JP2007240570A - Optical film roll and method of manufacturing polarizing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical film roll which hardly damages film surface thereof, hardly causes deposition of foreign matter and, moreover, can prevent foreign matter from additionally being stuck in a process of manufacturing a polarizing plate by using the film, and to provide a method of manufacturing polarizing plate using the optical film roll. <P>SOLUTION: The optical film roll is obtained by laminating and winding an optical film made of norbornene type resin and polyester type film. The method of manufacturing polarizing plate comprises: a process of making the longitudinal direction of the optical film in the optical film roll and the longitudinal direction of a polarizer coincide and continuously attaching the optical film and the polarizer to each other; and a process of removing the polyester type film. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an optical film roll and a method for producing a polarizing plate using the same. Specifically, the present invention relates to an optical film roll that is a wound body of an optical film made of a norbornene-based resin, and a method for manufacturing a polarizing plate using the optical film roll.

A polarizing plate (polarizing film) used for a liquid crystal display or the like is usually formed from a substrate (optical film) excellent in transparency and a polarizing film (polarizer). Moreover, the said polarizing plate may be formed from the film (phase difference film) which extended | stretched the optical film and provided the function which gives a phase difference to transmitted light, and a polarizing film.
Conventionally, polycarbonate films, polyester films, acetate films, and the like have been used as optical films used as polarizing plate substrates or retardation films. However, a polarizing plate using a polycarbonate film or a polyester film has a large photoelastic coefficient, which may change the phase difference given to transmitted light due to a minute change in stress, and the acetate film has low heat resistance. Since the water absorption is high, there is a problem that a polarizing plate using the same is easily deformed depending on the use environment.

By the way, norbornene-based resins are attracting attention as materials for various optical components because they are excellent in transparency, heat resistance, chemical resistance, and the like. Patent Document 1 proposes a polarizing film in which a norbornene-based resin sheet is laminated on a polarizing film as a protective layer.
A film roll obtained by winding a resin film in a roll shape has a problem that the surface is easily damaged by contact between the films, and the transparency is lowered. In particular, norbornene-based resins tend to be scratched compared to other resins such as acrylic resins, and tend to be brittle compared to polycarbonate-based resins. is there. In order to prevent this, a knurling process for forming irregularities on the film edge to prevent contact between the films, a process for bonding a protective film to the film surface, and the like are used.
However, the knurling process physically imparts fine irregularities on the edge of the film, so film debris is likely to be generated, and it adheres to the surface of the film product and becomes a foreign substance. There is a problem that the product yield is reduced when manufacturing the polarizing plate or the like. In addition, for the process of attaching a protective film such as polyethylene, norbornene resin has poor adhesion to other resin materials, so that the protective film may peel off or the adhesive may remain on the film surface during long-term use. There is a problem that fish eyes (fine irregularities due to polyethylene gel) present in the protective film are transferred to the surface of the norbornene resin film.
In addition, the norbornene-based resin film surface may be subjected to corona treatment for the purpose of hydrophilization, but fine irregularities are generated on the film surface by this treatment, and the hydrophilization imparted when stored for a long time. In addition, there is a problem in that the treatment effect is lost and the film surface property is unfavorable.
JP-A-6-511117

  The present invention is an optical film roll capable of preventing foreign matter newly attached in the process of producing a polarizing plate using the film, in addition to being less likely to be scratched on the film surface, and having less attached foreign matter. It is an object of the present invention to provide a manufacturing method of a polarizing plate.

  The optical film roll of the present invention is obtained by superposing and winding an optical film made of a norbornene resin and a polyester film.

  The method for producing a polarizing plate of the present invention includes a step of aligning the longitudinal direction of the optical film in the optical film roll of the present invention and the longitudinal direction of the polarizer, and continuously pasting both, and a step of removing the polyester film It is characterized by including.

  According to the present invention, the film can be prevented from being scratched, and in addition to having less adhered foreign matter in the film roll state, foreign matter newly attached in the process of producing a polarizing plate using the film can be prevented. Can greatly improve the product yield.

Hereinafter, the present invention will be specifically described.
The optical film roll of the present invention is composed of an optical film made of a norbornene resin (hereinafter also simply referred to as “norbornene resin film”), a polyester film, and usually a film core.
<Norbornene resin film>
The norbornene-based resin constituting the norbornene-based resin film used in the present invention is a resin obtained by polymerizing a monomer component containing at least one norbornene-based compound and, if necessary, further hydrogenating.

<Monomer component>
As a norbornene-type compound used for the said monomer component, the norbornene-type compound represented by following General formula (1) can be mentioned, for example.

[In General Formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom which may have a linking group containing oxygen, nitrogen, sulfur or silicon. 1 to 15 hydrocarbon groups or other monovalent organic groups are represented. Here, R ₁ and R ₂ or R ₃ and R ₄ may be bonded to each other to form an alkylidene group, and R ¹ and R ² , R ³ and R ^4, or R ² and R ³ may be mutually connected. May form a carbocycle or a heterocycle (these carbocycles or heterocycles may have a monocyclic structure, or other rings may be condensed to form a polycyclic structure). The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring. X represents 0 or an integer of 1 to 3, and y represents 0 or 1. When x is 0, y is 0. ]

Specific examples of the norbornene-based compound represented by the general formula (1) include, for example, the compounds shown below, but are not limited to these examples.
Bicyclo [2.2.1] hept-2-ene (norbornene)
5-methyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept 2-ene-5-phenyl-bicyclo [2.2.1] hept-2-ene-5- (4-biphenyl) -bicyclo [2.2.1] hept-2-ene-5-methoxycarbonyl- Bicyclo [2.2.1] hept-2-ene · 5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene · 5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2 -Ene, 5-phenylcarbonyloxy-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl- 5-phenoxycarboni -Bicyclo [2.2.1] hept-2-ene.5-methyl-5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene.5-vinyl-bicyclo [2.2.1] ] Hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5,5-dimethyl-bicyclo [2.2.1] hept-2-ene, 5,6-dimethyl -Bicyclo [2.2.1] hept-2-ene, 5-fluoro-bicyclo [2.2.1] hept-2-ene, 5-chloro-bicyclo [2.2.1] hept-2-ene 5-bromo-bicyclo [2.2.1] hept-2-ene5,6-difluoro-bicyclo [2.2.1] hept-2-ene5,6-dichloro-bicyclo [2.2 .1] Hept-2-ene-5,6-dibromo-bicyclo [2.2.1 Hept-2-ene, 5-hydroxy-bicyclo [2.2.1] hept-2-ene, 5-hydroxyethyl-bicyclo [2.2.1] hept-2-ene, 5-cyano-bicyclo [2 2.1] hept-2-ene, 5-amino-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, tricyclo [ 4.4.0.1 ^2,5 ] Undec-3-ene.7-methyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene.7-ethyl-tricyclo [4.3. 0.1 ^2,5] dec-3-ene-7-cyclohexyl - tricyclo [4.3.0.1 ^2,5] dec-3-ene-7-phenyl - tricyclo [4.3.0.1 ^{2 , 5]} dec-3-ene-7- (4-biphenyl) - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene-7,8 Methyl - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene-7,8,9- trimethyl - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene-8- Methyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene · 8-phenyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene · 7-fluoro-tricyclo [ 4.3.0.1 ^2,5 ] dec-3-ene.7-chloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene.7-bromo-tricyclo [4.3. 0.1 ^2,5] dec-3-ene-7,8-dichloro - tricyclo [4.3.0.1 ^2,5] dec-3-ene-7,8,9- trichloro - tricyclo [4. 3.0.1 ^2,5 ] dec-3-ene · 7-chloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene · 7-dichloromethyl-tricycl B [4.3.0.1 ^2,5 ] dec-3-ene · 7-trichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene · 7-hydroxy-tricyclo [4 .3.0.1 ^2,5 ] dec-3-ene · 7-cyano-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene · 7-amino-tricyclo [4.3.0 .1 ^2,5] deca-3-ene-tetracyclo [4.4.0.1 ^2,5. 1 ^7,10 ] dodec-3-ene pentacyclo [7.4.0.1 ^2,5 . 1 ^8,11 . 0 ^7,12] pentadeca-3-ene-hexacyclo [8.4.0.1 ^2,5. 1 ^7,14 . 1 ^9,12 . 0 ^8,13] heptadec-3-en-8-methyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8-ethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8-cyclohexyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-phenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8- (4-biphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-methoxycarbonyloxy - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-phenoxyethyl carbonyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-phenylcarbonyloxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-ethylidene - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8,8-dimethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8,9-dimethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-fluoro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-chloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-bromo - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene.8,8-dichloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene.8,9-dichloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene. 8,8,9,9-tetrachloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-hydroxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-cyano - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-amino-tetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] dodec-3-ene These norbornene compounds may be used alone or in combination of two or more.

The kind and amount of the norbornene-based compound used in the present invention are appropriately selected depending on the properties required for the obtained resin.
Of these, when a compound having a structure containing at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom in the molecule (hereinafter referred to as “polar structure”) is used. It is preferable because of excellent adhesion and adhesion to other materials. In particular, in the general formula (1), R ¹ and R ³ are a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and any one of R ^{2 and} R ⁴ A compound in which one is a group having a polar structure and the other is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable because the water absorption (wet) property of the resin is low. Furthermore, a norbornene compound in which the group having a polar structure is a group represented by the following general formula (2) is easy to balance the heat resistance and water absorption (wet) property of the resulting resin and can be preferably used.

-(CH ₂ ) _z COOR (2)
(In General Formula (2), R represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and z represents 0 or an integer of 1 to 10).
In the general formula (2), the smaller the value of z, the higher the glass transition temperature of the resulting hydrogenated product and the better the heat resistance. Therefore, z is preferably an integer of 0 or 1 to 3, A compound in which z is 0 is preferable because it can be easily synthesized. Further, R in the general formula (2) tends to decrease the water absorption (wet) property of the hydrogenated polymer obtained as the number of carbon atoms increases, but also tends to decrease the glass transition temperature. From the viewpoint of maintaining heat resistance, a hydrocarbon group having 1 to 10 carbon atoms is preferable, and a hydrocarbon group having 1 to 6 carbon atoms is particularly preferable.

  In the general formula (1), when an alkyl group having 1 to 3 carbon atoms, particularly a methyl group, is bonded to the carbon atom to which the group represented by the general formula (2) is bonded, heat resistance and water absorption It is preferable in terms of (wet) balance. Further, in the general formula (1), a compound in which x is 0 or 1 and y is 0 has high reactivity, a polymer can be obtained in a high yield, and polymer hydrogen having high heat resistance. It is preferably used because an additive is obtained and it is industrially easily available.

More preferable examples of the norbornene resin used in the present invention include a copolymer of a norbornene compound having a polar structure and a norbornene compound not having a polar structure. Particularly preferred are norbornene compounds having a group represented by the general formula (2), and R ^{1 to} R ⁴ in the general formula (1) are hydrogen atoms or unsubstituted carbon atoms of 1 to 15 carbon atoms. Examples thereof include a copolymer with a norbornene compound which is a hydrocarbon group.

In obtaining the norbornene-based resin used in the present invention, a monomer copolymerizable with the norbornene-based compound can be included in the monomer component and polymerized within a range that does not impair the effects of the present invention.
Examples of these copolymerizable monomers include cyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene and cyclododecene, and non-conjugated cyclic polyenes such as 1,4-cyclooctadiene, dicyclopentadiene and cyclododecatriene. be able to.
These copolymerizable monomers may be used alone or in combination of two or more.
The ratio of the copolymerizable monomer is preferably 50% by weight or less, more preferably about 30% by weight or less in the total monomer components.

<Polymerization method>
The method for polymerizing the monomer component containing the norbornene compound is not particularly limited as long as the monomer component can be polymerized. For example, the polymerization may be performed by ring-opening polymerization or addition polymerization. it can.

(A) Ring-opening polymerization The polymer can be produced by ring-opening polymerization by a known ring-opening polymerization reaction for the norbornene-based compound, and the monomer component containing the norbornene-based compound is used as a polymerization catalyst and a polymerization reaction. It can be produced by ring-opening polymerization using a solvent and, if necessary, a molecular weight regulator.

(A) Polymerization catalyst In the present invention, when the polymerization of the monomer component is performed by a ring-opening (co) polymerization reaction, it is performed in the presence of a metathesis catalyst.

This metathesis catalyst is
(A) at least one compound selected from compounds having W, Mo and Re (hereinafter referred to as compound (A));
(B) Deming periodic table group IA elements (for example, Li, Na, K, etc.), group IIA elements (for example, Mg, Ca, etc.), group IIB elements (for example, Zn, Cd, Hg, etc.), group IIIA A compound having an element (for example, B, Al, etc.), a group IVA element (for example, Si, Sn, Pb, etc.), or a group IVB element (for example, Ti, Zr, etc.), and a bond between this element and carbon Alternatively, the catalyst is a combination of at least one compound selected from compounds having at least one bond between this element and hydrogen (hereinafter referred to as compound (B)). Moreover, in order to improve the activity of a catalyst, the below-mentioned additive (C) may further be added.

Compound (A) includes W, Mo or Re halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, and derivatives thereof. Or a combination thereof, W and Mo compounds, particularly their halides, oxyhalides and alkoxyhalides are preferred from the viewpoint of polymerization activity and practicality. Moreover, you may use the mixture of 2 or more types of compounds which produce | generate the said compound by reaction. Further, these compounds may be complexed with an appropriate complexing agent such as P (C ₆ H ₅ ) ₅ , C ₅ H ₅ N, and the like.

Specific examples of the compound (A) include WCl ₆ , WCl ₅ , WCl ₄ , WBr ₆ , WF ₆ , WI ₆ , MoCl ₅ , MoCl ₄ , MoCl ₃ , ReCl ₃ , WOCl ₄ , MoOCl ₃ , ReOCl ₃ , ReOBr ₃ , W (OC ₆ H ₅ ) ₆ , WCl ₂ (OC ₆ H ₅ ) ₄ , Mo (OC ₂ H ₅ ) ₂ Cl ₃ , Mo (OC ₂ H ₅ ) ₅ , MoO ₂ (acac) ₂ , W (OCOR) ₅ , W (OC ₂ H ₅ ) ₂ Cl ₃ , W (CO) ₆ , Mo (CO) ₆ , Re ₂ (CO) ₁₀ , ReOBr ₃・ P (C ₆ H ₅ ) ₃ , WCl _{5 · P (C 6 H 5)} 3, WCl 6 · C 5 H 5 N, such as _{W (CO) 5 · P (} C 6 H 5) 3, W (CO) 3 · (CH 3 CN) 3 and the like . Among the above compounds, particularly preferred compounds include MoCl ₅ , Mo (OC ₂ H ₅ ) ₂ Cl ₃ , WCl ₆ , W (OC ₂ H ₅ ) ₂ Cl _{3 and the} like. Here, “acac” is an abbreviation for acetylacetonate.

Specific examples of the compound _{(B), n-C 4 H 5 Li} , n-C 5 H 11 Na, C 5 H 5 Na, CH 3 MgI, C 2 H 5 MgBr, CH 3 MgBr, n- C ₃ H ₇ MgCl, (C ₆ H ₅ ) ₃ Al, t-C ₄ H ₉ MgCl, CH ₂ = CHCH ₂ MgCl, (C ₂ H ₅ ) ₂ Zn, (C ₂ H ₅ ) ₂ Cd, CaZn ( C ₂ H ₅ ) ₄ , (CH ₃ ) ₃ B, (C ₂ H ₅ ) ₃ B, (nC ₄ H ₉ ) ₃ B, (CH ₃ ) ₃ Al, (CH ₃ ) ₂ AlCl, (CH ₃ ) ₃ Al ₂ Cl ₃ , CH ₃ AlCl ₂ , (C ₂ H ₅ ) ₃ Al, LiAl (C ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₃ Al-O (C ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₂ AlCl, C ₂ H ₅ AlCl ₂ , (C ₂ H ₅ ) ₂ AlH, (iso-C ₄ H ₉ ) ₂ AlH, (C ₂ H ₅ ) ₂ AlOC ₂ H ₅ , (iso-C ₄ H ₉ ) ₃ Al, (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ , (CH ₃ ) ₄ Ga, (CH ₃ ) ₄ Sn, (n−C ₄ H ₉ ) ₄ Sn, (C ₂ H ₅ ) ₃ It includes _{SiH, (n-C 6 H} 13) 3 Al, (n-C 4 H 17) 3 Al, LiH, NaH, etc. _{B 2 H 6, NaBH 4,} AlH 3, LiAlH 4, BiH 4 and TiH ₄ is It is done. Moreover, the mixture of 2 or more types of compounds which produce | generate these compounds by reaction can also be used. Preferred examples of these include (CH ₃ ) ₃ Al, (CH ₃ ) ₂ AlCl, (CH ₃ ) ₃ Al ₂ Cl ₃ , CH ₃ AlCl ₂ , (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , C ₂ H ₅ AlCl ₂ , (C ₂ H ₅ ) ₂ AlH, (C ₂ H ₅ ) ₂ AlOC ₂ H ₅ , (C ₂ H ₅ ) ₂ AlCN, (C ₃ H ₇ ) ₃ Al, (iso-C ₄ H ₉ ) ₃ Al, (iso-C ₄ H ₉ ) ₂ AlH, (C ₆ H ₁₃ ) ₃ Al, (C ₈ H ₁₇ ) ₃ Al, (C ₆ H ₅ ) ₅ Al and the like can be mentioned.

As the additive (C) that can be used together with the compound (A) and the compound (B), alcohols, aldehydes, ketones, amines and the like can be suitably used. For example, the following (1) to (1) to (9) can be exemplified.
(1) Non-organometallic compounds of boron such as simple boron, BF ₃ , BCl ₃ , B (OnC ₄ H ₉ ) ₃ , (C ₂ H ₅ O ₃ ) ₂ , BF, B ₂ O ₃ , H ₃ BO ₃ Silicon non-organometallic compounds such as Si (OC ₂ H ₅ ) ₄ ;
(2) alcohols, hydroperoxides and peroxides;
(3) water;
(4) oxygen;
(5) Carbonyl compounds such as aldehydes and ketones and polymers thereof;
(6) cyclic ethers such as ethylene oxide, epichlorohydrin, oxetane;
(7) Amides such as N, N-diethylformamide and N, N-dimethylacetamide, amines such as aniline, morpholine and piperidine, and azo compounds such as azobenzene;
(8) N-nitroso compounds such as N-nitrosodimethylamine and N-nitrosodiphenylamine;
(9) Compounds containing an S-Cl or N-Cl group such as trichloromelamine, N-chlorosuccinimide, phenylsulfenyl chloride and the like.

  The use amount of the metathesis catalyst is such that the molar ratio of the compound (A) and all monomer components to be subjected to polymerization (compound: all monomer components) is usually 1: 500 to 1: 50,000, preferably Is preferably in an amount of 1: 1,000 to 1: 10,000.

The ratio of the compound (A) to the compound (B) (compound (A): compound (B)) is 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atom ratio.
The ratio of the compound (A) to the compound (C) (compound (C): compound (A)) is 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1 in molar ratio. desirable.

(B) Polymerization solvent As the solvent used in the ring-opening polymerization reaction, the monomer component or catalyst used for the polymerization is dissolved and the catalyst is not deactivated. Is not particularly limited, for example, alkanes such as pentane, hexane, heptane, octane, nonane, decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; benzene, toluene , Xylene, ethylbenzene, cumene and other aromatic hydrocarbons; halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chloroform, tetrachloroethylene; halogenated aryl compounds such as chlorobenzene; ethyl acetate, n-acetate -Butyl, Examples thereof include saturated carboxylic acid esters such as iso-butyl acetate, methyl propionate and dimethoxyethane; ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane. These can be used alone or in admixture of two or more. Such a solvent is used as a solvent for dissolving the solvent constituting the molecular weight regulator solution, the norbornene-based compound, the copolymerizable monomer and / or the metathesis catalyst.
The amount of the solvent used is such that the weight ratio of the solvent to the monomer component used for polymerization (solvent: monomer component) is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. The amount is desirable.

(C) Molecular weight regulator The molecular weight of the resulting ring-opening polymer can be controlled by the polymerization temperature, the type of catalyst, and the type of solvent, but it is also controlled by allowing the molecular weight regulator to coexist in the reaction system. be able to.
Suitable molecular weight regulators include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and styrene, 4 -Methylstyrene, 2-methylstyrene, 4-ethylstyrene can be mentioned, and among these, 1-butene and 1-hexene are particularly preferable. These molecular weight regulators can be used alone or in admixture of two or more.
The usage-amount of a molecular weight regulator is 0.005-0.6 mol normally with respect to 1 mol of monomer components with which it uses for ring-opening polymerization reaction, Preferably it is 0.01-0.5 mol.

(D) Other polymerization conditions The ring-opening polymer can be obtained by ring-opening polymerization of the norbornene compound alone or a monomer copolymerizable with the norbornene compound. Conjugated diene compounds such as isoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, polynorbornene, and the like, such as unsaturated hydrocarbon polymers containing two or more carbon-carbon double bonds in the main chain In the presence, a monomer component containing a norbornene compound may be subjected to ring-opening polymerization.

(B) Addition polymerization The production of a polymer by addition (co) polymerization can be performed by a known addition polymerization reaction for a norbornene compound, and a monomer component containing the norbornene compound can be used as a polymerization catalyst, if necessary. Thus, it can be produced by addition polymerization using a solvent for polymerization reaction and, if necessary, a molecular weight regulator.

(A) Polymerization catalyst Examples of the polymerization catalyst for addition polymerization include single catalysts and multicomponent catalysts such as palladium, nickel, cobalt, titanium, and zirconium listed in (a-1) to (a-3) below. However, the polymerization catalyst used in the present invention is not limited thereto.

(A-1) Single catalyst system [Pd (CH ₃ CN) ₄ ] [BF ₄ ] ₂ , [Pd (PhCN) ₄ ] [SbF ₆ ]
[(Η ³ -crotyl) Pd (cycloocta-1,5-diene)] [PF ₆ ],
[(Η ³ -crotyl) Ni (cycloclota-1,5-diene)] [B (3,5- (CF ₃ ) ₂ C ₆ F ₃ ) ₄ ],
[(Η ³ -crotyl) Ni (cycloocta-1,5-diene)] [PF ₆ ],
[(Η ³ -allyl) Ni (cycloclota-1,5-diene)] [B (C ₆ F ₅ ) ₄ ],
[(Η ³ -crotyl) Ni (cycloocta-1,5-diene)] [SbF ₆ ],
Toluene · Ni (C ₆ F ₅ ) ₂ , Benzene · Ni (C ₆ F ₅ ) ₂ , Mesilene · Ni (C ₆ F ₅ ) ₂ , Ethylether · Ni (C ₆ F ₅ ) ₂
Etc.

(A-2) Multi-component catalyst system (1)
A combination of a palladium complex having a σ or σ, π bond and an organoaluminum or super strong acid salt.
Di-μ-chloro-bis (6-methoxybicyclo [2.2.1] hept-2-ene-endo-5σ, 2π) Pd, methylalumoxane (abbreviated as MAO), AgSbF6 or AgBF4 Combinations with different compounds,
A combination of [(η ³ -aryl) PdCl] ₂ and AgSbF ₆ or AgBF ₄ ;
A combination of [(cycloocta-1,5-diene) Pd (CH ₃ ) Cl], PPh ₃ and NaB [3,5- (CF ₃ ) ₂ C ₆ H ₃ ] ₄ may be mentioned.

(A-3) Multi-component catalyst system (2)
(I) transition metal compounds selected from nickel compounds, cobalt compounds, titanium compounds or zirconium compounds,
(II) a compound selected from super strong acids, Lewis acids and ionic boron compounds,
(III) A combination comprising three components of an organoaluminum compound.

(I) Examples of transition metal compounds (I-1) Examples of nickel compounds and cobalt compounds:
Compounds selected from nickel or cobalt organic carboxylates, organic phosphites, organic phosphates, organic sulfonates, β-diketone compounds,
For example, nickel 2-ethylhexanoate, nickel naphthenate, cobalt naphthenate, nickel oleate, nickel dodecanoate, cobalt dodecanoate, cobalt neodecanoate, nickel dibutyl phosphite, nickel dibutyl phosphate, nickel dioctyl phosphate, phosphoric acid Examples thereof include nickel salts of dibutyl ester, nickel dodecylbenzenesulfonate, nickel p-toluenesulfonate, nickel bis (acetylacetonate), and bis (ethylacetoacetate) nickel.

A compound obtained by modifying the organic carboxylate of nickel with a super strong acid such as hexafluoroantimonic acid, tetrafluoroboric acid, trifluoroacetic acid, hexafluoroacetone,
Nickel diene or triene coordination complexes,
For example, dichloro (1,5-cyclooctadiene) nickel, [(η ³ -crotyl) (1,5-cyclooctadiene) nickel] hexafluorophosphate, and its tetrafluoroborate, tetrakis [3,5-bis ( (Trifluoromethyl)] borate complex, nickel complex such as (1,5,9-cyclododecatriene) nickel, bis (norbornadiene) nickel, bis (1,5-cyclooctadiene) nickel,
A complex in which a ligand having atoms such as P, N, and O is coordinated to nickel.

For example, bis (triphenylphosphine) nickel dichloride, bis (triphenylphosphine) nickel dibromide, bis (triphenylphosphine) cobalt dibromide, bis [tri (2-methylphenyl) phosphine] nickel dichloride, bis [tri (4 - methylphenyl) phosphine] nickel dichloride, bis [N- (3-t- butylsalicylidene) phenyl aminate] nickel, Ni [PhC (O) CH] (Ph), Ni (OC ( C 6 H 4) PPh) (H) (PCy ₃ ), Ni [OC (O) (C ₆ H ₄ ) P] (H) (PPh ₃ ), bis (1,5-cyclooctadiene) nickel and PhC (O) CH═ a reaction product of PPh _{3, [2,6- (i-Pr) 2 C} 6 H 3 N = CHC 6 H 3 (O) (Anth) ] (Ph) (PP ₃₎ nickel complex such as Ni (here, Anth is 9-anthracenyl, Ph is Phenyl, Cy is an abbreviation for cyclohexyl.),
Is mentioned.

(I-2) Examples of titanium and zirconium compounds:
[T-BuNSiMe (Me ₄ Cp)] TiCl ₂ , (Me ₄ Cp) (O—iPr ₂ C ₆ H ₃ ) ₂ TiCl, (Me ₄ Cp) TiCl ₃ , (Me ₄ Cp) Ti (OBu) ₃ , [T-BuNSiMe ₂ Flu] TiMe ₂ , [t-BuNSiMe ₂ Flu] TiCl ₂ , Et (Ind) ₂ ZrCl ₂ , Ph ₂ C (Ind) (Cp) ZrCl ₂ , iPr (Cp) (Flu) ZrCl ₂ iPr (3-tert-But-Cp) (Ind) ZrCl ₂ , iPr (Cp) (Ind) ZrCl ₂ , Me ₂ Si (Ind) ₂ ZrCl ₂ , Cp ₂ ZrCl ₂ , (Cp is Cyclopentadienl, Ind is Indenyl, (Flu is an abbreviation for Fluorenyl, Me is Methyl, Pr is Propyl, and Bu is Butyl.)
Etc.

(II) Examples of super strong acids, Lewis acids and ionic boron compounds include:
Examples of super strong acids include hexafluoroantimonic acid, hexafluorophosphoric acid, hexafluoroarsenic acid, trifluoroacetic acid, fluorosulfuric acid, trifluoromethanesulfonic acid, tetrafluoroboric acid, tetrakis (pentafluorophenyl) boric acid, tetrakis [3, 5-bis (trifluoromethyl) phenyl] boric acid, p-toluenesulfonic acid, pentafluoropropionic acid, etc.
Examples of Lewis acid compounds include complexes of boron trifluoride with ethers, amines, phenols, etc., aluminum trifluoride ethers, complexes of amines, phenols, tris (pentafluorophenyl) borane, tris [3,5 Boron compounds such as bis (trifluoromethyl) phenyl] borane, aluminum compounds such as aluminum trichloride, aluminum tribromide, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum fluoride, tri (pentafluorophenyl) aluminum , Organic halogen compounds exhibiting Lewis acidity such as hexafluoroacetone, hexachloroacetone, chloranil, hexafluoromethyl ethyl ketone, and other Lewis acidity such as titanium tetrachloride and pentafluoroantimony Such as the compounds,
Examples of the ionic boron compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenylcarbeniumtetrakis (2,4 , 6-trifluorophenyl) borate, triphenylcarbenium tetraphenylborate, tributylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (Pentafluorophenyl) borate, N, N-diphenylanilinium tetrakis (pentafluorophenyl) borate and the like.

As an example of the organoaluminum compound (III),
Alkylalumoxane compounds such as methylalumoxane, ethylalumoxane, butylalumoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum chloride, diethylaluminum fluoride, ethylaluminum sesquichloride, ethylaluminum dichloride, etc. The alkylaluminum compound and the halogenated alkylaluminum compound, or the mixture of the alkylalumoxane compound and the alkylaluminum compound are preferably used.

These catalyst components are used, for example, in amounts used within the following ranges.
Transition metal compounds such as nickel compounds, palladium compounds, cobalt compounds, titanium compounds, and zirconium compounds are used in amounts of 0.02 to 100 mmol atoms per mole of monomer component, and organoaluminum compounds are added per mole of transition metal compounds. The non-conjugated diene, Lewis acid, and ionic boron compound are used in an amount of 0 to 100 mol with respect to 1 mol atom of the transition metal compound.

(B) Polymerization solvent As the solvent used in the addition polymerization reaction, the monomer component or catalyst used for the polymerization is dissolved and the catalyst is not deactivated, and the produced addition polymer is dissolved. For example, alicyclic hydrocarbon solvents such as cyclohexane, cyclopentane, and methylcyclopentane, aliphatic hydrocarbon solvents such as hexane, heptane, and octane, toluene, benzene, xylene, mesitylene, etc. And aromatic hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, and other halogenated hydrocarbon solvents. These can be used alone or in admixture of two or more.

(C) Molecular Weight Modifier In the present invention, the molecular weight of the norbornene addition polymer to be produced can be adjusted by adding hydrogen or α-olefin as a molecular weight regulator in the polymerization system. The molecular weight of the norbornene-based addition polymer produced decreases as the molecular weight regulator added increases.

《Hydrogenation reaction》
The polymer obtained by the ring-opening polymerization reaction has an olefinically unsaturated bond in the molecule. In the addition polymerization reaction, the polymer may have an olefinically unsaturated bond in the molecule. Thus, when an olefinically unsaturated bond is present in the polymer molecule, the olefinically unsaturated bond may cause deterioration such as coloration or gelation with time. It is preferable to perform a hydrogenation reaction that converts to a bond.

  In the hydrogenation reaction, a known hydrogenation catalyst is added to an ordinary method, that is, a polymer solution having an olefinically unsaturated bond, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is added to the solution. The reaction can be carried out at -200 ° C, preferably 20-180 ° C.

The hydrogenation rate of the hydrogenated polymer is usually 50% or more, preferably 70% or more, more preferably 90% or more, particularly preferably 98% or more, most preferably measured by 500 MHz and ¹ H-NMR. 99% or more. The higher the hydrogenation rate, the better the stability to heat and light, and it is preferable because stable characteristics can be obtained over a long period when used as a molded product.

  When the polymer obtained by the above method has an aromatic group in its molecule, the aromatic group does not cause deterioration such as coloring over time or gelation, but rather, mechanical properties and optical properties. Such aromatic groups do not necessarily have to be hydrogenated because they may have an advantageous effect on properties.

  As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.

Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania.
Homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium, dichloro Examples thereof include tris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like.
The form of the catalyst may be powder or granular.

These hydrogenation catalysts are usually used in a ratio such that the weight ratio of the ring-opening polymer to the hydrogenation catalyst (ring-opening polymer: hydrogenation catalyst) is 1: 1 × 10 ⁻⁶ to 1: 2. The
The norbornene resin used in the present invention has an intrinsic viscosity [η] _inh of preferably 0.2 to 2.0 dl / g, more preferably 0.35 to 1.0 dl / g, and particularly preferably 0.4 to The number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 0.85 dl / g. Is 15,000 to 250,000, and those having a weight average molecular weight (Mw) of 10,000 to 2,000,000, more preferably 20,000 to 1,000,000, particularly preferably 30,000 to 500,000 are suitable. When the intrinsic viscosity [η] _inh , the number average molecular weight and the weight average molecular weight are in the above ranges, the norbornene resin has excellent mechanical strength, and a norbornene resin substrate (optical film) that is not easily damaged can be obtained. .

  The glass transition temperature (Tg) of the norbornene resin is usually 100 ° C. or higher, preferably 120 ° C. or higher. When Tg is within the above range, a norbornene resin film excellent in film processability and optical properties can be obtained.

The saturated water absorption of the norbornene resin is 1% by weight or less, preferably 0.1 to 0.8% by weight. When the saturated water absorption rate exceeds 1% by weight, there may be a problem in durability such that the resin substrate obtained from the resin is subject to water absorption (wet) deformation over time depending on the environment in which it is used. On the other hand, if it is less than 0.1% by weight, there may be a problem in adhesion. Moreover, when the saturated water absorption rate is within the above range, deterioration of the image sensor due to moisture can be prevented particularly when used for the light-transmitting lid of the solid-state image sensor housing package.
In addition, the said saturated water absorption is a value obtained by immersing in 23 degreeC water for 1 week, and measuring an increase weight according to ASTM D570.

《Other ingredients》
In the present invention, additives such as an antioxidant and an ultraviolet absorber can be further added to the norbornene-based resin within a range that does not impair the effects of the present invention.

  Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [ And methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone. In addition, when a norbornene-based resin substrate (optical film) is manufactured by a solution casting method described later, the manufacturing of the resin substrate (optical film) is facilitated by adding a leveling agent or an antifoaming agent. Can do.

  These additives may be mixed together with a norbornene resin or the like when the norbornene resin substrate (optical film) used in the present invention is manufactured, or may be added when the norbornene resin is manufactured. It may be blended in advance. The addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2 parts per 100 parts by weight of norbornene resin. 0.0 part by weight is desirable.

<< Method for producing norbornene-based resin film >>
The norbornene-based resin film used in the present invention can be suitably molded by directly melt-molding a norbornene-based resin or by a method of dissolving in a solvent and casting (cast molding).

(A) Melt Molding The norbornene resin film used in the present invention can be produced by melt molding a norbornene resin or a resin composition containing a norbornene resin and the above-described additive. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

(B) Casting The norbornene-based resin film used in the present invention can also be produced by casting a liquid resin composition obtained by dissolving a norbornene-based resin in a solvent on an appropriate substrate and removing the solvent. For example, a norbornene-based resin film is formed by applying the liquid resin composition described above on a substrate such as a steel belt, a steel drum, or a polyester film, drying the solvent, and then peeling the coating film from the substrate. Can be obtained.

The amount of residual solvent in the norbornene-based resin film obtained by the above method is preferably as small as possible, and is usually 3% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less. When the residual solvent amount exceeds 3% by weight, the film may be deformed or the characteristics may change over time, and the desired function may not be exhibited.
Although the norbornene-type resin film used by this invention does not specifically limit the thickness, Usually, 5-500 micrometers, Preferably it is 10-150 micrometers, More preferably, it is desirable that it is about 20-100 micrometers. If the thickness of the film is too thin, the strength may be insufficient. On the other hand, if the film is too thick, the birefringence may be too high, or the transparency and appearance may be deteriorated.
The norbornene-based resin film used in the present invention desirably has a light transmittance of usually 80% or more, preferably 85% or more, more preferably 90% or more.
Further, the norbornene resin film used in the present invention has a pure water contact angle at room temperature of the film surface of preferably 60 degrees or more, particularly preferably 70 degrees or more. When the contact angle is 60 degrees or more, compatibility with the polyester film is improved, and film displacement and the like can be prevented, and a polarizing plate or the like is manufactured using the optical film roll of the present invention. The effect of preventing the occurrence of scratches and foreign matter adhesion is further increased.

<< Method for producing retardation film >>
When the norbornene resin film used in the present invention is used as a retardation film, the retardation film can be obtained by stretching the resin film obtained by the above method.
As a stretching method, a method of uniaxially stretching or biaxially stretching a resin film is used.
In the case of the uniaxial stretching treatment, the stretching speed is usually 1 to 5,000% / min, preferably 50 to 1,000% / min, and more preferably 100 to 1,000% / min.
In the case of the biaxial stretching method, a method in which stretching is performed in two directions at the same time, or a method in which stretching is performed in a direction different from the stretching direction in the stretching treatment after uniaxial stretching is used. At this time, the intersection angle of the two stretching axes is determined according to the characteristics required for the target optical film, and is not particularly limited, but is usually in the range of 120 to 60 degrees. The stretching speed may be the same or different in each stretching direction, and is usually 1 to 5,000% / min, preferably 50 to 1,000% / min. Preferably it is 100 to 1,000% / min, and particularly preferably 100 to 500% / min.

The stretching treatment temperature is not particularly limited, but based on the glass transition temperature (Tg) of the norbornene-based resin to be used, Tg ± 30 ° C., preferably Tg ± 15 ° C., more preferably Tg−5 to Tg + 15 ° C. Range. By setting the stretching treatment temperature within the above range, it is possible to suppress the occurrence of uneven retardation in the stretched film obtained, and it is preferable because the control of the refractive index ellipsoid becomes easy.
Although a draw ratio is determined according to the characteristic requested | required of the target optical film, it is not specifically limited, Usually, 1.01 to 10 times, Preferably it is 1.03 to 5 times, More preferably, it is 1.03. 3 times. When the draw ratio exceeds the above range, it may be difficult to control the retardation of the obtained stretched film. Although the stretched film may be cooled as it is, it is cooled after being held in a temperature atmosphere of Tg-20 ° C. to Tg for at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 to 60 minutes. It is preferable to do. Thereby, a stable retardation film can be obtained with little change over time in the retardation of transmitted light.

  The film subjected to the stretching treatment as described above gives a phase difference to the transmitted light as a result of the orientation of the molecules by the stretching treatment. This phase difference depends on the stretching ratio, the stretching temperature, or the thickness of the film. It can be controlled by.

The thickness of the norbornene-based resin film used as the retardation film is not particularly limited, but is usually 5 to 500 μm, preferably 10 to 150 μm, and more preferably about 20 to 100 μm.
Further, the retardation film may be subjected to surface treatment such as corona treatment.

<Polyester film>
The polyester film constituting the optical film roll of the present invention has a role of preventing damage to the surface of the norbornene resin film and adhesion of foreign matter by being used on the surface of the norbornene resin film.
Examples of the polyester film include polyethylene terephthalate (PET) film and polyethylene naphthalate (PEN). Among them, PET film is particularly preferably used.
The film thickness of the polyester film used in the present invention is usually 1 to 50 μm, preferably 10 to 30 μm. If it is thinner than 1 μm, the effect of preventing scratches may be insufficient. On the other hand, if it is thicker than 50 μm, handling may be difficult and the winding diameter of the film may be increased.
Moreover, it is calculated | required that the surface of the polyester-type film used for this invention does not have adhesions, such as slit waste. Since polyester film is a crystalline resin, if slit scraps adhere to it, the surface of the norbornene resin film may be scratched, and there may be a problem that it becomes a bright spot when used as a polarizing plate of the final product. It is.
The adhered foreign matter on the film surface of the polyester film of the present invention has a size of 10 μm or more per 1 m ² , preferably 1 or less, more preferably 0.5 or less, most preferably 0.1. It is as follows. The adhered foreign matter also includes the above-mentioned slit scraps of the polyester film itself.
The thickness distribution of the polyester film of the present invention is usually within 5 μm, preferably within 3 μm, more preferably within 1 μm, and most preferably within 0.5 μm. By making the thickness distribution of the film within this range, the norbornene-based resin film can be uniformly wound, and the occurrence of winding deviation, pressing damage, etc. can be suitably prevented.
The average surface roughness (Ra) of the polyester film of the present invention is usually 0.1 μm or less, preferably 0.01 μm or less, more preferably 0.005 μm or less, and most preferably 0.001 μm or less. . By setting the surface roughness of the film in the range, it is possible to suitably prevent scratches and pressings on the surface of the norbornene-based resin film.

<Film core>
The film core used in the present invention is a core for winding an optical film and a polyester film. Although the material of a film core is not specifically limited, Usually, plastics, such as ABS resin and a vinyl chloride resin, are used suitably. Further, the film core made of these materials may be covered with a material whose surface hardness is lower than the surface hardness of the optical film. Examples of the material having a low surface hardness used herein include cloth, rubber, sponge, and soft plastic, but are not particularly limited thereto. By performing such a process, it is possible to reduce a so-called core level difference in which a film step at the beginning of winding becomes a linear imprint and remains in the film outer direction.
The film core used in the present invention is usually 50 to 500 mm in diameter and 500 to 1,800 mm in length.

<Configuration of optical film roll>
In the optical film roll of the present invention, a norbornene-based resin film and a polyester-based film are usually stacked without bonding. The vertical relationship between the norbornene-based resin film and the polyester-based film is not particularly limited, but is preferably obtained by winding the film on a film core with the norbornene-based resin film side facing down, for the reason that the outermost surface can be protected.
As shown in FIG. 1A, the optical film roll of the present invention has a portion in which at least one edge (preferably both edges) has a polyester film that does not overlap with the optical film. It is preferable. That is, it is preferable to have a structure in which the edge of the polyester film protrudes outside the edge of the optical film. The portion where the polyester film exists in one layer (the protruding portion) has a certain width in the longitudinal direction of the optical film roll, and this width (a in FIG. 1B) is: The thickness is preferably 1 mm to 40 mm, particularly preferably 2 mm to 20 mm. By adopting such a structure, winding pressure is applied to the edge of the film roll, so that there is an effect of preventing winding deviation and suppressing the occurrence of scratches on the optical film surface. In order to obtain such an optical film roll, it is preferable that the edge of the polyester film and the edge of the optical film are overlapped while being shifted in the range of 1 mm to 20 mm, preferably in the range of 3 to 10 mm. Specifically, it is preferable to form the optical film roll using a polyester film having a width of 2 mm to 10 mm wider than the optical film.
Further, when the norbornene resin film and the polyester film are overlapped and wound in a roll shape, for example, when the width of the norbornene resin film is 1,300 mm, it is preferably 3 to 50 kgf, more preferably 5 to 20 kgf. It is preferable to wind with tension. When the winding tension is less than 3 kgf, winding deviation tends to occur. On the other hand, when the winding tension exceeds 50 kgf, film pressing scratches are likely to occur.

<Production method of polarizing plate>
In the present invention, the polarizing plate is a water-based adhesive composed of an aqueous solution mainly composed of a PVA resin, with a retardation film obtained from a norbornene-based resin film on one side and / or the other side of a polarizer made of a PVA-based film. It can be manufactured by laminating using an adhesive or a polar group-containing adhesive, heating and pressure-bonding, and bonding (compositing) the polarizer and the retardation film.
In the production of the polarizing plate, the retardation film is attached to at least one surface of the polarizer so that the absorption axis of the polarizer and the optical axis of the retardation film are parallel or orthogonal.
The retardation film obtained by the production method of the present invention preferably has an optical axis in the transverse direction and is usually obtained as a film roll, and therefore a film roll of a polarizer having an absorption axis in the longitudinal direction; It can be bonded continuously by so-called roll to roll. That is, the polarizing plate can be produced by aligning the longitudinal direction of the retardation film and the longitudinal direction of the polarizer having the absorption axis in the longitudinal direction and sticking both together. For this reason, according to the method for producing a polarizing plate of the present invention, a retardation film having an optical axis in the longitudinal direction is cut according to the width of the polarizer, and then the direction of the retardation film is perpendicular to the absorption axis of the polarizer. In this direction, the individually bonded polarizing plates can be continuously manufactured, and the manufacturing efficiency can be significantly improved.
In the manufacturing method of the polarizing plate of the present invention, a retardation film made of norbornene resin obtained by the manufacturing method of the present invention is used. This retardation film has low gas permeability and excellent moisture resistance. Since the protective film can also serve as a protective film, it is not necessary to use a protective film that the conventionally known polarizing plate usually has in addition to the retardation film. For this reason, in the manufacturing method of the polarizing plate of this invention, it is not necessary to stick the protective film which protects a polarizer separately other than retardation film, and the transmission by the number of films to laminate | stack and the amount of adhesives to be used is large. In addition to greatly reducing problems such as a decrease in accuracy and accuracy due to adhesion of a large number of films, the manufacturing process can be simplified, and the polarizing plate can be made thinner and lighter. .

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the following, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.
The measuring method of the various measured values described below is shown below.
[Glass transition temperature (Tg)]
Using a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc., the measurement was performed under conditions of nitrogen atmosphere and heating rate: 20 ° C./min.
[Saturated water absorption]
In accordance with ASTM D570, the sample was immersed in water at 23 ° C. for 1 week, and the change in weight before and after immersion was measured and determined.
[Total light transmittance, haze]
Haze meter manufactured by Suga Test Instruments Co., Ltd .: Measured using HGM-2DP type.
[Phase difference of transmitted light]
The phase difference measurement of the transmitted light was performed using KOBRA-21ADH manufactured by Oji Scientific Instruments and KOBRA-CCD.
[Film surface roughness (Ra)]
Using Kosaka Laboratory Ltd. made fine shape measuring instrument, in conformity with JIS B0601 film 1m Measure ² around 9 points (the nine points uniformly vertical 3 × horizontal 3 points) in each length 3 cm, and averaged The value was obtained.

<Synthesis example>
8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (monomer A-1) 225 parts, bicyclo [2.2.1] hept-2-ene (monomer B-1) 25 parts, and 1-hexene (Molecular weight regulator) 22 parts and 750 parts of toluene were charged into a nitrogen-substituted reaction vessel, and this solution was heated to 60 ° C. Next, 0.62 parts of a toluene solution of triethylaluminum (1.5 mol / l) as a polymerization catalyst and tungsten hexachloride modified with t-butanol and methanol (t-butanol: methanol: tungsten) were added to the solution in the reaction vessel. = 0.35 mol: 0.3 mol: 1 mol) of a toluene solution (concentration 0.05 mol / l) 3.7 parts was added, and the system was heated and stirred at 80 ° C. for 3 hours to open the ring. A ring-opening copolymer solution was obtained by copolymerization reaction. The polymerization conversion rate in this polymerization reaction was 97%, and the intrinsic viscosity (η _inh ) of the obtained ring-opening copolymer measured in chloroform at 30 ° C. was 0.55 dl / g.

The autoclave was charged with 4,000 parts of the ring-opening copolymer solution thus obtained, and RuCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ 0.48 part was added to the ring-opening copolymer solution. And a hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C.
After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was dried to obtain a hydrogenated polymer (specific cyclic polyolefin resin).
The hydrogenation rate of the thus obtained hydrogenated polymer (hereinafter referred to as “resin (a)”) was measured using 400 MHz ¹ H-NMR and found to be 99.9%.

It was 130 degreeC when the glass transition temperature (Tg) was measured by DSC method about the said resin (a). The resin (a) was measured for polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) by the GPC method (solvent: tetrahydrofuran). The number average molecular weight (Mn) was 26,000, The weight average molecular weight (Mw) was 78,000, and the molecular weight distribution (Mw / Mn) was 3.00.
With respect to the resin (a), the saturated water absorption rate at 23 ° C. was measured to be 0.3%.
The intrinsic viscosity (η _inh ) of the resin (a) measured in chloroform at 30 ° C. was 0.57 dl / g.

[Example 1]
The resin (a) was dried in a vacuum dryer at 80 ° C. for 4 hours, and then an 80 mmφ extruder equipped with a 1500 mmT die at the tip installed in a clean room of 100 was used, and the extruder cylinder temperature was set to 260 to Under conditions set at an appropriate temperature of 280 ° C., the film was melt-extruded and formed into a film under a shear rate of 32 (1 / second). The film melt-extruded from the T-die is sandwiched between the metal cast drum and a metal endless belt provided so as to be pressed against the cast drum along the circumferential direction thereof. After pressure-bonding to the endless belt and processing the film surface with high accuracy, the film was peeled off from the belt and both ends of the film were slit to produce a film having a width of 1,300 mm and a thickness of 100 μm. The cooling cast drum was set at a temperature of 130 ° C. for molding.

At this time, a polyethylene terephthalate (PET) film manufactured by Teijin DuPont with a thickness of 20 to 30 μm, a width of 1310 mm, and no foreign matter adhering to the film surface is exposed between the films made of the resin (a) by 5 mm each. The film roll (A-1) having a length of 2,000 m was obtained. Further, the winding tension at this time was 10 to 20 kgf.
It was 85 degree | times when the film which consists of resin (a) was taken out from the said film roll (A-1), and the contact angle of the pure water at room temperature was confirmed. Moreover, when the total light transmittance and the retardation in the film plane were confirmed, they were 93% and 3 nm, respectively. Furthermore, when the foreign material and the damage | wound adhering to the surface of the film which consisted of taken out resin (a) were investigated, it was not recognized. The film surface roughness (Ra) was 0.006 μm.

[Example 2]
Using the film roll (A-1) obtained in Example 1 and using a tenter type horizontal stretching machine installed in a clean room of 100, the temperature is 140 ° C. and the magnification is 1.3 times from the resin (a). The resulting film was stretched transversely. Thereafter, the width was 1,300 mm using a slitter, and the film was co-wound with a PET film in the same manner as in Example 1 to obtain a film roll (A-2) having a length of 1,500 m.
It was 86 degree | times when the film which consists of resin (a) was taken out from the said film roll (A-2), and the contact angle of the pure water at room temperature was confirmed. Moreover, when the total light transmittance and the in-plane retardation were confirmed, they were 93% and 140 nm, respectively. Further, when the film made of the taken out resin (a) was examined for foreign matters and scratches adhering to the surface, it was not recognized. The film surface roughness (Ra) was 0.005 μm.

[Example 3]
In a room with a cleanness of 100, a 50 μm thick polyvinyl alcohol film is uniaxially stretched up to 4 times in about 5 minutes while immersed in a 40 ° C. bath consisting of 5 g of iodine, 250 g of potassium iodide, 10 g of boric acid, and 1,000 g of water. On the surface of the polarizing film thus obtained, 100 parts of an acrylic resin obtained from a monomer of 90% by weight of n-butyl acrylate, 7% by weight of ethyl acrylate, and 3% by weight of acrylic acid, and tolylene diisocyanate (3 Mol) trimethylolpropane (1 mol) adduct was mixed with a pressure-sensitive adhesive obtained by mixing 2 parts of a 75 wt% ethyl acetate solution, and then the rolls obtained in Examples 1 and 2 respectively. Using the films (A-1) and (A-2), the films made of the resin (a) are respectively laminated on both sides of the polarizing film (A 3) was obtained.
The polarizing plate was subjected to an endurance test for 500 hours under the conditions of 80 ° C. and 90% relative humidity, and when the appearance change was visually observed, no abnormality was observed in the appearance, and the polarization degree maintained the initial value. (99.9%) and the durability was found to be good. Further, the polarizing plate was placed in a crossed Nicols state directly on the backlight of the liquid crystal TV, and the presence or absence of a bright spot was examined.

[Comparative Example 1]
At the time of film slit in Example 1, using a drum-shaped knurling device having a width of 15 mm and a large number of fine protrusions having a height of about 20 μm on the surface, knurling was applied to both ends of the film made of resin (a). A film roll (B-1) having a length of 2,000 m was obtained. At this time, the PET film was not co-wound.
It was 85 degree | times when the film which consists of resin (a) was taken out from the said film roll (B-1), and the contact angle of the pure water at room temperature was confirmed. Further, when the total light transmittance and the retardation in the film plane were confirmed, they were 92% and 3 nm, respectively. Further, when the film made of the resin (a) taken out was examined for foreign matters and scratches adhering to the surface, many scratches having a length of about 10 to 100 μm were observed. The film surface roughness (Ra) was 0.05 μm.

[Comparative Example 2]
Immediately before the film slit in Example 2, the film surface was corona-treated in air using an in-line corona treatment apparatus manufactured by Kasuga Denki so that the contact angle of pure water at room temperature was 45 degrees. Then, a film roll (B-2) having a length of 1,500 m was obtained by using a 30 μm-thick protective film made of polyethylene instead of the PET film at the time of winding the film.
When the film which consists of resin (a) was taken out from the said film roll (B-2) and the total light transmittance and the retardation in the film surface were confirmed, respectively, they were 92% and 140 nm. Further, when the foreign matter and scratches adhered to the surface of the film made of the resin (a) taken out were examined, fine irregularities due to fish eyes of the polyethylene protective film were found on the entire surface of the film. The film surface roughness (Ra) was 0.03 μm.

[Comparative Example 3]
A polarizing plate (B-3) was obtained in the same manner as in Example 3 except that the film rolls (B-1) and (B-2) were used.
The polarizing plate was subjected to an endurance test for 500 hours under the conditions of 80 ° C. and 90% relative humidity, and when the appearance change was visually observed, no abnormality was observed in the appearance, and the polarization degree maintained the initial value. (99.9%) and the durability was found to be good. However, when a crossed Nicol state was placed on the polarizing plate light box and the presence or absence of bright spots was examined, 3 pieces per 1 m ² were found.

(A) is the schematic of the optical film roll of this invention, (b) is detail drawing of A cross section.

Claims (6)

  An optical film roll obtained by superposing and winding an optical film made of a norbornene resin and a polyester film. The optical film roll according to claim 1, wherein the norbornene-based resin is a resin obtained by (co) polymerizing a monomer component containing at least one compound represented by the following general formula (1).
[In General Formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom which may have a linking group containing oxygen, nitrogen, sulfur or silicon. 1 to 15 hydrocarbon groups or other monovalent organic groups are represented. Here, R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form an alkylidene group, and R ¹ and R ² , R ³ and R ^4, or R ² and R ³ may be mutually connected. May form a carbocycle or a heterocycle (these carbocycles or heterocycles may have a monocyclic structure, or other rings may be condensed to form a polycyclic structure). The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring. X represents 0 or an integer of 1 to 3, and y represents 0 or 1. When x is 0, y is 0. ].   The optical film roll according to claim 1, wherein the optical film has a function as a retardation film.   The optical film roll according to claim 1, wherein the optical film has a contact angle of pure water at room temperature of the film surface of 60 degrees or more.   The optical film roll according to claim 1, wherein at least one edge of the optical film roll has a portion where the polyester film does not overlap with the optical film but exists in a single layer. The method includes the steps of aligning the longitudinal direction of the optical film in the optical film roll according to claim 1 and the longitudinal direction of the polarizer, and affixing both together, and the step of removing the polyester film. The manufacturing method of a polarizing plate.