TWI441731B - Optical film and its use and manufacturing method - Google Patents

Description

Optical film and use thereof and method of manufacture

The present invention relates to an optical film having antistatic energy, use of the optical film, and a method of manufacturing the same. More specifically, the present invention relates to an optical film having an antistatic property suitable for use in a polarizing plate or the like on an original borneol-based resin film, an antistatic layer, an application thereof, and a production method.

A polarizing plate (polarizing film) used for a liquid crystal display or the like is generally formed of a substrate (optical film) having excellent transparency and a polarizing film (polarizer). Further, the polarizing plate may be formed of a film (retardation film) which imparts a function of imparting a phase difference to the optical film and which is extended by the transmitted light, and a polarizing film.

In the past, as the optical film used for the substrate of the polarizing plate or the retardation film, a polycarbonate film, a polyester film, a polyethylene terephthalate (TAC) film, or the like can be used, but a polycarbonate film or a polyester film is used. In the polarizing plate, the photoelastic coefficient is too large, and the phase difference imparted to the transmitted light changes due to a change in minute stress or the like. Further, since the polyethylene terephthalate (TAC) film is too low in heat resistance and has excessive water absorbency, the polarizing plate used therein is liable to be deformed depending on the use environment, and has a problem that optical change is likely to occur.

However, since the norbornene-based resin is excellent in transparency, heat resistance, chemical resistance, and the like, it is considered as a material for various optical components, and is particularly suitable for use in optical films. For this reason, Patent Document 1 discloses a polarizing film in which an original borneol-based resin sheet is used as a protective layer and laminated on a polarizing film. Such a polarizing film is expected to be used for applications such as liquid crystal displays because of its excellent water resistance, moisture resistance, heat resistance, transparency, durability to an adhesive, and the like.

However, the original norbornene-based resin and other resin raw materials are inferior in adhesion, and the polarizing plate using the original borneol resin film is difficult to manufacture, and there is a problem that peeling occurs due to long-term use.

In addition, the original borneol resin is easy to generate static electricity due to low water absorption, and the optical film made of the original borneol-based resin is easily adhered as a film roll, and even if the film roll is released, static electricity is peeled off, and it is easily adsorbed from the environment. When foreign matter is laminated with other raw materials, there is a problem that foreign matter is taken out between the layers. For example, when a polarizing plate made of a polyvinylidene-based resin film and a polyvinyl alcohol (PVA) are laminated to produce a polarizing plate, if a foreign matter is mixed, the portion becomes a point defect, and the obtained polarizing plate is used for When there is a display, etc., there will be a problem of bright spots.

As a method of preventing static electricity at the time of lamination, it has been proposed to use an adhesive used between other raw materials laminated with a film made of an original borneol-based resin as an antistatic type, but in the method, an adhesive is used. The subsequent nature may be too weak, and the peeling static electricity or the like when the film roll is released may not be reduced. Therefore, it is expected that the film of the original borneol-based resin is self-static.

However, the original borneol-based resin film having a phase difference is bonded to a polarizing plate such as PVA, and the original borneol-based resin film is low in hygroscopicity and excellent in hardness, and functions as a protective film. Therefore, it is not necessary to further conform to the protective film of the polarizing plate, and the advantage of being easy to ensure transparency due to the small number of laminations can be simplified.

When the polarizing plate is bonded to the liquid crystal panel and the liquid crystal display is combined, the adhesive layer and the living film for protecting it are provided in advance on the bonding surface, and the living film is peeled off after bonding, followed by the polarizing plate and the liquid crystal. The method of the panel is adopted because of the simplicity of the steps.

However, when the living film on the polarizing plate is peeled off, the static electricity is peeled off, and the liquid crystal display obtained after the production is in a charged state. If the product cannot be inspected after the static electricity is removed, the production efficiency is deteriorated.

Therefore, generation of an optical film made of a raw borneol-based resin in which static electricity is sufficiently suppressed is expected.

As a technique for preventing static electricity such as a film, an antistatic agent is used for the film. However, when a large amount of the antistatic agent such as a surfactant is used, the adhesion may be inhibited, and the antistatic agent may have a low molecular weight. Friction, dissolution, leakage, etc. may cause the antistatic agent to fall off and reduce the antistatic effect.

The inventors of the present invention conducted detailed investigation results in view of such a situation, and found that the surface has an original borneol-based resin film having an antistatic layer formed of an antistatic coating material containing a specific acrylic resin and a curing agent, which has sufficient antistatic properties. At the same time, the present invention can be completed by exerting antistatic energy for a long period of time.

[Patent Document 1] JP-A-6-51117

The present invention provides an optical film made of a raw borneol-based resin which is excellent in adhesion to a polarizing film and excellent in properties such as transparency, heat resistance, and chemical resistance, and which can maintain excellent antistatic performance for a long period of time and its production. The method and the long-term use are also less prone to peeling, deformation, etc., and the polarizing plate of the optical film having less foreign matter incorporated into the environment, and the liquid crystal display using the polarizing plate As a subject.

The optical film of the present invention is obtained by laminating (A) a raw borneol-based resin film and (B) an acrylic resin having a (b1) side chain having a 4-stage ammonium salt represented by the following formula (i), and (b2) The antistatic layer formed by the antistatic coating material of the curing agent of polyethyleneimine and/or polyhydroxyalkane polyglycidyl ether is characterized.

-COO-Q ¹ -N(Q ² ) _a X _b (i) (in the formula (i), Q ¹ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Q ² is 1 having a carbon number of 1 to 3 a hydrocarbon group, X is a chlorine atom, a fluorine atom or -Q ³ -SO ₄ (however, Q ³ is a single bond, a methyl group or an ethyl group), and a and b are integers of 1 or 2 (however, a+b=3) When Q ² , Q ³ and X are plural, each may be the same or different).

Thus, the optical film of the present invention is preferably one in which the antistatic coating material further contains a filler.

Further, the optical film of the present invention preferably has a surface resistance value of from 1 × 10 ⁶ to 1 × 10 ¹² Ω/□ on the side of the antistatic layer.

The optical film of the present invention is preferably in the range of 50 to 70 mN/m in terms of the wettability of the surface of the antistatic layer measured in accordance with the method specified in JIS K6768.

In the optical film of the present invention, the acrylic resin (b1) is preferably a structural unit containing a (meth) acrylate having an alicyclic skeleton.

In the optical film of the present invention, the difference between the refractive index of the original borneol-based resin film (A) and the antistatic layer (B) at a wavelength of 589 nm is preferably 0.1 or less.

In the optical film of the present invention, in the antistatic layer (B), the metal atom content is 0.1% by weight or less, and the halogen atom content is preferably 1% by weight or less.

In the optical film of the present invention, the tensile modulus E1 of the norbornene-based resin film (A) and the tensile modulus E2 of the antistatic layer (B) at room temperature are measured in accordance with the method specified in JIS K7113. The relationship between E1 and E2 is better.

In the optical film of the present invention, the original borneol-based resin film (A) is preferably a film which is stretched in advance, and the phase difference film of the present invention is formed from the optical film of the present invention.

Further, the retardation film of the present invention is characterized by being obtained by extending the optical film of the present invention.

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.

In the polarizing plate of the present invention, the retardation film of the present invention is obtained by using an adhesive or an adhesive, followed by a polarizing plate obtained on the polarizing film, and the original borneol-based resin film (A) is measured in accordance with JIS K7113. The tensile modulus E1 and the tensile modulus E2 of the antistatic layer (B) and the tensile modulus E3 of the adhesive or the adhesive are characterized by a relationship of E1 > E2 > E3.

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

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

The method for producing an optical film of the present invention comprises an acrylic resin (b1) having a 4-grade ammonium salt represented by the following formula (i) in a side chain, and a polyethylene glycol and/or a polyhydroxyalkane polyglycidol. The antistatic coating material of the hardener (b2) formed by ether is applied onto the original borneol-based resin film (A), and is dried to form an antistatic layer (B).

-COO-Q ¹ -N(Q ² ) _a X _b (i) (in the formula (i), Q ¹ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Q ² is 1 having a carbon number of 1 to 3 a valence hydrocarbon group, X is a chlorine atom, a fluorine atom or -Q ³ -SO ₄ (however, Q ³ is a single bond, a methyl group or an ethyl group). a and b are integers of 1 or 2 (however, a+b=3 When Q ² , Q ³ and X are plural, each may be the same or different).

In the method for producing an optical film of the present invention, it is preferred that the norbornene-based resin film coated on the surface of the antistatic coating material has an average surface roughness (Ra) of 0.3 to 2.0 nm.

In the method for producing an optical film of the present invention, the method specified in JIS K6768 of the original borneol-based resin film (A) coated with the surface of the antistatic coating material is a surface wettability of 50 to 70 mN/m. The range is better.

In the method for producing an optical film of the present invention, the acrylic resin (b1) is preferably a structural unit containing a (meth) acrylate derived from an alicyclic skeleton.

In the method for producing an optical film of the present invention, the antistatic coating material is preferably a water-based coating material. Moreover, it is preferable that the antistatic coating material further contains a filler.

In the method for producing an optical film of the present invention, the applied antistatic coating material is dried by a drying step having 1) 80 ° C or less and 2) glass exceeding the original borneol resin film (A). The multi-stage drying step of the secondary drying step at a temperature of the transfer temperature (Tg) of -30 ° C is preferably carried out. In the method for producing an optical film of the present invention, it is preferred to carry out the stretching of the film in the secondary drying step.

In the method for producing an optical film of the present invention, the content of the halogen atom in the acrylic resin (b1) is preferably 1% by weight or less.

The present invention provides excellent adhesion to an optical material such as a polarizing film and the like, and is excellent in properties such as transparency, heat resistance, and chemical resistance, and can maintain excellent antistatic performance for a long period of time and excellent durability. The optical film made of the original borneol-based resin and the method for producing the same have high signalability such as peeling and deformation in a long-term use, and in the manufacturing step, the optical film which does not incorporate foreign matter from the environment is used. A polarizing plate, and a liquid crystal display using the polarizing plate.

Hereinafter, the present invention will be specifically described.

<<Optical film>>

In the optical film of the present invention, an antistatic layer (B) is laminated on at least one surface of the original borneol-based resin film (A), which is an optical film having antistatic properties.

(A) The original borneol-based resin film of the original borneol-based resin film (A) used in the present invention contains at least one kind of polymerization or copolymerization (hereinafter also referred to as (co)polymerization). A monomer or a monomer composition of a compound having a norbornene skeleton (hereinafter also referred to as a norbornene-based compound), which is obtained by hydrogenation if necessary.

<Monomer> The raw borneol compound which is a constituent monomer or a monomer composition is not particularly limited, and examples thereof include a norbornene-based compound represented by the following formula (1).

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms or the like containing oxygen, nitrogen, sulfur or hydrazine; The price is organic. Wherein R ¹ and R ² or R ³ and R ⁴ are bonded to each other to form an alkylene group Forming, R ¹ and R ² , R ³ and R ⁴ or R ² and R ³ are bonded to each other to form a carbocyclic or complex ring (the carbocyclic or complex ring may be a single ring structure, or other rings may be condensed to form a polycyclic ring). structure.). The carbocyclic or complex ring formed may be an aromatic ring or may be a non-aromatic ring. Also, x represents an integer from 0 to 3, and y represents 0 or 1].

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

Bicyclo [2.2.1] hept-2-ene (formylbornene), 5-methyl-bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene , 5-cyclohexyl-bicyclo[2.2.1]hept-2-ene, 5-phenyl-bicyclo[2.2.1]hept-2-ene, 5-(4-biphenyl)-bicyclo[2.2.1 ???hept-2-ene, 5-methoxycarbonyl-bicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonyl-bicyclo[2.2.1]hept-2-ene, 5-phenoxy Ethylcarbonyl-bicyclo[2.2.1]hept-2-ene, 5-phenylcarbonyloxy-bicyclo[2.2.1]hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo[ 2.2.1] Hept-2-ene, 5-methyl-5-phenoxycarbonyl-bicyclo[2.2.1]hept-2-ene, 5-methyl-5-phenoxyethylcarbonyl-bicyclo[ 2.2.1] Hept-2-ene, 5-ethylene-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl -bicyclo[2.2.1]hept-2-ene, 5,6-dimethyl-bicyclo[2.2.1]hept-2-ene, 5-fluoro-bicyclo[2.2.1]hept-2-ene, 5-chloro-bicyclo[2.2.1]g 2-ene, 5-bromo-bicyclo[2.2.1]hept-2-ene, 5,6-difluoro-bicyclo[2.2.1]hept-2-ene, 5,6-dichloro-bicyclo[2.2 .1]hept-2-ene, 5,6-dibromo-bicyclo[2.2.1]hept-2-ene, 5-hydroxy-bicyclo[2.2.1]hept-2-ene, 5-hydroxyethyl- Bicyclo[2.2.1]hept-2-ene, 5-cyano-bicyclo[2.2.1]hept-2-ene, 5-amino-bicyclo[2.2.1]hept-2-ene, tricyclo[4.3 .0.1 ^2,5 〕Indol-3-ene, tricyclo[4.4.0.1 ^2,5 ]undec-1-ene, 7-methyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene , 7-ethyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-cyclohexyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-phenyl-tricyclic [4.3.0.1 ^2,5 ] Indole-3-ene, 7-(4-biphenylyl)-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7,8-dimethyl-tricyclic [4.3.0.1 ^2,5 ] Indole-3-ene, 7,8,9-trimethyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 8-methyl-tricyclo[4.4. 0.1 ^2,5] undecane-3-ene, 8-phenyl - tricyclo [4.4.0.1 ^2,5] undecane-3-ene, 7-fluoro - Ring [4.3.0.1 ^2,5] dec-3-ene, 7-chloro - tricyclo [4.3.0.1 ^2,5] dec-3-ene, 7-bromo - tricyclo [4.3.0.1 ^2,5] dec 3-ene, 7,8-dichloro-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7,8,9-trichloro-tricyclo[4.3.0.1 ^2,5 ]癸-3 - alkene, 7-chloromethyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-dichloromethyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7- Trichloromethyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-hydroxy-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-cyano-tricyclo[4.3 .0.1 ^2,5 〕Indol-3-ene, 7-Amino-tricyclo[4.3.0.1 ^2,5 ]Indol-3-ene, Tetracycline [4.4.0.1 ^2,5 .1 ^7,10 ] Laurel - 3- ene, pentacyclo [7.4.0.1 ^2,5 .1 ^8,11 .0 ^7,12] pentadecyl-3-ene, hexacyclo [8.4.0.1 ^2,5 .1 ^7,14 .1 ^{9, 12} .0 ^8,13 】 heptadecan-3-ene, 8-methyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]lauro-3-ene, 8-ethyl-tetracyclo[4.4 .0.1 ^2,5 .1 ^7,10 〕 Laurel-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] Laurel-3-ene, 8-phenyl-tetracyclic [4.4.0.1 ^2,5 .1 ^{7 , 10} 〕 Laurel-3-ene, 8-(4-biphenyl)-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] Laurel-3-ene, 8-methoxycarbonyl-tetracycline 4.4.0.1 ^2,5 .1 ^7,10 〕 Laurel-3-ene, 8-phenoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] Laurel-3-ene, 8-phenoxy Ethyl ethyl carbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] lauryl-3-ene, 8-phenylcarbonyloxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] laurel 3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] lauryl-3-ene, 8-methyl-8-phenoxycarbonyl- Tetracycline [4.4.0.1 ^2,5 .1 ^7,10 ] Laurel-3-ene, 8-methyl-8-phenoxyethylcarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] Laurel-3-ene, 8-ethylene-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]lauro-3-ene, 8-ethylene-tetracyclo[4.4.0.1 ^2,5 .1 ^{7, 10} ] Laurel-3-ene, 8,8-dimethyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] Laurel-3-ene, 8,9-dimethyl-tetracyclo[4.4. 0.1 ^2,5 .1 ^7,10] lauryl-3-ene, 8-fluoro - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] lauryl-3-ene, 8- - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] lauryl-3-ene, 8-bromo - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] lauryl-3-ene, 8,8 -Dichloro-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] Laurel-3-ene, 8,9-dichloro-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] Laurel-3 -ene, 8,8,9,9-tetrachloro-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]lauro-3-ene, 8-hydroxy-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 〕 Laurel-3-ene, 8-hydroxyethyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] Laurel-3-ene, 8-methyl-8-hydroxyethyl-tetracyclic [4.4.0.1 ^2,5 .1 ^7,10 ] Laurel-3-ene, 8-cyano-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] Laurel-3-ene, 8-amino- Tetracycline [4.4.0.1 ^2,5 .1 ^7,10 ] Laurel-3-ene.

Further, these ortho-ene ene-based compounds may be used alone or in combination of two or more.

The type and amount of the raw borneol compound constituting the monomer or monomer composition can be appropriately selected depending on the properties required of the obtained raw borneol-based resin.

In the present invention, a compound having a structure (hereinafter also referred to as "polar structure") having at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom or a ruthenium atom in the molecule is used, and It is preferred that the raw material has excellent adhesion or adhesion. In particular, in the above formula (1), R ¹ and R ³ are a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and any of R ² or R ⁴ is a group having a polar structure. The compound which is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferred because the water absorption (wet) property of the resin is low. Further, the orogenic borneol-based compound having a group having a polar structure and having a group represented by the following formula (2) is preferred because it is easy to obtain a balance between heat resistance and water absorption (wet) of the obtained resin.

-(CH ₂ ) _Z COOR (2) (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 hydride, and the better the heat resistance, so it is preferable that z is 0 or 1 to 3 is an integer. The monomer having z of 0 is preferred from the viewpoint of easy synthesis. Further, in the above formula (2), the higher the carbon number of R, the lower the water absorption (wet) property of the obtained (co)polymer or the hydride thereof, but the glass transition temperature tends to decrease. From the viewpoint of maintaining heat resistance, a hydrocarbon group having 1 to 10 carbon atoms is preferred, and a hydrocarbon group having 1 to 6 carbon atoms is particularly preferred.

Further, in the above formula (1), the carbon atom to which the group represented by the formula (2) is bonded is bonded to the alkyl group having 1 to 3 carbon atoms, particularly when heat is bonded to the water, and the water is absorbed (wet). It is better to balance the point of view. Further, in the above formula (1), a compound wherein x is 0 or 1, and y is 0, which has a high reactivity, a polymer obtained at a high yield, and a polymer hydride having high heat resistance, and further industrial It is better to have an easy-to-obtain view.

In order to obtain the ornidylene-based resin to be used in the present invention, a monomer copolymerizable with the above-mentioned ortho-ene-based compound can be polymerized in a monomer composition in a range that does not impair the effects of the present invention. Examples of the copolymerizable monomer include cyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and cyclolaurene, or 1,4-cyclooctadiene and dicyclopentane. A non-conjugated cyclic polyene such as an alkene or a cyclolaurotriene.

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

<(co)polymerization method> The raw borneol-based resin constituting the original borneol-based resin film (A) used in the present invention is obtained by (co)polymerizing the monomer or monomer composition, and if necessary, Manufactured by hydrogenation. The method of (co)polymerization is not particularly limited, and examples thereof include a method of subjecting the monomer or the monomer composition to ring-opening polymerization or addition polymerization.

A. Ring-opening polymerization The production of a (co)polymer by ring-opening polymerization can be carried out by a known ring-opening polymerization reaction for a raw borneol-based compound, and polymerization of a monomer composition containing the aforementioned norbornene-based compound. The catalyst, the solvent for polymerization, and, if necessary, a molecular weight modifier, are produced by ring-opening polymerization.

. Ring-opening polymerization catalyst In the present invention, when the (co)polymerization of the monomer composition is carried out by ring-opening (co)polymerization, it is generally carried out in the presence of a metathesis catalyst.

The metathesis catalyst is (A) at least one compound selected from the group consisting of compounds having W, Mo, and Re (hereinafter also referred to as compound (A)), and (B) a group IA element having a Deming period (for example, Li). , Na, K, etc.), Group IIA elements (eg, Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg, etc.), Group IIIA elements (eg, B, Al, etc.), Group IVA elements (eg a compound of Si, Sn, Pb, or the like, or a group IVB element (for example, Ti, Zr, etc.), and at least one compound selected from the group consisting of a compound having at least one bond of the element and carbon or a bond of the element and hydrogen. A catalyst formed by a combination of a compound (hereinafter also referred to as a compound (B)). Further, in order to increase the activity of the catalyst, the additive (C) described later may be further added.

Examples of the compound (A) include a halide of W, Mo or Re, an oxyhalide, an alkoxy halide, an alkoxide, a carboxylate, an (oxy)acetone acrylate, a carbonyl complex, An acetonitrile complex, a hydride complex, and derivatives thereof, or a combination thereof, but a compound of W and Mo, particularly a halide, an oxyhalide and an alkoxy halide, in terms of polymerization activity and practicality It is better to look at it. Further, a mixture of two or more kinds of compounds which form the above compounds can be used by the reaction. Further, these compounds can be cleaved by a suitable deactivating agent, for example, by P(C ₆ H ₅ ) ₅ , C ₅ H ₅ N or the like.

Specific examples of the compound (A) include WCl ₆ , WCl ₅ , WCl ₄ , WBr ₆ , WF ₆ , WI ₆ , MoCl ₅ , MoCl ₄ , MoCl ₃ , ReCl ₃ , WOCl ₄ , MoOCl ₃ , and ReOCl _{3 .} , ReOBr ₃ , W(OC ₆ H ₅ ) ₆ , WCl ₂ (OC ₆ H ₅ ) ₄ , Mo(OC ₂ H ₅ ) ₂ Cl ₃ , Mo(OC ₂ H ₅ ) ₅ , MoO ₂ (acac) ₂ , W(OCOR) ₅ , W(OC ₂ H ₅ ) ₂ Cl ₃ , W(CO) ₆ , Mo(CO) ₆ , Re ₂ (CO) ₁₀ , ReOBr ₃ . P(C ₆ H ₅ ) ₃ , WCl ₅ . P(C ₆ H ₅ ) ₃ , WCl ₆ . C ₅ H ₅ N, W(CO) ₅ . P(C ₆ H ₅ ) ₃ , W(CO) ₃ . (CH ₃ CN) ₃ and so on. Further, among the above compounds, particularly preferred are MoCl ₅ , Mo(OC ₂ H ₅ ) ₂ Cl ₃ , WCl ₆ , W(OC ₂ H ₅ ) ₂ Cl ₃ and the like.

Specific examples of the compound (B) include n-C ₄ H ₅ Li, n-C ₅ H ₁₁ Na, C ₅ H ₅ Na, CH ₃ MgI, C ₂ H ₅ MgBr, CH ₃ MgBr, n-. C ₃ H ₇ MgCl, (C ₆ H ₅ ) ₃ Al, t-C ₄ H ₉ MgCl, CH ₂ =CHCH ₂ MgCl, (C ₂ H ₅ ) ₂ Zn, (C ₂ H ₅ ) ₂ Cd, CaZn ( C ₂ H ₅ ) ₄ , (CH ₃ ) ₃ B, (C ₂ H ₅ ) ₃ B, (n-C ₄ H ₉ ) ₃ B, (CH ₃ ) ₃ Al, (CH ₃ ) ₂ AlCl, (CH ₃ ) ₃ Al ₂ Cl ₃ , CH ₃ AlCl ₂ , (C ₂ H ₅ ) ₃ Al, LiAl(C ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₃ Al-O(C ₂ H ₅ ) ₂ , ( C ₂ H ₅ ) ₂ AlCl, C ₂ H ₅ AlCl ₂ , (C ₂ H ₅ ) ₂ AlH, (iso-C ₄ H ₉ ) ₂ AlH, (C ₂ H ₅ ) ₂ AlOC ₂ H ₅ , (iso- C ₄ H ₉ ) ₃ Al, (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ , (CH ₃ ) ₄ Ga, (CH ₃ ) ₄ Sn, (n-C ₄ H ₉ )Sn, (C ₂ H ₅ ) ₃ SiH, (n-C ₆ H ₁₃ ) ₃ Al, (n-C ₄ H ₁₇ ) ₃ Al, LiH, NaH, B ₂ H ₆ , NaBH ₄ , AlH ₃ , LiAlH ₄ , BiH ₄ and TiH ₄ . Further, a mixture of two or more kinds of these compounds which are produced by the reaction can be used. As such a preferable example, (CH ₃ ) ₃ Al, (CH ₃ ) ₂ AlCl, (CH ₃ ) ₃ Al ₂ Cl ₃ , CH ₃ AlCl ₂ , (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , C ₂ H ₅ AlCl ₂ , (C ₂ H ₅ ) ₂ AlH, (C ₂ H ₅ ) ₂ AlOC ₂ H ₅ , (C ₂ H ₅ ) ₂ AlCN, (C ₃ H ₇ ) ₃ Al, (iso-C ₄ H ₉ ) ₃ Al, (iso-C ₄ H ₉ ) ₂ AlH, (C ₆ H ₁₃ ) ₃ Al, (C ₈ H ₁₇ ) ₃ Al, (C ₆ H ₅ ) ₅ Al, and the like.

As the additive (C) which can be used together with the compound (A) and the compound (B), an alcohol, an aldehyde, a ketone, an amine or the like can be used, and examples thereof include the following (1) to (9). .

(1) Boron, such as boron, BF ₃ , BCl ₃ , B(O-n-C ₄ H ₉ ) ₃ , (C ₂ H ₅ O ₃ ) ₂ , BF, B ₂ O ₃ , H ₃ BO ₃ Non-organometallic compounds, non-organometallic compounds such as Si(OC ₂ H ₅ ) ₄ ; (2) alcohols, hydrogen peroxides and peroxides; (3) water; (4) oxygen; (5) a carbonyl compound such as an aldehyde or a ketone and a polymer thereof; (6) a cyclic ether such as ethylene oxide, epichlorohydrin or oxetane; (7) N,N-diethylformamidine An amine such as an amine or an amine such as N,N-dimethylacetamide, an amine such as aniline, morpholine or piperidine or an azo compound such as azobenzene; (8) N-nitrosodimethylamine; An N-nitroso compound such as N-nitrosodiphenylamine; (9) an S-Cl or N-Cl group such as chloroform, N-chlorosuccinimide or phenylsulfinyl chloride Compound.

The amount of the metathesis catalyst used is such that the molar ratio of the total monomer obtained by polymerizing the compound (A) (compound: all monomer) is generally from 1:500 to 1:50,000, preferably 1:1,000. ~1: 10,000.

The ratio of the compound (A) to the compound (B) (the compound (A): the compound (B)) has a metal atomic ratio of 1:1 to 1:50, preferably 1:2 to 1:30.

The ratio of the compound (A) to the compound (C) (the compound (C): the compound (A)) has a molar ratio of 0.005:1 to 15:1, preferably 0.05:1 to 7:1.

. The polymerization solvent is used as a solvent used in the ring-opening polymerization reaction, and the monomer composition or catalyst used in the polymerization is not deactivated by dissolution, and only the ring-opening polymer formed by dissolution can be used. It is not particularly limited, and examples thereof include alkanes such as pentane, hexane, heptane, octane, decane, and decane; cyclohexane, cycloheptane, cyclooctane, decalin, and raw spinel. Isocyclic alkanes; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, dichloromethane, dichloroethane, hexamethylene dibromide, chloroform Halogenated alkane such as tetrachloroethylene; halogenated aryl compound such as chlorobenzene; saturated carboxylic acid ester such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, dimethoxyethane An ether such as dibutyl ether, tetrahydrofuran or dimethoxyethane. These can be used individually or in mixture of 2 or more types. The solvent is used as a solvent constituting the molecular weight modifier solution and a solvent for dissolving the original borneol compound, the copolymerizable monomer, and/or the metathesis catalyst.

The amount of the solvent used, the weight ratio of the solvent to the monomer composition to be polymerized (solvent: monomer composition) is usually from 1:1 to 10:1, preferably from 1:1 to 5:1.

. The molecular weight of the ring-opening polymer obtained by the molecular weight modifier can be adjusted by the polymerization temperature, the type of the catalyst, and the type of the solvent, but can be adjusted by the coexistence of the molecular weight modifier in the reaction system.

Preferred examples of the molecular weight modifier include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-decene. Such as α-olefins and styrene, 4-methylstyrene, 2-methylstyrene, 4-ethylstyrene, with 1-butene and 1-hexene being particularly preferred. These molecular weight modifiers can be used alone or in combination of two or more.

The amount of the molecular weight modifier used is generally from 0.005 to 0.6 mol, preferably from 0.01 to 0.5 mol, for the monomer 1 mole used in the ring-opening polymerization.

. Other ring-opening polymerization conditions The ring-opening polymer can be obtained by ring-opening polymerization of the above-mentioned ortho-ene-based compound alone or the above-mentioned ortho-ene-based compound and a copolymerizable monomer, but a total of polybutadiene, polyisobutylene, and the like. a conjugated diene compound, a styrene-butadiene copolymer, an ethylene-nonconjugated diene copolymer, a polynorbornene, or the like, and an unsaturated hydrocarbon having two or more carbon-carbon double bonds in its main chain The monomer composition containing a norbornene-based compound is subjected to ring-opening polymerization in the presence of a polymer or the like.

. The polymer obtained by the above ring-opening polymerization is hydrogenated, and has an olefinic unsaturated bond in the molecule. Further, in the above-mentioned addition polymerization reaction, the polymer may have an olefinic unsaturated bond in the molecule. When an olefinic unsaturated bond is present in the polymer molecule, the related olefinic unsaturated bond is caused by deterioration over time or gelation, so that the olefinic unsaturated bond is converted into a hydrogenation of a saturated bond. The reaction is better.

The hydrogenation reaction is carried out by adding a known hydrogenation catalyst to a solution of a polymer having an olefinic unsaturated bond, wherein the atmospheric pressure is -300 atmospheres, preferably 3 to 200 atmospheres of hydrogen at 0 to 200. It is carried out at a temperature of ° C, preferably 20 to 180 ° C.

The hydrogenation ratio of the hydrogenated polymer is 500 MHz, and the value measured under ¹ H-NMR is generally 50% or more, preferably 70% or more, preferably 90% or more, particularly preferably 98% or more, and most preferably 99% or more. . The higher the hydrogenation rate, the better the stability to heat or light. When used as a molded article, it is preferable because it can obtain stable properties over a long period of time.

Further, when the polymer obtained by the above method has an aromatic group in the molecule, the related aromatic group does not cause deterioration such as time-lapse coloration or gelation, and it is advantageous in terms of mechanical properties or optical properties. The role does not necessarily require hydrogenation for the relevant aromatic groups.

As the hydrogenation catalyst, a user of a hydrogenation reaction of a general olefinic compound can be used. As the hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are exemplified.

Examples of the heterogeneous catalyst include noble metal catalyst materials such as palladium, platinum, nickel, rhodium, and ruthenium, and examples thereof include a solid catalyst supported on a carrier such as carbon, cerium oxide, alumina, or titania. Examples of the homogeneous catalyst include cycloalkyl nickel/triethyl aluminum, nickel acetonitrile pyruvate/triethyl aluminum, cobalt octylate/n-butyl lithium, and dichlorotitanium dichloride/diethyl. Monochloroaluminum, barium acetate, chloroform (triphenylphosphine) ruthenium, dichlorostilbene (triphenylphosphine) ruthenium, chlorohydrocarbonyl carbonyl (triphenylphosphine) ruthenium, dichlorocarbonyl ginseng (triphenylphosphine) )钌. The form of the catalyst can be powder or granular.

These hydrogenation catalysts, generally in a weight ratio of a ring-opening polymer to a hydrogenation catalyst (open-loop polymer: hydrogenation catalyst), are used in a ratio of 1:1 × 10 ^-6 to 1:2 × 10 ^-3 .

B. Addition Polymerization The production of a polymer obtained by addition (co)polymerization is carried out by a known addition polymerization reaction to a raw borneol-based compound, and a monomer composition containing the above-mentioned ortho-ene-based compound is used. The polymerization catalyst is produced by addition polymerization using a solvent for polymerization reaction and, if necessary, a molecular weight modifier.

. The addition polymerization catalyst is a polymerization catalyst for addition polymerization, and examples thereof include a single catalyst or a multi-component catalyst such as palladium, nickel, cobalt, titanium, or zirconium as described in the following (1) to (3). However, the polymerization catalyst used in the present invention is not limited thereto.

(1) Single catalyst system [Pd(CH ₃ CN) ₄ ][BF ₄ ] ₂ , [Pd(PhCN) ₄ ][SbF ₆ ] [(η ³ - Crotonyl) Pd (cycloxin-1,5- Diene)][PF ₆ ], [(η ³ -crotyl)Ni(cyclooctane-1,5-diene)][B(3,5-(CF ₃ ) ₂ C ₆ F ₃ ) ₄ ], [(η ³ - Crotonyl) Ni (cyclooctane-1,5-diene)][PF ₆ ], [(η ³ -allyl)Ni(cyclooctane-1,5-diene)][B(C ₆ F ₅ ) ₄ ], [(η ³ - Crotonyl) Ni (cyclooctane-1,5-diene)] [SbF ₆ ], toluene. Ni(C ₆ F ₅ ) ₂ , benzene. Ni(C ₆ F ₅ ) ₂ , trimethylbenzene. Ni(C ₆ F ₅ ) ₂ , diethyl ether (ethylether). Ni(C ₆ F ₅ ) ₂ and the like.

(2) The multi-component catalyst system may be a combination of a palladium complex having a σ or σ, π bond with an organoaluminum or a super acid salt, and a di-μ-chloro-bis(6-methoxybicyclo[2.2 .1]hept-2-ene-endo-5 σ,2 π)Pd, in combination with a compound selected from methyl titanium dioxide (MAO), AgSbF ₆ or AgBF ₄ , [(η ³ -aryl) PdCl ₂ , in combination with AgSbF ₆ or AgBF ₄ , [(cyclooctyl-1,5-diene) Pd(CH ₃ )Cl] and PPh ₃ with NaB[3,5-(CF ₃ ) ₂ C ₆ H ₃ ] ₄ combinations, etc.

(3) a multicomponent catalyst system (I) is selected from the group consisting of a nickel compound, a cobalt compound, a transition metal compound of a titanium compound or a zirconium compound, (II) a compound selected from the group consisting of super acid, Lewis acid and ionic boron compound, (III) The three components of the organoaluminum compound are combined.

(I) Examples of transition metal compounds (I-1) Examples of nickel compounds and cobalt compounds: organic carboxylates selected from nickel or cobalt, organic phosphites, organic phosphates, organic sulfonates, β-diketones a compound such as a compound; for example, nickel hexanoate, cycloalkyl nickel, cycloalkyl cobalt, nickel oleate, nickel laurate, cobalt laurate, cobalt neodecanoate, nickel dibutyl phosphite , dibutyl nickel phosphate, nickel dioctyl phosphate, salt of dibutyl phosphate, nickel lauryl benzene sulfonate, nickel p-toluene sulfonate, nickel bis(acetyl acetonate), double (ethyl ethyl醯acetate) nickel and the like.

The above-mentioned organic carboxylate of nickel is a compound modified with a super acid such as fluorinated acid, tetrafluoroboric acid, trifluoroacetic acid or hexafluoroacetic acid.

Nickel diene or triolefin coordination dislocation; for example, dichloro(1,5-cyclooctadiene)nickel, [(η ³ -butenyl)(1,5-cyclooctadiene)nickel]hexafluoro Phosphate, its tetrafluoroborate, bismuth [3,5-bis(trifluoromethyl)]borate complex, (1,5,9-cyclolauric triene) nickel, bis (original spinadiene) A nickel complex such as nickel or bis(1,5-cyclooctadiene) nickel.

a complex formed by the coordination of a ligand having a P, N, O atom such as nickel; for example, bis(triphenylphosphine)nickel dichloride, bis(triphenylphosphine)nickel dibromide, bis (three) Phenylphosphine)cobalt dibromide, bis[tris(2-methylphenyl)phosphine]nickel dichloride, bis[tris(4-methylphenyl)phosphine]nickel dichloride, bis[N-( 3-t-butyl sulfinyl) phenylamino acid salt] nickel, Ni[PhC(O)CH](Ph), Ni(OC(C ₆ H ₄ )PPh)(H)(PCy ₃ ), Ni[OC(O)(C ₆ H ₄ )P](H)(PPh ₃ ), bis(1,5-cyclooctadiene) nickel and PhC(O)CH=PPh ₃ with reactants, [2 , 6-(i-Pr) ₂ C ₆ H ₃ N=CHC ₆ H ₃ (O)(Anth)](Ph)(PPh ₃ )Ni and other nickel complexes (wherein Anth represents 9-fluorenyl, Ph represents Phenyl and Cy represent the abbreviation of cyclohexyl).

(I-2) Examples of titanium and zirconium compounds: [t-BuNSiMe(Me ₄ Cp)]TiCl ₂ , (Me ₄ Cp)(O-iPr ₂ C ₆ H ₃ ) ₂ TiCl, (Me ₄ Cp)TiCl ₃ , (Me ₄ Cp)Ti(OBu) ₃ , [t-BuNSiMe ₂ Flu]TiMe ₂ , [t-BuNSiMe ₂ Flu]TiCl ₂ , Et(Ind) ₂ ZrCl ₂ , Ph ₂ C(Ind)(Cp)ZrCl ₂ , iPr(Cp)(Flu)ZrCl ₂ , iPr(3-tert-But-Cp)(Ind)ZrCl ₂ , iPr(Cp)(Ind)ZrCl ₂ , Me ₂ Si(Ind) ₂ ZrCl ₂ , Cp ₂ ZrCl ₂ , (Cp represents short for Cyclopentadienl, Ind is abbreviated as Indenyl, and Flu is abbreviated as Fluorenyl).

(II) Examples of super acid, Lewis acid and ionic boron compound: Examples of the super acid include hexafluoroantimonic acid, hexafluorophosphoric acid, hexafluoroantimonic acid, trifluoroacetic acid, fluorosulfuric acid, and trifluoromethanesulfonic acid. , tetrafluoroboric acid, hydrazine (pentafluorophenyl)boronic acid, hydrazine [3,5-bis(trifluoromethyl)phenyl]boronic acid, p-toluenesulfonic acid, pentafluoropropionic acid, etc., as a Lewis oxide compound, Examples thereof include a complex of boron trifluoride with an ether, an amine, a phenol, an ether of aluminum trifluoride, a complex of an amine or a phenol, a quinone (pentafluorophenyl) borane, and a ginseng [3,5-double. (Trifluoromethyl)phenyl]borane, boron compound, aluminum trisallate, aluminum tribromide, ethyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum fluoride, three ( An aluminum compound such as pentafluorophenyl)aluminum, an organic halogen compound such as hexafluoroacetone, hexachloroacetone, tetrachlorophenyl hydrazine or hexafluoromethyl ethyl ketone which exhibits Lewis acidity, and others may also be titanium tetrachloride. Examples of the ionic boron compound such as pentafluoroindole and the like which exhibit a Lewis acid compound, and examples thereof include triphenylcarbonium (pentafluorophenyl) borate and triphenylcarbenium [3,5-bis ( Trifluoromethyl)benzene 】 borate, triphenylcarbenium (2,4,6-trifluorophenyl)borate, triphenylcarbonium tetraphenylborate, tributylammonium quinone (pentafluorophenyl) borate, N,N-dimethylanilinium quinone (pentafluorophenyl)borate, N,N-diethylanilinium quinone (pentafluorophenyl)borate, N,N-diphenylanilinium oxime (five Fluorophenyl) borate and the like.

An example of the organoaluminum compound of (III): an alkyltitanium compound such as methyltitanium dioxide, ethyltitanium dioxide or butyltitanium dioxide, trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum may be used. An alkyl aluminum compound such as hydride, diethyl aluminum chloride, diethyl aluminum fluoride, ethyl aluminum sesquichloride or ethyl aluminum dichloride; and an alkyl aluminum halide compound or the above alkyl titanium oxide compound and a mixture of the aforementioned alkyl aluminum compounds, and the like.

These catalyst components can be used, for example, in the following ranges.

The transition metal compound such as a nickel compound, a palladium compound, a cobalt compound, a titanium compound, and a zirconium compound is 0.02 to 100 mmol atoms for the monomer 1 mole; and the organoaluminum compound is 1 to the transition metal compound 1 molar atom. 5,000 mol; and the non-conjugated diene, the Lewis acid, and the ionic boron compound are 0 to 100 m to the 1 mol atom of the transition metal compound.

. The addition polymerization solvent is used as a solvent used in the addition polymerization reaction, and is dissolved in a monomer composition or a catalyst for polymerization, so that the catalyst is not deactivated, and the formed addition polymer can be dissolved immediately, and The alicyclic hydrocarbon solvent selected from the group consisting of cyclohexane, cyclopentane, and methylcyclopentane, and an aliphatic hydrocarbon solvent such as hexane, heptane, and octane, toluene, benzene, and xylene are exemplified. a solvent such as an aromatic hydrocarbon solvent such as mesitylene, a halogenated hydrocarbon solvent such as dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, chlorobenzene or dichlorobenzene; . These can be used individually or in mixture of 2 or more types.

. Molecular Weight Modifier In the present invention, the molecular weight of the produced norbornene-based addition polymer can be adjusted by adding hydrogen or an α-olefin as a molecular weight modifier to the polymerization system. The molecular weight of the produced orniolene-based addition polymer is lower as the amount of the molecular weight modifier added is increased.

<Proper properties of the original borneol-based resin> The intrinsic viscosity [η] _inh of the ortho-ene based resin used in the present invention is preferably 0.2 to 2.0 dl/g, more preferably 0.35 to 1.0 dl/g, and particularly preferably 0.4. ~0.85 dl / g, the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 1.5. 10,000 to 250,000, the weight average molecular weight (Mw) is 10,000 to 2 million, more preferably 20,000 to 1 million, and particularly good is 30,000 to 500,000. When the intrinsic viscosity [η] _inh , the number average molecular weight, and the weight average molecular weight are in the above range, the original norbornene-based resin is excellent in mechanical strength, and an orthorhombic resin film which is hard to be broken can be obtained.

The glass transition temperature (Tg) of the raw borneol-based resin is usually 100 ° C or higher, preferably 120 ° C or higher, and more preferably 150 ° C or higher. When Tg is in the above range, the processability of the original borneol-based resin film is excellent, and the stability characteristics of the optical film of the present invention can be obtained.

Further, the saturated water absorption of the original borneol-based resin is 1% by weight or less, preferably 0.01 to 0.8% by weight, more preferably 0.1 to 0.5% by weight. When the saturated water absorption ratio exceeds 1% by weight, the film obtained by the related resin may have durability problems such as temporal water absorption (wet) deformation due to the environment to be used. On the other hand, when it is less than 0.01% by weight, there may be a problem in adhesion. Further, when the saturated water absorption ratio is within the above range, when used as a polarizing plate in particular, it exhibits excellent properties due to durability stability. Further, the saturated water absorption rate is a value obtained by measuring the weight gain according to ASTM D570, immersed in water at 23 ° C for one week.

<Other components of the original borneol-based resin> In the present invention, an additive such as an antioxidant or an ultraviolet absorber may be further added to the original borneol-based resin in a range that does not impair the effects of the present invention.

Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol and 2,2'-dioxy-3,3'-di-t-butyl-5,5'. - dimethyldiphenylmethane, hydrazine [methyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] methane, and the like.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone. Moreover, when the original borneol-based resin film (A) is produced by a solution casting method to be described later, a resin film can be easily produced by adding a coating agent or an antifoaming agent.

In addition, when the raw borneol-based resin film (A) used in the present invention is produced, it may be mixed with an original borneol-based resin or the like, or may be added in advance when the original borneol-based resin is produced. Further, the amount of addition may be appropriately selected depending on the desired characteristics, but it is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, per 100 parts by weight of the original borneol-based resin.

<Production of the original borneol-based resin film (A)> The norbornene-based resin film (A) used in the present invention is obtained by directly melt-molding the original borneol-based resin or by dissolving in a solvent ( Forming by solvent casting method.

. Melt-forming The original borneol-based resin film (A) used in the present invention can be produced by melt-molding a resin composition containing a norbornene-based resin or a norbornene-based resin and the above additives. Examples of the melt molding method include injection molding, melt extrusion molding, and air blowing molding.

. Solvent casting The original borneol-based resin film (A) used in the present invention is produced by casting a liquid resin composition in which a raw borneol-based resin is dissolved in a solvent, casting it on a suitable substrate, and removing the solvent. For example, after coating the liquid resin composition on a substrate such as a steel strip, a steel drum or a polyester film, the solvent is dried, the coating film is peeled off from the substrate, and the coating film is peeled off from the substrate as needed, followed by drying. The original borneol-based resin film (A) was obtained.

The amount of residual solvent in the original borneol-based resin film (A) obtained by the above method is preferably as small as possible, and is usually 3% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less. When the amount of the residual solvent exceeds 3% by weight, the film may be deformed or the properties may change over time, and the desired function may not be exhibited.

. Surface Treatment The original borneol-based resin film (A) used in the present invention has a light transmittance of generally 80% or more, preferably 85% or more, more preferably 90% or more.

In addition, the original borneol-based resin film (A) used in the present invention may be applied to a surface treatment agent for the purpose of improving adhesion to an antistatic layer (B) to be described later. Examples of the surface treatment include plasma treatment, corona treatment, alkali treatment, plasma coating treatment, and the like.

When the corona treatment is used, the original borneol-based resin film (A) and the antistatic layer (B) can be adhered to each other. The corona treatment condition at this time is preferably 1 to 1000 W/m ² /min, and more preferably 10 to 100 W/m ² /min. Therefore, when the irradiation amount is too low, a sufficient surface modification effect may not be obtained, and if the irradiation amount is too high, the treatment effect may not reach the inside of the original borneol-based resin film (A) or the original borneol. The resin film (A) itself may be deteriorated. Further, the corona treatment is applied not only to the surface on which the antistatic layer (B) is provided but also to the reverse side.

. The original borneol-based resin film (A) used in the present invention may be an unstretched film or an extended film. In addition, the original borneol-based resin film (A) used in the present invention may be a film made of only the original borneol-based resin layer, or may be a layer of a raw material such as an original borneol-based resin layer and polyethylene. Composite film. When the composite film of the original borneol-based resin film (A) and the other raw material used in the present invention is at least one surface of the original borneol-based resin layer, the anti-static layer is provided on the original borneol-based resin layer. ) is better.

In particular, when the optical film of the present invention is a film having a phase difference, the original borneol-based resin film (A) obtained by preheating and stretching the unstretched original borneol-based resin film may be used, and an antistatic layer may be provided on the surface ( B). In such a method, when the surface treatment is applied to the original borneol-based resin film (A), the original borneol-based resin film before stretching is subjected to a surface treatment, and a heat-extended raw borneol-based resin film is prepared ( A) Further, the unstretched original borneol-based resin film may be subjected to a surface treatment to prepare an ortho-ene ene resin film (A) by heating and stretching. Further, the original borneol-based resin film (A) of the unstretched film may be subjected to surface treatment as necessary, and an antistatic layer (B) may be provided, and then heated and stretched to form an optical film having a phase difference. In this case, the original film of the unstretched film (A) is subjected to a surface treatment after the production of the optical film or the stability of the obtained properties, and the antistatic layer (B) is provided, followed by heating. Extension is better.

As a method of the elongation treatment, the antistatic layer (B) may be laminated, or the unstretched ornidyl resin film may be subjected to a one-axis extension or a biaxial stretching method.

When the one-axis stretching process is performed, the stretching speed (歪 speed) is generally 1 to 5,000%/min. It is preferably 50 to 1,000%/min, more preferably 100 to 1,000%/min.

When the biaxial stretching treatment method is performed, a method of performing the stretching treatment in the two directions at the same time or a method of performing the stretching treatment in the direction in which the extending direction of the stretching treatment is different after the one-axis stretching treatment is performed may be employed. At this time, the angle of intersection of the extension axes of 2 is not particularly limited depending on the characteristics required for the intended optical film, and is generally in the range of 120 to 60 degrees. Further, the stretching speed may be the same or different in each extending direction, and is generally 1 to 5,000%/min, preferably 50 to 1,000%/min, more preferably 100 to 1,000%/min, and particularly preferably 100. ~500% / minute.

The stretching treatment temperature is not particularly limited, but is generally Tg ± 30 ° C, preferably Tg ± 15 ° C, more preferably Tg - 5 °, based on the glass transition temperature (Tg) of the original borneol-based resin to be used. Tg + 15 ° C range. When the stretching treatment temperature is set within the above range, the phase difference unevenness caused by the obtained stretched film can be suppressed, and the control of the refractive index element can be easily performed, and the stretching treatment can be carried out stably, which is preferable.

The stretching ratio is not particularly limited depending on the characteristics required for the intended optical film, and is generally 1.01 to 10 times, preferably 1.03 to 5 times, more preferably 1.03 to 3 times. When the stretching ratio exceeds the above range, control of the phase difference of the obtained stretched film becomes difficult. The stretched film can be directly cooled, or at a temperature of from Tg-20 ° C to Tg for at least 10 seconds, preferably from 30 seconds to 60 minutes, more preferably for 1 to 60 minutes, and then cooled. Thereby, the change in the phase difference of the transmitted light, the size, and the like are relatively small, and the retardation film can be stabilized.

As described above, the film subjected to the stretching treatment is such that, by the alignment of the molecules subjected to the stretching treatment, a phase difference is imparted to the transmitted light, or the phase difference can be controlled by the stretching ratio, the stretching temperature, the thickness of the film, and the like.

The thickness of the norbornene-based resin film (A) used in the present invention is not particularly limited, but is generally 5 to 500 μm, preferably 10 to 150 μm, more preferably 20 to 100 μm. If the thickness of the film is too thin, the strength may be insufficient, and if it is too thick, the phase difference may be too high, and the transparency and the appearance may be lowered. When the original borneol-based resin film (A) used in the present invention is a composite film of a layer of an original borneol-based resin layer and another raw material, the thickness of the original borneol-based resin layer is usually 5 to 500 μm, preferably. It is about 10~150μm.

Further, the thickness of the original borneol-based resin film (A) constituting the optical film used as the retardation film is not particularly limited, but is usually 5 to 500 μm, preferably 10 to 150 μm, more preferably 20 to 100 μm. . When the thickness of the film is too thin or too thick, it may be broken during handling, which is not preferable.

The original borneol-based resin film (A) used in the present invention has a surface wettability of 50 to 70 mN/m, preferably 55 to 5, of the surface of the antistatic layer (B) laminated by the surface treatment or the like. 70mN/m. This wettability can be measured in accordance with the method described in JIS K6768. When such wettability is exhibited, the adhesion between the original borneol-based resin film (A) and the antistatic layer (B) is improved, which is preferable.

Further, the norbornene-based resin film (A) used in the present invention has an average surface roughness (Ra) of 0.3 to 2.0 nm, preferably 0.4 to 1.8 nm, on the side where the antistatic layer (B) is provided. . When the surface roughness of the antistatic layer side is in this range, excellent smoothness and excellent optical transparency can be exhibited, and the adhesion between the antistatic layer and the original borneol resin film is excellent, which is preferable.

Antistatic layer (B) The antistatic layer (B) of the present invention is (b1) an acrylic resin having a specific grade 4 ammonium salt in a side chain, and (b2) a polyethyleneimine and/or a polyhydroxyalkane-containing polymer. An antistatic coating material of a hardener made of glycidyl ether is formed.

<Acrylic Resin (b1)> The acrylic resin (b1) constituting the antistatic coating material is an acrylic resin having a 4-stage ammonium salt represented by the following formula (i) in a side chain.

-COO-Q ¹ -N(Q ² ) _a X _b (i) (in the formula (i), Q ¹ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Q ² is 1 having a carbon number of 1 to 3 A valence hydrocarbon group, X is a chlorine atom, a fluorine atom or -Q ³ -SO ₄ (however, Q ³ is a single bond, a methyl group or an ethyl group), and a and b are integers of 1 or 2 (however, a+b= 3) When Q ² , Q ³ and X are plural, they may be the same or different.

The acrylic resin (b1) is obtained by copolymerizing (1) a monomer having a -COOH group at the terminal, (2) a monomer having a 4-stage ammonium salt group, and (3) another monomer.

The monomer (1) having a -COOH group at the terminal is preferably used in the range of 1 to 20 mol% in the total monomer, and as the monomer (1), for example, (meth)acrylic acid or acrylonitrile oxide ether is exemplified. Succinic acid, phthalic acid, (meth) hexahydrophthalic acid, and the like. Further, the "(meth)acrylyl group" in the present specification means a propenyl group or a methacryl group.

The monomer (2) having a quaternary ammonium salt group is preferably used in the range of 10 to 40 mol% in the total monomer, and as the monomer (2), for example, dimethylaminoether acrylate 4 is exemplified. An oxide (containing an anion such as a halogen such as a counter ion chloride, a sulfate, a sulfonate or an alkylsulfonate). The acrylic resin (b1) used in the present invention preferably has a halogen atom content of 1% by weight or less, preferably 0.5% by weight or less, and a monomer having a 4-stage ammonium salt group (2) as a counter ion. It is preferred when it is not halogen.

The other monomer (3) is preferably used in the range of 8 to 80 mol% in the total monomer, and examples of the monomer (3) include an alkyl (meth) acrylate and an alicyclic skeleton (A). An ethylene derivative such as acrylate, styrene, vinyl acetate, vinyl halide or olefin. Among them, as the monomer (3), an alkyl (meth) acrylate or a (meth) acrylate having an alicyclic skeleton is preferred, and a (meth) acrylate having an alicyclic skeleton is preferred. Further, it is particularly preferable that the alkyl (meth) acrylate is used in combination with the (meth) acrylate having an alicyclic skeleton.

The content of the (meth) acrylate having an alicyclic skeleton is preferably 10 to 30 mol% based on the total monomer. Examples of the (meth) acrylate having an alicyclic skeleton include cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and Cyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and the like. The acrylic resin (b1) obtained by containing the (meth) acrylate having an alicyclic skeleton in a monomer contains a structural unit derived from a (meth) acrylate having an alicyclic skeleton, whereby The bornene-based resin film (A) is preferred because it has excellent adhesion.

The acrylic resin (b1) used in the present invention is a crosslinkable copolymer obtained by copolymerizing a monomer composition of these monomers, and has a 4-stage ammonium represented by the above formula (i) in a side chain. salt.

<Hardener (b2)> The curing agent (b2) used in the present invention is a polyethyleneimine and/or a polyhydroxyalkane polyglycidyl ether.

As the polyethyleneimine, a polyethyleneimine having a number average molecular weight of 300 to 70,000 is preferably used. Polyethyleneimine is generally linear, but may also have a branch. As the polyethyleneimine, for example, a product such as "EPOMIN" manufactured by Nippon Shokubai Co., Ltd. can be used.

The polyhydroxyalkane polyglycidyl ether 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 2,000.

In the present invention, as the curing agent (b2), polyethyleneimine or polyhydroxyalkane polyglycidyl ether may be used alone or in combination of two or more, and it is preferred to use both in combination. When the polyethyleneimine and the polyhydroxyalkane polyglycidyl ether are used in combination, it is preferred that the mixture ratio of the polyethyleneimine is 10 to 100 parts by weight based on 100 parts by weight of the hydroxyalkane polyglycidyl ether.

The amount of the curing agent (b2) to be used is preferably from 1 to 30 parts by weight, more preferably from 3 to 15 parts by weight, per 100 parts by weight of the acrylic resin (b1).

<Antistatic coating material> In the present invention, an antistatic coating material containing the acrylic resin (b1) and the curing agent (b2) is used, and an antistatic layer (B) is provided on the original borneol resin film (A). ).

The antistatic coating material used in the present invention contains the acrylic resin (b1) and the curing agent (b2). The ratio of the acrylic resin (b1) to the curing agent (b2) in the antistatic coating material is preferably from 1 to 30 parts by weight, preferably from 1 to 30 parts by weight, per 100 parts by weight of the acrylic resin (b1). The ratio of 3 to 15 parts by weight.

The antistatic coating material used in the invention may further comprise a crosslinking agent, an adhesion-imparting agent, an antioxidant, a coloring agent, an ultraviolet absorber, a light stabilizer, an organic decane coupling agent, a thermal polymerization inhibiting agent, a coating agent, Surfactant, storage stabilizer, plasticizer, slip agent, filler, aging inhibitor, wettability improver, coating improver, and the like.

The antistatic coating material used in the present invention is preferably an epoxy resin having an alicyclic skeleton in addition to the acrylic resin (b1) and the curing agent (b2). Examples of the epoxy resin include (3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxy group). Cyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, ethylene cyclohexene Oxide, 4-vinyl epoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methyl ring Hexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methyl bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide Ethylene glycol bis(3,4-epoxycyclohexylmethyl)ether, ethyl bis(3,4-epoxycyclohexanecarboxylate), epoxylated tetratyl alcohol , lactone modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, lactone modified epoxylated tetrahydrobenzyl alcohol, cyclohexyl An olefin oxide, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether or the like, and the like.

When the antistatic coating material is an epoxy group-containing resin, the content is preferably from 1 to 30 parts by weight based on 100 parts by weight of the acrylic resin (b1).

Moreover, 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"), and is particularly useful as a curing agent (b2). In the case of polyethyleneimine, an epoxy group-based crosslinking agent may be further used. The epoxy group-based 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 the epoxy group-based crosslinking agent include a bisphenol type epoxy compound, a phenolic epoxy group for lacquer, an alicyclic epoxy compound, an aliphatic epoxy compound, and an aromatic epoxy. A base compound, a glycidylamine type epoxy compound, a halogenated epoxy compound, or the like.

Specific examples thereof include bisphenol type epoxy compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and bisphenol S diglycidyl ether; and phenolic epoxy compounds for phenol paint, A A phenolic epoxy compound for lacquer type epoxy resin, etc.; 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-( 3,4-Epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl)hexane Acid ester, ethylene cyclohexene oxide, 4-ethylene epoxy cyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy -6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methyl bis(3,4-epoxycyclohexane), bicyclic Pentadiene diepoxide, ethylene glycol bis(3,4-epoxycyclohexylmethyl)ether, ethyl bis(3,4-epoxycyclohexanecarboxylate), epoxy Modified tetrabenzyl alcohol, lactone modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, lactone modified epoxylated tetrahydrogen benzene An alicyclic epoxy compound such as a base alcohol, a cyclohexene oxide, a hydrogenated bisphenol A diglycidyl ether, a hydrogenated bisphenol F diglycidyl ether, or a hydrogenated bisphenol AD diglycidyl ether; 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diepoxypropyl An aliphatic epoxy compound such as an ether; a halogenated epoxy compound such as brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether or brominated bisphenol S diglycidyl ether; An epoxypropylamine type epoxy compound such as oxypropylaminophenylmethane.

Among the above epoxy group-based crosslinking agents, polyethylene glycol diglycidyl ether is particularly preferred.

Further, examples of the compound include polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether; and one or two kinds of aliphatic polyvalent alcohols such as ethylene glycol, propylene glycol and glycerin are added. Polyglycidyl ethers of polyether polyols obtained from the above epoxides; diepoxypropyl esters of aliphatic long chain dibasic acids; monoglycidyl ethers of aliphatic higher alcohols; phenol, cresol , butyl phenol or a monoglycidyl ether of a polyether alcohol obtained by adding these epoxides; a glycidyl ester of a higher fatty acid; an epoxidized soybean oil, an butyl stearyl stearate , octyl epoxy stearate, epoxidized linseed oil, and the like.

Further, an epoxy resin obtained by polymerizing one or two or more kinds of these compounds in an appropriate range in advance may also be used.

Further, examples of the epoxy group-based compound to be used in the present invention include a polymer of a conjugated diene monomer, a copolymer of a conjugated diene monomer and a compound having an ethylenically unsaturated bond group, and A compound obtained by epoxidizing a copolymer of a diene monomer and a compound having an ethylenically unsaturated bond group, or a (co)polymer such as natural rubber.

The content of the epoxy group-based crosslinking agent in the antistatic coating material is preferably from 1 to 30 parts by weight, preferably from 3 to 20 parts by weight, per 100 parts by weight of the acrylic resin (b1).

Further, the antistatic coating material used in the present invention is preferably agglomerated when the optical film of the present invention having the antistatic layer (B) is prevented from overlapping each other, and is preferably contained when a filler is contained. The antistatic coating material can control the surface characteristics of the antistatic layer (B) because it contains a filler. The type of the filler which can be added to the antistatic coating material for this purpose is not particularly limited, and may be inorganic particles or organic particles or a mixture thereof. It is generally preferred to use organic particles from the viewpoint of particle uniformity.

For example, titanium oxide, zirconium oxide, zinc oxide, aluminum oxide, cerium oxide (cerium oxide particles), or tin oxide can be used as the inorganic particles, and cerium oxide is used from the viewpoint of uniformity and light permeability of the particles. Cerium oxide particles are preferred. Further, as the organic particles, for example, polystyrene-based resin particles or acrylic resin particles (acrylic particles) can be used. Among them, acrylic resin particles (acrylic particles) are preferred from the viewpoint of light permeability, and polystyrene resin particles (polystyrene particles) are preferred from the viewpoint of particle uniformity or material selectivity. . These organic particles are not particularly limited, and it is preferred to use three-dimensionally crosslinked particles. Further, the surface of the particles may be modified, for example, by a carboxyl group, an amine group, a hydroxyl group, or the like, or the surface of the surface may be modified by the stability of the antistatic coating material or the uniformity of the antistatic layer. .

Moreover, when the refractive index of the antistatic coating material substrate and the refractive index of the added filler are largely different, the refractive index of the filler is as close as possible to the base of the antistatic layer (B). The refractive index of the material is good. As such a filler, for example, a filler such as cerium oxide particles or acrylic particles having a refractive index of 1.5 or so can be suitably used.

To control the surface characteristics of the antistatic layer (B), the particle size of the filler can be selected in combination with the dry film thickness of the antistatic layer (B), generally 0.05 to 2 times the dry film thickness of the antistatic layer (B). Preferably, it is 0.1 to 1 times. Further, the particle size of the agglomerate preventing material formed by the filler is preferably a range in which the average particle diameter is 0.05 to 0.50 μm. In this case, the particles having an average particle diameter of 0.05 to 0.10 μm are preferably 50 to 99% by weight, more preferably 70 to 90% by weight, based on the entire particles. Further, the particles having an average particle diameter in the range of 0.10 to 0.50 μm are preferably 50 to 1% by weight, more preferably 30 to 10% by weight, based on the entire particles.

Further, the amount of the filler to be added is not particularly limited, but it is preferably 0.1 to 20% by weight based on the total amount of the antistatic coating material from which the solvent is removed. Moreover, the compounding ratio of the agglomerate preventing material formed from the filler is generally 0.1 to 20%, preferably 0.1 to 10%, more preferably in the antistatic layer (B) of the present invention. It is 0.1~5%. When the blending ratio of the particles is less than 0.1%, it is difficult to obtain an agglomeration preventing effect. On the other hand, when the blending ratio is 20% or more, light permeability is deteriorated.

The antistatic coating material used in the present invention is preferably applied to the original borneol-based resin film (A) in a state of being dissolved or dispersed in a solvent, and in the case of a water-based coating material, that is, an emulsifier type It is better when coating materials. When the antistatic coating material is a water-based coating material, the original borneol-based resin film (A) is coated with an antistatic coating material to form an antistatic layer (B), and the original borneol-based resin film is not formed. It is preferred that the surface of (A) is deteriorated or deteriorated.

The concentration of the antistatic coating material in the case of the water-based coating material depends on the coating method, etc., but generally, the total amount of the antistatic coating material containing water is preferably from 0.5 to 20% by weight based on the solid content.

In addition, it is required to satisfy the surface smoothness of the antistatic layer (B) as an optical film, and it is preferable to use two or more types as a solvent or a dispersion medium.

In the case of the water-based coating material, in order to improve the smoothness of the antistatic layer (B), it may be mixed in water at any ratio and is higher than the boiling point of water, and a water-soluble solvent may be used in combination. Specific examples of such a solvent include γ-butyrolactone, diethylene glycol monoethyl ether acetate, dimethylacetamide, N-methylpyrrolidone, triethylene glycol monomethyl ether, and triethyl ethane. Glycol dimethyl ether and the like. The mixing ratio of these solvents to water is preferably from 0.1 to 50 parts by weight, preferably from 1 to 10 parts by weight, per 100 parts by weight of water. When the amount is 0.1 part by weight or less, the effect of adding a solvent is not obtained, and when it is 50 parts by weight or more, the productivity is remarkably deteriorated.

The boiling point of such a solvent is preferably 150 ° C or more, more preferably 200 ° C or more.

<Formation of Antistatic Layer (B)> The antistatic layer (B) of the present invention can be generally applied to the original borneol-based resin film (A) and formed after drying. In this case, the relevant antistatic layer (B) may be one side or both sides of the original borneol-based resin film (A), and is not particularly limited.

The coating method of the antistatic coating material is not particularly limited, and for example, spin coating, coil coating, bar coating, roll coating, blade coating, curtain coating, screen printing, gravure coating can be used. Various methods such as reverse coating, spray coating, double roll coating, and inkjet coating.

The drying of the coated antistatic coating material can be carried out in one stage.

It is a temperature at which the drying step is 1) 80 ° C or less, and 2) the glass transition temperature (Tg) of the original borneol resin film (A) is -30 ° C, preferably more than the original borneol resin film. Preferably, the multi-stage drying step of the secondary drying step at the temperature of the glass transition temperature (Tg) of (A) is preferably carried out by the two-stage drying step of the primary drying step and the secondary drying step. When the secondary drying step is carried out at a temperature exceeding the glass transition temperature of the original borneol resin film (A), the strength of the obtained optical film-like antistatic layer (B) can be improved, which is preferable.

In order to prevent agglomeration of the roll of the original borneol-based resin film (A) during the first drying step, when the protective film is bonded to one surface in advance, the anti-static coating material on the reverse surface does not need to be peeled off under the protective film. It is preferable to apply and dry, and it is preferable that the drying temperature at this time is dried at 80 ° C or lower in view of the heat resistance of the protective film.

The secondary drying is performed as needed, but the strength of the antistatic coating layer can be positively increased by heating by extension of the original borneol-based resin film (A).

The antistatic coating material is a water-based coating material, and the drying thereof is performed at a temperature of 1) at 80 ° C or less, and 2) at a temperature exceeding a glass transition temperature (Tg) of -30 ° C of the original borneol resin film. When the second step of the secondary drying step is carried out, the solvent amount of the antistatic layer obtained by one drying is 0.1 to 5% by weight, and the solvent amount of the secondary drying antistatic layer is preferably 0.01 to 1% by weight.

In the present invention, when an optical film having a phase difference is produced, and an optical film of the stretched film is produced, an antistatic layer (B) may be provided on the pre-stretched original borneol-based resin film (A), but the original is not extended. The bornene-based resin film (A) is coated with an antistatic coating material, and after being subjected to a single drying step at 80 ° C or lower, at a temperature exceeding the glass transition temperature (Tg) of -30 ° C of the original borneol resin film. In the second drying step, the film extension is also preferred. When the optical film of the stretched film is produced, when the film is stretched in the secondary drying step, heating for heating and drying during stretching does not need to be performed separately, so that the thermal efficiency is excellent and economical, and the original borneol film (A) is There are fewer related thermal procedures, and it is more difficult to cause quality deterioration. When the film is extended in the secondary drying step, the temperature of the secondary drying step is preferably in the range of the glass transition temperature (Tg) of the original borneol resin film (Tg) ± 30 ° C, and the original borneol resin film (A) A glass transition temperature (Tg) of ±15 ° C is preferred.

The film is extended in the secondary drying step so that the original borneol-based resin film (A) is stretched only in the same manner as described above.

<Antistatic layer (B)> The thickness of the antistatic layer (B) of the present invention is not particularly limited, but is generally 0.01 to 5 μm, preferably 0.05 to 4 μm, and more preferably 0.1 to 3 μm. When the thickness of the antistatic layer (B) is 0.01 μm or more, the optical film preferably has sufficient antistatic property. Further, when the thickness of the anti-static layer (B) is 100 or less, the thickness of the original borneol-based resin film (A) is preferably 0.01 to 0.5, preferably 0.05 to 0.3. If the thickness of the antistatic layer (B) is too small, sufficient antistatic energy cannot be obtained, and if it is too large, the light transmittance may be lowered, or when the adhesive is applied to the final coating, the antistatic layer may be dissolved and become cloudy. phenomenon.

The total light transmittance in the antistatic layer (B) of the present invention is generally 80% or more, preferably 90% or more.

When the antistatic layer (B) is provided only on one side of the original borneol-based resin film (A), the optical film having the antistatic layer (B) is not only on the side having the antistatic layer (B) but also The anti-static energy can also be displayed on the reverse side.

Further, the antistatic layer (B) of the present invention has a saturated water absorption at room temperature (23 ° C) of 50 RH%, preferably 0.1 to 90% by weight, more preferably 1 to 50% by weight, particularly preferably 1 to 20% by weight. When the saturated water absorption ratio under the above conditions is in the above range, it is possible to easily obtain a stable surface resistance value or a stability property when used as a polarizing plate obtained by using the optical film of the present invention.

The antistatic layer (B) has a metal atom content of 0.1% by weight or less, preferably 0.05% by weight or less, and a halogen atom content of 1% by weight or less, preferably 0.5% by weight or less. In such a range, contamination of the coating path and transfer of metals and halogens to the materials used in combination can be prevented.

Optical film having an antistatic layer The optical film having the antistatic layer of the present invention has the above-mentioned original borneol-based resin film layer (A) and an antistatic layer (B).

The optical film of the present invention exhibits sufficient antistatic property, and the surface resistivity of the general antistatic layer side is 1 × 10 ⁶ to 1 × 10 ¹² Ω / □, preferably 1 × 10 ⁸ to 1 × 10 ¹¹ Ω / □. The scope. When the surface resistance value of the optical film is within this range, it is preferable to take out the roll-shaped optical film or to peel off the static electricity when the protective sheet is peeled off.

The optical film of the present invention is an antistatic layer (B) which is provided by an antistatic layer (B) having an acrylic resin (b1) having antistatic property and a conventional antistatic agent such as a surfactant. It is strongly bonded to the original borneol-based resin film (A) to reduce peeling or peeling of the antistatic agent, and the antistatic property can be stably maintained for a long period of time, and has excellent durability.

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

In the optical film of the present invention, the surface wettability on the side of the antistatic layer can be 50 to 70 mN/m, preferably 55 to 70 mN/m, by surface treatment such as corona discharge treatment. This wettability can be measured in accordance with the method described in JIS K6768. When the optical film of the present invention exhibits such wettability, it is excellent in adhesion or adhesion when laminated with other raw materials, and thus can be suitably used in various applications for forming a laminate when a polarizing plate is produced.

The optical film of the present invention can be used as a film with a bar coating, a film for preventing reflection film, a film for a transparent conductive film, and preventing infrared rays because of its excellent adhesion. It is used as a transparent substrate such as a film of ultraviolet rays. Further, the antistatic layer (B) may be present on one side of the original borneol-based resin film (A) or on both sides.

<Retardation film> The optical film of the present invention is formed by using a pre-stretched original borneol resin film (A) or an antistatic layer (B) on the unstretched original borneol resin film (A). When the stretching is carried out in the drying step, or the anti-static layer (B) is provided on the unstretched original borneol-based resin film (A), and then extended, or the like, when it is a stretched film, it is generally It exhibits a phase difference and can be used as a retardation film.

The phase difference of the retardation film of the present invention is not particularly limited, and is generally 0 to 300 nm, more preferably 5 to 150 nm, and is preferably 5 to 500 nm in the thickness direction, and is preferably 5 to 500 nm. It is 80~300nm.

The optical film of the present invention having a phase difference of the polarizing plate, that is, the retardation film of the present invention is formed by laminating with a polarizing film (polarizer) to form a polarizing plate. The lamination with the polarizing film is preferably carried out via a known adhesive. The optical film of the present invention has excellent moisture resistance and water resistance, and even when the polarizing plate of the present invention obtained by using the present invention is used for a polarizing film having hygroscopicity such as PVA, it is possible to provide polarizing without separately providing a protective layer. The film is thinned to impart weight reduction, and the reduction in transparency can be suppressed by thinning, and the cost of the material can be reduced by reducing the number of laminations, thereby simplifying the manufacturing steps. When the polarizing plate of the present invention can be produced by using the optical film of the present invention having sufficient antistatic property, foreign matter adsorption due to static electricity can be prevented, and the incorporation of foreign matter in the manufacturing step can be easily prevented, so that substantially High quality without point defects.

<Polarizing film> A polarizing film constituting the polarizing plate of the present invention functions as a polarizing film, that is, only two polarizing components that divide incident light into two straight lines, and pass through one of them to absorb or disperse another component. Any one of the functions is not particularly limited. Examples of the polarizing film used in the present invention include polyvinyl alcohol (hereinafter abbreviated as PVA). PVA on the iodine-based polarizing film and PVA-based film to align the dichroic dye. a dye-based polarizing film, a PVA formed by a PVA-based film, or a PVA formed by a polyethylene film dehydrochlorination reaction to form a polyene polyene polarizing film or a modified PVA having a cationic group in the molecule. A polarizing film having a dichroic dye on the surface and/or inside of the film. Among them, PVA is preferred. Iodine-based polarizing film.

Moreover, the method for producing the polarizing film used in the present invention is not particularly limited. For example, a method of adsorbing iodide ions after stretching on a PVA-based film, a method of dyeing a PVA-based film by dyeing with a dichroic dye, and a method of dyeing a PVA-based film by a dichroic dye after stretching may be mentioned. A known method such as a method in which a dichroic dye is stretched after printing on a PVA-based film, or a method in which a PVA-based film is stretched and a dichroic dye is printed. More specifically, the iodine is dissolved in the potassium iodide solution to make high-order iodide ions, and the ions are adsorbed on the PVA film and extended, followed by immersion in a 1-4% boric acid aqueous solution at a water bath temperature of 30-40 ° C. The method of polarizing the film, or the same as that of the PVA film, is carried out by boric acid treatment, and is extended by 3 to 7 times in one axis direction, and is impregnated in a 0.05 to 5% dichroic dye aqueous solution at a water bath temperature of 30 to 40 ° C and A method of producing a polarizing film by drying a dye at 80 to 100 ° C and thermally fixing it.

The polarizing film used in the present invention is not particularly limited, and is generally preferably 10 to 50 μm, preferably 15 to 45 μm.

These polarizing films can be directly used in the production of the polarizing film of the present invention, and are used for corona discharge treatment and plasma treatment on the surface to which the adhesive layer is bonded.

<Adhesive Layer> The polarizing plate of the present invention is produced by adhering the optical film of the present invention having the above-described phase difference to the 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. Among these, the adhesive includes an aqueous adhesive, a solvent-based adhesive, a two-liquid curing adhesive, an ultraviolet curing adhesive, and a pressure-sensitive adhesive (adhesive). Among them, an aqueous binder is preferably used, and a polyvinyl alcohol-based aqueous binder is particularly preferable.

As the polyvinyl alcohol-based aqueous adhesive, in addition to the partially saponified polyvinyl alcohol and the fully saponified polyvinyl alcohol, modification of a polyvinyl alcohol modified with a carboxyl group or a vinyl acetate-modified polyvinyl alcohol may be mentioned. An aqueous dispersion in which a polyvinyl alcohol polymer such as polyvinyl alcohol is dissolved or dispersed in water. The degree of polymerization of the polyvinyl alcohol-based polymer is preferably from a viewpoint of a degree of polymerization of from 500 to 2,000 in terms of a viscosity of the aqueous binder. Further, these polyvinyl alcohol-based polymers are used as a crosslinking agent as a main component, and may contain a component having a functional group obtained by reacting a hydroxyl group such as an isocyanate group. Further, the polyvinyl alcohol-based adhesive is generally used after being dissolved in water. However, in order to improve the wettability to the object to be coated, a solvent having excellent solubility in water such as an alcohol or a ketone may be added in a small amount.

The solvent-based adhesive may be an adhesive that dissolves a synthetic rubber, a synthetic resin, or the like in an organic solvent.

The two-liquid curing type adhesive agent may, for example, be an epoxy-based two-liquid curing type adhesive.

Examples of the pressure-sensitive adhesive include natural rubber and synthetic rubber. Elastomer, chlorinated ethylene/vinyl acetate copolymer, polyvinyl alkyl ether, polyacrylate, modified polyolefin resin, pressure-sensitive adhesive, etc., and hardening type pressure-sensitive property of adding a curing agent such as isocyanate The pressure-sensitive adhesive used in the subsequent step, particularly for the polyolefin foam or the polyester film, is preferably used.

Further, as the other adhesive, any of the adhesives used, such as polyethylene or polypropylene, may be used. For example, a dry laminating adhesive for a polyurethane-based resin solution and a polyisocyanate resin solution, a styrene-butadiene rubber-based adhesive, an epoxy-based two-liquid curing adhesive, and an ultraviolet curable acrylic adhesive For example, a two-liquid solution of an epoxy resin and a polythiol, a two-layer solution of an epoxy resin and a polyamine can be used, and a solvent-based adhesive or an epoxy-based two-liquid curing type is particularly used. It is preferred that the agent is transparent and transparent.

The thickness of the adhesive layer in the present invention is not particularly limited, and a film of 50 μm or less is preferred. Moreover, the light transmittance of the adhesive layer in the present invention is preferably 80% or more, and particularly preferably 90% or more.

In the present invention, the tensile modulus E3 of the adhesive layer, the tensile modulus E1 of the raw norbornene-based resin film (A), and the tensile modulus E2 of the antistatic layer (B) are E1>E2. In the case of the relationship of E3, it is preferable that the durability of the polarizing plate is excellent.

<Method for Producing Polarizing Plate> The polarizing plate of the present invention is obtained by laminating an optical film, an adhesive layer and a polarizing film of the present invention having a phase difference. Usually, an adhesive layer is formed on the side of the antistatic layer of the optical film of the present invention. In other words, the polarizing plate of the present invention is preferably produced by using the adhesive or the adhesive on the antistatic layer side of the retardation film of the present invention. Thus, the adhesion strength between the optical film of the present invention and the polarizing film can be improved. On the other hand, the adhesive layer may be provided on the reverse side of the antistatic layer side, or may be laminated on one surface of the optical film of the present invention having an antistatic layer on both sides. In this way, the surface resistance value on the other component side can be more stably controlled. For example, when the liquid crystal cell is attached via the adhesive, the amount of static electricity is lowered, which is preferable. .

In the method for producing a polarizing plate of the present invention, the antistatic layer (B) coated with the antistatic coating material is provided on the surface of the original borneol resin film (A) in advance, and after being appropriately dried and extended, It is preferred that the adhesive is applied to the side surface of the antistatic layer of the optical film.

As a specific method of the polarizing film and the optical film of the present invention, depending on the type of the polarizing film, the antistatic coating material, and the adhesive, the surface of the polarizing film or the surface of the antistatic layer of the optical film is coated with an adhesive. The optical film or the polarizing film is superposed thereon and pressed.

In this case, the pressing conditions can be carried out, for example, under a pressure of about 1 kg/cm ^{2 in} an environment of 18 to 25 ° C.

Further, the optical film of the present invention having an antistatic layer is preferably present on one side of the polarizing film, and may be present on both sides.

The polarizing plate of the present invention has a good polarizing function, and the original borneol-based resin film (A) and the polarizing film are strongly bonded, and are excellent in heat resistance and chemical resistance, and are not easily peeled or deformed even after long-term use. , phase difference change, etc., and has high reliability and excellent durability.

In the adhesion, the original borneol resin film and the polarizing film are not peeled off, and it is preferable that only the material is broken.

Thus, the polarizing plate of the present invention can be utilized for various display applications, and is particularly suitable for use in forming a liquid crystal display. Since the phase difference plate of the present invention is of a high quality which is substantially free from defects such as defects, the liquid crystal display of the present invention obtained by using the present invention can be a high quality without defects such as bright spots in a large screen. Further, the liquid crystal display is generally produced by a phase difference plate having an adhesive layer and a release film for protecting the adhesive layer, and then is applied to the surface of the display on which the release film is peeled off, and can sufficiently prevent static electricity when the film is peeled off. When it is produced, it is possible to prevent the foreign matter from entering the phase difference plate, and the obtained liquid crystal display can be subjected to quality inspection immediately after the production because no static electricity is generated, so that the manufacturing efficiency is also excellent.

[Examples]

The specific embodiments of the present invention are described below, but the present invention is not limited to the embodiments. In addition, the following "parts" means "parts by weight" unless otherwise specified.

Further, the surface resistance value, water resistance, tensile strength, glass transition temperature, total light transmittance, haze value, degree of polarization, phase difference of transmitted light, adhesion, moisture resistance test, dry heat test were measured by the following methods Out.

[Surface resistance value] According to JIS K7194, the surface resistance value was measured using a Lorez GP manufactured by Mitsubishi Chemical Corporation.

[Adhesiveness] The adhesive tape specified in JIS Z1522 was used, and the adhesion was evaluated in a checkerboard test of 25 grids in accordance with JIS K5400, and the residual film ratio was shown.

[Water resistance] At room temperature, a cotton cloth containing water on the outer surface of the jacket was loaded with a hammer of 100 g (contact area of the outer surface of the outer surface of 3 cm ² ), and the hammer was slid down five times, and the appearance of the outer surface was visually observed. The judgment is made based on the following criteria.

A: No appearance change B: 1 to several root injuries C: Innumerable injuries

[Tensile modulus] According to JIS K7127, the tensile modulus at room temperature was measured using an autograph AGS-Jseries (manufactured by Shimadzu Corporation).

[Glass transfer temperature (Tg)] The glass transition temperature was measured in accordance with JIS K7121, using a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Co., Ltd. under a nitrogen atmosphere at a temperature increase rate of 20 ° C /min. Also known as "Tg").

[Total Light Transmittance and Haze Value] The total light transmittance and the haze value were measured using a haze value measuring machine "HGM-2DP type" manufactured by Suga Test Instruments Co., Ltd. according to JIS K7105.

[Polarization degree] The degree of polarization at a wavelength of 547.7 nm was measured using "KOBRA-21ADH/PR" manufactured by Oji Scientific Instruments Co., Ltd.

[KOBRA-21ADH" manufactured by Oji Scientific Instruments Co., Ltd., measured at wavelengths of 480 nm, 550 nm, 590 nm, 630 nm, and 750 nm, and the phase difference of the wavelengths of the wavelengths other than the wavelength It is calculated using the Cauchy dispersion formula.

[Adhesiveness (adhesion of polarizer and protective film)] According to JIS K6854, a polarizer is bonded to a protective film, and a 90° tear strength test (peel test) is performed using a universal material testing machine 3366 manufactured by Instron. Peel strength. Moreover, the degree of destruction of the material and peeling between the films was visually observed.

[Surface roughness] The surface roughness Ra (arithmetic mean height) was measured using an atomic force microscope Nano Scope IIIa (manufactured by Digital Instrument Co., Ltd.).

[Wet tension] According to JIS K6768, the mixture for wet tension test (manufactured by Wako Pure Chemical Industries, Ltd.) was used for evaluation.

[Film take-up property] Two sheets of A4 size film were cut out, and the film was pressed with a rubber roller, and then allowed to stand, and then the film was scratched at a speed of 1 m/min in the horizontal direction and the surface of the film was scratched. Whether or not the assessment is based on the following criteria.

A: It is easy to move the film, and the surface of the film after moving is free from scratches.

B: The touch film is slightly touched, and the surface of the film after moving is slightly scratched.

C: The film agglomerates and cannot move smoothly, and the surface of the film after moving has many scratches.

Synthesis Example 1 A separator flask equipped with a stirrer, a thermometer, and a monomer-added 2L internal volume was charged with 150 parts of ion-exchanged water and a reactive emulsifier "Edikari Soby SE-10N" (Asahi) 2 parts of the electrochemical industry (manufactured by the company), with 0.5 parts of ammonium persulfate, the gas phase was replaced by a nitrogen gas in 15 minutes, and then the temperature was raised to 80 °C. Next, 50 parts of ion-exchanged water, 6 parts of methacrylic acid, 47 parts of MOETAS (manufactured by MRC unitec), 20 parts of methyl methacrylate, and ethyl methacrylate having a quaternary ammonium group methacrylate. 26 parts and one part of the reactive emulsifier "Edikari Sobi SE-10N" were mixed and stirred in another container to prepare a pre-emulsified product, and the obtained pre-emulsified product was continuously dropped into the above-mentioned separation for 3 hours. In a flask. Nitrogen gas was introduced during the dropwise addition of the pre-emulsion, and the temperature in the flask was maintained at 80 °C. After the completion of the dropwise addition, the reaction system was heated to 90 ° C and the reaction was continued for 2 hours. Next, after the system was cooled to 25 ° C, 5% ammonia water was added dropwise, the pH was adjusted to 8, and then ion-exchanged water was added to obtain a solid content concentration of 25% emulsifier type (average particle diameter of emulsifier particles: 0.06 μm). Emulsifier 1 for the coating agent.

Synthesis Example 2 An emulsifier 2 was obtained in the same manner as in Synthesis Example 1 except that 26 parts of ethyl methacrylate was added to 26 parts of isobornyl acrylate.

The emulsifier 1 (Preparation Example 1), the emulsifier 2 (Preparation Example 2), the ion-exchange water 120.7, and the EPOMINP-1000 (manufactured by Nippon Shokubai Co., Ltd.) obtained in the synthesis examples 1 to 2 were prepared. 0.3 parts of polyglycerol polyglycidyl ether were added in this order, and stirred at room temperature for 10 minutes to obtain an antistatic coating 1 and an antistatic coating 2, respectively. The elemental analysis of the antistatic coatings 1 and 2 was carried out by XRF measurement to obtain a halogen content of 0.5 wt% and 0.5 wt%, respectively, and the metal contents were 0.01 wt% and 0.01 wt%, respectively.

Each of the antistatic coatings 1 and 2 was applied onto a glass substrate, dried at 100 ° C for 120 minutes, and then peeled off to obtain a film having a thickness of 30 μm, and the tensile modulus at room temperature was measured to obtain 0.8 GPa.

Further, the refractive indices of the antistatic coating material 1 and the antistatic coating material 2 were measured by an Abbe refractometer, and both were obtained at 1.50.

Preparation Example 3 A fully saponified polyvinyl alcohol having an average degree of polymerization of 1,700 was dissolved in water to 3% by weight to obtain a polyvinyl alcohol-based adhesive. The obtained polyvinyl alcohol-based adhesive was concentrated and made to have a concentration of 10% by weight, coated on a glass substrate, dried at 100 ° C for 120 minutes, and then peeled off to obtain a film having a thickness of 30 μm, and the tensile elasticity at room temperature was measured. After the rate, 0.4 GPa is obtained.

In Preparation Example 4, 250 parts of distilled water was placed in a reaction vessel, and 90 parts of butyl acrylate, 8 parts of 2-hydroxyethyl methacrylate, 2 parts of divinylbenzene, and 0.1 parts of potassium oleate were added to the reaction container. This system was stirred and dispersed by a stirring blade made of Teflon (registered trademark). Thereafter, after the inside of the reaction vessel was replaced with nitrogen, the system was heated to 50 ° C, 0.2 parts of potassium persulfate was added, and polymerization was started. Two hours after the start of the polymerization, 0.1 part of potassium persulfate was further added to the polymerization reaction system, and the system was heated to 80 ° C, and polymerization was continued for 1 hour to obtain a polymer dispersion.

Next, the polymer dispersion was concentrated to a solid concentration of 70% by weight using a distiller to obtain a water-based pressure-sensitive adhesive (aqueous pressure-sensitive adhesive having a polar group) composed of an aqueous dispersion of an acrylate polymer. ).

8 parts of the emulsifier 1 (Preparation Example 5) or the emulsifier 2 (Preparation Example 6) obtained in the synthesis examples 5 to 6 were prepared, and the average particle diameter of 0.10 μm in the preparation example 5 was used as a filler. Polystyrene-based true spherical particles (refractive index: 1.59) contained in an amount of 10% by weight based on the total particle diameter of 90% by weight, and an average particle diameter of 0.10 μm in Preparation Example 6 for the total amount of particles In the case of 80% by weight, the average particle diameter of 0.30 μm is 20% by weight of the total amount of the acrylic-based true spherical particles (refractive index of 1.51), and when the antistatic layer is formed, each volume fraction is used up to 10%. The amount is 120.7 parts of ion-exchanged water, 1 part of EPOMINP-1000 (manufactured by Nippon Shokubai Co., Ltd.), and 0.3 parts of polyglycerol polyglycidyl ether are added in this order, and stirred at room temperature for 10 minutes to obtain each antistatic coating 3 And antistatic coating 4. The elemental analysis of the antistatic coatings 3 and 4 was carried out by XRF measurement, and the halogen contents were each 0.5 wt% and 0.5 wt%, and the metal contents were 0.01 wt% and 0.01 wt%, respectively.

The antistatic coatings 3 and 4 were applied onto each of the glass substrates, dried at 100 ° C for 120 minutes, and then peeled off to obtain a film having a thickness of 30 μm. The tensile modulus at room temperature was measured to be 0.8 GPa.

Further, the refractive indices of the antistatic coating 3 and the antistatic coating 4 were measured by an Abbe refractometer, and both were obtained at 1.50.

[Examples 1 to 10]

Any one of the original borneol-based resin film is made of ARTON FLYL100 (manufactured by JSR Co., Ltd.) or ZEONOR ZF14-100 (manufactured by Japan Zeon Co., Ltd.) on the original borneol-based resin film before the application of the antistatic coating. Conducted in the atmosphere with and without 50W. In each case of the corona discharge treatment of min/m ² , the antistatic coatings 1 to 4 were applied with a coating bar having a wet film thickness of 6 μm, and dried at 110 ° C for 3 minutes to obtain films 1 to 10. Further, in each of the examples, the type of the original borneol-based resin film to be used, the presence or absence of corona treatment, and the type of the antistatic coating to be used are shown in Table 1 or Table 2.

For ARTON FLYL100 and ZEONOR ZF14-100, the tensile modulus at room temperature was measured to be 1 GPa.

Further, the surface roughness Ra (nm) and the wet tension (mN/m) of the film before the application of the antistatic coating after corona treatment are shown in Tables 1 and 2. Further, the evaluation results of the antistatic coating after application of the antistatic coating are also shown in Tables 1 and 2. Further, with respect to Examples 1, 9, and 10 (films 1, 9, and 10), evaluation of haze value and film take-up property was also carried out, and the results are shown in Table 2.

[Comparative Examples 1, 2]

A film A and a film B were obtained in the same manner as in Example 2 except that the antistatic coating 2 was used in an aqueous solution of 2% by weight of guanamine betaine or a 2% by weight aqueous solution of polyethylene glycol. The evaluation results of Film A and Film B are shown in Table 3.

Film A has a low surface resistance value and exhibits sufficient antistatic properties, but the adhesion and water resistance of the antistatic layer are poor.

On the other hand, although the film B exhibits sufficient adhesion and water resistance, the surface resistance value is high, and the antistatic property is not good.

[Example 11]

ARTON FLYL100 (manufactured by JSR Co., Ltd.) was used as the original borneol-based resin film, and the original borneol-based resin film before the application of the antistatic coating was not subjected to 50 W in the atmosphere. For the corona discharge treatment of min/m ² , the antistatic coating 2 was applied by a coating bar having a wet film thickness of 6 μm, and dried at 75 ° C for 1 minute to obtain a film 11 . Moreover, the glass transition temperature of ARTON FLYL100 is 165 °C.

The film 11 was heated in a forced stirring dryer at 150 ° C for 3 minutes to obtain a film 11-1.

Further, the film 11 is heated at Tg+15° C. (180° C.) in a tenter, and is extended by a width of 300%/min to extend 1.3 times in the longitudinal direction of the in-plane direction of the film, and then extended 1.8 times in the lateral direction of the film in-plane direction. Thereafter, in a Tg-20 ° C (145 ° C) environment, the state is kept under cooling for 1 minute, and further cooled to room temperature. After being taken out from the tenter, the film is obtained by secondary drying after the film is stretched. 2.

On the other hand, ARTON FLYL100 was heated at Tg+15°C (180°C) in a tenter, and extended at a stretching speed of 300%/min in the longitudinal direction of the in-plane direction of the film by 1.3 times, and then in the lateral direction of the film in-plane direction. After extending 1.8 times, in a Tg-20 ° C (145 ° C) environment, the state was kept under cooling for 1 minute, and further cooled to room temperature, and taken out from the tenter to obtain a retardation film 1. The retardation film 1 was subjected to corona discharge treatment in the same manner as in Example 1, and coated by the antistatic coating 2. The film obtained after drying was used as the film 11-3.

For each of the obtained films, the evaluation items of Example 2 and the in-plane phase difference (@ 550 nm), the thickness direction phase difference (@ 550 nm), and the film thickness were measured or evaluated. The results are shown in Table 4.

[Example 12]

ZEONOR ZF14-100 (manufactured by Japan Zeon Co., Ltd.) was used as the original borneol-based resin film, and the original borneol-based resin film before the application of the antistatic coating was not subjected to 50 W in the atmosphere. For the corona discharge treatment of min/m ² , the antistatic coating 2 was applied with a coating bar having a wet film thickness of 6 μm, and dried at 75 ° C for 1 minute to obtain a film 12 . And the glass transition temperature of ZEONOR ZF14-100 is 140 °C.

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

Further, the film 12 was heated at Tg + 15 ° C (155 ° C) in a tenter, and extended 1.3 times in the longitudinal direction of the in-plane direction of the film at an elongation speed of 300%/min, and then extended in the lateral direction of the film in-plane direction. Then, in the environment of Tg-20 ° C (125 ° C), it is kept in this state for 1 minute, cooled to room temperature, taken out from the tenter, and then obtained after the film is stretched twice. Film 12-2.

On the other hand, the ZEONOR ZF14-100 was heated in a tenter at Tg+15°C (155°C), extended at a stretching speed of 300%/min in the longitudinal direction of the in-plane direction of the film by 1.3 times, and then inward in the direction of the film. It was extended 1.8 times in the horizontal direction, and thereafter, it was cooled in the state of Tg-20 ° C (125 ° C) for 1 minute, cooled to room temperature, and taken out from the tenter to obtain a retardation film 2. The retardation film 2 is subjected to corona discharge treatment in the same manner as in the first embodiment, and is coated by the antistatic coating 2. The film obtained after drying was used as the film 12-3.

For each of the obtained films, the evaluation items of Example 2 and the in-plane phase difference (@ 550 nm), the thickness direction phase difference (@ 550 nm), and the film thickness were measured or evaluated. The results are shown in Table 4.

[Example 13]

Polyvinyl alcohol (hereinafter abbreviated as "PVA") is subjected to stretching treatment in a dye bath at a temperature of 30 ° C in an aqueous solution having an iodine concentration of 0.03% by weight and a potassium iodide concentration of 0.5% by weight. In a crosslinking bath having a concentration of 5% by weight and an aqueous solution having a potassium iodide concentration of 8% by weight at a temperature of 55 ° C, the stretching ratio was doubled and then extended, and after drying, a polarizing film was obtained (hereinafter also referred to as "polarizer". ").

Next, on the both sides of the polarizer, the polyvinyl alcohol-based adhesive obtained in Preparation Example 3 was used, and then the film 2 and the film 11-2 were held by a polarizer to obtain a polarizing plate 1. At this time, the surface on which the antistatic coating is applied is disposed on the polarizer side simultaneously with the film 2 and the film 11-2.

The film 2 and the film 11-2 were replaced in the same manner, and the polarizing plate 2 was obtained using the film 11-3.

The obtained polarizing plates 1 and 2 had a transmittance of 44.0% and a degree of polarization of 99.9%.

When the adhesion of the obtained polarizing plates 1 and 2 was evaluated, it was found that no peeling between the polarizing film and the retardation film occurred, and only material destruction occurred. The peel strength at this time was 6.0 N/25 mm under a 90° peel strength test.

[Example 14]

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

The obtained polarizing plates 3 and 4 had a transmittance of 44.0% and a degree of polarization of 99.9%.

Evaluation of the adhesion between the obtained polarizing plates 3 and 4 revealed that no peeling between the polarizer and the retardation film occurred, and only material destruction occurred. The peel strength at this time was 4.9 N/25 mm under a 90° peel strength test.

In addition, the surface of the film 2 and the film 11-2 to which the antistatic coating was not applied was simultaneously disposed on the side of the polarizer, and the same operation as in Example 13 was carried out to obtain a polarizing plate 5.

When the adhesion of the obtained polarizing plate 5 was evaluated, it was found that peeling between the polarizer and the retardation film easily occurred. The peel strength at this time was 0.3 N/25 mm under a 90° peel strength test.

[Example 15]

To evaluate the characteristics of the polarizing plate 1 described above, the polarizing plate and the retardation film attached to the viewer side of the liquid crystal panel of the commercially available liquid crystal television are peeled off in a clean environment, and the polarizing plate 1 is used to make the film 11-2 side. On the panel side, a water-based pressure-sensitive adhesive prepared in Preparation Example 4 was used, and the liquid crystal panel 1 obtained by attaching it to the front surface (observer side) of the liquid crystal panel was replaced.

The liquid crystal panel 1 does not observe dot defects even when the panel is turned on.

Further, even after the liquid crystal panel 1 was left in an environment of 60 ° C and a relative humidity of 90% for 1,000 hours, no change in the appearance of the panel, peeling of the panel from the polarizing plate, or peeling of the film from the polarizer was observed.

Further, after the liquid crystal panel 1 was allowed to stand in an environment of 80 ° C for 1,000 hours, no change in the appearance of the panel, peeling of the panel from the polarizing plate, or peeling of the film from the polarizer was observed.

[Example 16]

A film 16 was obtained in the same manner as in Example 2, except that a coating of 3 parts by weight of triethylene glycol monomethyl ether (boiling point: 249 ° C) was added to 100 parts by weight of the coating material 2.

In the film 2, a halogen lamp was used, and when the transparency was visually confirmed, a white turbidity phenomenon was slightly observed. However, when the transparency was visually confirmed under the same conditions as the film 16, no white turbidity was observed at all.

[Industrial availability]

The optical film of the present invention is applicable to display applications such as liquid crystal displays, and is particularly suitable for use in a polarizing plate. In addition, it has excellent adhesion, and can be used as a polarizing plate as a polarizing plate. The film, the film with the anti-reflection film, the film with the transparent conductive film, and the anti-red. It is used as a transparent substrate such as an ultraviolet film or various protective films.

Claims (27)

An optical film characterized by laminating (A) a raw borneol-based resin film and (B) an acrylic resin containing (b1) a 4-stage ammonium salt represented by the following formula (i) on a side chain, and (b2) an antistatic layer formed of an antistatic coating material of a hardening agent made of polyethyleneimine and/or polyhydroxyalkane polyglycidyl ether; -COO-Q ¹ -N(Q ² ) _a X _b (i) (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 ₄ (however, Q ³ is a single bond, a methyl group or an ethyl group), a and b are integers of 1 or 2 (however, a+b=3); Q ² , Q ³ and X are plural When they exist, they can be the same or different. The optical film of claim 1, wherein the antistatic coating material further comprises a filler. The optical film of claim 1, wherein the surface resistivity of the antistatic layer side is in the range of 1 × 10 ⁶ to 1 × 10 ¹² Ω / □. The optical film of claim 1, wherein the wettability of the surface of the antistatic layer measured by the method specified in JIS K6768 is in the range of 50 to 70 mN/m. The optical film of claim 1, wherein the acrylic resin (b1) is a structural unit containing a (meth) acrylate derived from an alicyclic skeleton. The optical film according to claim 1, wherein the difference between the refractive index of the norbornene-based resin film (A) and the antistatic layer (B) at a wavelength of 589 nm is 0.1 or less. The optical film of claim 1, wherein 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. An optical film according to the first aspect of the invention, wherein the tensile modulus E1 and the antistatic layer (B) of the raw norbornene resin film (A) at room temperature, which are determined by the method specified in JIS K7113, are used. The tensile modulus E2 is a relationship of E1>E2. The optical film of claim 1, wherein the raw borneol-based resin film (A) is a previously stretched film. A retardation film characterized by being made of an optical film as in claim 9 of the patent application. A retardation film characterized by being obtained by extending an optical film as in claim 1 of the patent application. A polarizing plate characterized by using at least one optical film as in the first aspect of the patent application. The polarizing plate of claim 12, wherein an antistatic layer of the optical film is attached to the polarizing film by using an adhesive or an adhesive. A polarizing plate characterized by using at least one retardation film as in claim 10 or 11 of the patent application. The polarizing plate of claim 14, wherein the antistatic layer of the retardation film is attached to the polarizing film by using an adhesive or an adhesive. The polarizing plate of claim 15 wherein the tensile modulus E1 of the original borneol-based resin film (A) and the tensile modulus E2 of the antistatic layer (B) are measured in accordance with JIS K7113. The tensile modulus E3 of the agent or the adhesive is in the relationship of E1>E2>E3. A liquid crystal display characterized by using a polarizing plate as in claim 12 of the patent application. A liquid crystal display characterized by using a polarizing plate as in claim 14 of the patent application. A method for producing an optical film characterized by comprising an acrylic resin (b1) having a 4-stage ammonium salt represented by the following formula (i) in a side chain, and polycondensation with polyethyleneimine and/or polyhydroxyalkane The antistatic coating material of the hardener (b2) which is a glyceryl ether is applied onto the original borneol resin film (A) and dried to form an antistatic layer (B); -COO-Q ¹ -N (Q ² _a X _b (i) (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 ₄ (however, Q ³ is a single bond, a methyl group or an ethyl group), a and b are integers of 1 or 2 (however, a+b=3); Q ² , Q ³ and X are When plural are present, each may be the same or different). The method for producing an optical film according to claim 19, wherein the surface of the original borneol-based resin film (A) coated with the antistatic coating material has an average surface roughness (Ra) of 0.3 to 2.0 nm. The method for producing an optical film according to claim 19, wherein the surface of the original borneol-based resin film (A) coated with the antistatic coating material is measured by the method specified in JIS K6768. It is in the range of 50 to 70 mN/m. The method for producing an optical film according to claim 19, wherein the acrylic resin (b1) is a structural unit containing a (meth) acrylate derived from an alicyclic skeleton. The method for producing an optical film according to claim 19, wherein the antistatic coating material is a water-based coating material. The method for producing an optical film according to claim 19, wherein the antistatic coating material further contains a filler. The method for producing an optical film according to claim 19, wherein the dried antistatic coating material is dried by having a drying step of 1) at 80 ° C or less, and 2) exceeding the original borneol resin. The multi-stage drying step of the secondary drying step of the film (A) at a glass transition temperature (Tg) of -30 ° C is carried out. The method for producing an optical film according to claim 25, wherein the stretching of the film is performed in the secondary drying step. The method for producing an optical film according to claim 19, wherein the acrylic resin (b1) has a halogen atom content of 1% by weight or less.