JP2015066748A - Gas barrier substrate for optical film and method for producing the same, optical film, polarizing plate and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier laminate for an optical film excellent in water-vapor barrier properties and excellent in adhesiveness while using a triacetylcellulose resin substrate or an acrylic resin substrate.SOLUTION: There is provided a barrier laminate for an optical film which comprises a primer layer and a barrier layer in this order on one transparent resin substrate selected from a triacetylcellulose resin substrate or an acrylic resin substrate. In the barrier laminate for an optical film, the primer layer is composed of a resin composition for a primer layer comprising at least: a polyolefin resin modified with one or more selected from an unsaturated carboxylic acid, an unsaturated carboxylic acid ester and an unsaturated carboxylic acid anhydride; and a terpene-based resin, or a cured product thereof. The barrier layer is composed of a resin composition for a barrier layer comprising at least a cycloolefin-based resin and a terpene-based resin, or a cured product thereof.

Description

  The present invention relates to a gas barrier substrate for an optical film and a method for producing the same, an optical film, a polarizing plate, and a display device.

Substrates for display devices such as liquid crystal display devices and organic light-emitting display devices have been replaced with glass substrates from resin substrates due to demands for thinning, lightening, and large screens. Since the resin base material has higher gas permeability than the glass base material, the display element using the resin base material has a problem that it is liable to deteriorate due to contact with water vapor or oxygen.
In order to prevent the influence of water vapor or the like, for example, a gas barrier film in which an inorganic compound layer or the like is formed on a resin substrate is used. By using such a gas barrier film, it has been studied to block the contact between the display element and water vapor entering from the outside and prevent the deterioration of the light emitting performance.

  Patent Document 1 discloses a gas barrier laminate in which a unit composed of two layers in which an inorganic barrier layer and a polymer layer are arranged adjacent to each other is used as a unit on a plastic film substrate, and is laminated three to five times. A gas barrier film having a body is disclosed. However, the gas barrier laminate of Patent Document 1 is manufactured through at least six film forming steps, and the productivity is poor. Moreover, in the Example of patent document 1, the biaxially stretched polyethylene naphthalate (PEN) film with low gas permeability was used as the said plastic film base material.

  In Patent Document 2, an inorganic oxide vapor-deposited layer in which an inorganic oxide is formed as a vapor-deposited layer on a base film made of a plastic film, and a specific mixed solution on the vapor-deposited layer side is used to obtain the base film. There is disclosed a gas barrier laminated film provided with a specific gas barrier coating film formed by applying a coating liquid of a gas barrier composition to be formed and heating and drying.

  Patent Document 3 discloses a gas barrier laminate film characterized by having a gas barrier layer comprising an inorganic thin film layer and an overcoat layer on a substrate film containing an inorganic compound.

JP 2011-102042 A JP 2010-678 A JP 2005-104026 A

  In conventional gas barrier laminate films, polyethylene naphthalate resin (PEN) and polyethylene terephthalate resin (PET), which have high barrier properties, are widely used as a resin base material (Patent Documents 1 and 2). However, the PEN substrate and the PET substrate have a problem that they have birefringence and are liable to generate interference fringes. For display device applications, gas barrier laminates using triacetylcellulose resin bases and acrylic resin bases with low birefringence and excellent visible light transmittance are required from the viewpoint of further improving optical performance. ing.

The gas barrier layers of Patent Documents 1 to 3 all include an inorganic compound layer. Since such an inorganic compound layer has a hard and brittle nature, there is a risk of cracks. In addition, when the adhesion between the resin base material and the inorganic compound layer is low, peeling may occur due to stress applied when the film is bent, heat shrinkage, etc., and the gas barrier property may be deteriorated.
The gas barrier layers of Patent Documents 1 to 3 are all manufactured using a dry coating method such as vapor deposition or a sol-gel method. Due to demands for an optical film with a large area accompanying an increase in the size of an image display device, and demands for productivity and cost reduction, it has been desired to produce a gas barrier layer by a wet coating method.

  The present invention has been made in view of the above circumstances, and is a barrier laminate for optical films having excellent water vapor shielding properties and excellent adhesion while using a triacetyl cellulose resin substrate or an acrylic resin substrate, and the production thereof. It is an object of the present invention to provide a method, an optical film excellent in water vapor shielding properties, and reduced birefringence, a polarizing film, and a display device using them.

As a result of intensive studies to achieve the above object, the present inventor has a combination of a specific primer layer and a specific barrier layer, so that triacetyl cellulose has a higher gas permeability than a PET substrate. Even when a resin base material or an acrylic resin base material was used, it was found that excellent water vapor shielding properties were obtained and adhesion between layers was also excellent.
The present invention has been completed based on such knowledge.

That is, the barrier laminate for an optical film according to the present invention has a primer layer and a barrier layer in this order on one transparent resin substrate selected from a triacetyl cellulose resin substrate and an acrylic resin substrate. An optical film barrier laminate,
The primer layer contains at least a polyolefin resin modified with at least one selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic acid ester, and an unsaturated carboxylic acid anhydride, and a terpene resin. It consists of a resin composition for a primer layer or a cured product thereof,
The barrier layer comprises a resin composition for a barrier layer containing at least a cycloolefin resin and a terpene resin or a cured product thereof.

In the method for producing a barrier laminate for an optical film according to the present invention, a primer layer and a barrier layer are arranged in this order on one transparent resin substrate selected from a triacetyl cellulose resin substrate and an acrylic resin substrate. A method for producing a barrier laminate for an optical film comprising:
Forming a barrier layer comprising a resin composition for a barrier layer containing at least a cycloolefin-based resin and a terpene-based resin or a cured product thereof on a support substrate;
On the barrier layer, contains at least a polyolefin resin modified with one or more selected from the group consisting of unsaturated carboxylic acid, unsaturated carboxylic acid ester, and unsaturated carboxylic acid anhydride, and a terpene resin Forming a primer layer comprising a primer layer resin composition or a cured product thereof, and
A step of bonding the transparent resin substrate on the primer layer;
And a step of peeling the support substrate.

  In the barrier laminate for an optical film of the present invention and the method for producing the barrier laminate for an optical film of the present invention, the primer layer resin composition further contains an elastomer. And it is preferable from the point which adhesiveness improves.

  The optical film according to the present invention has at least one selected from a hard coat layer, an antireflection layer, an antiglare layer, and an antistatic layer on at least one surface of the barrier laminate for optical films according to the present invention. It has a layer.

  The polarizing film according to the present invention has the barrier laminate for an optical film according to the present invention on at least one surface side of the polarizing layer.

  The display device according to the present invention includes at least one selected from the group consisting of the barrier laminate for optical films according to the present invention, the optical film according to the present invention, and the polarizing film according to the present invention. It is characterized by that.

  According to the present invention, while using a triacetyl cellulose resin base material or an acrylic resin base material, it is excellent in water vapor shielding properties and has excellent adhesion, a barrier laminate for optical films, excellent in water vapor shielding properties, and has reduced birefringence. An optical film, a polarizing film, and a display device using these can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of a barrier laminate for an optical film according to the present invention. FIG. 2 is a schematic cross-sectional view showing an example of an optical film according to the present invention. FIG. 3 is a schematic cross-sectional view showing another example of the optical film according to the present invention. FIG. 4 is a schematic cross-sectional view showing an example of a polarizing film according to the present invention. FIG. 5 is a schematic cross-sectional view showing another example of the polarizing film according to the present invention. FIG. 6 is a schematic cross-sectional view showing another example of the polarizing film according to the present invention. FIG. 7 is a schematic cross-sectional view showing another example of the polarizing film according to the present invention. FIG. 8 is a schematic view showing an example of a display device according to the present invention.

Hereinafter, the barrier laminate for an optical film, the optical film, the polarizing film, and the display device according to the present invention will be described in order.
In the present invention, (meth) acryl represents each of acryl or methacryl, and (meth) acrylate represents each of acrylate or methacrylate.
Further, in the present invention, the cured product means a material that has been hardened through a chemical reaction, and the curability means a property that becomes hard through a chemical reaction.

[Barrier laminate for optical film]
The barrier laminate for an optical film according to the present invention has a primer layer and a barrier layer in this order on one transparent resin substrate selected from a triacetyl cellulose resin substrate and an acrylic resin substrate. A barrier laminate for film,
The primer layer contains at least a polyolefin resin modified with at least one selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic acid ester, and an unsaturated carboxylic acid anhydride, and a terpene resin. It consists of a resin composition for a primer layer or a cured product thereof,
The barrier layer comprises a resin composition for a barrier layer containing at least a cycloolefin resin and a terpene resin or a cured product thereof.

  The barrier laminate for optical films of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of a barrier laminate for an optical film of the present invention. As shown in the example of FIG. 1, the barrier laminate 10 for an optical film of the present invention has a primer layer 2 and a barrier layer 3 in this order on a triacetyl cellulose resin substrate or an acrylic resin substrate 1. doing.

  The barrier laminate for an optical film of the present invention is a polyolefin resin modified with one or more selected from the group consisting of unsaturated carboxylic acid, unsaturated carboxylic acid ester, and unsaturated carboxylic acid anhydride (hereinafter, And a modified polyolefin resin.), A primer layer made of a cured product of a resin composition for a primer layer containing at least a terpene resin, a cycloolefin resin, and a terpene resin Even when a triacetyl cellulose resin base or an acrylic resin base having a high water vapor permeability is used by combining a resin composition for a barrier layer or a barrier layer made of a cured product thereof, a high water vapor A laminate having shielding properties and excellent adhesion between layers can be obtained.

The present inventor uses a combination of a cycloolefin resin and a terpene resin, so that the cycloolefin resin and the terpene resin are compatible with each other and the solvent solubility is improved. The knowledge that high water vapor shielding property was expressed was acquired. However, the resin composition containing such a cycloolefin-based resin has a problem of poor adhesion to a triacetyl cellulose resin substrate or an acrylic resin substrate and poor film forming properties. On the other hand, by providing a primer layer comprising a resin composition for a primer layer containing the modified polyolefin resin and a terpene resin or a cured product thereof on a triacetyl cellulose resin substrate or an acrylic resin substrate. In addition, a barrier layer using a combination of a cycloolefin-based resin and a terpene-based resin can be satisfactorily formed on a triacetyl cellulose resin base or an acrylic resin base while being closely attached.
From the above, the barrier laminate for optical films of the present invention is excellent in water vapor shielding properties while using a triacetyl cellulose resin substrate or an acrylic resin substrate. Since the barrier laminate for optical films of the present invention does not have an inorganic compound layer, cracks are not generated even by stress generated when the film is bent or thermal contraction.
Moreover, since the barrier laminate for optical film of the present invention can be produced by a wet coating method as described later, there is an advantage that it is excellent in productivity and can be reduced in cost compared with a sol-gel method or a dry coating method. .

The barrier laminate for an optical film of the present invention has at least a base material, a primer layer, and a barrier layer, and has other layers as necessary unless the effects of the present invention are impaired. It may be.
Hereinafter, each configuration of the barrier laminate for an optical film of the present invention will be described in detail in order.

<Barrier layer>
The barrier layer in the barrier laminate for optical films of the present invention is characterized by comprising a resin composition for a barrier layer containing at least a cycloolefin resin and a terpene resin, or a cured product thereof. It is estimated that when the cycloolefin resin has a bulky skeleton derived from cycloolefin, water vapor hardly penetrates the barrier layer. By using a combination of a cycloolefin-based resin and a terpene-based resin, the barrier layer has high gas barrier properties, excellent film forming properties, and excellent adhesion to a primer layer described later.

  The barrier layer resin composition contains at least a cycloolefin resin and a terpene resin, and may further contain other components as long as the effects of the present invention are not impaired. Hereinafter, each component of such a resin composition for barrier layers is demonstrated in order.

(Cycloolefin resin)
In the present invention, the cycloolefin-based resin represents a polymer having a monomer structural unit composed of cycloolefin. Specifically, it may be a cycloolefin polymer obtained by ring-opening polymerization of cycloolefin, and cycloolefin obtained by addition polymerization of cycloolefin and one or more selected from a chain olefin and an aromatic compound having a vinyl group. A copolymer may be sufficient and the one part or all part may be hydrogenated.

Specific examples of the cycloolefin include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethyl-bicyclo [2.2.1] hept-2-ene, and 5-butyl. -Bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] hept-2-ene , 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene), tetracyclo [ 8.4.0.1 ^11,14. 0 ^3,7 ] pentadeca-3,5,7,12,11-pentaene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4-methano -1,4,4a, 5,10,10a hexa hydro anthracene, 8-phenyl - tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as “1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene”), pentacyclo [7.4.0 ^.1,3,6 . 1 ^10,13 . 0 ^2,7] pentadeca-4,11-diene, pentacyclo [9.2.1.1 ^4,7. 0 ^2,10 . 0 ^3,8 ] pentadeca-5,12-diene and the like, and may further have a substituent. Examples of the substituent that may have, for example, carboxyl group (hydroxycarbonyl group), sulfonic acid group, phosphoric acid group, hydroxyl group, primary amino group, secondary amino group, tertiary amino group, Primary amide group, secondary amide group (imide group), N-substituted imide group, thiol group, ester group (referred to generically as alkoxycarbonyl group and aryloxycarbonyl group), epoxy group, halogen atom, cyano Group, oxycarbonyl group (acid anhydride residue of dicarboxylic acid), alkoxy group, carbonyl group, acryloyl group and the like. These cycloolefins can be used alone or in combination of two or more.

Examples of the chain olefin used in the cycloolefin copolymer include α-olefins having 3 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1- Examples include hexene, 1-octene, and 1-decene. Specific examples of the aromatic compound having a vinyl group include styrene, vinyl naphthalene, methyl styrene, propyl styrene, cyclohexyl styrene, dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene, m-divinylbenzene, p-divinylbenzene, bis (4-vinylphenyl) methane and the like can be mentioned.
The chain olefin and the aromatic compound having a vinyl group can be used alone or in combination of two or more.

  Specific examples of the cycloolefin resin include the following chemical formulas (I) to (V).

(In the chemical formulas (I) to (V), x and y are each a number of 1 or more. Further, R in the chemical formula (V) each independently represents a carbon atom that may contain a hydrogen atom or an oxygen atom. Represents a hydrogen group, and adjacent Rs may be bonded to form a ring structure.)

  The cycloolefin resin is preferably a cycloolefin copolymer from the viewpoint of solubility in a solvent, and moreover, from the viewpoint of excellent balance between solubility in a solvent, film-forming property, and gas barrier property. A cycloolefin copolymer obtained by addition polymerization of a cyclic cycloolefin and a chain olefin is preferable, and a cycloolefin copolymer represented by the general formula (I) or the general formula (II) is still more preferable.

  When the cycloolefin resin is a cycloolefin copolymer, the content of the cycloolefin-derived structural unit in the cycloolefin copolymer is 10 to 90 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. From the viewpoint of excellent balance between film forming properties and gas barrier properties. Among them, for example, when the cycloolefin is norbornene or a derivative thereof, it is preferably 50 to 90 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer, and when the cycloolefin is tetracyclododecene or a derivative thereof. Is preferably 10 to 50 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. If the content rate of the structural unit derived from a cycloolefin is more than the said lower limit, it is excellent in the solubility to a solvent. Moreover, if it is below the said upper limit, it is excellent in gas-barrier property.

  What is necessary is just to select suitably the glass transition temperature (Tg) of cycloolefin type resin according to a use. Especially, it is preferable that the glass transition temperature (Tg) of cycloolefin type resin is 60-200 degreeC from the point of film forming property and gas barrier property, and it is more preferable that it is 60-150 degreeC.

The cycloolefin-based resin may be synthesized by ring-opening polymerization or addition polymerization of cycloolefin by a conventionally known method, or a commercially available product may be used.
Examples of the cycloolefin copolymer include TOPAS manufactured by Polyplastics and APEL manufactured by Mitsui Chemicals. Examples of the cycloolefin polymer include ZEONOR, ZEONEX, ZEOCOAT, and JSR ARTON manufactured by Nippon Zeon.

The content of the cycloolefin resin in the barrier layer resin composition is not particularly limited. Especially, it is preferable that cycloolefin resin is 5-95 mass parts with respect to 100 mass parts of total solids in the resin composition for barrier layers from the point which is excellent in gas barrier property, and is 10-90 mass parts. More preferred is 45 to 90 parts by mass.
In addition, in this invention, solid content represents all components other than a solvent.

(Terpene resin)
In the present invention, the terpene resin refers to a polymer of terpenes, a copolymer of terpenes and other monomers, and those obtained by hydrogenation of these polymers. In the present invention, terpenes refer to monomers in which isoprene (C ₅ H ₈ ) is a structural unit and two or more of the isoprene are polymerized, and are monoterpene (C ₁₀ ), sesquiterpene (C ₁₅ ), diterpene (C ₂₀ ). ), Sesterterpenes (C ₂₅ ), triterpenes (C ₃₀ ), tetraterpenes (C ₄₀ ), and the like, and further terpenoids having substituents such as carbonyl groups and hydroxy groups. Specific examples of the terpenes include pinene, dipentene, karen, myrcene, ocimene, limonene, terpinolene, terpinene, sabinene, tricyclene and the like.
Examples of other monomers that can be polymerized with terpenes include aromatic monomers such as styrene, α-methylstyrene, and vinyl toluene, and phenolic monomers such as phenol, cresol, and bisphenol A.

  In the present invention, the terpene resin is a terpene resin, which is a polymer of the terpenes, and a terpene and a phenol monomer, from the viewpoint of the film forming property of the barrier layer and the adhesion to the primer layer described later. It is preferably a polymerized terpene phenol resin, an aromatic modified terpene resin obtained by modifying the terpene resin with an aromatic monomer, and a hydrogenated product thereof, and more preferably a terpene phenol resin and a hydrogenated product thereof. .

The terpene resin can be obtained, for example, by copolymerizing terpenes alone or terpenes with other monomers in the presence of a Friedel-Crafts type catalyst in an organic solvent. In addition, hydrogenation products of various terpene resins can be obtained by hydrogenating the obtained polymer with hydrogen gas in the presence of a hydrogenation catalyst.
Commercial products such as YS Polystar T, YS Polyster U, YS Resin PX, YS Resin TO, YS Resin TR, Clearon, Mighty Ace, etc., manufactured by Yasuhara Chemical Co., Ltd. may be used.

  The content ratio of the terpene resin in the barrier layer resin composition is not particularly limited. Among these, from the viewpoint of film forming properties of the barrier layer and adhesion with the primer layer described later, the terpene resin is 5 to 95 parts by mass with respect to 100 parts by mass of the total solid content in the resin composition for the barrier layer. It is preferable that it is 10-90 mass parts, and it is still more preferable that it is 10-55 mass parts.

(solvent)
The resin composition for a barrier layer usually contains a solvent from the viewpoint of coatability. The solvent does not react with each component in the composition, and can be appropriately selected from solvents that can dissolve or disperse each component. Specific examples of such solvents include hydrocarbon solvents such as benzene, toluene, xylene, hexane and cyclohexane, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone, tetrahydrofuran, and 1,2-dimethoxy. Ether solvents such as ethane and propylene glycol monoethyl ether (PGME), alkyl halide solvents such as chloroform and dichloromethane, ester solvents such as methyl acetate, ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, N, N -Amide solvents such as dimethylformamide, sulfoxide solvents such as dimethyl sulfoxide, anone solvents such as cyclohexane, alcohols such as methanol, ethanol, and propanol It can be exemplified solvents, but not limited thereto. Moreover, the solvent used for the said composition may be used individually by 1 type, and the mixed solvent of two or more types of solvents may be sufficient as it.

  When using a solvent for the resin composition for a barrier layer, the ratio of the solid content with respect to the total amount of the resin composition for the barrier layer is preferably 3 to 20% by mass, more preferably 5 to 15% from the viewpoint of coating properties. % Is preferably used.

(Other ingredients)
The resin composition for a barrier layer may further contain other components as long as the effects of the present invention are not impaired.
Examples of other components include surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, viscosity modifiers, and the like. Can be mentioned.
You may contain a well-known acrylic polymer from the point of adhesiveness with the primer layer mentioned later.
Moreover, in order to provide sclerosis | hardenability to the resin composition for barrier layers, you may contain a well-known thermosetting component thru | or a photocurable component.

<Primer layer>
The primer layer in the barrier laminate for optical films of the present invention is a polyolefin resin modified with one or more selected from the group consisting of unsaturated carboxylic acid, unsaturated carboxylic acid ester, and unsaturated carboxylic acid anhydride And a resin composition for a primer layer containing at least a terpene resin or a cured product thereof. By interposing such a primer layer, the adhesive strength between the layers is increased and the adhesion with the barrier layer is improved.

  The primer layer resin composition contains at least the specific modified polyolefin resin and the terpene resin, and may further contain other components as long as the effects of the present invention are not impaired. Is. Hereinafter, each component of such a resin composition for primer layers is demonstrated in order. In addition, about terpene-type resin, since it can be set as the thing similar to what was demonstrated in the said resin composition for barrier layers, description here is abbreviate | omitted.

(Polyolefin resin modified with one or more selected from the group consisting of unsaturated carboxylic acid, unsaturated carboxylic acid ester, and unsaturated carboxylic acid anhydride)
The modified polyolefin resin used in the primer layer resin composition is a polymer or copolymer of an olefin monomer, and at least a part thereof is an unsaturated carboxylic acid, an unsaturated carboxylic acid ester, and an unsaturated carboxylic acid. It is a resin modified with one or more selected from the group consisting of anhydrides.

As the olefin monomer, one or two or more kinds can be appropriately selected from compounds having one or more ethylenically unsaturated double bonds in one molecule. In the present invention, the polyolefin-based resin is preferably mainly composed of a chain olefin, and more preferably composed mainly of ethylene or an α-olefin having 3 to 20 carbon atoms, from the viewpoint of adhesion. Preferably, propylene is the main component.
In addition, in this invention, a main component means the component which occupies 50 mass% or more with respect to the whole monomer which comprises resin.

  Moreover, when polymerizing a polyolefin resin, an unsaturated carboxylic acid or an unsaturated carboxylic acid ester may be used in combination as a monomer component. Specific examples of such monomers include (meth) acrylic acid, (meth) acrylate monomers, vinyl acetate, and the like.

Specific examples of the polyolefin-based resin mainly containing propylene include polypropylene, ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-propylene-butene copolymer.
In the present invention, the polyolefin resins can be used singly or in combination of two or more.

In the present invention, one or more selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid esters, and unsaturated carboxylic acid anhydrides are used as the modifier for the polyolefin resin.
Specific examples of such modifiers include fumaric acid, maleic acid, itaconic acid, citraconic acid, aconitic acid, nadic acid, and anhydrides thereof; methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate , Dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, maleimide N-phenylmaleimide; (meth) acrylic acid and various (meth) acrylate monomers, among which unsaturated carboxylic acid anhydride and (meth) acrylate monomer are preferable, itaconic anhydride, maleic anhydride, Methyl (meth) acrylate, Le (meth) acrylate are more preferred. These modifiers can be used alone or in combination of two or more.

  The amount of the modifier used is not particularly limited, and may be adjusted as appropriate. Above all, it is preferably 0.1 to 20 parts by mass, and 0.5 to 12 parts by mass with respect to 100 parts by mass of the polyolefin resin. More preferably, it is a part.

The weight average molecular weight of the modified polyolefin resin is not particularly limited and may be appropriately selected. Especially, it is preferable that the weight average molecular weights of modified polyolefin resin are 700-200000, and it is more preferable that it is 800-150,000.
In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography using polystyrene as a standard substance.

In the case of a modified polyolefin resin having a relatively small weight average molecular weight, that is, a modified polyolefin resin having a weight average molecular weight of 700 to 30000, preferably 800 to 20000, the terminal of the polyolefin resin is an unsaturated carboxylic acid, It is preferably a modified polyolefin resin modified with one or more selected from the group consisting of a saturated carboxylic acid ester and an unsaturated carboxylic acid anhydride, and a low molecular weight polypropylene which is a thermal degradation product of a high molecular weight polypropylene is It is preferably modified by at least one selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid esters, and unsaturated carboxylic acid anhydrides.
On the other hand, in the case of a modified polyolefin resin having a relatively large weight average molecular weight, that is, a modified polyolefin resin having a weight average molecular weight of 15,000 to 200,000, preferably 20000 to 150,000, a polyolefin resin mainly composed of propylene, Modified with one or more selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic acid ester, and an unsaturated carboxylic acid anhydride, and an ethylene α-olefin copolymer having an unsaturated bond at one end It is preferable. As the ethylene α-olefin copolymer having an unsaturated bond at one end, it is preferable to select and use one having a weight average molecular weight of 800 to 30,000 as appropriate.

The method for producing the modified polyolefin resin can be appropriately selected from conventionally known methods. For example, methods such as pamphlet of International Publication No. 2008/013085, Japanese Patent No. 2526132, Japanese Patent No. 3513768 can be referred to.
In addition, for example, Auroren manufactured by Nippon Paper Chemicals, Aronmelt PPET manufactured by Toagosei Co., Ltd., Umex manufactured by Sanyo Chemical Industries, Admer manufactured by Mitsui Chemicals, Sumifit CK1D manufactured by Sumika Chemtex, Hardren manufactured by Toyobo, A commercially available product containing a modified polyolefin resin may be used.

The content ratio of the modified polyolefin resin in the primer layer resin composition is not particularly limited, but from the viewpoint of adhesion to the barrier layer and the base material, with respect to 100 parts by mass of the solid content of the primer layer resin composition, The amount is preferably 10 to 90 parts by mass, and more preferably 20 to 80 parts by mass.
Further, the content ratio of the terpene resin in the primer layer resin composition is not particularly limited, but from the viewpoint of adhesion to the barrier layer and the substrate, the solid content of the primer layer resin composition is 100 parts by mass. 10 to 90 parts by mass, preferably 20 to 80 parts by mass.

(solvent)
The resin composition for primer layers usually contains a solvent from the viewpoint of coatability. The solvent does not react with each component in the composition, and can be appropriately selected from solvents that can dissolve or disperse each component. For example, the same solvent as mentioned in the description of the barrier layer resin composition can be used. Of these, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone are preferably used.

  When using a solvent for the primer layer resin composition, from the viewpoint of coating properties, it is preferably used so that the ratio of the solid content to the total amount of the primer layer resin composition is 10 to 60% by mass. It is more preferable to use so that it may become -50 mass%.

The resin composition for a primer layer may further contain other components as long as the effects of the present invention are not impaired.
Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, silicon-based or fluorine-based leveling agents, stabilizers, antifoaming agents, anti-repellent agents, oxidation Examples thereof include an inhibitor, an aggregation inhibitor, a viscosity modifier, and a release agent.

  Moreover, it is preferable that the resin composition for primer layers contains an elastomer further from the point which improves water vapor | steam shielding property. In the present invention, an elastomer represents a resin exhibiting rubber elasticity, and includes synthetic rubber and the like. Among them, the elastomer preferably contains at least one selected from polyisobutylene and styrene-based copolymers. Examples of the styrene copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, and among them, a styrene-isoprene-styrene block copolymer is preferable.

  The elastomer used in the present invention preferably has a softening point of 80 ° C to 160 ° C, and more preferably 100 ° C to 150 ° C. The melt viscosity of the elastomer is not particularly limited, but among them, the melt viscosity at 190 ° C is preferably 200 to 5000 mPa · s, and more preferably 300 to 4000 mPa · s. The weight average molecular weight of the elastomer is not particularly limited, but is preferably 10,000 to 5,000,000, and more preferably 30,000 to 4,000,000.

  Further, the content ratio of styrene in the styrene-based copolymer is not particularly limited, but it is 13 to the entire styrene-based copolymer from the viewpoint of excellent adhesion and ensuring applicability of the primer layer resin composition. It is preferable that it is -37 mass%.

The elastomer may be appropriately produced from conventionally known methods, or a commercially available product may be used.
Examples of the styrenic copolymer include Kuraray Co., Ltd., Septon 2063, Septon 2002, Septon 2004, Septon 2005, Septon 2006, Septon 2007, Septon 2104; Clayton Polymer Japan, Kraton G1633, Kraton G1640, Kraton G1641 and Kraton G1642 Clayton G1643, Clayton G1645, Clayton G1650, Clayton G1651, Clayton G1652, Clayton G1654, Clayton G1657, Clayton G1660, Clayton G1726; Ube Industries, Ltd. UT2535, UT2304, etc. Moreover, as polyisobutylene, OPSFOL B-10N, B-12N, B-15N, B-30SF, B-50SF, B-80, B-100, B-150, and B-220 manufactured by BASF are suitable. It is mentioned as a thing.

  When polyisobutylene and a styrene-based copolymer are used for the primer layer resin composition, the content ratio is not particularly limited, but from the point of improving the adhesion, the total solid content of the primer layer resin composition is 100 parts by mass. On the other hand, it is preferable to set it as 1-40 mass parts, and it is more preferable to set it as 5-30 mass parts.

<Base material>
In the present invention, one transparent resin substrate selected from a triacetyl cellulose resin substrate and an acrylic resin substrate is used as the substrate. By using these, even when used for an optical film, problems of birefringence and interference fringes are suppressed.

  The triacetyl cellulose base material may be appropriately selected from known triacetyl cellulose base materials used for optical films. As triacetyl cellulose in the present invention, in addition to pure triacetyl cellulose, cellulose acetate propionate and cellulose acetate butyrate may be used in combination with components other than acetic acid as fatty acids forming esters with cellulose. . These triacetyl celluloses may be added with other cellulose lower fatty acid esters such as diacetyl cellulose or various additives such as a plasticizer, an antistatic agent, and an ultraviolet absorber as required.

  The acrylic resin base material may be appropriately selected from known acrylic resin base materials used for optical films. For example, the base material formed from the acrylic resin obtained by superposing | polymerizing monomers, such as (meth) acrylic acid ester, acrylamide, acrylonitrile, (meth) acrylic acid, or its derivative (s) is mentioned. Among these, in terms of transparency and weather resistance, polymethyl methacrylate, a copolymer having a methyl methacrylate unit as a main constituent, or a styrene-methyl methacrylate copolymer substrate is preferable.

  What is necessary is just to set suitably the thickness of a triacetylcellulose resin base material and an acrylic resin base material within the range which can provide required self-supporting property according to the use etc. of the barriering laminated body for optical films. Usually, it exists in the range of about 10-500 micrometers, and 20-250 micrometers is especially preferable.

  The triacetyl cellulose resin base material and the acrylic resin base material used in the present invention preferably have a transmittance in the visible light region of 80% or more, and more preferably 90% or more. Here, the transmittance | permeability of a base material can be measured by JISK7361-1 (the test method of the total light transmittance of a plastic-transparent material).

<Method for producing barrier laminate for optical film>
What is necessary is just to select the manufacturing method of the barriering laminated body for optical films of this invention suitably from a conventionally well-known method. Among them, it is preferable to use a wet coating method from the viewpoints of easy application of continuous production by roll-to-roll, an increase in the area of the optical film, and improvement of productivity. Specific examples of the wet coating method include, for example, a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, a wire bar coating method, a gravure coating method, a die coating method, a blade coating method, a micro gravure coating method, and a spray. Examples thereof include a coating method, a spin coating method, and a comma coating method.

As a manufacturing method of the barriering laminated body for optical films using the wet coat method, the following manufacturing method is mentioned, for example. First, the primer layer resin composition containing at least a modified polyolefin resin and a terpene resin on one side of one transparent resin substrate selected from a triacetyl cellulose resin substrate and an acrylic resin substrate The primer layer is formed by coating by a wet coating method.
Next, on the primer layer, a barrier layer resin composition containing at least a cycloolefin resin and a terpene resin is applied by the wet coating method, dried, cured as necessary, and barrier layer. By forming the layer, the barrier laminate for optical films of the present invention is obtained.

On the other hand, from the viewpoint of improving adhesion and water vapor shielding properties, the following production method is preferred. That is, in the method for producing a barrier laminate for an optical film of the present invention, a primer layer and a barrier layer are placed on one transparent resin substrate selected from a triacetyl cellulose resin substrate and an acrylic resin substrate. In order to have a method for producing a barrier laminate for an optical film,
Forming a barrier layer comprising a resin composition for a barrier layer containing at least a cycloolefin-based resin and a terpene-based resin or a cured product thereof on a support substrate;
On the barrier layer, contains at least a polyolefin resin modified with one or more selected from the group consisting of unsaturated carboxylic acid, unsaturated carboxylic acid ester, and unsaturated carboxylic acid anhydride, and a terpene resin Forming a primer layer comprising a primer layer resin composition or a cured product thereof, and
A step of bonding the transparent resin substrate on the primer layer;
And a step of peeling the support substrate.

  According to the production method of the present invention, the barrier layer is first formed on the support substrate, and then the primer layer having excellent adhesion with the barrier layer is formed on the barrier layer. Thus, an optical film barrier laminate having excellent water vapor shielding properties can be obtained.

  The support substrate can be appropriately selected from those having excellent barrier layer film-forming properties and easily peelable from the barrier layer. Specific examples of such a support substrate include known release films. Among them, a polyethylene terephthalate film (PET film) is preferable because it is excellent in film forming properties and release properties of the barrier layer.

  The method for forming the barrier layer and the primer layer can be the same as a conventionally known method, and can be appropriately selected from the above wet coating methods.

  In the step of laminating the transparent resin substrate on the primer layer, the transparent resin substrate used is not particularly limited, and is a triacetyl cellulose resin substrate or an acrylic resin substrate used for the barrier laminate for optical films. Can be appropriately selected.

  What is necessary is just to select the bonding method suitably from conventionally well-known methods. For example, the method of facing a transparent resin base material on a primer layer, and pressurizing using a roller etc. is mentioned.

The barrier laminate for an optical film obtained by the above production method may be subjected to a surface treatment in order to further improve the adhesion. As the surface treatment, known resin surface modification techniques such as corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, chemical treatment, plasma treatment, grafting treatment, heat treatment, etc. Can be applied. Only one type of surface treatment may be performed, or two or more types may be performed.
In the present invention, from the viewpoint of adhesion, it is preferable to carry out surface treatment by heating, such as a method of heating to 70 ° C. or higher and heat laminating, or a method of heating under pressure using an autoclave.

In the barrier laminate for optical films of the present invention, the thickness of the primer layer may be appropriately adjusted according to the application. Especially, it is preferable that it is 1-20 micrometers, and it is more preferable that it is 5-15 micrometers.
Moreover, what is necessary is just to adjust the film thickness of a barrier layer suitably according to a use. Especially, it is preferable that it is 1-20 micrometers, and it is more preferable that it is 5-15 micrometers.

The barrier laminate for an optical film of the present invention can achieve excellent water vapor shielding properties with a water vapor permeability of 25 g / m ² · day or less. Among them, it is preferable that water vapor permeability is not more than 20g ^/ m 2 · day, more preferably at most 17g ^/ m 2 · day.

In the present invention, the water vapor transmission rate is in accordance with the infrared sensor method of JIS K 7129 (1992) “Test method for water vapor transmission rate of plastic film and sheet”, test temperature 40 ° C. ± 0.5 ° C., relative humidity (90 ± 2) Measured under test conditions of% RH.
As a device used for the above measurement, a water vapor transmission rate measuring device manufactured by MOCON, PERMATRAN-W3 / 33 series, or the like can be used.

<Use of barrier laminate for optical film>
The barrier laminate for optical films of the present invention has high visible light transmittance, low birefringence, and excellent gas barrier properties. Therefore, it is suitable as a substrate for optical films described later and a protective layer for polarizing plates. Can be used.

[Optical film]
The optical film according to the present invention has at least one selected from a hard coat layer, an antireflection layer, an antiglare layer, and an antistatic layer on at least one surface of the barrier laminate for optical films according to the present invention. It has a layer.
Since the optical film of the present invention has the above-mentioned barrier laminate for optical films of the present invention having a small birefringence and a high visible light transmittance, it can easily achieve desired optical performance and has excellent gas barrier properties.

  The optical film of this invention is demonstrated with reference to FIG.2 and FIG.3. FIG.2 and FIG.3 is a schematic cross section which shows an example of the optical film 20 of this invention. As shown in the example of FIG. 2, the optical film 20 of the present invention has a hard coat layer, an antireflection layer, an antiglare layer, and a charge on the barrier layer 3 side of the optical film barrier laminate 10 of the present invention. One or more layers 4 selected from the prevention layer may be included, and as shown in the example of FIG. 3, the optical film 20 of the present invention is the barrier laminate 10 for optical films of the present invention. One or more layers 4 selected from a hard coat layer, an antireflection layer, an antiglare layer, and an antistatic layer may be provided on the substrate 1 side. Although not shown, the optical film barrier laminate 10 of the present invention has at least one layer 4 selected from a hard coat layer, an antireflection layer, an antiglare layer, and an antistatic layer on both surfaces. May be.

<Hard coat layer>
The hard coat layer is a layer having a function of protecting the surface of the optical film by increasing the hardness. The hard coat layer can be appropriately selected from conventionally known ones. The hard coat layer is preferably a layer made of a cured product of the curable resin composition. As a curable resin that can also be applied as a hard coat layer, an ionizing radiation curable resin, other known curable resins, and the like may be appropriately employed depending on required performance. Examples of the ionizing radiation curable resin include acrylate-based, oxetane-based, and silicone-based resins. For example, acrylate-based ionizing radiation curable resins include monofunctional (meth) acrylate monomers, bifunctional (meth) acrylate monomer monomers, (meth) acrylate monomers such as trifunctional or higher (meth) acrylate monomers, urethane ( It consists of (meth) acrylate ester oligomers such as (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate, or (meth) acrylate prepolymers. Examples of tri- or higher functional (meth) acrylate monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

The hard coat layer is obtained by applying and curing the resin composition for a hard coat layer containing the curable resin on at least one side of the optical film barrier laminate of the present invention.
What is necessary is just to adjust the film thickness of a hard-coat layer suitably in the optical film of this invention. Especially, it is preferable that it is 1-50 micrometers, and it is more preferable that it is 3-25 micrometers.

<Antireflection layer>
The antireflection layer is a layer that prevents reflection of a background due to specular reflection of extraneous light. In the present invention, the antireflection layer can be appropriately selected from conventionally known antireflection layers. For example, a material with a high refractive index and a material with a low refractive index are laminated alternately, and the outermost surface is multilayered (multi-coat) so that it becomes a low refractive index layer. It is possible to obtain an antireflection layer or the like that suppresses the reflection of light and obtains a good antireflection effect.

<Anti-glare layer>
The antiglare layer is a layer that scatters or diffuses extraneous light. For example, extraneous light can be diffused by roughening the light incident surface. This roughening treatment includes a method of directly roughing the surface of the substrate by forming fine irregularities by a sandblasting method, an embossing method, etc., in a resin binder that hardens the surface of the substrate by radiation or heat or a combination thereof. Examples thereof include a method of providing a roughened layer with a coating film containing an inorganic filler such as silica and an organic filler such as resin particles, and a method of forming a porous film having a sea-island structure on the substrate surface. As the resin of the resin binder, a curable acrylic resin, an ionizing radiation curable resin, or the like is preferably used in the same manner as the hard coat layer because surface strength is desired as the surface layer.

<Antistatic layer>
In order to suppress static electricity of the optical film, an antistatic layer may be provided. The antistatic layer can be appropriately selected from conventionally known ones. For example, the antistatic layer can be obtained by mixing and using a known antistatic agent in the hard coat resin composition.
Specific examples of the antistatic agent include quaternary ammonium salts, pyridinium salts, various cationic compounds having cationic groups such as primary to tertiary amino groups, sulfonate groups, sulfate ester bases, and phosphate ester bases. , Anionic compounds having an anionic group such as phosphonate group, amphoteric compounds such as amino acid series and aminosulfate ester series, nonionic compounds such as amino alcohol series, glycerin series and polyethylene glycol series, and alkoxides of tin and titanium And metal chelate compounds such as acetylacetonate salts thereof, and compounds obtained by increasing the molecular weight of the compounds listed above. In addition, it has a tertiary amino group, a quaternary ammonium group, or a metal chelate portion, and has a monomer or oligomer that can be polymerized by ionizing radiation, or a polymerizable functional group that can be polymerized by ionizing radiation, and Polymerizable compounds such as organometallic compounds such as coupling agents can also be used as antistatic agents. Further, a conductive polymer or the like may be used.

[Polarized film]
The polarizing film according to the present invention has the barrier laminate for an optical film according to the present invention on at least one surface side of the polarizing layer.

The polarizing film of this invention is demonstrated with reference to FIGS. 4 to 7 are schematic cross-sectional views showing an example of the polarizing film 30 of the present invention. 4 and 5, the polarizing film 30 of the present invention has the optical film barrier laminate 10 of the present invention on at least one surface side of the polarizing layer 5. As shown in the example of FIG. 4, the substrate 1 side surface of the barrier laminate for optical film 10 may be in contact with the polarizing layer 5, and the optical film as shown in the example of FIG. 5. The barrier layer 3 side surface of the side barrier laminate 10 and the polarizing layer 5 may be in contact with each other. Moreover, as shown in the examples of FIGS. 6 and 7, the optical film barrier laminate 10 of the present invention may be provided on both surfaces of the polarizing layer 5. As shown in the example of FIG. 6, the substrate 1 side surface of the barrier laminate for optical film 10 and the polarizing layer 5 may be in contact with each other. As shown in the example of FIG. The barrier layer 3 side surface of the side barrier laminate 10 and the polarizing layer 5 may be in contact with each other.
Although not shown, an adhesive layer or the like may be provided between the polarizing layer 5 and the optical film barrier laminate 10.
Since the polarizing film of the present invention has the barrier laminate for optical films according to the present invention having excellent gas barrier properties on at least one surface side of the polarizing layer, the polarizing layer is hardly deteriorated.

<Polarizing layer>
As the polarizing layer, for example, a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer saponified film, which is dyed with iodine or dye and stretched can be used.

[Display device]
The display device according to the present invention comprises at least one selected from the group consisting of the barrier laminate for optical films according to the present invention, the optical film according to the present invention, and the polarizing film according to the present invention. It is characterized by.
Since the display device of the present invention has the barrier laminate for optical films according to the present invention, the permeation of water vapor and oxygen is blocked, and deterioration of optical elements and the like in the panel can be prevented.

  The display device of the present invention includes (1) a display device using the barrier laminate for optical films according to the present invention instead of various substrates used in known display devices, and (2) a known liquid crystal display device. (3) Those using the polarizing film according to the present invention instead of the polarizing plate in (3), those having the optical film according to the present invention on the display surface of a known display device, and combinations thereof. It is done.

A specific example will be described with reference to FIG. FIG. 8 is a schematic view showing an example of a display device according to the present invention. In the example of FIG. 8, an example of a liquid crystal display device is shown as an example of the display device 100. The display device 100 normally includes a surface light source device 50 and a liquid crystal panel 60. The surface light source device 50 includes a light source 31, a light guide plate 32, a light reflection plate 34, and the like, and has an optical film 33 having light diffusibility and the like on the light emission surface side. The liquid crystal panel includes a liquid crystal layer 37, a color filter 38, a transparent electrode, and the like between the glass substrates 36 and 39, and polarizing films 35 and 40 on the surface of the glass substrates 36 and 39 opposite to the liquid crystal layer 37. Is arranged.
The liquid crystal device of the present invention has the optical film barrier laminate according to the present invention in a part of the display device 100. For example, the liquid crystal device of the present invention can be used as a substrate of an optical film included in the surface light source device 50. The barrier laminate for an optical film according to the invention may be used, and at least one of the polarizing films 35 and 40 may be the polarizing film according to the invention, and the optical film according to the invention is provided on the outermost surface. 41 may be included.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

(Production Example 1: Preparation of primer layer composition a)
Aurolen 353S (manufactured by Nippon Paper Chemical Co., Ltd., modified polyolefin resin obtained by modifying a polyolefin resin containing propylene with maleic anhydride and an ethylene-α olefin copolymer having an unsaturated bond at one end; solid content 100% 7 parts by mass, 3 parts by mass of YS Polystar TH130 (manufactured by Yashara Chemical Co., Ltd., terpene phenol resin) and 90 parts by mass of toluene were mixed to obtain a primer layer composition a.

(Production Example 2: Preparation of primer layer composition b)
A primer was prepared in the same manner as in Production Example 1 except that Opanol B-50SF (manufactured by BASF, polyisobutylene, weight average molecular weight 400,000) was used, and the blending ratio was changed as shown in Table 1. A layer composition b was obtained.

(Production Example 3: Preparation of primer layer composition c)
Production Example 2 except that Opanol B-30SF (manufactured by BASF, polyisobutylene, weight average molecular weight 200,000) was used instead of Opanol B-50SF in Production Example 2, and the blending ratio was changed as shown in Table 1. In the same manner as in No. 2, a primer layer composition c was obtained.

(Production Example 4: Preparation of composition d for primer layer)
In Production Example 2, Opanol B-12N (manufactured by BASF, polyisobutylene, weight average molecular weight 50,000) was used instead of Opanol B-50SF, and the production ratio was changed as shown in Table 1 except that Production Ratio was changed as shown in Table 1. In the same manner as in No. 2, a primer layer composition d was obtained.

(Production Example 5: Preparation of composition e for primer layer)
Production Example 2 except that Opanol B-10N (manufactured by BASF, polyisobutylene, weight average molecular weight 30,000) was used instead of Oppanol B-50SF, and the blending ratio was changed as shown in Table 1. In the same manner as in No. 2, a primer layer composition e was obtained.

(Comparative Production Example 1: Preparation of comparative primer layer composition f)
In Production Example 5, a comparative primer layer composition f was obtained in the same manner as in Production Example 5, except that YS polystar TH130 was not used and the blending ratio was changed as shown in Table 1.

(Comparative Production Example 2: Preparation of comparative primer layer composition g)
In Production Example 5, a comparative primer layer composition g was obtained in the same manner as in Production Example 5 except that Aurolen 353S was not used and the blending ratio was changed as shown in Table 1.

(Production Example 6: Preparation of resin composition A for barrier layer)
TOPAS8007 (manufactured by Polyplastics Co., Ltd., cycloolefin copolymer represented by the above general formula (I): COC, cycloolefin content in polymer of 65% by mass, Tg: 78 ° C.) 7 parts by mass, YS polystar TH130 (Yasuhara Chemical) The resin composition A for barrier layers was obtained by mixing 3 parts by mass of a terpene phenol resin (manufactured by company) and 90 parts by mass of toluene.

(Production Examples 7 to 8: Preparation of barrier layer resin compositions B to C)
In Production Example 6, barrier layer resin compositions B to C were obtained in the same manner as in Production Example 6 except that the blending ratios were changed as shown in Table 2.

(Comparative Production Example 3: Preparation of Comparative Barrier Layer Resin Composition D)
In Production Example 6, a comparative barrier layer resin composition D was obtained in the same manner as in Production Example 6, except that YS polystar TH130 was not used and the blending ratio was changed as shown in Table 2.

(Example 1: Production of barrier laminate for optical film)
On the polyethylene terephthalate release film, the barrier layer resin composition A was applied and dried to form a barrier layer A having a thickness of 10 μm.
Next, the primer layer resin composition a was applied onto the barrier layer A and dried to form a primer layer a having a thickness of 10 μm.
A TAC substrate having a thickness of 40 μm was laminated on the primer layer by heat laminating at 90 ° C., and after pressure bonding at 50 ° C. and 5 MPa for 30 minutes by an autoclave, the support substrate was peeled off from the barrier layer A. Thus, a barrier laminate A for optical films was obtained.

(Examples 2 to 5: Production of barrier laminate for optical film)
In Example 1, instead of the primer layer resin composition a, the optical film barrier laminates B to E were prepared in the same manner as in Example 1 except that the primer layer resin compositions be to e were used. Obtained.

(Example 6: Production of barrier laminate for optical film)
In Example 5, a barrier laminate F for optical films was obtained in the same manner as in Example 5 except that the thickness of the primer layer was changed to 25 μm.

(Example 7: Production of barrier laminate for optical film)
In Example 1, instead of the primer layer resin composition a, Alonmelt PPET1401SG (resin composition containing a modified polyolefin resin as a main component and containing a terpene resin and a styrene-isoprene-styrene block copolymer; solid content; 40%, manufactured by Toagosei Co., Ltd.) was used in the same manner as in Example 1 to obtain an optical film barrier laminate G.

(Example 8: Production of barrier laminate for optical film)
In Example 7, an optical film barrier laminate H was obtained in the same manner as in Example 7 except that the thicknesses of the barrier layer and the primer layer were changed to 25 μm.

(Example 9: Production of barrier laminate for optical film)
A barrier laminate I for optical films was obtained in the same manner as in Example 7, except that the barrier layer resin composition B was used instead of the barrier layer resin composition A in Example 7.

(Example 10: Production of barrier laminate for optical film)
In Example 7, except that the barrier layer resin composition C was used instead of the barrier layer resin composition A, a barrier laminate J for optical films was obtained in the same manner as in Example 7.

(Example 11: Production of barrier laminate for optical film)
In Example 7, an optical film barrier laminate K was obtained in the same manner as in Example 7 except that a TAC substrate having a thickness of 25 μm was used instead of the TAC substrate having a thickness of 40 μm.

(Comparative Examples 1-2: Production of barrier laminate for comparative optical film)
In Example 1, instead of the primer layer resin composition a, the comparative primer layer resin compositions f to g were used in the same manner as in Example 1 except that the comparative primer layer resin compositions f to g were used. M was obtained.

(Comparative Example 3: Production of barrier laminate for comparative optical film)
In Example 7, a comparative optical film barrier laminate N was obtained in the same manner as in Example 7 except that the comparative barrier layer resin composition D was used instead of the barrier layer resin composition A.

(Comparative Example 4: Production of barrier laminate for comparative optical film)
In Example 11, a comparative optical film barrier laminate O was obtained in the same manner as in Example 11 except that the comparative barrier layer resin composition D was used instead of the barrier layer resin composition A.

(Comparative Example 5: Production of barrier laminate for comparative optical film)
In Example 1, instead of the primer layer resin composition a, an ultraviolet curable adhesive UVX-5457 (manufactured by Toagosei Co., Ltd.) was used, and the film thickness of the primer layer was changed to 40 μm. Thus, a barrier laminate P for a comparative optical film was obtained.

<Water vapor permeability evaluation>
Test pieces were prepared from the barrier laminates for optical films of Examples and Comparative Examples, respectively, and using a water vapor permeability measuring device manufactured by MOCON, PERMATRAN-W3 / 33, JIS K 7129 (1992) “Plastic film and The water vapor transmission rate was measured under the test conditions of a test temperature of 40 ° C. ± 0.5 ° C. and a relative humidity (90 ± 2)% RH in accordance with the infrared sensor method of “Test method for water vapor transmission rate of sheet”.
The results are shown in Table 3. If the water vapor permeability is 25 g / m ² · day or less, it is evaluated that the gas barrier property is excellent.

<Adhesion evaluation>
The adhesion of the barrier layer and the primer layer of the barrier laminate for optical films obtained in Examples and Comparative Examples was performed according to the cross-cut test of JIS K5400. That is, the barrier layer and the primer layer were cut into a grid pattern at intervals of 1 mm using a cutter knife to form a lattice of 100 squares. Next, cellophane tape (Nichiban Co., Ltd.) was applied on the lattice and then peeled off. After repeating this 5 times, peeling of the barrier layer or primer layer was observed. Adhesion was evaluated according to the following evaluation criteria. The results are shown in Table 3. If the following evaluation result is (circle) or (double-circle), it will be evaluated that it is excellent in adhesiveness.
(Adhesion evaluation criteria)
(Double-circle): The peeling of the barrier layer and the primer layer was less than 5%.
(Circle): The peeling of the barrier layer and the primer layer was 5% or more and less than 20%.
Δ: Separation of the barrier layer and the primer layer was 20% or more and less than 50%.
X: The peeling of the barrier layer and the primer layer was 50% or more.

DESCRIPTION OF SYMBOLS 1 Triacetylcellulose resin base material or acrylic resin base material 2 Primer layer 3 Barrier layer 4 One or more layers selected from a hard-coat layer, an antireflection layer, and an anti-glare layer 5 Polarizing layer 10 Barrier laminate for optical films Body 20 Optical film 30 Polarizing film 31 Light source 32 Light guide plate 33 Optical film 34 Light reflecting plate 35 Polarizing film 36 Glass substrate 37 Liquid crystal layer 38 Color filter 39 Glass substrate 40 Polarizing plate 41 Optical film 50 Surface light source device 60 Liquid crystal panel 100 Display device

Claims (6)

A barrier laminate for an optical film having a primer layer and a barrier layer in this order on one transparent resin substrate selected from a triacetyl cellulose resin substrate and an acrylic resin substrate,
The primer layer contains at least a polyolefin resin modified with at least one selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic acid ester, and an unsaturated carboxylic acid anhydride, and a terpene resin. It consists of a resin composition for a primer layer or a cured product thereof,
A barrier laminate for an optical film, wherein the barrier layer comprises a resin composition for a barrier layer containing at least a cycloolefin resin and a terpene resin or a cured product thereof.   The barrier laminate for an optical film according to claim 1, wherein the primer layer resin composition further contains an elastomer.   An optical having at least one layer selected from a hard coat layer, an antireflection layer, an antiglare layer, and an antistatic layer on at least one surface of the barrier laminate for an optical film according to claim 1 or 2. the film.   The polarizing film which has the barriering laminated body for optical films of Claim 1 or 2 in the at least one surface side of a polarizing layer.   A display device comprising at least one selected from the group consisting of the barrier laminate for an optical film according to claim 1, the optical film according to claim 3, and the polarizing film according to claim 4. . A method for producing a barrier laminate for an optical film, comprising a primer layer and a barrier layer in this order on one transparent resin substrate selected from a triacetyl cellulose resin substrate and an acrylic resin substrate,
Forming a barrier layer comprising a resin composition for a barrier layer containing at least a cycloolefin-based resin and a terpene-based resin or a cured product thereof on a support substrate;
On the barrier layer, contains at least a polyolefin resin modified with one or more selected from the group consisting of unsaturated carboxylic acid, unsaturated carboxylic acid ester, and unsaturated carboxylic acid anhydride, and a terpene resin Forming a primer layer comprising a primer layer resin composition or a cured product thereof, and
A step of bonding the transparent resin substrate on the primer layer;
A method for producing a barrier laminate for an optical film, comprising a step of peeling the support substrate.