an orange liquid. The boiling point is 135 ° C./0.05 mbar. b) Starting from 8.03 g (39 mmol) of 3-cyclohexylideneaminoxypropionic acid and 15.34 g (35 mmol) of 2,2′-ethylidenebis [4,6-di-tert-butylphenol] to Synthesis Example 16b The described procedure is followed to obtain 15.3 g (72%) of compound 221 as a white powder. The melting point is 118 to 121 ° C. (methanol). Compounds 222-224 are produced in the same manner as described in Synthesis Example 13 (Production Method B). Compound 225 is produced in the same manner as described in Synthesis Example 14b (Production Method B).

Synthesis Example 18 Production of Compound 301 (Oxidation of Thioether Obtained by Process A)
a) 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylphenylmethyl) -4-methylphenyl 3- (octylthio) propionate in a 200 ml sulfonation flask, 2,2′-methylenebis 9.86 g (25 mmol) of [6-tert-butylphenol] monoacrylate and 4.02 g (27.5 mmol) of octanethiol are dissolved in 50 ml of toluene.

  Next, 0.75 ml (1.25 mmol) of a 1.7 mol / L solution of potassium tert-pentylate in toluene is added dropwise at room temperature. The reaction mixture is heated to about 55 ° C. and then stirred at this temperature for 1 hour. The mixture is cooled to room temperature and poured into dilute hydrochloric acid (0.1 mol / L).

  After repeated extraction with ethyl acetate, the organic phases are combined, dried using sodium sulfate, and concentrated on a vacuum rotary evaporator. Unreacted bisphenol is removed (bulb tube distillation at 200 ° C./10 mbar) to give 11.35 g (84%) of the desired compound as a pale yellow oil.

  b) In a 250 ml sulfonation flask, dissolve 10.82 g (20 mmol) of the compound of Synthesis Example 18a in 130 ml of dichloromethane under nitrogen. A solution of 6.59 g (21 mmol) of m-chloroperbenzoic acid in 70 ml of dichloromethane is then added dropwise to this solution at −15 ° C.

  The reaction mixture is stirred at −15 ° C. for 30 minutes and poured into an aqueous saturated solution of sodium bicarbonate. After repeated extraction with dichloromethane, the organic phases are combined, washed with water, dried with sodium sulfate and concentrated on a vacuum rotary evaporator. The residue is dried under high vacuum to give 11.13 g (100%) of compound 301 as a colorless highly viscous oil.

Synthesis Example 19 Production of Compound 302 (Oxidation of Thioether Obtained by Process A)
In a 250 ml sulfonation flask, 10.82 g (20 mmol) of the compound of Synthesis Example 18a is dissolved in 80 ml of dichloromethane under nitrogen. A solution of 13.82 g (42 mmol) of m-chloroperbenzoic acid in 120 ml of dichloromethane is added dropwise at −15 ° C. to this solution. The thick suspension is further stirred until warmed to room temperature and poured into an aqueous saturated solution of sodium bicarbonate.

  After repeated extraction with dichloromethane, the organic phases are combined, washed with water, dried using sodium sulfate, and concentrated on a vacuum rotary evaporator.

  Crystallization of the residue from isopropanol gives 8.05 g (70%) of compound 302 as a light beige powder. The melting point is 108-113 ° C.

Synthesis Example 20 Production of Compound 401 (Production Method A)
Of 12.2 g (0.025 mol) of 2,2′-ethylidenebis [4,6-di-tert-butylphenol] monoacrylate, 2.07 g (0.03 mol) of 1,2,4-triazole and a few drops of pyridine. The mixture is stirred at 150 ° C. for 3 hours.

  The reaction mixture is cooled to about 100 ° C., filtered after about 30 m of isopropanol and hot. Upon cooling to room temperature, compound 401 crystallizes out.

  The crystallized product is collected by suction filtration and dried to give 9.10 g (65%) of compound 401 as a white powder. The melting point is 160-162 ° C.

  Compound 402 is prepared in a manner similar to that described in Synthesis Example 20, except that the reaction is performed at 170 ° C. instead of 150 ° C.

Synthesis Example 21 Production of Compound 403 (Production Method B)
0.68 ml (1.15 g; 7.5 mmol) of phosphoryl chloride was added to 4.39 g (10 mmol) of 2,2′-ethylidenebis [4,6-di-tert-butylphenol] in 40 ml of tetrahydrofuran, 3-benzotriazole-1 -A colorless solution of 2.5 g (13 mmol) of yl-propionic acid (see Wiley et al; JASC 76, 4933 (1954)) and 2.02 g (20 mmol) of triethylamine at 50 ° C., N ₂ Add to the drop below. The reactant suspension is stirred at reflux for 5 hours.

  The reaction mixture is cooled to room temperature, the salts are removed by filtration and concentrated on a vacuum rotary evaporator. The residue is poured into water and extracted twice with ethyl acetate, then the organic phases are combined, washed with an aqueous saturated solution of NaCl, dried over sodium sulfate and concentrated on a vacuum rotary evaporator. Crystallization of the residue from ethanol gives 3.9 g (80%) of compound 403 as a white powder. The melting point is 174-178 ° C.

Synthesis Example 22 Production of Compound 404 (Production Method A)
Number of 2,2′-ethylidenebis [4,6-di-tert-butylphenol] monoacrylate in 14.25 g (0.03 mol), 2-mercaptobenzothiazole 5.02 g (0.03 mol) and pyridine in 25 ml of dichloromethane The drop mixture is stirred at reflux for 15 hours. The reaction mixture is concentrated on a rotary evaporator.

Purification by chromatography (SiO ₂ ; hexane / ethyl acetate: 40: 1) and crystallization from acetonitrile gives 7.65 g (39%) of compound 404 as a white powder. The melting point is 123-128 ° C.

Synthesis Example 22a: Preparation of Compound 405 14.78 g (0.03 mol) of 2,2′-ethylidenebis [4,6-di-tert-butylphenol] monoacrylate in 25 ml of dichloromethane, 5.02 g of 2-mercaptobenzothiazole ( 0.03 mol) and a few drops of pyridine are stirred at 90 ° C. under reflux for 15 hours. The reaction mixture is concentrated on a rotary evaporator.

Chromatography (SiO ₂ ; hexane / ethyl acetate: 40: 1) gives 7.7 g (39%) of compound 405 as an amorphous powder. After crystallization from acetonitrile, the melting point is 123-128 ° C.

Example 1
[Production of Optical Film 1 Containing Cellulose Ester]
As described below, an optical film 1 was produced by melt casting using a cellulose ester and various additives.

Cellulose ester C-1 (see later) 100 parts by mass TMPTB 10 parts by mass IRGANOX-1010 (manufactured by Ciba Specialty Chemicals) 0.5 parts by mass tetrakis (2,4-di-tert-butyl-5-methylphenyl) [1 , 1-biphenyl] -4,4'-diylbisphosphonite 0.25 parts by mass Exemplary compound 1 0.7 parts by mass Tinuvin 928 (manufactured by Ciba Specialty Chemicals) 1.8 parts by mass Cellulose ester C-1 at 70 ° C, After drying under reduced pressure for 3 hours and cooling to room temperature, the additives were mixed.

  The above mixture was melt-mixed at 230 ° C. using a twin-screw extruder and pelletized.

  Using this pellet, it is melted at 250 ° C. in a nitrogen atmosphere and extruded from the casting die 4 onto the first cooling roll 5, and an optical film is sandwiched between the first cooling roll 5 and the touch roll 6 to form it. did.

  Further, 200 V of silica particles (manufactured by Nippon Aerosil Co., Ltd.) was added as a slip agent from the hopper opening in the middle of the extruder 1 so as to be 0.5 parts by mass.

  The heat bolt was adjusted so that the gap width of the casting die 4 was 0.5 mm within 30 mm from the end in the width direction of the optical film and 1 mm at other locations.

  The touch roll A was used as the touch roll, and 80 ° C. water was poured as cooling water therein.

  From the position P1 at which the resin extruded from the casting die 4 contacts the first cooling roll 5 to the position P2 at the upstream end in the rotation direction of the first cooling roll 5 in the nip between the first cooling roll 5 and the touch roll 6. 1 The length L along the peripheral surface of the cooling roller 5 was set to 20 mm.

  Thereafter, the touch roll 6 was separated from the first cooling roll 5, and the temperature T of the melted part immediately before being sandwiched between the first cooling roll 5 and the touch roll 6 was measured.

  In the present embodiment, the temperature T of the melted portion immediately before being squeezed by the nip between the first cooling roll 5 and the touch roll 6 is a position 1 mm upstream from the nip upstream end P2, and a thermometer (an independent meter). It was measured by HA-200E manufactured by Co., Ltd.

  As a result of the measurement in this example, the temperature T was 141 ° C. The linear pressure of the touch roll 6 against the first cooling roll 5 was 14.7 N / cm.

  Furthermore, after being introduced into a tenter and stretched 1.3 times at 160 ° C in the width direction, it was cooled to 30 ° C while relaxing 3% in the width direction, then released from the clip, the clip gripping part was cut off, and the optical film Both ends were knurled with a width of 10 mm and a height of 5 μm, and wound on a core with a winding tension of 220 N / m and a taper of 40%.

  In addition, the extrusion amount and the take-up speed were adjusted so that the optical film had a thickness of 80 μm, and the finished optical film was slit and wound so that the width of the finished optical film was 1430 mm. The winding core had an inner diameter of 152 mm, an outer diameter of 165 to 180 mm, and a length of 1550 mm. A prepreg resin obtained by impregnating glass fibers and carbon fibers with an epoxy resin was used as the core material for the core.

  The surface of the core was coated with an epoxy conductive resin, the surface was polished, and the surface roughness Ra was finished to 0.3 μm. The winding length was 2500 m. This optical film original fabric sample of the present invention is referred to as an optical film 1.

[Preparation of optical films 2 to 25]
Optical films 2 to 25 were prepared in the same manner as in the production of the optical film 1 except that the type of cellulose ester or the additive replacing the exemplified compound 1 was changed as shown in Table 1. In addition, the addition amount of the cellulose ester substituted for the used cellulose ester C-1 is the same mass part as the cellulose ester C-1, and the addition amount of the additive substituted for the used exemplary compound 1 is the same as that of the exemplary compound 1. It was set as the mass part.

C-1: Cellulose acetate propionate (acetyl group substitution degree 1.4, propionyl group substitution degree 1.3, molecular weight Mn = 86,000, Mw / Mn = 2.5)
C-2: Cellulose acetate propionate (acetyl group substitution degree 1.3, propionyl group substitution degree 1.2, molecular weight Mn = 66,000, Mw / Mn = 3.0)
C-3: Cellulose acetate propionate (acetyl group substitution degree 1.7, propionyl group substitution degree 1.0, molecular weight Mn = 73,000, Mw / Mn = 2.9)
C-4: Cellulose acetate propionate (acetyl group substitution degree 2.0, propionyl group substitution degree 0.7, molecular weight Mn = 91,000, Mw / Mn = 2.4)
[Evaluation of optical film]
The obtained optical film was evaluated by the following method. The evaluation results are shown in Table 1.

(Horse spine failure, core transfer)
The wound optical film was wrapped twice with a polyethylene sheet, and stored for 30 days under conditions of 25 ° C. and 50% by the storage method shown in FIG. Then, it was taken out of the box, the polyethylene sheet was opened, the fluorescent lamp tube lit on the optical film surface was reflected and reflected, the distortion or fine disturbance was observed, and the horse back failure was ranked to the following level.

A: Fluorescent lamps appear straight B: Fluorescent lamps appear to be bent partially C: Fluorescent lamps appear to be mottled In addition, the optical film after storage is rewound to form a spot-like deformation or width of 50 μm or more It was measured how many meters the core transfer, in which the band-like deformation in the hand direction was clearly visible, occurred from the core portion, and was ranked according to the following levels.

A: Less than 15 m from the core part B: Less than 15 to 30 m from the core part C: Less than 30 to 50 m from the core part D: 50 m or more from the core part (winding wrinkle)
When the original optical film was wound around the winding core, and wrinkles occurred at the beginning of the winding, the original optical optical film was removed from the winding core, and the winding operation was performed again. The number of defects at this time was counted. This operation was repeated 10 times, the average value was obtained, and the ranking was performed to the following levels.

A: 0 times or more and less than 1 time B: 1 time or more and less than 3 times C: 3 times or more and less than 5 times D: 5 times or more

  From Table 1, optical film No. containing the compound represented by General formula (1) based on this invention. It can be seen that Nos. 1 to 19 are optical films that are less susceptible to horse back failure and core transfer even when stored for a long period of time, and are less prone to deformation failures of the original optical film such as wrinkles at the beginning of winding. That is, it has been found that even when the optical film is wide and the winding length is long, the failure can be reduced and the productivity can be greatly improved.

Example 2
The following composition was prepared:

(Antistatic layer coating composition (1))
Polymethyl methacrylate (weight average molecular weight 550,000, Tg: 90 ° C.) 0.5 part Propylene glycol monomethyl ether 60 parts Methyl ethyl ketone 16 parts Ethyl lactate 5 parts Methanol 8 parts Conductive polymer resin P-1 (0.1-0. 3 μm particles) 0.5 parts

(Hardcoat layer coating composition (2))
Dipentaerythritol hexaacrylate monomer 60 parts Dipentaerythritol hexaacrylate dimer 20 parts Dipentaerythritol hexaacrylate trimer or higher component 20 parts Diethoxybenzophenone photoinitiator 6 parts Silicone surfactant 1 part Propylene Glycol monomethyl ether 75 parts Methyl ethyl ketone 75 parts (Anti-curl layer coating composition (3))
Acetone 35 parts Ethyl acetate 45 parts Isopropyl alcohol 5 parts Diacetyl cellulose 0.5 part Ultrafine silica 2% acetone dispersion (Aerosil: 200V, manufactured by Nippon Aerosil Co., Ltd.) 0.1 part Functionalized polarizing plate protection according to the following A film was prepared.

(Polarizing plate protective film)
The optical film 1 of the present invention produced in Example 1 is double wrapped with a polyethylene sheet, and stored for 30 days under conditions of 25 ° C. and 50% RH by the storage method as shown in FIG. It was stored under the condition of% RH. Thereafter, the polyethylene sheet was removed, and the anti-curl layer coating composition (3) was gravure-coated to a wet film thickness of 13 μm on one side of the optical film unwound from each original fabric sample, and the drying temperature was 80 ±. Dry at 5 ° C. This is designated as Sample 1A.

  On the other side of the optical film, the antistatic layer coating composition (1) was coated at an optical film conveyance speed of 30 m / min so that the wet film thickness was 7 μm in an environment of 28 ° C. and 82% RH. The film was applied at 1 m and then dried in a drying section set at 80 ± 5 ° C. to provide a resin layer having a dry film thickness of about 0.2 μm to obtain an optical film with an antistatic layer. This is designated as Sample 1B.

Further, the hard coat layer coating composition (2) was applied on the antistatic layer so as to have a wet film thickness of 13 μm, dried at a drying temperature of 90 ° C., and then irradiated with ultraviolet rays at 150 mJ / m ² . The clear hard coat layer having a dry film thickness of 5 μm was provided. This is designated as Sample 1C.

  The obtained optical film samples 1A, 1B, and 1C of the present invention did not cause brushing, no cracks were observed after drying, and the coating property was good.

  It replaced with the optical film 1, and it applied by the same method except having changed into the optical films 2-19 of this invention. As a result, good applicability was confirmed in all cases.

  For comparison, the comparative optical film 20 was coated by the same method as described above.

  An anti-curl layer coating composition (3) coated sample 2016A, an antistatic layer coating composition (1) coated sample 2016B, and a hard coat layer coating composition ( The sample coated with 2) was designated as Sample 2016C.

  As a result, brushing occurred in sample 2016A when applied in a high humidity environment. Further, in sample 2016B, fine cracks after drying were sometimes observed, and in sample 2016C, fine cracks after drying were clearly recognized.

(Production and evaluation of polarizing plate)
A 120 μm-thick polyvinyl alcohol film was immersed in an aqueous solution containing 1 part by mass of iodine, 2 parts by mass of potassium iodide, and 4 parts by mass of boric acid, and stretched 4 times at 50 ° C. to produce a polarizer.

  The optical films 1 to 19 of the present invention produced in Example 1 and the comparative optical film 20 are double-wrapped with a polyethylene sheet, and stored for 30 days under conditions of 25 ° C. and 50% RH by the storage method as shown in FIG. Thereafter, it was stored under conditions of 40 ° C. and 80% RH. Thereafter, each polyethylene sheet was removed, and the optical film unwound from each original fabric sample was alkali-treated with a 2.5 mol / L sodium hydroxide aqueous solution at 40 ° C. for 60 seconds, and further washed with water and dried to alkali-treat the surface. .

  On both sides of the polarizer, the optically treated surfaces of the optical films 1 to 19 of the present invention and 20 of the comparative optical film were bonded from both sides using a completely saponified polyvinyl alcohol 5% aqueous solution as an adhesive, The formed polarizing plates 1 to 19 of the present invention and comparative polarizing plate 20 were produced.

  Since the obtained polarizing plates 1 to 19 of the present invention are both protected by a protective film that is flat and physically superior to the comparative polarizing plate 20, very good polarizing plate characteristics It has a remarkably excellent effect of having

(Characteristic evaluation as a liquid crystal display device)
The polarizing plate of 15-type TFT color liquid crystal display LA-1529HM (manufactured by NEC) was peeled off, and each of the polarizing plates prepared above was cut according to the size of the liquid crystal cell. A polarizing plate of an optical film was prepared by adhering the two polarizing plates produced so as to sandwich the liquid crystal cell so that the polarizing axes of the polarizing plates were not perpendicular to each other so as to be orthogonal to each other. As a result, the polarizing plates 1 to 19 of the present invention showed a high contrast with the comparative polarizing plate 20 and exhibited excellent display properties. Thereby, it was confirmed that it is excellent as a polarizing plate for an image display device such as a liquid crystal display.

It is a general | schematic flow sheet which shows one embodiment of the apparatus which enforces the manufacturing method of the optical film which concerns on this invention. It is a principal part expansion flow sheet of the manufacturing apparatus of FIG. 3A is an external view of the main part of the casting die, and FIG. 3B is a cross-sectional view of the main part of the casting die. It is sectional drawing of 1st Embodiment of a pinching rotary body. It is sectional drawing in the plane perpendicular | vertical to the rotating shaft of 2nd Embodiment of a pinching rotary body. It is sectional drawing in the plane containing the rotating shaft of 2nd Embodiment of a pinching rotary body. It is a disassembled perspective view which shows the outline of the block diagram of a liquid crystal display device. It is a figure which shows the state of the optical film original fabric storage.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Extruder 2 Filter 3 Static mixer 4 Casting die 5 Rotating support body (1st cooling roll)
6 Nipping pressure rotating body (touch roll)
7 Rotating support (second cooling roll)
8 Rotating support (3rd cooling roll)
9, 11, 13, 14, 15 Transport roll 10 Optical film 16 Winding device 21a, 21b Protective film 22a, 22b Phase difference film 23a, 23b Film slow axis direction 24a, 24b Polarizer transmission axis direction 25a, 25b Polarizers 26a, 26b Polarizing plate 27 Liquid crystal cell 29 Liquid crystal display device 31 Die body 32 Slit 41 Metal sleeve 42 Elastic roller 43 Metal inner cylinder 44 Rubber 45 Cooling water 51 Outer cylinder 52 Inner cylinder 53 Space 54 Coolant 55a, 55b Rotating shaft 56a, 56b Outer cylinder support flange 60 Fluid shaft cylinder 61a, 61b Inner cylinder support flange 62a, 62b Intermediate passage 110 Winding core body 117 Support plate 118 Base 120 Optical film original

Claims (6)

An optical film having a cellulose ester, wherein the optical film contains a compound represented by the following general formula (I).

(Wherein R ₁ represents a substituent; R ₂ represents a hydrogen atom or a substituent; R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ₄ represents a hydrogen atom or 1 carbon atom) Represents an alkyl group of ˜8, R ₅ represents a hydrogen atom or a substituent, R ₆ represents a hydrogen atom or a substituent, R ₇ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₈ Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, n represents an integer of 1 to 4, and A represents a 1 to 4 valent group.) The optical film according to claim 1 is produced by a melt casting method using a melt containing at least one selected from a cellulose ester and a compound represented by the following general formula (I). Manufacturing method of optical film.

(Wherein R ₁ represents a substituent; R ₂ represents a hydrogen atom or a substituent; R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ₄ represents a hydrogen atom or 1 carbon atom) Represents an alkyl group of ˜8, R ₅ represents a hydrogen atom or a substituent, R ₆ represents a hydrogen atom or a substituent, R ₇ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₈ Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, n represents an integer of 1 to 4, and A represents a 1 to 4 valent group.) A polarizing plate comprising an optical film according to claim 1 or an optical film obtained by the method for producing an optical film according to claim 2 on at least one surface of a polarizer. A method for producing a polarizing plate, comprising: winding the polarizing plate according to claim 3 into a roll-like long shape, then drawing out from the wound state and bonding to a polarizer. A liquid crystal display device comprising the polarizing plate according to claim 3 on at least one surface of a liquid crystal cell. A liquid crystal display device comprising the polarizing plate obtained by the method for producing a polarizing plate according to claim 4 on at least one surface of a liquid crystal cell.

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