JP2009175721A - Polarizing plate and manufacturing method thereof - Google Patents

Abstract

Provided are a polarizing plate having a good polarizing function, excellent optical characteristics, heat resistance, chemical resistance, and the like, capable of being thinned, and obtained by a simple method, and a method for producing the same.
A norbornene-based polymer film is formed through an adhesive layer containing (A) a polymer component having a repeating unit derived from a (meth) acrylic acid ester having an alicyclic structure, and (B) a polyvinyl alcohol component. A polarizing plate, wherein the polarizing plate is laminated.
[Selection figure] None

Description

  The present invention relates to a polarizing plate and a method for producing the same. More specifically, the present invention relates to a polarizing plate in which a norbornene polymer film, a polarizing film, an adhesive layer and, if necessary, a hard coat layer are laminated.

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 (retardation film) which has the function to provide retardation to transmitted light obtained by extending | stretching an optical film, and a polarizing film.
The polarizing film is generally made of polyvinyl alcohol (hereinafter abbreviated as “PVA”), but PVA is hygroscopic and its characteristics change depending on the external environment. A polarizing plate having a structure in which a film is sandwiched between protective layers such as a triacetyl cellulose film (hereinafter also referred to as “TAC film”) is generally used.

  On the other hand, norbornene polymers are attracting attention as materials for various optical components such as retardation films and the above-mentioned protective layers 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 polymer sheet is laminated as a protective layer on a polarizing film.

However, the above-mentioned polarizing plate, when a conventional adhesive is used, has insufficient adhesive force with the norbornene polymer film, and for example, peeling occurs at the interface between the polarizing film and the retardation film. was there.
For this reason, after placing the polarizing plate on the glass cell, if it is necessary to reattach the polarizing plate due to a defect in the polarizing plate (rework), the pressure-sensitive adhesive is used to bond the polarizing plate and the glass cell. Since the adhesive force in the laminated structure of the polarizing plate (for example, the adhesive force for bonding the polarizing film and the retardation film) becomes insufficient with respect to the force, the retardation is applied on the glass cell from which the polarizing plate is removed. There was a problem that only the film remained and the glass cell could not be reused. Therefore, a conventional polarizing plate using a norbornene polymer has a configuration in which a protective layer such as a TAC film is laminated on both sides of a polarizer and a retardation film made of a norbornene polymer is laminated thereon. From the viewpoints of thinning, improving optical characteristics, simplifying processes, etc., development of a polarizing plate in which a norbornene polymer film is directly laminated on a polarizing film has been demanded.
JP-A-6-511117

  The present invention is intended to solve the problems associated with the prior art as described above, has a good polarization function, is excellent in properties such as optical properties, heat resistance, chemical resistance, etc., and is thinned. An object of the present invention is to provide a polarizing plate obtained by a simple method and a method for producing the same.

The polarizing plate of the present invention has at least one surface of the polarizing film,
(A) a polymer having a repeating unit derived from a (meth) acrylic acid ester having an alicyclic structure (hereinafter also referred to as “polymer (A)”), and (B) PVA (hereinafter referred to as “polymer (B)”. A norbornene-based polymer film is laminated through an adhesive layer containing a component))).
The adhesive layer preferably contains a mixture of the polymer (A) and the polymer (B).
The adhesive layer preferably contains a graft copolymer of the polymer (A) and the polymer (B).
The norbornene-based polymer film is preferably a film made of a polymer obtained by (co) polymerizing a monomer containing at least one compound represented by the following formula (1).

(In the formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, or a monovalent group that may contain oxygen, nitrogen, sulfur or silicon. R ¹ and R ² Or R ³ and R ⁴ may be bonded to each other to form an alkylidene group, or R ¹ and R ² , R ³ and R ⁴ , or R ² and R ³ may be bonded to each other. And may form a monocyclic or polycyclic carbocyclic or heterocyclic ring, where x is 0 or an integer of 1 to 3, and y is 0 or 1.)

The norbornene polymer film is preferably a retardation film.
Moreover, it is preferable that the said norbornene-type polymer film contains a benzotriazole type ultraviolet absorber.
The method for producing a polarizing plate of the present invention comprises a polarizing film and a norbornene polymer film,
It has the process of adhere | attaching using the adhesive agent containing a polymer (A) component and a polymer (B) component, It is characterized by the above-mentioned.
The adhesive preferably further contains (C) a water-soluble epoxy compound or (D) a water-dispersed isocyanate.

  According to the present invention, it is possible to obtain a polarizing plate having a good polarizing function, excellent optical characteristics, heat resistance, chemical resistance, and the like, capable of being thinned, and obtained by a simple method. .

Hereinafter, the present invention will be specifically described.
The polarizing plate of the present invention has a laminated structure of polarizing film / adhesive layer / norbornene polymer film, and the adhesive layer comprises a polymer (A) component and a polymer (B) component. It is formed from the containing adhesive.
In the polarizing plate of the present invention, it is preferable that a hard coat layer is laminated directly or via another layer on the surface of the norbornene-based polymer film opposite to the polarizing film.
Further, on the surface of the polarizing film opposite to the norbornene polymer film, the norbornene polymer is bonded to the surface opposite to the norbornene polymer film through an adhesive layer containing the polymer (A) component and the polymer (B) component. The film may be laminated | stacked and the protective film obtained from other polymers, such as a triacetyl cellulose, may be laminated | stacked.

As the laminated structure of the polarizing plate of the present invention, for example, the following structure is preferably used.
(1) (Hard coat layer) / norbornene polymer film [protective film] / adhesive layer / polarizing film / adhesive layer / norbornene polymer film [retardation film]
(2) Other polymer film [protective film] / polarizing film / adhesive layer / norbornene polymer film [retardation film] /

<Polarizing film>
The polarizing film used in the present invention has a function as a polarizing film, that is, a film having a function of dividing incident light into two polarization components orthogonal to each other, allowing only one of them to pass, and absorbing or dispersing the other components. If it is, it will not specifically limit, Any polarizing film can be used.

  Examples of the polarizing film that can be used in the present invention include a PVA / iodine polarizing film; a PVA / dye polarizing film in which a dichroic dye is adsorbed and oriented on a PVA film; a dehydration reaction or polychlorination of the PVA film. Polyene polarizing film in which polyene is formed by dehydrochlorination reaction of vinyl film; polarizing film having dichroic dye on the surface and / or inside of PVA film made of modified PVA containing a cationic group in the molecule Is mentioned. Of these, PVA / iodine polarizing films are preferred.

  The manufacturing method of the polarizing film used by this invention is not specifically limited, A conventionally well-known method is applicable. For example, a method of adsorbing iodine ions after stretching a PVA film, a method of stretching a PVA film after dyeing with a dichroic dye, a method of stretching a PVA film and then dyeing with a dichroic dye, two colors Examples thereof include a method of stretching a sexual dye on a PVA film and then stretching, a method of printing a dichroic dye after stretching a PVA film, and the like. More specifically, iodine is dissolved in a potassium iodide solution to form higher-order iodine ions, the ions are adsorbed on a PVA film and stretched, and then a 1 to 5% by weight boric acid aqueous solution has a bath temperature of 30. A method for producing a polarizing film by immersing at ~ 40 ° C; or, after treating a PVA film with boric acid in the same manner as described above and stretching it about 3 to 7 times in a uniaxial direction, 0.05 to 5% by weight of two colors And a method of producing a polarizing film by immersing in an aqueous dye solution at a bath temperature of 30 to 40 ° C. to adsorb the dye, followed by drying at 80 to 100 ° C. and heat setting.

The thickness of the polarizing film used in the present invention is not particularly limited, but is 10 to 50 μm, preferably 15 to 45 μm.
These polarizing films may be used as they are for the production of the polarizing plate according to the present invention, but can also be used after being subjected to corona discharge treatment or plasma treatment on the surface in contact with the adhesive layer.

<Adhesive layer>
The adhesive layer in the present invention is a layer formed from an adhesive having a polymer (A) component and a polymer (B) component. In the present invention, a norbornene-based polymer film and a polarized light are used using the adhesive. Adhere to the membrane.
As for the adhesive used in the present invention, the polymer (B) component can express a good adhesive force with respect to the polar material, and the polymer (A) component with respect to the nonpolar material, Good adhesive force can be expressed. As described above, since the adhesive contains adhesive components for each of the polar material and the nonpolar material, the adherends having different polarities such as the polar material and the nonpolar material have a high adhesive force. Can be glued.

The adhesive used in the present invention may be a mixture containing the polymer (A) and the polymer (B), or a graft copolymer obtained by graft polymerization of the polymer (A) and the polymer (B). It may contain a polymer.
Hereinafter, each component of the adhesive will be described in more detail.

[Polymer (A) component]
The polymer (A) is a monomer comprising a (meth) acrylic acid ester having an alicyclic structure (hereinafter also referred to as “monomer (A-1)”) and a monomer copolymerizable with this monomer as necessary. It is a copolymer obtained by polymerizing a monomer component. Since the polymer (A) includes a repeating unit derived from a monomer having an alicyclic structure, for example, high adhesion to an adherend having an alicyclic structure such as a norbornene resin can be expressed. .

  The content ratio of the monomer (A-1) in the monomer component is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, particularly preferably the total amount of monomers in the polymer (A). It is 50-85 mass%. If the monomer (A-1) is less than 30 parts by mass, there is a possibility that the adhesive force to the nonpolar material may not be expressed. On the other hand, if it exceeds 95 parts by mass, defective film formation of the adhesive occurs, and the preferable adhesive force is May not be obtained.

The monomer (A-1) is a (meth) acrylic acid ester having an alicyclic structure, and specifically, an ester of (meth) acrylic acid and an alcohol having an alicyclic structure.
Specific monomers (A-1) include, for example, cyclohexyl (meth) acrylate, isobornyl acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. Preferred examples include cycloalkyl (meth) acrylates such as dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl (meth) acrylate. Particularly preferred is cyclohexyl methacrylate.

  Monomers that can be copolymerized with the monomer (A-1) include (meth) acrylic acid, itaconic acid, fumaric acid, 2-ethylhexyl (meth) acrylate, butyl (meth) acrylate, ethyl (meth) acrylate, glycidyl (meth) ) Acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, styrene, α-methylstyrene and the like.

  The manufacturing method of a polymer (A) is not specifically limited, For example, an emulsion polymerization method, suspension polymerization method, and solution polymerization method can be used. Among these, it is preferable to manufacture by an emulsion polymerization method.

  When producing by emulsion polymerization, first, for example, a monomer component containing each monomer in water is emulsified using a surfactant. Thereafter, a radical polymerization initiator such as a peroxide catalyst or a redox catalyst as a polymerization initiator, and a molecular weight regulator such as a mercaptan compound or a terpene compound as necessary are added, for example, polymerization at 50 to 90 ° C. By carrying out, an aqueous emulsion containing the (meth) acrylic acid ester copolymer that is the polymer (A) can be obtained.

  The polymer (A) used in the present invention may be used in the state of the aqueous emulsion thus obtained, or may be used after being isolated from the aqueous emulsion. In addition, the adhesive agent of this invention can be used as a water-system adhesive agent by using in the state of an above-mentioned water-system emulsion.

  The polymer (A) used in the adhesive of the present invention preferably has a glass transition temperature (Tg) of -50 to 80 ° C, more preferably -20 to 50 ° C, and preferably 0 to 40 ° C. It is particularly preferred. If the temperature is lower than −50 ° C., the adhesive may cause cohesive failure, and a preferable adhesive force may not be obtained. There is a fear.

[Polymer (B) component]
The polymer (B) is polyvinyl alcohol, and is an adhesive component that develops an adhesive force to an adherend made of a polar material such as a polarizing film.

  Examples of such a polymer (B) include polyvinyl alcohol obtained by saponifying polyvinyl acetate obtained by polymerizing general vinyl acetate, as well as polyvinyl alcohol having active terminal groups such as a crosslinking reactive polyvinyl alcohol and a carboxyl group. Etc. Among these, from the viewpoint of expressing adhesive force due to chemical bonding with the polymer (A), cross-linking reactive polyvinyl alcohol and polyvinyl alcohol having an active end group are preferable.

  Moreover, as a polymer (B) used for the adhesive agent in this invention, it is preferable that the saponification degree is 50-100 mol%, It is still more preferable that it is 70-100 mol%, 80-100 It is particularly preferred that it is mol%. By comprising in this way, high adhesive force can be expressed.

[(C) Water-soluble epoxy compound]
The adhesive used in the present invention further contains (C) a water-soluble epoxy compound (hereinafter also referred to as “(C) component”) in addition to the polymer (A) component and the polymer (B) component. It may be a thing. By further containing the component (C), the adhesive force of the adhesive of the present invention can be further improved.

As the component (C), water-soluble epoxy compounds used in conventional adhesives can be used. For example, polyethylene glycol diglycidyl ether, diglycerol polyglycidyl ether, glycerin diglycidyl ether and the like are preferable examples. be able to.
[(D) Water-dispersed isocyanate compound]
The adhesive used in the present invention may contain (D) a water-dispersed isocyanate compound (hereinafter also referred to as “(D) component”) instead of the (C) component. By further containing the component (D), a urethane bond is formed with the polymer (A), the polymer (B), the polarizing film and the norbornene polymer film after corona treatment, and the adhesive strength of the adhesive of the present invention Can be further improved.
As the component (D), water-dispersed isocyanate compounds used in conventional adhesives can be used. For example, any one or more of aliphatic, alicyclic and aromatic diisocyanate compounds, ethylene glycol, Preferred examples include adducts added with propylene glycol, hexanetriol, and the like, and isocyanurates obtained by trimerizing isocyanate.

[Method for producing adhesive]
When producing the adhesive used in the present invention, first, an aqueous emulsion containing the polymer (A) is produced using, for example, the emulsion polymerization method described above. As the polymerization method, a suspension polymerization method or a solution polymerization method can also be used.
In the case of an adhesive having a mixture of the polymer (A) and the polymer (B), an aqueous emulsion containing the above-described polymer (A) component is added to the polymer (B), and (C ) Component or (D) component can be added and mixed to produce an adhesive.

On the other hand, in the case of an adhesive containing a graft copolymer of a polymer (A) component and a polymer (B) component, for example, it can be produced as follows.
First, a monomer component containing the monomer (A-1) is prepared.
Next, an aqueous solution containing the polymer (B) component is put into an autoclave or the like, and a radical polymerization initiator such as a peroxide catalyst or a redox catalyst as a polymerization initiator, and a molecular weight such as a mercaptan compound or a terpene compound as necessary. A regulator is added and heated to, for example, 50-90 ° C.
Next, the monomer component containing the above-mentioned monomer (A-1) is continuously supplied into the autoclave over a certain period of time, and the monomer (A-1) is (co) polymerized and obtained. The polymer (A) component and the polymer (B) component are graft polymerized. In this way, an adhesive containing a graft copolymer of the polymer (A) and the polymer (B) can be produced.

<Norbornene polymer film>
The norbornene polymer constituting the norbornene polymer film used in the present invention is a resin obtained by (co) polymerization of a monomer containing at least one norbornene compound or, if necessary, this resin This is a resin obtained by hydrogenation.

(Monomer)
As said norbornene-type compound, the norbornene-type compound represented by the said Formula (1) can be mentioned, for example.

In formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; or a monovalent group that may contain oxygen, nitrogen, sulfur or silicon. Examples of the monovalent group include a monovalent organic group, a cyano group, and an amino group. Furthermore, examples of the monovalent organic group include substituted or unsubstituted hydrocarbon groups having 1 to 15 carbon atoms, which may have a linking group containing oxygen, nitrogen, sulfur or silicon. x represents 0 or an integer of 1 to 3, and y represents 0 or 1.

R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form an alkylidene group, or R ¹ and R ² , R ³ and R ⁴ , or R ² and R ³ may be bonded to each other to form a monocyclic or polycyclic carbocyclic ring or a monocyclic or polycyclic heterocyclic ring. Here, “R ¹ and R ² are bonded to each other to form an alkylidene group” means that either R ¹ or R ² is eliminated and the remaining group is bonded to the ring structure by a double bond. This means a state (the following formula (1 ′)). The same applies to R ³ and R ⁴ . Examples of the carbocyclic or heterocyclic ring include alicyclic and aromatic rings.

The norbornene compounds represented by the above formula (1) may be used singly or in combination of two or more.
Examples of the norbornene-based compound represented by the above formula (1) include the following compounds, but are not limited to these compounds.
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- En-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-phenoxycarbonyl-bicyclo [2.2. ] 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- En5-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 -Ene 5,6-difluoro-bicyclo [2.2.1] hept-2-ene 5,6-dichloro-bicyclo [2.2.1] hept-2-ene 5,6-dibromo-bicyclo [2. 2.1] Hept-2-ene 5-hydroxy-bicyclo [ 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 -entylcyclo [4.3.0.1 ^2,5 ] dec-3-entylcyclo [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-dimethyl - tricyclo [4.3.0.1 ^2,5] dec-3-ene 7,8,9- Rimechiru - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene 8-methyl - tricyclo [4.4.0.1 ^{2, 5]} undec-3-en 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 ] deca -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 ] deca- 3-ene 7-dichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene 7-trichloromethyl-tricyclo [4.3.0.1 ^2,5 Deca-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 ] dec-3-enetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-enepentacyclo [7.4.0.1 ^2,5 . 1 ^8,11 . 0 ^7,12] pentadeca-3-ene hexamethylene cyclo [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 ] dodec-3-ene 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-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 ] dodec-3-ene 8-methoxycarbonyl-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 ] dodec-3-ene 8-phenoxyethylcarbonyl-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 ] dodec-3-ene 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 8,8-dimethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-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 ] dodec-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 ] dodec-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 The kind and amount of the norbornene-based compound used in the present invention are appropriately selected according to the required properties of the resin.

Among the norbornene compounds represented by the above formula (1), a structure containing at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom (hereinafter referred to as “polar structure”). Is preferable in that it has excellent adhesion and adhesion to other materials. In particular, in the above 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 or R ⁴ is a polar structure. A compound having a hydrogen atom and the other being a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable in that the water absorption (wet) property of the obtained resin is lowered. Furthermore, a norbornene-based compound in which a group having a polar structure is a group represented by the following formula (2) has a good balance between the heat resistance and water absorption (humidity) of the resulting resin and is preferably used.

− (CH ₂ ) _z COOR ”(2)
(In 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 above formula (2), the smaller the value of z, the higher the glass transition temperature of the resulting polymer hydrogenated product and the better the heat resistance, so z is preferably an integer of 0 or 1 to 3, Furthermore, a monomer in which z is 0 is preferable because it can be easily synthesized. In addition, R ″ in the above 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 above formula (1), a compound in which 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 above formula (2) is bonded has heat resistance and water absorption (humidity). From the viewpoint of balance of sex. Further, in the above 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 hydrogenation with high heat resistance It can be suitably used because it can be obtained and can be easily obtained industrially.

  In obtaining the norbornene-based polymer used in the present invention, the monomer composition can be polymerized with a monomer copolymerizable with the norbornene-based compound as long as the effects of the present invention are not impaired. .

  Examples of these copolymerizable monomers include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and cyclododecene; and non-conjugated cyclic polyenes such as 1,4-cyclooctadiene, dicyclopentadiene, and cyclododecatriene. Can be mentioned.

These copolymerizable monomers may be used alone or in combination of two or more.
(Polymerization method)
The polymerization method of the norbornene polymer used in the present invention is not particularly limited as long as the monomer composition containing the norbornene compound can be polymerized. For example, ring-opening polymerization or addition It can be polymerized by polymerization.

(1) Ring-opening polymerization Production of a polymer by ring-opening polymerization can be performed by a known ring-opening polymerization reaction for a norbornene-based compound, and a monomer composition containing the norbornene-based compound is polymerized as a polymerization catalyst and polymerized. It can be produced by ring-opening polymerization using a reaction solvent and, if necessary, a molecular weight regulator.

(A) Polymerization catalyst In the present invention, when the monomer composition is polymerized by a ring-opening (co) polymerization reaction, it is preferably 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 elements (For example, B, Al, etc.), a compound having a group IVA element (for example, Si, Sn, Pb, etc.), or a group IVB element (for example, Ti, Zr, etc.), The catalyst comprises 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)). In order to enhance the activity of the catalyst, an additive (C) described later may be further added.

Examples of the compound (A) include W, Mo or Re halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, and derivatives thereof. Alternatively, combinations thereof may be mentioned, and W and Mo compounds are preferable from the viewpoint of polymerization activity and practicality, and halides, oxyhalides and alkoxyhalides thereof are particularly preferable. Moreover, you may use the mixture of 2 or more types of compounds which produce | generate the said compound by reaction. In addition, these compounds are suitable complexing agents such as P (C ₆ H ₅ ) ₅ , C ₅ H ₅ N
It may be complexed by.

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 , ReO
OBr 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, W (CO) ₅ · P (C ₆ H ₅ ) ₃ , W (CO) ₃ · (CH ₃ CN) _{3 and the} like. Of these compounds, MoCl ₅ , Mo (OC ₂ H ₅ ) ₂ Cl ₃ , WCl ₆ , W (OC ₂ H ₅ ) ₂ Cl _{3 and the} like are particularly preferred.

As 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, (n-C 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 SiH, (n—C ₆ H ₁₃ ) ₃ Al, (N-C ₄ H ₁₇ ) ₃ Al, LiH, NaH, B ₂ H ₆ , NaBH ₄ , AlH ₃ , LiAlH ₄ , BiH _4, TiH _{4 and the} like can be mentioned. Moreover, the mixture of 2 or more types of compounds which produce | generate these compounds by reaction can also be used. Of these compounds, (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 are preferable.

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) simple substance boron, BF ₃ , BCl ₃ , B (On-C ₄ H ₉ ) ₃ , (C ₂ H ₅ O ₃ ) ₂ , BF,
Non-organometallic compounds of boron such as B ₂ O ₃ and H ₃ BO ₃ , non-organometallic compounds of silicon 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 S—Cl or N—Cl groups such as trichloromelamine, N-chlorosuccinimide, phenylsulfenyl chloride and the like.

  The amount of the metathesis catalyst used is such that the molar ratio of the compound (A) to the total monomers to be subjected to polymerization (compound (A): total monomers) is usually from 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 composition or catalyst to be used for the polymerization is dissolved and the catalyst is not deactivated. Although it will not specifically limit if a compound melt | dissolves, For example, alkanes, such as pentane, hexane, heptane, octane, nonane, decane; Cycloalkanes, such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; benzene, Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene; halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chloroform, tetrachloroethylene; halogenated aryl compounds such as chlorobenzene; ethyl acetate, acetic acid n-butyl And saturated carboxylic acid esters such as iso-butyl acetate, methyl propionate, and dimethoxyethane; and ethers such as dibutyl ether, tetrahydrofuran, and dimethoxyethane. These can be used alone or in admixture of two or more. Such a solvent can be used not only as a solvent for dissolving the norbornene-based compound, copolymerizable monomer and / or metathesis catalyst, but also as a solvent constituting a molecular weight regulator solution.

The amount of the solvent used is such that the weight ratio of the solvent to the monomer composition used for polymerization (solvent: monomer composition) is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. 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 can also be adjusted by allowing a 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, Aromatic vinyl compounds such as 4-methylstyrene, 2-methylstyrene and 4-ethylstyrene can be exemplified, 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 modifier is 0.005-0.6 mol normally with respect to 1 mol of monomers with which a ring-opening polymerization reaction is provided, 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 or ring-opening copolymerization of the norbornene compound and a copolymerizable monomer. Conjugated diene compounds such as polybutadiene, polyisoprene, styrene-butadiene copolymers, ethylene-nonconjugated diene copolymers, polynorbornene, etc., unsaturated hydrocarbons containing two or more carbon-carbon double bonds in the main chain A monomer composition containing a norbornene compound may be subjected to ring-opening polymerization in the presence of a polymer.

(Hydrogenation reaction)
The polymer obtained by the ring-opening polymerization reaction has an olefinically unsaturated bond in the molecule. Since the olefinically unsaturated bond present in the polymer molecule may cause deterioration such as coloring over time or gelation, it is preferable to perform a hydrogenation reaction that converts this olefinically unsaturated bond to a saturated bond. .

  In the hydrogenation reaction, a known hydrogenation catalyst is added to an ordinary method, that is, a polymer solution containing an olefinically unsaturated bond, and hydrogen gas at atmospheric pressure to 300 atm, preferably 3 to 200 atm, is added thereto. The reaction can be carried out at 0 to 200 ° C, preferably 20 to 180 ° C.

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

  When the polymer obtained by the above method has an aromatic group in the molecule, the aromatic group does not cause deterioration such as coloring over time or gelation, but rather is advantageous in mechanical properties and optical properties. Therefore, it is not always necessary to hydrogenate such an aromatic group.

  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. These catalysts 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

(2) 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 composition containing the norbornene compound is used as a polymerization catalyst. Depending on the case, it can be produced by addition polymerization using a solvent for polymerization reaction and, if necessary, a molecular weight regulator.

Examples of the polymerization catalyst used for addition polymerization include known single catalysts such as palladium, nickel, cobalt, titanium, and zirconium, and multi-component catalysts. However, the polymerization catalyst used in the present invention is limited to these. It is not something.
In addition, as a solvent used in the addition polymerization reaction, a monomer composition or a catalyst to be subjected to polymerization is dissolved, the catalyst is not deactivated, and a generated addition polymer is dissolved. For example, cycloaliphatic hydrocarbon solvents such as cyclohexane, cyclopentane, and methylcyclopentane; aliphatic hydrocarbon solvents such as hexane, heptane, and octane; aromatics such as toluene, benzene, xylene, and mesitylene Group hydrocarbon solvents; halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene and the like. These can be used alone or in admixture of two or more.

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

(Characteristics of norbornene polymer)
The norbornene-based polymer used in the present invention preferably has an intrinsic viscosity [η] _inh in chloroform at 30 ° C. of preferably 0.2 to 2.0 dl / g, more preferably 0.35 to 1.0 d.
1 / g, particularly preferably 0.4 to 0.85 dl / g, and the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000. It is preferably 15,000 to 250,000, and the weight average molecular weight (Mw) is 10,000 to 2,000,000, more preferably 20,000 to 1,000,000, and particularly preferably 30,000 to 500,000. When the intrinsic viscosity [η] _inh , the number average molecular weight and the weight average molecular weight are in the above ranges, the norbornene polymer is excellent in mechanical strength and can be easily damaged.

  The glass transition temperature (Tg) of the norbornene-based polymer is usually 120 ° C. or higher, preferably 130 ° C. or higher. When Tg is within the above range, a norbornene polymer film having high reliability even in long-term use can be obtained.

Further, the water vapor permeability of the norbornene-based polymer is preferably 5 to 200 (as a value measured in accordance with the humidity sensor method of JIS K7129 under the conditions of a measurement temperature of 40 ° C. and a relative humidity of 90% RH. g · 25 μm / m ² · 24 hr), particularly preferably 50 to 150 (g · 25 μm / m ² · 24 hr). If the water vapor transmission rate is less than 5 (g · 25 μm / m ² · 24 hr), it is not preferable because moisture drying of the polarizing film is not successful during the production of the polarizing plate. On the other hand, if it exceeds 200 (g · 25 μm / m ² · 24 hr), water permeates into the polarizing film inside the polarizing plate in a high-temperature and high-humidity atmosphere, which is not preferable.

(UV absorber)
In the present invention, the norbornene-based polymer film may contain an ultraviolet absorber, and in that case, it is preferable to use a benzotriazole-based ultraviolet absorber. The ultraviolet absorber absorbs ultraviolet rays, thereby suppressing the generation of active radical species that cause the norbornene-based polymer to deteriorate, preventing coloring and transparency from being deteriorated due to the deterioration, and ultraviolet rays to the polarizing film. Has a role of preventing the polarization film from being deteriorated.
The melting point of the benzotriazole ultraviolet absorber is preferably Tg−35 ° C. to Tg + 75 ° C., particularly preferably Tg−30 ° C. to Tg + 70 ° C. with respect to the glass transition temperature (Tg) of the norbornene polymer. When the melting point is lower than Tg-35 ° C., there is a problem that the volatility of the ultraviolet absorber is increased and the ultraviolet absorber or a decomposition product thereof adheres to a film or a film forming machine. On the other hand, if the melting point is higher than Tg + 75 ° C., the ultraviolet absorber bleeds on the film surface during film molding and the like, and the melting point is high during the cooling process, so it cannot be compatible and solidifies on the surface. There is a problem of sticking.

Examples of the benzotriazole ultraviolet absorber include 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- [2H-benzotriazol-2-yl] phenol] 2- (2H-1,2,3-benzotriazol-2-yl) -4,6-di-tert-butylphenol, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- ( 3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis- (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 ′-(1-methyl-1-phenylethyl) -5 ′-(1,1,3,3-tetramethylbutyl) -benzotriazole and the like.
Of these, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- [2H-benzotriazol-2-yl] phenol] is particularly preferably used.
In the present invention, an ultraviolet absorber other than benzotriazole may be used in combination as the ultraviolet absorber. Examples of ultraviolet absorbers that may be used in combination include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, tetrakis [methylene-3- (3,5-ditert-butyl-4hydroxyphenyl) propionate. ] Methane etc. are mentioned.

The addition amount of the ultraviolet absorber is usually 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the norbornene polymer. When the addition amount of the ultraviolet absorber is less than 0.1 parts by weight, a sufficient ultraviolet absorption effect is not seen, and the effect of the present invention is hardly exhibited. Moreover, when it exceeds 20 weight part, the light transmittance in the visible region of the obtained film may fall.
Moreover, the ratio of the benzotriazole type | system | group ultraviolet absorber in a total ultraviolet absorber is 10 weight% or more normally, Preferably it is 50 weight% or more.

(Other ingredients)
In the present invention, an additive such as an antioxidant can be further added to the norbornene polymer as long as the effects of the present invention are not impaired.
Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.
Moreover, when manufacturing a norbornene-type polymer film by the solution casting method mentioned later, manufacture of a resin film can be made easy by adding a leveling agent and an antifoamer.

  These additives may be mixed together with the norbornene polymer when producing the norbornene polymer film used in the present invention, or may be added in advance by adding the norbornene polymer. May be. 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 2.0 parts by weight, based on 100 parts by weight of the norbornene polymer. Part is desirable.

(Manufacturing method of norbornene polymer film)
The norbornene polymer film used in the present invention is cast by directly melt-molding the norbornene polymer or the resin composition containing the norbornene polymer and the additive, or by dissolving in a solvent. (Cast molding) can be suitably molded.

(A) Melt molding The norbornene polymer film used in the present invention is manufactured by melt extrusion molding the norbornene polymer or the resin composition containing the norbornene polymer and the additive. Can do.

(B) Casting The norbornene-based polymer film used in the present invention is prepared by casting a liquid resin composition obtained by dissolving the norbornene-based polymer and, if necessary, the additive in a solvent, on a suitable substrate. It can also be manufactured by removing. For example, the norbornene polymer film is obtained by applying the liquid resin composition 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 polymer 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 is in the above range, the norbornene-based polymer film having a desired function can be obtained because the film is less likely to be deformed or changed with time.

  Although the thickness of the norbornene-type polymer film used by this invention is not specifically limited, Usually, 5-500 micrometers, Preferably it is 10-150 micrometers, More preferably, it is desirable that it is 20-100 micrometers. When the thickness of the film is in the above range, a film having sufficient strength can be obtained, and a film having good birefringence, transparency, and appearance can be obtained.

The norbornene polymer 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.
Moreover, the norbornene-type polymer film used by this invention may give the surface treatment in order to improve adhesiveness with the adhesive bond layer mentioned later. Examples of the surface treatment include primer treatment, plasma treatment, corona treatment, alkali treatment, and coating treatment.

Among the above surface treatments, the norbornene polymer film and the adhesive layer can be firmly adhered by using a corona treatment in particular. As corona treatment conditions in this case, the irradiation amount of corona discharge electrons is preferably 1 to 1000 W / m ² / min, and 10 to 100 W / min.
m ² / min is more preferable. When the irradiation amount is in the above range, the treatment effect does not reach the inside of the film, and a sufficient surface modification effect can be obtained without altering the film. Further, this corona treatment may be performed not only on the surface in contact with the adhesive layer but also on the opposite surface.

<Method for producing retardation film>
The norbornene-based polymer film used in the present invention can be used as a retardation film by performing a stretching treatment.
As a stretching method, a method of stretching the resin film uniaxially or biaxially 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 treatment, a method of simultaneously stretching in two directions, or a method of performing a stretching treatment in a direction different from the direction of the stretching treatment after the uniaxial stretching treatment can be applied. At this time, the intersection angle of the two stretching axes is appropriately determined according to the characteristics required for the target optical film (retardation film), and is not particularly limited, but is usually in the range of 60 to 120 degrees. The stretching speed is usually 1 to 5,000% / min, preferably 50 to 1,000% / min, more preferably 100 to 1,000% / min, and particularly preferably 100 to 1,000% / min. It is 500% / min, and may be the same or different in each stretching direction.

  The stretching treatment temperature is not particularly limited, but based on the glass transition temperature (Tg) of the norbornene polymer used, Tg ± 30 ° C., preferably Tg ± 15 ° C., more preferably Tg−5 to Tg + 15. It is in the range of ° C. 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 in that the refractive index ellipsoid can be easily controlled.

  The draw ratio is appropriately determined according to the properties required for the target optical film, and is not particularly limited, but is usually 1.01 to 10 times, preferably 1.03 to 5 times, and more preferably 1.03. ~ 3 times. When the draw ratio is in the above range, the retardation of the obtained stretched film can be easily controlled. 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 can give a retardation to transmitted light as a result of the orientation of the molecules by the stretching treatment. This retardation is determined by the stretching ratio, the stretching temperature, or the thickness of the film. It can be controlled by such factors.

  The thickness of the norbornene-based polymer 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 20 to 100 μm.

<Polarizing plate>
The polarizing plate of the present invention is a laminate in which the norbornene-based polymer film is bonded to at least one surface of the polarizing film via the adhesive. The norbornene-based polymer film is preferably one in which the norbornene-based polymer film that is not in contact with the liquid crystal cell contains the ultraviolet absorber, and particularly preferably, the double-sided norbornene-based polymer film has the ultraviolet absorber. It contains.

  Such a polarizing plate can be produced by, for example, uniformly applying the above-mentioned adhesive on one surface of a norbornene polymer film or a polarizing film and overlaying the other film (film) on the coated surface with a roll or the like. And a method of heating as necessary. The temperature at the time of application of the adhesive is usually in the range of 15 to 40 ° C, and the bonding temperature is usually in the range of about 15 to 30 ° C.

  At this time, the adhesive may be applied so that the thickness of the adhesive layer after drying is preferably 0.01 to 50 μm, more preferably 0.01 to 30 μm, and particularly preferably 0.01 to 3 μm. preferable. When the thickness of the adhesive layer after drying is in the above range, the transparency of the polarizing plate is maintained, and the norbornene polymer film and the polarizing film are bonded with sufficient adhesive force, and delamination of these occurs. Hateful.

  The polarizing plate according to the present invention has a good polarizing function, excellent properties such as heat resistance and chemical resistance, and is not easily peeled off, deformed or changed in polarization degree even in long-term use, and has high reliability. And has excellent durability. Such a polarizing plate can be suitably used for applications such as a liquid crystal display device.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the following description, “part” means “part by weight” unless otherwise specified.
Moreover, the glass transition temperature, the single-piece | unit transmittance | permeability, the measurement of the polarization degree, and the adhesive force test (adhesive force of a polarizing film and a norbornene-type resin film) of the polarizing plate were implemented with the following method.
<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc., the glass transition temperature (hereinafter also referred to as “Tg”) was measured in a nitrogen atmosphere under a temperature rising rate of 20 ° C./min.
<Moisture permeability>
Measurement was performed using L80-4000 manufactured by LYSSY under the conditions of a measurement temperature of 40 ° C. and a relative humidity of 90% RH in accordance with the JIS K7129 humidity sensor method.
<Phase difference of transmitted light>
Using “KOBRA-21ADH” manufactured by Oji Scientific Instruments, phase differences R0 (550) and Rth (550) at a wavelength of 550 nm were measured.
When the maximum refractive index in the film plane at a light wavelength of 550 nm is nx, the refractive index in the direction orthogonal to nx in the film plane is ny, the refractive index in the film thickness direction is nz, and the film thickness is d [nm]. The retardation in the film plane is R0 (550) [nm] = (nx−ny) × d, and the retardation in the film thickness direction is Rth (550) [nm] = {(nx + ny) / 2−nz} × d. It was.
<Single transmittance>
The single transmittance of the polarizing plate was measured using a spectrophotometer V7300 manufactured by JASCO Corporation.
<Degree of polarization>
The polarization degree of the polarizing plate was measured using a spectrophotometer V7300 manufactured by JASCO Corporation.
<Adhesive strength test of polarizing plate (adhesive strength between polarizing film and norbornene resin film)>
The adhesion between the polarizing film of the polarizing plate and the norbornene-based resin film was peeled at an angle of 90 degrees using a tensile testing machine (manufactured by Instron Japan Co., Ltd., universal material testing machine 5564 type). Evaluation was performed under the condition of a tensile speed of 50 mm / min.

[Synthesis Example 1] (Synthesis of norbornene resin)
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 227.5 parts, bicyclo [2.2.1] hept-2-ene 22.5 parts, 1-hexene (molecular weight regulator) 18 parts, toluene (for ring-opening polymerization reaction) (Solvent) 750 parts were charged into a nitrogen-substituted reaction vessel, and this solution was heated to 60 ° C. Next, 0.62 part of a toluene solution of triethylaluminum (1.5 mol / l) and tungsten hexachloride modified with t-butanol / methanol (t-butanol: methanol: tungsten) were added to the solution in the reaction vessel. 37 parts of a toluene solution (concentration 0.05 mol / l) of 35 mol: 0.3 mol: 1 mol) was added, and this system was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction. Thus, a ring-opening copolymer solution was obtained. The polymerization conversion rate in this polymerization reaction was 97%.

The autoclave was charged with 4,000 parts of the ring-opening copolymer solution thus obtained, and RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ 0.48 part was added to the ring-opening copolymer solution. And the hydrogenation reaction was carried out 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 160 ° C.
After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. The reaction solution was poured into a large amount of methanol to separate and collect the coagulated product, and dried to obtain a hydrogenated cyclic olefin resin A. The Tg of Resin A was 140 ° C. Moreover, Mn, Mw, and Mw / Mn in terms of polystyrene measured by the GPC method were 24,000, 67,000, and 2.8, respectively, and the intrinsic viscosity (η _inh ) was 0.49 dl / g. . Further, the moisture permeability of the resin A was 110 (g · 25 μm / m ² · 24 hr).

[Production Example 1] (Film forming)
Resin A obtained in Synthesis Example 1 is dissolved in toluene so as to have a concentration of 30% (solution viscosity at room temperature is 30,000 mPa · s), and pentaerythrityl tetrakis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate] with respect to 100 parts by weight of resin and, as a benzotriazole compound, 2,2′-methylenebis [4- (1,1,3 , 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] was added, a metal fiber sintered filter with a pore diameter of 5 μm manufactured by Nippon Pole was used, and the differential pressure was 0. The solution was filtered while controlling the flow rate of the solution so that it was within 4 MPa.
The resin solution produced by the above method is extruded downstream using a gear pump while degassing toluene with a 3-stage vent using a twin screw extruder (manufactured by Toshiba Machine Co., Ltd .; TEM-48). The resin flown out of the strand die was cooled in a cooling water tank, then sent to a strand cutter, and cut into rice grains to obtain a granulated resin.
The granulated resin was dried at 100 ° C. for 4 hours in a nitrogen atmosphere, then sent to a single screw extruder (90 mmΦ), and melted at 270 ° C., and quantitative extrusion was performed with a gear pump, with a nominal opening of 10 μm. Using a metal fiber sintered filter made by Nippon Seisen, melt filtration is performed, and a coat hanger die (1700 mm width) is used to form a film at 270 ° C. with a gap at the coat hanger die outlet of 0.5 mm. Extruded. The die land length (the length of the parallel part of the die exit) of the die used at this time was 20 mm. The distance from the die exit to the roll crimping point is set to 65 mm, and the extruded film is sandwiched between a 250 mmφ mirror surface roll with a surface roughness of 0.1 S and a metal belt with a thickness of 0.3 mm to gloss the film surface. Transferred to the surface. The metal belt (width 1650 mm) is held by a rubber-coated roll (the diameter of the roll to be held is 150 mmΦ) and a cooling roll (roll diameter 150 mm), and a commercially available sleeve type transfer roll (manufactured by Chiba Machine Industry) is used. And transcribed. The roll interval during transfer was 0.35 mm, and the transfer pressure was 0.35 MPa.
The peripheral speed of the outer periphery of the mirror surface roll at this time was 10 m / min. At this time, the temperature of the mirror surface roll was set to 135 ° C. using an oil temperature controller, and the temperature of the rubber coating roll was set to 125 ° C.
A cooling roll 1 having a diameter of 250 mm is arranged on the downstream side of the mirror surface roll, and the film peeled off from the mirror surface roll is cooled for 2.1 seconds until the film is pressure-bonded to the cooling roll 1 set to 125 ° C. .
After cooling roll 2, the film is peeled off at a peeling tension of 0.4 MPa · cm, a masking film is bonded to one side, wound up by a winder, a film having a thickness of 150 μm, a width of 1500 mm and a length of 2000 m (I-1) was obtained. The residual solvent amount of the obtained film was 0.1%, the total light transmittance was 93%, and the glass transition temperature (Tg) was 140 ° C. The film thickness variation was 1 μm (0.7%).

Using the film (I-1) obtained above, in the layer where the temperature distribution in the stretching machine furnace was controlled within 163 ± 0.2 ° C., the longitudinal speed was 2.2 m in the furnace direction at 8.0 m / min. Doubled, uniaxial stretching of the film longitudinal direction without fixing the film width direction was performed to obtain a retardation film having R0 of 351 nm, R0 variation of ± 3 nm, and optical axis of 0 ± 1 degree with respect to the film longitudinal direction. Further, using the obtained uniaxially stretched film, the temperature distribution in the stretching machine furnace was controlled within 153 ± 0.2 ° C., and the speed in the furnace was 8.0 m / min. A stretched film (I-2) was obtained by uniaxial stretching with the film longitudinal direction fixed to 3 times. The obtained stretched film had a thickness of 43 μm, R0 of 20.5 nm, and Rth of 186 nm.
Similarly, in a tenter-conveying horizontal stretching furnace in which the film (I-1) was previously slit into a width of 750 mm and the temperature distribution in the stretching machine furnace was controlled within 165 ± 0.2 ° C., the in-furnace speed A stretched film (I-3) was obtained by uniaxially stretching at a rate of 3.1 m in the direction perpendicular to the longitudinal direction of the film at 8.0 m / min and in the width direction of the film with the longitudinal direction of the film fixed. The obtained stretched film had a thickness of 48 μm, R0 of 100.0 nm, and Rth of 80 nm.

[Production Example 2] (Production of Polarizing Film)
PVA was pre-stretched at a stretch ratio of 3 in a dyeing bath at a temperature of 30 ° C. consisting of an aqueous solution having an iodine concentration of 0.03% by weight and a potassium iodide concentration of 0.5% by weight. A post-stretching process at a stretching ratio of 2 in a crosslinking bath at a temperature of 55 ° C. consisting of an aqueous solution having a boric acid concentration of 5% by weight and a potassium iodide concentration of 8% by weight, followed by drying treatment allows polarization. A membrane was obtained.

[Preparation Example 1] (Adjustment of adhesive)
Monomer component by mixing 69 parts by mass of cyclohexyl methacrylate as monomer (A-1) and 25 parts by mass of 2-ethylhexyl acrylate, 3 parts by mass of 2-hydroxyethyl methacrylate and 3 parts by mass of methacrylic acid as other monomers. (Mixture of monomers) was prepared.
In an autoclave equipped with a stirrer, a temperature controller, and a reflux condenser, 420 parts by mass of water, 2 parts by mass of trade name “KH1025” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as an emulsifier, and potassium persulfate 0 as a polymerization initiator 3 parts by mass, and the temperature was raised to 75 ° C.
In this autoclave, 100 parts by mass of the above monomer component, 1 part by mass of a trade name “KH1025” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and 146 parts by mass of water are added as an emulsifier, and then emulsified by stirring. By carrying out polymerization at 75 ° C. while continuously feeding 247 parts by mass of the total amount of the pre-emulsion prepared by performing the polymerization for 3 hours, and further stirring at 80 ° C. for 3 hours to complete the polymerization reaction. An aqueous emulsion containing the polymer (A) was obtained.
The solid content concentration of the aqueous emulsion was 15.1%, and the average particle size of the polymer particles made of the polymer (A) was 65 nm.
After adjusting the aqueous emulsion containing the obtained polymer (A) to pH 7.5 with ammonia, PVA (trade name “GOHSENOL GL-03”, manufactured by Nippon Synthetic Chemical Co., Ltd.) 15 is used as the polymer (B) component. 200 parts by mass (30 parts by mass as the polymer (B)) was added to expand the sales to prepare an adhesive 1. Table 1 shows the formulation of the adhesive.

[Preparation Examples 2 to 4, 7 and Comparative Preparation Example 1]
An aqueous emulsion containing the polymer (A) was obtained in the same manner as in Preparation Example 1 except that the monomer components shown in Table 1 were used, and the polymer (B) shown in Table 1 was obtained using the obtained aqueous emulsion. Adhesives 2 to 4 and 7 and comparative adhesive i were prepared in the same manner as in Preparation Example 1 except that they were used. Table 1 shows the formulation of the adhesive.

[Preparation Example 5]
Monomer component by mixing 69 parts by mass of cyclohexyl methacrylate as monomer (A-1) and 25 parts by mass of 2-ethylhexyl acrylate, 3 parts by mass of 2-hydroxyethyl methacrylate and 3 parts by mass of methacrylic acid as other monomers. Was prepared.
In an autoclave equipped with a stirrer, a temperature controller, and a reflux condenser, 467 parts by mass of water and 10% of PVA (trade name “GOHSENOL GL-03”, manufactured by Nippon Synthetic Chemical Co., Ltd.) as a polymer (B) component The aqueous solution was charged with 300 parts by mass (30 parts by mass as the polymer (B)) and 0.3 part by mass of potassium persulfate as the polymerization initiator, and the temperature was raised to 75 ° C.
While continuously supplying 100 parts by mass of the monomer component to the autoclave over 3 hours, the monomer component is polymerized at 75 ° C., and further stirred at 80 ° C. for 3 hours to conduct a polymerization reaction. Was completed to obtain an aqueous emulsion containing a graft copolymer obtained by graft polymerization of the polymer (A) component and the polymer (B) component. The solid content concentration of this aqueous emulsion was 15.0%, and the average particle size of the polymer particles was 80 nm. The aqueous emulsion thus obtained was adjusted to pH 7.5 with ammonia to prepare an adhesive 5. Table 1 shows the formulation of the adhesive.

[Preparation Example 6]
Adhesive 6 was prepared in the same manner as Preparation Example 5 except that the polymer (B) shown in Table 1 was used. Table 1 shows the formulation of the adhesive.
[Comparative Preparation Example 2]
An aqueous emulsion was obtained in the same manner as in Preparation Example 1, and the aqueous emulsion was adjusted to pH 7.5 with ammonia without using the polymer (B) component to prepare a comparative adhesive ii. Table 1 shows the formulation of the adhesive.

[Example 1]
The film (I-2) and the TAC film (hereinafter referred to as “film (II)” obtained in Production Example 1 are attached to both surfaces of the polarizing film obtained in Production Example 2 via the adhesive 1 obtained in Preparation Example 1. Was adhered so as to be film (I-2) / adhesive layer / polarizing film / adhesive layer / film (II) to obtain a polarizing plate of the present invention. In addition, as the film (II), a cellulose resin film “TDY80uL” manufactured by Fuji Film Co., Ltd. was used. The moisture permeability of the film (II) was 700 (g · 25 μm / m ² · 24 hr) and the thickness was 80 μm.
At the time of bonding, first, the surface of the film (I-2) is corona-treated under the condition of 30 W · min / m ² , the adhesive 1 is dropped on the treated surface, and the polarizing film is immediately overlaid and pressed by a nip roll. (Nip temperature 23 ° C., nip pressure 100 N / cm), this was dried for 20 minutes in a constant temperature bath at 80 ° C. under a load of 30 g per 1 cm of film width, and then for 2 days in a constant temperature bath at 50 ° C. It preserve | saved and the polarizing plate was produced.
The single transmittance and polarization degree of the obtained polarizing plate and the adhesive strength of the adhesive were measured. The measurement results are also shown in Table 1.

[Examples 2-7, Comparative Examples 1-3]
A polarizing plate was produced by the same method as in Example 1 except that the adhesive and film shown in Table 1 were used, and the single transmittance and polarization degree of the obtained polarizing plate and the adhesive strength of the adhesive were measured. . The measurement results are also shown in Table 1.

*1)：商品名「ゴーセノールＧＬ−０３」、日本合成化学社製
*2)：商品名「ポバールＫＬ３１８」、クラレ社製
*3)：商品名「ポバールＭ２０５」、クラレ社製
*4)：商品名「デナコールＥＸ−４２１」、ナガセケムテックス社製
*5)：商品名「デュラネートＷＴ３０−１００」、旭化成ケミカルズ社製

* 1): Trade name “GOHSENOL GL-03”, manufactured by Nippon Synthetic Chemical Co., Ltd.
* 2): Product name “Poval KL318”, manufactured by Kuraray Co., Ltd.
* 3): Product name “Poval M205”, manufactured by Kuraray Co., Ltd.
* 4): Product name “Denacol EX-421”, manufactured by Nagase ChemteX Corporation
* 5): Product name “Duranate WT30-100”, manufactured by Asahi Kasei Chemicals Corporation

Claims (9)

On at least one side of the polarizing film,
(A) A norbornene polymer film is laminated through an adhesive layer containing a polymer component having a repeating unit derived from a (meth) acrylic acid ester having an alicyclic structure, and (B) a polyvinyl alcohol component. The polarizing plate characterized by the above-mentioned. The polarizing plate according to claim 1, wherein the adhesive layer contains a mixture of (A) a polymer and (B) polyvinyl alcohol. The polarizing plate according to claim 1, wherein the adhesive layer contains a graft copolymer of (A) a polymer and (B) a polyvinyl alcohol. The norbornene-based polymer film is a film comprising a polymer obtained by (co) polymerizing a monomer containing at least one compound represented by the following formula (1): The polarizing plate as described in any one.

(In the formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, or a monovalent group that may contain oxygen, nitrogen, sulfur or silicon. R ¹ and R ² Or R ³ and R ⁴ may be bonded to each other to form an alkylidene group, or R ¹ and R ² , R ³ and R ⁴ , or R ² and R ³ may be bonded to each other. And may form a monocyclic or polycyclic carbocyclic or heterocyclic ring, where x is 0 or an integer of 1 to 3, and y is 0 or 1.) The polarizing plate as described in any one of Claims 1-4 whose norbornene-type polymer film is retardation film. The polarizing plate according to any one of claims 1 to 5, wherein the norbornene-based polymer film contains a benzotriazole-based ultraviolet absorber. A polarizing film and a norbornene polymer film,
(A) It has the process of adhere | attaching using the adhesive agent containing the polymer component which has a repeating unit derived from the (meth) acrylic acid ester which has alicyclic structure, and (B) polyvinyl alcohol component, It is characterized by the above-mentioned. The manufacturing method of a polarizing plate. The method for producing a polarizing plate according to claim 7, wherein the adhesive further contains (C) a water-soluble epoxy compound. The method for producing a polarizing plate according to claim 7, wherein the adhesive further contains (D) a water-dispersed isocyanate compound.