WO2008007590A1

WO2008007590A1 - Optical film, and use and production method thereof

Info

Publication number: WO2008007590A1
Application number: PCT/JP2007/063365
Authority: WO
Inventors: Naoki Sugiyama; Yosuke Fukuse; Masayuki Sekiguchi
Original assignee: Jsr Corporation
Priority date: 2006-07-12
Filing date: 2007-07-04
Publication date: 2008-01-17

Abstract

Disclosed is an optical film having antistatic properties, which is characterized in that a norbornene resin film (A) and an antistatic layer (B), which is made of an antistatic coating material containing a specific acrylic resin (b1) having a quaternary ammonium salt in a side chain and a curing agent (b2) composed of a polyethyleneimine and/or a polyhydroxyalkane polyglycidyl ether, are arranged in layers. Specifically disclosed is an optical film made of a norbornene resin, which film is excellent in characteristics such as adhesion, transparency, heat resistance and chemical resistance, while having excellent durability. This optical film maintains excellent antistatic properties over a long time. Also specifically disclosed are a method for producing the optical film, a polarizing plate using the optical film, and a liquid crystal display using the polarizing plate.

Description

Optical film, use thereof and production method

Technical field

The present invention relates to an optical film having antistatic ability, a use of the optical film, and a production method. More specifically, the present invention relates to an optical film having an antistatic ability, which has an antistatic layer formed on a norbornene-based resin film, and is suitably used for applications such as a polarizing plate, and uses and production methods thereof.

Background art

A polarizing plate (polarizing film) used for a liquid crystal display or the like is usually formed from a substrate (optical film) having excellent transparency and a polarizing film (polarizer). Further, the polarizing plate may be formed of a film (retardation film) provided with a function of stretching an optical film and imparting a retardation to transmitted light, and a polarizing film.

Conventionally, polycarbonate films, polyester films, polyacetylcellulose (TAC) films, and the like are used as optical films used as polarizing plate substrates or retardation films. The polarizing plate used may change the phase difference given to the transmitted light due to a small change in stress with a large photoelastic coefficient. Polyacetylcellulose (TAC) film is a water-absorbing material with low heat resistance. Due to its high properties, there is a problem that a polarizing plate using the same is easily deformed depending on the use environment and is easily optically changed!

[0004] By the way, norbornene-based resin is excellent in transparency, heat resistance, chemical resistance, and the like, and therefore has been attracting attention as a material for various optical components, and has been particularly suitably used for optical film applications. Patent Document 1 proposes a polarizing film in which a norbornene-based resin sheet is stacked as a protective layer on a polarizing film. Since such a polarizing film is excellent in water resistance, moisture resistance, heat resistance, transparency, durability against adhesive materials, etc., it is expected to be used for applications such as liquid crystal displays.

[0005] However, since norbornene-based resin and other resin materials have poor adhesiveness, polarizing plates using norbornene-based resin films are difficult to manufacture and can be used for a long time. And peel off There was a problem of being prone to peeling!

[0006] Norbornene resin has a low water absorption property, so the optical film made of norbornene-based resin can be easily charged immediately after it is made into a film roll or just by feeding the film roll. Since this may occur, there is a problem in that foreign substances of environmental power are adsorbed, and when they are laminated with other materials, foreign substances are easily trapped between the layers. For example, when a polarizing plate is formed by stacking a norbornene-based resin film with a polybulal alcohol (PVA) polarizer, if there is foreign matter mixed in, the part becomes a point defect, which is obtained. When the obtained polarizing plate is used for a display or the like, there is a problem that a bright spot is generated.

[0007] As a method for preventing charging at the time of lamination, there has been proposed a method in which an adhesive used between a norbornene-based resin film and another material to be laminated is an antistatic type. In this method, the adhesiveness of the adhesive may be weakened, and it is not possible to reduce the peeling charge when the film roll is fed out. Therefore, it is desirable to prevent the norbornene-based resin film itself from being charged. And

[0008] By the way, a polarizing plate in which a norbornene-based resin film having a phase difference is directly attached to a polarizer such as PVA, the norbornene-based resin film itself has low moisture absorption and excellent hardness, and is used as a protective film. Since it also plays a role, it is possible to simplify the process that does not require the attachment of a protective film for the polarizing plate, and it has the advantage that transparency can be easily secured due to the small number of layers.

[0009] When a liquid crystal display is assembled by attaching such a polarizing plate to a liquid crystal panel, an adhesive layer and a living film for protecting it are provided in advance on the surface to be attached, and the living film is peeled off at the time of attachment. The method of adhering the polarizing plate and the liquid crystal panel is suitably employed because the process is simple.

[0010] While peeling force, peeling electrification occurs when the living film on the polarizing plate is peeled off.

However, there was a problem that the liquid crystal display obtained was charged immediately after production, and product inspection could not be performed without static electricity removal after standing, resulting in poor production efficiency.

[0011] For this reason, there has been a demand for the appearance of an optical film made of norbornene-based resin in which charging is sufficiently suppressed.

[0012] As a technique for preventing charging of a film or the like, an antistatic agent is allowed to act on the film. However, conventional antistatic agents such as surfactants may interfere with adhesiveness when used in large amounts, and because the antistatic agent has a low molecular weight, friction, There is also a problem that the antistatic agent falls off due to dissolution, bleed-out, etc. and the antistatic effect is lowered.

[0013] As a result of earnest research under such circumstances, the present inventor has an antistatic layer formed on the surface of an antistatic coating material containing a specific acrylic resin and a curing agent. The present inventors have found that the norbornene-based resin film has sufficient antistatic ability and can exhibit the antistatic ability for a long time, and has completed the present invention.

Patent Document 1: JP-A-6-51117

Disclosure of the invention

Problems to be solved by the invention

[0014] The present invention is a norbornene-based film that is excellent in adhesion to a polarizing film, is excellent in properties such as transparency, heat resistance, and chemical resistance, and can maintain excellent antistatic performance over a long period of time. Oil optical film and its manufacturing method, peeling and deformation occur even after long-term use << high reliability and less contamination of foreign matter from the environment in its manufacturing process! / It is an object of the present invention to provide a polarizing plate using a film and a liquid crystal display using the polarizing plate.

Means for solving the problem

[0015] The optical film of the present invention comprises:

(A) a norbornene-based resin film,

(B) (bl) an acrylic resin having a quaternary ammonium salt represented by the following formula (i) in the side chain, and (b2) a curing comprising polyethyleneimine and Z or polyhydroxyalkane polyglycidyl ether. And an antistatic layer formed of an antistatic coating material containing an agent.

[0016] -COO-Q'-N CQ ² ) X "-(i)

a b

(In the formula (i), Q ¹ is a divalent hydrocarbon group having 1 to 6 carbon atoms, Q ² is a monovalent hydrocarbon group having 1 to 3 carbon atoms, and X is a chlorine atom or a fluorine atom. Or — Q ³ — SO (where Q ³ is simply

Four

A bond, a methylene group or an ethylene group; A and b are integers of 1 or 2 However, a + b = 3). Q ² , Q ³ and X may be the same or different when there are a plurality of Q ² , Q ³ and X. )

In such an optical film of the present invention, the antistatic coating material preferably further contains a filler.

The optical film of the present invention has a surface resistance value on the antistatic layer side of 1 × 10 ⁶ to 1 × 10 ^12.

It is preferably in the range of Ω Z port.

[0018] The optical film of the present invention preferably has a wettability of the surface on the antistatic layer side measured in accordance with the method defined in JIS K6768 in the range of 50 to 70 mNZm! /.

In the optical film of the present invention, the acrylic resin (bl) preferably includes a structural unit derived from a (meth) acrylic acid ester having an alicyclic skeleton.

[0020] The optical film of the present invention preferably has a refractive index difference of 0.1 or less at a wavelength of 589 nm between the norbornene-based resin film (A) and the antistatic layer (B).

[0021] The optical film of the present invention preferably has a metal atom content of 0.1 wt% or less and a halogen atom content of 1 wt% or less in the antistatic layer (B).

[0022] The optical film of the present invention has a tensile modulus E 1 of a norbornene-based resin film (A) at room temperature and a tensile property of an antistatic layer (B) measured according to the method specified in JIS K7113. The rate E2 is preferably in the relationship E1> E2.

The optical film of the present invention is preferably a film obtained by stretching the norbornene-based resin film (A) in advance, and the retardation film of the present invention is such an optical film camera of the present invention.

[0024] The retardation film of the present invention is characterized by being obtained by stretching the optical film of the present invention.

[0025] The polarizing plate of the present invention is characterized by using at least one of the optical film and the retardation film of the present invention.

[0026] Such a polarizing plate of the present invention is a polarizing plate obtained by adhering the retardation film of the present invention to a polarizing film using an adhesive or a pressure-sensitive adhesive, and measured according to JIS K7113. The tensile elastic modulus E1 of the norbornene-based resin film (A), the tensile elastic modulus E2 of the antistatic layer (B), and the tensile elastic modulus E3 of the adhesive or adhesive are in the relationship of E1>E2> E3 That features It is said.

The polarizing plate of the present invention is preferably obtained by adhering the antistatic layer side of the optical film or retardation film to a polarizing film using an adhesive or an adhesive.

The liquid crystal display of the present invention is characterized by using the polarizing plate of the present invention.

[0029] The method for producing the optical film of the present invention comprises:

Charging comprising an acrylic resin (bl) having a quaternary ammonium salt represented by the following formula (i) in the side chain and a curing agent (b2) comprising polyethyleneimine and Z or polyhydroxyalkane polyglycidyl ether An anti-coating material is coated on the norbornene-based resin film (A) and dried to form an antistatic layer (B).

[0030] -COO-Q'-N CQ ² ) X "-(i)

a b

Four

A bond, a methylene group or an ethylene group; A and b are integers of 1 or 2 (where a + b = 3). Q ² , Q ³ and X may be the same or different when there are a plurality of Q ² , Q ³ and X. )

In such a method for producing an optical film of the present invention, the average surface roughness (Ra) force of the norbornene-based resin film on the surface on which the antistatic coating material is applied should be in the range of 0.3 to 2. Onm. preferable.

[0031] In the method for producing an optical film of the present invention, the wettability of the surface measured according to the method specified in JIS K6768 of the norbornene-based resin film (A) on the surface to which the antistatic coating material is applied is 50 Preferable to be in the range of ~ 70mNZm! / ,.

In the method for producing an optical film of the present invention, it is preferable that the acrylic resin (bl) includes a structural unit derived from a (meth) acrylic acid ester having an alicyclic skeleton.

[0033] In the method for producing an optical film of the present invention, the antistatic coating material is preferably an aqueous coating material. The antistatic coating material preferably further contains a filler.

[0034] In the method for producing an optical film of the present invention, the applied antistatic coating material is dried.

1) a primary drying step at 80 ° C or lower; 2) The glass transition temperature (Tg) of the norbornene-based resin film (A) is preferably carried out by a multi-stage drying process including a secondary drying process at a temperature exceeding 30 ° C. In such a method for producing an optical film of the present invention, the film is preferably stretched in the secondary drying step.

[0035] In the method for producing an optical film of the present invention, the halogen atom content in the acrylic resin (bl) is preferably 1% by weight or less.

The invention's effect

[0036] According to the present invention, it has excellent adhesion to an optical material that is another material force such as a polarizing film, and is excellent in properties such as transparency, heat resistance, and chemical resistance, and has excellent antistatic ability. An optical film made of norbornene-based resin that is maintained for a long period of time and has excellent durability, its manufacturing method, high reliability that prevents peeling and deformation even during long-term use, and its manufacturing process In addition, it is possible to provide a polarizing plate using the optical film, and a liquid crystal display using the polarizing plate, in which foreign substances are less likely to be trapped from the environment! BEST MODE FOR CARRYING OUT THE INVENTION

[0037] The present invention will be specifically described below.

<<Optical film>>

The optical film of the present invention is an optical film having an antistatic ability in which an antistatic layer (B) is laminated on at least one surface of a norbornene-based resin film (A).

(A) Norbornene-based resin film

The norbornene resin constituting the norbornene resin film (A) used in the present invention is a monomer containing at least one compound having a norbornene skeleton (hereinafter also referred to as a norbornene compound)! It is a resin obtained by polymerizing or copolymerizing a monomer composition (hereinafter referred to as (co) polymerization) and hydrogenating as necessary.

The norbornene compound constituting the monomer or monomer composition is not particularly limited, and examples thereof include a norbornene compound represented by the following formula (1).

[0038] [Chemical 1]

[In the formula (1), Ri to R ⁴ each independently represents a hydrogen atom; a halogen atom; a substituted or unsubstituted group which may have a linking group containing oxygen, nitrogen, iodo or kaen; It represents a hydrocarbon group having 1 to 15 carbon atoms or other monovalent organic group. Here, R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form an alkylidene group. R ¹ and R ² , R ³ and R ^4, or R ² and R ³ are They may be bonded to each other to form a carbocycle or a heterocycle (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure). Good. The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring. X represents an integer from 0 to 3, and y represents 0 or 1. ]

Specific examples of the norbornene-based compound represented by the general formula (1) include, for example, the following compounds, but are not limited to these examples.

[0040] Bicyclo [2.2.1] Heptoe 2 (norbornene),

5-methylbicyclo [2.2.1] hepto-2

5 ethyl bicyclo [2.2.1] heptoe 2

5 cyclohexyl-bicyclo [2.2.1] hepto-2

5- Hue-Rubicyclo [2.2.1] heptoe 2

5— (4-biphenyl) monobicyclo [2. 2. 1] hept-2-ene,

5-methoxycarbo-rubicyclo [2.2.1] hepto-2

5 Phenoxycarbo-rubicyclo [2.2.1] hepto-2

5 Phenoxetylcarbo-rubicyclo [2. 2. 1] hepto-2-ene, 5-phenyl-bi-bicyclo [2. 2. 1] hepto-2-ene, 5-methyl 5-methoxycarbo-rubicyclo [ 2. 2. 1] Hepto-2-ene, 5-methyl-5 phenoxycarbo-rubicyclo [2. 2. 1] Hepto-2, 5-methyl-5-phenoxycetylcarbo-rubicyclo [2. 2. 1] Hepto-2 Yen 5—Bulbibicyclo [2. 2. 1] Heptou 2—Yen,

5-ethylidene bibicyclo [2. 2. 1] heptoe-2-ene,

5, 5-dimethylbicyclo [2.2.1] hepto-2-ene,

5, 6-dimethylbicyclo [2.2.1] hepto-2-ene,

5-Fluorobicyclo [2. 2. 1] hepto-2-ene,

5—black mouth bicyclo [2. 2. 1] heptoe 2-ene,

5-bromobromobicyclo [2.2.1] hepto-2-ene,

5, 6-difluoro-bicyclo [2.2.1] hepto-2-ene,

5, 6-dichloro-bicyclo [2.2.1] hepto-2-ene,

5, 6-jib mouth mobicyclo [2. 2. 1] heptoe 2-ene,

5-hydroxybicyclo [2.2.1] hepto-2-ene,

5-hydroxyethyl bibicyclo [2.2.1] hepto-2-ene,

5—Cyanobicyclo [2. 2. 1] Heptoe 2—

5-aminobicyclo [2. 2. 1] hepto-2-ene,

Tricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3-Yen,

Tricyclo [4. 4. 0. I ² ' ⁵ ]

7-methyl monotricyclo [4. 3. 0. I ² ' ⁵ ]

7 Echiru one tricyclo ^{^{[4. 3. 0. I 2 '5}} ] dec-one 3-E down, to 7-cyclopropyl carboxymethyl route re cyclo ^{^{[4. 3. 0. I 2' 5}} ] Deka 3 E down,

7—Fuel tricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3—

7— (4-biphenyl) monotricyclo [4. 3. 0. I ² ' ⁵ ] deca 3-en 7, 8-dimethyl-tricyclo [4. 3. 0. I ² ' ⁵ ] deca 1—Yen,

7, 8, 9-trimethyl-tricyclo [4. 3. 0. I ² ' ⁵ ]

8—Methyl monotricyclo [4. 4. 0. I ² ' ⁵ ]

8-Fuel tricyclo [4. 4. 0. I ² ' ⁵ ] Wunde force 1- 3-, 7-Fluorotricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3-- ,

7-chloro-tricyclo [4. 3. 0. I ² ' ⁵ ] 7 Promotricyclo [4. 3. 0. I ² ' ⁵ ]

7, 8 dichloro-tricyclo [4. 3. 0. I ² ' ⁵ ]

7, 8, 9 Trichloro-tricyclo [4. 3. 0. I ² ' ⁵ ]

7 Chloromethyl-tricyclo [4. 3. 0. I ² ' ⁵ ]

7 Dichloromethyl monotricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3,

7 Trichloromethyl-tricyclo [4. 3. 0. I ² ' ⁵ ]

7 Hydroxy monotricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3

7 Sierra Recyclo [4. 3. 0. I ² ' ⁵ ] Deca 3

7 amino-tricyclo [4. 3. 0. I ² ' ⁵ ]

Tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ]

Pentacyclo ^{^{[7. 4. 0. I 2 '5}} . I 8' 11. 0 7 '12] Pentade force one 3 E down,

To Kisashikuro ^{^{[8. 4. 0. I 2 '5}} . I 7' 14. I 9 '12. 0 8' 13] Heputadeka 3 E down,

8-methyl-one tetracyclo ^{^{[4. 4. 0. I 2 '5}} . 1 ".] Dodecane force one 3 E down,

8 ethyl-tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ]

8 hexyl one tetracyclo cyclohexane ^{^{[4. 4. 0. I 2 '5}} . 1 ".] Dodecane force one 3 E down,

8 Phenol Tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ]

8— (4 biphenyl) monotetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ]

8-methoxycarbo-tetracyclo [4. 4. 0. I ² ' ^5. L ⁷ ' ¹⁰ ]

8 Fuenokishikarubo - Le one tetracyclo ^{[4. 4. 0. I 2 '.} 5 1 "°] de de force one 3 E down, 8 off enoki Chez Chill carbo - Lou tetracyclo [4. 4. 0. I ^2' ^5. 1 "°] de de force one 3 E down,

8 Ferrocarbonoxytetracyclo [4. 4. 0. I ² ' ^5. L ⁷ ' ¹⁰ ]

8-methyl-8-methoxycarbonyl - Lou tetracyclo ^{[. 4. 4. 0. I 2 '} 5 1 "°] de de force one 3-E down,

8-methyl 8 Fuenokishikarubo - Lou tetracyclo ^{[. 4. 4. 0. I 2 '} 5 1 "°] de de force one 3 E down,

8-Methyl 8 phenoxycetylcarbo-rutetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] Deca 3-Yen,

8 Bull and Tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ]

8 Ethylidene monotetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ]

8, 8 Dimethyl monotetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ]

8, 9 Dimethyl monotetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ]

8 Fluorotetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ]

8 Chloroteslacyclo [4. 4. 0. I ² ' ^5. 1 ⁷ . ]

8 Bromo monotetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ]

8, 8 Dichloromonotetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ]

8, 9 Dichloromonotetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] Dodeca 3,

8, 8, 9, 9—Tetrachrome 1 tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] Dode force 1, 8 hydroxy 1 tetracyclo [4. 4. 0. I ² ' ^5. 1 ⁷ . ]

8 Hydroxyethyl monotetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] Dode force 3-ene, 8-methyl 8-hydroxyethyl tetratetracyclo [4. 4. 0. I ² ' ^5. l ⁷ ^'10] de de force one 3 E down,

8 Cyan tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ]

8 Amino-tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ]

[0041] These norbornene compounds may be used alone or in combination of two or more.

[0042] The type and amount of the norbornene compound constituting the monomer or monomer composition are appropriately selected depending on the properties required for the resulting norbornene-based resin.

[0043] In the present invention, among these, a structure containing at least one atom selected from an oxygen atom, a nitrogen atom, a nitrogen atom, or a carbon atom in the molecule (hereinafter referred to as "polar structure") It is preferable to use a compound having) because it is excellent in adhesion and adhesion to other materials. In particular, in the 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 is polar. A compound having a structure and the other being a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable because of its low water absorption (wet) property. Further, a group having a polar structure A norbornene-based compound in which is a group represented by the following formula (2) can be preferably used because the balance between the heat resistance and water absorption (wet) property of the resulting resin is easy.

[0044]-(CH) COOR--(2)

2 Z

(In the 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 obtained (co) polymer or its hydrogen additive and the better the heat resistance, so that z is 0 or 1 to 3 Furthermore, it is preferable that the number is z, and a monomer in which z is 0 is preferable because it is easy to synthesize. Further, R in the above formula (2) is a force that tends to decrease the water absorption (wet) property of the (co) polymer or hydrogenated product obtained as the number of carbon atoms tends to decrease. Accordingly, the viewpoint power for maintaining heat resistance is preferably a hydrocarbon group having 1 to 10 carbon atoms, particularly preferably a hydrocarbon group having 1 to 6 carbon atoms.

[0045] In the above 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 above formula (2) is bonded, This is preferable in terms of a balance of water absorption (wet). Further, in the formula (1), the compound in which X is 0 or 1, and y is 0 is a highly reactive polymer with a high yield, and a polymer having high heat resistance. It is preferably used because it is easy to obtain hydrogenated products and industrially.

[0046] In obtaining the norbornene-based resin used in the present invention, the effects of the present invention are not impaired! In the range, a monomer copolymerizable with the norbornene compound can be contained in the monomer composition for polymerization. Examples of the copolymerizable monomer include cyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclootaten, and cyclododecene, and non-covalent cyclic such as 1,4-cyclooctagen, dicyclopentagen, and cyclododecatriene. Polyene can be mentioned.

[0047] These copolymerizable monomers may be used alone or in combination of two or more.

<(Co) polymerization method>

The norbornene-based resin constituting the norbornene-based resin film (A) used in the present invention is The monomer or monomer composition can be produced from (co) polymerization and further hydrogenated as necessary. The (co) polymerization method is not particularly limited, and examples thereof include a method of ring-opening polymerization or addition polymerization of the monomer or monomer composition.

[0048] A. Ring-opening polymerization

The production of the (co) polymer by ring-opening polymerization can be carried out by a known ring-opening polymerization reaction for the norbornene compound, and the monomer composition containing the norbornene compound is polymerized as a polymerization catalyst, a polymerization reaction solvent, And if necessary, it can be produced by ring-opening polymerization using a molecular weight regulator.

[0049] Ring-opening polymerization catalyst

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

[0050] This metathesis catalyst is

(A) Compound power having W, Mo and Re and at least one selected compound (hereinafter referred to as compound (A) t ヽぅ) and (B) Deming periodic table IA group elements (eg Li, Na, K), I Group IA elements (eg Mg, Ca, etc.), Group IV elements (eg Zn, Cd, Hg etc.), Group IIIA elements (eg B, A1, etc.), Group IVA elements (eg Si , Sn, Pb, etc.), or a compound having a group IV B element (eg, Ti, Zr, etc.), and a compound having at least one bond between this element and carbon or at least one bond between this element and hydrogen The catalyst is a combination force with at least one compound (hereinafter referred to as compound (B)). Further, in order to enhance the activity of the catalyst, an additive (C) described later may be further added.

[0051] The compound (A) includes W, Mo or Re halides, oxyhalides, alkoxy halides, alkoxides, carboxylates, (oxy) acetylethylacetonates, carbol complexes, and acetonitrile complexes. , Hydride complexes, and their derivatives, or combinations thereof W and Mo compounds, especially their halides, oxyhalides, and alkoxyhalides are preferred from the viewpoint of polymerization activity and practicality Yes. Also, a mixture of two or more compounds that produce the compound by reaction may be used. In addition, these compounds can be combined with suitable complexing agents such as P (CH), CHN, etc. It may be confused.

[0052] Specific examples of the compound (A) include WC1, WC1, WC1, WBr, WF, WI, MoCl,

6 5 4 6 6 6 5

MoCl, MoCl, ReCl, WOC1, MoOCl, ReOCl, ReOBr, W (OC H), WC1 (OC H

4 3 3 4 3 3 3 6 5 6 2 6 5

), Mo (OC H) CI, Mo (OC H), MoO (acac), W (OCOR), W (OC H) CI, W (CO)

4 2 5 2 3 2 5 5 2 2 5 2 5 2 3 6

, Mo (CO), Re (CO), ReOBr 'P (C H) ゝ WC1' P (C H) ゝ WC1 * C H N, W (CO) · Ρ (

6 2 10 3 6 5 3 5 6 5 3 6 5 5 5

C H), W (CO) 2-(CH 3 CN) and the like. Of the above compounds, particularly preferred

6 5 3 3 3 3

Examples of the compound include MoCl, Mo (OC H) CI, WC1, and W (〇C H) CI.

5 2 5 2 3 6 2 5 2 3

[0053] Specific examples of the compound (B) include n—C H Li, n—C H Na, C H Na, CH Mgl, C

4 5 5 11 5 5 3 2

H MgBr ゝ CH MgBr ゝ n—C H MgCl, (C H) Al, t— C H MgCU CH = CHCH MgCl, (

5 3 3 7 6 5 3 4 9 2 2

C H) Zn, (C H) Cd, CaZn (C H), (CH) B ゝ (C H) B, (n—C H) B, (CH) Al, (CH)

2 5 2 2 5 2 2 5 4 3 3 2 5 3 4 9 3 3 3 3

A1C1, (CH) Al CI, CH A1C1, (C H) Al, LiAl (C H), (C H) Al—0 (C H), (C H)

2 3 3 2 3 3 2 2 5 3 2 5 2 2 5 3 2 5 2 2 5 2

A1C1, C H A1C1 ゝ (C H) deer, (iso- C H) deer, (C H) AIOC H, (iso- C H) Al, (C H

2 5 2 2 5 2 4 9 2 2 5 2 2 5 4 9 3 2

) Al CK (CH) Ga ゝ (CH) Sn ゝ (n—C H) Sn ゝ (C H) SiH ゝ (n—C H) Al, (n—C H)

5 3 2 3 3 4 3 4 4 9 2 5 3 6 13 3 4 17 3

Al, LiH, NaH, BH, NaBH, A1H, LiAlH, BiH and TiH. Also

2 6 4 3 4 4 4

Mixtures of two or more compounds that produce these compounds by reaction can also be used. Preferred examples of these include (CH) Al, (CH) A1CU (CH) Al CI, CH

3 3 3 2 3 3 2 3

A1C1, (C H) Al, (C H) A to 1, (C H) A1C1, C H A1C1, (C H) A1H, (C H) AIOC

3 2 2 5 3 2 5 2 2 5 1.5 1.5 2 5 2 2 5 2 2 5 2

H, (C H) A1CN, (C H) Al, (iso— C H) Al, (iso— C H) deer, (C H) Al, (C H) A

2 5 2 5 2 3 7 3 4 9 3 4 9 2 6 13 3 8 17 3

1, (C H) Al and the like.

6 5 5

[0054] 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 preferably used. (1) to (9) can be exemplified.

(1) Boron such as simple boron, BF, BC1, B (0-n-C H), (C H 0), BF, B 0, H BO

3 3 4 9 3 2 5 3 2 2 3 3 3

Non-organometallic compounds of silicon, non-organometallic compounds of silicon such as Si (OC H);

2 5 4

(2) alcohols, hydrobaroxides and peroxides;

(3) water;

(4) oxygen;

(5) Carbon compounds such as aldehydes and ketones and polymers thereof; (6) Cyclic ethers such as ethylene oxide, epichlorohydrin, oxetane;

(7) Amides such as Ν, Ν-jetylformamide, Ν, Ν-dimethylacetamide, amines such as aline, morpholine, piperidine and azo compounds such as azobenzene;

(8) Ν—-troso compounds such as Ν—-trosodimethylamine, Ν—-trosodiphenylamine;

(9) Compounds containing S—C or N—C1 groups such as trichloromelamine, N-chlorosuccinimide, and phenylsulfuryl chloride.

[0055] The use amount of the metathesis catalyst is such that the molar ratio of the compound (A) to the total monomers used for polymerization (compound: total monomers) is usually 1: 500 to 1: 50,000, preferably An amount satisfying 1: 1,000 to 1: 10,000 is desirable.

[0056] The ratio of compound (A) to compound (B) (compound (A): compound (B)) is 1: 1 to 1:50, preferably 1: 2 to 1:30 is desired!

[0057] The ratio of the compound (A) to the compound (C) (compound (C): compound (A)) is in a molar ratio of 0.005: 1 to 15: 1, preferably 0.05: 1 to 7 : 1 is desirable.

[0058] Polymerization solvent

Solvents used in the ring-opening polymerization reaction are those in which the monomer composition and catalyst used for polymerization are dissolved and the catalyst is not deactivated, and the produced ring-opening polymer is dissolved. For example, alkanes such as pentane, hexane, heptane, otatan, nonane, decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; benzene, toluene, Aromatic hydrocarbons such as xylene, ethylbenzene, and cumene; Halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylenedibutamide, chlorophonolem, tetrachloroethylene; Halogenated aryl compounds such as chlorobenzene; Acetic acid Ethyl, n-butyl acetate, iso- Chill, methyl propionate, saturated carboxylic acid esters such as dimethoxy E Tan; dibutyl ether, tetrahydrofuran, and the like ethers such as dimethoxyethane down. These can be used alone or in combination of two or more. Such a solvent dissolves the solvent constituting the molecular weight regulator solution, the norbornene-based compound, the copolymerizable monomer, and Z or the metathesis catalyst. It is used as a solvent for

[0059] The amount of the solvent used is the weight ratio of the solvent to the monomer composition used for the polymerization (solvent: monomer composition) force usually 1: 1 to: LO: 1, preferably 1: 1 to An amount of 5: 1 is desirable.

[0060], Molecular weight regulator

The molecular weight of the resulting ring-opened polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent, but can also be adjusted by allowing a molecular weight regulator to coexist in the reaction system. .

[0061] Suitable molecular weight regulators include α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. And styrene, 4-methylstyrene, 2-methylstyrene, and 4-ethylstyrene. 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.

[0062] The amount of the molecular weight regulator used is usually 0.005 to 0.6 mol, preferably 0.01 to 0.5 mol, with respect to 1 mol of the monomer subjected to the ring-opening polymerization reaction. .

[0063] Other ring-opening polymerization conditions

The ring-opening polymer can be obtained by ring-opening polymerization of the norbornene compound alone or the norbornene compound and a copolymerizable monomer. Monomer containing a norbornene compound in the presence of an unsaturated hydrocarbon polymer containing two or more carbon-carbon double bonds in the main chain, such as butadiene copolymer, ethylene non-conjugated gen copolymer, polynorbornene, etc. Let the body composition ring-open polymerization.

[0064], Hydrogenated Caro

The polymer obtained by the ring-opening polymerization reaction has an olefinic unsaturated bond in the molecule. In the addition polymerization reaction, the polymer may have an olefinic unsaturated bond in the molecule. Thus, if an olefinic unsaturated bond is present in the polymer molecule, the olefinic unsaturated bond may cause deterioration over time such as coloring or gelation. It is preferable to carry out a hydrogenation reaction to convert to. [0065] In the hydrogenation reaction, a known hydrogenation catalyst is added to an ordinary method, that is, a solution of a polymer having an olefinic unsaturated bond, to which atmospheric pressure to 300 atm, preferably 3 to 200 atm. It can be carried out by allowing hydrogen gas to act at 0 to 200 ° C, preferably 20 to 180 ° C.

[0066] The hydrogenation rate of the hydrogenated polymer is 500 MHz, the value measured by ^ -NMR is usually 50% or more, preferably 70% or more, more preferably 90% or more, and particularly preferably 98% or more. Most preferably, it is 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.

[0067] 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, mechanical properties. In some cases, the aromatic group may have an advantageous effect on the optical characteristics, and therefore it is not necessary to hydrogenate the aromatic group.

[0068] As the hydrogenation catalyst, those used in the usual hydrogenation reaction of olefinic compounds can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.

[0069] Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as radium, platinum, nickel, rhodium, or ruthenium is supported on a carrier such as carbon, silica, alumina, or titanium. Can do. Homogeneous catalysts include nickel naphthenate, Z triethyl chloride, nickel acetyl acetate, z triethyl aluminum, oxalate cobalt, Zn-butyl lithium, titanocene dichloride, Z jetyl aluminum monochloride, rhodium acetate, chlorotris (Triphenylphosphine) rhodium, dichlorotris (trifluorophosphine) ruthenium, chlorohydrocarbonyltris (trifluorophosphine) ruthenium, dichlorocarbo-trithris (triphenylphosphine) ruthenium

. The form of the catalyst may be powder or granular.

[0070] These hydrogenation catalysts, generally the weight ratio of ring-opened polymer and the hydrogenation catalyst (ring-opening polymer: hydrogenation catalyst) ^{is, 1: 1 X 10- 6 ~1} : 2 X 10- Used at a rate of ³ .

[0071] B. Addition polymerization The production of the polymer by addition (co) polymerization can be carried out by a known addition polymerization reaction with a norbornene compound, and a monomer composition containing the norbornene compound is prepared as a polymerization catalyst, if necessary. Accordingly, it can be produced by addition polymerization using a solvent for polymerization reaction and, if necessary, a molecular weight regulator.

[0072] Addition 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 the following (1) to (3). The polymerization catalyst used for is not limited to these

[0073] (1) Single catalyst system

(Pd (CH CN)) (BF), (Pd (PhCN)) (SbF)

3 4 4 2 4 6

[(η ― crotyl) Pd (cycloocta—1, 5— diene)] [PF],

6

[(R? ³ — crotyl) Ni (cycloocta— 1, 5— diene)] [B (3, 5— (CF) CF)],

3 2 6 3 4

[(77-crotyl) Ni (cycloocta- 1, 5- dienej J (PF),

6

[(R? ³ — allyl) Ni (cycloocta—1, 5— diene)] [B (CF)],

6 5 4

[(77 ― crotyl) Ni (cycloocta― 1, 5― dienej J (SbF),

6

Toluene -Ni (C F), Benzene -Ni (C F), Mesitylene -Ni (C F), Ethylethe

6 5 2 6 5 2 6 5 2

r-Ni (C F)

6 5 2

Etc.

[0074] (2) Multi-component catalyst system

a combination of a palladium complex having a σ or σ, π bond and an organoaluminum or super strong acid salt,

Di-chloro-bibis (6-methoxybicyclo [2.2.1] hepto-2-enone-end 5 σ, 2 π) Pd, methylalumoxane (abbreviated as MAO), AgSbF or AgBF, force selection

6 4 Combining with the garlic compound,

[(Η ³ — Allele) PdCl] in combination with AgSbF or AgBF,

2 6 4

[(cycloocta- 1, 5— diene) Pd (CH) C1] and PPh and NaB [3, 5— (CF) C H]

Combination of 3 3 3 2 6 3 4 Etc.

[0075] (3) Multi-component catalyst system

(I) transition metal compounds selected from nickel compounds, cobalt compounds, titanium compounds or zirconium compounds,

(II) a compound selected from superacids, Lewis acids and ionic boron compounds,

(III) Organoaluminum compound

A combination of the three components.

[0076] (I) Examples of transition metal compounds

(1-1) Examples of nickel compounds and cobalt compounds:

Nickel or Conoleto organic carboxylates, organic phosphites, organophosphates, organic sulfonates, β-diketones, and other selected 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, phosphorus Examples include nickel salt of acid dibutyl ester, nickel dodecylbenzenesulfonate, nickel ρ-toluenesulfonate, nickel bis (acetylacetate), nickel bis (ethylacetate).

[0077] A compound obtained by modifying the organic carboxylate of nickel with a super strong acid such as hexafluoroantimonic acid, tetrafluoroboric acid, trifluoroacetic acid, or hexafluoroacetone.

[0078] Gen or trien coordination complex of nickel;

For example, dichloro (1,5-cyclooctagen) nickel, [(7? ³ -crotyl) (1,5-cyclopentagen) -ckkenole] hexafluorophosphate, and its tetraloborate, tetrakis [3,5 -Beckenore complexes such as —bis (trifluoromethyl)] borate complexes, (1, 5, 9-cyclododecatriene) nickel, bis (norbornagen) nickel, bis (1,5-cyclooctagen) dickenole .

[0079] A complex in which a ligand having atoms such as Ρ, Ν, and Ο is coordinated to nickel;

For example, bis (triphenylphosphine) nickel dichloride, bis (triphenylphosphine) nickel dibromide, bis (triphenylphosphine) cobalt dibromide, bis [tri (2 Methylphenol) phosphine] nickel dichloride, bis [tri (4 methylphenol) phosphine] nickel dichloride, bis [N— (3-tert-butylsalicylidene) phenolaminate] nickel, Ni [PhC (O ) CH] (Ph), Ni (OC (CH) PPh) (H) (PCv), Ni [0

6 4 3

C (O) (C H) P] (H) (PPh), bis (1,5 cyclooctagen) nickel and PhC (O) C

6 4 3

H = reaction product with PPh, [2, 6— (i—Pr) C H N = CHC H (O) (Anth)] (Ph) (PPh

3 2 6 3 6 3

) Nickel complexes such as Ni (where Anth is 9-anthracenyl, Ph is phenyl, Cy is cy

Three

Abbreviation for clohexyl. ;).

[0080] (1-2) Examples of titanium and zirconium compounds:

[t-BuNSiMe (Me Cp)] TiCl, (Me Cp) (O— iPr C H) TiCl, (Me Cp) TiCl

4 2 4 2 6 3 2 4 3

, (Me Cp) Ti (OBu), (t-BuNSiMe FlujTiMe, (t-BuNSiMe FlujTiCl,

4 3 2 2 2 2

Et (lnd) ZrCl, Ph C (Ind) (Cp) ZrCl, iPr (Cp) (Flu) ZrCl, iPr (3— tert- But

2 2 2 2 2

— Cp) (Ind) ZrCl, iPr (Cp) (Ind) ZrCl, Me Si (Ind) ZrCl, Cp ZrCl, (Cp is C

2 2 2 2 2 2 2

yclopentadienl, Ind is an abbreviation for Indenyl, and Flu is an abbreviation for Fluorenyl. )

Etc.

[0081] (II) Examples of super strong acids, Lewis acids and ionic boron compounds:

Examples of super strong acids include hexafluoroantimonic acid, hexafluorophosphoric acid, hexafluoroarsenic acid, trifluoroacetic acid, fluorosulfuric acid, trifluoromethanesulfonic acid, tetrafluoroboric acid, tetrakis (pentafluorophenol) boric acid, Tetrakis [3,5-bis (trifluoromethyl) phenol] boric acid, ρ-toluenesulfonic acid, pentafluoropropionic acid, etc.

Examples of Lewis acid compounds include complexes of boron trifluoride with ethers, amines, phenols, and the like, aluminum trifluoride ethers, amines, phenols, and other complexes, tris (pentafluorophenyl) borane, tris [ 3,5-bis (trifluoromethyl) phenol] borane, boron compounds such as aluminum trichloride, aluminum tribromide, ethyl aluminum dichloride, ethyl aluminum sesqui-chloride, jetyl aluminum fluoride, Aluminum compounds such as tri (pentafluorophenyl) aluminum, organic halogen compounds exhibiting Lewis acidity such as hexafluoroacetone, hexachloroacetone, chlorael, hexafluoromethylethyl ketone, and others, titanium tetrachloride, penta Shows Lewis acidity such as fluoroantimony Such as 匕合 products, Examples of ionic boron compounds include triphenylcarbene tetrakis (pentafluorophenol) borate, triphenylcarbtetrakis [3,5-bis (trifluoromethyl) phenol] borate, triphenylcarbtetrakis (2 , 4, 6-trifluorofluoro) borate, triphenylcarboletetraphenol, tributylamine tetrakis (pentafluorophenol) borate, N, N-dimethylaureum tetrakis (pentafluorophee) -L) borate, N, N-jetylaureum tetrakis (pentafluorophenol) borate, N, N-diphenylaureum tetrakis (pentafluorophenol) borate and the like.

[0082] Examples of the organoaluminum compound (III):

Alkylalumoxane compounds such as methylalumoxane, ethylalumoxane, butylalumoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, jetylaluminum chloride, jetaluminum fluoride, ethyl Alkyl aluminum compounds and halogenated alkyl aluminum compounds such as aluminum sesquichloride, ethyl aluminum dichloride, or a mixture of the alkyl alumoxane compound and the alkyl aluminum compound are preferably used. The

[0083] These catalyst components are used, for example, in amounts used within the following ranges.

[0084] Transition metal compounds such as nickel compounds, palladium compounds, cobalt compounds, titanium compounds and zirconium compounds are used in an amount of 0.02 to: LOO millimole atoms per mole of monomer; 1 to 5,000 moles per mole atom of the metal compound; non-conjugated gen, Lewis acid, and ionic boron compound are about 0 to 100 moles per mole atom of the transition metal compound.

[0085] Addition polymerization solvent

As the solvent used in the addition polymerization reaction, any monomer composition or catalyst to be used for the polymerization can be dissolved and the catalyst is not deactivated, and the produced addition polymer can be dissolved. Although not particularly limited, 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. Aromatic carbonization Examples include solvents selected from hydrogen solvents, halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, black benzene, and dichlorobenzene. These can be used alone or in admixture of two or more.

[0086], Molecular weight regulator

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

[0087] <Norbornene-based resin properties>

The norbornene-based resin used in the present invention preferably has an intrinsic viscosity [r?] Of 0.2-2.

uih

Odl / g, more preferably 0.35-1. Odl / g, particularly preferably 0.4 to 0.85 dl / g, and the number average in terms of polystyrene measured by gel permeation chromatography (GPC). The molecular weight (Mn) force is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, particularly preferably 1.50,000 to 250,000, and the weight average molecular weight (Mw) is 10,000 to 2,000,000, more preferably. Is preferably 20,000 to 1,000,000, particularly preferably 30,000 to 500,000. Intrinsic viscosity [7?]

in

When the number average molecular weight and the weight average molecular weight are in the above ranges,

Is superior in mechanical strength and is not easily damaged, and a solbornene-based resin film can be obtained.

[0088] The glass transition temperature (Tg) of the norbornene-based resin is usually 100 ° C or higher, preferably 120 ° C or higher, more preferably 150 ° C or higher. When Tg is within the above range, the processability of the norbornene-based resin film is excellent and the stable characteristics of the optical film of the present invention can be obtained.

Further, the saturated water absorption of norbornene-based rosin is 1% by weight or less, preferably 0.01-0. 8% by weight, and more preferably 0.1-0.5% by weight. When the saturated water absorption exceeds 1% by weight, the film force obtained from such a resin may cause a problem in durability such as water absorption (wet) deformation over time depending on the use environment. On the other hand, if the content is less than 0.01% by weight, there may be a problem in adhesion. In addition, the saturated water absorption rate is within the above range. In particular, excellent characteristics can be exhibited due to durability stability when used as a polarizing plate. The saturated water absorption is a value obtained by immersing in 23 ° C water for 1 week according to ASTM D570 and measuring the increased weight.

[0090] <Other components of norbornene-based rosin>

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 not impairing the effects of the present invention.

[0091] Examples of the antioxidant include 2, 6-di-tert-butyl-4-methylphenol, 2, 2, -dioxy-3, 3, -di-tert-butyl-5,5, -dimethyldiphenylmethane, tetrakis.

[Methylene-1- (3,5-di-tert-butyl 4-hydroxyphenol) propionate] methane.

[0092] Examples of the ultraviolet absorber include 2,4 dihydroxybenzophenone and 2hydroxy-4-methoxybenzophenone. Further, when the norbornene-based resin film (A) is produced by the solution casting method described later, the production of the resin film can be facilitated by adding a leveling agent or an antifoaming agent.

[0093] These additives may be mixed with the norbornene-based resin or the like when the norbornene-based resin film (A) used in the present invention is produced, or the norbornene-based resin is manufactured. You may mix | blend beforehand by adding in the case. In addition, the addition amount is appropriately selected according to the desired characteristics, and is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2 parts per 100 parts by weight of norbornene-based resin. Desirably 0 parts by weight.

[0094] <Manufacture of norbornene-based resin film (A)>

The norbornene-based resin film (A) used in the present invention can be suitably formed by directly melt-molding norbornene-based resin, or by dissolving in a solvent and casting (solvent casting).

[0095], Melt molding

The norbornene-based resin film (A) used in the present invention can be produced by melt-molding a norbornene-based resin or a resin composition containing the norbornene-based resin and the above-mentioned additives. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding. [0096] 'Solvent casting

The norbornene-based resin film (A) used in the present invention can also be produced by casting a liquid resin composition in which a norbornene-based resin is dissolved in a solvent on an appropriate substrate to remove the solvent. . For example, the above-mentioned liquid resin composition is applied onto a substrate such as a steel belt, a steel drum, or a polyester film, the solvent is dried, and then the coating film is peeled off from the substrate. The norbornene-based resin film (A) can be obtained by further drying after peeling the coating film from the material.

[0097] The amount of residual solvent in the norbornene-based resin film (A) obtained by the above method should be as small as possible, usually 3% by weight or less, preferably 1% by weight or less, more preferably 0. 5% by weight or less. If the amount of residual solvent exceeds 3% by weight, the film may be deformed or its characteristics may change over time, making it impossible to perform the desired function.

[0098] · Surface treatment

The norbornene-based resin film (A) used in the present invention desirably has a light transmittance of usually 80% or more, preferably 85% or more, more preferably 90% or more.

[0099] Further, the norbornene-based resin film (A) used in the present invention may be subjected to a surface treatment for the purpose of improving the adhesion to the antistatic layer (B) described later. Examples of the surface treatment include plasma treatment, corona treatment, alkali treatment, primer coating treatment, and the like.

[0100] In particular, by using corona treatment, adhesion between the norbornene-based resin film (A) and the antistatic layer (B) can be strengthened. The corona treatment conditions in this case are preferably 1 to 1000 WZm ² Zmin, more preferably 10 to 100 W / m ² Zmin, as the dose of corona discharge electrons. If the irradiation dose is lower than this, a sufficient surface modification effect may not be obtained, and if the irradiation dose is higher than this, the treatment effect reaches the inside of the norbornene resin film (A). However, the norbornene-based resin film (A) itself may be deteriorated. The corona treatment may be performed not only on the surface on which the antistatic layer (B) is provided, but also on the opposite surface.

[0101] · Stretching treatment

The norbornene-based resin film (A) used in the present invention may be an unstretched film. It may be a stretched film. In addition, the norbornene-based resin film (A) used in the present invention may be a film composed only of a norbornene-based resin layer, or a norbornene-based resin film and a layer made of other materials such as polyethylene. Can be a composite film with. When the norbornene-based resin film (A) used in the present invention is a composite film with another material, it is desirable that at least one of the surfaces is a norbornene-based resin layer on the norbornene-based resin layer. It is desirable to provide a prevention layer (B).

[0102] In particular, in the case of a film having an optical film force retardation according to the present invention, a norbornene-based resin film (A) obtained by subjecting an unstretched norbornene-based resin film to heat-drawing treatment in advance is used. An antistatic layer (B) may be provided on this surface. In such a method, when the surface treatment is applied to the norbornene-based resin film (A), the surface treatment is performed on the norbornene-based resin film before stretching, and then the film is heated and stretched with the norbornene-based resin film. (A) may be prepared. Alternatively, a norbornene-based resin film (A) may be prepared by heating and stretching an unstretched norbornene-based resin film and then performing surface treatment. In addition, an optical film having a phase difference is obtained by subjecting the norbornene-based resin film (A), which is an unstretched film, to surface treatment as necessary, providing an antistatic layer (B), and then heat stretching. It is good. At this time, due to the productivity of the optical film and the stability of the obtained characteristics, the anti-bacterial layer (B) is provided after the surface treatment is performed on the norbornene-based resin film (A) which is an unstretched film, Thereafter, heating and stretching are preferably performed.

[0103] As the stretching method, a method of uniaxially stretching or biaxially stretching an unstretched norbornene-based resin film that may be laminated with an antistatic layer (B) is used.

[0104] In the case of uniaxial stretching treatment, the stretching speed (strain rate) is usually 1 to 5,000% Z, preferably 50 to: L, 000% Z, more preferably 100 to 1. , 000% Z minutes.

[0105] 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 crossing angle of the two stretching axes is determined according to the properties 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. Usually 1 to 5,000% Z min, preferably 50 to: L, 000% Z min, more preferably 100 to 1,000% Z min, particularly preferably 100 to 500% Z min It is.

[0106] The stretching temperature is not particularly limited, but is usually Tg ± 30 ° C, preferably Tg ± 15 ° C, more preferably based on the glass transition temperature (Tg) of the norbornene-based resin used. It is preferably in the range of Tg—5 to Tg + 15 ° C. By setting the stretching treatment temperature within the above range, it is possible to suppress the occurrence of uneven retardation in the obtained stretched film, and it becomes easy to control the refractive index ellipsoid, and the stretching treatment is also stable. It is preferable because it can be performed.

[0107] The draw ratio is 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 to 3 times. When the draw ratio exceeds the above range, it may be difficult to control the retardation of the obtained stretched film. The stretched film may be cooled as it is, but after holding it 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 cool. As a result, a stable retardation film can be obtained with little change over time in the retardation and dimensions of transmitted light.

[0108] The film that has been subjected to the stretching treatment as described above gives a phase difference to transmitted light as a result of the orientation of the molecules by the stretching treatment. This phase difference depends on the stretching ratio and the stretching temperature. Can be controlled by the thickness of the film.

[0109] The norbornene-based resin film (A) used in the present invention is not particularly limited in thickness. Usually 5 to 500 m, preferably 10 to 150 m, more preferably 20 to: LO 0 m The degree is desirable. If the film is too thin, the strength may be insufficient. If it is too thick, the retardation may be too high, and the transparency and appearance may be deteriorated. When the norbornene-based resin film used in the present invention is a composite film of a norbornene-based resin layer (A) ί norbornene-based resin layer and a layer having other material strength, the thickness of the norbornene-based resin layer is usually 5 to 500 m, Preferably it is about 10 to 150 m.

[0110] The thickness of the norbornene-based resin film (A) constituting the optical film used as the retardation film is not particularly limited, but is usually 5 to 500 / ζ πι, preferably 10 to 150. / ζ πι, more preferably about 20 to 100 m. Film If the thickness is too thin or too thick, it may break during handling.

[0111] The norbornene-based resin film (A) used in the present invention has a surface wettability of 50 to 70 mNZm, preferably 55 to 70 mNZm, on the surface on which the antistatic layer (B) is laminated by the surface treatment described above. can do. This wettability can be measured according to the method described in IS K6768. Such wettability is preferable because the adhesion between the norbornene-based resin film (A) and the antistatic layer (B) is high.

[0112] The norbornene-based resin film (A) used in the present invention has an average surface roughness (Ra) force on the side on which the antistatic layer (B) is provided 0.3 to 2. Onm, preferably 0.4 to 1. It is preferably in the range of 8 nm. When the surface roughness of the antistatic layer is in this range, it is preferable because it has excellent smoothness, excellent optical transparency, and excellent adhesion between the antistatic layer and the norbornene-based resin film. .

The antistatic layer (B) according to the present invention is

(b l) an acrylic resin having a specific quaternary ammonium salt in the side chain;

(b2) It is formed from an antistatic coating material containing a curing agent composed of polyethyleneimine and Z or polyhydroxyalkane polyglycidyl ether.

[0114] Acrylic resin (b l)>

The acrylic resin (bl) constituting the antistatic coating material is an acrylic resin having a quaternary ammonium salt represented by the following formula (i) in the side chain.

[0115] COO— Q ¹ — N (Q ² ) X "-(i)

a b

Four

Such an acrylic resin (bl) is obtained by copolymerizing (1) a monomer having a COOH group at the end, (2) a monomer having a quaternary ammonium base, and (3) other monomers. Obtained. [0116] The monomer (1) having a COOH group at the terminal is preferably used in the range of 1 to 20 mol% of all monomers. ) Acrylic acid, acrylochelette succinic acid, phthalic acid, (meth) hexahydrophthalic acid and the like. In the present specification, “(meth) acryl” means acrylic or methacrylic.

[0117] The monomer (2) having a quaternary ammonium base is preferably used in the range of 10 to 40 mol% of the total monomers. Examples thereof include dimethylamino ether acrylate 4 oxide (including halogen such as chloride as counter ion, sulfate, sulfonate, alkylsulfonate, and other ions). The acrylic resin (bl) used in the present invention preferably contains a quaternary ammonium base having a halogen atom content of preferably 1% by weight or less, more preferably 0.5% by weight or less. More preferably, the body (2) does not contain halogens as counterions!

[0118] The other monomer (3) is preferably used in the range of 8 to 80 mol% in the total monomers. Examples of the monomer (3) include alkyl (meth) acrylate, Examples thereof include (meth) acrylate having a cyclic skeleton, styrene, butyl acetate, halogenated bur, olefin and other bur derivatives. Among these, as the monomer (3), alkyl (meth) acrylate and (meth) acrylate having an alicyclic skeleton are preferably used, and (meth) acrylate having an alicyclic skeleton is more preferable. Used. In addition, it is particularly preferred that alkyl (meth) acrylate and (meth) acrylate having an alicyclic skeleton are used in combination.

[0119] The content of the (meth) acrylate having an alicyclic skeleton is more preferably 10 to 30 mol% in all monomers. Examples of the (meth) acrylate having an alicyclic skeleton include, for example, cyclohexyl (meth) acrylate, dicyclopental (meth) acrylate, dicyclopentate.

-L (meth) atarylate, dicyclopente-luccihetyl (meth) atarylate, isobornyl (meth) atarylate and the like. The acrylic resin (bl) obtained by incorporating (meth) acrylate having such an alicyclic skeleton in a monomer is a structure derived from a (meth) acrylic acid ester having an alicyclic skeleton. Including units, which is preferred because it provides better adhesion to norbornene-based resin film (A).

[0120] The acrylic resin (bl) used in the present invention is a crosslinkable copolymer obtained by copolymerizing a monomer composition comprising these monomers, and is represented by the formula (i). 4th grade Ammonium It has a salt in the side chain.

[0121] Hardener (b2)>

The curing agent (b2) used in the present invention is composed of polyethyleneimine and Z or polyhydroxylcan polyglycidyl ether.

[0122] As the polyethyleneimine, polyethyleneimine having a number average molecular weight of 300 to 70,000 is preferably used. Polyethyleneimine may have a force branch which is usually linear. As the polyethyleneimine, for example, a commercial product such as “Epomin” manufactured by Nippon Shokubai Co., Ltd. can be suitably used.

[0123] The polyhydroxylanocan polyglycidinoreatenore is a polymer compound having the following structural units (m) and (n), and has a molecular weight of 500 to 5,000, preferably 1,000 to 2 , 00 0 can be suitably used.

[0124] [Chemical 2]

(m) (n)

[0125] In the present invention, as the hardener (b2), polyethyleneimine or polyhydroxyalkanepolyglycidyl ether may be used alone, or a combination of both may be used. It is desirable to use both in combination. When polyethyleneimine and polyhydroxyalkane polyglycidyl ether are used in combination, the mixing ratio of polyethyleneimine to 100 parts by weight of polyhydroxyalkane polyglycidyl ether should be 10 to L00 parts by weight. preferable.

[0126] The curing agent (b2) is preferably used in an amount of about 1 to 30 parts by weight, more preferably about 3 to 15 parts by weight with respect to 100 parts by weight of the acrylic resin (bl).

[0127] <Antistatic coating material> In the present invention, the antistatic layer (B) is provided on the norbornene-based resin film (A) using the antistatic coating material containing the acrylic resin (bl) and the curing agent (b2).

[0128] The antistatic coating material used in the present invention contains the acrylic resin (bl) and the curing agent (b2). The ratio of acrylic resin (bl) to curing agent (b2) in the antistatic coating material is 1 to 30 parts by weight of curing agent (b2) to 100 parts by weight of acrylic resin (bl). The ratio is preferably about 3 to 15 parts by weight.

[0129] The antistatic coating material used in the present invention further includes a crosslinking agent, a tackifier, an antioxidant, a colorant, an ultraviolet absorber, a light stabilizer, a silane coupling agent, a thermal polymerization inhibitor, and a leveling agent. Agents, surfactants, storage stabilizers, plasticizers, lubricants, fillers, anti-aging agents, wettability improvers, coating surface improvers and the like can be blended.

[0130] The antistatic coating material used in the present invention preferably further contains an epoxy resin having an alicyclic skeleton in addition to the acrylic resin (bl) and the curing agent (b2). Examples of the epoxy resin include (3, 4-epoxycyclohexenolemethinole 3 ', 4'- epoxycyclohexane strength noroxylate, 2- (3, 4 epoxycyclohexyl 5,5-spiro 3 , 4-epoxy) cyclohexane monomethadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bulucyclohexene oxide, 4 buluoxycyclohexane, bis (3,4-epoxy 6-methylcyclohexylmethyl) azi Pate, 3, 4 Epoxy 6-Methylcyclohexylene 3 ', 4'-Epoxy 6'-Methylcyclohexanecarboxylate, Methylenebis (3,4-epoxycyclohexane), Dicyclopentagenjepoxide, Ethylene glycol Di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4- Poxycyclohexanecarboxylate), epoxidized tetrabenzil alcohol, latathone-modified 3, 4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, latataton-modified epoxidized tetrahydrobenzyl alcohol, Cyclohexene oxide, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, etc.)

[0131] When the antistatic coating material contains an epoxy resin, the content thereof is The amount is preferably about 1 to 30 parts by weight per 100 parts by weight of ril-based rosin (bl).

[0132] Further, it is preferable that the antistatic coating material used in the present invention further contains a crosslinking agent having an epoxy group (hereinafter, also referred to as "epoxy crosslinking agent"), particularly as the curing agent (b2). When only polyethyleneimine is used, it is preferable to further use an epoxy-based crosslinking agent. The epoxy crosslinking agent used in the present invention is not particularly limited as long as it has at least one epoxy group in the molecule! /. Examples of such epoxy cross-linking agents include bisphenol type epoxy compounds, novolac type epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, darisidylamine type epoxy compounds. Examples thereof include a compound and a halogenated epoxy compound.

[0133] Specifically, bisphenol type epoxy compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether;

Novolac epoxy compounds such as phenol novolac epoxy compounds and cresol novolac epoxy compounds;

3, 4 Epoxycyclohexenolemethynole 3 ′, 4′—Epoxycyclohexane force noroxylate, 2- (3,4 Epoxycyclohexylene 5, 5-spiro 3, 4 epoxy) cyclohexane meta dioxane, Bis (3,4-epoxycyclohexylmethyl) adipate, Butylcyclohexene oxide, 4-Bulepoxycyclohexane, Bis (3,4-epoxy 6-Methylenocyclohexinolemethinole) adipate, 3, 4 Epoxy 6-Methylcyclohex Xylou 3 ', 4' Epoxy 6'-Methylcyclohexanecarboxylate, Methylenebis (3,4-Epoxycyclohexane), Dicyclopentagenjepoxide, Diethyl of ethylene glycol (3,4-Epoxycyclohexylmethyl) Ether, ethylene bis (3,4-epoxycyclohexanecarboxylate) , Epoxidized tetrabenzyl alcohol, rataton-modified 3, 4-epoxycyclohexylmethyl 3 ', 4'-epoxy cyclohexane hexane carboxylate, rataton-modified epoxidized tetrahydrobenzyl alcohol, cyclohexene oxide, hydrogenated bisphenol Alicyclic epoxy compounds such as A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether; Aliphatic epoxy compounds such as 1,4 butanediol diglycidyl ether, 1,6 hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether; Halogenated epoxy compounds such as phenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether;

Examples thereof include glycidylamine type epoxy compounds such as tetraglycidylaminophenylmethane.

[0134] Among the above epoxy-based crosslinking agents, polyethylene glycol diglycidyl ether is particularly preferable.

[0135] In addition to the above compounds, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers; aliphatic polyhydric alcohols such as ethylene glycolanol, propylene glycol, and glycerin, or one or more alkylene oxides. Polyglycidyl ethers of polyether polyols obtained by addition; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; phenol, cresol, butyl phenol, or alkylene oxide attached thereto Monoglycidyl ethers of polyether alcohol obtained by koji; glycidyl esters of higher fatty acids; epoxidized soybean oil, epoxy stearic acid tablets, epoxy stearic acid otaku , Epoxidized flax - and the like oils.

[0136] Epoxy rosin obtained by polymerizing one or more of these compounds in a suitable range in advance can also be used.

[0137] Furthermore, as the epoxy compound used in the present invention, a polymer of a conjugated gen monomer, a copolymer of a conjugated gen monomer and a compound having an ethylenically unsaturated bond group, a gen monomer and an ethylenic monomer are used. Examples thereof include a copolymer with a compound having a saturated bonding group, and a compound obtained by epoxy-coating a (co) polymer such as natural rubber.

[0138] The content of these epoxy crosslinking agents in the antistatic coating material is determined based on acrylic resin

(bl) It is preferably 1 to 30 parts by weight with respect to 100 parts by weight, more preferably 3 to 20 parts by weight. [0139] Further, the antistatic coating material used in the present invention preferably contains a filler in order to prevent blocking when the optical films of the present invention having the antistatic layer (B) are overlapped with each other. . When the antistatic coating material contains a filler, the surface characteristics of the antistatic layer (B) can be controlled. For this purpose, the kind of filler that may be added to the antistatic coating material may be inorganic particles, organic particles, or a mixture thereof without any particular limitation. Ordinary particle uniformity force Organic particles are preferably used.

[0140] For example, for inorganic particles, titanium oxide, acidic zirconium, zinc oxide, acidic aluminum, acidic silica (silica particles), and tin oxide can be used. Oxygen silicate (silica particles) is preferably used for the surface strength of light and light transmittance. In addition, as the organic particles, for example, polystyrene-based resin beads or acrylic resin-based beads (acrylic particles) are preferably used. Among them, acrylic resin beads (acrylic particles) such as light-transmitting surfaces are preferred, and polystyrene resin beads (polystyrene particles) are preferably used because of the uniformity of the particles and the wide range of material selectivity. It is done. These organic particles are not particularly limited, but suitably three-dimensionally crosslinked particles are used. In addition, these surface-modified particles are preferably used from the viewpoints of stability with an antistatic coating material that may be modified with, for example, a carboxyl group, a amino group, or a hydroxyl group, and uniformity with an antistatic layer. Used.

[0141] In addition, if there is a large difference between the refractive index of the base material of the antistatic coating material and the refractive index of the filler to be added, light scattering occurs, so the refractive index of the filler is as low as possible in the antistatic layer (B). It is preferable that the refractive index of the base material is close. As such a filler, specifically, a filler having a refractive index of about 1.5, such as silica particles and acrylic particles, can be preferably used.

[0142] In order to control the surface characteristics of the antistatic layer (B), the particle size of the filler should be selected according to the dry film thickness of the antistatic layer (B). ) Is 0.5 to 2 times, preferably about 0.1 to 1 times the dry film thickness. Moreover, the particle size of the anti-blocking material that also serves as the power of the filler is preferably an average particle size usually in the range of 0.05 to 0.50 m. At this time, particles having an average particle diameter in the range of 0.05 to 0.10 m are preferably used in which the entire particle is preferably contained in an amount of 50 to 99 wt%, more preferably 70 to 90 wt%. In addition, particles having an average particle size in the range of 0.10 to 0.50 _i um are preferably 50 to lwt as a whole. %, More preferably 30 to 10%, is preferably used.

[0143] The addition amount of the filler is not particularly limited, but is preferably 0.1 to 20% by weight based on the total amount of the antistatic coating material excluding the solvent. The blending ratio of the anti-blocking material comprising the filler is usually 0.1 to 20%, preferably 0.1 to 10%, more preferably in the antistatic layer (B) of the present invention. 0.1 to 5%. If the blending ratio of the particles is less than 0.1%, it is difficult to obtain an anti-blocking effect, while if it is 20% or more, there may be a problem in light transmission.

[0144] The antistatic coating material used in the present invention is a water-based coating material that is preferably in a form that can be applied to the norbornene-based resin film (A) in a state of being dissolved or dispersed in a solvent. That is, an emulsion type coating material is more preferable. When the antistatic coating material is a water-based coating material, an antistatic coating material is applied on the norbornene-based resin film (A) to form the antistatic layer (B). This is preferable because the surface of the oil film (A) is not altered or deteriorated.

[0145] The concentration of the antistatic coating material in the case of a water-based coating material depends on the coating method, but the solid content is usually 0.5 to 20% by weight based on the total amount of the antistatic coating material containing water. It is preferable to include a degree.

[0146] In order to satisfy the surface smoothness of the antistatic layer (B) required as an optical film, it is also preferable to use two or more kinds in combination as a solvent or a dispersion medium.

[0147] Specifically, in the case of a water-based coating material, in order to improve the smoothness of the antistatic layer (B), a water-soluble solvent that can be mixed in water at an arbitrary ratio and has a boiling point higher than that of water. It is preferable to use in combination. Specific examples of such solvents include γ-butyrolatatone, diethylene glycol monoethyl ether acetate, dimethylacetamide, Ν-methylpyrrolidone, triethylene glycol monomethyl ether, and triethylene glycol dimethyl ether. The mixing ratio of these solvents and water is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of water, and more preferably 1 to LO parts by weight. When the amount is less than 1 part by weight, the effect of adding a solvent cannot be obtained, and when the amount is more than 50 parts by weight, the productivity may be extremely inferior.

[0148] The boiling point of such a solvent is preferably 150 ° C or higher, preferably 200 ° C or higher. It is more preferable.

[0149] <Formation of antistatic layer (B)>

In general, the antistatic layer (B) according to the present invention can be suitably formed by applying the above-described antistatic coating material on the norbornene-based resin film (A) and drying. At this time, the antistatic layer (B) is not particularly limited as it may be on one side or both sides of the norbornene-based resin film (A).

[0150] The application method of the antistatic coating material is not particularly limited, but for example, spin coating, wire coating, no coating, ronole coating, blade coating, curtain coating, screen printing, gravure coating, reverse coating, spray coating, comma coating. Various methods such as die coating can be used.

[0151] The applied antistatic coating material may be dried in one step,

1) a primary drying step at 80 ° C or lower;

2) Glass transition temperature (Tg) of norbornene-based resin film (A)-temperature exceeding 30 ° C, preferably at temperature exceeding glass transition temperature (Tg) of norbornene-based resin film (A) It is more preferable to carry out by a two-stage drying process of the primary drying process and the secondary drying process, which is preferably carried out by a multi-stage drying process having a secondary drying process. When the secondary drying step at a temperature exceeding the glass transition temperature of the norbornene-based resin film (A) is performed, the strength of the resulting antistatic layer (B) in the form of an optical film is preferably increased.

[0152] In the primary drying process! In order to prevent blocking of the norbornene-based resin film (A) when rolling off the roll, if a protective film is pre-bonded on one side, the anti-static is applied to the opposite side. In the case where it is preferable to coat and dry the coating material without peeling off the protective film, the drying temperature is preferably 80 ° C. or less in view of the heat resistance of the protective film.

[0153] Secondary drying force used as needed The strength of the antistatic coating layer can be positively improved by utilizing heating during stretching of the norbornene-based resin film (A).

[0154] The antistatic coating material is a water-based coating material, and the drying is performed by 1) a primary drying step at 80 ° C or lower, and 2) the glass transition temperature (Tg) -30 of the norbornene-based resin film. When it is carried out in two stages with a secondary drying process at a temperature exceeding ° C, the antistatic layer obtained by the primary drying The solvent amount is preferably 0.1 to 5% by weight, and the solvent amount of the antistatic layer by secondary drying is preferably about 0.01 to 1% by weight.

[0155] In the present invention, when producing an optical film that is a stretched film, such as when producing an optical film having a retardation, the antistatic layer (B) is formed on the pre-stretched norbornene-based resin film (A). However, after applying an antistatic coating material on the unstretched norbornene-based resin film (A) and performing a primary drying step at 80 ° C. or lower, the norbornene-based resin film It is also preferred to stretch the film in the secondary drying step at a glass transition temperature (Tg) of over 30 ° C. When producing an optical film that is a stretched film, when the film is stretched in the secondary drying step, it is not necessary to separately perform heating during stretching and heating for drying, resulting in excellent thermal efficiency. This is preferable because it is economical and the thermal history exerted on the norbornene-based film (A) is small and the quality is hardly deteriorated. When the film is stretched in the secondary drying process, it is preferable that the temperature of the secondary drying process be in the range of glass transition temperature (Tg) of the norbornene resin film of 30 ° C. The glass transition temperature (Tg) of the oil film (A) is more preferably in the range of ± 15 ° C.

[0156] The conditions for stretching the film in the secondary drying step are norbornene-based resin films

The same conditions as described above in the case of stretching only (A).

[0157] <Antistatic layer (B)>

The thickness of the antistatic layer (B) according to the present invention is not particularly limited, but is usually from 0.01 to 5 111, preferably from 0.05 to 4 111, more preferably from 0.1 to It is desirable to be about 3 / ζ πι. When the thickness of the antistatic layer (Β) is 0.01 μm or more, it is preferable because the optical film has sufficient antistatic ability. The thickness of the antistatic layer (B) is usually from 0.01 to 0.5, preferably from 0.05 to 0.3, when the thickness of the norbornene-based resin film (A) is 100. It is preferable that the thickness be a ratio of about. If the thickness of the antistatic layer (B) is too small, sufficient antistatic ability may not be obtained. If it is too large, the light transmittance may be reduced or an adhesive may be overcoated. When used as an antistatic layer, the antistatic layer may dissolve and become cloudy.

[0158] The antistatic layer (B) according to the present invention has a total light transmittance of usually 80% or more, preferably 90%. Desirably over%! /.

[0159] An optical film having such an antistatic layer (B) can be used even when the antistatic layer (B) is provided only on one side of the norbornene-based resin film (A). ) On the opposite side as well as the side! Even if it shows even antistatic ability.

[0160] The saturated water absorption rate of the antistatic layer (B) according to the present invention at room temperature (23 ° C) 50RH% is preferably 0.1 to 90 wt%, more preferably 1 to 50 wt%, particularly preferably. Is preferably 1 to 20 wt%. When the saturated water absorption rate under the above conditions is in this range, it becomes easy to obtain a stable surface resistance value and stable characteristics when a polarizing plate is formed using the optical film of the present invention.

[0161] The antistatic layer (B) preferably has a metal atom content of 0.1 wt% or less, preferably 0.05 wt% or less, and has a halogen atom content of 1 wt%. In the following, it is preferable to be in the range of 0.5% by weight or less. In such a range, it is possible to prevent contamination of the paint line and migration of metal and halogen to the material used in combination.

[0162] Optical film with lightning protection layer I

The optical film having the antistatic layer of the present invention has the norbornene-based resin film layer (A) and the antistatic layer (B) described above.

[0163] The optical film of the present invention exhibits a sufficient antistatic ability, and generally has a surface resistance value of 1 X 10 ⁶ to 1 X 10 ¹² Ω / mouth, preferably 1 X 10 ⁸ to 1 on the antistatic layer side. X 10 ¹¹ Ω range. If the surface resistance value of the optical film is within this range, it is preferable because peeling charges such as when the roll-shaped optical film is fed out or when the protective sheet is peeled off are negligible.

[0164] The optical film of the present invention has an antistatic layer (B) containing an acrylic resin (bl) having an antistatic ability, so that a conventional antistatic agent such as a surfactant is used. Compared with the antistatic layer (B) and the norbornene-based resin film (A), the antistatic ability can be stably maintained over a long period of time, with less antistatic agent peeling and dropping. Excellent durability.

[0165] The optical film of the present invention comprises a norbornene-based resin film (A) and an antistatic layer (B). The refractive index difference at a wavelength (589) nm is 0.1 or less, preferably 0.05 or less.

The optical film of the present invention can have a surface wettability of 50 to 70 mNZm, preferably 55 to 70 mNZm, by surface treatment such as the corona discharge treatment described above. This wettability can be measured according to the method described in IS K6768. When the optical film of the present invention exhibits such wettability, it is excellent in adhesiveness or tackiness when laminated with other materials, and therefore suitable for various uses for forming laminates, such as when producing polarizing plates. Can be used.

[0167] The optical film according to the present invention is not only used for polarizing plates but also a film with a hard coat, a film with an antireflection film, a film with a transparent conductive film, an infrared'UV film, etc., because of its excellent adhesiveness. It can be suitably used also as a transparent substrate. The antistatic layer (B) may be present on one side of the norbornene-based resin film (A) or may be present on both sides.

Optical film strength of the present invention An antistatic layer (B) is formed on a pre-stretched norbornene-based resin film (A) or on an unstretched norbornene-based resin film (A). When it is obtained by stretching in the drying step, or when it is obtained by providing an antistatic layer (B) on an unstretched norbornene-based resin film (A) and then stretching In the case of a stretched film, it usually exhibits a retardation and can be suitably used as a retardation film.

[0168] The retardation of the retardation film of the present invention is not particularly limited, but the in-plane retardation is usually 0 to 300 nm, more preferably 5 to 150 nm. It is usually preferred to be 5 to 500 nm, more preferably 80 to 300 nm! /.

[0169] Partial

The optical film of the present invention having a retardation, that is, the retardation film of the present invention can be laminated with a polarizing film (polarizer) to form a polarizing plate. The lamination with the polarizing film is preferably performed via a known adhesive. Since the optical film of the present invention is excellent in moisture resistance and water resistance, the polarizing plate of the present invention obtained using the optical film is a polarizing film having hygroscopicity such as PVA. Even if a film is used, it is possible to reduce the thickness of the polarizing plate without providing a separate protective layer, which contributes to light weight and suppresses a decrease in transparency by using a thin film. In addition, by reducing the number of stacked layers, the cost of materials can be reduced, and the manufacturing process can be simplified. Since the polarizing plate of the present invention is manufactured using the optical film of the present invention having sufficient antistatic performance, it can prevent foreign matter from being taken in due to static electricity, and easily prevent foreign matter from entering the manufacturing process. Therefore, it is of high quality with virtually no point defects.

[0170] <Polarizing film>

The polarizing film constituting the polarizing plate of the present invention functions as a polarizing film, that is, functions to divide incident light into two polarization components perpendicular to each other, pass only one of them, and absorb or disperse the other components. Any of these can be used and is not particularly limited. As a polarizing film that can be used in the present invention, for example, polybulal alcohol (hereinafter abbreviated as PVA) 'iodine-based polarizing film, PVΑ / dye-based polarizing film in which a dichroic dye is adsorbed and oriented on a PVA-based film Also, a PVA film composed of a PVA-based polarizing film in which a dehydration reaction is induced from a PVA-based film or a polychlorinated polyvinyl film is formed by dehydrochlorination, and a modified PVA containing a cationic group in the molecule. Examples thereof include a polarizing film having a dichroic dye on the surface and Z or inside of the system film. Among these, PVA'iodine polarizing film is preferable.

[0171] The method for producing the polarizing film used in the present invention is not particularly limited. For example, a method of adsorbing iodine ions after stretching on a PVA film, a method of stretching a PVA film after dyeing with a dichroic dye, a method of stretching a PVA film with a dichroic dye after stretching, a dichroic dye Known methods such as a method of stretching after printing on a PVA-based film and a method of printing a dichroic dye after stretching a PVA-based film may be mentioned. More specifically, iodine is dissolved in a potassium iodide solution to form higher-order iodine ions, which are adsorbed on a PVA film and stretched, and then bathed in a 1 to 4% boric acid aqueous solution. A method for producing a polarizing film by immersing at a temperature of 30 to 40 ° C, is a method in which a PVA film is treated with boric acid in the same manner and stretched about 3 to 7 times in the uniaxial direction. Immerse the dye in an aqueous dye solution at a bath temperature of 30-40 ° C to adsorb the dye, dry at 80-100 ° C, and heat-set to produce a polarizing film. The method etc. are mentioned.

[0172] The polarizing film used in the present invention is not particularly limited, but desirably has a thickness of about 10 to 50 m, preferably about 15 to 45 μm.

These polarizing films may be used as they are for the production of the polarizing film according to the present invention, but can also be used after the corona discharge treatment and the plasma treatment are performed on the surface in contact with the adhesive layer.

[0174] <Adhesive layer>

The polarizing plate of the present invention is produced by bonding the optical film of the present invention having the above-described retardation and a polarizing film via an adhesive layer. The adhesive layer constituting the polarizing plate of the present invention is a layer obtained by applying an adhesive. Examples of the adhesive herein include water-based adhesives, solvent-type adhesives, two-component curable adhesives, ultraviolet curable adhesives, and pressure-sensitive adhesives (adhesives). Of these, water-based adhesives are preferably used, and polyvinyl alcohol-based water-based adhesives are particularly preferably used.

[0175] Examples of water-based adhesives based on polybulal alcohol include modified polybulal alcohols such as partially saponified polybulualcohol and fully saponified polybulualcohol, carboxyl group-modified polybum alcohol or acetocetyl group-modified polybum alcohol, etc. An aqueous dispersion obtained by dissolving or dispersing the polyvinyl alcohol polymer in water may be mentioned. The degree of polymerization of the polybutyl alcohol-based polymer is preferably about 500 to 2000 on average from the viewpoint of making the viscosity of the aqueous adhesive suitable. Furthermore, a component having a functional group capable of reacting with a hydroxyl group such as an isocyanate group may be contained as a component for crosslinking an adhesive mainly composed of such a polyvinyl alcohol polymer. In addition, polybulualcoal adhesives are usually used by dissolving them in water. To improve the wettability of the coated body, a small amount of a solvent with excellent water solubility, such as alcohol and ketones, is added. It is also preferable.

[0176] Examples of the solvent-type adhesive include an adhesive obtained by dissolving synthetic rubber, synthetic resin, and the like in an organic solvent.

[0177] Examples of the two-component curable adhesive include an epoxy-type two-component curable adhesive.

[0178] Examples of pressure-sensitive adhesives include natural rubber, synthetic rubber, elastomer, vinyl chloride Z acetate copolymer, polyalkyl alkyl ether, polyacrylate, and modified polyolefin. Examples include in-series oil-based pressure-sensitive adhesives, and hardened-type pressure-sensitive adhesives to which a curing agent such as isocyanate is added. Especially, pressure-sensitive adhesives used for adhesion of polyolefin foam and polyester film. Is preferred.

[0179] As the other adhesive, any adhesive used for bonding polyethylene or polypropylene can be used. For example, an adhesive for dry laminate that mixes polyurethane resin solution and polyisocyanate resin solution, styrene butadiene rubber adhesive, epoxy two-component curable adhesive, UV curable acrylic adhesive, such as epoxy It is possible to use one that has two liquids of rosin and polythiol, one that has two liquids of epoxy resin and polyamide, and in particular, solvent-type adhesives and epoxy two-part curable adhesives are preferred. Are preferred.

[0180] The thickness of the adhesive layer in the present invention is not particularly limited, but a thin film of m or less is preferable. Further, the adhesive layer in the present invention preferably has a light transmittance of 80% or more, particularly preferably 90% or more.

[0181] Between the tensile elastic modulus E3 of the adhesive layer in the present invention, the tensile elastic modulus E1 of the norbornene-based resin film (A) described above, and the tensile elastic modulus E2 of the antistatic layer (B), E1> E2 It is preferable that the relationship> E3 holds because the polarizing plate has excellent durability.

[0182] <Polarizing plate manufacturing method>

The polarizing plate of the present invention is formed by laminating the optical film of the present invention having a retardation, an adhesive layer, and a polarizing film. Usually, the adhesive layer is formed on the antistatic layer side of the optical film of the present invention. That is, the polarizing plate according to the present invention is preferably produced by adhering the antistatic layer side of the retardation film of the present invention described above to a polarizing film using an adhesive or a pressure-sensitive adhesive. By doing so, the adhesive strength between the optical film of the present invention and the polarizing film can be made higher. On the other hand, the adhesive layer may be opposite to the antistatic layer side, or may be laminated on one side of the optical film of the present invention having both sides as antistatic layers. By doing so, the surface resistance value on the other member side can be controlled more stably. For example, the amount of charge can be reduced when the liquid crystal cell is bonded via an adhesive.

[0183] As a method for producing such a polarizing plate of the present invention, a norbornene-based resin film is devised. The antistatic coating material described above is applied to the surface of the rumm (A) to provide an antistatic layer (B), and after appropriate drying and stretching, the antistatic layer side of the optical film is passed through an adhesive. It is preferable to adhere the surfaces.

[0184] The specific method for adhering the polarizing film and the optical film of the present invention depends on the kind of the polarizing film, the antistatic coating material and the adhesive, but the surface of the polarizing film or the antistatic layer of the optical film. An adhesive is applied to the side surface, and an optical film or a polarizing film is superposed on the surface and pressure-bonded.

[0185] Here, the pressure bonding can be performed under a pressure condition of about 1 kgZcm ^{2 in} an atmosphere of 18 to 25 ° C, for example.

[0186] The optical film of the present invention having an antistatic layer may be present on one side of the polarizing film or may be present on both sides.

[0187] Such a polarizing plate according to the present invention has a good polarizing function, and the norbornene-based resin film (A) and the polarizing film are firmly bonded to each other, such as heat resistance and chemical resistance. It also has excellent characteristics, and is highly reliable and resistant to peeling, deformation and phase change even after long-term use.

[0188] For adhesion, it is preferable that only material destruction occurs without peeling between the norbornene resin film and the polarizing film!

[0189] The polarizing plate of the present invention can be suitably used for various display applications, and in particular, can be suitably used for applications for forming liquid crystal displays. Since the retardation plate of the present invention is of a high quality substantially free of dot-like defects, the liquid crystal display of the present invention obtained by using the retardation plate has defects such as bright spots even on a large screen. It can be of high quality without possession. In addition, a liquid crystal display is usually produced by peeling a release film having a pressure-sensitive adhesive layer and a release film that protects the pressure-sensitive adhesive layer, and then bonding the retardation film to the display surface. In addition, since charging is sufficiently prevented, foreign matter can be prevented from adhering to the phase difference plate, and the resulting liquid crystal display is not charged, enabling quality inspection immediately after production. Thus, the manufacturing efficiency is excellent.

Example [0190] In the following, the ability to explain specific examples of the present invention The present invention is not limited to these examples. In the following, “parts” means “parts by weight” unless otherwise specified.

[0191] In addition, the surface resistance value, water resistance, tensile strength, glass transition temperature, total light transmittance, haze, degree of polarization, phase difference of transmitted light, adhesion, moisture resistance test, and dry heat test are as follows. It was measured.

[0192] [Surface resistance value]

In accordance with JIS K7194, the surface resistance value was measured using a Loresta GP manufactured by Mitsubishi Igaku.

[0193] [Adhesion]

Adhesive tape specified in JIS Z1522 was used, and adhesion was evaluated in a 25 square grid peel tape test in accordance with JIS K5400, and the remaining film ratio was shown.

[0194] [Water resistance]

Place the 1 OOg weight (contact area 3 cm ² ) on the coated surface through gauze containing water on the coated surface at room temperature. It was observed visually and judged according to the following criteria.

[0195] A: No change in appearance

B: l ~ several scratches occur

C: Countless scratches occur

[Tensile modulus]

The tensile modulus at room temperature was measured using Autograph AGS-J series (manufactured by Shimadzu Corporation) in accordance with JIS K7127.

[0196] [Glass transition temperature (Tg)]

In accordance with JIS K7121, the glass transition temperature was measured using a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc. under the conditions of a temperature rise rate of 20 ° CZ in a nitrogen atmosphere (hereinafter referred to as `` Tg ") was measured.

[0197] [Total light transmittance, haze]

In accordance with JIS K7105, the total light transmittance is a haze meter “HGM” manufactured by Suga Test Instruments Co., Ltd. Using 2DP type, total light transmittance and haze were measured.

[0198] [degree of polarization]

The polarization at a wavelength of 547.7 nm was measured using “KOBRA-21ADHZPR” manufactured by Oji Scientific Instruments.

[0199] [Phase difference of transmitted light]

Measured at wavelengths of 480 nm, 550 nm, 59 Onm, 630 nm, and 750 nm using “KOBRA-21ADH” manufactured by Oji Scientific Instruments Co., Ltd. Calculated using the Cauchy dispersion formula.

[0200] [Adhesiveness (Adhesiveness between polarizer and protective film)]

In accordance with JIS K6854, a polarizer and a protective film were bonded, and then a 90 ° peel test was conducted using an Instron universal material testing machine 3366 to measure the peel strength. Furthermore, the degree of occurrence of material destruction and peeling between films was visually observed.

[0201] [Surface roughness]

The surface roughness Ra (arithmetic average height) was measured using an atomic force microscope Nano Scopellla (Digital Instrument).

[0202] [Wetting tension]

In accordance with JIS K6768, evaluation was performed using a wet tension test mixture (Wako Pure Chemical Industries, Ltd.).

[0203] [Film winding property]

Two pieces of A4 size cut out film are overlapped, pressed with a rubber roller and allowed to stand, and then the ease of movement and the presence or absence of scratches on the film surface when the top film is shifted horizontally by lmZ min. Evaluated by level.

[0204] A: The film can be moved easily, and there is no scratch on the film surface after movement.

[0205] B: The film can be moved with a slightly heavy touch, and the film surface after the movement has some scratches.

[0206] C: The film is blocking! / ヽ The film cannot move very well, and there are many scratches on the film surface after the movement.

[0207] Synthesis Example 1

2L separable flask with stirrer, thermometer and monomer addition pump 150 parts of ion-exchanged water, 2 parts of reactive emulsifier “ADEKA rear soap SE-10N” (manufactured by Asahi Denka Kogyo Co., Ltd.) and 0.5 part of ammonium persulfate are charged into the gas phase. The part was replaced with nitrogen gas for 15 minutes and then heated to 80 ° C. Next, 50 parts of ion-exchanged water, 6 parts of methacrylic acid, 47 parts of MOETAS (MRC Dutec Co., Ltd.) which is a metatalate having a quaternary ammonia group, 20 parts of methyl methacrylate, 26 parts of ethyl acetate and 1 part of a reactive emulsifier “ADEKA rear soap SE-10N” were mixed and stirred in a separate container to prepare a pre-emulsion, and the resulting pre-emulsion was separated into the separable product over 3 hours. It was dripped continuously into the flask. During the dropwise addition of the pre-emulsion, nitrogen gas was introduced and the temperature in the flask was kept at 80 ° C. After completion of the dropwise addition, the reaction system was heated to 90 ° C and the reaction was continued for 2 hours. Next, after the temperature of the system was lowered to 25 ° C., 5% ammonia water was added dropwise to adjust the pH to 8, and then ion exchange water was added to obtain a solid content concentration of 25%. Emulsion 1 was obtained as a coating agent of the marjiyon type (average particle size of emerald particles: 0.06 m).

[0208] Synthesis Example 2

Emulsion 2 was obtained in the same manner as in Synthesis Example 1, except that 26 parts of isobutyl acrylate was added instead of 26 parts of methacrylic methacrylate.

[0209] Preparation Examples 1-2

8 parts of Emulsion 1 (Preparation Example 1) or Emulsion 2 (Preparation Example 2) obtained in the synthesis example, 10.7 parts of ion-exchanged water, 1 part of Epomin P-1000 (manufactured by Nippon Shokubai Co., Ltd.) Part and 0.3 part of polyglycerin polyglycidyl ether were added in this order, and the mixture was stirred at room temperature for 10 minutes to obtain antistatic paint 1 and antistatic paint 2, respectively. When elemental analysis of the antistatic paints 1 and 2 was performed by XRF measurement, the halogen contents were 0.5 wt% and 0.5 wt%, respectively, and the metal contents were 0.01 wt% and 0 wt%, respectively. 01wt% to get it.

[0210] Antistatic paints 1 and 2 were each applied on a glass substrate, dried at 100 ° C for 120 minutes, and then peeled to obtain a 30-m thick film. The tensile modulus at room temperature was measured. However, both were 0.8 GPa.

[0211] In addition, when the refractive index of antistatic paint 1 and antistatic paint 2 was measured with an Abbe refractometer, both were 1.50. [0212] Preparation Example 3

A fully saponified polybulualcohol having an average polymerization degree of 1,700 was dissolved in water to a concentration of 3% by weight to obtain a polybulualcohol-based adhesive. Concentrate the resulting polybulualcohol-based adhesive to a concentration of 10% by weight, apply it onto a glass substrate, dry at 100 ° C for 120 minutes, and then peel off to obtain a 30 m thick film. The tensile modulus at room temperature was measured and found to be 0.4 GPa.

[0213] Preparation Example 4

Charge a reaction vessel with 250 parts of distilled water, and add 90 parts of butyl acrylate, 8 parts of 2-hydroxyethyl methacrylate, 2 parts of dibutene, and 0.1 part of potassium oleate to this reaction container. After that, the system was stirred with a stirring blade made of Teflon (registered trademark) and dispersed. Thereafter, the inside of the reaction vessel was purged with nitrogen, and then the temperature of the system was raised to 50 ° C., and 0.2 part of potassium persulfate was added to initiate polymerization. After 2 hours from the start of the polymerization, 0.1 parts of potassium persulfate was further added to the polymerization reaction system, and then the temperature of the system was raised to 80 ° C and the polymerization reaction was continued for 1 hour. A dispersion was obtained.

[0214] Next, by using an evaporator, the polymer dispersion is concentrated until the solids concentration reaches 70% by weight, whereby an aqueous pressure-sensitive adhesive (polar) A pressure-sensitive adhesive having a group) was obtained.

[0215] Preparation Examples 5-6

Emulsion 1 (Preparation Example 5) or Emulsion 2 (Preparation Example 6) obtained in Synthesis Example was used as 8 parts and filler, and in Preparation Example 5, the average particle size of 0.10 μm was 9 (^ % unrealized, and polystyrene sphericity particle element containing 10 wt% relative to the total amount of particles the average particle size 0. 30 mu m (refractive index 1.59), the average particle size 0. 10 _i um in preparation example 6 When acrylic anti-spherical particles (refractive index of 1.51) containing 80 wt% of the total particle amount and 20 wt% of the average particle size of 0.30 μm are formed on the antistatic layer The volume fraction is 10% each, using 120.7 parts of ion-exchanged water, 1 part of Epomin P-1000 (manufactured by Nippon Shokubai Co., Ltd.), and 0.3 parts of polyglycerin polyglycidyl ether. Were mixed in this order and stirred at room temperature for 10 minutes to obtain antistatic paint 3 and antistatic paint 4, respectively. When elemental analysis of 3 and 4 was performed, the halogen content Were 0.5 wt% and 0.5 wt%, respectively, and the metal contents were 0.01 wt% and 0.01 wt%, respectively.

[0216] Antistatic paints 3 and 4 were each coated on a glass substrate, dried at 100 ° C for 120 minutes, and then peeled to obtain a 30-m thick film. The tensile modulus at room temperature was measured. However, both were 0.8 GPa.

In addition, the refractive index of antistatic paint 3 and antistatic paint 4 was measured with an Abbe refractometer, and both were 1.50.

[0218] [Examples 1 to 10]

Use either ARTON FLYL100 (manufactured by JSR) or ZEO NOR ZF14-100 (manufactured by ZEON Co., Ltd.) as the norbornene-based resin film, and apply anti-static paint to the norbornene-based resin film before coating. Apply antistatic coating 1 to 4 with a 6 micron wet wire bar and dry at 110 ° C for 3 minutes for each case with and without 50W.minZm ² corona discharge treatment in the atmosphere. Films 1 to 10 were obtained. In each example, the types of norbornene-based resin films used, the presence or absence of corona treatment, and the types of antistatic paint used are as shown in Table 1 or Table 2.

[0219] ARTON FLYL100 and ZEONOR ZF14-100 were each measured for tensile modulus at room temperature, and both were lGPa.

[0220] Tables 1 and 2 show the surface roughness Ra (nm) and wetting tension (mNZm) of the film before application of the antistatic paint after corona treatment. Tables 1 and 2 also show the evaluation results of the antistatic film after the antistatic paint was applied and dried. Examples 1, 9, and 10 (films 1, 9, 10) were also evaluated for haze and film winding property, and the results are shown in Table 2.

[0221] [Table 1] Example 1 2 3 4 5 6 7 8 Film ART0N ART0N ART0N ART0N ZEON0R ZE0N0R ZE0N0R ZE0N0R Corona treatment Yes Yes No No Yes Yes No No Surface roughness (nra) 1 1 0. 2 0. 2 1 1 0, 2 0. 2 Norho'Runen resin film

55 55 43 43 55 55 43 43 Tension (m / m)

Antistatic coating material Paint 1 Painter 2 Paint 1 Paint 2 Paint 1 Paint 2 Paint 1 Paint 2 Finale name Film 1 Film 2 Film 3 Film 4 Film 5 Film 6 Film 7 Film 8 Wetting on the antistatic layer side

69 69 63 63 69 69 63 63 Tension (m / m)

Surface resistance (Ω / port) 10 ⁹ 10 ⁹ 10 ⁹ 10 ⁹ 10 ⁹ 10 ⁹ 10 ⁹ 10 ⁹ Adhering ft 25/25 25/25 15/15 20/25 25/25 25/25 15/25 15/25 Sex AABBAABB Overall percentage (%) 93 93 93 93 93 93 93 93 2]

Example 1 Example 9 Example 1 0

ARTON ARTON ARTON

Corona treatment Yes Yes Yes

Surface roughness (nm) 1 1 1

5 5 55 5 5

Tension (mN / m)

Antistatic coating material Paint 1 Paint 3 Paint 4 Film name F 1 Film 9 Film 1 0 Antistatic layer side

69 6 7 67

Wetting tension (mN / m)

Surface resistance j straight (Ω / D) 10 ⁹ 1 0 ⁹ 1 0 ⁹ Adhesion 25/25 25/2 5 2 5/25 Water resistance AAA Total light transmission rate (%) 93 9 3 93 Haze (%) 0 1 0. 1 0. 1 Film winding property BAA

[0223] [Comparative Examples 1 and 2]

Instead of antistatic paint 2, film A and film B were prepared in the same manner as in Example 2 except that a 2% by weight aqueous solution of amide betaine or a 2% by weight aqueous solution of polyethylene glycol was used. Obtained. The evaluation results of Film A and Film B are shown in Table 3.

[0224] Film A exhibited a sufficient antistatic ability with a low surface resistance, but the antistatic layer had poor adhesion and water resistance.

[0225] On the other hand, film B exhibited sufficient performance in terms of adhesion and water resistance, but had a high surface resistance value and inferior antistatic ability. [0226] [Table 3]

[Example 11]

As a norbornene-based resin film, manufactured by ARTON FLYLlOO iSR Co., Ltd.), the corona discharge treatment of 50 W * minZm ² was performed in the atmosphere on the norbornene-based resin film before application of antistatic coating. The prevention paint 2 was applied with a wire bar having a wet film thickness of 6 microns and dried at 75 ° C. for 1 minute to obtain a film 11. The glass transition temperature of ARTON FLYL 100 was 165 ° C.

[0228] Film 11 was heated at 150 ° C for 3 minutes in a forced agitation dryer to obtain Film 11-1.

[0229] Further, after the film 11 was heated to Tg + 15 ° C (180 ° C) in a tenter and stretched 1.3 times in the longitudinal direction in the in-plane direction of the film at a stretch rate of 300% Z, Stretch in the transverse direction in the in-plane direction of the film 1. 8 times, and then maintain this state for 1 minute in an atmosphere of Tg—20 ° C (145 ° C). The film was cooled while being held, further cooled at room temperature, and taken out from the tenter to obtain a film 11-2 after secondary drying accompanied by film stretching.

[0230] On the other hand, ARTON FLYL100 was heated in a tenter to Tg + 15 ° C (180 ° C) and stretched 1.3 times in the longitudinal direction in the in-plane direction of the film at a stretch rate of 300% Z. Stretched 1.8 times in the transverse direction in the in-plane direction, and then cooled while maintaining this state for 1 minute in an atmosphere of Tg—20 ° C (145 ° C), and further cooled at room temperature. The retardation film 1 was obtained. A film obtained by subjecting this retardation film 1 to corona discharge treatment in the same manner as in Example 1 and coating and drying the antistatic coating 2 was designated as Film 11-3.

[0231] For each of the obtained films, the evaluation items of Example 2, the in-plane retardation (@ 550ηm), the thickness direction retardation (@ 550nm), and the film thickness were measured or evaluated, and the results are shown in Table 4. Indicated.

[Example 12]

ZEONOR ZF14-100 (manufactured by Zeon Corporation) is used as the norbornene-based resin film, and the corona discharge treatment of 50 W 'minZm ² is performed on the norbornene-based resin film before application of antistatic paint in the atmosphere. ! / ..., antistatic paint 2 was applied with a 6 micron thick wet bar and dried at 75 ° C. for 1 minute to obtain film 12. The glass transition temperature of ZEON OR ZF14-100 was 140 ° C.

[0233] Film 12 was heated at 125 ° C for 3 minutes in a forced stirring dryer to obtain film 12-1.

[0234] In addition, the film 12 was heated to Tg + 15 ° C (155 ° C) in a tenter and stretched 1.3 times in the longitudinal direction in the in-plane direction at a stretching speed of 300% Z min. Stretch in the transverse direction in the in-plane direction by 1. 8 times, and then cool in an atmosphere of Tg—20 ° C (125 ° C) for 1 minute while maintaining this state, and further cool at room temperature. By taking out from the inside, film 12-2 after secondary drying accompanied by film stretching was obtained.

[0235] On the other hand, ZEONOR ZF14-100 was heated to Tg + 15 ° C (155 ° C) in a tenter and stretched 1.3 times in the longitudinal direction in the film plane at a stretching rate of 300% Z. After that, the film was stretched 1.8 times in the lateral direction in the in-plane direction of the film, and then cooled in an atmosphere of Tg—20 ° C (125 ° C) for 1 minute, and further cooled at room temperature. And take it out of the tenter A phase difference film 2 was obtained. A film obtained by subjecting this retardation film 2 to corona discharge treatment in the same manner as in Example 1 and coating and drying the antistatic coating 2 was designated as Film 12-3.

[0236] For each of the obtained films, the evaluation items of Example 2, the in-plane retardation (@ 550ηm), the thickness direction retardation (@ 550nm), and the film thickness were measured or evaluated, and the results are shown in Table 4. Indicated.

[0237] [Table 4]

[Example 13]

Polybur alcohol (hereinafter abbreviated as “PVA”) in a dyeing bath at a temperature of 30 ° C. comprising an aqueous solution having an iodine concentration of 0.03% by weight and a potassium iodide concentration of 0.5% by weight. In the cross-linking bath at a temperature of 55 ° C composed of an aqueous solution having a boric acid concentration of 5% by weight and a potassium iodide concentration of 8% by weight. A polarizing film (hereinafter also referred to as “polarizer”) was obtained by post-stretching and drying.

[0239] Next, by using the polyvinyl alcohol-based adhesive obtained in Preparation Example 3 on both sides of the polarizer, the polarizers were adhered so that the polarizer was sandwiched between the film 2 and the film 11-2. Got one. At this time, both the film 2 and the film 11-2 were placed on the side of the polarizer where the antistatic coating was applied.

[0240] Similarly, a polarizing plate 2 was obtained using the film 11-3 instead of the film 2 and the film 11-2.

[0241] The transmittances of the obtained polarizing plates 1 and 2 were both 44.0% and the degree of polarization was 99.9%.

[0242] When the adhesive properties of the obtained polarizing plates 1 and 2 were evaluated, peeling between the polarizer and the retardation film did not occur, and only material destruction occurred. The peel strength at that time was 6. ONZ25mm in the 90 ° peel test.

[0243] [Example 14]

A polarizing plate 3 and a polarizing plate 4 were obtained in the same manner as in Example 13 except that the film 6 was used instead of the film 2 and the film 12-2 or the film 12-3 was used instead of the film 11-2.

[0244] The transmittances of the obtained polarizing plates 3 and 4 were 44.0% and the polarization degree was 99.9%.

[0245] When the adhesive properties of the obtained polarizing plates 3 and 4 were evaluated, peeling between the polarizer and the retardation film did not occur, and only material destruction occurred. The peel strength at that time was 4.9 NZ25 mm in the 90 ° peel test.

[0246] In addition, the coated surfaces of film 2 and film 11-2 that were not coated with antistatic paint were both polarized. A polarizing plate 5 was obtained in the same manner as in Example 13 except that the polarizing plate 5 was disposed on the child side.

[0247] When the adhesive property of the obtained polarizing plate 5 was evaluated, peeling between the polarizer and the retardation film occurred easily. The peel strength at that time was 0.3 N / 25 mm in the 90 ° peel test.

[Example 15]

In order to evaluate the characteristics of the polarizing plate 1, in a clean environment, the polarizing plate and the retardation film attached to the observer side of a liquid crystal panel of a commercially available liquid crystal television are peeled off, and the polarizing plate 1 is used instead. A liquid crystal panel 1 was obtained by sticking to the front surface (observer side) of the liquid crystal panel using the water-based pressure-sensitive adhesive prepared in Preparation Example 4 so that the film 112 side became the panel side.

[0249] The liquid crystal panel 1 was strong even when the panel was lit, but no point-like defects were observed.

[0250] In addition, the liquid crystal panel 1 changed its appearance, peeled off from the polarizing plate, and removed from the polarizer even after 1000 hours in an environment of 60 ° C and 90% relative humidity. No film peeling was observed.

[0251] In addition, the liquid crystal panel 1 was observed to change the appearance of the panel and peel the polarizing plate from the panel and the film from the polarizer even after 1000 hours in an 80 ° C environment. Was not.

[Example 16]

Triethylene glycol monomethyl ether (boiling point 249) to 100 parts by weight of paint 2

A film 16 was obtained in the same manner as in Example 2 except that the paint added with 3 parts by weight of ° C) was used.

[0253] In film 2, a slight white turbidity was observed when the transparency was visually confirmed using a halogen light. In film 16, the transparency was observed when the transparency was visually confirmed under the same conditions. Was not confirmed at all.

Industrial applicability

[0254] The optical film according to the present invention can be preferably used for a polarizing plate, which is preferably used for a display application such as a liquid crystal display. In addition to its excellent adhesiveness, the optical film can be used for a hard coat. Film, antireflection film, transparent conductive film It can also be suitably used as a transparent substrate for attached films, infrared and ultraviolet cut films, various protective films and the like.

Claims

The scope of the claims

[1] (A) a norbornene-based resin film,

(B) (bl) an acrylic resin having a quaternary ammonium salt represented by the following formula (i) in the side chain, and (b2) a polyethylimine and Z or polyhydroxyalkane polyglycidyl ether Antistatic coating material containing a formed antistatic layer and

An optical film characterized by being laminated.

COO— Q ¹ — N (Q ² ) X

a b

(In the formula (i), Q ¹ is a divalent hydrocarbon group having 1 to 6 carbon atoms, Q ² is a monovalent hydrocarbon group having 1 to 3 carbon atoms, and X is a chlorine atom or a fluorine atom. Or — Q ³ — SO (where Q ³ is

Four

A single bond, a methylene group or an ethylene group. A and b are integers of 1 or 2 (where a + b = 3). Q ² , Q ³ and X may be the same or different when there are multiple. )

[2] The optical finer according to [1], wherein the antistatic coating material further contains a filler.

[3] The optical film of [1] or [2], wherein the surface resistance value on the antistatic layer side is in the range of 1 × 10 ⁶ to 1 × 10 ¹² Ω.

[4] The anti-wetting layer surface wettability measured according to the method specified in JIS 6768 is

The optical film according to any one of claims 1 to 3, wherein the optical film has a range of 50 to 70 mNZm.

[5] The optical film according to any one of [1] to [4], wherein the acrylic resin (bl) includes a structural unit derived from a (meth) acrylic acid ester having an alicyclic skeleton.

[6] The refractive index difference at a wavelength of 589 nm between the norbornene-based resin film (A) and the antistatic layer (B) is 0.1 or less, Optical finale.

7. The antistatic layer (B) has a metal atom content of 0.1% by weight or less and a halogen atom content of 1% by weight or less. The optical finem described in Crab.

[8] Norbornene-based resin at room temperature measured according to the method specified in JIS K7113 8. The optical film according to claim 1, wherein the tensile elastic modulus El of the film (A) and the tensile elastic modulus E2 of the antistatic layer (B) are in a relationship of E1> E2.

[9] The optical film according to any one of [1] to [8], wherein the norbornene-based resin film (A) is a stretched film.

[10] The retardation film having the optical film force according to [9].

[11] A retardation film obtained by stretching the optical film according to any one of claims 1 to 8.

[12] A polarizing plate using at least one of the optical films according to any one of claims 1 to 9, and at least one of the retardation films according to claim 10 or 11.

[13] A polarizing plate obtained by adhering the retardation film according to claim 10 and Z or 11 to a polarizing film using an adhesive or a pressure-sensitive adhesive, and measured according to JIS K7113. The tensile elastic modulus E1 of the rubornene-based resin film (A), the tensile elastic modulus E2 of the antistatic layer (B), and the tensile elastic modulus E3 of the adhesive or adhesive are in the relationship of E1> E2> E3 The polarizing plate according to claim 12, which is characterized.

[14] An adhesive or a pressure-sensitive adhesive is used for the antistatic layer side of the optical film according to any one of claims 1 to 9 or the antistatic layer side of the retardation film according to claim 10 or 11. 14. The polarizing plate according to claim 12, wherein the polarizing plate is obtained by adhering to a polarizing film.

[15] A liquid crystal display using the polarizing plate according to any one of claims 12 to 14.

[16] An acrylic resin (bl) having a quaternary ammonium salt represented by the following formula (i) in the side chain, a curing agent (b2) comprising polyethyleneimine and Z or polyhydroxyalkane polyglycidyl ether; A method for producing an optical film, comprising: applying an antistatic coating material containing a nonbornene-based resin film (A) and drying to form an antistatic layer (B).

COO— Q ¹ — N (Q ² ) X

a b

(In the formula (i), Q ¹ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Q ² is a monovalent hydrocarbon group having 1 to 3 carbon atoms. Is a hydrocarbon group, X is a chlorine atom, a fluorine atom or — Q ³ — SO (where Q ³ is a single atom

Four

[17] The average surface roughness (Ra) of the norbornene-based resin film (A) on the surface to which the antistatic coating material is applied is in the range of 0.3 to 2. Onm. 2. A method for producing an optical film as described in 1. above.

[18] The surface wettability of the norbornene-based resin film (A) on the surface to which the antistatic coating material is applied, measured according to the method specified in JIS K6 768, is in the range of 50 to 70 mNZm. The method for producing an optical film according to claim 16 or 17.

[19] The optical film according to any one of claims 16 to 18, wherein the acrylic resin (bl) includes a structural unit derived from a (meth) acrylic acid ester having an alicyclic skeleton. Manufacturing method.

[20] The method for producing an optical film according to any one of [16] to [19], wherein the antistatic coating material is an aqueous coating material.

[21] The method for producing an optical film according to any one of [16] to [20], wherein the antistatic coating material further contains a filler.

[22] Drying the applied antistatic coating material,

1) a primary drying step at 80 ° C or lower;

2) Glass transition temperature (Tg) of norbornene-based resin film (A)-secondary drying process at a temperature exceeding 30 ° C

The method for producing an optical film according to any one of claims 16 to 21, which is carried out by a multi-stage drying process having:

23. The method for producing an optical film according to claim 22, wherein the film is stretched in the secondary drying step.

24. The method for producing an optical film according to any one of claims 16 to 23, wherein the halogen atom content in the acrylic resin (bl) is 1% by weight or less.